Effect of Particle Morphology and Interaction on the Stabilization of Water/Water
Emulsions by Protein Particles
Alberto GONZALEZ-JORDAN, Taco NICOLAI, Lazhar BENYAHIA [email protected] Université du Maine, IMMM UMR CNRS 6283, PCI, 72085 Le Mans Cedex Category : Molécules Matériaux Water/water (W/W) emulsions have a promising potential for many applications, especially in the food and cosmetics industries. These emulsions cannot be stabilized by surfactants, but in recent years it was found that they can be stabilized by adding solid particles in a manner similar to so-called Pickering oil/water emulsions. Protein particles in the form of microgels, fractal aggregates or fibrils were made from the same protein, ß-lactoglobulin by heating at different conditions. The effect of the morphology on the stability and structure of W/W emulsions made by mixing aqueous solutions of PEO and dextran was investigated at different pH. Interestingly, excess proteins partioned to the dextran phase at pH>4 and to the PEO at pH<3.0. Fibrils were found to be most effective stabilizers at pH 7, whereas fractals were most effective at pH 3. At pH values between 5.5 and 3.5 the protein particles aggregated leading to cold gelation. If excess proteins were in the continuous phase W/W emulsion formed gels that were very weak, but strong enough to prevent creaming of sedimentation of the dispersed droplets. If excess proteins were in the dispersed phase, the droplets were transformed into stable microscopic protein particles. CLSM images (160x160 µm) of PEO in dextran (top) and dextran in PEO (bottom) emulsions in the presence of ß-lactoglobulin fractal aggregates (0.5%) at pH 6.5, 5.5, 5.0, 4.5, 4.0, 3.5 (from left to right) . The inserts of the right images represent a zoom (40x40 µm). Graphene-modified conjugated polymer/titanium dioxide composites: Their
structures, optical properties and applications in photocatalysis
Yuanqing Song 12, Florian Massuyeau 1, Tanxiao Shen 2, Jianling Zhang 2, Long Jiang 2, Yi Dan 2, Philippe Le Rendu 1, Thien-Phap Nguyen 1 [email protected] (1)Institut des Matériaux Jean Rouxel, Nantes (2)Research Institute of Sichuan University Category : Molécules X Matériaux
Abstract : Graphene blended with the conjugated polymer poly(3-hexylthiophene) (P3HT) is known to be as an efficient absorber in organic solar cells. By its high charge mobility, graphene using in composite materials improves significantly their conductivity. Furthermore, charge separation in these materials is favored as graphene usually acts as quencher in the fluorescence of conjugated polymers and consequently, enhances the performance of devices. Conjugated polymer doping TiO2 is an effective method for extending the photoresponse of TiO2 to visible light. To improve the photocatalytic activity of conjugated polymers based photocatalyst, a new graphene-modified poly(3-hexylthiophene) (P3HT) / titanium dioxide (TiO2) (P3HT/TiO2/GE) composite were prepared. Ultraviolet-visible diffuse reflection spectroscopy (UV-vis DRS), steady-state photoluminescence spectroscopy (PL) and time-resolved photoluminescence spectroscopy (TR-PL) were used to analyze the energy and charge-transfer mechanisms between the conjugated polymer and the inorganic nanoparticles. The photocatalytic activity of the composite films were investigated by studying the decolorization of rhodamine B (RhB) solution under the visible light irradiation. The result shows that, the P3HT/TiO2/Graphene composite can make rhodamine B be degraded more efficiently than the P3HT/TiO2 composite does. Charge transfer process was also evidenced in composites. Furthermore, we have fabricated and studied composites made of P3HT and graphene with different concentrations and qualities (expressed by the graphene weight per surface unit). Using optical spectroscopy including absorption, infrared, Raman, PL and TR-PL we analyzed the electronic structure of the composites as a function of the graphene concentration and quality. Funding and acknowledgement : China Scholarship Council (CSC) and Campus France  L. Wang, T. Sasaki. Titanium Oxide Nanosheets: Graphene Analogues with Versatile Functionalities. Chemical Reviews, 2014, 114(19): 9455-9486  M. Dahl, Y. Liu, Y. Yin. Composite Titanium Dioxide Nanomaterials. Chemical Reviews, 2014, 114(19): 9853-9889 Characterization of Holmium-166 microparticles for radiotherapy by Field Flow
Fractionation (FFF) techniques.
Estelle N'TSIBA a,b,c [email protected] aLaboratoire Subatech, UMR 6457, 4 Rue A. Kastler, BP 20722, F-44307 Nantes Cedex 3, France bGIP ARRONAX, 1 rue Aronnax, F-44817 Nantes Cedex, France cAdvanced Accelerator Application, 20 rue Diesel, 01630 Saint-Genis Pouilly, France Molécules Matériaux
Micro-curie-therapy consists in injecting a radioactive and microscopic source into or close to a
tumor in order to destroy cancerous cells by irradiation (1). Among the different isotopes for
radiotherapy, 166Ho can be used to target large tumors. The Arronax cyclotron produces 166Ho (T1/2=
26.8h) via the 165Ho n, pγ 166Ho nuclear reaction. 166Ho is a high-energy β- emitter (1854 keV) and a γ
emitter (80 keV), that could be used for both therapy and SPECT imaging. In addition, the stable
natural isotope 165Ho has magnetic properties, allowing its use for MRI imaging. By using 165Ho and
166Ho in the same vector, detection by MRI and SPECT (so called multimodal imaging) is thus possible.
In the frame of Personalized Medicine development, micro-particles are envisaged to be injected by
intra-tumoral for large tumors that are composed of polysiloxane coated with macrocyclic ligands.
