annual meeting 2015 - Ecole Doctorale de Chimie de Lyon

MAY
7
ANNUAL
MEETING 2015
Ecole Doctorale de Chimie
Lyon
Discover the frontiers of chemistry through the researches of PhD
Candidates in Chemistry in Lyon, France - 2 Plenary lectures, 15 oral
communications by the PhD candidates and poster sessions.
Main Library Theater, Université Lyon 1, Villeurbanne, France, ,
Thursday May 7, 2015, 9h-18h
www.edchimie-lyon.fr
Annual Meeting 2015 Programm
Reception/Posters installation.
8h45 - 10h00 - Opening Ceremony/ Plenary 1 : Prof. Dr. Uwe J. Meierhenrich, Nice Sophia
8h30-8h45 Antipolis University, Institut de Chimie de Nice, CNRS UMR 7272.
Coee Break/Poster Presentation.
10h30-12h30 - Oral communications of PhD Students :
10h00-10h30 10h30-10h45 : Hamou Reverse Flow Reactor : Design and Process Evaluation for Trapping of
Molecular Ruthenium Catalysts
10h45-11h : Locial CO2 for Energy : Cu2 O/Pt/TiO2 composite materials for photo-catalytic
valorization of CO2 11h-11h15 : Catherin Selective ring opening of decalin over bifunctional catalysts in the
presence of sulfur
11h15-11h30 : Dooms About the hydrolytic and acidogenic stage in dry temperature phased
anaerobic digestion : inuence of temperature and retention time
11h30-11h45 : Guérin Bis-triazolyl BODIPY's : a simple core with high red-light emission
11h45-12h : Li Analoges of DIcinnamic Quinic Acid Derivatives as potential new biopesticides
12h-12h15 : Juban Process Induced Transformations (PITs) during tablet manufacturing :
Investigations of a polymorphic transition of a model pharmaceutical active ingredient (caffeine)
12h15-12h30 : Troussicot Dynamic-Based Ligand Design : Application to Human Peroxiredoxin 5
Lunch/Poster Presentation
13h45-14h45 - Plenary 2, Jean-Luc Duplan, IFP Energies nouvelles, Direction de l'établissement
12h30-13h45 de Lyon.
Coee Break/ Poster Presentation.
15h45-17h45 - Oral communications of PhD Students :
14h45-15h45 15h45-16h :Balogh Luminescent core/shell crystals based on lanthanide complexes, bioinspired and recyclable
2
16h-16h15 : Gondrand Magnetogenic probes for in vitro and in vivo detection of enzymes by
Magnetic Resonance Imaging
16h15-16h30 : Paredes-Nunez Study of cobalt-based Fisher-Tropsch catalysts exposed to trichloethylene by operando DRIFTS
16h30-16h45 : Prieto Copper catalysed triuoromethylation of N,N-Disubstituted hydrazones
16h45-17h : Bertarello Paramagnetic metalloproteins with MAS over 100 KHz : NMR nally
gets onto the metal center
17h-17h15 : Galeandro-Diamant Platinum nanoparticles are as active as Karstedt's catalyst
in alkene hydrosilylation
17h15-17h30 : Zhang A Fluorescent Heteroditopic Hemicryptophane Cage for The Selective
Recognition of Choline Phospate
17h30-17h45 : Palfy Planted Detentive lters for treating combined sewer overow
17h45 -18h :
Rewarding of the Best Posters/End of the day.
3
Oral Communications
4
Reverse Flow Reactor : Design and Process Evaluation for Trapping of
Molecular Ruthenium Catalysts.
M.Hamou, V. Meille and C. de Bellefon
Laboratory for Catalytic Process Engineering, CNRS-CPE-Lyon.
43, bd du 11 Nov 1918, 69616 Villeurbanne Cedex, France
Introduction
Despite
high
activities
and
selectivities
of
homogeneous
catalysts,
their
difficult
removal from the reacting mixture limits their industrial applications. In the case of methyl oleate self-metathesis, an
original process is being studied.
The
use
of
a
reverse
flow
reactor
that
combines
self-metathesis
and
the
adsorption/desorption
ruthenium catalysts on a support is proposed.
the
of
homogeneous
the
reaction
of
homogeneous
The reverse flow technology is based on reversible catalyst-support interactions. The catalysts are adsorbed by physical
forces occurring between the surface of the support and the ruthenium based catalyst.
In a reverse flow reactor, the catalyst is desorbed and released in solution during the reaction and readsorbed at the end
of the reaction.
This combines the benefits of homogeneous catalysis (high activity and selectivity) and heterogeneous catalysis
(catalyst separation and recovering).
In the fixed bed reverse flow reactor, the midle of the column is preloaded by catalyst. When the process is started, the
reagents enter to the reactor and are transformed into products. Catalyst moves and migrates inside the column as in
chromatography, and when it reaches the end of the reactor, flow is stopped and then reversed to keep catalyst inside the
reactor.
During the reverse flow cycle, catalyst moves and migrates inside the column in the opposite direction, and when it
reaches the other end of the reactor, the flow is stopped and then reversed, and so on.
Results and discussion
1) The results of the simulation (without catalyst makeup) are summarized in Fig.1.
They show the catalyst concentration profiles in the liquid phase for some cycles. The adsorption/ desorption front is
broadening during the reversible process due to the axial dispersion and mass transfer. Leaching starts to occur after the
70th cycle. Due to leaching and without catalyst makeup, reactor losses it performance and stable operation can not be
reached.
2) With catalyst makeup (Fig.2), leaching is compensated and reactor performance are kept. Cyclic steady state (CSS) is
reached after 1000 cycles, and concentration profiles become time independent.
3) The influence of the process parameters are also studied. The concentration
profiles of the adsorbing species depends on the adsorbent properties (adsorbent capacity, effective diffusion coefficient,
particle size, etc) and on the hydrodynamics inside the reactor.
JED Chimie Lyon 2015
CO2 for Energy: Cu2O/Pt/TiO2 composite materials for photocatalytic valorization of CO2
D. Lofficial1,2, A. Fécant 1, D. Uzio1, C. Geantet2, E. Puzenat *,2,
1
2
IFPEN-établissement de Lyon Rond-point de l'échangeur de Solaize, BP 3, 69360 Solaize
IRCELYON UMR 5256 CNRS-Université Lyon I, 2 Avenue Albert Einstein69626 Villeurbanne cedex
(*) corresponding author: [email protected]
Keywords: photocatalytic reduction, CO2, Z-scheme, heterojunctions, titania
1
Introduction
In the last decades, the increase of atmospheric concentration of CO2, identified as the principal greenhouse gas
in the atmosphere, seems to be one of our major environmental concerns. In May 2013, the concentration of CO2
measured at Mauna Loa station reached 400ppm for the first time [1] representing an important turning point for the
climate change. For our energy-hungry civilization the reduction of CO2 emissions seems to be a difficult task.
Thus, the valorization of this greenhouse gas appears as the alternative solution to reduce its atmospheric concentration.
In the context of renewable energy use, it could be attractive to employ sunlight energy to transform the CO 2 into hydrocarbon molecules. Nature works wonders: indeed the photosynthesis process is able to convert CO 2 and
H2O in hydrocarbon compounds by using the sunlight. This capture and transformation of light energy by plants is
based on a Z-scheme, first described by Robin Hill and Fay Bendall [2].
Inspired by these mechanisms, we propose a photocatalytic strategy using inorganic composite semiconductors
with heterojunctions to convert CO2 into various value added compounds. Indeed, the formation of heterojunctions
leads to an efficient separation of electron-hole pairs to minimize the energy-wasteful electron-hole recombination,
and enhanced photocatalytic activity [3]. The objective of this research is to synthesize a composite material composed of two different semiconductors and one metal to create SC2-M-SC1 heterojonction. This photocatalyst, by
reaching the suitable potentials, should be able to convert CO2 and H2O into hydrocarbons, alcohols or acids, under
artificial or natural light.
The first efforts were focused on the synthesis of the composite material Cu2O/Pt/TiO2 according to the electronic properties of its different components apart. The main challenge is to cover selectively the metal (platinum)
nanoparticles deposited on TiO2 by Cu2O.
2
Experimental/methodology
This kind of composite materials were already synthesised by various techniques such as co-precipitation, solgel method, impregnation...[4,5]. However, the selective coverage of the metal does not seem to be fully achieved.
In order to reach a selective covering of metallic particles and to specifically localise them on the electrons pathways, we built our material by successive photodeposition [6] of Pt and Cu2O. The different steps of this process
will be explained.
3
Results and discussion
Various characterizations were conducted to verify specific architecture of obtained hybrid materials. XPS analysis confirms the reduction of 70% of Cu +II into Cu +I on the catalyst surface. TEM images evidences the presence of Cu2O-Pt-TiO2 heterojunctions. Different parameters such as sacrificial agent, light flux, Pt content were
optimized to obtain the targeted material. A tentative mechanism of the photoreduction has been established and
will be discussed.
This material was tested in photocatalytic reduction of CO2, its specific reactivity will be discussed.
4 Conclusions
A specific strategy was implemented to build suitable photocatalysts to convert CO 2. The recombination process
must be limited by heterojunctions and proper potentials must be achieved to reduce CO 2 and to oxidize H2O or H2
simultaneously. Original syntheses were carried out to obtain the catalyst Cu2O/Pt/TiO2 with selective coverage of
Pt by Cu2O. This catalyst seems to present a specific activity towards photocatalytic reduction of compared to Pt/
TiO2 and TiO2. We are further investigating the reaction mechanism and improving our catalytic systems.
References
[1] http://www.esrl.noaa.gov/gmd/ccgg/trends/
[2] R.Hill, F. Bendall, Nature Lond. 186 (1960)
[3] J. S. Jang, H. G. Kim, J. S. Lee, Catal. Today 185 (2012)
[4] Z. Li, J. Liu, D. Wang, Y. Gao, J. Shen, Int. J. Hydrogen Energy 37 (2012)
[5] H. Lin, J. Cao, B. Luo, B. Xu, S. Chen, Catal. Comm. 21 (2012)
[6] Z. Zhang, J. T. Yates, Chem. Rev. 112 (2012)
Selective ring opening of decalin over bifunctional
catalysts in the presence of sulfur
Nelly Catherin,1 Luca Di Felice,1 Laurent Piccolo,1 Dorothée
Laurenti,1 Christophe Geantet,1 Vincenzo Calemma2
1
Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), CNRS &
Université Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex, France
2
Eni S.p.A., DO& T/ Research & Technological Innovation, Via F. Maritano 26, 20097 San
Donato Milanese, Italy
The Selective Ring Opening (SRO) of aromatic and naphthenic hydrocarbons contained in
petroleum cuts such as Light Cycle Oil (LCO) is required for the improvement of gas oil fuel
combustion properties. The desired products are linear paraffins, which exhibit the highest
cetane numbers.
We focus our study on the SRO of a saturated bicyclic molecule, decalin, in order to screen
the catalysts and understand the mechanisms of ring opening. We use bifunctional catalysts
containing both an acidic function (oxide support) leading to cracking and isomerization
reactions, and a metallic function (metal or sulfide nanoparticles) leading to hydrogenation,
dehydrogenation and hydrogenolysis reactions. Both hydrogenolysis and cracking steps
permit in principle the ring opening.
The reaction was performed in a flow fixed
bed reactor at 200-300 °C under 4 MPa H2.
The first difficulty of this work was the
identification and quantification of the
hundreds of products formed from decalin
hydroconversion. With the help of twodimensional gas chromatography coupled
to mass spectrometry (Figure 1), the
products could be classified into five
families: 2-ring-opening (2ROP), 1-ringopening
(1ROP/AROP),
skeletal
isomerization (SkIP), cracking (CkP) and
dehydrogenation (DHP) products.
Figure 1 : GCxGC-MS chromatogram obtained from decalin
hydroconversion over a RuS2/HY catalyst at 240°C, 5.0 MPa H2, 23 kPa
decalin, 1 % H2S.
In general, the presence of H2S in the reaction feed (as in the case of real petroleum cuts),
leads to a lower catalyst activity and selectivity to ROP. Thus, the challenge is to conceive a
highly thioresistant and selective catalyst. In this regard, our first approach is to optimize the
metal-acid site balance through the independent tuning of support acidity and metal identity.
ORAL PRESENTATION
LUMINESCENT CORE/SHELL CRYSTALS BASED ON LANTHANIDE
COMPLEXES, BIO-INSPIRED AND RECYCLABLE
C. Balogha,b, F. Riobéa, L. Veyreb, C. Thieuleuxb, O. Maurya
a
b
École Normale Supérieure de Lyon, 46 allée d'Italie - 69364 Lyon
Laboratoire C2P2, CPE Lyon, 43 bd du 11 novembre 1918 - 69616 Villeurbanne
[email protected]
Taking inspiration from natural systems,[1] guanidium is an excellent countercation for lanthanide complexes since it facilitates the crystallization of this water
soluble molecules and improves their luminescent properties in the solid state.[2]
Control of crystallization is a very delicate issue, hence only a few examples can
be found in the literature.[3] Using the guanidinium counter-cation, we studied the
entire lanthanide series of [Ln(DPA)3]-3 complexes (DPA = pyridine-2,6dicarboxylate) and found interesting changes of the lattice parameters, the
complexes not being isostructural throughout the series. Applying this new
information, we could successfully control the growth during crystallization,
obtaining epitaxial core/shell crystals. A non-emissive Ln complex surrounding a
Tb or Eu core led to the interesting phenomenon of shielding effect induced by the
outer layer which blocks the excitation wavelength. Furthermore, a more
interactive effect can be observed using dual Tb/Eu core/shell systems by
specifically choosing the excitation wavelength.
Figure. Tb@Eu core/shell crystal under UV (λex=365nm).
References
[1] G. Pompidor, A. D’Aléo, O. Maury, Angew. Chem.2008, 47, 3388–3391.
[2] A. D’Aléo, C. Andraud, O. Maury, Optical Materials 2008, 30, 1682-1688.
[3] E. Brès, S. Ferlay, M. Hosseini, J. Mater. Chem. 2007, 17, 1559-1562.
Bis-triazolyl BODIPYs: a simple core with high red-light emission
Charles Guérin, Dr Ludivine Jean-Gérard, and Pr. Bruno Andrioletti
Laboratory CASYEN, ICBMS UMR CNRS 5246, Bât. Curien/CPE
43 Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex - FRANCE
BODIPYs (boron dipyrromethenes) have received a considerable attention due to their interesting
spectroscopic properties.1 Application properties of BODIPYs can be reached after appropriate
functionalization. Among them, the development of optical probes for the recognition of anions, metals,
oxidants has been investigated.2
Considering the demand in new markers for medical imaging and in vivo applications,3 the research
has been extended to red-emitting BODIPYs, a class of fluorophores specifically designed for the red-light
emission and compatibility toward organism.4
FG
Ar
Ar
N
B
N
Ar
N
B
Ar
N
F F
F F
FG
Naked BODIPY core
λem = 504 nm
FG
Fonctionnalized red-emitting BODIPY model
λem ≥ 580 nm
We have designed a new class of BODIPY derivatives, obtained by Click-chemistry.5 These
BODIPYs possess very good spectral properties in organic solvents and water (red-light emission around
600 nm, with high quantum yield). Permeability and cytotoxicity was evaluated by incubation of HeLa cells
in lipophilic and water-soluble fluorophores solutions.
N
N
Ts
N
H
N
N
R
N
N
N N
R
B
N
F F
N
N N
R
λem = 590-606 nm
Φ = 81-100%
ε = ~ 65000
(1)
(2)
(3)
(4)
(5)
Loudet, A.; Burgess, K. Chem. Rev. 2007, 107, 4891–4932.
Boens, N.; Leen, V.; Dehaen, W. Chem. Soc. Rev. 2012, 41, 1130–1172.
Kowada, T.; Maeda, H.; Kikuchi, K. Chem. Soc. Rev. 2015.
Lu, H.; Mack, J.; Yang, Y.; Shen, Z. Chem. Soc. Rev. 2014, 43, 4778–4823.
Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. Engl. 2001, 40, 2004–2021.
Annual meeting of the graduate school of chemistry, Lyon, 7th May 2015
Analogues of Dicinnamic Quinic Acid Derivatives as potential new biopesticides
Xiubin Li,1,2 Lucie Grand,1,2Thomas Pouleriguen,1,2Yves Queneau,1,2Sylvie Moebs-Sanchez.1,2
Pedro da Silva,3 Yvan Rahbé,3
1 INSA-Lyon, Chimie Organique et Biorganique, Bât Jules Verne, F-69621, Villeurbanne Cedex.
2 Institut de Chimie et de Biochimie Moléculaires et Supramoléculaires, UMR 5246, CNRS, Université de Lyon,
INSA-Lyon, Université Claude Bernard Lyon 1, CPE-Lyon
3- BF2I (Biologie Fonctionnelle, Insectes et Interactions), INRA - INSA-Lyon, F-69621, Villeurbanne
Dicinnamic quinic acids (DCQA) are natural compounds found in a wide range of dietary and
medicinal plants and have been reported to exhibite a wide biological activities.1 DCQA possess a
quinic acid unit and two trans-cinnamic acid units. Recently, biologists from INSA-Lyon-BF2I reported
the potential of DCQA as biopesticides,2 3,5-dicaffeoylquinic acid being found to exhibite a higher
activity than other CQA derivatives.
Nevertheless, the reports of synthesis of DCQA are rather limited compared to those for
monosubstituted derivatives.3 We have so far focused on the synthesis of various DCQA or esters
derivatives and analogs, both to try getting a better understanding of the mechanism of toxicity and to
find other potentially active derivatives. The migration of cinnamic acid unit often leads to a mixture of
isomers, specially during the insecticidal bioassays. With a purpose of avoiding the isomerization,
multi-step synthesis of 4- deoxy derivatives have been undertaken starting from D-quinic acid and
cinnamic acids through a 4-deoxy intermediate to get fair quantities of regioisomerically defined
isomers. In this communication, will be presented the synthesis of this intermediate followed by the
optimisation of the bis coupling with different cinnamic acids. Carefully chosen deprotection strategies
have been applied to get the methyl esters but also the carboxylic acid derivatives via 7 or 8 steps from
D-quinic acid. All the compounds were fully characterized.
Some preliminary bioactivity tests have provided some positive information about the relative
toxicity of the 4-deoxy-3, 5-diCQ methyl ester. The biological tests of the carboxylic acid derivative and
other analogues should be soon performed to get a better understanding of the potential activities of
these compounds.
1. (a) Hui, P. S.et al, Chem. Commun. 2015, 51, 1494. (b) Zhao, J.G. et al. Food Chem. 2014, 161, 22.
2. Poëssel, J. L. et al, WO 2009/095624 A2, PCT/FR2009/0501372008
3. (a) Shigemori, H. et al, Chem. Pharm. Bull. 2011, 59, 502. (b) Raheem, K. S. et al, Tetrahedron Lett.
2011, 52, 7175. (c) Jaiswal, R. et al, Org. Biomol. Chem. 2012, 10, 5266.
Abstract Submission Template for 2015 Annual Meeting 2015 ED Chimie Lyon
Process Induced Transformations (PITs) during tablet manufacturing:
Investigations of a polymorphic transition of a model pharmaceutical active
ingredient (caffeine)
a
Audrey JUBAN , Stéphanie BRIANCONa, François PUELa,b.
a
Université de Lyon, F-69622 Lyon, France. Université Lyon 1, Villeurbanne, CNRS, UMR5007,
Laboratoire d’Automatique et de Génie des Procédés (LAGEP), CPE-Lyon, 43 bd du 11 Novembre 1918,
69622 Villeurbanne Cedex, France
b
Université de Paris Saclay, Ecole Centrale Paris, Laboratoire de Génie des Procédés et Matériaux
(LGPM), EA4038, Grande voie des vignes, 92295 Chatenay-Malabry Cedex, France.
Email: [email protected]
Purpose: During tableting, API and excipients are stressed and it is not uncommon to
observe undesired phase transition during this manufacturing step and during the tablet
storage. These situations are known in the literature as phase induced transformations
(PITs). Many parameters in the process itself could have an impact on the average
transformation in final tablets like pressure, temperature and mechanical stress. This
work is focused on the effect of the operating conditions (process and formulation) on
the phase transition of a model API anhydrous caffeine Form I in a direct compression
process.
Methods: The phase transition of caffeine Form I was studied during tableting process
monitored with the compression simulator Styl'One Classic® from MEDELPHARM
equipped with flat punches of 11.28mm diameter. The tablets were prepared with a
mixture of anhydrous caffeine Form I and microcrystalline cellulose as a binder/diluent.
Three formulations with different content of Caffeine were studied (100 wt%, 77.8 wt%
and 60 wt% of caffeine) at three compression pressures (50 MPa, 100 MPa and 200
MPa). The quantitative methods of analysis used were Differential Scanning Calorimetry
(DSC) with a heating rate of 10◦C/min and the temperature range was 20–270◦C. DSC
takes into account a macroscopic fraction (10 mg) of the tablet and was applied in order
to estimate transformation degree in tablet parts (core and border).
Results: Whatever the compression load applied the transition degree of caffeine Form
I toward Form II was almost constant and was much higher than the one encountered in
uncompressed formulated blend. This difference remained even though the phase
transition degree continued to change with time. There was no significant difference of
transition degree between the tablet core and border. However the transition degree
increased with the caffeine content in tablet (24% to 38% just after compression).
Conclusions: Investigations shows that compression triggers the polymorphic transition
which seems not influenced by the level of the compression load but depends on the
caffeine content in tablets. Also, phase transition degree continues to increase with time
in the tablet during the storage.
