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Owing to high interfacial conductivity, organic heterostructures hold great promises to augment the electrical performances of electronic devices. In this endeavor, the present work reports fabrication of novel polyporphine/phthalocyanine heterostructures and investigates the modulation of charge transport induced by structural change of polyporphine and its implication on ammonia sensing properties. Polyporphines materials are electrosynthesized by oxidation of zinc(II) porphine monomer that corresponds to the fully unsubstituted porphyrin. At less-positive anodic potential, low conducting meso,meso-singly-linked type-1 polymer (pZnP-1) is formed in which a monomer unit stays orthogonal to its neighbors. At higher anodic potential, monomer units are fused in the 2D plane to produce β,β-meso-meso-β,β-triply-fused type-2 polymer (pZnP-2), having a π-conjugated structure and high conductivity. Association of these polymers in organic heterojunction devices with lutetium bis-phthalocyanine (LuPc2) reveals non-linear current–voltage (I-V) characteristics typical for interfacial accumulation of charges in the heterostructure for pZnP-1 and a linear I-V behavior for pZnP-2. Characterization of these heterojunctions by impedance spectroscopy further confirms the predominance of interfacial charge transport in pZnP-1/LuPc2 which is improved with increasing bias, while largely bulk charge transport independent of bias prevails in pZnP-2/LuPc2 device. Different regimes of charge transport influence ammonia-sensing properties of the devices, such that pZnP-1/LuPc2 demonstrates highly sensitive, reversible and stable response, while pZnP-2/LuPc2 shows low and unstable response.

International audience; Flavor is one of the main drivers of food consumption and acceptability. It is associated with pleasure feels during eating. Flavor is a multimodal perception corresponding to the functional integration of information from the chemical senses: olfaction, gustation, and nasal and oral somatosensory inputs. As a result, astringency, as a sensation mediated by the trigeminal nerves, influences food flavor. Despite the importance of astringency in food consumer acceptance, the exact chemosensory mechanism of its detection and the nature of the receptors activated remain unknown. Herein, after reviewing the current hypotheses on the molecular origin of astringency, we proposed a ground-breaking hypothesis on the molecular mechanisms underpinning this sensation as a perspective for future research.

In this work, bismuth oxide nanoparticles were successfully deposited on porous silicon (PSi) in order to enhance the light absorption and reduce the optical losses. The obtained bismuth oxide $$(\hbox {Bi}_{2}\hbox {O}_{3})/\hbox {PSi}$$ samples were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM) combined with energy-dispersive spectroscopy (EDS), atomic force microscopy (AFM), photoluminescence (PL), UV–visible absorption and reflection spectroscopy techniques. The XRD studies revealed the formation of the monoclinic $$\upalpha \hbox {-Bi}_{2}\hbox {O}_{3}$$ phase. The XPS analysis demonstrates the formation of highly pure $$\hbox {Bi}_{2}\hbox {O}_{3}$$ nanoparticles in accordance with XRD results. The SEM and AFM analyses confirmed that the bismuth oxide nanoparticles are well incorporated and uniformly distributed over the surface of PSi without changes in the arrangement and shape of the pores, resulting in an optimized microstructure. The $$\hbox {Bi}_{2}\hbox {O}_{3}/\hbox {PSi}$$ films showed better absorption than PSi layers as indicated by UV–Vis absorption technique. The reflection measurements confirmed a further reduction in reflectivity of PSi from 6.4 to 3.5% after the inclusion of $$\hbox {Bi}_{2}\hbox {O}_{3}$$ nanoparticles, which is of significant importance for solar cells application since it can enhance its conversion efficiency. The $$\hbox {Bi}_{2}\hbox {O}_{3}/\hbox {PSi}$$ films have a great promise to be used as efficient antireflection coatings in innovative concepts of higher efficiency and cost-effective solar cells.

