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Improving the selectivity of gas sensors is crucial for their further development. One effective route to enhance this key property of sensors is the use of selective nanomembrane materials. This work aims to present how metal-organic frameworks (MOFs) and thin films prepared by atomic layer deposition (ALD) can be applied as nanomembranes to separate different gases, and hence improve the selectivity of gas sensing devices. First, the fundamentals of the mechanisms and configuration of gas sensors will be given. A selected list of studies will then be presented to illustrate how MOFs and ALD materials can be implemented as nanomembranes and how they can be implemented to improve the operational performance of gas sensing devices. This review comprehensively shows the benefits of these novel selective nanomaterials and opens prospects for the sensing community., Competing Interests: The authors declare no conflict of interest.

Protein adsorption at the liquid-solid interface is an old but not totally solved topic. One challenge is to find an easy way to characterize the protein behavior on nanoparticles and make a correlation with its intrinsic properties. This work aims to investigate protein adsorption on gold nanoparticles and the colloidal properties. The protein panel was chosen from different structural categories (mainly-α, mainly-β or mix-αβ). The result shows that the colloidal stability with salt addition does not depend on the structural category. Conversely, using the single nanopore technique, we show that the mainly-α proteins form a smaller corona than the mainly-β proteins. We assign these observations to the lower internal energy of α-helices, making them more prone to form a homogeneous corona layer.

Nanolaminate membranes made of two-dimensional materials such as graphene oxide are promising candidates for molecular sieving via size-limited diffusion in the two-dimensional capillaries, but high hydrophilicity makes these membranes unstable in water. Here, we report a nanolaminate membrane based on covalently functionalized molybdenum disulfide (MoS 2 ) nanosheets. The functionalized MoS 2 membranes demonstrate >90% and ~87% rejection for micropollutants and NaCl, respectively, when operating under reverse osmotic conditions. The sieving performance and water flux of the functionalized MoS 2 membranes are attributed both to control of the capillary widths of the nanolaminates and to control of the surface chemistry of the nanosheets. We identify small hydrophobic functional groups, such as the methyl group, as the most promising for water purification. Methyl- functionalized nanosheets show high water permeation rates as confirmed by our molecular dynamic simulations, while maintaining high NaCl rejection. Control of the surface chemistry and the interlayer spacing therefore offers opportunities to tune the selectivity of the membranes while enhancing their stability.

Chronic kidney disease is characterized by a gradual decline in renal function that progresses toward end-stage renal disease. Podocytes are highly specialized glomerular epithelial cells which form with the glomerular basement membrane (GBM) and capillary endothelium the glomerular filtration barrier. GBM is an extracellular matrix (ECM) that acts as a mechanical support and provides biophysical signals that control normal podocytes behavior in the process of glomerular filtration. Thus, the ECM stiffness represents an essential characteristic that controls podocyte function. Hydrolyzed Polyacrylamide (PAAm) hydrogels are smart polyelectrolyte materials. Their biophysical properties can be tuned as desired to mimic the natural ECM. Therefore, these hydrogels are investigated as new ECM-like constructs to engineer a podocyte-like basement membrane that forms with cultured human podocytes a functional glomerular-like filtration barrier. Such ECM-like PAAm hydrogel construct will provide unique opportunity to reveal podocyte cell biological responses in an in vivo-like setting by controlling the physical properties of the PAAm membranes. In this work, Hydrolyzed PAAm scaffolds having different stiffness ranging between 0.6-44 kPa are prepared. The correlation between the hydrogel structural and mechanical properties and Podocyte morphology, elasticity, cytoskeleton reorganization, and podocin expression is evaluated. Results show that hydrolyzed PAAm hydrogels promote good cell adhesion and growth and are suitable materials for the development of future 3D smart scaffolds. In addition, the hydrogel properties can be easily modulated over a wide physiological range by controlling the cross-linker concentration. Finally, tuning the hydrogel properties is an effective strategy to control the cells function. This work addressed the complexity of podocytes behavior which will further enhance our knowledge to develop a kidney-on-chip model much needed in kidney function studies in both healthy and diseased states.

