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The combination of inorganic heterogeneous catalysts and enzymes, in so-called hybrid chemoenzymatic heterogeneous catalysts (HCEHCs), is an attractive strategy to effectively run chemoenzymatic reactions. Yet, the preparation of such bifunctional materials remains challenging because both the inorganic and the biological moieties must be integrated in the same solid, while preserving their intrinsic activity. Combining an enzyme and a zeolite, for example, is complicated because the pores of the zeolite are too small to accommodate the enzyme and a covalent anchorage on the surface is often ineffective. Herein, we developed a new pathway to prepare a nanostructured hybrid catalyst built from glucose oxidase and TS-1 zeolite. Such hybrid material can catalyse the in situ biocatalytic formation of H2O2, which is subsequently used by the zeolite to trigger the epoxidation of allylic alcohol. Starting from an enzymatic solution and a suspension of zeolite nanocrystals, the hybrid catalyst is obtained in one step, using a continuous spray drying method. While enzymes are expectedly unable to resist the conditions used in spray drying (temperature, shear stress, etc.), we leverage on the preparation of “enzyme– polyelectrolyte complexes” (EPCs) to increase the enzyme stability. Interestingly, the use of EPCs also prevents enzyme leaching and appears to stabilize the enzyme against pH changes. We show that the one-pot preparation by spray drying gives access to hybrid chemoenzymatic heterogeneous catalysts with unprecedented performance in the targeted chemoenzymatic reaction. The bifunctional catalyst performs much better than the two catalysts operating as separate entities. We anticipate that this strategy could be used as an adaptable method to prepare other types of multifunctional materials starting from a library of functional nanobuilding blocks and biomolecules.

Antimicrobial peptide loaded poly(2-hydroxyethyl methacrylate) particles were synthesized in supercritical carbon dioxide via one-pot free-radical dispersion polymerisation of 2-hydroxyethyl methacrylate and a cross-linker. Discrete particles with a well-defined spherical morphology and a diameter as low as 450 nm have been obtained in mild conditions. The encapsulation and release of the peptide were confirmed by antimicrobial tests that demonstrated for the first time a sustained release of the peptide from poly(2-hydroxyethyl methacrylate) microgels prepared by one-pot dispersion polymerization in supercritical carbon dioxide and then dispersed in water.

Nanoplasmonic sensors based on surface-enhanced spectroscopies carry profound promise toward ultrasensitive detection of biomolecular analytes within miniaturized measurement footprints. High sensi...

Providing inert materials with a biochemical function, for example using proteins, is a cornerstone technology underlying many applications. However, the controlled construction of protein thin films remains a major challenge. Here, an innovative solvent-free approach for protein deposition is reported, using lysozyme as a model. By diverting a time-of-flight secondary ion mass spectrometer (ToF-SIMS) from its standard analytical function, large argon clusters were used to achieve protein transfer. A target consisting of a pool of proteins was bombarded with 10 keV Ar5000+ ions, and the ejected proteins were collected on a silicon wafer. The ellipsoidal deposition pattern was evidenced by ToF-SIMS analysis, while SDS-PAGE electrophoresis confirmed the presence of intact lysozyme on the collector. Finally, enzymatic activity assays demonstrated the preservation of the three-dimensional structure of the transferred proteins. These results pave the way to well-controlled protein deposition using ion beams and to the investigation of more complex multilayer architectures.

The combination of heterogeneous catalysts and enzymes, in so-called hybrid catalysts, is an attractive strategy to effectively run chemoenzymatic reactions. Yet, the preparation of such bifunctional materials remains challenging because both the inorganic and the biological moieties must be integrated in the same solid, while preserving their intrinsic activity. Combining an enzyme and a zeolite, for example, is complicated because the pores of the zeolite are too small to accommodate the enzyme and a covalent anchorage on the surface is often ineffective. Herein, we developed a new pathway to prepare a hybrid catalyst built from glucose oxidase and TS-1 zeolite. Such hybrid material can catalyze the in situ formation of H2O2, which is subsequently used by the zeolite to trigger the epoxidation of allylic alcohol. Starting from an enzymatic solution and a suspension of zeolite nanocrystals, the hybrid catalyst is obtained in one step, using a continuous spray drying method. While enzymes are expectedly unable to resist the conditions used in spray drying (temperature, shear stress, etc.), we leverage on the preparation of “enzyme-polyelectrolyte complexes” (EPCs) to increase the enzyme stability. Importantly, the use of EPCs also appears to prevent enzyme leaching and to stabilize the enzyme against pH changes. We show that the one-pot preparation by spray drying gives access to hybrid catalysts with unprecedented performance in the targeted chemoenzymatic reaction. Interestingly, the hybrid catalyst performs much better than the two catalysts operating as separate entities. We anticipate that this strategy could be used as an adaptable method to prepare other types of multifunctional materials.