International audience; Titanium dioxide (TiO2) is very employed in solar cells due to its interesting physicochemical and optical properties allowing high device performances. Considering the extension of applications in nanotechnologies, nanocrystalline TiO2 is very promising for nanoscale components. In this work, nanocrystalline TiO2 thin films were successfully deposited on porous silicon (PSi) by metal organic chemical vapor deposition (MOCVD) technique at temperature of 550°C for different periods of times: 5, 10 and 15 min. The objective was to optimize the physicochemical and optical properties of the TiO2/PSi films dedicated for photovoltaic application. The structural, morphological and optical properties of the elaborated TiO2/PSi samples were analyzed by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), photoluminescence (PL) and UV-Visible absorption spectroscopy methods. The effect of deposition time on the microstructural properties which influences the optical characteristics of the obtained samples was also examined. The XRD analysis confirms the nanocrystalline structure of the deposited TiO2 composed only by anatase phase. The SEM characterization evidenced an increase in the TiO2 film thickness showing more uniform surfaces as the deposition time rises. Correspondingly, the surface roughness increases with the particle size and film thickness as indicated by AFM studies. The TiO2/PSi/Si sandwich structure evidenced by cross-sectional SEM confirms the good adherence of the TiO2 nanocrystalline film on the porous silicon forming with silicon a composite material. The UV-Vis measurements showed a considerable enhancement in optical absorption of porous silicon after the deposition of TiO2 films. Indeed, the TiO2 coatings deposited on PSi for 15 min with thickness of 200 nm have the best structure quality and exhibit, consequently, the highest absorption. From these interesting results, we demonstrate the viability of the use of the MOCVD as reproducible process for the elaboration of high-quality TiO2/PSi films.

International audience; The mucosal pellicle, also called salivary pellicle, is a thin biological layer made of salivary and epithelial constituents, lining oral mucosae. It contributes to their protection against microbiological, chemical, or mechanical insults. Pellicle formation depends on the cells’ surface properties, and in turn the pellicle deeply modifies such properties. It has been reported that the expression of the transmembrane mucin MUC1 in oral epithelial cells improves the formation of the mucosal pellicle. Here, we describe an approach combining classical and functionalized tip atomic force microscopy and scanning microwave microscopy to characterize how MUC1 induces changes in buccal cells’ morphology, hydrophobicity, and electric properties to elucidate the physicochemical mechanisms involved in the enhancement of the anchoring of salivary proteins. We show that MUC1 expression did not modify drastically the morphology of the epithelial cells’ surface. MUC1 expression, however, resulted in the presence of more hydrophobic and more charged areas at the cell surface. The presence of salivary proteins decreased the highest attractive and repulsive forces recorded between the cell surface and a functionalized hydrophobic atomic force microscopy (AFM) tip, suggesting that the most hydrophobic and charged areas participate in the binding of salivary proteins. The cells’ dielectric properties were altered by both MUC1 expression and the presence of a mucosal pellicle. We finally show that in the absence of MUC1, the pellicle appeared as a distinct layer poorly interacting with the cells’ surface. This integrative AFM/scanning microwave microscopy approach may usefully describe the surface properties of various cell types, with relevance to the bioadhesion or biomimetics fields.

The carboxysome is a bacterial micro-compartment (BMC) subtype that encapsulates enzymatic activities necessary for carbon fixation. Carboxysome shells are composed of a relatively complex cocktail of proteins, their precise number and identity being species dependent. Shell components can be classified in two structural families, the most abundant class associating as hexamers (BMC-H) that are supposed to be major players for regulating shell permeability. Up to recently, these proteins were proposed to associate as homo-oligomers. Genomic data, however, demonstrated the existence of paralogs coding for multiple shell subunits. Here, we studied cross-association compatibilities among BMC-H CcmK proteins of Synechocystis sp. PCC6803. Co-expression in Escherichia coli proved a consistent formation of hetero-hexamers combining CcmK1 and CcmK2 or, remarkably, CcmK3 and CcmK4 subunits. Unlike CcmK1/K2 hetero-hexamers, the stoichiometry of incorporation of CcmK3 in associations with CcmK4 was low. Cross-interactions implicating other combinations were weak, highlighting a structural segregation of the two groups that could relate to gene organization. Sequence analysis and structural models permitted the localization of interactions that would favor formation of CcmK3/K4 hetero-hexamers. The crystallization of these CcmK3/K4 associations conducted to the elucidation of a structure corresponding to the CcmK4 homo-hexamer. Yet, subunit exchange could not be demonstrated in vitro. Biophysical measurements showed that hetero-hexamers are thermally less stable than homo-hexamers, and impeded in forming larger assemblies. These novel findings are discussed within the context of reported data to propose a functional scenario in which minor CcmK3/K4 incorporation in shells would introduce sufficient local disorder as to allow shell remodeling necessary to adapt rapidly to environmental changes., PLoS ONE, 14 (10), ISSN:1932-6203