The 166Ho microparticles are produced with high activities of and their integrity should be ensured.
Microparticles should be characterized as far as their size, size distribution, viscosity and surface
charge are concerned. An approach by As-FFFF-UV-MALS (2) is used for determining the size and size
distribution of holmium micro-particles for monitoring their integrity after neutronic activation.
Viscosity measurements were performed on the suspension and surface charge was determined by
zeta potential measurements to better understand the colloidal behavior of the suspension.
Analytical methods to fully characterize the nanoparticles (stability, integrity, size, surface charge)
will be described together with the associated nanometrological tools required. The viscosity
measurements have led to determine that the suspension has a non-newtonian behaviour. As-FFFF-
UV-MALS has shown that the non-irradiated suspensions are complex, exhibiting objects of
nanometric to micrometric scale with polydispersity and polymodality; in contrast to DLS
observations. The irradiated suspensions exhibited a quite different profile of size distribution. A
discussion will be given on the integrity of particles induced by the irradiation process. The
advantages, drawbacks and limitations of each technique will be also considered.
FFF-based techniques are suitable for characterizing nano and micro objects and for monitoring the
potential polydispersity and/or polymodality, and are powerful tools especially in the case of
particles that have been submitted to irradiation and for radiopharmaceutical purposes.
Funding and acknowledgement: ANRT, AAA
(1) Évolution de la curiethérapie en France et perspectives Cancer/Radiothérapie. Peiffert, D. et Hannoun-Lévi,
J.-M. Volume 17, Issue 2, pp. 76-80.
(2) Giddings J. C., et al., The conceptual basis of field-flow fractionation. J. Chem., 1973. 50: p.667-669.
Ultrafast 2D NMR on a 43 MHz compact spectrometer
Boris GOUILLEUX [email protected] CEISAM, Nantes Category : High field (HF) NMR is a powerful and widely used spectroscopy in a broad range of applications. The great performance reached HF NMR relies on strong magnetic fields, involving an expensive equipment with the need for dedicated laboratories. These economic and practical drawbacks have hampered the use of HF NMR in industrial sites and synthetic laboratories. A new generation of benchtop NMR spectrometers, more compact and cryogen-free, emerges as a relevant alternative to extend the scope of NMR in harsh environments.1 Obviously, the use of these permanent magnets involves a reduced frequency dispersion leading to crowded spectra with numerous overlaps. 2D NMR experiments offer an appealing solution, unfortunately their inherent long acquisition duration is incompatible with the time scale of applications such as reaction monitoring. In order to circumvent this time constraint, we developed Ultrafast (UF) NMR2 on a benchtop spectrometer, yielding homonuclear 2D spectra within a single scan.3 These developments were performed on a 43 MHz Spinsolve (Magritek) including a gradient coil originally designed for diffusion experiments. 43 MHz cryogen-free
by Ultrafast COSY spectra
Figure 1. On-line reaction monitoring of a Pd-coupling reaction by ultrafast 2D NMR on a benchtop spectrometer We illustrate the potential of UF NMR at 43 MHz through the real-time monitoring of a Heck-Matsuda coupling reaction in an on-line fashion.4 In the course of the reaction performed in a conventional flask, the mixture is directly analyzed through a by-pass system connected to the compact spectrometer, which records a series of UF COSY spectra with well-resolved cross-peaks (Figure 1). Another potential of this approach relates to a long-standing concern: the screening of edible oils. Relevant results were recently reported using benchtop NMR for the adulteration with cheap substitutes into olive oil. Albeit promising, the accuracy of the 1D approach remains limited by the overlapped resonances from glycerides protons and those arising from the unsaturated chains. The UF COSY experiments overcome this issue by delivering well-resolved cross peaks, whose integration provides an efficient authentication tool in a reasonable time of 2.5 min.4 These first results shed light on the potential of UF NMR at 43 MHz as a promising rapid screening tool. Funding and acknowledgement : (Région Pays de la Loire ; Magritek: E. Danieli, J. Perlo and A. Coy) 1. E. Danieli, J. Perlo, B. Blümich and F. Casanova, Angew. Chem. Int. Edit., 2010, 49, 4133-4135. 2. L. Frydman, T. Scherf and A. Lupulescu, Prod. Natl. Acad. Sci. USA, 2002, 99, 15858-15862. 3. B. Gouilleux, B. Charrier, E. Danieli, J.-N. Dumez, S. Akoka, F.-X. Felpin, M. Rodriguez-Zubiri and P. Giraudeau, Analyst, 2015, 140, 7854-7858. 4. B. Gouilleux, B. Charrier, S. Akoka, F.-X. Felpin, M. Rodriguez-Zubiri and P. Giraudeau, 2016, Trends Anal. Chem., in press, doi: 10.1016/j.trac.2016.01.014 Generation of ultrashort shear acoustic pulses by femtosecond laser driven
demagnetostriction of thin Terfenol films
Tymur – PARPIIEV [email protected] IMMM, Le Mans Category : Mol cules ■ Mat riaux Abstract. Since the pioneering demonstration of the subpicosecond demagnetization by a 60
fs laser pulse by Beaurepaire and co-workers , manipulating and controlling magnetization with ultrafast laser pulses has become a big challenge. These findings triggered booming field of ultrafast laser manipulation of magnetization . Although there is a clear evidence that ferromagnetic thin film can be demagnetized within timescale of the order of 100 fs by fs laser pulses, the underlying physical mechanisms are still controversial . Recent results demonstrating all-optical switching in a broad variety of rare earth-transition metal compounds with pronounced magnetostriction [4,5] challenge present theories of ultrafast optical switching and rise fundamental questions about the role of the spin-lattice coupling in such type of magnetostrictive compounds. In particular the role of phonons during the demagnetization/remagnetization process is attaching increasingly more attention [6,7,8]. In the present work, by probing the excited ultrafast longitudinal and shear acoustic pulses - rather than the magnetization dynamics, as it is already the case - during ultrafast demagnetization of Terfenol, we demonstrate the possibility to assess crucial information on the spin-lattice relaxation channel.We have conducted experiments with Terfenol (TbFe2) which is known as one of the best magnetostrictive materials . The (110) single crystals TbFe2 thin films have been grown on sapphire substrates by molecular beam epitaxy and coated with a transparent dielectric layer of SiO2. The samples were laser excited with a 800 nm 150 fs pump pulse focused on the TbFe2 layer where, upon both thermoelastic transient heating and ultrafast release of magnetostrictive stress, the acoustic waves were launched in the adjacent SiO2 layer. These acoustic waves were detected by a time delayed probe pulse while propagating back and forth in the top SiO2 layer. Our results give the proof of concept of ultrafast laser demagnetostriction for the excitation of ultrashort shear acoustic pulses. For the moment, efficient and simple ultrafast shear transducers are lacking and a new generation of THz shear transducers based on laser-mediated release of magnetostrictive stresses would be of great interest for the viscoelastic investigation of many materials (liquids, glasses, mixed multiferroics, correlated electron systems and magnetic materials). Acknowledgements. The authors thank Agence Nationale de la Recherche ANR-14-CE26-
