0000000000527378
AUTHOR
Eric Finot
Diene/polar monomer copolymers, compatibilisers for polar/non-polar polymer blends. A controlled block copolymerisation with a single-site component samarocene initiator
A well-controlled two-step process, the polymerisation of isoprene or isoprene/hex-1-ene copolymerisation followed by e-caprolactone polymerisation, affords trans-polyisoprene or (trans-polyisoprene/hex-1-ene copolymer)–poly(e-caprolactone) diblocks of various lengths. The single component initiator is an allylsamarocene compound. An atomic force microscopy study shows that these copolymers are efficient compatibilisers for poly(e-caprolactone) and polyisoprene blends. Poly(e-caprolactone) chain growth from Sm–polyisoprene chain.
Investigations of Surface Forces between Gypsum Microcrystals in Air Using Atomic Force Microscopy
This article introduces a new approach to the study of the interactions between gypsum faces in air. We have mounted a gypsum crystal on the end of a microcantilever to measure local forces (van der Waals, capillary forces, electrostatic) directly between two crystals. A systematic study with respect to the orientation of crystalline faces, relative humidity, and the duration of contact between crystals improves the understanding of the mechanism involved in the hardening of plaster in air. In dry air, a physicochemical process of matter transfer is added to the van der Waals forces to ensure the cohesion. Others force measurements were performed by varying the shape of the contact (interac…
Atomic Force Microscopy: Interaction Forces Measured in Phospholipid Monolayers, Bilayers, and Cell Membranes
Atomic force microscopy (AFM) is a powerful technique which is commonly used to image surfaces at the nanoscale and single-molecule level, as well as to investigate physical properties of the sample surface using a technique known as force spectroscopy. In this chapter, we review our recent research where we used AFM to investigate physical properties of phospholipid monolayers, bilayers, and cell membranes. We describe the experimental procedures for AFM imaging, force measurements, and theoretical models to analyze force spectroscopy data. The data obtained allowed correlations between AFM topography and local adhesion and mechanoelastic properties of supported lipid bilayers in water, su…
Sorting of Enhanced Reference Raman Spectra of a Single Amino Acid Molecule
In this contribution, we report the identification of the principal reference Raman spectra of a single cystein molecule. To that purpose, we design an active Surface Enhanced Raman Spectroscopy (SERS) template based on surfactant-less Chebyshev nanoparticles operating in a microfluidic platform. A principal component analysis is obtained from fluctuating spectra to sort the reference spectra of cystein. The assignment of Raman bands brings new insight into the conformation of an amino acid adsorbed onto gold nanoparticle.
Surface plasmon near-field imaging of very thin microstructured polymer layers.
We report on the near-field imaging of microstructured polymer layers deposited on an homogeneous metal thin film on which a surface plasmon mode is excited. The microstructures in the polymer layers are designed by electron beam lithography, and the near-field imaging is performed with a photon scanning tunneling microscope (PSTM). We show that, despite their very small height, the microstructures can be conveniently imaged with a PSTM thanks to the field enhancement at the surface of the metal thin film supporting the surface plasmon. The influence of the illumination conditions on the contrast of the PSTM images is discussed. In particular, we show that both the field enhancement and the…
Nanoscale Blends between Immiscible Polymers via Simultaneous Non-Interfering Polymerisation
An important topic in polymer science seeks to improve the performances of polymer blends using nanoscale phase segregation. Here, blends between polystyrene and polycaprolactone are realised by a chemical route. The non-interfering character of the radical polymerisation of styrene and the lanthanide halide initiated ring-opening polymerisation of caprolactone is assessed. The molecular weights range from 2 000 to 3 500 for polycaprolactone and up to 140 000 for polystyrene, with reasonable polydispersity indexes. From calorimetry measurements, it is shown that polystyrene and low molecular weight polycaprolactone are immiscible. The morphology of the blends between the two immiscible poly…
Effects of temperature and pressure on microcantilever resonance response.