Conductive indium-tin oxide (ITO) and non-conductive glass substrates were successfully modified with embedded gold nanoparticles (AuNPs) formed by controlled thermal annealing at 550 &deg, C for 8 h in a preselected oven. The authors characterized the formation of AuNPs using two microscopic techniques: scanning electron microscopy (SEM) and atomic force microscopy (AFM). The analytical performances of the nanostructured-glasses were compared regarding biosensing of Hsp70, an ATP-driven molecular chaperone. In this work, the human heat-shock protein (Hsp70), was chosen as a model biomarker of body stress disorders for microwave spectroscopic investigations. It was found that microwave screening at 4 GHz allowed for the first time the detection of 12 ng/&micro, L/cm2 of Hsp70.

International audience; Supported lipid bilayers represent a very attractive way to mimic biological membranes, especially to investigate molecular mechanisms associated with the lateral segregation of membrane components. Observation of these model membranes with high-speed atomic force microscopy (HS-AFM) allows the capture of both topography and dynamics of membrane components, with a spatial resolution in the nanometer range and image capture time of less than 1 s. In this context, we have developed new protocols adapted for HS-AFM to form supported lipid bilayers on small mica disks using the vesicle fusion or Langmuir-Blodgett methods. In this chapter we describe in detail the protocols to fabricate supported artificial bilayers as well as the main guidelines for HS-AFM imaging of such samples.

Metallic nanoparticles are considered as active supports in the development of specific chemical or biological biosensors. Well-organized nanoparticles can be prepared either through expensive (e.g., electron beam lithography) or inexpensive (e.g., thermal synthesis) approaches where different shapes of nanoparticles are easily obtained over large solid surfaces. Herein, the authors propose a low-cost thermal synthesis of active plasmonic nanostructures on thin gold layers modified glass supports after 1 h holding on a hot plate (~350 °C). The resulted annealed nanoparticles proved a good reproducibility of localized surface plasmon resonance (LSPR) and surface enhanced Raman spectroscopy (SERS) optical responses and where used for the detection of low concentrations of two model (bio)chemical molecules, namely the human cytochrome b5 (Cyt-b5) and trans-1,2-bis(4-pyridyl)ethylene (BPE).

International audience; An original sub-surface, high spatial resolution tomographic technique based on scanning microwave microscopy (SMM) is used to visualize in-depth materials with different chemical compositions. A significant phase difference in SMM between aluminum and chromium buried patterns has been observed. Moreover this technique was used to characterize a solid solution of a light chemical element (oxygen) in a metal lattice (zirconium). The large solubility of the oxygen in zirconium leads to modifications of the properties of the solid solution that can be measured by the phase shift signal in the SMM technique. The signal obtained in cross-section of an oxidized Zr sample shows the excellent agreement between phase shift profiles measured at different depths. Such a profile can reveal the length of diffusion of the oxygen in zirconium under the surface. The comparison with the oxygen concentration measured by nuclear reaction analysis shows excellent agreement in terms of length of diffusion and spatial distribution of the oxygen. A rapid calibration shows a linear dependence between the phase shift and the oxygen concentration. The SMM method opens up new possibilities for indirect measurements of the oxygen concentration dissolved in the metal lattice

International audience; A technique based on scanning microwave microscopy (SMM) has recently been developed to analyze solid solutions of light elements. This technique consists in local measurements of effects produced by electrical conductivity variations produced by light elements solutions in metals. The penetration of the microwaves into the metals depends on their frequency and the material parameters. Information regarding the local conductivity of the material at different depths can be recorded using various frequencies. In this paper, SMM measurements of the oxygen-enriched zone are presented for several materials: TA6V, pure Ti, and pure Zr. Comparisons with concentration measurements made by nuclear reaction analysis allow one to affirm that for all the materials investigated here the phase shift measured by SMM is proportional to the oxygen concentration dissolved into the metal. Calibration functions are proposed for each material and frequency used. After calibration, the SMM can be used to measure local enrichments.