This review gives an overview of protein adsorption at solid/liquid interface. Compared to the other ones, we have focus on three main questions with the point of view of the protein. The first question is related to the kinetic and especially the using of Langmuir model to describe the protein adsorption. The second question is about the concept of hard and soft protein. In this part, we report the protein structural modification induced by adsorption regarding their intrinsic structure. This allows formulating of a new concept to classify the protein to predict their behavior at solid/liquid interface. The last question is related to the protein corona. We give an overview about the soft/hard corona and attempt to make correlation with the concept of hard/soft protein., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The heparin contamination by oversulfated chondroitin (OSCS) was at the origin of one major sanitary problem of last decade. Here we propose a novel strategy to detect OSCS from heparin solution based on conical nanopore functionalized with poly-L-lysine deposition to ensure its re-usability. This sensor is an excellent to detect low heparin concentration (from 25 ng/ml to 3 μg/ml) using the modification of ionic current rectification. It also allows following the kinetic of heparin degradation by heparinase with a good correlation with results obtained by classical methods. The sensor is sensitive to the inhibition of heparinase by OSCS until a concentration of 200 pg/ml representing 0.01% in weight in a heparin. This resolution is one order of magnitude lower than the one obtained by chromatography. For the first time, it was reached without fluorescence labeling., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The salinity gradient between brine and fresh water is an abundant source of power which can be harvested by two major membrane methods: pressure-retarded osmosis and reversed electrodialysis. Nowadays, the latter technology is close to real application, but it still suffers from low power yield. Low membrane selectivity and complex membrane fabrication are the main limiting factors. To improve that, we design a couple of ion-selective membranes based on the track-etched polymer nanopore functionalized by highly charged hydrogels. Two nanopore geometries are compared (cylindrical and conical shape) to generate osmotic energy with gel functions and more importantly can be scaled up. Experiments from the single nanopore and multipore membrane to stacked membranes show complete characterization from ionic transportation to energy generation and a clear relationship from the single pore to stacked membranes. In the actual experiment conditions, a power density of 0.37 W m -2 at pH 7 was achieved. By improving ionic tracks and reducing intermembrane distances, it can be a good candidate for industrial applications.

Atomic layer deposition (ALD) is a thin film deposition technique currently used in various nanofabrication processes for microelectronic applications. The ability to coat high aspect ratio structures with a wide range of materials, the excellent conformality, and the exquisite thickness control have made ALD an essential tool for the fabrication of many devices, including biosensors. This mini-review aims to provide a summary of the different ways ALD has been used to prepare biosensor devices. The materials that have been deposited by ALD, the use of the ALD layers prepared and the different types of biosensors fabricated are presented. A selected list of studies will be used to illustrate how the ALD route can be implemented to improve the operational performance of biosensors. This work comprehensively shows the benefits of ALD and its application in various facets of biosensing and will help in exploiting the numerous prospects of this emerging and growing field., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Amyloid fibrils are involved in several neurodegenerative diseases. However, because of their polymorphism and low concentration, they are challenging to assess in real-time with conventional techniques. Here, we present a new approach for the characterization of the intermediates: protofibrils and "end-off" aggregates which are produced during the amyloid formation. To do so, we have fashioned conical track-etched nanopores that are functionalized to prevent the fouling. Using these nanopores, we have followed the kinetic of amyloid growth to discriminate the different intermediates protofibrils and "end-off. Then, the nanopore was used to characterize the effect of promoter and inhibitor of the fibrillation process. Finally, we have followed in real-time the degradation of amyloid with peptase. Compare with the SiN nanopore, the track-etched one features exceptionally high success rate via functionalization and detection in "one-pot". Our results demonstrate the potential for a conical nanopore to be used as a routine technique for the characterization of the amyloid growth and/or degradation.

We investigated ionic transport behavior in the case of uncharged conical nanopores. To do so, we designed conical nanopores using atomic layer deposition of Al2O3/ZnO nanolaminates and then coated these with trimethylsilane. The experimental results are supported by molecular dynamics simulations. The ionic transport reveals an unexpected behavior: (i) a current rectification and (ii) a constant conductance at low salt concentration which are usually reported for charged conical nanopore. To explain these results, we have considered different assumptions: (i) a default of functionalization, (ii) the adsorption anion and (iii) the slippage. The first one was refuted by the study of the poly-l-lysine transport through the nanopore. To verify the second assumption, we investigate the effect of pH on the current rectification and the molecular dynamics simulations. Finally our study demonstrates that the unexpected ionic transport is provided to a predominant effect of slippage due to the water organization at the solid/liquid interface.

The antibiotic intercalation inside the layered double hydroxide (LDH) layers was usually considered for water decontamination but rarely for drug delivery. Here, tetracycline (TCH) and oxytetracycline (OXY) were immobilized in Zn 2 Al-Cl LDH following two methods: co-precipitation and anionic exchange. The interfacial concentration of antibiotic varies from 0.04 to 0.5 depending the method of immobilization. The antibiotics are not intercalated in the interlayer space allowing their release in 10 Hours. The antibacterial activity against both E. coli and S. epidermidis revealed that the loaded antibiotics are still active but less efficient compared to the free ones. After exposition to UV light or to high temperature storage (30, 60 and 120 °C), their antibacterial activity significantly decreases due to their degradation especially when antibiotic is loaded on material by co-precipitation. These results are promise to reduce antibiotic contamination in waters., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The understanding of the interactions between nanomaterials, biomolecules, and polyphenols is fundamental in food chemistry, toxicology, and new emerging fields, such as nanomedicine. Here, we investigated the effect of the resveratrol, a principal actor in drug-delivery application on the interaction between bovine serum albumin (BSA), employed as a vector for the delivery of polyphenol drugs, and gold nanoparticle (gNP), the most promising tool in theranostic applications. Through a combination of experimental techniques, which includes an initial evaluation by dynamic light scattering and surface plasmon resonance spectroscopy, we were able to evaluate the evolution of the gold nanoparticle aggregation with increasing ionic strength and the consequences of the BSA and resveratrol addition. To investigate the mechanisms of the interactions, we pursued at the single-molecule level using solid-state nanopore and fluorescence correlation spectroscopy. Our results show that without resveratrol, the BSA is adsorbed on the gNP in water or saline solution. In the presence of resveratrol, the BSA is normally absorbed on gNP in water, but the salt addition leads to its desorption. The resveratrol clearly plays a fundamental role, changing the protein behavior and making the BSA adsorption a reversible process in the presence of salt.