1
Dynamic - Based Ligand Design: Application
to Human Peroxiredoxin 5
L. Troussicot*, F. Guilliere* , S. Vidal$, O. Walker* and J-M. Lancelin*
* Univ ersité de Ly on, Institut des Sciences Analy tiques, Univ ersité Claude Bernard Ly on1 – CNRS – ENS Ly on, Villeurbanne, France
$ Univ ersité de Ly on, Institut de Chimie et Biochimie Mo léculaire et Supr amoléculaire, Univ ersité Claude B ernard Ly on1 – CNRS, Villeu rbann e,
France
Biological macromolecules define their functions in living cells by their capacity to
interact selectively with other molecules in their environment. Human peroxiredoxin 5 (hPrx5)
was found to be involved in peroxide signaling pathways occurring in crucial cell functions
such as post-ischemic inflammation in the brain. The design of specific ligand with high
affinity would provide a new tool to better understand the biological roles of hPrx5 through its
interactions.
Our method is based on funnelmetadynamics 1, to accurately estimate
protein-ligand
affinities
using
an
energetic approach which calculates the
binding free energy at atomic resolution,
and to study the dynamics of the active
site2. Moreover, solution-state NMR
provides qualitative and quantitative
experimental data of the protein-ligand
system in equilibrium between its
different micro states in solution.
We present here the design of a
new ligand: 4-neopentylbenzene-1,2-diol
(4-npb-diol), not based on structural
information given by crystallography, but
mostly on the molecular dynamics of
hPrx5. Its affinity was first evaluated by
simulation and, once it was synthesized,
NMR data were collected and found to
be in agreement with simulation. The
affinity of this new ligand is greater by
Figure: Funnel shaped restraint potential applied
two order of magnitude compared to the
to PRDX5/4-neopent ylbenzene-1,2-diol system,
catechol, one of the first published hPrx5
used for met adynamics free-energy calculations
inhibitor.
This result provides a novel approach for the design of high affinity ligand, and is an
initial step to better understanding hPrx5 biological roles.
Key words: free energy, funnel-metadynamics, peroxiredoxins, solution NMR
1. Limongelli, V., Bonomi, M. & Parrinello, M. (2013). Funnel metadynamics as accurate binding free energy method. Proc Natl Acad Sci U S A 110, 6358-63.
2. Troussicot, L., Guillière, F., Limongelli, V., Walker, O. & Lancelin, J.M. (2015) Funnel -Metadynamics
and Solution NMR to Estimate Protein−Ligand Affinities. J. Am. Chem. Soc. 137(3):1273-81
About the hydrolytic and acidogenic stage in dry temperature phased
anaerobic digestion: influence of temperature and retention time.
M. Dooms*/**, M. Bonhomme**, S. Hattou**, H. Benbelkacem*, P. Buffière*
* Université de Lyon, INSA-Lyon, LGCIE-DEEP, 9 Rue de la Physique, F-69621 Villeurbanne Cedex
** Arkolia Energies, 65 Rue de la Garriguette, Saint Aunès, France
(E-mail: [email protected])
Keywords
Hydrolysis, Acidogenesis, TPAD, Dry Anaerobic Digestion, Manure, Straw, Silage
Introduction
Anaerobic digestion (AD) allows turning agricultural wastes into biogas (energy) and digestate (soil
amendment) relying on a biological process. Among the different types of reactors used in the
industry, temperature phased anaerobic digesters (TPAD) are known to improve the global process
yield (Lv et al, 2010). This configuration permits to separate the biochemical steps involved during AD
in order to optimize each step. In two-phase systems for instance, the organic matter is degraded into
soluble material and VFA in the first stage, which are then converted into biogas. Using a higher
temperature in the first stage may favour higher hydrolytic activity (Ge et al., 2011).
The present work focuses on the first stage – hydrolysis and acidogenesis.of such reactors We
addressed the effect of temperature (mesophilic, thermophilic or hyperthermophilic) and retention time
(2, 3, 4 and 2+2 days) on the hydrolytic and acidogenic activity in the first stage of temperature phased
dry digestion system treating cow manure with co-substrates (straw and grass silage).
Experimental setup
We used 1L reactors with thermal regulation. The reactors were fed once a day with the amount of
biowaste required by the experimental condition (fixed by the retention time). The reactors were
monitored for biogas production and composition, pH, total and soluble COD and Volatile Fatty Acids.
Experiments lasted at least one month per condition.
Different inputs (cattle manure, straw, slurry, silage), temperatures (65°C, 55°C, 37°C) and retention
times (2days, 3days, 4 days, 2+2days) have been tested in four different runs.
VFA content, Run #3
30
[VFA] (gCOD.kg-1)
Results
Hydrolytic and acidogenic activities were monitored
through the analysis of COD (which is kept along
anaerobic processes). This allowed us to draw
comparisons between the different runs (Tables not
shown). We showed dramatic changes of both
hydrolytic and acidogenic activities depending on the
temperature with 3days and 4days reactors. In 2+2
days series, the influence of temperature became
weaker, while the splitting effect was strong.
20
10
0
Input 55°C, 2d 55°C, 65°C, 2d 65°C,
+2d
+2d
ac
prop
isobut+but
isoval+val
We also analysed the partition of the COD in each Figure 1 - VFA content of run #3
step. This allowed us to highlight the changes in VFA reactors. For each temperature, two
concentrations for instance, as shown on figure 1.
reactors with a 2 days retention
time are used in series.
Discussion
The impact of the temperature was found dominant compared to the influence of the retention times
when the reactors were operated at 3 and 4 days HRT. However, the hydrolysis and acidification
yields were improved when an easily degradable compound (grass silage) was added.
When the 4 days HRT reactors were split into 2 reactors in series with 2 days HRT each, the hydrolytic
activity was reinforced in the first stage. The effect of temperature was less obvious. According to Boe
et al. (2008), the use of different stages not only increases the performance of the process, but also its
resilience and stability.
Boe K, Angelidaki I. 2009. Serial CSTR digester configuration for improving biogas production from
manure. Water Research 43: 166-172.
Ge H, Jensen PD, Batstone DJ. 2011. Increased temperature in the thermophilic stage in temperature
phased anaerobic digestion (TPAD) improves degradability of waste activated sludge. Journal of
Hazardous Materials 187: 355-361.
Lv W, Schanbacher FL, Yu Z. 2010. Putting microbes to work in sequence: recent advances in
temperature phased anaerobic digestion processes. Bioresource Technology 101: 9409-9414.
Magnetogenic probes for in vitro and in vivo detection of enzymes by Magnetic Resonance Imaging (1)
(2)
Corentin Gondrand *, Sophie Gaillard , Olivier Beuf(2) and Jens Hasserodt(1) (1) Laboratoire de Chimie, UMR CNRS UCBL 5182, Ecole Normale Supérieure de Lyon, 46 allée d'Italie, 69007 Lyon. (2) CREATIS, Université de Lyon, UMR CNRS 5220 , INSERM U1044, INSA-­‐Lyon, Bâtiment Blaise Pascal, 7, avenue Jean Capelle, 69621 Villeurbanne. Biologists and health professionals increasingly often demand molecular tools to allow for mapping of biochemical activities. MRI (Magnetic Resonance Imaging) is already widely used in hospitals as an accurate anatomic imaging method of unlimited penetration depth. Up to now, most enzyme-­‐responsive probes were derived from clinically used, standard gadolinium chelates acting as T1 contrast agents. However, in spite of the satisfactory relaxivity of the activated molecules, the fact that the probes are already good contrast agents before activation unfortunately makes image interpretation ambiguous. For this reason, we proposed a line of smart probes that are initially MRI silent. Their in vivo encounter of the targeted enzyme results in the passage from a non-­‐magnetic to a magnetic state. Our magnetogenic probes are iron (II) complexes based on a fragmentable hexadentate ligand. Injected into the body in a diamagnetic non-­‐relaxing (MRI OFF) form, the probe undergoes fragmentation upon removal of a trigger group by the enzyme resulting in the formation of a paramagnetic species (MRI ON). Our system distinguishes itself from gadolinium-­‐based responsive probes by an unparalleled signal-­‐to-­‐background ratio. The concept of magnetogenesis has previously been proven with a molecule displaying rapid activation though only at non-­‐physiological pH (pH 3) and triggered by a non-­‐enzymatic, simple chemical (sodium dithionite). Here we disclose the achievement of the concept with a biochemical trigger: the model enzyme Leucine Aminopeptidase. Chemical design, synthesis and evaluation of a suitable compound will be presented, as well as preliminary results of in vitro monitoring of this enzymatic activity in cell extracts using a specifically fabricated miniature MRI device. This assessment bodes well for the eventual application to the in vitro diagnosis of cancer through biomarkers quantification. * Correspondance: corentin.gondrand@ens-­‐lyon.fr; jens.hasserodt@ens-­‐lyon.fr Study of cobalt-based Fischer-Tropsch catalysts exposed to
tricloroethylene by operando DRIFTS
Anaelle Paredes-Nuneza, Davide Loritoa, Nolven Guilhaumea, Yves Schuurmana and
Frederic Meuniera*
a
Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et
l’environnement de Lyon, 2 avenue Albert Einstein, 69626 Villeurbanne (France)
Biomass-derived syngas contain significant concentrations of chlorine that may contaminate
downstream Fisher-Tropsch catalysts. We report herein an operando diffuse reflectance FTIR spectroscopy (DRIFTS) study in which the hydrogenation of CO is monitored in the
presence of 150 ppm of chlorine (introduced as 50 ppm of trichloroethylene, noted “TCE”) at
ambient pressure.
The experimental setup was described elsewhere [1]. The rates of formation of the main
products of interest sharply decreased upon the introduction of the chlorinated compound,
typically showing a 10-fold drop (Fig. 1, left). Interestingly, the drop in the carbonyl band area
was far less marked and mostly due the removal of bridged/multi-bonded carbonyls (Fig. 1,
middle 1950-1750 cm-1 region). This suggests that each Cl atoms poisoned several surface
sites and/or selectively poisoned the most active sites. The effect of Cl was partly and slowly
reversible. Surprisingly, the Cl poisoning hardly affected the position of the on-top CO(ads)
IR band, in contrast to the effect of surface coverage when CO was removed from the feed
(Fig. 1, right). In addition to site poisoning, our operando DRIFTS data highlights a strong
electronic effect of Cl, which is able to counteract the effects of surface coverage of CO on
the position of the IR band (Fig. 1, right). Similar effects were observed on a silica-supported
cobalt catalyst (data not shown).
Figure 1. (Left) Rate of formation of products as a function of time before, during and after exposure
to TCE. (Middle) DRIFTS spectra collected before, during and after exposure to TCE. Feed: 30% CO
+ 60 % H2 (+ 50 ppm C2HCl3 if any) in Ar. T = 220°C, P = 1 atm. (Right) Wavenumber of the on-top
CO(ads) band as a function of band area during (open square) CO removal and (full circle) chlorine
removal.
References
1. Paredes-Nunez A., Lorito D., Guilhaume N., Mirodatos C., Schuurman Y., Meunier F.C., Catal. Today, 2014
(246) 178-183
Copper-catalysed trifluoromethyaltion of N,N-Disubstituted hydrazones
Alexis Prieto a, Mélissa Landart a, Nuno Monteiroa*, Didier Bouyssi a* and Olivier Baudoin a
Université Claude Bernard Lyon 1, CNRS UMR 5246
Institut de Chimie et Biochimie Moléculaires et Supramoléculaires
CPE Lyon, 43 Boulevard du 11 novembre 1918, 69622 Villeurbanne (France)
e-mail: [email protected]
The trifluoromethyl (CF3) group has gained tremendous importance in various areas of
medicinal and agrochemical chemistries owing to its unique functional properties. It is lipophilic,
strongly electron-withdrawing and bulky, and can mimic various groups as an isostere1. On this basis,
the search for new efficient methods for the incorporation of this group into target molecules is highly
desirable and has been the subject of intense renewed activity in recent years 2. The development of
efficient, general methods for the direct, C(sp2)-H trifluoromethylation of aldehyde hydrazones could
therefore significantly increase the range of applications of these versatile compounds.
We recently developed a very mild procedure for the trifluoromethylation of aldehyde N,Ndialkylhydrazones using the Togni hypervalent iodine reagent (1) under copper chloride-catalysis3.
However, a significant drawback of the method lay in the low efficiencies obtained so far for aliphatic
aldehyde hydrazones, the substrate scope being primarily limited to (hetero)aromatic derivatives (eq.
1).
Access to trifluoromethylated aliphatic aldehyde hydrazones would greatly improve the
synthetic utility of the methodology. For instance, these compounds are particularly attractive owing
to their inherent capability to tautomerize to the ene-hydrazine form making them potential precursors
of a variety of valuable fluorinated heterocyclic compounds4 through diverse cyclization processes that
include, but are not limited to, the Fischer indole-type heteroannulations.
References
1
Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev., 2008, 37, 320.
Charpentier, J.; Früh, N.; Togni, A.; Chem. Rev. 2015, 115, 650.
3
Pair, E.; Monteiro, N.; Bouyssi, D.; Baudoin, O. Angew. Chem., Int. Ed. 2013, 52, 5346.
4
Fluorinated heterocyclic compounds: synthesis, chemistry, and applications (Ed. V.A.Petrov), 2009, Wiley,
Hoboken.
2
PARAMAGNETIC METALLOPROTEINS WITH MAS OVER 100 KHZ: NMR FINALLY
GETS ONTO THE METAL CENTRE
Andrea Bertarello1, Kevin J. Sanders1, Daniela Lalli1, Andrew J. Pell1, Hugh R. W. Dannatt1, Leonardo
Gonnelli2, Roberta Pierattelli2, Isabella C. Felli2, Guido Pintacuda1
1
Université de Lyon, Institut de Sciences Analytiques, (CNRS / ENS-Lyon / UCB Lyon 1), Centre de RMN à Très Hauts Champs,
69100 Villeurbanne, France
2
CERM, University of Florence, Via L. Sacconi 6, 50019 Sesto Fiorentino, Italy
The presence of metals containing unpaired electrons causes severe difficulties in solidstate NMR: signals with large shifts and shift anisotropies are spread over a huge
spectral window, possess extremely short relaxation times, and are broadened by
inhomogeneous susceptibility effects.
In this work, we show how the application of a set of NMR experiments, recently
developed for the study of complex paramagnetic inorganic battery materials, can be
adapted to the solid-state NMR analysis of paramagnetic metalloproteins, and can be
used to increase the information obtainable from these systems.
These experiments combine ultra-fast (>60 kHz) magic-angle spinning frequencies and
short high-powered adiabatic pulses (SHAPs), and are applied to triply-2H,13C,15Nlabelled, fully back-exchanged microcrystalline metalloenzyme superoxide dismutase
(SOD). SOD has two high-affinity binding sites for metal cations, and the metallation
state can be experimentally controlled to obtain samples with the desired paramagnetic
effects with minimal structural perturbation. The most common physiological form
contains Cu2+ and Zn2+ at the active site: however, the presence of the slowly-relaxing
Cu2+ ion causes severe line broadening, hindering the detection of signals surrounding
the active site. Here we show that by replacing Zn 2+ with fast-relaxing Co2+ - thereby
increasing the relaxation rate of the Cu2+ ion - and by spinning the sample at rates of up
to 111 kHz, the line broadening is dramatically reduced, allowing the detection of 15N 13C
and 1H signals from residues directly coordinating the metal centres.
Under these experimental conditions, the coherence lifetimes of these signals are long
enough to allow the acquisition of well resolved multidimensional spectra, dramatically
improving the quality of information obtainable from these systems, and opening up a
new avenue for the study of structure and reactivity of metal centres in complex
insoluble systems.
Platinum nanoparticles are as active as Karstedt's catalyst in alkene
hydrosilylation
Thomas Galeandro-Diamant1,2, Marie-Line Zanota1, Reine Sayah2, Laurent Veyre2, Clémence
Nikitine1, Claude de Bellefon1, Sébastien Marrot3, Chloé Thieuleux2* and Valérie Meille1*
1
Université de Lyon, Institut de Chimie de Lyon, Laboratoire de Génie des Procédés Catalytiques
(UMR 5285 CNRS-ESCPE Lyon), 43 Bd du 11 Novembre 1918, 69616 Villeurbanne, France.
2
Université de Lyon, Institut de Chimie de Lyon, Laboratoire de Chimie, Catalyse, Polymères et
Procédés (UMR 5265 CNRS-Université Lyon 1-ESCPE Lyon), Ėquipe Chimie Organométallique de
Surface, 43 Bd du 11 Novembre 1918, 69616 Villeurbanne, France.
3
Bluestar Silicones France SAS., 85 Avenue des Frères Perret, 69192 Saint-Fons, France.
*[email protected] ; [email protected]
Alkene hydrosilylation is a reaction used in the silicone industry to produce functional silicone fluids
(Fig. 1a) and cross-linked silicones [1]. This reaction is generally carried out using Pt(0) complexes, in
particular Karstedt's catalyst (Fig. 1b), which is active at the 10 ppm level, but tends to decompose into
ill-stabilized platinum aggregates during the reaction, decreasing its activity and giving the silicone
fluids an undesired yellow-brown coloration [2].
a)
b)
Fig. 1: a) Alkene hydrosilylation of polymethylhydrosiloxanes. b) Karstedt's catalyst.
Catalysts based on platinum nanoparticles were already reported
for alkene hydrosilylation, but reached Turnover Numbers (TONs)
of 4000 at most.
We demonstrate here that small and well-stabilized platinum
nanoparticles (1.5-2.0 nm diameter) were as active as Karstedt's
catalyst for the reaction, and able to reach TONs of 10 5 in the
hydrosilylation of 1-octene with a polymethylhydrosiloxane
containing 50 SiH units, chosen as a model reaction. The
nanoparticles were typically synthesized by decomposition of
Pt(dba)2 in toluene in presence of 1 equivalent of n-octylsilane as
stabilizer under hydrogen [3].
The synthesis of the platinum nanoparticles was monitored by
liquid state and DOSY NMR experiments, and the as-obtained Fig. 2: Platinum nanoparticles.
nanoparticle suspension was studied by UV/Visible spectroscopy.
The results demonstrate the full conversion of the Pt(0) precursor into 1-2 nm sized crystalline metallic
platinum nanoparticles.
Different Pt(0) precursors and silane stabilizers were used to generate the nanoparticles, and it was
found that neither the Pt(0) precursor nor the silane stabilizer influenced the nanoparticles
characteristics and catalytic performances.
Similar catalytic performances of both platinum nanoparticles of 2 nm diameter (with approximately half
of the platinum atoms accessible for catalysis) and Karstedt's catalyst tend to confirm that Karstedt's
catalyst is transformed within a few minutes of reaction into platinum nanoparticles during
hydrosilylation, as suggested by our group in a recent 29Si NMR study [4].
[1]
[2]
[3]
[4]
I. Ojima “Recent Advances in the Hydrosilylation and Related Reactions” in The Chemistry of
Organic Silicon Compounds (S. Patai, Z. Rappoport, Eds.), Wiley Interscience, New York, 2003,
pp. 1687–1792.
D. Troegel, J. Stohrer, Coord. Chem. Rev. 255 (2011) 1440-1459.
P. Laurent, D. Baudouin et al., New J. Chem. 18 (2014) 5952-5956.
V. Meille, M.-L. Zanota et al., Silicon 6 (2014) 247-255
A Fluorescent Heteroditopic Hemicryptophane Cage for The
Selective Recognition of Choline Phosphate
Dawei Zhang1,2, Guohua Gao2, Laure Guy1, Jean-Pierre Dutasta1, Alexandre Martinez1,
1
Laboratoire de Chimie, CNRS, École Normale Supérieure de Lyon, 46, Allée d’Italie, F69364 Lyon, France.
2
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of
Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062,
P. R. China.
Phosphorylated biomolecules play a central role in many biological processes and their
fluorescent sensing may provide a unique tool to study their metabolism and other
function.[1] Herein, we described a hemicryptophane cage combining a CTV unit, a Zn(II)
metal center and fluorescent properties (figure 1).[2] This first fluorescent hemicryptophane
has been developed as efficient fluorescent sensor for zwitterionic choline phosphate in
competitive media. The heteroditopic character of the host towards the guest was evidenced
since only the guest bearing both the ammonium and phosphate parts can give rise to the
most significant fluorescent quenching and largest binding constant.[3] Moreover, it was
found that the exchange between the free and complexed guest is slow on the NMR time
scale at r.t. while fast at high temperature. NMR experiments also indicate the formation of
an inclusion complex between the cage and guest, and a chiralization-like behavior of the
achiral choline phosphate occurred. The binding mode have been highlighted by DFT
calculations. The current research also the first time demonstrates the feasibility, efficiency
and reliability of hemicryptophane hosts for molecular recognition using fluorescence
properties.
Figure 1 The structures of Zn(II)@hemicryptophane cage and choline phosphate, and the designing concept.
Bibliography :
[1] T. Hunter, Protein Phosphorylation, Academic Press, New York, 1998; (b) T. Pawson, J. D. Scott,
Trends Biochem. Sci. 30 (2005) 286-290.
[2] (a) D. Zhang, G. Gao, L. Guy, J.-P. Dutasta, A. Martinez, Chem. Commun. 51 (2015) 2679-2682;
(b) B. Chatelet, E. Payet, O. Perraud, P. Dimitrov-Raytchev, L.-L. Chapellet, V. Dufaud, A. Martinez,
J.-P. Dutasta, Org. Lett.13 (2011) 3706-3709.
Planted detentive filters for treating combined sewer overflow
Tamás Gábor Pálfya, Daniel Meyera, Stéphane Troeschb,
Rémy Gourdonc, Pascal Mollea
a
Water Quality and Pollution Prevention Research Unit, IRSTEA Lyon, 5 rue de la Doua
Villeurbanne, 69626 France ([email protected])
b
Epur Nature SAS, 153 Avenue Marechal Leclerc, Caumont sur Durance, 84510 France
([email protected])
c
INSA Lyon, Laboratoire de Génie Civil et Ingénierie Environnementale, 20 avenue A.
Einstein, Villeurbanne, 69621 France ([email protected])
Constructed wetlands for combined sewer overflow treatment efficiently reduce negative
impacts on receiving waters by detaining flow peaks, filtering suspended solids and removing
organics and ammonium. The technology was brought to new levels in France based on experiences
from Germany1, from ‘French design’ CWs treating municipal wastewater2 and pilot-scale research3.