Charged nanofibers were prepared by electrospinning (ESP) poly(e-caprolactone) with a copolymer bearing carboxylic acid functions. The presence of these functions allowed exposing some negative charges on the fiber surface, by dipping the fibers in a phosphate buffer. A layer of chitosan, a polycation in acidic medium, was then deposited on the nanofiber surface, thanks to electrostatic attraction. Fibers were characterized at each step of the process and the influence of the copolymer architecture on chitosan deposition was discussed. The antibacterial activity of the resulting fibers was finally assessed.

Cu-Ni alloys are extensively used in contact with natural waters and are impacted by microbial activities of biofilms. The mechanisms by which surface changes occur upon immersion remain not well understood. Herein, an aerobic microbial activity of natural biofilms is mimicked by the enzymatic generation of an oxidizing agent and an organic acid. Surface changes are probed through a detailed analysis of XPS spectra which allowed a distinction between compounds of organic and inorganic nature to be made. Results show that the surface is composed of copper oxides/hydroxides, presumably Cu2O and Cu(OH)2 and Ni hydroxides. The enzyme-catalyzed reaction causes a significant depletion of Ni and inorganic oxygen, while the concentration of copper, CuI and CuII, varies only slightly. Surface changes concern the organic phase; the amount of organic compounds strikingly increases in the presence of enzymes, and the XPS spectra reveal the accumulation of compounds with high oxidized carbon content, attributed to adsorbed gluconate. Correlations between spectral data suggest the formation of Cu-gluconate complex, probably through coordinative bonds between gluconates and CuII on the oxide layer. These findings are particularly important to properly evaluate the impact of microbial activities on the sustainability of Cu-Ni alloys upon natural exposures.

Ionised cluster beams have been produced and employed for thin film deposition and surface processing for half a century. In the last two decades, kiloelectronvolt cluster ions have also proved to be outstanding for surface characterisation by secondary ion mass spectrometry (SIMS), because their sputter and ion yields are enhanced in a non-linear fashion with respect to monoatomic projectiles, with a resulting step change of sensitivity for analysis and imaging. In particular, large gas cluster ion beams, or GCIB, have now become a reference in organic surface and thin film analysis using SIMS and X-ray photoelectron spectroscopy (XPS). The reason is that they induce soft molecular desorption and offer the opportunity to conduct damageless depth-profiling and 3D molecular imaging of the most sensitive organic electronics and biological samples, with a nanoscale depth resolution. In line with these recent developments, the present review focuses on rather weakly-bound, light-element cluster ions, such as noble or other gas clusters, and water or alcohol nanodroplets (excluding clusters made of metals, inorganic salts or ionic liquids) and their interaction with surfaces (essentially, but not exclusively, organic). The scope of this article encompasses three aspects. The first one is the fundamentals of large cluster impacts with surfaces, using the wealth of information provided by molecular dynamics simulations and experimental observations. The second focus is on recent applications of large cluster ion beams in surface characterisation, including mass spectrometric analysis and 2D localisation of large molecules, molecular depth-profiling and 3D molecular imaging. Finally, the perspective explores cutting edge developments, involving (i) new types of clusters with a chemistry designed to enhance performance for mass spectrometry imaging, (ii) the use of cluster fragment ion backscattering to locally retrieve physical surface properties and (iii) the fabrication of new biosurface and thin film architectures, where large cluster ion beams are used as tools to transfer biomolecules in vacuo from a target reservoir to any collector substrate.

The immobilization of proteins to impart specific functions to surfaces is topical for chemical engineering, healthcare and diagnosis. Layer-by-Layer (LbL) self-assembly is one of the most used method to immobilize macromolecules on surfaces. It consists in the alternate adsorption of oppositely charged species, resulting in the formation of a multilayer. This method in principle allows any charged object to be immobilized on any surface, from aqueous solutions. However, when it comes to proteins, the promises of versatility, simplicity and universality that the LbL approach holds are unmet due to the heterogeneity of protein properties. In this review, the literature is analyzed to make a generic approach emerge, with a view to facilitate the LbL assembly of proteins with polyelectrolytes (PEs). In particular, this review aims at guiding the choice of the PE and the building conditions that lead to the successful growth of protein-based multilayered self-assemblies.