Wine chemistry inspires and challenges with its complexity and intriguing composition. In this context, the composites based on the use of a model protein, a polyphenol of interest and montmorillonite in a model hydroalcoholic solution have been studied. A set of experimental characterization techniques highlighted the interactions between the organic and the inorganic parts in the composite. The amount of the organic part was determined by ultraviolet-visible (UV-VIS) and thermal analysis. X-ray diffraction (XRD) and transmission electronic microscopy (TEM) informed about the stacking/exfoliation of the layers in the composites. Vibrational and nuclear magnetic resonance spectroscopies methods stressed on the formation of a complex between the protein and the polyphenol before adsorption on the clay mineral. The mobility/rigidity of the organic parts were determined by fluorescence time resolved spectroscopy. Changes in the secondary structure of the protein occured upon complexation with polyphenol on clay mineral due to strong interactions. Although not representating faithfully enological conditions, these results highlight the range and nature of mechanisms possibly involved in wine fining., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Solid-state nanopore technology for nanoparticle sensing is considered for the development of analytical tools to characterise their size, shape or zeta potential. In this field, it is crucial to understand how the nanopore inner surface influences the dynamic of nanoparticle translocation. Here, three single nanopores directly drilled in metal alloys (titanium nitride, titanium-tantalum and tantalum) are considered. The translocation of polystyrene nanoparticles coated with ssDNA is investigated by the resistive pulse method at different concentrations and voltages. The results show that the nanoparticle energy barrier for entrance into the pore decreases for nanopores that exhibits a higher surface energy and hydrophilicity, while the dwell time is found to depend on the nanopore surface state. Overall, this study demonstrates that the control of nanopore surface state must be taken into account for the resistive pulse experiments for nanoparticle detection.

Single conical nanopores were functionalised layer by layer with weak polyelectrolytes. We studied their influence on the ionic diode properties We have considered different couples of polyelectrolytes: poly-l-lysine/poly(acrylic acid) and poly(ethyleneimine)/poly(acrylic acid) as well as the influence of cross-linking. The results show that the nanopores decorated with poly(ethyleneimine)/poly(acrylic acid) exhibit an interesting behavior. Indeed, at pH 3, the nanopore is open only at the low salt concentration, while at pH 7, it is already open. The nanopores functionalized with poly-l-lysine/poly(acrylic acid) do not show an inversion of ionic transport properties with the pH as expected. After cross-linked to prevent large conformational changes, the ionic diode properties are dependent on the pH.

This article presents a novel procedure for preparing porous membranes from water-soluble polymers involving the formation of a Pickering emulsion. Gelatin is a biodegradable biopolymer obtained by the partial hydrolysis of collagen. A biopolymer such as gelatin is capable of adsorbing at an oil/water interface, resulting in decreased interfacial energy. Hence, gelatin is widely employed as an alternate for synthetic surfactants to stabilize emulsions in the food industry. However, high-molecular-weight gelatin leads to large emulsion droplets and poor emulsion stability. The amphoteric nature of graphene oxide (GO) nanosheets was helpful in stabilizing the oil/water interface and allows for the preparation of a stable gelatin/GO emulsion. Membranes fabricated using gelatin/GO have a uniformly distributed porous structure. However, prepared membranes are highly hydrosoluble, so the membranes were cross-linked without affecting their morphology. XRD results evidenced that gelatin effectively exfoliated the graphite oxide which is essential to stabilizing the emulsion. Fabricated gelatin/GO membranes possess uniformly distributed pores and are highly stable in aqueous solution. Pure water filtration tests were conducted on the membranes. The permeability results proved that the membranes fabricated by a Pickering emulsion are promising materials for filtration.