The concept has innovations such as i) the coarser media tolerates loadings without pre-treatment
thus there is no need for sludge management, ii) the bottom of the filter is permanently saturated
preventing water stress on reeds at dry periods, iii) the aeration pipes run above the permanently
saturated zone, iv) the media contains zeolite if higher ammonium removal is needed, v) the priority
of feeding on the dual filter basin is alterable which enhances sludge mineralization when events are
frequent, benefiting performance and extending life cycle.
The first full-scale facility at Marcy l’Etoile is monitored to improve the design and to calibrate a
design-support tool (Orage) which optimizes the scaling of planted detentive filters. We introduce
CSO-CWs and the principles of pollutant removal as well as the monitoring methods and first results
about hydraulics, from automatic sampling of flows and quality analysis and evaluation. Twelve highload feeding events (1–14 m3/m2 filter surface) were investigated. Results show high treatment
performance: SS were filtrated from 75–800 mg/L to a background concentration below 30 mg/L.
Total COD (inflow 60–1500 mg/L, outflow < 100 mg/L) and dissolved COD (inflow 30–400 mg/L,
outflow < 60 mg/L) were strongly decreased even after long ponding periods. Inflow NH4-N
concentrations up to 28 mg/L were reduced to 1–7 mg/L.
Keywords: constructed wetlands, stormwater treatment, combined sewer overflow, planted
detentive filters
1
Uhl M, Dittmer U (2005) Constructed wetlands for CSO treatment: an overview of practice and research in
Germany. Wat. Sci. Tech. 51(9):23-30.
2
Molle P, Liénard A, Boutin C, Merlin G, Iwema A (2005) How to treat raw sewage with constructed wetlands:
an overview of French systems. Wat. Sci. Tech. 51(9):11-21.
3
Fournel J (2012) Extensive systems for the treatment of urban stormwater [in French]. Systemes extensifs de
gestion et de traitement des eaux urbanies de temps de pluie. PhD dissertation, IRSTEA, France, 217 pp.
Posters
21
A general and scalable synthesis of aeruginosin marine
natural products based on two strategic C(sp3)‒H
activation reactions
a
a
a
David Dailler , Grégory Danoun , Olivier Baudoin *
a
, Université Claude Bernard Lyon 1, CNRS UMR 5246, Institut de Chimie et
Biochimie Moléculaires et Supramoléculaires, CPE Lyon, 43 Boulevard du 11
Novembre 1918, 69622 Villeurbanne, France.
*Corresponding author : [email protected]
In 1994, Murakami et al. reported the isolation of aeruginosin 298A from a
toxic blue algae Microcystis aeruginosa, the first compound of new family of
linear peptides.1 This new family contains currently more than twenty different
compounds, which all present biological activities as serine protease inhibitors. 2
We decided to synthesize this class of compounds using new methodologies
based on metal catalysis. Our retrosynthetic analysis envisaged classical
peptidic coupling reaction (blue) to form this class of compounds starting from
four molecules: two basic building blocks (1 and 3) and two more complex
building blocks (2 and 4). These latter might be synthesized using recent
C(sp3)–H activation reactions.3 Indeed, with regard to 2, the application of our
recent C–H functionnalization method (red) was envisaged to lead quickly to 2
in a diastereoselective manner.4 The synthesis of fragment 4 would be
synthesized by a directed C–H functionnalization (green) allowing the synthesis
of a large class of analogs of this fragment (Scheme1).5
In addition to the challenge of synthesizing these compounds using C–H
activation, our retrosynthesis provides a straightforward access to a large
library of analogous.6
References
1 M. Murakami, Y. Okita, H. Matsuda, T. Okino, K. Yamaguchi, Tetrahedron Lett. 1994, 35, 3129.
2 K. Ersmark, J. R. Del Valle, S. Hanessian, Angew. Chem. Int. Ed. 2008, 47, 1202.
3 a) G. Rouquet, N. Chatani, Angew. Chem. int. Ed., 2013, 52, 2; b) R. Jazzar, J. Hitce, A.
Renaudat, J. Sofack-Kreutzer, O. Baudoin, Chem. Eur. J., 2010, 16, 2654.
4 J. Sofack-Kreutzer, N. Martin, A. Renaudat, R. Jazzar, O. Baudoin, Angew. Chem. Int. Ed. 2012,
51, 10399.
5 D. Shabashov, O. Daugulis, J. Am. Chem. Soc. 2010, 132, 3965.
6 D. Dailler, G. Danoun, O. Baudoin, Angew. Chem. Int. Ed., 2015, DOI: 10.1002/anie.201500066
Effect of Core-Shell structure on latex properties
Lara, B. R., McKenna,T.F.L., C2P2 – UMR 5265, CNRS/UCB-Lyon 1/ESCPE-Lyon
Ouzineb, K., Toray Films Europe
The main goal of the present work is to improve an industrial acrylic latex formulation whose function is to promote the
adhesion between poly(ethylene terephthalate) substrate and metallic aluminum.
Due their versatility, polymers are widely used in the packaging field. They can be molded in innumerous ways, their properties
can be controlled by inserting different compounds, by changing process parameters / polymeric architecture, their price is very attractive,
and, quite importantly, they can be much more easily recycled than glasses and metals. The main drawback in using polymeric materials is
their significant permeability to small molecules, for instance water vapor and gases (1).
We know for a fact that most polymers does not present intrinsic barrier characteristics, nevertheless by controlling their
microstructure, we can tune some properties, for instance the Glass Transition Temperature (Tg ) that will act against the permeation of
small molecules through the polymeric matrix. A material which undergoes from glassy to rubbery state has a significant improvement in
the barrier property, once the polymeric chains motion, characteristic of a material in rubbery state, will force the permeant molecules to
find alternatives pathways to go through the matrix. On the other hand, glassy materials have free-volumes whereby the permeant can
pass freely. A wide range of reactional parameters able to play with the Tg is reported in the literature, being the most used the monomeric
composition. However, by altering the monomeric composition, one may also change other properties that can be already suitable for the
material’s purpose, for instance the functionality, polarity, molecular weight and so on. A simple and interesting way to avoid this is to play
with the polymer architecture. By working for example with core-shell structures, we may combine a hard core – which may work as
obstacles for the permeate molecules and can also improve mechanical properties – and a soft shell, which will play a crucial role at the
film formation properties and glass transition (2). In the present work, we were able to reduce the Tg in 30°C without changing the
monomeric composition, simply by working with seeded emulsion polymerization to produce hard/soft core/shell nanoparticles.
The chemical of the core and its Influence on barrier will also be evaluated. The effect of the polarity of different side groups
from polymers with similar glass transition will be studied to see at which extension we can improve the barrier property. (3)
1.
2.
3.
SIRACUSA, V. International Journal of Polymer Science 2012, 1
SONG, Z., DANIELS, E. S., SUDOL, D. E., KLEIN, A., EL-AASSER M. S. Colloid Polymer Science. 2014, 292, 645.
GUYOT, A. Advances in Colloid and Interface Science. 2004, 108-109, 3.
Methodology for process optimization : heat
integration of ethanol from sugarcane process
through modifications to separation sections
Rami Becharaa, Adrien Gomezb, Jean-Marc Schweitzerc and François Marechald
a
IFP Energies Nouvelles, Solaize, France, [email protected]
IFP Energies Nouvelles, Solaize, France, [email protected]
c
IFP Energies Nouvelles, Solaize, France, [email protected]
d
EPFL, Lausanne, Switzerland, [email protected]
b
Our research work deals with the construction of a methodology for the design of profitable, energy
efficient and environmentally compliant processes. This point is characterized by four main points :
(1) process design and simulation, (2) heat integration, (3) multi-objective optimization and (4)
process selection. All elements of this methodology have been developed and applied in various
literature cases, except the last one. Hence, within this context, the main contribution of this
research work is the handling of this step. Moreover, within the context of our work, this
methodology is developed and applied to ethanol production from sugarcane. The optimization of
the conventional process, most notably the separation section, is handled in a first time. In a second
time, the conversion of sugarcane bagasse to ethanol through second generation processes is
investigated. Finally, the balance between this bagasse conversion technology and other
technologies is performed.
This present abstract deals with the optimization of the separation section. This section consists of
juice concentration, ethanol concentration and ethanol dehydration steps. Moreover, it accounts for
a large share of the heat demand. In this work, we investigate the possibilities for heat integrating
the separation sections of an ethanol from sugarcane production process, without the bagasse nor
the leaves valorisation sections. This integration is realized by the analysis of process composite
curves and the proposal of adequate modifications. We follow a step by step procedure where a
base case, with base performances, is described. Multi-effect juice concentration, distillation and
extractive distillation are the technologies adopted for the constitutive sections respectively.
Proposed modifications include exchanging heat between in-process streams, modifying heat loads
in units to enhance integration, modifying temperature levels in units for the same purpose, and use
of multiple-effect distillation. The best alternative employed three distinct distillation columns,
operating under different pressures, and four evaporation effects. This hence created a seven level
heat cascade with pressures ranging from 3 atm to 0.1 atm, and temperatures ranging from 135 °C
to 61 °C. This alternative led to an 81% reduction in hot energy requirements, and a 78% reduction
in cold energy requirements. The obtained results compare well with values from other research
activities. The innovation brought about by this work is the holistic study of the process in
comparison to more section by section analyses performed in literature works. The realized work
paves the way to a more thorough thermo-economic analysis, and more integral optimization work.
Supported tungsten oxo species as robust olefin metathesis
catalysts
Nicolas Merle1, Guillaume Girard2, Nicolas Popoff1, Aimery de Mallmann1, Kai C. Szeto1,
Yassine Bouhoute1, Julien Trebosc2, Elise Berrier2, Jean-François Paul2, Christopher P.
Nicholas3, Iker Del Rosal4, Laurent Maron4, Régis M. Gauvin2, Laurent Delevoye2, Mostafa
Taoufik1,*
1
Laboratoire de Chimie Organométallique de surface, C2P2 - CNRS UMR 5265 – CPE – UCBL,
Villeurbanne, France
2
Unité de Catalyse et de Chimie du Solide, CNRS UMR 8181, Université de Lille Nord, Villeneuve
d’Ascq, France.
3
Exploratory Catalysis Research, UOP LLC, a Honeywell Company, Des Plaines (IL), USA
4
Laboratoire de Physico-Chimie des Nano-Objets, CNRS UMR 5215, Université de Toulouse – INSA
- UPS, Toulouse, France.
* [email protected]
Olefin metathesis is applicable in many industrial domains. Large scale processes in propylene
metathesis or for propylene production from ethylene/2-butene cross-metathesis have already been
commercialized using WO3/SiO2 as catalyst [1]. Moreover, olefin metathesis may also have important
application in fine chemistry [2]. During the previous decades, much attention has been directed to
group 6 transition state metals (Mo, W) bearing different imido ligands [3]. Although numerous
homogeneous and heterogeneous catalysts in this family with extremely high initial activity have been
published, more recent experimental [4] and theoretical [5] reports, exemplified by the tungsten
system, have revealed that there is a remarkable difference in robustness and stability between imido
and oxo based ancillary ligands. Consequently, current focus in the development of novel group 6
olefin metathesis catalysts is surrounded on metal oxo moiety with different spectator ligands.
As a continuous research in supported tungsten oxo species [6,7] amenable to metathesis catalysts,
this communication presents our recent findings in this topic. Large effort is dedicated to the wellcontrolled preparation (including the choice of precursor and method) of the catalyst by surface
organometallic chemistry and characterization of the resulted materials, particularly by spectroscopic
techniques. The catalytic performance in olefin metathesis will also be presented.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
J.C. Mol, J. Mol. Catal. A 213 (2004) 39.
A. J. Jiang, Y. Zhao, R.R. Schrock, A.H. Hoveyda, J. Am. Chem. Soc. 131 (2009) 16630.
R.R. Schrock, Chem. Rev. 109 (2009) 3211.
E. Mazoyer, N. Merle, A. de Mallmann, J.-M. Basset, E. Berrier, L. Delevoye, J.-F. Paul, C.P.
Nicholas, R.M. Gauvin, M. Taoufik, Chem. Commun. 46 (2010) 8944.
X. Solans-Monfort, C. Coperet, O. Eisenstein, Organometallics 31 (2012) 6812.
N. Merle, G. Girard, N. Popoff, A. de Mallmann, Y. Bouhoute, J. Trebosc, E. Berrier, J.-F. Paul,
C.P. Nicholas, I. Del Rosal, L. Maron, R.M. Gauvin, L. Delevoye, M. Taoufik, Inorg. Chem. 52
(2013) 10119.
Y. Bouhoute, A. Garron, D. Grekov, N. Merle, K.C. Szeto, A. de Mallmann, I. Del Rosal, L.
Maron, G. Girard, R.M. Gauvin, L. Delevoye, M. Taoufik, ACS Catal. 4 (2014) 4232.
Efficient C-3 Reductive Alkylation of 4-Hydroxycoumarin by
Dehydrogenative Oxidation of Benzylic Alcohols
Manon Boulven,a Adrien Montagut-Romans,b Marc Lemaire,b Florence Popowycza
a
Equipe Chimie Organique et Bioorganique, Institut National Des Sciences Appliquées,
Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246,
Bâtiment J. Verne, 1er étage, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex
b
Equipe Catalyse Synthèse Environnement, Institut de Chimie et Biochimie Moléculaires
et Supramoléculaires, Université Claude Bernard-Lyon 1, 43 Bd du 11 novembre 1918, F69622 Villeurbanne
 [email protected]
The family of 3-substituted 4-hydroxycoumarins has been reported to exhibit potent
efficiency on a wide range of therapeutic axes:1 anti-coagulants (such as Warfarin
developed in the 1950s), anti-viral agents potentially against HIV or antibacterial
molecules. The synthesis of 3-substituted 4-hydroxycoumarins has been largely described
by condensation of 4-hydroxycoumarin on benzylic alcohols by using Brønsted or Lewis
acidic catalysis: HClg at 160 °C,2 para-toluene sulfonic acid (free3 or supported4), iron5 or
multimetallic catalysis.6 A unique example on 4-hydroxycoumarin describing an iridiumcatalyzed alkylation with a large excess of benzylic alcohol (10 eq) under solvent-free
thermal conditions was reported by Grigg and co-workers in 2009.7
Metallo-catalyzed Transfer of Hydrogen
In this communication, efforts to develop a practical path of selective C-3
alkylation of 4-hydroxycoumarin through a catalytic coupling reaction with substituted
benzylic alcohols by optimizing the reaction parameters (catalyst, solvent, activation,
reaction time, temperature, base) are reported.8
References
1. J.-C. Jung; O.-S. Park, Molecules, 2009, 14, 4790.
2. P. S. van Heerden; B. C. B. Bezuidenhoudt; D. Ferreira, Tetrahedron 1997, 53, 6045.
3. D.-U. Chen; P.-Y. Kuo; D.-Y. Yang, Bioorg. Med. Chem. Lett. 2005, 15, 2665.
4. C. R. Reddy; B. Srikanth; N. N. Rao; D.-S. Shin, Tetrahedron 2008, 64, 11666.
5. (a) J. Kischel; K. Mertins; D. Michalik; A. Zapf; M. Beller, Adv. Synth. Catal. 2007,
349, 865; (b) P. Thirupathi; S. S. Kim, Tetrahedron 2010, 66, 2995.
6. (a) P. N. Chatterjee; S. Roy, Tetrahedron 2011, 67, 4569; (b) D. Das; S. Pratihar; U.
K. Roy; D. Mal; S. Roy, Org. Biomol. Chem. 2012, 10, 4537; (c) A. K. Maity; P. N.
Chatterjee; S. Roy, Tetrahedron 2013, 69, 942.
7. R. Grigg; S. Whitney; V. Sridharan; A. Keep; A. Derrick, Tetrahedron 2009, 65, 7468.
8. A. Montagut-Romans; M. Boulven; M. Lemaire; F. Popowycz, New J. Chem. 2014,
38, 1794.
TACN-based lanthanide(III) complexes as two-photon
luminescent bio-probes
Anh-Thy Bui,a Alexei Grichine,b,c Alain Duperray,b,c François Riobé,a
Chantal Andrauda and Olivier Maurya*
a
Laboratoire de Chimie, UMR 5182 (CNRS - Université de Lyon - ENS de Lyon), 46
allée d’Italie, F-69364 Lyon, France
b
INSERM, IAB, F-38000, Grenoble, France
c
Université Grenoble Alpes, IAB, F-38000, Grenoble, France
*e-mail: [email protected]
Lanthanide ions exhibit peculiar photophysical properties that stem from their 4f
electrons, thus attracting substantial attention in the development of luminescent
bioprobes. The advantages of their sharp and characteristic emissions, as well as their
long luminescence lifetimes, enable various applications in bio-imaging.1
In this context, we have designed a Tb(III) complex based on a triazacyclonane
(TACN) platform, decorated with suitable sensitizing two-photon antennae. In
combination with an analogous Eu(III) complex, such species illustrates the proof-ofconcept of two-photon multiplexing experiments using lanthanide luminescent
bioprobes (LLB).2 In this contribution, we will, moreover, exemplify the use of such
macrocyclic structures with other lanthanides, in particular Yb(III)3 and Sm(III), which
emit light in the near-infrared (NIR) range, giving rise to new developments in the
field of microscopy that combine NIR excitation with NIR detection.
(a)
(b)
Figure 1. Visible and NIR microscopy images of T24 cells fixed with PFA under laser
irradiation at 745nm, using [Sm(III)] emission: (a) visible channel (690HQ filter) (b)
NIR channel (850LP filter).
References
1. J.-C. G. Bünzli, Chem. Rev., 2010, 110, 2729-2755.
2. V. Placide, A. T. Bui, A. Grichine, A. Duperray, D. Pitrat, C. Andraud and O.
Maury, Dalton. Trans., 2015, 44, 4918-4924.
3. A. D’Aléo, A. Bourdolle, S. Brustlein, T. Fauquier, A. Grichine, A. Duperray, P. L.
Baldeck, C. Andraud, S. Brasselet, O. Maury, Angew. Chem. Int. Ed., 2012, 51,
6622-6625.
Vers une meilleure connaissance des propriétés acides des
catalyseurs hétérogènes en présence d’eau : application à la
déshydratation d’alcools biosourcés en oléfines
Z. Buniazet,1,* A. Cabiac,2 S. Maury,2 S. Loridant1,*
1
IRCELYON, UMR5256, 2 avenue Albert Einstein 69626 Villeurbanne cedex
2
IFPEN Lyon Rond-point de l'échangeur de Solaize BP3 69360 Solaize
Corresponding authors: [email protected],
[email protected]
Les oléfines qui sont des intermédiaires clés pour l’industrie des polymères sont aujourd’hui
produites essentiellement par voie pétrochimique. La déshydratation d’alcools issus de la
biomasse par catalyse acide fait partie des procédés alternatifs à la voie pétrochimique.
Toutefois, les catalyseurs acides développés pour la pétrochimie se révèlent peu adaptés à
la transformation des produits fortement hydratés issus de la biomasse. En effet, la plupart
d’entre eux subissent des modifications ainsi que des phénomènes d’inhibition en présence
d’eau. C’est pourquoi, la synthèse de catalyseurs performants et stables en présence d’eau
constitue un défi majeur. Pour cela, il est nécessaire de mieux comprendre les mécanismes
mis en jeux entre l’eau et les sites acides des catalyseurs hétérogènes, en conditions
réactionnelles. Il s’agit de déterminer comment l’eau agit sur les sites acides, pourquoi elle
les désactive et dans quelles conditions afin de concevoir des catalyseurs résistants à l’eau
dans ces conditions.
L’étude de la littérature révèle que le devenir des sites acides en présence d'eau est encore
largement débattu et suscite des contradictions. Les sites acides de Lewis présents à la
surface des catalyseurs sont souvent transformés en sites de Brønsted en présence d’eau.
Toutefois, plusieurs articles récents publiés par l’équipe de M. Hara1 ont montré que des
oxydes de métaux de transition comme Ta2O5, Nb2O5 et TiO2 supportés sur silice
possédaient des sites acides de Lewis actifs en présence de vapeur d’eau (« water
tolerant »).
Cette thèse a pour objectif principal le développement d’une méthodologie fine de
caractérisation des propriétés acides et structurales de catalyseurs hétérogènes modèles en
température sous vapeur d’eau et en conditions de réaction afin de les corréler à leurs
propriétés catalytiques.
La méthodologie choisie consiste à préparer une série solides de référence, soit
majoritairement acides de Lewis soit de Brønsted afin d’étudier leur comportement dans une
réaction modèle et corréler leur performances avec leurs propriétés acides. Notre but est
d’étudier le comportement des sites acides de Lewis et de Brønsted dans la réaction de
déshydratation et isomérisation de l’isobutanol en butènes linéaires mais également d’étudier
in situ et operando leur évolution en présence d’eau générée par la réaction ou ajoutée au
réactif.
1
H. Shintaku, K. Nakajima, M. Kitano, N. Ichikuni, M. Hara, ACS Catal. 4 (2014) 1198−1204
UV photolysis and UV/H₂O₂ photolysis processes for estrogens removal in
water
Bruno Cédat2, Christine de Brauer2, Hélène Métivier2, Jean-Noël Levrard1
1COMAP
2INSA
WT, Z.A les petis champs, 26120 Montélier, France
Lyon, LGCIE, 9 rue de la physique 69100, Villeurbanne
Abstract
The natural estrogens, estrone (E1), 17β-estradiol (E2) and the synthetic one, 17αethinylestradiol (EE2) are amongst the most active and commonly found estrogens in
wastewater. Growing concerns about steroid hormones have led European authorities to list
the natural steroid hormone 17β-estradiol (E2) and the synthetic steroid hormone 17 αethynylestradiol (EE2) as substances to watch under the Water Framework Directive.
Recently, great attention has been given to advanced oxidation processes (AOPs) due to their
ability to remove EDCs from wastewater. Highly reactive hydroxyl radicals generated by AOPs
can efficiently react with carbon-carbon double bonds and attack the aromatic nucleus of
refractory organic compounds such as estrogens.