Abstract The variation in resonance response of microcantilevers was investigated as a function of pressure (10 −2 –10 6 Pa) and temperature (290–390 K) in atmospheres of helium (He) and dry nitrogen (N 2 ). Our results for a silicon cantilever under vacuum show that the frequency varies in direct proportion to the temperature. The linear response is explained by the decrease in Young's modulus with increasing the temperature. However, when the cantilever is bimaterial, the response is nonlinear due to differential thermal expansion. Resonance response as a function of pressure shows three different regions, which correspond to molecular flow regime, transition regime, and viscous regime. …
Direct measurement of the melting temperature of supported DNA by electrochemical method
The development of biosensors based on DNA hybridization requires a more precise knowledge of the thermodynamics of the hybridization at a solid interface. In particular, the selectivity of hybridization can be affected by a lot of parameters such as the single-strand (ss)DNA density, the pH, the ionic strength or the temperature. The melting temperature, T(m), is in part a function of the ionic strength and of the temperature and therefore provides a useful variable in the control of the selectivity and sensitivity of a DNA chip. The electrochemical technique has been used to determine the T(m) values when the probe is tethered by a DNA self-assembled monolayer (SAM). We have built a speci…
High spatial resolution strain measurements at the surface of duplex stainless steels
International audience; The determination of local strain fields at the surface of materials is of major importance for understanding their reactivity. In the present paper, lithography is used to fabricate grid points at the microscale and to map strain gradients within grains and between grains. This method was applied to duplex stainless steels which exhibit heterogeneous strain distributions under straining conditions. The influence of various parameters (the specimen microstructure, the density of slip bands, the number of systems activated and the grid geometry) on the strain value was discussed.
Observation directe de la croissance d'hydrosilicate de calcium sur des surfaces d'alité et de silice par microscopie à force atomique
Direct observation of the growth of calcium silicate hydrates, the tricalcium silicate hydration products, at the solid-solution interface were performed by atomic force microscopy. The covering of the surface of alite or silica by a three-dimensional oriented aggregation of nano particles of calcium silicate hydrate is always observed whatever the sample. All observations and quantifications made on calcium silicate growth at the submicronic level are in agreement with the data deduced from the study of the system evolution at the macroscopic level.
Optical modeling of nickel-base alloys oxidized in pressurized water reactor
International audience; The knowledge of the aging process involved in the primary water of pressurized water reactor entails investigating a mixed growth mechanism in the corrosion of nickel-base alloys. A mixed growth induces an anionic inner oxide and a cationic diffusion parallel to a dissolution-precipitation process forms the outer zone. The in situ monitoring of the oxidation kinetics requires the modeling of the oxide layer stratification with the full knowledge of the optical constants related to each component. Here, we report the dielectric constants of the alloys 600 and 690 measured by spectroscopic ellipsometry and fitted to a Drude-Lorentz model. A robust optical stratificati…
Conformational Changes and Charge Transfer in Biomolecules Resolved Using Dynamic Enhanced Raman Correlation Spectroscopy
International audience; In this contribution, we report that conforma-tional changes of molecules that are often buried in a wide-distributed Gaussian distribution can be discerned by analyzing the dynamics of specific Raman lines. We investigate the pertinence of the auto-and cross-correlation functions applied to the dynamics of three Raman lines of an amino acid, the tryptophan. The cross-correlation between intensity and the Raman band is an indicator of the charge transfer during the diffusion limited reaction of tryptophan and the gold surface. The Pećlet number Pe can provide a valuable indicator of the convective and/or diffusive features of each Raman band. Adsorption induced confo…
Investigation and modeling of the anomalous yield point phenomenon in pure tantalum
International audience; The monotonic and cyclic behavior of commercially pure tantalum has been investigated at room temperature, in order to capture and understand the occurrence of the anomalous yield point phenomenon. Interrupted tests have been performed, with strain reversals (tensile or compressive loading) after an aging period. The stress drop is attributed to the interactions between dislocations and solute atoms (oxygen) and its macroscopic occurrence is not systematically observed. InfraRed Thermography (IRT) measurements supported by Scanning Electron Microscopy (SEM) pictures of the polished gauge length of a specimen during an interrupted tensile test reveal the nucleation an…
Surface investigation of adhesive formulation consisting of UV sensitive triblock poly(styrene–b-butadiene–b-styrene) copolymer
Abstract Atomic force microscopy (AFM) analysis in conjunction with macroscopic studies such as peel testing and contact angle measurement have been undertaken to explain the nanomechanical properties of adhesive formulation consisting of triblock poly(styrene–b-butadiene–b-styrene) (SBS) copolymers. The cross-linking of this photosensitive copolymer was investigated by analyzing the mechanical and morphological changes of each phase induced by the UV exposure. Main result is that the adhesive properties are strongly influenced by the cross-linking of the polybutadiene (PB) phase leading to an increase in the surface stiffness without affecting the surface energy. AFM analysis shows that th…