In nature, ion channels are highly selective pores and act as gate to ensure selective ion transport, allowing ions to cross the membrane. By mimicking them, single solid state nanopore devices emerge as a new, powerful class of molecule sensors that allow for the label-free detection of biomolecules (DNA, RNA, and proteins), non-biological polymers, as well as small molecules. In this review, we exhaustively describe the fabrication and functionalization techniques to design highly robust and selective solid state nanopores. First we outline the different materials and methods to design nanopores, we explain the ionic conduction in nanopores, and finally we summarize some techniques to modify and functionalize the surface in order to obtain biomimetic nanopores, responding to different external stimuli., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The formation of inverse Pickering emulsions using exfoliated hexagonal boron nitride (h-BN) as an effective particulate stabilizer without using any surfactants is reported for the first time. The stability and the type of h-BN Pickering emulsions formulated with different BN concentrations and by varying oil/water (o/w) ratios are studied and discussed. First the emulsion structure is analyzed microscopically through optical and epifluorescence microscopy and macroscopically by the study of the rheological behavior. The average droplet size decreases with h-BN concentration whereas the emulsions achieve good stability at 2 wt % BN concentrations and for a 1:1 o/w ratio. In all formulations, the emulsions are of water-in-oil (w/o) type due mainly to the hydrophobicity of h-BN.

Gelatin is a biodegradable biopolymer obtained by collagen denaturation, which shows poor mechanical properties. Hence, improving its mechanical properties is very essential toward the fabrication of efficient nontoxic material for biomedical applications. For this aim, various methods are employed using external fillers such as ceramics or bioglass. In this report, we introduce boron nitride (BN)-reinforced gelatin as a new class of two-dimensional biocompatible nanomaterials. The effect of the nanofiller on the mechanical behavior is analyzed. BN is efficiently exfoliated using the biopolymer gelatin as shown through Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). The exfoliated BN reinforces gelatin electrospun fibers, which results in an increase in the Young's modulus. The Electrospun Mats (ESM) are stable after the glutaraldehyde cross-linking, and the fibrous morphology is preserved. The cross-linked gelatin/BN ESM is highly bioactive in forming bonelike hydroxyapatite as shown by scanning electron microscopy. Due to their enhanced mineralization ability, the cross-linked ESM have been tested on human bone cells (HOS osteosarcoma cell line). The cell attachment, proliferation, and biocompatibility results show that the ESM are nontoxic and biodegradable. The analysis of osteoblast gene expression and the measurement of alkaline phosphatase activity confirm that these materials are suitable for bone tissue engineering.

In the present study, the adsorption capacities of two intercalated smectites, CTAB-saponite and CTAB-montmorillonite with a cationic surfactant, were investigated with three fluorescent dyes namely Rhodamine 640 perchlorate rhodamine (Rho), sulforhodamine B (SR) and Kiton red 620 (KR). The adsorption isotherms fit well with the non-linear Langmuir isotherm model and the maximum adsorption capacities of all the composites are determined. The photophysical properties such as anisotropy and fluorescence lifetime of all the fluorescent dyes over the clay materials are determined. The set of experimental data based on X-Ray diffraction (XRD), transmission electron microscopy (TEM), Thermal analysis (TG-DTA) and fluorescence measurements allow highlighting the presence or the absence of interactions between the dyes and the modified clay minerals., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Nanocomposites physical properties unexplainable by general mixture laws are usually supposed to be related to interphases, highly present at the nanoscale. The intrinsic dielectric constant of the interphase and its volume need to be considered in the prediction of the effective permittivity of nanodielectrics, for example. The electrostatic force microscope (EFM) constitutes a promising technique to probe interphases locally. This work reports theoretical finite-elements simulations and experimental measurements to interpret EFM signals in front of nanocomposites with the aim of detecting and characterizing interphases. According to simulations, we designed and synthesized appropriate samples to verify experimentally the ability of EFM to characterize a nanoshell covering nanoparticles, for different shell thicknesses. This type of samples constitutes a simplified electrostatic model of a nanodielectric. Experiments were conducted using either DC or AC-EFM polarization, with force gradient detection method. A comparison between our numerical model and experimental results was performed in order to validate our predictions for general EFM-interphase interactions.