This study aimed at investigating the degradation of a mixture of estrogenic hormones
(Estrone (E1), β-Estradiol (E2), and 17α-Ethinyl Estradiol (EE2)) in water by UV photolysis and
UV/H₂O₂ photolysis. Firstly, the effects of water matrices (drinking water and treated
wastewater) and H₂O₂ concentrations (10, 40, and 90 mg/L) were determined. The hormones
were added in a UVC (λ=254 nm) pilot system running in semi-batch. Hormones degradation
rates were measured by HPLC-UV. Secondly, a single concentration of H₂O₂ (20 mg/L) was
tested in order to optimize oxidant cost. Hormones degradation rates as well as changes in
estrogenic activity, measured by Yeast Estrogen Screen (YES), were followed at the same
time.
First results showed negligible degradation of E2 and EE2 by UV photolysis in both
matrices. High UV fluences were needed to degrade 80% of E1 in drinking water (1300
mJ/cm²) and treated wastewater (1800 mJ/cm²). All hormones degradation rates were
significantly improved in both water matrices at H2O2 concentration as low as 10mg/L. UV
fluence of 400 mJ/cm² and 90mg/L of H₂O₂ would enable to remove 80% of all hormones in
treated wastewater. Water quality could highly influence the treatment efficiency as shown by
higher UV fluences required to reach the same result in treated wastewater than in drinking
water. Estogenic activity, measured by YES bioassay, could not be removed by UV photolysis
whereas it decreased in the same trend than E2 and EE2 removal rate when combining UV
and 20 mg/L of H₂O₂. No high estrogenic by-products were formed. These results pointed out
that estrogens removal can be highly enhanced by UV/H₂O₂ photolysis in drinking water and
treated wastewater. By combining the approriate concentration of H₂O₂ and UV fluence, it
would be possible to design a cost effective treatment for small and midlle sized WTPs.
ABSTRACT
INHIBITION OF HUMAN PEROXIREDOXIN 5 BY CATECHOL
DERIVATIES: AN ENZYMATIC KINETIC APPROACH
Melissa CHOW1, Florence GUILLIERE1, Bastien DOUMECHE2, Laura
TROUSSICOT1, Olivier WALKER1, Jean-Marc LANCELIN1.
1: Institut des Sciences Analytiques, CNRS – Université Claude Bernard Lyon1 –
ENS Lyon, UMR 5280, 5, rue de la doua, 69100, Villeurbanne, France.
2: Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, Université
Claude Bernard Lyon1 – UMR 5246, 43 Bd du 11 novembre 1918, F-69622,
Villeurbanne, France.
Strokes are a common cause of death and disabilities effecting millions worldwide.
Ischemic strokes are the most common type. They are characterized by clotted brain
vessels that restrict cerebral blood flow, ultimately resulting in the death of brain
cells. Since stroke patients suffer from a multitude of pathological effects as a
consequence of brain inflammation, research is currently focused on preventative
measures to delay post-ischemic inflammatory response. Recently, human
peroxiredoxin proteins (hPrx1, 2, 5 and 6) have been found to regulate the brain
inflammation cascade. It is therefore of interest to characterize inhibitors against
Prx’s. Through NMR-screening and modeling studies, small molecules catechol
derivatives have been identified to bind and interact with hPrx5. In this study, hPrx5
peroxidase activity is assessed through an in vitro enzymatic assay, to understand how
these catechol derivatives can bind and potentially inhibit hPrx5. It has been
determined these catechol derivatives can bind and reversibly inhibit hPrx5. The
catechol inhibitors, have been ranked according to their half maximal inhibition
concentration value (IC50) and correlate to the binding dissociation constants (Kd)
previously reported by NMR. Currently, the inhibition mechanism of these inhibitors
is being evaluated through enzymatic kinetics. Overall, this research can provide
greater insight for designing higher affinity inhibitors to bind and inhibit Prx’s and
therefore contribute to the delay and prevention of post-ischemic inflammation.
Electrostatic tuning of retinal chromophore properties: From biological understanding to bio-­‐engineered proteins. Baptiste Demoulin, Ivan Rivalta, Élise Dumont, Marco Garavelli Laboratoire de Chimie UMR CNRS-­‐ENS 5182, 15 Parvis Descartes, BP7000, 69342 Lyon Cedex 07, France. Opsin proteins are photoactive proteins found in a wide variety of species, where they can act as signal transmitter (for instance, the visual protein rhodopsin) or as proton pump (like the bacteriorhodopsin). These proteins contains a single retinal chromophore, covalently binded to a lysine to form a protonated Schiff base. The photochemical and photophysical properties of this chromophore is finely tuned by its close environment. Understanding the nature of this tuning is of crucial importance to design a new generation of bio-­‐inspired opto-­‐electronic devices. Here, we present a theoretical study of two natural opsin proteins (bacteriorhodopsin[1] and xanthorhodopsin[2]), and three bio-­‐engineered rhodopsin mimics [3]. We use a QM/MM framework, in which the chromophore is treated at the CASSCF/CASPT2 level, a multi-­‐reference method that has been proven to correctly reproduce the photophysical properties of the retinal[4], while the embedding protein is treated at the molecular mechanics level; the computations are handled by the COBRAMM interface[5]. We investigate the vertical absorption of these proteins, as well as the electronic properties in the Franck-­‐Condon region, to better understand the influence of the counter-­‐anion structure. [1] Fujimoto, K. ; et al., J. Chem. Theory Comput., 2007, 3, pp 605-­‐618 [2] Luecke, H. ; et al., PNAS, 2008, 105, pp 16561-­‐16565 [3] Wang, W. ; et al., Science, 2012, 338, pp 1340—1343 [4]Ferré, N. ; Olivucci, M. , J. Am. Chem. Soc, 2007, 125, pp 6868-­‐6869 [5] Altoè, P. ; et al., Theor. Chem. Acta, 2007, 118, pp 219-­‐240 Synthèse d’un nouvel ergol pour les lanceurs spatiaux
Etude de l’interaction UDMH / Chloramine
A. Dhenain, C. Darwich, D.M. Le, A.J. Bougrine, H. Delalu
Laboratoire Hydrazines et Composés Energétiques Polyazotés
UMR 5278 Université Lyon 1/CNRS/CNES/HERAKLES-SAFRAN
69922 Villeurbanne cedex, FRANCE.
Les dérivés tétraazotés tels que les tétrazènes ont été identifiés comme des candidats
intéressants pour la propulsion, en raison notamment de la faible masse des produits de combustion
générés, de l'énergie élevée des liaisons N-N et de leurs densités plus élevées que celles des
hydrazines actuellement utilisées en propulsion. En particulier, Le (E)-1,1,4,4-tétraméthyl-2-tétrazène
(TMTZ) suscite aujourd’hui un grand intérêt dans le domaine aérospatial puisqu’il pourrait être utilisé
en tant qu’ergol liquide pour la propulsion des lanceurs spatiaux, en vue de remplacer les hydrazines,
menacées par la réglementation REACH et sans alternative depuis une soixantaine d'années.
La synthèse du TMTZ a été reportée dans la littérature selon différentes méthodes,
essentiellement par oxydation de la 1,1-dimethylhydrazine (UDMH) par l’un des oxydants suivants :
Ag2O [1-3], HgO [2-5], I2 ou Br2 [2, 6-9], KIO3 ou KBrO3 [6, 9], PhSeO2H ou SeO2 [10, 11]. Cependant,
ces méthodes ne sont pas transférables à grande échelle en raison des inconvénients suivants :
utilisation d'oxydants coûteux, faibles rendements en TMTZ, niveau de risque élevé en raison de
l'instabilité des sous produits de réaction, non respect de l'environnement.
Une nouvelle méthode de synthèse du TMTZ utilisant la chloramine comme oxydant, a donc
été développée au laboratoire [12] , ce qui permet d'atteindre des rendements en TMTZ de l'ordre
de 80 à 90% et une pureté de 85 à 95% (figure ). Après purification, le TMTZ peut être obtenu avec
une pureté ≥ 99%. Cette méthode se démarque des méthodes précédemment décrites sur plusieurs
points : elle se différentie par son caractère économique (NH2Cl au lieu de HgO) et peu polluant
(NH4Cl comme produit secondaire), ce qui lui permet d'être transposable industriellement pour une
production de tetraméthyl-2-tetrazène en continu.
L’optimisation des paramètres de synthèse est donc essentielle à l’optimisation des
conditions de synthèse en vue d’un transfert industriel. Pour cela, une étude cinétique et
mécanistique de l’interaction UDMH / Chloramine a été réalisée.
Les cinétiques de formation du TMTZ ont été étudiées en milieu faiblement alcalin (pH 8 à 9),
à une température comprise entre 15 et 45°C. Compte tenu de la valeur élevée des vitesses
réactionnelles, les essais ont été réalisés en milieu dilué, en mettant en œuvre des concentrations en
réactifs comprises entre 1.10-4 and 3.10-3 M. Dans ces conditions, les paramètres cinétiques de la
réaction UDMH + NH2Cl ont été déterminés en utilisant la spectrométrie UV pour le suivi de la
concentration en TMTZ. L’influence de la température et du pH ont été étudiées et un modèle
cinétique a été proposé. L’étude cinétique de la principale réaction secondaire est en cours, il s’agit
de l’interaction entre la chloramine et le TMTZ.
Layered Double Hydroxide materials for Microbial Fuel Cells electrodes
M.A. Djebbi1,2, P. Namour1,3, A. Elabed4, K. Charradi2, S. Elabed4, N. Jaffrezic-Renault1, A. Ben
Haj Amara2
1
Institut des Sciences Analytiques UMR CNRS 5280, Université Claude Bernard-Lyon 1, 5 Rue de la
Doua, 69100 Villeurbanne, France.
2
Laboratoire de Physique des Matériaux Lamellaires et Nano-Matériaux Hybrides (PMLNMH),
Faculté des Sciences de Bizerte, Zarzouna 7021, Tunisie
3
Cemagref, UR MALY, CP 220, F-69336, Lyon cedex 09, France
4
Laboratoire de Biotechnologie Microbienne, Faculté des Sciences et Techniques de Fès-Saïs, Fès,
Morocco
[email protected]/[email protected]
Keywords: Layered Double Hydroxide (LDH), Microbial Fuel Cell (MFC), Electrode,
Coprecipitation method.
The materials used to make electrodes and their internal structures significantly affect the
performances of microbial fuel cells (MFCs) [1]. In this study, we describe layered double
hydroxide (LDH) modified carbon electrodes prepared by soft chemical process.
The control of the performances of LDH materials demands an understanding of increasingly
fine structure and relations between structure, morphology, electrochemical behavior and
chemical composition (i.e. substituted samples vs physical mixtures). MgAl and ZnAl LDHs
were successfully synthesized by coprecipitation reaction. The crystal structure of LDHs was
characterized by X-Ray Diffraction. The morphology of the products was observed using
Scanning Electron Microscopy. The wetting and hydrophilicity/hydrophobicity properties and
surface free energy of all prepared LDHs were investigated by Contact Angle measurement.
The electrochemical behaviors of the LDHs were investigated by Cyclic Voltammetry,
Electrochemical Impedance Spectroscopy and Chronoamperometry measurements.
The results of XRD and SEM analyses showed that single-phase LDH were formed during
synthesis. The resulting surface free energy components were compared. The interaction free
energy between LDHs and support materials in aqueous medium was calculated and
correlated. The spreading kinetics of water droplets on Mg/Al and Zn/Al surfaces was studied
and compared. Relationship between chemical composition of the two LDH compounds and
their electrochemical properties is discussed. Special attention was paid to i) their
biocompatibility and their ability to harbor bacteria and to ii) the role of the bivalent cations
(Mg2+ and Zn2+) in improving electron transfer in the materials.
REFERENCES
1.
Xie X., Ye M., Hu L., Liu N., McDonough J.R., Chen W., Alshareef H.N., Criddle C.S., Cui Y.,
2012, Carbon nanotube-coated macroporous sponge for microbial fuel cell electrodes, Energy
Environ. Sci., vol. 5, pp. 5265-5270.
Résumé
Contribution des détergents, désinfectants et antiseptiques à l’écotoxicité des effluents
hospitaliers
Application aux effluents d’hôpitaux de l’agglomération lyonnaise
J. DROGUET
ENTPE/LEHNA - HCL
L’étude consiste à caractériser la pollution des effluents hospitaliers.
La bibliographie montre que l’écotoxicité globale d’établissements hospitaliers a déjà été
évaluée et qu’elle apparaît significative. Toutefois, la contribution des différents services qui
les composent n’a jamais été étudiée. De plus, si l’hypothèse que cette écotoxicité est
attribuable aux détergents, désinfectants, antiseptiques et aux résidus médicamenteux a
déjà été avancée, elle n’a jamais été démontrée.
Dans le cadre de la présente étude, plusieurs services constitutifs de l’activité globale d’un
établissement de santé vont être étudiés. Ces services relèvent soit de l’activité médicale,
soit de l’activité « technico-logistique ». Il s’agit de :
un service d’hématologie (à très haut risque
infectieux)
un service de réanimation (à haut risque infectieux)
un service de gériatrie (à risque modéré d’infection)
un bloc opératoire avec une activité de prédésinfection
un service d’endoscopie avec une activité de
désinfection
un service de dialyse
une unité centralisée de
alimentaire (UCPA)
une blanchisserie centrale,
une stérilisation centrale
un ensemble de laboratoires
production
une piscine de ré-éducation
un bâtiment d’activité médicale dont le réseau
d’eau est chloré
un service de traitement dentaire
un service de consultations
Pour chaque service retenu, une étude spécifique est réalisée avant toute campagne pour :
- Evaluer les contraintes d’échantillonnage,
- Identifier les produits détergents, désinfectants et antiseptiques utilisés, ainsi que les
médicaments prescrits parmi une liste fermée de 12 substances.
- Décrire les pratiques d’utilisation de ces produits ainsi que les quantités utilisées.
Les analyses portent sur 3 types de paramètres (réalisés tous ou en partie selon chaque
service) :
- Des paramètres physico-chimiques globaux : débit, pH, température, SEH (graisses),
DCO, DBO, H2S, conductivité, sulfures, MES, NTK.
- Des paramètres chimiques spécifiques : AOX, chlore libre, NH4+, ammonium IVre,
chlorure de didécyldiméthylammonium, détergents anioniques / cationiques / nonioniques, 4-nonylphénol, chlorexidine, hexétidine ; paracétamol, ibuprofen, atenolol,
diclofenac, econazole, vancomycin, ciprofloxacin, carbamazepine, acide salicylique…
- Des paramètres d’écotoxicité : mobilité des daphnies, croissance des micro-algues,
reproduction des rotifères, SOS chromotest, test YES/YAS de perturbation
endocrinienne.
Une première campagne de prélèvements a eu lieu fin mars 2015 à l’UCPA. Une autre est
prévue courant juin dans un établissement de gériatrie.
Abstract Doctoral School Mai 7th
As a recent discipline, supramolecular chemistry is one of the most active and fastgrowing fields of chemical research. Driven by the challenge that “host-guest” complexation
represents, a large interest has grown for the design and synthesis of functionalized
macrocycles. In particular, cyclophanes such as Calix[n]arenes1, Resorcin[n]arenes1 and
Pillar[n]arenes2 are known to provide good binding properties thanks to a hydrophobic
cavity and a functionalized ring. We recently developed a new class of accessible and
versatile molecular receptors: Dynarenes. This new class of macrocycles is made from 1,4dithiophenols units functionalized in ortho position and assembled by thiols oxidation to
provide cyclic aromatic disulfide oligomers.3,4,5,6 (Figure 1) Unlike the synthesis of the
traditional cyclophanes, this strategy of macrocyclization allows us to produce large amounts
of final product in very mild conditions. As well as to design architectures with compatible
broad spectrum of functions for molecular recognition.
Because of the complexity of these new molecular objects their characterization and study is
an interdisciplinary task involving organic, physical and computational chemistry.
Figure 1: Synthesis of Dynarenes
In this presentation, we will provide an overview of Dynarenes chemistry, the structure of
macrocycles 1, 2 and 3, and their behavior as host for different kind of guests: anions,
zwitterions and polyamines.
Mélissa Dumartin 2nd year PhD, Applied Supramolecular Chemistry Group-ICBMS, Director J. Leclaire
1”
Calixarenes and Resorcinarene: Synthesis, Properties and Applications” WILEY W. Sliwa and C. Kozlowski 2009
Y. Nakamoto, J. Am. Chem. Soc. 2008, 130, 5022-5023
3
A.S. Hay, Macromolecules, 1996, 29, 6386-6392
4
S. Otto, J. Am. Chem. Soc, 2006, 128, 10253-10257
5
M.S. Raasch, J.Org.Chem, 1979, 44, 2629
6
N. Furukawa, J. Org. Chem. 2001, 66, 2085-2090
2
A new method for measuring the stability of emulsion polymer particles using Turbidity Measurements
Ana Carolina Méndez-Ecoscia, C2P2-UMR 5265, Université de Lyon
Timothy McKenna, C2P2-UMR 5265, Université de Lyon
Nida Sheibat-Othman, LAGEP UMR 5007, Université de Lyon
Key Words: Latex, Coagulation, Turbidity, multiple light scattering.
Stability of latex particles is a key issue in many emulsion systems, whether it is during the reaction or during
post-polymerization treatments. While information on the coagulation of certain well-known polymer/surfactant
systems is available, to the best of our knowledge there is a lack of information about the coagulation of PVDF
latexes stabilized by fluoro-surfactants. For this reason, we investigated the stability of PVDF latex using
TM
turbidity measurements on a Turbiscan LAB. Typically, the characterization of the colloidal stability are
performed using light scattering techniques based on single diffusion model, and the range of operability of this
equipment requires dispersion diluted at minimum 1000 times. In this work, we employed a multiple light
scattering technique which can be used to study more concentrated dispersions, and so allow us to understand
how coagulation takes place in more realistic systems.
Coalescence of the latex particles at different volume fraction was provoked by the addition of an aliquot of a
concentrated solution of monovalent electrolyte (NaCl). The backscattering spectra obtain using a Turbiscan
Off-line turbidimeter was used to follow the coagulation and to identify the critical coagulation concentration
(CCC) of the system under investigation. Additional tests with other systems were also performed. The
experimental stability data collected may be used to model the electrostatic stability of the system.
Synthesis of Enantiopure Arylamines Ligands by Dehydrogenative
Alkylation and Evaluation of their Interests in Asymmetric Catalysis
Bilal El-Asaada,b, Estelle Métaya, Iyad karaméb, Marc Lemairea
CAtalytic SYnthesis and ENvironment (CASYEN team). Université Claude Bernard Lyon 1.
[email protected]
b
Laboratory of OrganoMetallic Catalysis and Coordination chemistry. Universitè Libanais (UL) –
Beyrouth Faculté des Sciences. [email protected]
a
In CASYEN laboratory, the preparation of aryl ethers was done by dehydrogenative
alkylation of cyclohexanone derivatives with alcohols in the presence of catalytic amount of
palladium on carbon (Pd/C) and without any additional solvent via two pathways; in an open
reactor under air without additives and in a closed reactor, under argon, with alkenes. (1) On
the other hand, syntheses of arylamines in good to excellent yields from nonaromatic
substrates were approved by this reaction.
(2)
The dehydrogenative alkylation was also
extended to prepare a variety of aromatic chiral amine.
Figure 1: Dehydrogenative alkylation of tetralone derivatives with (1R, 2R)-cyclohexane-1, 2-diamine
Inspired by Carreira conditions,(3) with slight modifications, the chiral amine ligands
have been tested in the asymmetric transfer hydrogenation of various aromatic ketones
using iridium complex, which led to complete conversion and high enantioselectivity (ee up to
93%), our results demonstrate the interest of this family of ligands.
Figure 2: Reduction of ketone
References:
(1) M. Sutter; N. Sotto; Y. Raoul; E. Métay ; M. Lemaire, European Journal of Organic Chemistry, 2013, 15, 347-352.
(2) M. Sutter; M. Duclos; B. Guicheret; Y. Raoul; E. Métay, M. Lemaire, ACS Sustainable Chemistry and Engineering, 2013, 1
(11), 1463–1473
(3) H. Vzquez-Villa; S. Reber; M. Ariger; E. Carreira, Angewandte Chemie International Edition, 2011, 50, 8979 –8981
Abstract
Titre : Amélioration des performances sur la réduction des émissions de
gaz à effet de serre et de la teneur en hydrocarbures des effluents rejetés.
Auteurs du travail : Bob Cherubin Emerson MOMBO, Koffi FIATY et Jean
Mathurin NZIKOU
Laboratoire d’attache : LAGEP (Laboratoire d’automatique et de génie des
procédés)
Résumé du travail :
De nos jours l’élévation de la température de la basse atmosphère liée au rejet de gaz
issus de l’activité industrielle qui emprisonnent la chaleur du soleil , ajouté à cela
l’action des hydrocarbures en suspension présents dans les eaux à l’état libre ou
faiblement émulsionnés à l’image des eaux pluviales et aussi de ces hydrocarbures
que l’on trouvent à l’état d’émulsion , comme les eaux de production et procédé ,
relèvent une grande interrogation pour l’impact environnemental.
C’est dans ce souci, que les travaux de cette thèse visent à proposer une estimation de
la procédure à suivre compatible et en corrélation avec le monde industriel. Pour cela
une conduite optimisée des gaz de rejets est envisagée et un traitement au préalable
des effluents constitués de plusieurs phases successives sera mis en œuvre, y compris
l’élaboration d’une méthode permettant de stimuler l’activité des bactéries se
nourrissant de façon naturelle de ces hydrocarbures, en les soumettant en culture
dans un laboratoire. Tout ceci vise à améliorer les teneurs en effluent de 25 à 40ppm
dans le but d’avoir des mesures propres par respect pour l’environnement.