0008 and Strat gie international NNN-Telecom for financial support. References
 E. Beaurepaire et al., Phys. Rev. Lett. 76, 4250 (1996).
 Aeschlimann et al., Phys. Rev. Lett. 79, 5158 (1997).  B. Koopmans et al., Nature Physics 9, 259 (2009).
 A. Hassdenteufel et al., Adv. Mat. 25, 3122 (2013).
 S. Mangin et al, Nature Materials 13, 286 (2014).
 L. Thevenard et al., Phys. Rev. B 82, 104422 (2010).
 J.-W. Kim, M. Vomir, J.-Y. Bigot, Phys. Rev. Lett. 109, 166601 (2012).
 O. Kovalenko, T. Pezeril, V.V. Temnov, Phys. Rev. Lett. 110, 266602 (2013).
New cryogenic processes implemented for 3 imaging with liquid Xenon
SUBATECH Laboratory, Nantes Category: Matter The XEMIS project (XEnon Medical Imaging System) initiated by SUBATECH proposes a new nuclear imaging modality based on the detection in coincidence of 3 rays. The main profit of this medical imaging technique called 3 imaging is the significant reduction of the injected dose. A first prototype XEMIS1 has successfully shown the concept feasibility. A second device XEMIS2 dedicated to carry out small animal imaging will be ready to use this year after several tests. The Xenon amount increase between XEMIS1 and XEMIS2 has required a reconsideration of the cryogenic processes. XEMIS2 is based on a Time Projection Chamber (TPC) filled with pure liquid Xenon only during the medical exam. Used in a closed loop, the fluid is purified and liquefied permanently. The limited thickness of XEMIS2 cryostat makes the TPC a low pressure vessel (< 2 bar abs) incompatible with a long term cryogenic storage. For all these reasons, a purification device, condenser, reversible transferring system, safe tank storage (able to insulate the TPC) are necessary. A deported high-pressure proof subsystem called ReStoX (Recovery and Storage of Xenon) gathers the three last elements. Its modular cooling power allows it to bring and maintain the Xenon into the right pressure and temperature (adjustable boil-off condensation). That feature explains why ReStoX constitutes by itself the Xenon liquefaction site, the distribution and recovering device. It combines the essential cryogenic processes implemented and progressively tested for this new 3 medical imaging. Scheme and photo of the 3 plant subsystems (ReStoX in 1, XEMIS2 in 2 and purification loop in 3) Funding & acknowledgements: Écoles des Mines Nantes, Université Nantes, CNRS IN2P3, Air Liquide Advanced Business and Technologies, Région Pays de la Loire, Nantes Métropole, Union Européenne Towards the synthesis of enantiopure cyclopropanes: asymmetric synthesis using titanium
Julien – CAILLE [email protected] IMMM, Le Mans Category: Cyclopropanes are three-membered cycles present in numerous natural molecules that show biological activities.1 Despite several methods of synthesis starting from alkenes, their preparation from readily available carbonyl derivatives is only described using a titanium complex. Cyclopropanation reactions using titanium complexes have been discovered in 1989 by the bielorussian chemist Oleg G. Kulinkovich.2 Initially applied to the synthesis of cyclopropanols from esters, the preparation of tertiary and primary cyclopropylamines was developped in the last decades.3 However, no efficient asymmetric version has been developed yet. In this talk we will present our results in the asymmetric synthesis of cyclopropanes starting from cyanoesters. Different parameters were studied in order to optimize the reaction conditions, such as the nature of solvent, the amount of titanium and the nature of the alkoxy moiety. We then synthesized and screened several chiral ligands derived from TADDOL or from aminodiols. Their effects on the enantioselectivity of the catalysis were evaluated. Cyclopropanation reaction mediated by titanium complex and chiral ligands
Funding and acknowledgement: Ministère de l'Enseignement Supérieur et de la Recherche
1 a) Salaün, J. Top. Curr. Chem. 2000, 207, 1. (b) Faust, R. Angew. Chem. Int. Ed. 2001, 40, 2251. (c) Gnad, F.;
Reiser, O. Chem. Rev. 2003, 103, 1603
2 Kulinkovich, O.G.; Sviridov, S.V.; Vasilevskii, D.A.; Pritytskaya, T.S. Russ. J. Org. Chem. 1989, 25, 2027
3 (a) Chaplinski, V. ; De Meijere, A. Angew. Chem. Int. Ed. 1996, 35, 413. (b) Bertus, P.; Szymoniak, J. Chem.