Lysozyme from hen egg white is composed by a unique linear chain of 129 amino acids. It is known to inhibit Gram positive bacteria and to form amyloid fibrils at low pH, under 75°C. This work investigates the effect of the fibrillation and/or adsorption onto a layered double hydroxide material on the antibacterial properties of lysozyme. The kinetics of adsorption follows a behavior of pseudo second order model. The X-ray diffraction and the Fourier transform infrared spectroscopy highlight that adsorption occurs only on the external surface of the material. Interestingly, the amyloid fibrils of lysozyme retain their antibacterial properties when they are adsorbed on the layered double hydroxide; even if their activity is lowered, the active site of the enzyme is not fully denatured and is still accessible. This is confirmed by the study of the tryptophan using time-resolved fluorescence spectroscopy., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Layered double hydroxide (LDH) nanohybrid intercalated biomolecules, including oligonecluotides, genes and peptides/proteins, have attracted particular attention since they exhibit improved safety and effectiveness as successful delivery biosystems. The current study specifically investigated the adsorption of nisin peptide and precisely the control of the release of the payload. Adsorption occurred from peptide solution in contact with zinc-aluminum LDH at room temperature, looking out over the influence of the Zn 2+ /Al 3+ ratio, the anion exchange capacity, the nature of the intercalated anion, the host matrix, and the host morphology. Higher adsorption was obtained, around 80% of the loaded nisin and successful intercalation was verified by X-ray diffraction. The in-vitro release tests of the nisin from the biohybrid formulation was held over 25days in PBS medium (0.01M, pH7,4) and showed that no burst release phenomenon occurred at the beginning step, in addition, a sustained-time release of nisin was obtained compared with the free nisin. Therefore, these preliminary results are encouraging for the development of bioprotectors based on nisin intercalated LDH and being implemented in the food and medical industries., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Novel sensitive optical biosensor for determination of Grapevine virus A-type (GVA) proteins (GVA-antigens) has been designed. This biosensor was based on thin films of Zinc Oxide (ZnO) deposited by atomic layer deposition (ALD). The ZnO-based films have demonstrated favorable surface-structural properties for the direct immobilization of antibodies against GVA-antigens in order to form a biosensitive layer sensitive to GVA-antigens. The immobilization was confirmed by intensity changes in the main near band emission (NBE) peak of ZnO and by the formation of intense photoluminescence band, discovered in the visible range around 425nm, caused by the immobilized proteins. The GVA-antigen detection was performed by the evaluation of changes and behavior of a corresponding luminescence band. The sensitivity of as-formed label-free biosensor towards the GVA-antigens was determined in the range from 1pg/ml to 10ng/ml; in addition, the selectivity of biosensor was evaluated., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this work, we report the design and the fine-tuning of boron nitride single nanopore and nanoporous membranes by atomic layer deposition (ALD). First, we developed an ALD process based on the use of BBr 3 and NH 3 as precursors in order to synthesize BN thin films. The deposited films were characterized in terms of thickness, composition, and microstructure. Next, we used the newly developed process to grow BN films on anodic aluminum oxide nanoporous templates, demonstrating the conformality benefit of BN prepared by ALD, and its scalability for the manufacturing of membranes. For the first time, the ALD process was then used to tune the diameter of fabricated single transmembrane nanopores by adjusting the BN thickness and to enable studies of the fundamental aspects of ionic transport on a single nanopore. At pH = 7, we estimated a surface charge density of 0.16 C·m -2 without slip and 0.07 C·m -2 considering a reasonable slip length of 3 nm. Molecular dynamics simulations performed with experimental conditions confirmed the conductivities and the sign of surface charges measured. The high ion transport results obtained and the ability to fine-tune nanoporous membranes by such a scalable method pave the way toward applications such as ionic separation, energy harvesting, and ultrafiltration devices.

Biological channels have served as inspiration to design stimuli-response artificial nanopores. Here we propose an original approach to design a pH-gate nanopore based on polyethylenimine and chondroitin-4-sulfate (ChS) layer-by-layer self-assembly. This approach is interesting because it is rapid and permits monitoring in real time of functionalization. The study of ionic transport through these single nanopores reveals a selectivity on anions and pH-gate properties at low salt concentration. It is open at pH below 4 or 5 depending on salt concentration. These properties are explained by the modification of both charge and conformation of ChS as well as swelling of the polyelectrolyte complex.

Influenza A virus displays one of the highest infection rates of all human viruses and therefore represents a severe human health threat associated with an important economical challenge. Influenza matrix protein 2 (M2) is a membrane protein of the viral envelope that forms a proton selective ion channel. Here we report the expression and native isolation of full length active M2 without mutations or fusions. The ability of the influenza virus to efficiently infect MDCK cells was used to express native M2 protein. Using a Calixarene detergents/surfactants based approach; we were able to solubilize most of M2 from the plasma membrane and purify it. The tetrameric form of native M2 was maintained during the protein preparation. Mass spectrometry shows that M2 was phosphorylated in its cytoplasmic tail (serine 64) and newly identifies an acetylation of the highly conserved Lysine 60. ELISA shows that solubilized and purified M2 was specifically recognized by M2 antibody MAB65 and was able to displace the antibody from M2 MDCK membranes. Using a bilayer voltage clamp measurement assay, we demonstrate a pH dependent proton selective ion channel activity. The addition of the M2 ion channel blocker amantadine allows a total inhibition of the channel activity, illustrating therefore the specificity of purified M2 activity. Taken together, this work shows the production and isolation of a tetrameric and functional native M2 ion channel that will pave the way to structural and functional characterization of native M2, conformational antibody development, small molecules compounds screening towards vaccine treatment., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The fundamental understanding of the transport mechanisms of objects across a single nanopore is one key point to develop Coulter counters at the nanoscale for macromolecule or nanoparticle detection. In this area, nanoparticles have been less investigated than biomacromolecules such as DNA or proteins due to their self-aggregation in the presence of salts. In this work, the transport of modified latex nanoparticles across solid-state nanopores was investigated. To prevent their aggregation, their surface was modified with a low molecular weight single strand DNA coating. Then the coated nanoparticles were successfully detected across a single pore material in 200 mM NaCl buffer. The experimental capture rate was compared to that of the predictive model. It reveals that the nanoparticle entrance inside the nanopore is mainly governed by diffusion and required a weak energy. For relative current blockades, the predictive model should take into account both the nanopore shape and the additional charge due to ssDNA coating.