Aluminum hydroxide (AH) salts are widely used as vaccine adjuvants and controlling antigen-AH interactions is a key challenge in vaccine formulation. In a previous work, we have developed a quartz crystal microbalance (QCM) platform, based on stable AH-coated sensors, to explore the mechanisms of model antigen adsorption. The QCM study of bovine serum albumin (BSA) adsorption at different pH and ionic strength (I) values showed that protein adsorption on AH adjuvant at physiological pH cannot be explained mainly by electrostatic interactions, in contrast with previous reports. Here, we exploit further the developed QCM platform to investigate the role of phosphate-hydroxyl ligand exchanges in the adsorption mechanism of BSA, human serum albumin (HSA) and ovalbumin (OVA) on two commercial AH adjuvants. BSA adsorption decreased on immobilized AH particles previously treated with KH2PO4, highlighting the role of exchangeable sites on AH particles in the adsorption process. BSA and OVA were dephosphorylated by treatment with an acid phosphatase to decrease their phosphate content by about 80% and 25%, respectively. Compared to native BSA, adsorption of dephosphorylated BSA decreased significantly on one AH adjuvant at pH 7. Adsorption of dephosphorylated OVA was comparable to the one of native OVA. Further QCM assays showed that phospho-amino acids (PO4-serine and PO4-threonine) displaced previously adsorbed BSA and OVA from AH particles in conditions that were depending on the protein and the AH. Taken together, these observations suggest that phosphate-hydroxyl ligand exchange is an important adsorption mechanism of proteins on AH. These results moreover confirm that the developed AH-coated QCM sensors offer a new platform for the study of antigen adsorption, to the benefit of vaccine formulation.

Controlling the sequencein which macromoleculesinteract allows creating self-assemblies that only exist because of theconstruction path that was followed. Because structure correlates withfunction, exploring paths of self-assembly holds the potential to confervarious functionalities to the assembly. In this paper, lysozyme (Lyz) wasused as a templating agent in the layer-by-layer (LbL) self-assembly ofpoly(allylamine hydrochloride) (PAH) with poly(styrenesulfonate)(PSS). To do so, Lyz was complexed with PSS, and the resultingcomplex was alternately adsorbed with PAH. By carrying the LbLassembly at low pH and in pure water, PAH adsorption causes thesubsequent release of Lyz. The result is that even though it was used forassembly, only a very small fraction of Lyz is present in the resultingfilm.Using quartz crystal microbalance with dissipation monitoring mountedwith a humidity module, the swelling/deswelling behavior and the composition of these polyelectrolyte multilayers (PEMs) wereinvestigated. It appears that such PEMs obtained via a complex adsorption sequence are much thicker and trapped in anonequilibrium state. Their dehydration is irreversible as it causes their collapse into denser PEMs. After dehydration, the PEMsshare a common composition with the ones constructed without the use of Lyz as a templating agent. Fitting the Flory−Hugginsequation to the data suggests that both PEM types separate into a polymer-rich phase and a water-rich phase when exposed toincreasing water vapor pressure. Nevertheless, the presence of a swelling hysteresis in the PEMs templated with Lyz suggests thatthey possess a different internal structure or that trace amounts of Lyz affect the polymer relaxation kinetics. The use of proteins astemplating elements thus allows to construct PEMs that are thick, highly hydrated, and gel-like at the nanoscale level rather than thindense PE blends, which is topical for biomedical applications.

© 2018 Elsevier Ltd Fused deposition modeling (FDM), a low-cost and easy-to-use additive manufacturing technique, was used to produce poly(lactic acid) (PLA) gyroid scaffolds. Such morphology was selected for its spring shape, high porosity leading to good nutrient and waste diffusion, and favorable mechanical properties. Printing parameters were optimized and the need of a support material to improve printing was evidenced. The gyroid was compared to the common strut-based structure. Scaffold porosity was measured by micro-CT, and mechanical properties were determined by compression tests, taking into account the effect of geometry, printing resolution, and PLA crystallinity. The impact of scaffold geometry and crystallinity on its degradation was studied in vitro. Porosity of the gyroid structure was 71%, as expected from the printing model. The compression tests showed an isotropic behavior for the gyroid, in contrast with the strut-based scaffold. Upon aging in physiological conditions, gyroid scaffolds retained their integrity during 64 weeks, while control scaffolds lost struts starting from week 33, in a way that depended on crystallinity and printing resolution. Based on these results, the gyroid design is proposed as a suitable mesh architecture for tissue engineering scaffolds that can be elaborated using FDM techniques, to produce low-cost and personalized implants. ispartof: MATERIALS & DESIGN vol:151 pages:113-122 status: published

The high specific strength and stiffness and excellent damping behavior promote the use of flax fibre composites in the construction sector. However, the limited compatibility between raw flax fibres and bio-epoxy resin often leads to composites with mechanical properties well below their theoretical capacities. Moreover, the incomplete understanding of the intrinsic non-linear mechanical behavior of flax fibre composites forces the application of larger safety factors. In this study, three chemical treatments are applied to improve the interphase properties and gain further insight in the longitudinal tensile behavior of flax fibre bio-epoxy composites. Both alkali and APS treatment result in a threefold improvement in the transverse flexural strength to ∼30MPa. Both treatments additionally shift the weakest link to the elementary fibre interphase strength. Analysis of the longitudinal tensile stress-strain curves of UD flax fibre composites results in a tri-linear shape that is preserved after treatment.