Commun. 2001, 1792
Nuclear fuel cycle simulaon tool development and applicaons
Fanny COURTIN fanny.cour [email protected] Laboratoire Subatech, Nantes Category : Nuclear fuel cycle simulaon studies aim to provide an overview of the impacts of possible strategies (plants deployment, fuel recycling.) on an electronuclear )eet. They might be useful de -vices to advise polical decisions. To invesgate innovave scenarios and alternave technologies, adynamic fuel cycle simulaon tool, CLASS (Core Library for Advanced Scenario Simulaon), is underdevelopment at Subatech Laboratory since 2011, in the framework of a collaboraon between theCNRS/IN2P3 and the IRSN. This tool models the enre fuel cycle, from fuel fabricaon to spent fuel storage, and calcu- late nuclei inventories and material )ows evoluon in each unit. Thus, all the units of the fuel cycleshall be included (fuel fabricaon and separaon plants, reactors, cooling pools, storage.) and all theprocesses occurring during fuel evoluon (nuclear reacons, radioacve decays) have to be preciselydescribed. The code implementaon relies on physical models which build the fresh fuel and calcu -late its isotopic evoluon under irradiaon. These models are based on neural networks built usingdatabanks inventorying fuel characteriscs (isotopic composion, mulplicaon factor, averagedcross secons) evoluon from previous reactors simulaons performed with the depleon codeMURE (MCNP Ulity for Reactor Evoluon) based on the transport code MCNP (Monte-Carlo NParcle).
In this study, the code CLASS is used to invesgate plutonium mul-recycling and incineraon in Pressurized Water Reactors (PWR). In the current French )eet, the plutonium produced during UOXfuel irradiaon in PWR is mono-recycled in MOX fuel. Spent MOX fuel is then stored, waing for apossible Sodium Fast Reactors (SFR) deployment. In the meanme, several fuels dedicated to pluto -nium mul-recycling in PWR are invesgated to stabilize plutonium inventory, since it is the main con -tributor of spent fuel radiotoxicity. The implementaon in CLASS of a MOX enriched uranium sup -port fuel (MOX-EUS), allowing plutonium mul-recycling in PWR, will be presented. References B. Mouginot , B. Leniau et al. "CLASS Core Library for Advance Scenario Simula on." URL h)ps://forge.in2p3.fr/projects/classforge.
 O. Méplan, A. Nu0n, O. Laulan, S. David et al., 2005. MURE: MCNP u lity for reactor evolu on. In: ENC 2005- European Nuclear Conference, France.
 D. Pelowitz, 2013. MCNP6 User's Manual, Ver. 1, Tech. Rep., LA-CP-13-00634. Los Alamos Na onal Labora-tory.
 M. Ernoult, 2014. Ges on avancée du plutonium en REP – Complémentarité des cycles thorium et uranium (Ph.D. thesis). Université Paris-Sud.
 G. Youiniou, A. Vasile, 2005. Plutonium Mul recycling in Standard PWRs Loaded with Evolu onary Fuels, Nu-clear Science and Engineering vol(151), 25–45 Etude des interactions défauts géométriques/microstructure dans les mécanismes
e de y les d'alliages étalli ues Benoît BRACQUART [email protected] Laboratoire Angevin de Mécanique Procédés et innovAtion (LAMPA, Arts et Métiers Paristech), Angers Moltech Anjou, Angers Category : Molécules Matériaux It is well known that the high cycle fatigue resistance of metallic alloys is largely reduced when geometrical notches are introduced. As shown by Lukas et al , the notch influence is predominant when its size is important. Also, there is a critical dimension below which the fatigue behavior is no longer affected by the presence of a geometrical defect. Although the knowledge of critical dimensions is very important in order to design fatigue-resistant structures, the influence of microstructure upon critical dimensions has yet to be fully understood. Recent work  enabled to study, experimentally and numerically, the influence of microstructure in the not h neigh orhood, ut only y varying the latter's size. The obtained results enabled to study the influence of the local microstructure, but failed to explain the existence of a critical notch size below which the fatigue limit is no longer affected. In this study, we seek to extend this work by exploring the evolution of the fatigue behavior as a function of the ratio between the characteristic defect dimensions and the grain size. In order to meet this objective, a mixed experimental and numerical approach is proposed. On the experimental front, different thermomechanical treatments are applied to aluminium 1050 (commercial purity) polycristals to obtain two microstructures with respective mean grain sizes of 100 and 1000 µm. Strain controlled cyclic tests are then carried out for both microstructures. According to the results, the aluminium alloy display high ductility, maximum stresses strongly depend on the strain amplitude, and strain-rate sensitivity is negligible. For the same imposed amplitude, the coarse grain microstructure displays lower stress amplitudes. For both microstructures, specimens with an artificial hemispherical notch of diameter 1 mm are then submitted to stress-controlled cyclic loadings. It is noted that the fatigue dispersion decreases when the applied level of stress increases, for both the number of cycles to failure and the one necessary for surface crack initiation. Also, the increase of grain size reduces the fatigue strength. In-situ observations show that the specimen lifetime is, in the studied range, highly dependent of the crack propagation stage, rather that the initiation one. Those test results will be complemented by Electron BackScattered Diffraction (EBSD) observations in the surrounding of notches, in order to better understand interactions between the local microstructure and the notch with respect to their relative sizes. These experimental results will help in generating numerical models of realistic microstructures containing notches of several dimensions. A proper description of the anisotropic elastoplastic crystalline behavior as well as the introduction of internal length scales within constitutive relations should enable the estimation of local mechanical field, which cannot be determined via experimental tests. Funding and acknowledgement: Carnot (ARTS), Région Pays de la Loire. References :  P. Lukas et al. Notch size effect in fatigue. Fatigue Fract. Engng Mater. Struct., 12(3), pp 175-186, 1989.  R. Gue hais. I flue e d'a idents géométriques et du mode de chargement sur le comportement en fatigue à g a d o les d'u a ie i o da le austé iti ue 316L. Ph.D. Thesis, LAMPA, 2014. Calcium carbonate and its applications