Surface investigation of plasma HMDSO membranes post-treated by CF4/Ar plasma
Fluorination treatment has been performed on polysiloxane membranes using a plasma glow discharge of a gases mixture CF4 and argon (plasma enhanced chemical vapor deposition). Atomic force microscopy, XPS analyses and contact angle measurements have been undertaken to explain the surface transformation and behavior, which strongly depend on the morphology, the composition and the hydrophilic/hydrophobic character of the plasma-polymerized initial membranes. Main result is that fluorination, which leads to hydrophobic membranes, has a more relevant effect on amorphous silica-like membranes than on polymer-like ones, according to their chemical composition whereas the plasma surface reaction …
Potential-assisted deposition of mixed alkanethiol self-assembled monolayers
Abstract Preparation of self-assembled monolayers (SAMs) usually involves passive incubation. The recently developed potential-assisted deposition is indeed more selective as well as 100-fold faster than passive adsorption, thereby enhancing the reproducibility of the monolayer deposition. This article aims to identify the electrodeposition conditions necessary to prepare mixed alkanethiol SAMs on gold surface. Parameters such as concentrations in solution, electrode polarization and deposition time were examined for two chain lengths, C 3 (mercaptopropionic acid, MPA) and C 18 (octadecanethiol, ODT). The kinetics and composition of the SAMs were systematically characterized by reductive st…
Capteurs de pression plasmoniques pour aplications biomédicales
International audience
Measurement of Mechanical Properties of Cantilever Shaped Materials
Microcantilevers were first introduced as imaging probes in Atomic Force Microscopy (AFM) due to their extremely high sensitivity in measuring surface forces. The versatility of these probes, however, allows the sensing and measurement of a host of mechanical properties of various materials. Sensor parameters such as resonance frequency, quality factor, amplitude of vibration and bending due to a differential stress can all be simultaneously determined for a cantilever. When measuring the mechanical properties of materials, identifying and discerning the most influential parameters responsible for the observed changes in the cantilever response are important. We will, therefore, discuss the…
New insight into the aptamer conformation and aptamer/protein interaction by surface-enhanced Raman scattering and multivariate statistical analysis
International audience; We study the interaction between one aptamer and its analyte (the MnSOD protein) by the combination of surface-enhanced Raman scattering and multivariate statistical analysis. We observe the aptamer structure and its evolution during the interaction under different experimental conditions (in air or in buffer). Through the spectral treatment by principal component analysis of a large set of SERS data, we were able to probe the aptamer conformations and orientations relative to the surface assuming that the in-plane nucleoside modes are selectively enhanced. We demonstrate that the aptamer orientation and thus its flexibility rely strongly on the presence of a spacer …
Tunable sensitivity of a biosensor by strain modulation of a gap between gold dimers
International audience
Fluorescence relaxation in the near-field of a mesoscopic metallic particle : distance dependence and role of plasmon modes
International audience; We analytically and numerically analyze the fluorescence decay rate of a quantum emitter placed in the vicinity of a spherical metallic particle of mesoscopic size (i.e with dimensions comparable to the emission wavelength). We discuss the efficiency of the radiative decay rate and non–radiative coupling to the particle as well as their distance dependence. The electromagnetic coupling mechanisms between the emitter and the particle are investigated by analyzing the role of the plasmon modes and their nature (dipole, multipole or interface mode). We demonstrate that near-field coupling can be expressed in a simple form verifying the optical theorem for each particle …
La mesure directe des forces de liaison entre les hydrates appliquée à la prise de plâtre
Le phenomene de prise est un phenomene general, observable sur tous les liants mineraux, ciments siliceux, alumineux... et le plâtre. S'il existe des lois gouvernant la prise, elles doivent s'appliquer a tous ces liants. Aussi, il peut etre justifie de prendre tel ou tel liant pour modele si cela peut simplifier la premiere approche. Ici, l'objectif est de mesurer les forces entre les grains de silicate de calcium hydrate (phase C-S-H) qui est l'hydrate le plus caracteristique des ciments courants. Ces grains sont extremement petits et il a ete choisi de mettre au point les methodes travaillant sur le plâtre qui s'hydrate sous forme de gypse en formant des cristaux de 10 a 100 fois plus gro…
Early-stage detection of surface stress corrosion cracking at the subgranular level
The strain field at the interface between an alloy and its oxide layer has been mapped using nanopatterned gauges resistant to the environment of the primary nuclear medium. It was found that oxidation has decreased the alloy ductility, thereby enabling some grain boundary opening to be detectable from 1.8 % strain. It is shown that statistics of extreme rare events of hotspots quantify the occurrence of the local opening of intergranular cracks, and thereby the ageing process.