Proteins at interfaces are a key for many applications in the biomedical field, in biotechnologies, in biocatalysis, in food industry, etc. The development of surface layers that allow to control and manipulate proteins is thus highly desired. In previous works, we have shown that mixed polymer brushes combining the protein-repellent properties of poly(ethylene oxide) (PEO) and the stimuli-responsive adsorption behavior of poly(acrylic acid) (PAA) could be synthesized and used to achieve switchable protein adsorption. With the present work, we bring more insight into the rational design of such smart thin films by unravelling the role of PEO on the adsorption/desorption of proteins. The PEO content of the mixed PEO/PAA brushes was regulated, on the one hand, by using PEO with different molar masses and, on the other hand, by varying the ratio of PEO and PAA in the solutions used to synthesize the brushes. The influence of ionic strength on the protein adsorption behavior was also further examined. The behavior of three proteins-human serum albumin, lysozyme, and human fibrinogen, which have very different size, shape, and isoelectric point-was investigated. X-ray photoelectron spectroscopy, quartz crystal microbalance, atomic force microscopy, and streaming potential measurements were used to characterize the mixed polymer brushes and, in particular, to estimate the fraction of each polymer within the brushes. Protein adsorption and desorption conditions were selected based on previous studies. While brushes with a lower PEO content allowed the higher protein adsorption to occur, fully reversible adsorption could only be achieved when the PEO surface density was at least 25 PEO units per nm

A standard method of protein immobilization is proposed, based on the use of protein-polyelectrolyte complexes (PPCs) as building blocks for layer-by-layer assembly. Thicker multilayers, with a higher polyelectrolyte fraction, are obtained with PPCs compared to single protein molecules. Biological activity is not only maintained, but specific activity is also higher, as demonstrated for lysozyme-poly(styrene sulfonate) complexes. This is attributed to the more hydrated state of the assemblies. This new method of protein immobilization opens up perspectives for biotechnology and biomedical applications.

A new photo-sensitive diblock copolymer composed of a hydrophilic sequence of poly(ethylene oxide) (PEO) linked to a CO2-philic sequence of poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate) (PFDA) by a light sensitive o-nitrobenzyl group was successfully synthesized by RAFT polymerization and used as a stabilizer for the free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) dispersion in α,α,α-trifluorotoluene and supercritical carbon dioxide (scCO2). Thanks to this fluorinated stabilizer, well-defined particles of PHEMA down to 350 nm diameter were produced in scCO2. Advantageously, the photocleavable group at the block junction of the stabilizer could be cleaved by exposing the particles to UV light so that the fluorinated block could be extracted in TFT or scCO2. As supported by X-ray photoelectron spectroscopy (XPS) analysis, up to 80% of the fluorinated block of the stabilizer can be removed, leading to efficient swelling and dispersion of the resulting PHEMA nanogels in water.

Selective protein adsorption is a key challenge for the development of biosensors, separation technologies, and smart materials for medicine and biotechnologies. In this work, a strategy was developed for selective protein adsorption, based on the use of mixed polymer brushes composed of poly(ethylene oxide) (PEO), a protein-repellent polymer, and poly(acrylic acid) (PAA), a weak polyacid whose conformation changes according to the pH and ionic strength of the surrounding medium. A mixture of lysozyme (Lyz), human serum albumin (HSA), and human fibrinogen (Fb) was used to demonstrate the success of this strategy. Polymer brush formation and protein adsorption were monitored by quartz crystal microbalance, whereas protein identification after adsorption from the mixture was performed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) with principal component analysis and gel electrophoresis with silver staining. For the ToF-SIMS measurements, adsorption was first performed from single-protein solutions in order to identify characteristic peaks of each protein. Next, adsorption was performed from the mixture of the three proteins. Proteins were also desorbed from the brushes and analyzed by gel electrophoresis with silver staining for further identification. Selective adsorption of Lyz from a mixture of Lyz/HSA/Fb was successfully achieved at pH 9.0 and ionic strength of 10 M, while Lyz and HSA, but not Fb, were adsorbed at ionic strength 10 M and pH 9.0. The results demonstrate that by controlling the ionic strength, selective adsorption can be achieved from protein mixtures on PEO/PAA mixed brushes, predominantly because of the resulting control on electrostatic interactions. In well-chosen conditions, the selectively adsorbed proteins can also be fully recovered from the brushes by a simple ionic strength stimulus. The developed systems will find applications as responsive biointerfaces in the fields of separation technologies, biosensing, drug delivery, and nanomedicine.