Oxana Cherkas [email protected] IMMM, Université du Maine, Le Mans Category: Materials Calcium carbonate is one of the most useful and versatile material in the world with a the global market estimated by Global Analysts, Inc. to about 100 Million of Tons in 2015. Formation of calcium carbonate is one of the most widely investigated precipitation systems. The complexity introduced by its polymorphism also makes it interesting as a purely academic challenge and as possibility for different applications. Calcium carbonate is used as fillers and coated pigments in paper, paints and coatings, adhesives, medical, sealants and plastics industries. In the pharmaceutical industry, CaCO3 can be utilized as a drug carrier to encapsulate active principles for instance, as an effective dietary calcium supplement or as base material for medicinal tablets. So for this application the precipitation of hollow capsule have the primary importance. After the precipitation the problem is to probe the presence of a hollow core in the particle. So far such particles have been mainly observed by scanning electron microscopy (SEM) or transmission electron microscopy (TEM) with the major drawback of providing only a projected 2D view. In our study to obtain internal structures of particles we used the coherent X-Ray diffraction imaging at synchrotron ESRF in Grenoble. This study permitted us to not only obtain the 2D image, but also have access into the particles. For the paper application, the calcium carbonate added in the slurry of cellulose to make form the paper. Because of low retention, the calcium carbonate remains in large quantities in the waste water going through the wire. It is therefore interesting to develop some methods to analyze in a non destructive way the content of calcium carbonate that remains in the paper. One of the important characteristic for certain paper makers is the porosity or alternatively the permeability of the paper. To determine the total porosity of a paper, the total volume of the sample, the volume of the pores space or alternatively the complementary volume to the solid phase are required. All these parameters are rather difficult to determine with a good precision. It is therefore interesting to find some other alternatives to obtain these valuable quantities for the paper makers. We propose a procedure based on X-ray analysis to determine both parameters the content of calcium carbonate in a non destructive way and the porosity of the paper. Funding and acknowledgement: ANRT, ESRF ID10A beamline References: 1. K. Robinson and al. Physical review, 60 (1999) 9965-9972 2. H. Sixta WILEY-VCH Verlag GmbH, Vol.1 (2006) 1-1352. 3. French Cellulose, 21 (2014) 885-896.
OMO Multilayer Structures as TCO for Solar Cells and Optoelectronics Applications
Mohammed Rasheed1, Mihaela Girtan2 [email protected] 1,2 Laboratoire de Photonique d'Angers (LPHIA), Université Angers Category : Molécules ☒ Matériaux Abstract Transparent Conductive Oxide (TCO) films are widely used in many thin films devices. Since now single thin films of In2O3:Sn, ZnO:Al or SnO2:F deposited on glass substrate were typically used as transparent conductive electrodes. At present, the most promising material as transparent electrode seems to be the Flurine Tin Oxide and Indium Tin Oxide (FTO & ITO). However the limited resources of Flurine and Indium on earth and the expensive cost of these elements pushed many researchers around the world to conduct research works to look for other materials with equivalent qualities in terms of electrical and optical properties. The thickness of FTO and ITO thin films used as transparent electrodes for optoelectronic devices ranges in general, between 150nm and 700nm. Due to the classical size effect, the reduction of the thickness under 150nm increases the electrical resistivity. On the other hand, the system of oxide/metal/oxide (OMO) is a promising alternative as TCO. The realisation of transparent electrodes using OMO multilayer structures has many advantages. First, Compared with FTO and ITO, one of the advantage is the reduction of the indium and Flurine quantities by the reduction of thin films thickness from 150nm to a total of 50-60nm for both oxide layers. Second, the mechanical properties are considerably improved due to the ductile metallic interlayer. In the same time, the optical and electrical qualities of electrodes are perfectly conserved and even improved if we talk about the electrical conductivity. The suggested systems of OMO multilayer structures are: TiO2-Au-TiO2, ITO-Au-ITO, AZO-Au-AZO, Bi2O3-Au-Bi2O3, TiO2:Nb-Au-TiO2:Nb and NiO-Au-NiO deposited on glass and plastic substrates as shown in Figure 1. Figure (1-a,b): The structure of (Oxide/metal/Oxide) Transparent electrodes on glass and plastic substrate. High energy combined PIXE/PIGE analysis on geological samples