Influence des contraintes sur les propriétés élastiques de surface du gypse sondées par microscopie à force atomique
Resume La modulation de force en microscopie a force atomique (AFM) permet de cartographier les inhomogeneites des proprietes elastiques de surface. L'influence des contraintes laterales sur l'elasticite de surface a pu etre mise en evidence par modulation de force. L'etude a porte sur la face (010) du gypse. Au niveau atomique, les images topographiques different de celles sondant l'elasticite de surface. Au niveau microscopique, les images d'elasticite dependent des contraintes exercees sur le cristal. Sans contrainte, la surface presente une elasticite uniforme. Cependant, les contraintes laterales revelent des phenomenes de glissement, de cisaillement et de nœuds d'elasticite.
Simultaneous imaging of the surface and the submembraneous cytoskeleton in living cells by tapping mode atomic force microscopy
Contact and tapping mode atomic force microscopy have been used to visualize the surface of cultured CV-1 kidney cells in aqueous medium. The height images obtained from living cells were comparable when using contact and tapping modes. In contrast, the corresponding, and simultaneously acquired, deflection images differed markedly. Whereas, as expected, deflection images enhanced the surface features in the contact mode, they revealed the presence of a filamentous network when using the tapping mode. This network became disorganized upon addition of cytochalasin, which strongly suggests that it corresponded to the submembraneous cytoskeleton. Examination of fixed cells further supported th…
Discrimination between Single Protein Conformations Using Dynamic SERS
In biomedicine and biophysics, the discrimination of protein conformations is of critical importance for identifying the unfolding states in the diagnosis of neurodegenerative diseases. We develop a dynamic Raman spectroscopic approach based on a statistical analysis of the time series of spectral fingerprints of single protein. We show that the unfolded state of bovine serum albumin can be identified in the time series using the fluctuations of the Raman bands of some amino acids, tryptophan, tyrosine, leucine, and histidine, acting as biomarkers. The statistical analysis induces also the sorting between physisorption and chemisorption events. This is confirmed by the spectral analysis of …
Correlation between surface forces and surface reactivity in the setting of plaster by atomic force microscopy
Abstract The setting of mineral binders (cement, plaster, etc.) arises as a direct consequence of surface reactivity by a process of dissociation and rehydration. This transformation induces a complete change of surface forces, of which the nature remains still unknown. The general process of the setting has been studied by means of plaster (CaSO 4 ·0.5H 2 O) crystals, chosen for an experimental convenience. The surface alteration (growth, dissolution, atomic resolution) of the plaster crystal with respect to the introduction of the calcium sulfate solution has been followed by using atomic force microscopy (AFM. Alternatively, this apparatus has been adapted by gluing a plaster microcrysta…
Reactive direct current magnetron sputtered TiO2 thin films with amorphous to crystalline structures.