The deconstruction of self-assemblies based on proteins and polyelectrolytes (PEs) and the subsequent release of intact proteins requires either a switch from attractive to repulsive mode or particular PE properties (degradability, responsiveness, differential affinity). Here, an interfacial self-assembly made of three charged species, i.e. a strong polyacid complexed with a protein and a weak polybase, is shown to self-reorganize upon pH shift. When the pH takes a value that is one pH unit lower than the pKa of the weak polybase, the two PEs associate, thereby releasing the protein. The disassembly thus relies on associative forces rather than on the alteration of the protein-PE coupling strength. Hence, it allows the release of a protein using two simple PEs. The method is illustrated for lysozyme, which recovered up to half of its initial bioactivity after release. In contrast, a control self-assembled film that could not reorganize only maintained about 21% of the protein bioactivity after disassembly. This versatile approach is valuable for drug delivery devices and biomaterials as it allows the release of large amounts of active protein molecules.

Layer-by-layer (LbL) assembly is a surface modification method which may bring complexity to biointerfaces designed to control cell-material interactions. This work aims at investigating the LbL assembly of two extracellular matrix proteins, collagen (Col) and fibronectin (Fn), on polystyrene substrates. LbL assembly, which is widely applied to polyelectrolytes, is not easily transferred to proteins. Different buffers and conditions are tested, and LbL assembly is compared to the simultaneous adsorption of Fn and Col. Build-up and properties of the films are monitored using quartz crystal microbalance, ellipsometry, water contact angle measurements, and atomic force microscopy. Results show that denatured Col leads to smoother films, and that the addition of a polyethyleneimine anchoring layer increases film thickness. A more regular construction and thicker films are obtained with Hepes (pH 7.4) compared to other buffers. However, the LbL assembly is not sustainable and stops after the deposition of a few layers. Films obtained by simultaneous adsorption have lower water contact angles, different morphologies, lower water content and are as thick or thicker compared to the ones prepared by the LbL method. The present work shows that collagen and fibronectin are not involved in a true LbL assembly process. The obtained biointerfaces however exhibit different properties compared to those obtained by the one-step adsorption of these proteins. These differences could be exploited to control cell fate.

Graphite rods were modified by substituted aryldiazonium salts allowing subsequent laccase immobilisation and direct electron transfer at the cathode. Two covalent enzyme immobilisation methods were performed with carboxy and amino substituted grafted groups, either via the formation of an amide bond or a Schiff base between the glycosidic groups of the enzyme and the amino groups on the electrode surface, respectively. Laccase adsorption efficiency was consistently compared to the covalent attachment method on the same carbon surface, showing that the latter method led to a higher immobilisation yield when the electrode surface was functionalised with carboxylic groups, as shown from both laccase activity measurement towards an organic reducing substrate, ABTS, and quantitative XPS analysis. Both analytical methods led to similar laccase surface coverage estimations. From activity measurements, when laccase was covalently immobilised on the electrode functionalised with carboxylic groups, the surface coverage was found to be 43 ± 2% whereas it was only 10 ± 3% when laccase was adsorbed. Biocatalysed dioxygen reduction current was also higher in the case of covalent immobilisation. For the first time, oxidised laccase performances were compared to unmodified laccase, showing significant improved efficiency when using oxidised laccase: the current obtained with oxidised laccase was 141 ± 37 μA cm− 2 compared to 28 ± 6 μA cm− 2 for unmodified laccase after covalent immobilisation of the enzyme on a graphite electrode functionalised with carboxylic groups.

Sulindac loaded poly(HEMA) cross-linked microparticles were synthesized via one-pot free-radical dispersion polymerisation in supercritical carbon dioxide (scCO2) in presence of photocleavable diblock stabilisers based on polyethylene oxide (PEO) and poly(heptadecafluorodecyl acrylate) (PFDA) bearing a o-nitrobenzyl photosensitive junction (hv) (PEO-hv-PFDA), and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Poly(HEMA) cross-linked microparticles either empty or sulindac loaded were obtained with well-defined spherical morphology with the sizes between 250 and 350 nm. Additionally, upon UV-photolysis the stabiliser on the surface was cleaved which permits to microparticles to be redispersed in water leading to water swollen microgels about 2.1–3.6 µm. Moreover, the release behaviour from obtained microgels indicated the sustained release of sulindac over 10 days. Besides, the surface modification after UV-photolysis was studied and proved that the particles can be functionalised with further chemistries.

To evaluate compatibility between a substrate and a thermoplastic polymer, the established methodology is to estimate their surface composition in terms of surface energy components, utilizing the results of contact angle measurements of probe liquids onto substrate and polymer surfaces at room temperature. Using this methodology, polymer surfaces are studied in solid state, however, during spreading of polymers on a substrate, polymers are in molten state and at high temperature, having different surface energies and more complex polymer/substrate interactions due to polymer chain mobility. This paper presents a model study with practical relevance to predict polymer/substrate compatibility including contact angle measurements at high temperature directly performed between molten thermoplastics; polypropylene (PP), polyvinylidene fluoride (PVDF) and maleic anhydride-grafted polypropylene (MAPP), on smooth glass fibres and plates. The values of total surface energy of thermoplastics at high temperature (260 °C) are down to 57% of that measured at room temperature, which has a strong influence on the wetting prediction. Surface energies of both the polymer and the substrate were found not to be the only factor controlling the wetting behaviour of molten polymers and the level of adhesion with the substrate, but also some intrinsic characteristics of the polymer melt play a role. We also observed that the wetting behaviour of molten MAPP is affected by the maleic anhydride (MA) content, demonstrating dramatically different results to room temperature measurements, which is suspected to be due to the formation of covalent bonds of MA groups with the glass surface enhancing the interface strength beyond the shear strength of MAPP.