For the past 2 decades, emerging single-nanopore technologies have opened the route to multiple sensing applications. Besides DNA sensing, the identification of proteins and amyloids is a promising field for early diagnosis. However, the influence of the interactions between the nanopore surface and proteins should be taken into account. In this work, we have selected three proteins (avidin, lysozyme, and IgG) that exhibit different affinities with the SiNx surface, and we have also examined lysozyme amyloid. Our results show that the piranha treatment of SiNx significantly decreases protein adsorption. Moreover, we have successfully detected all proteins (pore diameter 17 nm) and shown the possibility of discriminating between denatured lysozyme and its amyloid. For all proteins, the capture rates are lower than expected, and we evidence that they are correlated with the affinity of proteins to the surface. Our result confirms that proteins interacting only with the nanopore surface wall stay long enough to be detected. For lysozyme amyloid, we show that the use of the nanopore is suitable for determining the number of monomer units even if only the proteins interacting with the nanopore are detected.

A water molecule is the foundation of life and is the primary compound in every living system. While many of its properties are understood in a bulk solvent, its behavior in a small hydrophobic nanopore still raises fundamental questions. For instance, a wetting/dewetting transition in a hydrophobic solid-state or a polymer nanopore occurs stochastically and can only be prevented by external physical stimuli. Controlling these transitions would be a primary requirement to improve many applications. Some biological channels, such as gramicidin A (gA) proteins, show a high rate of water and ion diffusion in their central subnanochannel while their external surface is highly hydrophobic. The diameter of this channel is significantly smaller than the inner size of the lowest artificial nanopore in which water drying occurs (i.e. 1.4 nm). In this paper, we propose an innovative idea to generate nanopore wetting as a result of which the application of an external field is no longer required. In a nanopore, the drying or wetting of the inner walls occurs randomly (in experiments and in simulations). However, we have shown how the confinement of gA, in a dried hydrophobic nanopore, rapidly generates a stable wetting of the latter. We believe that this simple idea, based on biomimetism, could represent a real breakthrough that could help to improve and develop new nanoscale applications.

Amphotericin B (AmB) is a well-known polyene which self-organizes into membrane cell in order to cause the cell death. Its specific action towards fungal cell is not fully understood but was proved to become from sterol composition. The mechanism was shown experimentally to require the formation of stable sterol/polyene couples which could then organize in a nanochannel. This would allow the leakage of ions responsible for the death of fungal cells, only. In this present study, we investigate the arrangement of AmB/sterols in biological membrane using molecular dynamic simulations in order to understand the role of the sterol structure on the antifungal action of the polyene. We show in particular that the nanochannels tend to close up when cell was composed with cholesterol (animal cell) due to strong interaction between amphotericin and sterol. On the other side, with ergosterol (fungal cell) the largest interactions between amphotericin and lipid membrane lead to the appearance of large hole that could favor the important leakage of ions and thus, the fungal cell death. This work appears as a good complement in the extensive studies linked to the understanding of the antifungal molecules in membrane cells.

The aim of this study was to synthesize stable gelatin electrospun mats (ESMs) (cross-linked by glutaraldehyde (GTA) vapors) with tunable drug release properties using pH as a stimulus. Gelatin ESMs loaded with rhodamine as a model drug were first synthesized. The in vitro release of rhodamine was characterized to understand the mechanisms of drug release and the effects of both cross-linker concentration and pH on drug release. An optimal cross-linker concentration of 5% was evidenced to provide ESMs allowing both sustainable release of drugs at pH 7 and burst release at pH 2. The release profiles were then fitted with a power law model to describe the release kinetics. The chlorhexidine antibiotic drug was finally loaded into the optimal electrospun mat and its bactericidal activity was demonstrated against Gram-negative (E. coli) and Gram-positive (S. epidermidis) bacteria by agar diffusion tests. This biocompatible material was shown to efficiently destroy bacterial biofilms and prevent bacterial growth within a short time (3 h), while maintaining its antibacterial activity up to at least 72 h. This study provides a promising material, which could treat infected sites and prevent infections, with tunable drug releasing properties using pH as a stimulus.