International audience; TiO2 thin films were deposited on soda–lime glass substrates by reactive direct current magnetron sputtering in a mixture of pure argon and oxygen. The influence of both the deposition time, td, and the post-annealing treatments on the films morphology, composition and structure was analyzed by scanning electron microscopy, ellipsometry, X-ray photoelectrons spectroscopy, X-ray diffraction (XRD) and Raman spectroscopy. Amorphous TiO2 was obtained for the shortest deposition time, td=15 min. Increasing td up to 30 min, poorly crystallized anatase and rutile phases were formed together with amorphous TiO2, as was revealed by complementary XRD patterns and Raman spectra…
Reactivity of gypsum faces according to the relative humidity by scanning force microscopy
Abstract This article reports the experimental observation of the stability of the different faces of calcium sulphate dihydrate (gypsum CaSO 4 .2H 2 O) according to the relative humidity. Scanning Force Microscopy experiments were carried out with a view to discerning the topography of the surfaces, the chemical compositional domains, and in an attempt to evaluate the friction and viscoelastic properties of the surface. Our results indicate that the (010) face of gypsum is hydrophilic and very reactive contrary to the less hydrophilic (120) and (101) faces which remain stable depending on the relative humidity. It is clear from our results that a precipitation like process can be induced b…
Changes in surface stress, morphology and chemical composition of silica and silicon nitride surfaces during the etching by gaseous HF acid
Abstract HF acid attack of SiO2 and Si3N4 substrates is analyzed to improve the sensitivity of a sensor based on microcantilever. Ex situ analysis of the etching using XPS, SIMS and AFM show significant changes in the anisotropy and the rate of the etching of the oxides on SiO2 and Si3N4 surface. Those differences influence the kinetic evolution of the plastic bending deflection of the cantilever coated with SiO2 and Si3N4 layer, respectively. The linear dependence between the HF concentration and the Si3N4 cantilever bending corresponds to a deep attack of the layer whereas the non-linear behavior observed for SiO2 layer can be explained by a combination of deep and lateral etching. The ca…
Effect of cholesterol on the physical properties of pulmonary surfactant films: Atomic force measurements study
International audience; Atomic force measurements were performed on supported pulmonary surfactant (PS) films to address the effect of cholesterol on the physical properties of lung surfactant films. We recently found that cholesterol in excess of a physiological proportion abolishes surfactant function, and is the reason that surfactant fails to lower the surface tension upon compression. In this study, we investigated how the loss of mechanical stability observed earlier is related to the local mechanical properties of the film by local force measurements. The presence of 20% of cholesterol in bovine lipid extract surfactant (BLES) resulted in a decrease of the observed adhesive interacti…
Activation process of reversible Pd thin film hydrogen sensors
Abstract Microcantilever-based thin film palladium hydrogen sensors have high selectivity and sensitivity. Reproducibility and accuracy of the sensor performance depend on the activation process of the polycrystalline palladium film deposited on the cantilever. When the hydrogen is in solid solution ( α -phase), the cantilever bending is mostly governed by the residual film stress induced by the swelling at the grain boundaries in the film. When the palladium hydride ( β -phase) starts to be formed, the cantilever undergoes a large deflection due to hydrogen absorption-induced film swelling (10% change in volume). Differences in the phase diagrams of the palladium hydride for two film thick…
In situ measurement of elastic properties of PdH , PdD , and PdT
Abstract The Young’s modulus E of palladium hydride PdH x , deuteride PdD x and tritide PdT x were measured for studying the effect of both hydrogen stoichiometry x and isotope nature. A special technique based on optical detection of flexural modes of a palladium cylindrical microcantilever was adapted to in situ measurements to guarantee the sample homogeneity during the hydriding process. A 10% decrease in E was found between pure polycrystalline palladium and hydride phases. The non linear dependence observed with the H content was discussed in terms of lattice expansion, phonons and electronic properties. Sensitivity of the technique enables to distinguish an isotope effect on E .
Influence of the Number of Nanoparticles on the Enhancement Properties of Surface-Enhanced Raman Scattering Active Area: Sensitivity versus Repeatability
In the present work, the combination of chemical immobilization with electron beam lithography enables the production of sensitive and reproducible SERS-active areas composed of stochastic arrangements of gold nanoparticles. The number of nanoparticles was varied from 2 to 500. Thereby a systematic analysis of these SERS-active areas allows us to study SERS efficiency as a function of the number of nanoparticles. We found that the experimental parameters are critical, in particular the size of the SERS-active area must be comparable to the effective area of excitation to obtained reproducible SERS measurements. The sensitivity has also been studied by deducing the number of NPs that generat…
DNA nanofilm thickness measurement on microarray in air and in liquid using an atomic force microscope.