Photocatalysis by TiO2 applied to water treatment
Maxime FRANCAIS(1), Corinne FERRONATO(1), Arnaud SALVADOR(2), Ludovic FINE(1), Jean-Marc
CHOVELON(1)
(1)
IRCELYON, CNRS-Université Claude Bernard Lyon 1, 2 av. Albert Einstein, 69626 Villeurbanne
Cedex, France
(2)
UMR 5280 CNRS, Institut des Sciences Analytiques, Université de Lyon, Lyon 1, 5 rue de la
Doua, 69100 Villeurbanne, France
For many years, there is a growing concern about river water, drink water and industrial effluent
quality. Indeed in these waters, various organic pollutants were highlighted at various
concentrations. Moreover, their impacts on both the environment and the human health are
uncertain. In waste water treatment plant (WWTP), pollutant concentration can reach up to several
µg/L. In fact, cleaning process efficiency is not maximal because it depends on the compound. WWTP
represents thus the most important source of environmental pollution.
To complete organic compound degradation, photocalysis can be combined to usual biological
process. TiO2 photocalysis mineralize the major part of organic compounds. It can be used due to the
fact that TiO2 is cheap, harmless and efficient on a large range of pollutant. One drawback is the lack
of knowledge on the mechanistic pathway.
The aim of this study is thus to upgrade our knowledge on TiO2 degradation mechanism. Different
parameters were investigated: water quality and compound structure effect. In a first time, we
needed to comprehend a pollutant degradation pathway. We used a model molecule, furosemide
(loop diuretic), which is present in WWTP and river water at 6.4 µg/L and 255 ng/L respectively.
Elimination rate by common WWTP is only of 34% for furosemide.
Degradation was also realized on 4-Chloro-3-sulfamoylbenzoic acid a similar compound (without
furan cycle) to elucidate regioselectivity of hydroxyl attack and compare the degradation rate.
Degradation kinetic was monitored by LC-MS/MS and headspace Trap GC/MS in order to identify
products. On Furosemide, a rapid cleavage of C-N bond is observed. In furosemide structure C-N
bond is localized between a benzoic ring and a furan one. The cleavage is due to negative inducing
effect of furan ring combined with delocalization of sulfanilamide group electrons. One interesting
point is the non-impact of water quality; in fact, no modification of degradation rate was observed
for furosemide. However, it is not the same for 4-Chloro-3-sulfamoylbenzoic acid since its
degradation is widely inhibited in natural water. Same experiments were carried in pure water with
an increase concentration of bicarbonate. Similar results were obtained: furosemide degradation
increase and 4-Chloro-3-sulfamoylbenzoic acid decrease. We can then assume that bicarbonate
radical generated are highly reactive with the nitrogen of derived aniline part
Cl
C-N bond
O
S
O
O
NH2
N
H
O
OH
Catalytic reactivity at high coverage, a theoretical approach
Butadiene hydrogenation on Pt(111) and Sn/Pt(111)
Sarah Gautiera, Philippe Sauteta
a
École Normale Supérieure of Lyon, 46 allée d’Italie, 69007 Lyon, France
Theoretical hydrogenation studies are usually carried out at low coverage of hydrogen to compare
with UHV experiments. However, industrial production of alkenes implies to work under pressure of
hydrogen of about 1 to 10 bar. Butadiene hydrogenation into 1-butene is one reaction involved in
the production of linear low-density polyethylene (LLDPE) and requires a hydrogen pressure of about
5 bar. This implies to treat the problem considering a high coverage of hydrogen (θH) on the surface.
In this work we first studied the coadsorption of butadiene and hydrogen on two well known surface
catalysts that are Pt(111) and Pt/Sn-Pt(111). To understand the effects of the polarizability of
butadiene on its reactivity, we compared the results obtained with two types of functionals: PBE and
the optPBE van der Walls functional, the latter selected to be the most accurate with respect to
micro calorimetric data obtained by Campbell et al. [1,2]. A thermodynamic model was coupled to
the DFT calculations carried out with the VASP code. This allowed us to obtain the optimal
configuration on Pt and Pt/Sn at 300 K and 5 bar of hydrogen. With PBE, we found θH=5/9 ML on Pt
and 1/3 ML on Pt/Sn as optimal coverages of hydrogen around the butadiene molecule. With
optPBE, only the adsorption sites of hydrogen differ. The hydrogenation mechanism considered in
those cases is the Langmuir-Hinshelwood mechanism involving transition states very similar to those
obtained at low coverage (θH=1/9 ML). However, we also studied the weak adsorption of butadiene
on the surface fully covered by hydrogen. Indeed, the hydrogenation pathway is quite affected by
the increase of the coverage: the structures are destabilised. We need to consider another reaction
mechanism, called Eley-Rideal mechanism, where butadiene comes from the gas phase to physisorb
on the surface precovered with hydrogen (θH=1 ML on Pt, θH=2/3 ML on Sn/Pt). In this case, the
dispersion forces have a quite large component in the total energy which justifies the use of optPBE.
We found new types of transition states which opened new routes with lower barriers (see figure).
We also show that the competition between the two mechanisms is very tight and implies the need
of a deep study of both the thermodynamics and the kinetics of the system to understand the weight
of each mechanism in this reaction.
G (kJ.m ol -1 )
TS8
103
TS7 80
TS1
78
BD
(gas)
0
74
TS6
BD phy
2B1R
5
1B
-2
-8
2B1R
3.78
-23
B13R
-29
2B
-73
1
1
1
0.89
θ H (ML)
1
1
0.89
Figure: butadiene hydrogenation partial pathway starting from the physisorbed structure using optPBE
[1] J. Klimes et al., J. Phys.: Condens. Matter 22, 022201, 2010
[2] O. Lytken et al., Chem. Soc. Rev. 37, 2172, 2008
Investigation of surfactants in atmospheric aerosols
and of their role on cloud formation: SONATA project
Violaine Gérarda, Barbara Nozièrea, Amanda Frossardb, Ronald C. Cohenb, Anne-Marie Delortc
a
IRCELYON (Institut de Recherche sur la Catalyse et sur l‘Environnement de Lyon), CNRS, University of
Lyon, France
b
Berkeley Atmospheric Science Center, Department of Chemistry, University of California, Berkeley,
USA
c
ICCF (Institut de Chimie de Clermont-Ferrand), University of Clermont-Ferrand, France
The formation of clouds is the main cooling factor in the climate budget but also the main source of
uncertainties. These uncertainties are partly due to the lack of understanding of some fundamental
processes controlling cloud droplet formation, in particular the role of surfactants [1]. Cloud droplets
are formed exclusively by the condensation of water on aerosol particles in the atmosphere. The
surface tension of the forming droplet is one of the only two fundamental parameters controlling
droplet growth, and the presence of surfactants in the aerosol particles is therefore expected to
enhance cloud formation. However, the instruments built until now to study these processes are not
able to measure the surface tension of atmospheric particles, which was recently shown to be due to
kinetic limitations [2]. To obtain information on the surfactants present in atmospheric aerosols and
their role on cloud formation an analytical method was recently developed and its application to
aerosols from different regions already demonstrated the presence of strong surfactants all these
aerosols [3]. In this work, the analysis of atmospheric surfactants was further improved by
developing a method to measure their absolute concentration, which is currently unknown yet
essential to quantify their role on cloud formation. This work is performed at IRCELYON and is part of
the international project SONATA (StrOng surfactaNts in ATmospheric Aerosols and their role on
cloud formation). The first results and their implications for cloud formation will be presented.
[1] Boucher, O., D. Randall, P. et al., 2013: Clouds and Aerosols. in: Climate Change 2013: The Physical
Science Basis, Cambridge University Press
[2] Nozière, B., Baduel, C., Jaffrezo, J.-L., Nat. Commun., 2014, 5, 1
[3] Ekström, S., Nozière, B. et al., Biogeosciences, 2010, 7, 387 ; Baduel, C., Nozière, B., Jaffrezo, J.-L.,
Atmos. Environ., 2012, 47, 413
Title: PHOTOCATALYTIC DEGRADATION OF CARBOXYLIC
ACID IN PRESENCE OF TiO2
Name: NGO Ha-Son
Advisor: Chantal GUILLARD
Host lab: IRCE Lyon
Authors: NGO Ha-Son, Chantal GUILLARD and Frederic DAPOZZE.
ABSTRACT
The treatment of water pollution and air is one of the major challenges of the XXI
century. Indeed, these two elements are essential to our lives. At the level of air, the
problem seems to be more and more important. In fact, contacting with pollutants can
cause serious long-term risks (cardiovascular effects, carcinogenic), but also clinical or
symptomatic effects in short and medium term (allergies, discomfort reaction or
discomfort, sick building syndrome).
Technical solutions exist, mostly based on adsorption; however, is only a transfer of
pollution. For the time being, an emerging technique, photocatalysis is increasingly
implemented to address these issues. This method, based on the activation of a
semiconductor by visible UV photons, has the advantage of working at room temperature.
However, details are still being missed in degradation mechanisms in which
potentially toxic intermediates were formed. Furthermore, although a total mineralization
is conceivable, processing time can be very long as some of these intermediates could be
transformed to other types. Up to now, several studies mention the formation of hydrogen
peroxide or the formation of hydrocarbons.
The aim of the research is to try to develop the useful degradation products obtained
during the decomposition of different families of simple organic acids with 1 to 5 carbon
atoms under different processing conditions in presence of various photocatalysts.
During the work, the degradation kinetics and primary degradation products will be
studied in gaseous media under various conditions and also photocatalytic materials will
be prepared and characterized in order to improve the formation of useful compounds
such as hydrogen peroxide and hydrocarbons. Conventional material characterization
techniques will be used (electron microscopy, Raman spectroscopy, UV-visible
spectroscopy…) as well as analytical techniques such as gas chromatography coupled to
different types of detectors: PED, PDHID, ATD/MS for analysing products’ traces.
Vanillin Esterification and Incorporation into a Polyester – Abstract Poster Journée des Doctorants
Lydia Heinrich (PhD student) - Laboratoire CASYEN, ICBMS
Prof. Bruno Andrioletti (Thesis Supervisor), Dr. Catherine Goux-Henry (Co-Supervisor)
Campus La Doua, Bat. Curien (CPE) - 43, Bd. Du 11 Novembre 1918 - 69622 Villeurbanne
E-Mail : [email protected]
In the general context of Green Chemistry and more specifically in view of the diminishing petrol
resources, the replacement of traditionally oil-based chemicals, including those used as monomers in
large scale industrial syntheses of polyesters, with greener, renewable biosourced compounds has
become a desirable means to prepare for future legislation and gain an advantage over competitors.
While recently, a variety of linear diacids and diols have become available from natural sources,
there remains a lack of rigid, aromatic monomers which are needed to provide crucial properties
such as rigidity and hardness.
One of the most promising candidates to fill this void is the widely available and benign Vanillin,
which can be derived from Lignin.1 Several strategies have been employed to incorporate it into
polymers, including through functionalisation with organohalides such as epichlorohydrin, or Acyclic
Diene Metathesis.2 To our knowledge, however, a direct condensation reaction to yield copolymers
such as they are used for example to produce resins for coating applications has not yet been found.
We propose a study of the reactivity towards polycondensations both of the phenol and the
aldehyde moiety of Vanillin and of its derivatives such as Ferulic Acid to explore the different
possibilities of flexible incorporation into existing formulations.
Model reactions were employed to evaluate possible substrates; and different catalysts traditionally
used in polyester synthesis as well as some organic alternatives were tested. Finally, first steps were
taken to estimate the key properties that can be expected from a polyester made up partially from
Vanillin.
1.
Fache, M.; Darroman, E.; Besse, V.; Auvergne, R.; Caillol, S.; Boutevin, B., Vanillin, a promising biobased
building-block for monomer synthesis. Green Chemistry 2014, 16 (4), 1987-1998.
2.
Firdaus, M.; Meier, M. A. R., Renewable co-polymers derived from vanillin and fatty acid derivatives.
European Polymer Journal 2013, 49 (1), 156-166; Stanzione, J. F.; Sadler, J. M.; La Scala, J. J.; Reno, K. H.; Wool,
R. P., Vanillin-based resin for use in composite applications. Green Chemistry 2012, 14 (8), 2346-2352.
CO2-Fischer-Tropsch on iron nano-particles catalysts
Joffrey Huve, David Farrusseng, Yves Schuurman
ABSTRACT
The Fischer-Tropsch process is an interesting pathway
to convert natural gas into transportation fuels. The
strategic element to improve the Fischer-Tropsch
process is the development of active catalysts with high
selectivity for longer hydrocarbons chain and high
activity. Iron-based Fischer-Tropsch catalysts are being
more and more reinvestigate due to their better
resistance to harsh conditions of operations
(temperature, sintering effect), its high water-gas-shift
activity and because of its comparative low price.
However relationships between the catalyst structural
features and catalytic performances (activation, actives
phases, deactivation…) during the Fischer-Tropsch
synthesis are still under investigation due to its high complexity. Here we described a
synthesis process, based on the “Ship-in-the-bottle” method1,2, to develop model ironcatalysts which answer to those different problematics. Well-designed iron nanoparticles
encapsulated in zeolite (ZSM-5 or Silicalite-1) were successfully prepared through
impregnation by incipient wetness following by a dissolution-recrystallization process in the
presence of TPAOH. During this process, the highly defective core of the zeolite crystal is
preferentially dissolved and the silica species recrystallizes on the outer surface upon
hydrothermal treatment. Catalysts with iron particles size between 1-50 nm were
synthesized by this method. A series of Fischer-Tropsch synthesis experiments using
different range of H2/CO/CO2 syngas mixture were performed to provide better
understanding of the structural features-catalytic performance relationship of iron catalysts.
Temperature, size of particles, effect of CO2 and promoters were investigate. Various
techniques such as Transmission electron microscopy (TEM), Mössbauer spectroscopy, X-ray
Diffraction were used to characterize the state of the iron catalyst before, during and after it
was spent during the Fischer-Tropsch synthesis. We anticipate our results to give a better
understanding of the behavior of iron catalyst during the Fischer-Tropsch synthesis.
S. W. Li, L. Burel, C. Aquino, A. Tuel, F. Morfin, J. L. Rousset and D. Farrusseng, Chem.
Commun., 2013, 49, 8507
2 S.W. Li, T. Boucheron, A. Tuel, D. Farrusseng, F. Meunier, Chem. Commun., 2014, 50,
pp.1824-1826
1
Adsorption and diffusion of gold and copper atoms on pristine, reduced
and hydrated TiO2 (110) surfaces from DFT calculations
Mathilde Iachella1, Axel Wilson2,3, Geoffroy Prévot2, David Loffreda1
1
Laboratoire de chimie, UMR CNRS 5182, ENS Lyon, 46 Allée d'Italie 69364 Lyon Cedex 07,
France
2
Institut des NanoSciences de Paris, UMR CNRS 7588, Université Pierre et Marie Curie - Paris 6,
4, Place Jussieu, 75005 Paris, France
3
Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, 91192 Gif-sur-Yvette cedex, France
In heterogeneous catalysis, various model studies aim to understand how complex catalytic
systems effectively work in operando at the atomic scale. However, only a few experimental
techniques really allow the progress on this question. In numerous industrial processes, the
catalytic system is composed of metallic particles supported on a large range of amorphous
materials, with high partial pressure of reactants in a gaseous or a liquid environment. Since
Haruta’s works at the end of the 80’s, the scientific interest conceded to catalysis by gold keeps on
growing throughout the decades. Recently, the nucleation, the growth and the morphology of gold
nanoparticles deposited on rutile support have been studied by various techniques such as STM,
UPS [1], HAADF STEM [2] and GISAXS [3]. In spite of the accuracy of these methods, there are
still open questions related to, the mechanisms at the origin of the particle growth, the role of the
oxide support (synergy with the metallic particle, presence of surface and subsurface oxygen
vacancies), and the effect of the support hydration.
In this context, the theoretical modelling at the atomic scale is essential to tackle those
problems by a close comparison between calculations and state-of-the-art measurements. In the
last decade, a large number of theoretical studies have reported on the adsorption properties of
atomic gold and gold clusters at the sub-nanoscale through density functional theory (DFT)
calculations. Although many efforts have been conceded to advance in the description of those
systems, there are still controversies regarding the adsorption sites and bonding strength. In
particular, due to the presence of oxygen vacancies, the possible hydration of the support, and to
the semi-empirical DFT+U methodology have to be investigated carefully in these delicate models.
Moreover almost no information is available in the literature for the case of Cu/TiO2 (110).
In our study, we propose DFT+U calculations for the adsorption and the diffusion of single
gold and copper atoms on a rutile TiO2 (110) surface (pristine and
reduced, hydrated or clean supports). The most stable adsorption
structures and diffusion activation barriers have been obtained by
exploring the potential energy surface through bidimensional
maps (Figure 1) on the bare surface. Then, the hydroxyl
coverage effect on the rutile support has been studied for each
stable adsorption structure. On the basis of a thermodynamic
model, the most stable catalytic system for the nucleation
process has been predicted by combining the effects of
temperature and hydration. In particular, the optimal position of
gold atom appears to be sensitive to the presence of surface
Figure 1: Potential energy map for the
adsorption of a single Au atom on TiO2
hydroxyls. These results open interesting perspectives for the
(110) support.
understanding of the nucleation and the growth of gold and
copper nanoparticles on this support.
[1] Wahlström, Phys. Rev. Lett., 90 (2003) 026101
[2] Shibata, Phys. Rev. Lett., 102 (2009) 136105
[3] Saint-Lager, Faraday Discuss., 162 (2013) 179–190
Assessment of the importance of the role of •OH
radicals in the photocatalytic degradation of
sulfaclozine.
Liliane Ismaila,b, Ahmad Rifaib, Corinne Ferronatoa, Ludovic Finea, Farouk Jaberb,c,
Jean-Marc Chovelona
a
Université lyon 1, UMR CNRS 5256, Institut de recherches sur la catalyse et
l'environnement de Lyon (IRCELYON), 2 avenue Albert Einstein, F-69626 Villeurbanne,
France
b
Conseil national de la recherche scientifique, Comission Libanaise de l'Energie
atomique, Laboratoire d'analyse des pesticides et des polluants organiques, B.P. 118281, Riad El Solh, 11072260 Beyrouth, Liban
c
Laboratoire d'Analyse des Composés Organiques (509), Faculté des sciences,
Université libanaise, Hadath, Liban
Abstract
The photocatalytic degradation of sulfaclozine in TiO2 suspensions under UV light was
investigated and a complete degradation of 88 µM of sulfaclozine was obtained after 60
min. The addition of methanol, •OH scavenger, to the system inhibited c.a 70% of the
degradation at the concentration of 500 mM which allowed us to conclude that the
degradation of sulfaclozine occurs not only by •OH radicals.
The second order rate constant of the reaction between sulfaclozine and •OH radicals was
determined by a competitive kinetic method and a value of (7.2×109 M-1 s-1) was found.
HPLC/DAD and LC-MS/MS analysis were used to identify and follow the kinetics of
appearance and disappearance of sulfaclozine as well as its intermediates. Twelve main
intermediates were identified from the photocatalytic degradation of sulfaclozine on TiO2
Theranostic gadolinium-based nanoprobes to improve radiotherapy
Authors: Shady Kotb1, F.Lux1, C.Rodriguez2, O.Tillement1, L.Sancey1
Affiliation
1
Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Team FENNEC.
Medical Unit of Molecular Oncology and Transfer, Department of Biochemistry and Molecular Biology, University
Hospital of Lyon Sud .
2
Abstract
A gadolinium-based theranostic agents (AGuIX)® has been developed for image-guided radiation
therapy. These particles consist of a polysiloxane network surrounded by gadolinium chelates.
Due to their small size (< 5 nm), the nanoparticles so-called AGuIX® are characterized by renal
clearance without any undesired accumulation in healthy tissues, properties which confer to the
particles some optimal characteristics for both diagnostic and therapeutic purposes. Due to the
particular tumor vascularization, the AGuIX are able to passively accumulated in solid tumors by
EPR (Enhanced Permeability and Retention) effect. The radiosensitizing effect of the particles
has been demonstrated on B16F10 cells, a highly metastatic and radioresistant mouse
melanoma cell line. In vitro, the particles were significantly able to improve the biological effect
of radiation, at 2 and 5 Gy with an enhancing factor of 14% and 35% respectively as compared
to radiation alone. Similar in vivo effect has been demonstrated when tumors cells were
implanted into mouse brain, with a significant improvement of the animals half live as
compared to radiation treatment.
In addition to the highly favorable safety evaluation of the particles, these results demonstrated
a promising translation to the clinic in the near future, in particular for patients with multiple
brain melanoma metastases.
Experimental and theoretical study of iron(III) complexes with Schiff
base ligands
Walid Lamine,a, b Valérian Forquet,a Salima Boughdiri,b Christophe Morell,a Lorraine
Christ,c Henry Chermette a
a
Université de Lyon, Institut des Sciences Analytiques, UMR CNRS 5280, Université Claude Bernard
Lyon 1, ENS-Lyon, 69622 Villeurbanne Cedex, France
b
Université de Tunis El Manar, Faculté des Sciences de Tunis, UR11ES19 Unité de recherche
Physico-Chimie des Matériaux condensés, 2092, Tunis, Tunisie
c
Université de Lyon, Institut de Recherches sur la Catalyse et l’Environnement de Lyon, IRCELYON,
UMR CNRS 5256, Université Lyon 1, 69626 Villeurbanne Cedex, France
Different spin states may be easily accessible in some transition metal complexes. In
that cases, the small gaps in energy between d-orbitals enable different combinations of
occupation depending on the metal oxidation state, the nature of the ligands and the
geometry.
In this work, Density Functional Theory (DFT) was used to analyse and explain spin state
energetics of two mononuclear tetradentate complexes of an iron(III) metallic centre with N4Schiff base ligands (N4-Fe). Satisfactory validation carried out by DFT was obtained with the
OPBE exchange-correlation functional, catching the diversity of the spin state of the iron
complexes studied. The importance of the calculation parameters closely associated to
chemical environment (solvent…) and the choice of the used of basis set was underlined.