Subercaze Alexandre, Haddad Ferid, Métivier Vincent, Koumeir Charbel SUBATECH, UMR 6457, Nantes Category : Molécules Matériaux PIXE (Particle Induced X-ray Emission) and PIGE (Particle Induced Gamma-ray Emission) are two complementary multi-elemental and non-destructive analysis techniques widely used with protons around few MeV of incident energy. In the past, several attempts have been made to apply PIXE with high energy protons (HEPIXE) . Indeed, high energy PIXE analysis allows to increase the analysis depth so that thick samples (mm range) can be studied. It allows exciting the K-shell elec-trons leading to the emission of high energy X-rays. Additionally, the production cross sections for X-rays and gamma vary barely, making easier the experimental analysis. To our knowledge, high energy PIGE combined with HEPIXE  has not been reported and we are developing, at the ARRONAX facility , the possibility to use these two techniques with different particles as projectile to be able to study geological samples. The main difficulty when coupling the two techniques at high energy is the increase of the gamma background. We overcome this disad-vantage by shielding our gamma detector (HPGe) and by irradiating at low intensities (50-100 pA). Experiments were performed using 68 MeV protons and 17 MeV deuterons on sand samples (5 mm thick) as their mass fractions and density can be easily modified by adding water. Two differ-ent kinds of sand have been used: Fontainebleau and volcanic sand. Results show that usi g proto bea s, PIGE allows to get i for atio o the de sity, ρSi, (number of atoms per volume) whereas using deuterons beams, PIGE is sensitive to the Si mass fractions, aSi. With the help of a standard, in our case the Fontainebleau sand, it is possible to get infor-mation on the matrix elements (density and mass fractions of silicium and oxygen)  and there-fore we can access to the irradiated area density (g/cm3) for every sample. With the help of PIXE technique, it is then possible to get the volcanic sand composition. In conclusion, by properly setting experimental conditions and by using different probes at differ-ent energies, it is possible to get all the required information to determine the full composition and the density of a sample using combined PIGE and PIXE techniques at high energies. Funding and acknowedgement : Pays de La loire, Equipex ARRONAX Plus no ANR-11-EQPX-0004 « Investissements d'Avenir », CPER 2007-2013 (operation « matériaux ») including FEDER fundings  A. Denker, K. H. Maier, Nuclear Inst. and Meth. in Phys. Res. B, 161-163. 2000,  D. Ragheb and al. J. of Radio. and Nucl. Chem, 301, 2014.  F. Haddad and al, Eur. J. Nucl. Med. Mol. Imag, 35, 2008.  A. Climent-Font and al, Nuclear Inst. and Meth. in Phys. Res. B, 266, 2008. Nanoporous carbon for sensing applications
Laetitia– DONERO Laetitia.Donero@cnrs‐imn.fr Institut des Matériaux Jean Rouxel de Nantes (IMN) et Institut d'électronique et de télécommunication de Rennes (IETR) Over the last few years, a broad panel of carbon materials was proposed for sensing applications. Among these materials, nanoporous carbon (np-C) is of particular interest due to its high specific surface area and low fabrication cost. In this contribution we report on the synthesis of np-C thin films using an original approach combining the growth of copper/carbon nanocomposite thin films by co-sputtering followed by a selective wet etching of copper in nitric acid Fig.1-a. We show that the metal nanoparticles of such heterogeneous material must be percolated to obtain an open nanoporosity. We further show how the pore size and the structure of the carbon skeleton can be controlled by adjusting the deposition conditions (e.g., powers applied to the targets, deposition temperature) of the nanocomposite thin films . Furthermore, the possibility of integrating such nanoporous materials in field effect transistors for sensing application will also be discussed. Theoretical Test and Application of the method based on Variance Decomposition
for Uncertainty and Sensitivity Analysis
Yueying–ZHU, Qiuping –WANG, Wei –LI, Xu –CAI [email protected] IMMM, Le Mans Category : Molécules Matériaux Abstract: In the complexity modeling, the method based on variance decomposition is widely used to study the uncertainty of output variables and the importance of input parameters. In this work, an exact formula for calculating the variance of output variable which only depends on the first order terms of each input variable or/and their products is given as a function of output's derivatives and inputs' variances. Based on this formula, the method of complete variance decomposition based on Latin hypercube sample (LHS) is verified via linear and nonlinear analytical functions connecting output and input parameters. It is found that the results of the variance decomposition based on LHS are consistent with those of theoretical test. Finally, a nonlinear model for opinion evolution is analyzed by the method of variance decomposition for understanding the impacts of different parameters and of their interactions on the formation of opinion dynamics. Funding and acknowledgement : (NSFC, China ; CSC, China) References . I.M. Sobol', Sensitivity analysis for non-linear mathematical models, Matematicheskoe Modelirovanie, 2 (1) (1990) 112–118 (in Russian), English translation in: Math. Model. Comput. Exper. 1 (4) (1993) 407–414. . A. Saltel i, S. Tarantola, K.P.S. Chan, A quantitative model-independent method for global sensitivity analysis of model output, Technometrics 41 (1) (1999) 39-56. . J.C. Helton, F.J. Davis, Sampling-based methods for uncertainty and sensitivity analysis, Albuquerque: Sandia National Laboratories (2000). . I.M. Sobol', Global sensitivity indices for nonlinear mathematical models and their Monte Carlo estimates, Math. Comput. Simul. 55 (1) (2001) 271-280. . J.C. Helton, J.D. Johnson, C.J. Sal aberry, C.B. Storlie, Survey of sampling-based methods for uncertainty and sensitivity analysis, Reliab. Eng. Syst. Safe. 91 (10) (2006) 1175-1209. . J.C. Helton, Uncertainty and sensitivity analysis for models of complex systems, Computational Methods in Transport: Verification and Validation. Springer Berlin Heidelberg (2008) 207-228. . A. Saltel i, M. Ratto, T. Andres, F. Campolongo, J. Cariboni, D. Gatel i, M. Saisana, S. Tarantola, Global sensitivity analysis, The Primer, John Wiley & Sons (2008). . A. Saltel i, P. Annoni, I. Azzini, F. Campolongo, M. Ratto, S. Tarantola, Variance based sensitivity analysis of model output. Design and estimator for the total sensitivity index, Comput. Phys. Commun. 