International audience; The measurement of the thickness of DNA films on microarray as a function of the medium (liquid, air) is gaining importance for understanding the signal response of biosensors. Thiol group has been used to attach DNA strands to gold micropads deposited on silicon surface. Atomic force microscopy (AFM) was employed in its height mode to measure the change in the pad thickness and in its force mode to measure the indentation depth of the nanofilm. A good coherence between the height and force modes is observed for the film thickness in air. The adhesion force was found to be an alternative way to measure the surface coverage of the biolayer at nanoscopic scale. However…
Adhesive interaction measured between AFM probe and lung epithelial type II cells
The toxicity of inhaled nanoparticles entering the body through the lung is thought to be initially defined by the electrostatic and adhesive interaction of the particles with lung's wall. Here, we investigated the first step of the interaction of nanoparticles with lung epithelial cells using atomic force microscope (AFM) as a force apparatus. Nanoparticles were modeled by the apex of the AFM tip and the forces of interaction between the tip and the cell analyzed over time. The adhesive force and work of adhesion strongly increased for the first 100 s of contact and then leveled out. During this time, the tip was penetrating deeply into the cell. It first crossed a stiff region of the cell…
Effect of Cholesterol on Electrostatics in Lipid−Protein Films of a Pulmonary Surfactant
We report the changes in the electrical properties of the lipid-protein film of pulmonary surfactant produced by excess cholesterol. Pulmonary surfactant (PS) is a complex lipid-protein mixture that forms a molecular film at the interface of the lung's epithelia. The defined molecular arrangement of the lipids and proteins of the surfactant film gives rise to the locally highly variable electrical surface potential of the interface, which becomes considerably altered in the presence of cholesterol. With frequency modulation Kelvin probe force microscopy (FM-KPFM) and force measurements, complemented by theoretical analysis, we showed that excess cholesterol significantly changes the electri…
Detection of gas trace of hydrofluoric acid using microcantilever
Abstract Microcantilevers have been used as a gas sensor in order to detect Hydrofluoric acid (HF) in the concentration range of 0.26–13 ppm. Silicon derived elements (Si 3 N 4 , SiO x ) were chosen to serve as chemical sensitive layer. Cantilever deflection and frequency shift were analyzed and compared as a function of the flow rate and the concentration of the HF molecules. The stoichiometry and roughness of the sensitive layer were found to be of major importance. Results show that the most appropriate signal at the lowest concentration ( x surface by HF. The frequency shift that is mainly governed by the loss in cantilever mass can be used at higher concentration.
Tuning of an Optical Dimer Nanoantenna by Electrically Controlling Its Load Impedance
International audience; Optical antennas are elementary units used to direct optical radiation to the nanoscale. Here we demonstrate an active control over individual antenna performances by an external electrical trigger. We find that by an in-plane command of an anisotropic load medium, the electromagnetic interaction between individual elements constituting an optical antenna can be controlled, resulting in a strong polarization and tuning response. An active command of the antenna is a prerequisite for directing light wave through the utilization of such a device.
SVET, AFM and AES study of pitting corrosion initiated on MnS inclusions by microinjection
As pitting is a random phenomenon, it is difficult to predict where a pit will appear on the surface and consequently the use of local probes is rendered difficult. In this work, a new method to study pitting corrosion on a MnS inclusion on 316L stainless steel is proposed. It consists in modifying locally the chemistry in its vicinity by injecting with a microcapillary an aggressive solution of NaCl, H2SO4 or HCl. Once a pit appears, scanning vibrating electrode technique (SVET) is used to follow the current fluctuations over and around the pit when the metal is polarized at a passive potential. In another series of experiments the effect of local activation of MnS inclusion was studied ex…
Measurements of thickness dispersion in biolayers by scanning force microscopy and comparison with spectroscopic ellipsometry analysis.