Furthermore, predicting Mössbauer parameters (isomer shifts and quadrupole
splitting) of Fe atoms was supported by a correlation between experimental data and the
corresponding DFT calculated electron densities at the Fe nuclei and quadrupole splitting. In
addition, the UV absorption spectra of the two iron(III) complexes were predicted by
relativistic Time-Dependent Density Functional Theory (TD-DFT) using the OPBE exchangecorrelation functional and AUG/ATZ2P basis set. The calculations provided a good
agreement with experimental data for the assignation of the transition types involved in the
corresponding absorption spectra.
The tetradentate ligand used herein was synthetized following a procedure reported
in the literature [1]. Addition of iron(III) chloride led subsequently to the novel iron complexes
catalysts desired.
[1] I. Karamé, M.L. Christ-Tommasino, R. Faure, M. Lemaire, Eur. J. Org. Chem, 2003 1271–1276.
e-mail: [email protected]
e-mail: [email protected]
e-mail: [email protected]
Gelation of pectin with chlorhexidine: A comparison with the well-known
Pectin-calcium binding
Manon Lascol1, Claire Bordes1, Florence Guillière1, M. Hangouet1, Guy Raffin1, Pedro Marote1,
Sandrine Bourgeois2, Pierre lanteri1
1
UMR 5280 CNRS, Institut des Sciences Analytiques, Université de Lyon, Université Claude Bernard
Lyon 1, France
2
UMR 5007 CNRS, Laboratoire d’Automatique et de Génie des Procédés, Université de Lyon,
Université Claude Bernard Lyon 1, France
Pectin is an anionic polysaccharide obtained by extraction from cell walls of plants. This polymer is
biodegradable and biocompatible and it’s usually used in the pharmaceutical field for drug delivery
system, such as encapsulation. Low methyl pectin forms a gel in contact with divalent cations (Ca2+,
Zn2+…). The gelation mechanism is known as the “egg-box model” [Grant et al., 1973].
Figure: Schematic representation of LM pectin gelation:
the « eggs box » model [Dupuis et al., 2006]
Chlorhexidine (Cx) is an antiseptic substances used in buccal treatment. To improve its
biodisponibility, preliminary encapsulation tests with pectin were done. These assays showed that
there is spontaneous gelation of pectin with Cx, without using calcium ions.
In the present study, gelation mechanisms of pectin with calcium and with Cx were investigated in
dilute solutions using preliminary RMN studies, Potential Zeta measurements, viscosimetry
techniques and Electronic Microscopy.
The results show that the interaction between pectin/Cx is stronger than these of pectin/Ca2+ but the
gelation mechanism of pectin seems to be the same with the two different cations: a two steps
mechanisms.
« P OL YBO R AM INES AS HYDROGEN RESERVOIRS »
Audrey Ledoux,a Paolo Larini,b Jean Raynaud*,a Emmanuel Lacôte*a
Université Claude Bernard Lyon 1, Institut de Chimie de Lyon–CPE Lyon C2P2,
Université Claude Bernard Lyon 1, Institut de Chimie et Biochimie Moléculaires et
Supramoléculaires, 43, Bd du 11 Novembre 1918, 69616 Villeurbanne (France)
a
b
Dihydrogen storage and controlled release has become an essential area of research aspiring
to answer the ever-growing energetic demand. If ammonia-borane (NH3BH3) was early on
identified as a premium candidate to constitute a H2 reservoir, due to its maximum storage
capacity (20 mol% H2),1 researchers have then identified its shortcomings such as poor
processability and troublesome material recycling.2,3
We have proposed to address these issues throughout the synthesis of new amine-borane
polymers, via a polyaddition methodology, harnessing the reactivity and joint H 2-storing
capacity of amine and borane moieties. We aimed at an ease of preparation, an enhanced
processability but also at a straightforward access to recyclable materials via simple rehydrogenation techniques, allowing to sidestep the loss of hydrogen storage capacity
regarding ammonia-borane.
We have synthesized Polyboramines from simple protected organic building blocks. H2storing polymers could be obtained featuring molar masses up to 15,000 g/mol (M n). They
possess a Tg (~60°C) and are soluble in THF. H2 equivalents are readily available.
Interestingly the polymers obtained after dehydrogenation (H 2 release) still feature interesting
mechanical and chemical properties which, in addition to computational studies, give us hope
to envisage a possible re-hydrogenation.4
__________________________
1
2
3
4
A. Staubitz, A. P. M. Robertson and I. Manners, Chem. Rev., 2010, 110, 7
Z. Liu and T. B. Marder, Angew. Chem. Int. Ed. 2008, 47, 242
W. Luo, L.N. Zakharov, and S.Y. Liu, J. Am. Chem. Soc., 2011, 133, 13006
A. Staubitz, M. Besora, J. N. Harvey and I. Manners, Inorg. Chem., 2008, 47, 5910
NMR of D76N β-2-microglobulin Crystals and Fibrils at Ultra-Fast Magic-Angle Spinning
Tanguy Le Marchand (a), Loren Andreas (a), Emeline Barbet-Massin (a), Hugh H. W. Dannatt
(a), Michael J. Knight (a), Stefano Ricagno (b), Martino Bolognesi (b), Sofia Giorgetti (c), Vittorio
Bellotti (c,d), Lyndon Emsley (a), and Guido Pintacuda (a)
(a) CRMN, Institut des Sciences Analytiques, Université de Lyon, Villeurbanne, France
(b) Department of Biotechnology, University of Milano, Italy
(c) Department of Molecular Medicine, University of Pavia, Italy
(d) Centre for Amyloidosis and Acute Phase Proteins, University College London, UK
β-2-microglobulin (β2m), is a 99-residue protein responsible for dialysis-related amyloidosis, and
is recognized as a molecular archetype for the study of folding and amyloid transition
processes. Fibrils of a newly described mutant of β2m (D76N), have been discovered in kindred
patients suffering from gastrointestinal syndromes and autonomic neuropathy. The aptitude of
this mutant to form fibrils in vitro has been revealed to be spectacularly higher than for the wild
type protein. Understanding how a single point mutation can induce such a change in reactivity
would provide a better understanding on the mechanism of formation of fibrils.
Using a combination of ultra-fast (>60 kHz) spinning rates with 100% NH re-protonation in a
1
perdeuterated background and high magnetic fields, we acquire spectacularly resolved Hdetected correlations allowing resonance assignment of both native D76N β2m in microcrystalline
form, and of the fibrils.
On one hand, the good resolution of the CP-based HSQC spectra of microcrystalline D76N and
15
WT β2m allowed us to investigate the backbone dynamics by N relaxation experiments. The
analysis of R1 and R1ρ data with a 1D Gaussian Axial Fluctuation (GAF) model gives site-specific
information about nano- to milli-second backbone motions. The comparison of the dynamical
behavior of the two proteins highlights regions of the protein where the D76N mutant is
particularly destabilized, shedding light on the mechanism of formation of the fibrils.
On the other hand, the influence of growth conditions on D76N fibrils morphology was
investigated. The comparison of fingerprint spectra and resonance assignment performed on two
different samples of D76N fibrils brought to light a structural difference at the molecular level. For
a further investigation of this highlighted polymorphism, homonuclear recoupling based
1
1
experiments were set to find long-range H- H contacts. The results provided strong evidence for
a polymorphism occurring not only on the assembly of the protofilaments as previously observed
for other kind of fibrils but at the level of the beta-sheets organization.
Figure 1: a) 15N R1ρ relaxation curves for microcrystalline D76N and WT beta-2 microglobulin. b)
Representation of the motion of the peptide plane in the GAF model. c) Comparison of the dynamics of
D76N and WT beta-2 microglobulin: projection of the difference in order parameters (S 2) onto the
structure of WT b2m (PDB code: 2d4f).
Acidity of heteropolyacids measured by probe adsorption calorimetry under
static vacuum or in liquid phase
a
A. Lilic a, S. Bennici a, A. Auroux a
IRCELYON, UMR5256 CNRS- Université Lyon1, 2 avenue Albert Einstein, 69626-Villeurbanne cedex
Thermodynamic parameters of solids are highly relevant for practical applications in industrial
reactions. In particular, surface energies and acid-base properties of catalysts are of high interest since
they reflect properties of active sites involved in the catalytic process and the initial adsorption step.
Adsorption calorimetry techniques are interesting tools for the determination of these properties. They
can easily and reproducibly be applied to powders and a wide variety of probe molecules can be
selected.
In this work, adsorption calorimetry in gas phase using ammonia and in liquid phase using
phenylethylamine (PEA) has been used to characterize the acid-base properties of a series of
heteropolyacids. Using ammonia in gas phase, the figure below shows the differential heats of
adsorption vs coverage.
200
HPMo
180
Qdif (kJ/mol)
160
HPW
140
HSiMo
120
HSiW
100
80
60
40
20
0
0
500
1000
1500
NH3 adsorbed volume (µmol/g)
H3PW 12O40 displays the strongest acidity, followed by H4SiW 12O40, while the two other samples
containing molybdenum oxide are weakly acidic. In n-decane, the strength and number of acid sites are
strongly affected by the solvent surrounding the sample, diminishing the accessibility to the Brønsted
sites.
The obtained energy parameters will be discussed in order to compare both techniques and the
influence of the medium.
[1] S. Bennici, A. Auroux, Thermal analysis and calorimetric methods. S.J. Hargreaves, S.D.
Jackson, Eds., Metal oxide catalysis. VCH-Wiley 2009, 391-441.
A new approach for coupling CAD or CFD data into MCNP6 for Monte
Carlo simulation of radiotracer experiments
Zhenhua Lin1, Benoit Hautefeuille1, Olivier Tillement2
1
2
AXINT SAS, 181 Route de l’Azergues 69480 Lucenay France
Institut Lumière Matière, UMR 5306 Université Lyon1-CNRS, Université de Lyon, 69622 Villeurbanne Cedex
Monte Carlo N-particle Transport Code (MCNP) developed by Los Alamos National Laboratory is
used primarily for the simulation of nuclear process, such as fission, but it is also extended to simulate neutron,
photon, electron, or coupled neutron/photon/electron transport. Specific areas of application include radiation
protection and dosimetry, radiation shielding, radiography, medical physics, nuclear criticality safety, detector
design and analysis, accelerator target design and so on. Recently, MCNP Version 6 (MCNP6) has been
extended to include a new capability that permits tracking of neutrons and photons in an unstructured mesh that
is embedded as a mesh universe. This new capability provides an easier, faster and more accurate way of
building complex geometries which is a large advantage over traditional CSG (constructive solid geometry)
modeling in MCNP code. The mesh geometry in MCNP6 is intended to be created through Abaqus/CAE using
its solid modeling capabilities. Instead of creating through Abaqus/CAE and because of its inherent limitations,
we developed a new method for the CAD conversion, which is highly compatible with many CAD or model
meshing softwares. The new implementations and features were tested to simulate several gamma and beta
experiments. The first example simulates the signals from a complex geometry radiation source, made for the
French waste management agency (ANDRA: Agence National pour la gestion des Déchets Radioactifs)
emplaced in a clay rich geological medium. These simulations are used for designing a long term 22Na
diffusion experiment in-situ in this medium deep underground laboratory. The second example shows the
simulation of a beta Thin Layer Chromatography scanner that is used for medical radiotracer quality control.
Ultra fast microwave synthesis of V-(Al/Ti)-MCM-41 catalysts
for oxidation reactions
a,b
a
b
Xinnan LU , Belén ALBELA , Yong LU , Laurent BONNEVIOT
a
a. Laboratoire de Chimie, UMR-CNRS 5182, . cole Normale Supérieure de Lyon,
Université de Lyon, Lyon, France
b. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department
of Chemistry, East China Normal University, Shanghai, China
[email protected]
Incorporation of catalytic transition metal ions into high surface area porous silica as well as
search for fast, clean and energy saving catalysts syntheses are highly desirable for practical
large-scale applications in catalysis of oxidation [1-2]. Among metal supports, mesoporous silica
MS family (hexagonal structural MCM-41 or cubic structural MCM-48 have widely used for
catalytic application, especially for the reaction of large molecules owing to large their surface
areas and narrow pore-size distribution, in the nano scale range 3-10 nm [1]. Therefore, ultra-fast
microwave assisted direct synthesis of V-Al-MCM-41 and V-Ti-MCM-41 were investigated with a
special attention brought to vanadium dispersion, V leaching and surfactant recycling as criteria to
address environmental issues.
The incorporation of vanadium was concomitant to the synthesis of MCM-41. Stable and
well-structured V-MCM-41 was obtained in a very short period of time as 10 minutes at 180 oC
with microwave assisted method. Aluminum and titanium was simultaneously incorporated as
anchor heteroatoms during the one-pot microwave synthesis of V-MCM-41 to improve the
dispersion and stability of vanadium active sites.
In addition to the incorporation of aluminum and titanium, we also expect to incorporate other
metal ions (such as zirconium, cerium etc.) on mesoporous silica with the efficient microwave
assisted one-pot synthesis, and to improve their retention in the systems for catalytic application in
oxidation reaction conditions.
REFERENCES:
[1] Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature 1992,
359, 710-712.
[2] Solsona, B.; Blasco, T.; López Nieto, J. M.; Peña, M. L.; Rey, F.; Vidal-Moya, A. J.
Catal. 2001, 203, 443-452.
New fast micro-analyzer equipped with an On-line Liquid
Injection System
Adrien Maniquet1; Alain Delauzun2; Ronan Cozic2; Sandra Grimaldi1; Franck BacoAntoniali1; Jérôme Randon3
1
Department of Industrial Analysis, IDEEL, 69360 Solaize, FRANCE
2 SRA Instruments, 69280 Marcy l’Etoile, FRANCE
3 Institute of Analytical Sciences, 69100 Villeurbanne, FRANCE
Abstract
Process control is a major challenge for the chemical and petrochemical industries and in the field
of energy to ensure product quality, cost control, productivity and risk control. Direct analysis at
the heart of process is essential, but compared to laboratory analysis the market still suffers from
a lack of analytical technologies. In this context, a collaboration between IDEEL and SRA
Instruments companies has been set up to develop solutions for on-line analysis to answer
industrial needs.
A new generation of microGC has been developed for the rapid analysis of liquid flows. The
analyzer is equipped with an on-line sampling valve developed and commercialized by SRA
Instruments. This injection device uses a piston with a micro machined groove (at its lower
extremity), designed to contain the pressurized sample. The volume of liquid will be vaporized
during the injection step thanks to the very fast and very powerful heating of the groove. Sample
is then injected directly in a short capillary column without saturation risk before detection by a
µFID. This µFID presents a strong interest for micro-analyzer, because of its low gas consumption
and low power requirements for operation. It gives also similar sensitivity compared to
conventional ones. A first prototype is presently being evaluated in IDEEL’s Laboratory.
Experimental evaluations are intended to measure performances of the instrument in terms of
separation, repeatability and detection limit.
This new generation of micro-analyzer will extend the possibilities of in-situ process control. It
represents a powerful tool to monitor complex liquid matrices.
Annual Meeting 2015
BENEFITS OF PASSIVE SAMPLING FOR THE MONITORING OF PESTICIDES IN SURFACE AND
SUBSURFACE WATERS
A. Martin, C. Guillemain, M. Le-Dréau, L. Liger, X. Peyrard, V. Gouy, C. Margoum (1)
(1) Irstea 5, rue de la Doua, CS 70077, 69626 Villeurbanne cedex, France – [email protected]
The use of pesticides in agricultural fields leads to nonpoint source contamination of
freshwaters by various pathways (runoff, infiltration, lateral flows…). Different research
programs have been developed to study and explain these transfer mechanisms. They required
specific sampling strategies for each compartment of the aquatic environments. Passive
sampling has been introduced as an alternative to grab or average automated sampling, in
order to obtain at lower cost, more realistic estimates of the contamination levels of pesticides
in water. This technique allows the in situ accumulation of chemicals over exposition periods
ranging from days to months.
Silicone rods, investigated in this work, are single-use and low cost new passive samplers.
Extraction and quantification of pesticides from silicone rods were performed by liquid
desorption followed by UHPLC-MS/MS. The nature and mass of pesticides sorbed on in situ
exposed silicone rods can be used as qualitative and semi-quantitative measures to assess
trends or gradients of contamination at different scales: from plots to rivers or watersheds.
The aim of this study was to investigate the use of silicone rods as a passive sampling
technique in different water bodies and to assess their benefits for the monitoring of pesticides
and metabolites with various physico-chemical properties.
Firstly, silicone rods have been exposed during one month (four exposition periods of one
week) in a river located in a vineyard watershed with a marked pesticide contamination.
Fifteen pesticides, mainly fungicides, were sorbed on silicone rods, but also insecticides that
could not be detected in parallel grab samples. A strong gradient of contamination was clearly
shown according to the increase of land use. Contamination reaches a maximum in the second
week corresponding to a rainy period after a dry one.
A second application of silicone rods consisted in their deployment inside a network of
piezometers in an instrumented vineyard plot to evaluate the spatial propagation of pesticide
contamination during a rainfall event. Silicone rods allowed for the qualitative detection of
seventeen pesticides from different families and origins. The spatial dispersion of pesticides
highlighted a strong axial subsurface transfer following the slope of the plot. The comparison
of upslope and downslope masses of pesticides sorbed on the rods permitted to discriminate
the behaviour of the pesticides either in controlled conditions (for pesticides injected during a
simulation event) or in natural conditions (for pesticides applied on the plot by the farmer).
We illustrated here that sensitive passive samplers can now be considered as an alternative or
complement to grab sampling to improve the monitoring of pesticides in aquatic
environments by integrating pesticide concentration variations over exposition periods.
Xenobiotics removal by phototransformation in the context of tertiary
treatment: Conception of a database and first results
Baptiste MATHON, Jean-Marc CHOUBERT, Cécile MIEGE, Marina COQUERY
Irstea, UR MALY, 5 rue de la Doua – CS 70077, 69 626 Villeurbanne cedex, France
{[email protected]; [email protected]; [email protected]}
Abstract:
Conventional waste water treatment plants (WWTP) partially eliminate xenobiotics present in domestic and
industrial discharges (Choubert et al., 2011). However, some xenobiotics are still present in the effluents of
WWTP at concentrations close to 0.1 μg/L for some pesticides (ex. diuron) and pharmaceuticals (e.g.,
carbamazepine,
sotalol,
diclofenac),
and
even
over
1
μg/L
for
certain
xenobiotics,
including
aminomethylphosphonic acid (AMPA), ibuprofen, and gemfibrozil (Gabet-Giraud et al., 2010; Martin Ruel et
al., 2010).
Phototransformation appears to be a process that can be used to improve the treatment of these xenobiotics in
tertiary treatment. The aim of this work is to give an in-depth overview of the phototransformation of 13
pesticides and pharmaceuticals present in effluents of conventional wastewater treatment plants: erythromycin
and roxithromycin (antibiotics), carbamazepine (antiepileptic), diazepam (benzodiazepine), diclofenac (antiinflammatory drug) metoprolol, timolol, propranolol, atenolol and sotalol (beta-blockers), simazine, diuron and
isoproturon (pesticides). We performed a qualitative and quantitative overview of literature data describing the
phototransformation of pesticides and pharmaceuticals. In this aim, we built a database compiling results on
phototransformation experiments from 70 scientific publications covering 13 xenobiotics commonly found in
secondary effluents. Special attention was devoted to compile reliable data on phototransformation half-life. We
also included information on experimental operating conditions and about phototransformation products. The
first outputs of the database consist on (i) a proposition of a classification of the 13 xenobiotics according to their
ability to be phototransformed, with identification of the fast, medium and low phototransformable ones; (ii) the
comparison of degradation kinetics under direct and indirect phototransformation conditions; (iii) and the list of
140 phototransformation products formed during these two pathways.
Keywords: Photodegradation, micropollutant, polishing ponds, database, by-products
Design and Synthesis of Retroviral Integrases
Oligomerisation Inhibitors
M. Mosser(1), H. Yajjou(2), B. Bourdon(1), N. Aronssohn(1), X. Robert(2), M.P. Confort(3),
S. Paul(4), H. Belrhali(5), E. Dumont(1), C. Ronfort(3), P. Gouet(2), P. Maurin(1)
(1)
Laboratoire de Chimie UMR 5182 CNRS/UCBL/ENS de Lyon
Equipe de Biocristallographie et Biologie structurale des Cibles Thérapeutiques, UMR 5086 IBCP-BMSI CNRS-Lyon 1
(3)
Equipe Rétrovirus Intégration Virale et vaccin, UMR 754 Rétrovirus et pathologie comparée INRA-ENVL-UCBL-EPHE Lyon
(4)
Crystallography Synchrotron, UMI 3265 UVHCI CNRS-UJF-EMBL Grenoble
(5)
Groupe sur l’immunité des Muqueuses et Agents pathogènes, EA3064 Saint Etienne
(2)
Key words : integrase, inhibitor, multidrug therapies, organic synthesis
Abstract :
This project is part of a preliminary study for the development of potential inhibitors of
RAV-1 integrase, an avian virus used as a model for HIV-1. In the current context of new
multidrug therapy strategies we aim to develop an inhibitor modulating the integrase
oligomerization. This mechanism of action being complementary of the one of known
competitive integrase inhibitors such as Raltegravir or Dolutegravir, this could help to develop
new strategies against the variability of the AIDS virus.
Through our collaboration involving theoretical chemists, biologists and structural
biologists we identified, via molecular modeling and docking studies, two series of potential
inhibitors involving disubstituted indole or coumarin rings moieties. To obtain those original
targets we developed a short and efficient synthetic access to a new class of indole derivatives
bearing differentiated carboxylic groups in positions 3 and 5. Moreover we synthesized a range of
substituted coumarins that, from docking results, could exhibit a high affinity with our target. The
protein-ligand affinity measurements will be performed by our partners.