Hybrid nanobiointerfaces were designed as an original contribution to the challenge of synthesizing nanostructured biomaterials integrating a set of cell fate-determining cues, originally provided to cells by the extracellular matrix (ECM). The produced biointerfaces consist of a stiff framework of intersected polypyrrole (PPy) nanotubes supporting a soft multilayer composed of ECM-derived biomacromolecules: collagen (Col) and hyaluronic acid (HA). PPy frameworks with highly tunable characteristics were synthesized through chemical oxidative polymerization of pyrrole monomers, templated within track-etched polycarbonate (PC) membranes featuring a network of intersected nanopores. PPy interfaces with a porosity of 80%, composed of nanotubes with an average diameter ranging from 40 to 300 nm, intersecting at an angle of 90°, were shown to be self-supported. These rigid PPy nanostructured interfaces were functionalized with a self-assembling (HA/Col) multilayer deposited via a layer-by-layer process. Biofunctionalized and unmodified PPy frameworks were both shown to promote sustained cell adhesion, therefore demonstrating the cytocompatibility of the engineered matrices. Such nanobiointerfaces, combining a mechanically-stable framework of tunable dimensions with a soft biopolymeric multilayer of highly versatile nature, pave the way towards cell-instructive biomaterials able to gather a wide range of cues guiding cell behavior. The developed self-supported structures could be used as a coating or as membranes bridging different tissues.

Aluminum hydroxide (AH) salts are the most widely used adjuvants in vaccine formulation. They trigger immunogenicity from antigenic subunits that would otherwise suffer from a lack of efficiency. Previous studies focusing on antigen-AH interaction mechanisms, performed with model proteins, suggested that electrostatic interactions and phosphate-hydroxyl ligand exchanges drive protein adsorption on AH. We however recently evidenced that NaCl, used in vaccine formulation, provokes AH particle aggregation. This must be taken into account to interpret data related to protein adsorption on AH. Here, we report on the successful development and use of a stable AH-coated surface to explore the mechanisms of protein adsorption by means of ultrasensitive surface analysis tools. Bovine serum albumin (BSA) adsorption was studied at different pHs and ionic strengths (I) using quartz crystal microbalance. The results show that protein adsorption on the AH adjuvant cannot be explained solely by electrostatic interactions and ligand exchanges. Hence, a higher adsorption was observed at pH 3 compared to pH 7, although AH and BSA respectively undergo repulsive and attractive electrostatic interactions at these pH values. Almost no effect of I on adsorption was moreover noted at pH 7. These new developments and observations not only suggest that other mechanisms govern protein adsorption on AH but also offer a new platform for the study of antigen adsorption in the context of vaccine formulation. Immobilizing particles on QCM sensors also enriches the range of applications for which QCM can be exploited, especially in colloid science.

Administration of antibiotics by inhalation can greatly improve drug targeting to the site of respiratory infections. In addition, dry powder inhalers are particularly convenient for the patients. The purposes of this study were to demonstrate the interest of pulmonary temocillin delivery to reach high temocillin concentrations locally in the lungs as well as to prepare a spray-dried temocillin powder for inhalation using a minimal amount of generally recognized as safe excipients. Intratracheal instillation of a temocillin solution allowed to reach higher and more sustained drug concentrations in the lungs than intravenous injection in mice, although a 10-fold lower temocillin dose was delivered intratracheally than systemically. A spray-dried powder of pure temocillin presented a fine particle fraction of 9% of the dose loaded in the inhaler. However, the incorporation of 0.5% to 20% of dipalmitoylphosphatidylcholine (DPPC) in the powder increased the fine particle fraction 4- to 5-fold. X-ray photoelectron spectroscopy and X-ray diffraction revealed that DPPC concentrated at the particle surface with its aliphatic chains laterally packed. The minimal amount of DPPC needed to improve the aerosol performance of temocillin supports the use of this excipient in the formulation of cohesive antibiotic powders for inhalation.