Measuring the thickness of biological films remains a difficult task when using differential measurements by atomic force microscopy (AFM). The use of microstructured substrates combined with a selective adsorption constitutes an alternative to tribological measurements. The statistical thickness analysis of biological layers, especially via the dispersion measurements, can provide a way to quantify the molecular orientation. AFM thicknesses were then compared with those obtained optically by spectroscopic ellipsometry (SE) and surface plasmon resonance enhanced ellipsometry (SPREE). The biolayers could then be modeled using a vertical gradient of optical index, which reflects height disper…
Investigation of Temperature-Induced Phase Transitions in DOPC and DPPC Phospholipid Bilayers Using Temperature-Controlled Scanning Force Microscopy
Under physiological conditions, multicomponent biological membranes undergo structural changes which help define how the membrane functions. An understanding of biomembrane structure-function relations can be based on knowledge of the physical and chemical properties of pure phospholipid bilayers. Here, we have investigated phase transitions in dipalmitoylphosphatidylcholine (DPPC) and dioleoylphosphatidylcholine (DOPC) bilayers. We demonstrated the existence of several phase transitions in DPPC and DOPC mica-supported bilayers by both atomic force microscopy imaging and force measurements. Supported DPPC bilayers show a broad L(beta)-L(alpha) transition. In addition to the main transition …
A Methodology to Deduce the Microstructural Spatial Deformation of Polycrystalline Structures: Application to the Alloy 600
Studying the corrosion of the alloy 600, under water pressure, is of high importance to understand the ageing process of pressurized water reactors. Today, the impact of the oxide growth on the mechanical properties of nickel alloys is a challenge. The surface analysis and the quantification of the local deformation are key factors to deduce the surface damage of the substrate produced by corrosion. Here, we introduce a new methodology to determine the deformation distribution of the alloy 600 by using polycrystalline samples. The method is based on nanopads disposed on the surface samples, which allow a mapping, at the microscopic scale, of the spatial deformation. We applied to the sample…
Germanium Doped CHxMicroshells for LMJ Targets
AbstractAt the CEA Laser “Megajoule” facility, amorphous hydrogenated carbon (a-C:H or CHx) is the nominal ablator used to achieve inertial confinement fusion experiments. These targets are filled with a fusible mixture of deuterium-tritium in order to perform ignition.Since the achievement of ignition greatly depends on the physical properties of the shell, there must be precise control of thicknesses, doping concentration, and roughness. Experimental devices associated with suitable characterizations are described in this paper. The tolerances and yields for each specification are also presented. Some specifications are largely reached; high-frequency surface roughness due to isolated sur…
AFM study of interaction forces in supported planar DPPC bilayers in the presence of general anesthetic halothane
International audience; In spite of numerous investigations, the molecular mechanism of general anesthetics action is still not well understood. It has been shown that the anesthetic potency is related to the ability of an anesthetic to partition into the membrane. We have investigated changes in structure, dynamics and forces of interaction in supported dipalmitoylphosphatidylcholine (DPPC) bilayers in the presence of the general anesthetic halothane. In the present study, we measured the forces of interaction between the probe and the bilayer using an atomic force microscope. The changes in force curves as a function of anesthetic incorporation were analyzed. Force measurements were in go…
Sorting of Single Biomolecules based on Fourier Polar Representation of Surface Enhanced Raman Spectra
AbstractSurface enhanced Raman scattering (SERS) spectroscopy becomes increasingly used in biosensors for its capacity to detect and identify single molecules. In practice, a large number of SERS spectra are acquired and reliable ranking methods are thus essential for analysing all these data. Supervised classification strategies, which are the most effective methods, are usually applied but they require pre-determined models or classes. In this work, we propose to sort SERS spectra in unknown groups with an alternative strategy called Fourier polar representation. This non-fitting method based on simple Fourier sine and cosine transforms produces a fast and graphical representation for sor…
Gain, detuning, and radiation patterns of nanoparticle optical antennas
International audience; For their capability to localize and redirect electromagnetic field, metal nanoparticles have been recently viewed as efficient nanoantenna operating in the optical regime. In this article, we experimentally investigated the optical responses of coupled gold antenna pairs and measured the critical parameters defining antenna characteristics: resonant frequencies and bandwidths, detuning and gains, and radiation patterns.