Fundamental understanding of ionic transport at the nanoscale is essential for developing biosensors based on nanopore technology and new generation high-performance nanofiltration membranes for separation and purification applications. We study here ionic transport through single putatively neutral hydrophobic nanopores with high aspect ratio (of length L = 6 μm with diameters ranging from 1 to 10 nm) and with a well controlled cylindrical geometry. We develop a detailed hybrid mesoscopic theoretical approach for the electrolyte conductivity inside nanopores, which considers explicitly ion advection by electro-osmotic flow and possible flow slip at the pore surface. By fitting the experimental conductance data we show that for nanopore diameters greater than 4 nm a constant weak surface charge density of about 10(-2) C m(-2) needs to be incorporated in the model to account for conductance plateaus of a few pico-siemens at low salt concentrations. For tighter nanopores, our analysis leads to a higher surface charge density, which can be attributed to a modification of ion solvation structure close to the pore surface, as observed in the molecular dynamics simulations we performed.

We investigate the influence of a nanopore surface state and the addition of Mg(2+) on poly-adenosine translocation. To do so, two kinds of nanopores with a low aspect ratio (diameter ∼3-5 nm, length 30 nm) were tailored: the first one with a negative charge surface and the second one uncharged. It was shown that the velocity and the energy barrier strongly depend on the nanopore surface. Typically if the nanopore and polyA exhibit a similar charge, the macromolecule velocity increases and its global energy barrier of entrance in the nanopore decreases, as opposed to the non-charged nanopore. Moreover, the addition of a divalent chelating cation induces an increase of energy barrier of entrance, as expected. However, for a negative nanopore, this effect is counterbalanced by the inversion of the surface charge induced by the adsorption of divalent cations.

Here we propose a new approach to tailor nanopores, which combines both pH gating and sensing properties. This strategy is based on PEG like-avidin grafting in nanopores designed by atomic layer deposition (ALD). Below pH 5 the nanopore is blocked. We show that the PEG chains are at the origin of these properties.

The development of nanometric Coulter counters for nanoparticle detection is an attractive and promising field of research. In this work, we have studied the influence of the nanopore surface state on charged polymer nanoparticle translocations. To make this, the translocation of carboxylate modified polystyrene microspheres (diameter 40, 70 and 100 nm) has been investigated through two kinds of high aspect ratio nanopores (negative and uncharged). The latter were tailored by a single track-etched and atomic layer deposition technique. It was shown that the mobility and the energy barrier are strongly dependent on nanopore surface charge. Typically if the latter exhibits negative surface charge, the microsphere mobility increases and the global energy barrier of entrance inside the nanopore decreases with its diameter, converse to the uncharged nanopore.

Detection of a single macromolecule based on the use of artificial nanopores is an attractive and promising field of research. In this work, we report a device based on a 5 nm single nanopore with a high length/diameter ratio, tailored by the track etching and atomic layer deposition techniques. The translocation of neutral polyethylene glycol (PEG) and charged polyethylene glycol-carboxylate (PEG-carboxylate) molecules of low molar masses (200 and 600 g mol(-1)) through this nanodevice was studied. It was shown that charged PEG-carboxylate molecules, which permeate through the pore, promote an unusual blockade of ionic current whereas the neutral PEG molecules do not show such behaviour. The molecular dynamics simulation shows that both neutral and charged PEGs permeate through the nanopore close to its inner surface. The main difference between the two macromolecules is the existence of a structured shell of cations around the charged PEG, which is likely to cause the observed unusual current blockade.

The hybrid biological/polymeric solid-state nanopore membrane offers several opportunities to combine the advantage of biological channel (selectivity) and material (robustness). Based on this technology, the challenge is to obtain selective ionic exchange membranes, with no energy intake. The direct insertion of an ionic channel inside a nanopore should be a promise solution. Here, the authors report a hybrid nanopore based on nystatin A1 confinement in commercial nanopore membrane. Ionic transport and selectivity studies show that the hybrid nanopores exhibit mainly an anionic behaviour, on the contrary to biological conditions. However, the order of magnitude between the different ratios of permeation of several cationic species is retained even if the blocking of divalent cation is not totally proved.

Biological ion channels present unique ionic properties. They can be highly permeable to ions, while selecting only one type of ions, without external energy supply. An important research field has been developed to transfer these properties to solid state nanoporous membranes in order to develop artificial biomimetic nanofilters. One of the promising ways to develop biomimetic structures is based on the direct insertion of the gramicidin A, i.e. an ionic channel, inside a nanopore. Experiments have recently proved the feasibility of such a hybrid membrane with very interesting results regarding the ionic selectivity. Here, we propose to interpret these experiments using theoretical molecular dynamic simulations which allow us to analyze more profoundly the structures of the proteins confined inside the nanopore and the relation between their conformation and the observed ionic properties.

We report the formation of a hybrid biological/artificial nanopore by the direct insertion of non-modified α-hemolysin at the entrance of a high aspect ratio (length/diameter) biomimetic nanopore. In this robust hybrid system, the protein exhibits the same polynucleotide discrimination properties as in the biological membrane and the polynucleotide dwell time is strongly increased. This nanopore is very promising for DNA sequencing applications where the high DNA translocation velocity and the fragility of the support are the main bottlenecks.