Here, we report on modification of one of the model biomedical polymers, poly L-lactide-co-glycolide (PLGA; 85:15), by reactive ion etching (RIE) oxygen plasma treatment. PLGA's major disadvantage is high hydrophobicity which restrains binding of cell-adhesive proteins and host cells. In the current approach, we aimed to answer two questions: (1) will only short (10 s) and moderate (20-200 mTorr, 45-90 W) RIE oxygen plasma treatment, leading to decrease of water contact angle by only up to 10°, sufficiently improve PLGA adherence to cells, and (2) how will this affect osteoblasts and activation of the immune system? All obtained modified PLGAs had improved hydrophilicity but unaltered roughness (as revealed by water contact angle measurements, X-ray photoelectron spectroscopy, and atomic force microscopy) resulting in significantly improved adhesion of osteoblasts (MG-63) and their low activation. Importantly, macrophages (RAW 264.7), one of the key cells initiating inflammation and bone resorption, responded significantly less vigorously to the modified polymers, expressing/releasing lower amounts of nitric oxide, matrix metalloproteinases (MMP-9), and pro-inflammatory cytokines (TNF-α, IL-6, IL-12p70, IFN-γ, IL-10). We conclude that already slight RIE oxygen plasma modification of PLGA is sufficient to improve its surface properties, and enhance cytocompatibility. Most importantly, this type of modification prevents excessive immune response.

Glass and stainless steel (StSteel, AISI304-2R), previously cleaned with ethanol (-Eth) or with ethanol and UV–Ozone treatment (-UVO), were soiled with quartz suspensions in water and in a β-lactoglobulin (β-LGB) solution, and dried. The cleanability (ease of quartz particle detachment) in water was evaluated using a radial-flow cell. The soiling suspension containing β-LGB was used as such or after heating for 4 h at 75 °C, which provoked coagulation of about 75% of β-LGB. The substrate–solution interfaces were characterized by X-ray photoelectron spectroscopy (XPS) analysis of conditioned substrates and by contact angle measurements. The substrate surfaces are covered by a layer of organic contaminants which are not removed by pre-cleaning or are adsorbed from the surroundings. The presence of β-LGB in the soiling suspension leads to protein adsorption, but a significant amount of contaminants remains at the surface. For three of the substrates tested (Glass-Eth, Glass-UVO, StSteel-UVO) the increase of cleanability when the soiling suspension contained β-LGB may be explained by lower capillary forces acting upon drying. Capillary forces are proportional to the liquid surface tension and depend in a less important way on substrate contact angle. However the order of cleanability observed for the substrates soiled with a suspension of quartz particles in water (Glass-Eth≅Glass-UVO

Hybridization of polyoxometalates (POMs) via an organic-inorganic association constitutes a new route to develop heterogeneous POM catalysts with tunable supramolecular architecture. As the structural stability of POMs is strongly influenced by the pH conditions, a quantitative understanding of the POMs-polymer association is important in practical applications. Herein, we use Quartz Crystal Microbalance (QCM) to systematically investigate the interactions of Keggin phosphotungstic acid POM with a polyampholyte polymer-coated QCM sensor as a function of pH. The mass of adsorbed POMs increases when pH decreases from 5.6 to 2, indicating that electrostatic forces play a major role in the formation of POM-polymer hybrids. This finding is complemented by AFM images that show an increase in the size of the hybrid entities from 5 to 12 nm as the pH decreases from 5.6 to 2. The POM adsorbed amount at a particular pH value reaches an equilibrium level with time. The hybrids further gain in adsorbed mass only when lowering the pH value of the POM solution. The hybrid structure formed above pH 2 shows resistance to leaching as indicated by the steady level of the adsorbed mass during a rinsing step with water. However, at pH 2, the rinsing step causes desorption of some weakly adsorbed POMs. It is shown that leached POMs can be re-adsorbed back into the polymer matrix during a second contact with a POM solution at pH 2. This adsorption-desorption cycles of POMs were successfully repeated. Our experiments shed light into the coexistence of tightly as well as loosely bound POMs in hybrid catalyst formed at pH 2. The loosely bound POMs can potentially act as homogeneous catalysts when desorbed. However, these leached POMs can be re-adsorbed back into the matrix, preserving the heterogeneous state of the catalyst. Our results show that QCM is a powerful technique to study in situ the dynamics of the adsorption of POMs on a polymer matrix under different pH conditions.

Physical adhesion was experimentally determined by measuring contact angles with different liquids on bamboo and glass fibers, using the Wilhelmy technique, and by applying the acid-base theory for calculating the surface energy components and the theoretical work of adhesion. The mechanical strength of the interfaces was assessed by single fibre pull-out tests. In order to consider the real mechanisms of interfacial failure of natural fiber composites, the fibre matrix interfacial bond strength was characterized by the critical local value of interfacial shear stress, τ_d, and the radial normal stress at the interface, σult, at the moment of crack initiation. Both interfacial parameters are used for correlating thermodynamic work of adhesion and practical adhesion. Pull-out tests (taking into account friction), XPS, and profilometry techniques were used to study the influence of rough natural fibre surfaces on the interface between the fibre and a thermoplastic matrix, by comparing the mechanical behaviour at the interface of a smooth optical glass fibre with that of rough natural fibres. The results suggest that the physical and chemical compatibility between the bamboo fibre and the matrix does not improve substantially the composite performance if compared with glass composites. The relatively low off-axis strength of the bamboo fibres is suggested as the main reason for the low stress transfer capability at the fibre-matrix interphase. Furthermore, the pull-out process may be friction-dominated in bamboo fibre systems. ispartof: Composites Science and Technology vol:109 issue:10 pages:40-47 status: published