International audience; Different types of PLA films treated by corona are currently available in the market for coating or printing applications. However, data relative to its impact on PLA film properties are scarce and do not generally consider industrial scale production. The objective of this study was to assess the impact of corona treatment on the surface, structure and barrier properties of bi-oriented PLA films produced at industrial scale. Thus, a comparative study between corona treated (CT) and non-corona treated (NCT) PLA films was conducted.The surface of films was studied using Attenuated Total Reflectance Fourier Infrared Spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and goniometry measurements. The structure of films was analyzed with thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and uniaxial tensile analysis. The barrier properties of films to three gases (He, O-2, CO2) were also determined.This study unambiguously revealed that corona treatment led to modifications in both surface and bulk of PIA films. In particular, surface analysis displayed the well-known capability of corona treatment to chemically and physically modify the surface of PLA films at the nanometer scale by increasing polarity and roughness. The structural analysis displayed a slight increase in the crystallinity degree and slight modifications in mechanical properties of films. This probably originated from temperature increase associated to corona treatment, which favored physical changes (e.g. relaxation, crystallization) of a part of the bi-orientated PIA chains, and therefore highlights the importance of such an industrial step on the film properties for packaging applications. As a result of these modifications, the barrier properties of films to three gases (He, O-2, CO2) are also slightly improved.

International audience; Based on the skin effect, our recent developments using scanning microwave microscopy lead to propose a non-destructive method to detect located buried defect in metal samples like stainless steel. A 3D tomography is possible by taking advantage of microwave measurement, using a vector network analyzer in bandwidth frequencies, and the nanometer resolution positioning capabilities with atomic force microscopy. At each used frequency, an incident electromagnetic wave is sent to the sample and the reflected wave gives information on a specific depth layer in the material. With diagnostic tools of nanotechnologies (SEM. AFM, etc.), different stainless steel samples (from Areva NP) presenting local buried defects are studied. The materials used in this study are conventional stainless steels like a 304 stainless steel which is the most versatile and widely used stainless steel. The results of the tomography applied on these samples are in accordance with the skin effect equation.

We propose a new analytical approach combining vibrational spectroscopy and acoustic tomography for the detection and characterization of vesicles inside Streptomyces bacteria. Using atomic force microscopy and infrared spectroscopy (AFM-IR), we detect the presence of triglyceride vesicles. Their sizes in depth are measured with high accuracy using mode synthesizing atomic force microscopy (MS-AFM). We conducted a comparative study of AFM-IR and MS-AFM, and highlighted the advantages of the coupling of these techniques in having a full characterization (chemical, topographical, and volumetric) of a biological sample. With these complementary techniques, a complete access to the vesicle size distribution has been achieved with an accuracy of less than 50 nm. A 3D reconstruction of bacteria showing the in-depth distribution of vesicles is given to underline the great potential of the acoustic method.

Synthetic proteo-nucleic structures (PDNAs) encompassing a single-stranded DNA sequence covalently attached to a redox protein domain able to interact with surface or matrix were designed and characterized. They constitute versatile building blocks alternative to regular DNA for creating scaffolds with optical, electrical, or catalytic properties. PDNAs self-assemble in the presence of complementary oligonucleotides, to form a network of protein domains linked by double-stranded DNA segments. Electrophoretic and hydrodynamic behaviors of PDNAs and corresponding DNA were compared under electrophoresis and gel filtration conditions. Hybridization rates between small and large assemblies were characterized by rapid-mixing experiments. Results showed that the protein part significantly contributes to hydrodynamic behaviors of structures but marginally affects the conformation and hybridization properties of the nucleic domain. PDNA metal-mediated complexes with nitriloacetate-modified phospholipids can diffuse and interact at the surface of vesicles or supported membranes. Surface plasmon resonance analysis of membrane-PDNA interactions indicated that two protein units are required to allow stable surface association and that surface occupancy constrains assembly sizes. High-speed atomic force microscopy illustrated rapid lateral diffusion of assemblies on mica, revealing transient association between noncomplementary PDNA extremities and frequent trapping by surface defects. Regularly organized protein domains were visualized using a larger DNA framework.