181 (2) (2010) 259-270. . M. Fonoberova, V.A. Fonoberov, I. Mezi´c, Global sensitivity/uncertainty analysis for agent-based models, Reliab. Eng. Syst. Safe., 118 (2013) 8-17. . Y. Zhu, W. Li, X. Cai, Opinion evolution on a BA scaling network, Physica A 392 (24) (2013) 6596-6602. Stud of Si gle Electro Sig als i XENON Kevin Micheneau [email protected] Subatech, Nantes Category : Matière Despite the a azi g p og ess i ph si s, so e i te a ts ith the li uid e o , it e ites a d io izes its ato s. The photo s of de-e itatio a e dete ted photo ultiplie s tu es, eati g the sig al alled S . The the ele t o s f o io izatio e of photoele t o dete ted pe ele t o a d ho this gai is used to o ito the dete to sta ilit . The i pli atio of Si gle Ele t o o da k atte sea hes is also dis ussed. The mass of the dark matter is unknown and the XENON program mainly focuses in the 10 GeV to 10 TeV range. For a lighter mass, the S1 signal is too small to be detected efficiently and a new detection on only S2 is needed. In this case, the analysis is sensitive to our knowledge on Single Electrons. A dedicated study on isolated Single Electron signal (i.e. not following a main signal) is in development and presented. Single electron distribution (in black) fitted by the emission model. The contribution of the different number of electron in the total signal is identified. The detection efficiency (in blue) takes into account the trigger condition for very low signals. CNRS, Région Pays de la Loire On chip 3D metal-air microbatteries: a new approach to design zinc-air anode
Jérémy FREIXAS [email protected] Institut des Matériaux de Nantes Jean Rouxel (IMN JR), Nantes, France I stitut d'Elect o i ue, de Mic oélect o i ue et de Na otech ologie IEMN , Ville euve d'Acs , France I stitut de Reche che su les Co posa ts logiciels et até iels pou l'I fo Ava cée IRCICA , Ville euve d'Asc Category : Molécules x Matériaux Global trends concerning technological developments require new standards for energy storage devices . To fulfill with the energy requirements of smart miniaturized sensors, they need to be more compact and to have a high storage capacity. Moreover, the fabrication process has to be greener regarding environmental issues. In this work, material science and microelectronics fabrication processes are combined to conceive 3D metal-air microbatteries on silicon wafer (fig. 1a.) that could meet the expectations
previously listed. On the one hand, microelectronics processes allow to fabricate 3D silicon high
aspect ratio microstructures that could be plated with metallic thin films (Zn, Al, etc) to produce 3D
metal anode. Such microfabrication technologies will be used, on the other hand, to achieve the
fabrication of the air electrode composed of porous and conducting material plated with ORR
catalysts (e.g. MnO2). Contrary to many studies in literature (e.g. Zn-air micropile by B. Dunn et al.
), it is not the metallic deposit that is processed but the substrate used to create the anode.
Our main achievement consists in designing a 3D zinc-air thin film electrode. Electroplated zinc is used as a metal layer on high aspect ratio 3D silicon scaffold (fig. 1b.). The deep etching
process to get silicon microstructures is optimized to reach a high area enlargement factor to
significantly improve the electrode capacity . A first prototype was assembled comprising the 3D
metal electrode, a commercial available air cathode separated by a KOH aqueous electrolyte (6M)
(fig. 2.). Future developments will aimed at designing a rechargeable 3D metal-air microbattery.
Fig. 1a. Schematic view of the 3D
Fig. 1b. Zn electroplating on
Fig. 2. Discharge characteristics of
microbattery (a) air cathode, (b) electrolyte, microtubes (depth : 45µm) (a) 2D and (b) 3D Zn-air microbattery (c) anode, (d) current collector on silicon microstructure Acknowledgment: This research is financially supported by the RS2E and the DGA  Ellwanger, R. C. et al. (2013). Three Global Megatrends and the Implications for the Semiconductor Ecosystem, TowerJazz  Chamran, F. et al. (2007), Zinc-Air Microbattery with Electrode Array of Zinc Microposts, MEMS 2007, Kobe, Japan, 21-25 January 2007  Eustache, E. et al. (2014). Silicon-Microtube Scaffold Decorated with Anatase TiO2 as a Negative Electrode for a 3D Litium-Ion Microbattery, Adv. Energy Mater. 4 (8), #1301612 Detection of molecular changes induced by antibiotics in Escherichia coli
using Raman and infrared spectroscopy
Ngoc Thanh Xuan NGUYENa,b, Samira SARTERc, Ngoc Hai NGUYENa, and Philippe DANIELb a Faculty of Animal Science and Veterinary Medicine, Nong Lam University, Viet Nam b Institut des Molécules et des Matériaux du Mans – IMMM – UMR CNRS 6283 Le Mans, Université du Maine, France c UMR Cirad Qualisud, F-34398 Montpel ier, France Category: Matière ☒ Molécules Matériaux
Vibrational spectroscopy is a noninvasive and nondestructive technique for both the identification of
bacteria and studies involving cell injury and inactivation. Raman and infrared (IR) spectroscopy provide
complementary information about the biochemical properties of bacterial cells. In this work, Escherichia
coli TOP10 strain was exposed to antibiotics to which it is sensitive in order to detect molecular changes
depending on the mechanism of action of the antibiotics, using Raman and IR spectroscopy with the
help of chemometric analysis. Micro-Raman spectra were measured in the range 400-1800 cm-1 with an
excitation wavelength of 638 nm using XploRA ONETM spectrometer (Jobin Yvon, Horiba). IR absorption
spectra were recorded in the range 4000-400 cm-1 using Bruker Vertex 70v spectrometer with 4 cm-1
resolution. Three groups of antibiotics: ampicil in, cefotaxime (cell wal synthesis inhibitors), tetracycline
(protein synthesis inhibitor), and ciprofloxacin (DNA synthesis inhibitor) were chosen to perform the
study. The minimal inhibitory concentration (MIC) and the minimal bactericidal concentration (MBC)
were determined by drug macrodilution method. The MIC values of ampicil in, cefotaxim, tetracycline,
and ciprofloxacin against E.coli TOP10 were 5 µg/ml, 0.2 µg/ml, 6 µg/ml, 0.1 µg/ml respectively.