Développement d’un Lab-on-Chip adapté au dosage volumique de
l’acidité libre de solutions chargées
Nom, Prénom : NERI QUIROZ, José Antonio
Responsable CEA : F. CANTO/ A. MAGNALDO
Directeur universitaire : Vincent DUGAS
Laboratoire d’accueil : DRCP/SERA/LAMM
Date de début de thèse : 12/2013
Contrat : CEA
Organisme co-financeur : AREVA
Université d'inscription : Université Lyon 1
Ecole doctorale : ED 206 - Lyon
Master : Diplôme Ingénieur en génie chimique +
Master 2 Recherche en sciences analytiques
-----------------------------------------------------------------------------------------------------------------------------------------------
Dans le cadre des recherches des procédés de retraitement pour les usines futures, le domaine
technique de l’analyse doit être identifié comme un des points clés, du fait de la part très
importante du contrôle analytique dans le coût de fonctionnement des usines de retraitement, dans
son temps de réponse, et dans la garantie du suivi de bon fonctionnement de l’usine pour le grand
public. Cette attente pourrait être particulièrement aigüe en ce qui concerne les effluents rejetés,
qui n’offriront une vraie garantie que par un « maillage analytique » adéquat de l’installation. Le
retour d’expérience des usines actuelles, mené avec des exploitants d’AREVA LH, ainsi que
l’analyse des schémas de procédé de référence ont permis d’établir une liste de point de mesures
à créer ou à améliorer de façon prioritaire pour les usines futures. Parmi ces points figurent en
premier lieu la mesure d’acidité libre sur tout le procédé. En effet, l’acidité est un des paramètres
les plus souvent mesurés et doit être connu avec précision pour pouvoir piloter correctement le
procédé.
L’acidité libre d’une solution contenant des ions hydrolysables est définie comme la mesure de
l’acidité sans prendre en compte les ions H3O+ provenant de l’hydrolyse de métaux lourds
contenus dans la solution. Autrement dit, c’est l’acidité qui est mesuré lorsqu’on complexe ou
enlève les ions hydrolysables pour qu’ils n’interfèrent pas pendant la mesure. Les ions
hydrolysables d’intérêt sont l’UO2, U4+, Pu4+ parmi d’autres sous-produits de fission.
Par exemple pour l’hydrolyse du Pu4+
Pu4+ + H2O
PuOH3+ + H+
Dans ce cas, les ions H+ libérés lors de la réaction d’hydrolyse nous amèneront à une fausse
quantification de l’acidité de la solution(1). Pour répondre à cette problématique la méthode actuelle
proposée par la CETAMA nécessite la complexation des ions de métaux lourds pour supprimer
leur pouvoir d’hydrolyse avant de mesurer l’acidité. Cependant, les méthodes utilisées génèrent
beaucoup d’effluents. L’objectif du projet sera alors de développer un outil d’analyse miniaturisé
« lab-on-chip » pour mesurer l’acidité libre de solutions chargées. Le lab-on-chip à développer
devra permettre la réduction du temps d’analyse des échantillons, devra être automatisable pour
permettre la multiplication des mesures, devra être fabriqué d’un matériau résistant aux
rayonnements et aux fortes acidités pour rendre le dispositif nucléarisable à de coûts de fabrication
et de maintenance raisonnables. Finalement, la petite taille du dispositif à développer permettra de
réduire la quantité d’effluent rejeté et de diminuer le risque de contamination radiologique pour les
analystes effectuant les mesures.
1) M. K. Ahmed, D. S. Suryanarayana, K. N. Sabharwal, N. L. Sreenivasan. Anal. Chem.,
1985, 57, 2358-2360.
Les 14èmes Journées Scientifiques de Marcoule
10 – 13 juin 2014
Kinetic Modeling of Quinoline Hydrodenitrogenation over a
NiMo(P)/Al2O3 catalyst in a batch reactor
Minh Tuan Nguyen1,2, Melaz Tayakout-Fayolle1, Christophe Geantet1*, Gerhard D.
Pirngruber2, Fabien Chainet2
1
Institut de recherches sur la catalyse et l’environnement de Lyon, IRCELYON, UMR 5256CNRS, 2 avenue Albert Einstein, F-69626 Villeurbanne, France
2
IFP-Energies Nouvelles – Etablissement de Lyon, 69390 Vernaison, France
Abstract
The kinetic approach of quinoline hydrodenitrogenation (HDN) is indispensable in order to
understand the effect of support or doping materials in favor of the development of more
efficient catalytic systems. In our study, the quinoline HDN is performed in the batch reactor,
over NiMo(P)/γ-Al2O3 sulfide catalyst, at the range of temperature of 340-360°C and
concentration of 1000-2000 ppmw of quinoline. The kinetic model is described by LangmuirHinshelwood model, assumes the competitive adsorption of quinoline, intermediate and
ammonia on the same active site, and takes into account the liquid gas transfer. The activation
energies of every elementary reaction and adsorption enthalpies of nitrogen compounds are
calculated. The kinetic modeling shows that the hydrogenation of 1,2,3,4-tetrahydroquinoline
into decahydroquinoline is the rate-determining step of the principal reaction pathway. The
self-inhibition effect due to competitive adsorption of nitrogen containing compounds is
confirmed. The adsorption constants of nitrogen compounds decrease by the order: saturated
amines > NH3 > quinoline = 5,6,7,8-tetrahydroquinoline > 1,2,3,4-tetrahydroquinoline = opropylaniline, which shows good agreement with the relative order of pKa. Moreover, the
kinetic model is validated by an additional experiment using the ammonia as an inhibitor.
Effect of water content to the esterification of lactic acid with
ethanol using acidic solid catalysts
V. C. NGUYEN1,2, N. ESSAYEM1*, T. T. H. VU2, N. Q. BUI1, P. FONGARLAND1
Institut de Recherche sur la Catalyse et l’environnement de Lyon, CNRS, Lyon1, 2 Avenue Albert
Einstein, 69626 Villeurbanne, France
2
Key Laboratory for Petrochemical and Refinery Technologies, 2 rue Pham Ngu Lao, Hanoi,
Vietnam
1
* [email protected]
The effect of water content to the esterification of lactic acid with ethanol has been studied in
the presence of the commercial acid resin Amberlyst 15, Niobic acid and Sulfonated carbon.
Sulfonated carbon was successfully prepared via carbonization of spruce wood, followed by
sulfonation with concentrated sulfuric acid. The effect of water content, nature catalyst,
catalyst loading on reaction kinetics was evaluated. In order to study the effect of water
content on the activity of the catalysts, a simplified kinetic model was used to determine the
kinetic constants. The results show that kinetic constant was increased as linear trendline with
the increase of Amberlys 15 amount, it means that the esterification reaction was carried out
in the chemical region, and there was no diffusion limitation. At low level of water,
sulfonated carbon was the most active catalyst but it suffered strongly from inhibition of
water; Amberlyst 15 was affected by inhibition but it was still active; Niobic was very low
activity and rapidly no catalytic effect was observed.
Synthèse et caractérisations de suspensions abrasives à haute efficacité
Le saphir possède des propriétés optiques et structurales adaptées à une large gamme
d’applications. Parmi les plus connues, on peut citer : les supports semi-conducteurs pour la
croissance épitaxiale de GaN pour diodes électroluminescente (LEDs) ou les lentilles pour des
dispositifs tel que les lasers haute-puissance [1]. La préparation de surfaces en saphir reste une étape
stratégique du fait des propriétés de dureté, d’anisotropie structurale et d’inertie chimique
intrinsèque du cristal [2, 3]. Le nombre d’étapes de polissage peut être réduit en optimisant les
suspensions abrasives utilisées [4, 5]. Ainsi, il est possible d’améliorer les procédés de polissage du
saphir, en termes de rugosité (nm) et de taux d’enlèvements de matière (µm.s-1). De par son
accessibilité et ses propriétés structurales, le diamant reste l’abrasif le plus utilisé pour les étapes de
polissage mécanique. La mise en œuvre de particules de diamants permet d’atteindre de bon taux
d’enlèvement de matière mais induit cependant un certain nombre de dommages à la surface [5].
Lors des travaux de thèse réalisés, l’incorporation de particules métalliques dans les suspensions
diamantées pour le polissage de saphir plan a s’est révélée concluante (Figure 1). En effet, une
augmentation du taux d’enlèvement et une amélioration de la rugosité pour deux types de saphir
différents (rubis et corrindon) a été observée. La variation de la taille des abrasifs et la maîtrise de la
formulation des suspensions (stabilité colloïdale, additifs, etc.) ont permis d’obtenir des surfaces de
haute qualités optiques. En outre, l’utilisation du tensioactif Triton X 100 pour la formulation des
suspensions a démontré de bonnes performances en polissage. La caractérisation des particules
abrasives post-polissage a permis de mettre en évidence la formation d’un matériau composé d’une
particule de fer dans laquelle sont indentés des diamants (Figure 2).
Figure 2 : Evolution de l'enlèvement en fonction de la
concentration en diamants (500 nm). Influence de
l'incorporation de particules de Fer6-9µm
Figure 1 : Clichés MEB (15 KeV) Fer50µm / NDs2-3µm
Figure 2 : Evolution de l'enlèvement en fonction
1.
2.
3.
4.
5.
de la concentration
diamants
(500 nm).
Dobrovinskaya, E., L. Lytvynov, and V. Pishchik, Application of Sapphire,
in Sapphire.en2009,
Springer
US.
Influence de l'incorporation de particules de Fer69µm
p. 1-54.
Voloshin, A.V., L.A. Litvinov, and E.V. Slyunin, The influence of sapphire crystallographic orientation on
surface roughness achievable by diamond abrasive machining. Journal of Superhard Materials, 2013.
35(1): p. 56-59.
Zhu, H.L., et al., Chemical mechanical polishing (CMP) anisotropy in sapphire. Applied Surface Science,
2004. 236(1-4): p. 120-130.
Cherian, I.K. and A.K. Bakshi, Polishing of sapphire with composite slurries. 2014, Google Patents.
Saito, T., et al., Lattice Strain and Dislocations in Polished Surfaces on Sapphire. Journal of the
American Ceramic Society, 2005. 88(8): p. 2277-2285.
Mahmoud Ould Metidji – PhD student -- Institut Lumière Matière équipe FENNEC -- CONFIDENTIEL
Three-Dimensional Structure Determination of Surface Species by
DNP Enhanced Solid-state NMR
†
†
†
†
o
Pierrick Berruyer, Moreno Lelli, Alexandre Zagdoun, David Gajan, Aaron J. Rossini, Matthew
‡
‡
†
†o
P. Conley, Olivier Ouari,§ Paul Tordo,§ Christophe Copéret, Anne Lesage, Lyndon Emsley,
†
Institut des Sciences Analytiques, Centre de RMN à Très Hauts Champs (CNRS/ENS
‡
Lyon/UCB Lyon 1), Université de Lyon, France. Department of Chemistry, Laboratory of
Inorganic Chemistry, ETH Zürich, Switzerland. § Aix-Marseille Universite. (CNRS, ICR UMR
o
7273), France. Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de
Lausanne, Switzerland.
NMR spectroscopy (often in conjunction with diffraction methods) is the method of choice for
characterizing surfaces whenever possible, but the detection limit of NMR is far too low to allow
many modern materials to be examined. Because it provides dramatic sensitivity enhancement,
solid-state Dynamic Nuclear Polarization (DNP) NMR is currently emerging as a powerful tool to
study samples previously inaccessible to NMR. We have recently shown how DNP could be used
to selectively enhance the NMR signals from surfaces in a wide range of samples, including
nanoporous and nanoparticulate materials (DNP SENS) (1). With the recent introduction of
polarizing agents of high molecular weight like TEKPOL (2), enhancements greater than 100 are
now routinely obtained at 9.4 T and 100 K for mesostructured materials. Such signal amplification
factors enable multi-dimensional correlation experiments and thus offer the prospect of obtaining
unprecedented quantitative structural information about species at the surface of these materials.
Here we will show that multi-nuclear correlation techniques can be applied to obtain
13
15
29
15
measurements of C- N and Si- N distances in mesoporous silicas incorporating organic
fragments as well as well-defined organometallic catalysts. These experiments lead to the
determination of the three-dimensional structure of the surface species for both precursor and
metal-organic catalyst.
(1) a. Rossini, A. J et al. Dynamic Nuclear Polarization Surface Enhanced NMR
Spectroscopy. Acc. Chem. Res. 2013, 46, 1942–1951.
b. Lesage, A et al. Surface enhanced NMR spectroscopy by dynamic nuclear
polarization. J. Am. Chem. Soc. 2010, 132, 15459–15461.
c. Lelli, M. et al. Fast Characterization of Functionalized Silica Materials by Silicon-29
Surface-Enhanced NMR Spectroscopy Using Dynamic Nuclear Polarization J. Am. Chem.
Soc. 2011, 133, 2104-2107
d. Samantaray, M.K. et al. Evidence for Metal Surface Interactions and Their Role in
Stabilizing Well-Defined Immobilized Ru NHC Alkene Metathesis Catalysts. J. Am. Chem.
Soc. 2013, 135, 3193 3199.
e. Wolf, P et al. NMR signatures of the active sites in Sn- zeolite. Angew. Chem. Int. Ed.
Engl. 2014, 53, 10179–10183.
f. Protesescu, L. et al. Unraveling the core-shell structure of ligand-capped Sn/SnOx
nanoparticles by surface-enhanced nuclear magnetic resonance, Mössbauer, and X-ray
absorption spectroscopies. ACS Nano 2014, 8, 2639–2648.
(2) Zagdoun, A. et al. Large Molecular Weight Nitroxide Biradicals Providing Efficient
Dynamic Nuclear Polarization at Temperatures up to 200 K. J. Am. Chem. Soc. 2013, 135,
12790–12797.
Preparation and characterization of Cyclodextrin-anethole
inclusion complex loaded liposomes
Riham Ghariba.b, Lizette Auezovaa, Catherine Charcossetb, Hélène Greige-Gergesa.
[email protected]; [email protected]
a. Faculty of Sciences, Section II, Bioactive Molecules Research Group, Doctoral School of Sciences and
Technologies, Jdaidet El-Matn, Lebanese University, Lebanon.
b. Laboratoire d’Automatique et de Génie des Procédés, Université Claude Bernard Lyon I, France
The combined approach based on drug-in-cyclodextrin-in-liposome was used to
encapsulate anethole, major component of star anise and fennel essential oils. Although
anehole is well-known for its antimicrobial activity, its sensitivity to light and oxygen, its
volatility and hydrophobicity limit its large-scale application. To avoid these drawbacks,
various formulations based on hydroxypropyl-beta-cyclodextrin (HPß-CD) and soybean
phosphatidycholine were prepared, characterized and tested for anethole photostability.
The effect of saturation of the lipid acylchain on the liposome charcateristics was
determined using either hydrogenated (Phospholipon 90H) or non-hydrogenated (Lipoid
S100) soybean phospholipids. Results of dynamic light scattering analysis showed that
the presence of HPß-CD did not affect significantly the size of liposomes compared to
anethole loaded liposomes whether Lipoid S100 or Phospholipon 90H. With the
exception of HPß-CD/anethole inclusion complex loaded Lipoid S100-liposomes, the
polydispersity index for all liposomal formulations showed homogeneous population.
Moreover there was no significant difference in zeta potential values for Lipoid S100
liposomes, while the zeta values decrease significantly in the presence of HPß-CD for
Phospholipon 90H liposome. The transmission electronic microscopic proved the
formation of all liposomes formulations. The encapsulation efficiency and loading rate
were calculated after separation of free anethole from anethole loaded liposomes and
determination of their concentrations by HPLC. Compared to anethole loaded liposomes,
CD/anethole inclusion complex loaded liposomes improved significantly the anethole
loading rate. This latter was also improved by the double loading technique. Among the
both phospholipid types, lipoid S100 showed the highest anethole encapsulation. When
the liposome batches and CD/anethole inclusion complex were exposed to UV light
Poster
Reduction of Organic Functional Groups Using Hypophosphites
Rim Mouselmani,a,b Estelle Métay,a Ali Hachem,b Ali Alaaeddineb and Marc
Lemairea
CAtalytic SYnthesis and ENvironment (CASYEN team), (ICBMS), Université Claude Bernard Lyon
1, Bâtiment Curien, 43 boulevard du 11 novembre 1918, F-69622 Villeurbanne Cedex, France Fax:
(+33)-4-72-43-14-08; phone: (+33)-4-72-43-14-07; [email protected]
b
Laboratoire de Chimie Médicinale et des Produits Naturels, Universitè Libanais (UL) – Beyrouth
Faculté des Sciences, Campus de Hariri Hadath, Beyrouth- LIBAN, phone:(+961)-3 31 95 49 ;
[email protected]
a
Reduction in organic synthesis could be a key transformation. A large number of efficient and
selective reductants are available to synthetic chemists. However, it is necessary to imagine
and elaborate new processes and reagents in order to reduce or eliminate the risks linked to
the utilization of some hazard substances. Consequently, the development of reductive
systems addressing ecologically and economically sustainable development is still required.
In this context, sodium hypophosphite, recently registered in REACH as a cheap and stable
to air molecule, was also studied in biphasic systems.1 In the laboratory, several
methodologies with sodium hypophosphite as reducing agent were successfully developed
with special care to environmental impact. Aliphatic and aromatic nitro compounds have
been efficiently reduced by hypophosphites in the presence of palladium on carbon.2 This
catalyst also allowed the commutative reduction of ketone to alcohol / alkane.3 Finally,
enantioselectivity was reached by use of Noyori’s catalyst in a non-classical biphasic
combination of two bio-sourced solvents (2-MeTHF / glycerol).3
This success push us to explore the reactivity of hypophosphite derivatives in the reduction
of differents functions and specifically conditions were developed to selectively reduce nitriles
in aldehydes.
References:
(1) http://echa.europa.eu.
(2) Baron, M.; Métay, E.; Lemaire, M.; Popowycz, F. Green Chem. 2013, 15, 1006–1015.
(3) a) C. Guyon; M. Baron, M. Lemaire, F. Popowycz, E. Métay, Tetrahedron, 2014, 70, 2088-2095; b) C. Guyon; E. Métay ; N.
Duguet; M. Lemaire, European Journal of Organic Chemistry, 2013, 5439-5444.
Toxicological study of α-cyclodextrins, and synthesis of new derivatives
Eszter Roka1,2, Miklos Vecsernyes1, Caroline Felix2, Ildiko Bacskay1 and Florent Perret2
1
University of Debrecen, Department of Pharmaceutical Technology, Debrecen, Hungary
2
University Lyon 1, ICMBS Equipe CSAp, Lyon, France
Poor water solubility of drugs is an emerging problem in today’s pharmacotherapy. It is
shown by the Biopharmaceutical Classification System (BCS) which classifies more than
60% of the active pharmaceutical ingredients (API) into class II and IV, due to their low
solubility in physiological environment. Bioavailability can be increased by the enhancement
of water solubility. Several chemical and pharmaceutical opportunities are available for this,
e.g. usage of complex-forming molecules, such as cyclodextrins (CDs) (1). [Fig. 1]
-CDs have been in the focus of pharmaceutical and
industrial research from decades. They are more
popular in use, considering the size of their
preferable cavity for the common used APIs. (2)
Nevertheless, evaluating the opportunities of α-CD
usage in pharmaceutical practice is worth, thus for
smaller APIs their smaller cavity could be more
convenient, and also their amphiphilic derivatives
Figure. 1 Natural CDs are built up from six
can form more stable nanoparticles which can be
(α), seven (β) or eight (γ) glucopyranose
further used in drug delivery. CDs, as
units. γ-CDs possess the biggest, α-CDs the
pharmaceutical excipients, are always in higher
smallest cavity diatmeter.
concentration in the products than stoichiometrically
required, thus evaluation of their effects on living organisms is indispensable. One aim of our
study was to investigate the cytotoxic properties of newly developed α-CD derivatives.
Toxicological studies were performed on Caco-2 cell line and human red blood cells (RBC).
By MTT cell viability assay, Real Time Cell Electronic
Sensing (RT-CES) and hemolysis test, the IC50 and
HC50 concentration values were determined. Based on
these values, comparison of the effect of chemical
changes can be made, and it drives to the selection of
derivatives which are the most safe to use in further
developments. However, CDs which are available on
market mostly possess only approximate degree of
substitution (DS), considering the difficulties and high
price of complete separation. Although for reaching the
clear conclusion of structure-toxicity correlations,
separated derivatives should be examined. This is one the
aims of our research group, to synthesize and separate
Figure. 2 Structure of the -CD
derivatives
alkyl-CD derivatives with well-defined DS. (3,4) [Fig. 2]
References:
1.
2.
3.
4.
Szejtli J. Medical applications of cyclodextrins. Medical Research Reviews1994. 14. 353-386.
Kiss T, Fenyvesi F, Pasztor N, Feher P, Varadi J, Kocsan R, Szente L, Fenyvesi E, Szabo G, Vecsernyes M, Bacskay I.
Cytotoxicity of different types of methylated beta-cyclodextrins and ionic derivatives Pharmazie. 62(7):557-8. 2007.
Takeo K., Ueraura K., Mitoh H. Derivatives of α-Cyclodextrin and the Syntesis of 6-O-α-D-glucopyranosyl-α-Cyclodextrin, J.
Carbohydrate Chemistry, 7 (2), 293-308. 1988.
Pitha J., L. M. Mallis, D. J. Lamb, T. Irie, K. Uekama Characterization of polydisperse and amorphous mixtures, Pharm. Res.,
Col. 8. No 9. 1991.