Scientists are currently truly committed to enhance the specificity of chemotherapeutics that target DNA. To this end, sequence-specific drugs have progressively given way to structure-specific therapeutics. However, while numerous strategies have been implemented to design high-affinity candidates, strategies devoted to the design of high-selectivity ligands are still rare. Here we report on such an approach via the study of an amphiphilic compound, TEGPy, that self-assembles at a liquid/solid interface to provide nanosized objects that are stable in water. The resulting aggregates, identified through atomic force microscopy measurements, were found to disassemble upon interaction with DNA in a structure-specific manner (quadruplex- versus duplex-DNA). Our results provide a fertile ground for devising new strategies aiming at concomitantly enhancing DNA structural specificity and the water-solubility of aggregation-prone ligands.

International audience; The bioassay of infinitesimal quantities of protein markers in biological samples is the way to early cancer detection. However, this detection can be limited by the diffusion of these macromolecules (analytes) from the bulk to the sensor chip (surface of ligands). Here, we propose a new method to overcome this drawback by the activation of the biological media during the detection step. The principle consists in using ultrasonic vibrations in order to disrupt the equilibrium states of such biomolecular reactions and performing simultaneous detection inside an acoustic micromixer. Technological realization and initial characterizations of the device have been performed and are presented in this work. Moreover, the capacity of our system to enhance the biosensors performances was studied and validated through a biological model related to breast cancer.

International audience; We constructed an original supramolecular assembly on a surface of sensor composed of an innovative combination of an engineered cytochrome b5 and a modified nucleic acid bound to a synthetic lipid hemimembrane. The protein/DNA block, called (PDNA) 2, was synthesized and purified before its immobilization onto a hybrid bilayer reconstituted on a gold surface. Surface plasmon resonance (SPR) and atomic force microscopy (AFM) were engaged in parallel on the same substrates in order to better understand dynamic events that occur at the surface of the biosensor. Good correlations were obtained in terms of specificity and reversibility. These findings allow us to present a first application of such biosensor in the study of the interaction processes between nuclear receptor and DNA

Synthesis of a titanocene dichloride derivative functionalized with 3,4-etylenedioxythiophene group, Tc1EDOT (Cl 2TiCpC5H4(CH2) (3,4ethylenedioxythiophene)) has been described. Redox behavior of the monomer in tetrahydrofuran (THF), dichloromethane (DCM) and acetonitrile (AN) at different scan rates has been discussed in terms of different ability of these solvents to coordination with the reduced titanocene (Tc) complex and the solvation of Cl − anions. Electrooxidation of Tc1EDOT to get a conducting polymer film with immobilized titanocene dichloride centers and electrochemical properties of its polymer matrix in background acetonitrile solution have been compared with those of non-substituted PEDOT and PEDOT-methanol derivative (PEDOTMet), to elucidate the effect of substituents both on polymerization and redox potentials of the matrix. STM and AFM images of p(Tc1EDOT) films obtained with potentiodynamic and potentiostatic regimes are compared to illustrate that the films deposited at constant potential are better ordered and more compact than those obtained by cyclic voltammetry. A comparison of the cyclic voltammograms of p(Tc1EDOT) and poly(titanocene-propyl-pyrrole) (p(Tc3Py)) films in 0.1 TBAPF6 in THF has shown that the electroactivity of the polymer matrix of p(Tc1EDOT) is extended to more negative potentials in comparison to that of p(Tc3Py). This results in the anodic shift of redox potential of Tc centers immobilized in p(Tc1EDOT) film with respect to that of the centers fixed in p(Tc3Py). © 2005 Elsevier Ltd. All rights reserved.