Firstly, bacterial growth was evaluated by Raman and IR spectroscopy at different growth times of
incubation (3, 6, 8, and 24 hours). Metabolic modifications within the bacteria as a function of time were
reflected in intensity changes of some spectral bands assigned to proteins (1230 cm-1, and 1660 cm-1),
carbohydrates (1088 cm-1), nucleic acids (1560 cm-1), and amino acids (785 cm-1). Then in order to study
the influence of various antimicrobial agents on bacteria, E.coli TOP10 was grown in Mueller Hinton
Broth and it was characterized in the presence and absence of the antibiotic by means of Raman and IR
spectroscopy. The antibiotic concentrations were 40 µg/ml, 1.6 µg/ml, 40 µg/ml, and 0.8 µg/ml for
ampicil in, cefotaxime, tetracycline, and ciprofloxacin respectively. These antibiotic concentrations
inactivated the viable cells by 50-60%. This was calculated by standard plate count (in comparison with
the control sample). Significant changes were observed in the spectra of treated cells compared to their
respective controls (samples without treatment). For Raman spectra, most important changes occurred
around 532 cm-1 (glycosidic ring), 785 cm-1 (cytosine, uracil in DNA and RNA), 1088 cm-1 (DNA and RNA
backbone, glycosidic ring), 1279 cm-1 (protein), and 1575 cm-1 (nucleic acids). For IR spectra, the largest
spectral changes were observed in the wavenumber region at 1639 cm-1, 1537 cm-1, 1230 cm-1 (protein
contribution), and 1080 cm-1. Principal component analysis and cluster analysis (using Unscrambler
software 10.2) were applied to differentiate control and antibiotic-treated bacterial cells. These findings
suggest that Raman and IR spectroscopy in combination with chemometric analysis hold the potential
for a fast and reliable evaluation of antibiotic mechanisms against bacteria.
Key words: Raman spectroscopy; infrared spectroscoopy; bacteria; antibiotic
 Ute Neugebauer. PhD thesis Friedrich-Schil er - Universität Jena, 2007.
 K. Maquelina, C. Kirschner, L.-P. Choo-Smith, N. van den Braak, H. Ph. Endtz, D. Naumann, G.J. Puppels.
J.Microbiol.Methods, 51 (2002) 255-271
Spectroelectrochemistry of Perylenediimide-based Self-Assembled Monolayers.
BKHACH – Sihame [email protected] Laboratoire MOLTECH-Anjou, UMR CNRS 6200, 2 boulevard Lavoisier, 49045 Angers, FRANCE Molécules X Matériaux Since their initial discovery in 1946, self-assembled monolayers (SAMs) have become an ideal system for the theoretical study of interfacial phenomena, especially in the field of electrochemistry when they are immobilized on conductive substrates like gold.1 This work presents the design, synthesis and elaboration of robust SAMs of perylenediimide (PDI), a class of compounds well-known for their great fluorescence quantum yields and redox activity,2 in order to investigate their structural organization and provide insightful information for fundamental understanding. PDI based SAMs have been studied by quartz crystal microbalance, X-ray photoelectron spectroscopy and cyclic voltammetry. Besides these conventional methods, PDI based SAMs have been investigated using an efficient time-resolved spectroelectrochemical bench developed by our group,3 capable of monitoring the evolution of the spectroscopic signature under the control of the potential. This technique has an essential part in advances towards the investigation and identification of electroactive species at nanometric scale. This work reports pioneering absorption and luminescence spectroelectrochemical studies on PDI based SAMs and shows that the electrochemical behaviour of PDI in solution is preserved on Au substrate.4 (1) Love, J. C.; Estroff, L. A.; Kriebel, J. K.; Nuzzo, R. G.; Whitesides, G. M.; Chem.Rev. 2005, 105, 1103–
(2) Würthner, F.; Chem. Commun. 2004, 1564 – 1579.
(3) Alévêque, O. ; Levillain, E. ; Sanguinet, L. ; Electrochem. Commun. 2015, 51,108 –112.
(4) Bkhach, S. ; Le Duc, Y. ; Alévêque, O. ; Gautier, C. ; Hudhomme,P. ; Levillain, E. ; ChemElectroChem
Glycated Hemoglobin, Diabetes, and Cardiovascular Risk in Nondiabetic Adults Elizabeth Selvin, Ph.D., M.P.H., Michael W. Steffes, M.D., Ph.D., Hong Zhu, B.S., Kunihiro Matsushita, M.D., Ph.D., Lynne Wagenknecht, Dr.P.H., James Pankow, Ph.D., M.P.H., Josef Coresh, M.D., Ph.D., and Frederick L. Brancati, M.D., M.H.S. From the Department of Epidemiology Fasting glucose is the standard measure used to diagnose diabetes in the United States.
SPECIAL SUPPLEMENTARY ISSUE—FEB 2008 By Philip C. Fox, DDS, FDS, RCSEd sponsored by To obtain one ceu credit, take our online CE test. Xerostomia: Recognition and Management By Philip C. Fox, DDS, FDS, RCSEd Epidemiology and Etiology of Xerostomia Xerostomia (dry mouth) is the subjective feeling of oral dry-