Effect of progesterone, its hydroxylated and methylated derivatives, and
dydrogesterone on lipid bilayer membranes
Rola Abboud a,b, Hélène Greige-Gergesa, Catherine Charcossetb*
a
Bioactive Molecules Research Group, PRASE, Doctoral School of Sciences and
Technologies, Department of Chemistry and Biochemistry, Faculty of Sciences 2,
Lebanese University, Lebanon.
b
Laboratoire d’Automatique et de Génie des Procédés (LAGEP), UMR-CNRS 5007,
Université Claude Bernard Lyon 1, CPE Lyon, Bat 308G, 43 Boulevard du 11 Novembre
1918, F-69622 Villeurbanne Cedex, France
Corresponding author: Catherine Charcosset
[email protected]
Tel: 33 [0] 4 72 43 18 67
Fax: 33 [0] 4 72 43 16 99
Absolute quantification of Dengue virus serotype 4 chimera
vaccine candidate in Vero cell culture by targeted mass
spectrometry
Rougemont Blandine1, Simon Romain1, Carrière Romain1, Biarc Jordane1, Fonbonne
Catherine1, Salvador Arnaud1, Huillet Céline2, Berard Yves2, Adam Olivier2, Manin
Catherine2 and Lemoine Jérôme1,3
1
Institut des Sciences Analytiques, UMR 5280 CNRS Université Lyon 1, Université de Lyon,
5 rue de la Doua, 69450 Villeurbanne
2
Sanofi Pasteur, 1541 av. Marcel Mérieux, 69280 Marcy l’étoile
3
To whom correspondence should be addressed
Abstract
Infection by dengue flavivirus is transmitted by mosquitoes and affects tens to hundreds of
millions people around the world each year. Four serotypes have been described, all of which
cause similar disease. Currently, there no approved vaccines or specific therapeutics for
dengue, although several vaccine prototypes are in different stages of clinical development.
Amongst them, a chimeric vaccine, built from the replication machinery of the yellow fever
17D virus, has shown promising results in phase III trials. Accurate quantitation of expressed
viral particles in alive attenuated viral antigen vaccine is essential and determination of
infectious titer is usually the method of choice. The current paper describes an alternative or
orthogonal strategy, namely, a multiplexed and absolute assay of four proteins of the chimera
Optical Response of Single Metallic Nano-objects in a Liquid Environment
Using Spatial Modulation Spectroscopy
J-M. Rye1,2, C. Bonnet1, F. LeRouge2, J. Lermé1, A. Mosset1, M. Broyer1, M. Pellarin1, S. Parola2
and E. Cottancin1
1
Institute of Light and Matter, Claude Bernard University Lyon 1, CNRS UMR 5306,
University of Lyon, Villeurbanne, France
2
Laboratoire de Chimie, École Normale Supérieure de Lyon, University Claude Bernard Lyon 1, CNRS UMR 5182,
University of Lyon, Lyon, France
Depending on their size, shape, composition and immediate environment, metallic nanoobjects may exhibit a strong optical response known as Localized Surface Plasmon Resonance
(LSPR) which often appears prominently in optical spectra. Spatial Modulation Spectroscopy
(SMS) [1], which is a highly sensitive technique for measuring this reponse in individual nanoobjects, can therefore be used to probe for changes in the local environment through the detection
of induced changes in the LSPR, which opens the door for sensing applications.
Here we report on our current work to develop an SMS setup for the measurement of
extinction and scattering spectra in a liquid environment for the purpose of biosensing. This setup
permits the mapping (fig. 1a) and optical characterization (fig. 1b) of individual nano-objects on
a sample immersed in a controlled liquid environment. Optical measurements of individual nanoobjects may then be correlated to morphological data acquired via electron microscopy for
detailed analysis of the studied objects. Our initial focus lies on the development of
functionalized gold bipyramids samples for biosensing due to their prominent and configurable
LSPR peak in the near-IR region [2].
Figure 1 :(a) Transmission map of sample with individual gold bipyramids. (b) Transmission
(extinction) and reflection (scattering) measurements of an individual gold bipyramid.
References
[1] Billaud, P. et al. Absolute optical extinction measurements of single nano-objects by spatial
modulation spectroscopy using a white lamp. Review of Scientific Instruments 2010, 81, 043101.
[2] Navarro, J. R. G. et al. Synthesis, electron tomography and single-particle optical response of
twisted gold nano-bipyramids. Nanotechnology 2012, 23, 145707.
Solid-state NMR of Paramagnetic Materials above 100 kHz Magic Angle Spinning
!
!
Kevin J. Sanders and Guido Pintacuda
Recently there has been increased activity in the development of new nuclear magnetic
resonance (NMR) methods studying structural and electronic properties of
paramagnetic solids and their application to systems of interest in catalysis, energy
conversion and storage, and biochemistry. However, large interactions between the
unpaired electrons of paramagnetic nuclei and surrounding nuclear magnetic moments
cause complications in recording NMR spectra, notably (i) large paramagnetic
relaxation enhancements, (ii) large contact shifts and shift anisotropies, and (iii) bulk
magnetic susceptibility effects. The combination of these effects sometimes causes the
failure to yield any data using modern solid-state NMR technology.
!
We investigate the advantages for the study of paramagnetic materials offered by a new
probe capable of magic angle spinning (MAS) rates higher than 100 kHz using a 0.7mm
rotor. Important benefits include (i) an improved averaging of dipolar couplings and the
separation of sidebands, with a spectacular increase of both resolution, sensitivity and
coherence lifetimes compared to previously available MAS rates; (ii) the possibility of
reaching very large RF fields with very small amplifier powers, with an astounding
improvement in excitation bandwidth and pulse efficiency; (iii) the completely new
possibility of applying broadband irradiation schemes which are based on low-power RF
elements.
!
The approach is demonstrated on two highly paramagnetic inorganic complexes,
microcrystalline Na3Tb(DPA)3•nD2O, a luminescent paramagnetic organic complex, and
LiMg0.5Mn0.5PO4, a promising paramagnetic battery cathode material.
!
We anticipate that the possibilities offered by this new spinning regime could
revolutionize the study of paramagnetic samples which are central in many areas of
modern chemistry and materials science.
Stereoselective Recognition of Carbohydrates with chiral receptors based on
Cyclotriveratrylene unit
Sara Lefevre1, Alexandre Heloin1, Delphine Pitrat1, Jean-Christophe Mulatier1, Laure Guy1,
Alexandre Martinez1, Jean-Pierre Dutasta1
1
Laboratoire de Chimie, Ecole Normale Superieure de Lyon,
46 allée d’Italie, F-69634 Lyon 07, FRANCE
[email protected]
Abstract
Molecular containers are very attractive as they can act as molecular receptors and so mimic
biological entities such as protein.1
In the past, hemicryptophanes (receptors derived from cyclotriveratrylene (CTV) units) have
shown good complexation abilities with carbohydrate guests.2 Hence, CTV receptors bearing
chiral binaphtyl substituents have been synthesized. They display very interesting properties for
the stereoselective recognition of carbohydrate derivatives. The comparison of opened and
closed receptors has been studied and shows interesting results.
References
1
B. Dietrich, J.M. Lehn, J.P. Sauvage. Tetrahedron Lett., 1969,2889-2892
2
O. Perraud, A. Martinez, J.P. Dutasta, Chem. Commun., 2011, 47, 5861-5863
Comparison between on-line RPLCxSFC and on-line RPLCxRPLC for the separation of a
complex sample of neutral compounds
Morgan Sarrut1; Amélie Corgier1; Agnès Le Masle2 ; Stéphane Dubant3; Gérard Crétier1; Sabine Heinisch1
1
Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Lyon1, ENS, 5, rue de la
DOUA, 69100 Villeurbanne, France
2
IFP Energies nouvelles, Rond-Point de l’échangeur de Solaize, BP3, 69360 Solaize, France
3
Waters SAS, BP608, 78056 St Quentin en Yvelines, France
The interest for multidimensional techniques has been growing over the last decades. Theoretically, the peak
capacity in comprehensive two-dimensional liquid chromatography (LCxLC) is the product of the peak capacity
in each dimension leading potentially to a very high peak capacity. However, the effective peak capacity depends
on the degree of orthogonality which is strongly related to the percentage of the 2D retention surface coverage
(γ). The lack of correlation between the retention times in both dimensions leads to high  values, thus
recommended for achieving very high peak capacities. While acceptable  values can be obtained in
RPLCxRPLC for ionizable compounds by changing the pH between the two dimensions, suitable 2D-conditions
are more challenging for neutral compounds. In this respect, the significant difference in retention mechanisms
between RPLC and SFC can be very attractive.
Accordingly, on-line RPLCxSFC and on-line RPLCxRPLC were compared for the separation of an aqueous
extract of bio-oil, made up principally of neutral compounds. For a better comparison, the first RPLC dimension,
and hence the analysis time were identical for the two configurations. The quality of the separation was assessed
by means of both effective peak capacity and sensitivity. A comparison of the two set-ups as well as software
considerations are also presented.
Full orthogonality (γ=1) was reached in RPLCxSFC while the  value was 0.6 only in RPLCxRPLC. However the
effective peak capacity was quite similar for the two couplings (i.e. 620 in RPLCxSFC vs 560 in RPLCxRPLC,
both separations being carried out in 100 min). This somewhat disappointing result is likely to be due to more
significant injection effects in RPLCxSFC on the one hand, and to more substantial contribution of SFC
instrument to peak band broadening on the other hand. Extra-column contributions may be also the cause of
the net decrease in peak height and hence in sensitivity observed in SFC compared to RPLC making on-line
RPLCxSFC less attractive from this point of view.
In conclusion, this study highlights the high potential of on-line RPLCxSFC to separate neutral compounds. Yet,
we need to be aware that mobile phase compatibility issues as well as current instrumental and software
limitations may presently hinder its use, thus requiring further developments.
Investigations of soot combustion on Yttria-Stabilized Zirconia
by Environmental Transmission Electron Microscopy (ETEM)
A. Serve, T. Epicier1,2,M. Aouine1, F. J. Cadete Santos Aires1, E. Obeid1, M. Tsampas1, K. Pajot3, P. Vernoux1*
1
Université de Lyon, Institut de Recherches sur la Catalyse et l’Environnement de Lyon, UMR 5256, CNRS, Université C.
Bernard Lyon 1, 2 avenue A. Einstein, 69626 Villeurbanne, France
2
Université de Lyon, MATEIS, UMR 5510, CNRS, INSA de Lyon, 69621 Villeurbanne Cedex, France
3
PSA PEUGEOT CITROËN, Centre technique de Vélizy, Route de Gisy 78943 Vélizy-Villacoublay, France
Soot particle emissions by light Diesel vehicles are regulated by the EURO standards. Since
2011, EURO 5 standards generalized the use of Diesel Particle Filter (DPF) to achieve low
enough emissions. DPF allows the filtration of the major part of the particles, which is
collected in the inlet channels. As soot is collected, a “cake” of soot is formed in the DPF,
slowly obstructing the exhaust. To eliminate the soot, and therefore regenerate the DPF, one
needs to reach temperature high enough for the soot to burn. Such method requires postinjection of fuel to increase the exhaust temperature and results in an overconsumption. To
limit the fuel consumption, various catalysts for soot oxidation have been investigated. By
coating the inlet channels of the DPF with such catalyst, one can expect the soot particles to
get in contact with the catalyst layer, and therefore diminish the soot-oxidation temperature,
allowing a non-assisted regeneration.
We focus our attention on yttria-stabilized zirconia (YSZ) which displays good thermal
stability (allowing it to resist the temperature variations in the exhaust) and soot oxidation
activity. The mechanism involved in the soot oxidation is similar to a fuel-cell mechanism
where the soot acts both as an anode and as reactant. YSZ furnishes oxygen ions to the soot
and recharges itself through the gas phase. To investigate further the mechanism, we
performed E-TEM (Environmental Transmission Electronic Microscopy) observations of a
mixture of soot and catalyst at high temperature (550°C) and under low oxygen partial
pressure (3mbar).
Soot mixture was obtained by grinding YSZ powder and soot obtained from a burner in an
agate mortar for 20 min with a catalyst to soot mass ratio of 4/1. A portion of the mixture was
dispersed by ultrasound in an ethanol solution and deposited on a silica grid.
Observations were conducted at a 1nm resolution (Figure 1) and underline the importance of
contact between soot and catalyst. Soot oxidation only happens at the boundary layer between
YSZ and the soot particles. Particles not in contact are not oxidized although being in contact
with the O2 gas phase (Figure 1d). During soot oxidation, soot particles appear to move
toward YSZ surface and are consumed at the interface, contact lines range between 20 and
40nm. High resolution observations show YSZ surface remain unaltered after soot oxidation.
Such results confirm the mechanism previously proposed: oxidation occurs through the
oxygen ions from YSZ lattice phase and not from the gaseous oxygen, this was also
confirmed by isotopic exchange experiments.
Figure 1: Oxidation of soot over YSZ at 550°C, under 3mbar O2 and 80kV. Time interval is 40s
Carbohydrate phosphates and phosphodiesters:
synthetic and biological aspects
Si-Zhe LI,a,b Laurent Soulère,a,b Mohamed Ahmar,a,b and Yves Queneaua,b
a
INSA Lyon, ICBMS, laboratoire de Chimie Organique et Bioorganique, Bât J. Verne, 20 av A. Einstein, 69621
Villeurbanne Cedex, France
b
CNRS, UMR 5246, ICBMS, Université Lyon 1, INSA-Lyon, CPE-Lyon, Bât CPE, 43 bd du 11 novembre 1918,
69622 Villeurbanne Cedex, France.
Phosphoesters are abundant in carbohydrate structures, either possessing a phosphate group in
anomeric position, or a phosphate group attached to an alcoholic OH. In this communication, we report
our recent work on two aspects of carbohydrate phosphate chemistry: one methodological study on the
synthesis of alcohol phosphates using triallylphosphite, and one synthetic investigation of the role of
carbohydrate phosphodiester agrocinopine A in Agrobacterium tumefaciens.
A direct method for the phosphorylation of alcohols, phenols, carbohydrates and nucleosides using
triallyl phosphite has been investigated [1]. From primary or secondary alcohols, the corresponding diallyl
protected phosphorylated compounds are obtained in good to high yields. Diols or polyls possessing both
primary and secondary alcohol functions can be selectively phosphorylated on their primary position. The
method was applied to simple primary and secondary alcohols, as well as more complex substrates such
as nucleosides or carbohydrate derivatives, including glycosyl-1-phosphates.
The other part of the work concerns Agrocinopine A, a phosphodiester of sucrose and L-arabinose
produced by plant cells modified by Agrobacterium tumefaciens. Transported by the PBP protein AccA, it
serves as nutrient for the bacteria. Interestingly, the natural antibiotic agrocin 84, constructed a
nucleosidic backbone, is also able to bind AccA. To investigate the binding mode of these compounds
and propose the minimal scaffold recognized by AccA in collaboration with biologists of the SENSOR
ANR consortium, we prepared agrocinopine A and diverse analogues. Agrocinopine A was synthetized by
coupling an adequately protected sucrose and a phosphate precursor bearing an L-arabinose substituent
using an alternative phosphinylation reagent compared to previous reports.[2,3] Following a similar strategy,
we then focused on the synthesis of L-arabinose phosphate, L-arabinose isopropyl 2-phosphate and
glucose 2-phosphate and thus defined the structural basis for the recognition by AccA.
Références : [1]. (a). Stowell, J. K.; Widlanski, T. S.Tetrahedron Lett. 1995, 36, 1825. (b). Soulère, L.; Aldrich, C.; Daumke, O.;
Gail, R.; Kissau, L.; Wittinghofer, A.; Waldmann, H. Chembiochem 2004, 5, 1448. (c). Ladame, S.; Claustre, S.; Willson,
M.Phosphorus Sulfur Silicon Relat. Elem. 2001, 174, 37. (d). Owen S. Fenton, Emily E.Allen, Kyle P. Pedretty, Bianca R.
Sculimbrene. Tetrahedron. 2012, 68, 9023-9028.
[2]. Franz Kowiak, M.; Thiem, J. Liebigs Ann. Chem. 1987, 1065-1071;
[3]. Lindberg, M.; Norberg, T. J. Carbohydrate Chemistry 7 (4), 1988,749-755.
Graduate School Meeting, May 7th, 2015
Catalytic combustion of polycyclic aromatic hydrocarbons (PAH) over zeolite type
catalysts : effect of Si/Al ratio, structure and acidity
Jihène SOUFI *1,2, Isabelle PITAULT3, Patrick GELIN1, Valérie Meille2, Laurent
VANOYE2, Fréderic BORNETTE2, Emmanuel FIANI4
1
Université Lyon1,CNRS, UMR 5256, Institut de Recherches sur la Catalyse et l'Environnement de Lyon,
2 avenue A. Einstein, F-69626 Villeurbanne Cedex, France
2
Ecole de Chimie Physique éléctronique de Lyon, CNRS, UMR 5285, Laboratoire de Génie des Procédés
Catalytique,43 boulevard du 11 novembre 1918, 69616 Villeurbanne Cedex
3
Université lyon1, CNRS, UMR 5007, Laboratoire d'Automatique et de Génie des Procédés, 43 boulevard
du 11 novembre 1918, 69622 Villeurbanne Cedex, France
4
ADEME Agence de l'Environnement de la Maîtrise de l'Energie, 20 avenue du Gresillé 49004 Angers
Cedex01, France
*email: [email protected]
Keywords: catalytic oxidation, 1-methylnaphtalene conversion, zeolite, acidity, structure, 1methylnaphtalene
Introduction
PAHs show adverse health effects. For instance, benzo(a)pyrene is classified as carcinogenic by
IARC. Therefore, at the international level, many countries have committed themselves to
minimizing air emissions through the Aarhus Protocol on POPs which was signed in 1998 under
the Geneva Long Range Transboundary Air Pollution Convention. At the French level, emission
limit values for PAHs have been introduced in a recent regulation on combustion plants with a
thermal input higher than 20 MWth (Ministerial Decree of 26 August 2013).
Catalytic oxidation is one of the most promising technologies to reduce the emissions of air
pollutants [1]. Metal oxides or supported noble metals methods are the most investigated
catalysts for the destruction of organic pollutants.
Acid zeolites (protonic forms) have been considered as effective cheap alternative catalysts to
metal oxides for hydrocarbons oxidation [2]. Catalytic performances of these zeolites were
associated with the presence of Bronsted acide sites.
In this work, the removal of 1-methylnaphtalene (1-MN), a model compound representative of
PAH, by catalytic combustion in the presence of steam is investigated.
The behavior of various acidic zeolites towards the gas-phase catalytic oxidation of 1-MN is
investigated. The effect of some parameters on 1-MN oxidation is studied: the structure of the
zeolite, Lewis and Bronsted acidity and Si/Al ratio. The performance of these zeolites is
compared to 0.97 wt% Pt/Al2O3 which is one of the most active catalysts in complete oxidation
of naphthalene [3].
References
[1] M. Taralunga, J. Mijoin, P. Magnoux, Applied Catalysis B: Environmental 60 (2005) 163171.
[2] S. C. Marie-Rose, T. Belin, J. Mijoin, E. Fiani, M. Taralunga, F. Nicol, X. Chaucherie, P.
Magnoux, Applied Catalysis B: Environmental 90 (2009) 489-496.
[3] Xiao-Wen., Shen, Shou-Cang., Yu, L. E., Kawi, S., Hidajat, K., Simon Ng, K. Y. Zhang,
Applied Catalysis A: General 250 (2003) 341-352.
CO : Communication orale
Journée ED Chimie / Annual Meeting 2015
Pd-catalyzed telomerization of ethanol amine with isoprene in the
presence of phosphine ligands
W. Zahreddine,a,b Q. Lelong,a I. Karamé,b Ali Kanj,b
C. Pinel,a L. Djakovitcha et F. Rataboula
a
b
Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et
l’environnement de Lyon, 2 avenue Albert Einstein, F-69626 Villeurbanne, France
Laboratoire de Catalyse Organométallique et Chimie de Coordination, Département de Chimie,
Faculté des Sciences I, Université Libanaise, Campus Rafic Hariri, Hadath, Liban
The telomerization reaction is a powerful tool for the preparation of functionalized
compounds bearing a long hydrocarbon chain. This reaction involves the dimerization of 1,3dienes in the presence of a nucleophile1. It is usually catalyzed by Pd complexes in the
presence of phosphines or NHC ligands. The telomerization of amine derivatives with
isoprene is of particular interest for the synthesis of terpenes.
We present here for the first time the telomerization of ethanol amine with isoprene.
Selected examples of obtained results are given in Table 1. We will discuss in details the
influence of the phosphine structure and the stoichiometry of the reactants on both efficiency
and selectivity of this transformation.
Figure 1. Examples of products obtained from the telomerization of ethanol amine with
isoprene.
Table 1. Telomerization of ethanol amine with isoprene.a
Selectivity (%)
Ligand
Total yield
(%)
1
2
3
4
PPh3
66
5.1
71.1
6.9
16.9
PPh3b
PPh3c
44
3.6
77.8
5.6
13
85
0.3
47.4
1.5
50.8
P(o-tolyl)3
0
a
ethanol amine 90 mmol, isoprene 180 mmol, Pd(acac)2 18 mg (0.06 mol%/ethanol amine), ligand 2 equiv./Pd,
methanol 40 mL, argon 2 MPa, 90 °C, 20 h. b isoprene 90 mmol. c isoprene 450 mmol.
1- A. Behr, M. Becker, T. Beckmann, L. Johnen, J. Leschinski, S. Reyer, Angew. Chem. Int. Ed., 2009 (48) 3598.
Design of two-photon absorbing probes for the in-vivo
monitoring of oxygen pressure
Zheng Zheng, Yann Bretonnière, Chantal Andraud
Laboratoire de Chimie de l’Ecole Normale Supérieure de Lyon, 46 allée d’Italie, 69007 Lyon, France
Four new fluorene-based two-photon absorbing (TPA) chromophores have been
synthesized and their one- and two-photon photophysical properties have been
investigated. These chromophores all display obvious TPA activity. One of them was
successfully attached covalently to a central palladium porphyrin complex by the Cu(I)
catalyzed click reaction. The new compounds contain four or eight TPA
chromophores donor connected to a Pd porphyrin acceptor via 1, 2, 3-triazole linkages,
in which two-photon chromophores singlet excited state emission is significantly
quenched. Compounds 1 and 2 demonstrate that the incorporation of a suitable donor
chromophore can enhance the effective TPA cross section of the system, allowing
efficient sensitivity towards oxygen at 800 nm.


98.9 %
FRET
Reference
=
98.3
%
1) W. Dichtel et al. J. Am. Chem. Soc. 2004, 126, 5380-5381; 2) S. Sakadžić et al. Nat. Methods 2010, 7, 755-759.