Specific separations of protons and cations are usually performed by electromembrane processes, which require external electric energy. An easier process would be using a membrane able to separate both entities by passive diffusion. Presently, such synthetic nanoporous membranes do not exist. Here, we report the production of a robust hybrid biological/artificial solid-state membrane, which allows selective permeation of alkali metal cations without competing or concurrent permeation of protons. This membrane is simple to prepare and is based on the hydrophobic nature of the polymeric pore walls, and the confined gramicidin A molecules within. This work opens a new route for separation in the domain of nanobiofiltration, especially for tunable nanodevices based on differential ion conduction, with a fundamental understanding of the confinement mechanism.

The potential of solid-phase microextraction on polyacrylate coated fibre, with sequential or simultaneous trimethylsilyl derivatisation followed by gas chromatographic-mass spectrometric analysis, was evaluated for a rapid determination of the distribution of the phytosterols in aqueous food matrixes. Influences of different parameters (bis(trimethylsilyl)trifluoro-acetamide and sterol exposure time, sterol concentration and experimental protocol) on the recovery of sterols were investigated to determine optimum conditions which were tested for sterol extraction and analysis from orange juice. Best selectivity, sterol recovery and derivatisation yields were obtained by extraction and simultaneous derivatisation through immersion of the SPME-PA fibre in the orange juice (10min, 65°C) after headspace absorption of BSTFA (30min, 65°C) on the fibre. Nevertheless the method developed cannot be used for quantitative analysis. But the possibility to effect rapid screen of phytosterol containing in complex media have been shown., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

A hybrid nanoporous membrane made of a solid-state polymeric thin film in which an ion channel is confined is realized. The primary and extremely encouraging results obtained by confocal fluorescence spectroscopy and ion diffusion measurement demonstrate respectively that (i) the considered ion channel, that is, Gramicidin-A, can be confined selectively inside the nanopores and (ii) the ionic permeability of the membrane is enhanced. Atomistic molecular simulations are also reported and fruitfully compared to the experimental findings.

Dehydration of a series of homoionic alkali-exchanged montmorillonites is studied at different treatment temperatures by means of thermogravimetric analysis. More specifically, we investigate the last stages of dehydration when the number of adsorbed water molecules corresponds, at maximum, to a monolayer. Weight losses are measured at several constant temperatures as a function of time. Application of Van't Hoff's law yields the dehydration enthalpy. Trends and data similar to those reported from other experimental conditions are found. Comparison with X-ray data and with the dissociation enthalpy of alkali cation/water complexes shows that dehydration of weakly hydrated homoionic alkali montmorillonites results from the competition between opposite energy contributions due to (i) the cation solvation, (ii) the hydration of the silicate interlayer surface, and (iii) the structural swelling. So, depending on the balance between these various energy contributions, different behaviors are observed according to the nature of the alkali cations.

The synthesis of a series of fully O-derivatised para-acyl-calix[8]arenes is described, where the acyl function is either octanoyl or hexadecanoyl. The groups attached at the phenolic face are, carboxymethoxy (anionic), carboxypropoxy (anionic), 4-sulfonatobutoxy (anionic), ethoxycarboxymethoxy (neutral), ethoxycarboxypropoxy (neutral), 2-methoxyethoxy (neutral) and 2-(2-methoxy)diethoxy (neutral). The use of specific synthetic routes has allowed complete substitution in high yields for all the compounds obtained. The interfacial properties of the compounds have been studied and stable monolayers have been obtained for certain compounds in the series having para-octanoyl substituents; all compounds studied in the series having para-hexadecanoyl substituents formed stable monolayers at the air-water interface. The interactions between O-4-sulfonatobutoxy-para-ocatanoylcalix[8]arene and a series of serum albumins have been studied by dynamic light scattering and specific adsorption of the calix-[8]-arene derivative onto the proteins observed. The anionic derivatives O-4-sulfonatobutoxy-para-ocatanoylcalix[8]arene and O-carboxymethoxy-para-ocatanoylcalix[8]arene have been shown to possess anticoagulant properties but to have no haemolytic toxicity.

3-Hydroxyflavone (3-OHF) was incorporated in zeolite micropores by ship-in-a-bottle synthesis. This strategy consists of constructing the molecule by reaction of small precursors within the cavity. 3-OHF molecules exhibit excited-state intramolecular proton transfer (ESIPT) and a tautomeric equilibrium between the 3-OHF-excited structures N* and T*exists. This equilibrium is strongly affected by the protic nature and polarity of the surrounding medium. The textural and spectroscopic characterization of the dye-loaded zeolite colloids enabled the study of the correlation between the optical properties of the dye and the zeolite micropore environment.