Discerning the Origins of the Amplitude Fluctuations in Dynamic Raman Nanospectroscopy
International audience; We introduce a novel experimental and analytical method for discerning rare surface-enhanced Raman scattering (SERS) events observable at the nanoscale. We show that the kinetics of the Raman activity recorded on an isolated nanostructure is punctuated by intense and rare events of large amplitude and spectral variations. The fluctuations of thousands of SERS spectra were analyzed statistically in terms of power density functions, and the occurrence of the rare events was quantified by a wavenumber statistics. Our analysis enables one to extract valuable and unique spectroscopic signature of Raman variations usually hidden in time-average or space-average measurement…
Visible photothermal deflection spectroscopy using microcantilevers
International audience; Photothermal deflection spectroscopy based on bi-material cantilevers combines the sensitivity of miniature sensors and the selectivity of optical spectroscopy. In this paper, we report on the photothermal response of the microcantilevers functionalized with nanometer thin organic films in the visible region. Unlike responses in the infrared regime, in the optical region, light absorption by all the cantilever constituents must be considered for extraction of the physical parameters of the organic layer. A model of photothermal deflection for the optical region has been developed for two absorbing layers consisting of a thick metal (>200 nm) and a thin organic film. …
Correlating surface forces with surface reactivity of gypsum crystals by atomic force microscopy. Comparison with rheological properties of plaster
Abstract Atomic Force Microscopy (AFM) was used to image the surface reactivity as well as to characterize quantitatively the surface forces between two gypsum (CaSO 4 , 2H 2 O) crystals. Measurements on different crystal faces, which vary in morphology, structure, hydrophilicity, surface charge, were performed in both air and ionic solutions. In ionic solutions, varying the experimental parameters, the ionic nature and the concentration as well as the duration of the contact leads to the conclusion that the adhesion occurs whatever the orientation of faces. Nevertheless, the magnitude of the adhesion of a physical nature (Van der Waals and ionic correlation) depends on the surface charge d…
On the correlation between mechanical and TEM studies of the aging of palladium during tritium storage
Abstract Tritium has considerable technological applications in nuclear industry. Since it is a radioactive element, its storage is often considered in the form of tritides which ensure the required safety. However, the decay of tritium into 3 He alters the tritide properties during aging. With the aim of understanding the aging mechanisms of palladium tritide, a macroscale approach coupled with a microscopic study was performed on palladium aged up to eight months after tritium loading. The macroscale investigation based on the vibration of microcantilevers allowed the mechanical response of the material to be followed during its aging. The microscopic study was performed by Transmission E…
Strain mapping near a triple junction in strained Ni-based alloy using EBSD and biaxial nanogauges
A key element for analyzing the crack initiation in strained polycrystalline alloys is the local quantification of the surface strain distribution according to the grain texture. Using electron backscattered diffraction, the local microstructure was determined to both localize a triple junction and deduce the local Schmid factors. Kernel average misorientation (KAM) was also used to map the areas of defect concentration. The maximum principal strain and the in-plane shear strain were quantified using the biaxial nanogauge. Distortions of the array of nanodots used as spot markers were analyzed near the triple junction. The crystallographic orientation and the surface strain were then invest…
Mapping the 3D-surface strain field of patterned tensile stainless steels using atomic force microscopy.
Abstract The quantification of microstructural strains at the surface of materials is of major importance for understanding the reactivity of solids. The present paper aims at demonstrating the potentialities of the atomic force microscopy (AFM) for mapping the three-dimensional surface strain field on patterned tensile specimens. Electron beam (e-beam) lithography has been used to deposit 16×16 arrays of gold-squared pads. Monitoring the evolution of such a pattern under applied strain allows to quantify the triaxial strains both at the micro-(plastic) domain and nanoscale (elastic) domain vs. applied strain. The proposed method was applied to stainless steels after 4.5% plastic strain.
Performance of interdigitated nanoelectrodes for electrochemical DNA biosensor.
An electrochemical methodology for bio-molecule sensing using an array of well-defined nanostructures is presented. We describe the fabrication by e-beam lithography of nanoelectrodes consisting of a 100 micro m x 50 micro m area containing interdigitated electrodes of 100 nm in width and interelectrode distance of 200 nm. Sensitivity and response time of the nanoelectrodes are compared to the responses of macro- and microelectrodes. The specificity of the sensor is studied by modifying the gold electrodes with DNA. The technique enables to characterize both single and double-stranded DNA of 15 nucleotides. A special electrochemical cell is adapted to control the temperature and measure the…
Monitoring the chemical changes in Pd induced by hydrogen absorption using microcantilevers.
Abstract The reactivity of the palladium shaped as a microcantilever is investigated as a function of the hydrogen stoichiometry. A small cell holding the microcantilever is designed to monitor the deflection and the flexural resonance response from high vacuum to a hydrogen gas pressure of several bars. The measurements show that the Young's modulus is accurate if the cantilever is thick enough to be described by a continuum mechanics approach. The orientation distribution function of the palladium grains determined by X-ray diffraction enables to correlate Young's modulus measured using microcantilevers with the elastic constant tensor issued from the literature. The surface stress induce…