In this paper, we describe the successful construction, characteristics and interaction with proteins of stimuli-responsive thin nanostructured films prepared by layer-by-layer (LbL) sequential assembly of PNIPAM-containing polyelectrolytes and PAH. PAA-b-PNIPAM block copolymers were synthesized in order to benefit from (i) the ionizable properties of PAA, to be involved in the LbL assembly, and (ii) the sensitivity of PNIPAM to temperature stimulus. The impact of parameters related to the structure and size of the macromolecules (their molecular weight and the relative degree of polymerization of PAA and PNIPAM), and the interaction with proteins under physico-chemical stimuli, such as pH and temperature, are carefully investigated. The incorporation of PAA-b-PNIPAM into multilayered films is shown to be successful whatever the block copolymer used, resulting in slightly thicker films than the corresponding (PAA/PAH)n film. Importantly, the protein adsorption studies demonstrate that it is possible to alter the adsorption behavior of proteins on (PAA-b-PNIPAM/PAH)n surfaces by varying the temperature and/or the pH of the medium, which seems to be intimately related to two key factors: (i) the ability of PNIPAM units to undergo conformational changes and (ii) the structural changes of the film made of weak polyelectrolytes. The simplicity of construction of these PNIPAM block copolymer-based LbL coatings on a large range of substrates, combined with their highly tunable features, make them ideal candidates to be employed for various biomedical applications requiring the control of protein adsorption.

Collagen is a large anisotropic and self-assembling extracellular matrix protein. Understanding and controlling its adsorption and assembly at interfaces is expected to increase our general knowledge of protein adsorption as well as to open the way to the development of biointerfaces of interest for biomaterials science and tissue engineering. The work related to type I collagen adsorption performed in our laboratory over the past twenty years is reviewed. Substrate chemical nature and adsorption conditions (collagen concentration, adsorption duration) were shown to affect collagen adsorbed amount and supramolecular organization. Collagen assemblies were formed starting from the interface, and assembly was favored by hydrophobic substrates and high adsorbed amount. Substrates were designed to better control collagen adsorption and assembly. The spatial control of adsorption was ensured by chemically heterogeneous substrates, which also affected collagen assembly when domains with a dimension smaller than the length of the collagen molecule (i.e. 300nm) were prepared. Mixed polymer brushes were used to achieve a temporal control of adsorption: adsorption and desorption were reversibly triggered by changes of pH and ionic strength. Layer-by-layer assembly of collagen in a nanoporous template was used to elaborate collagen-based nanotubes, which were further deposited on ITO glass substrates by electrophoretic deposition. Finally, the evaluation of cell behavior on the created biointerfaces showed that the control of collagen organization can be successfully used to alter cell behavior.

The goal of the present work was to evaluate in vitro and in vivo the influence of various types and compositions of natural hydrogels on the viability and metabolic activity of SCAPs.Two alginate, three hyaluronic-based (Corgel™) hydrogel formulations and Matrigel were characterized for their mechanical, surface and microstructure properties using rheology, X-ray photoelectron spectroscopy and scanning electron microscopy, respectively. A characterized SCAP cell line (RP89 cells) was encapsulated in the different experimental hydrogel formulations. Cells were cultured in vitro, or implanted in cyclosporine treated mice. In vitro cell viability was evaluated using a Live/Dead assay and in vitro cellular metabolic activity was evaluated with a MTS assay. In vivo cell apoptosis was evaluated by a TUNEL test and RP89 cells were identified by human mitochondria immunostaining.Hydrogel composition influenced their mechanical and surface properties, and their microstructure. In vitro cell viability was above 80% after 2 days but decreased significantly after 7 days (60-40%). Viability at day 7 was the highest in Matrigel (70%) and then in Corgel 1.5 (60%). Metabolic activity increased over time in all the hydrogels, excepted in alginate SLM. SCAPs survived after 1 week in vivo with low apoptosis (1%). The highest number of RP89 cells was found in Corgel 5.5 (140cells/mm(2)).Collectively, these data demonstrate that SCAP viability was directly modulated by hydrogel composition and suggest that a commercially available hyaluronic acid-based formulation might be a suitable delivery vehicle for SCAP-based dental pulp regeneration strategies.

Creating substrates mimicking the extracellular matrix (ECM) is a promising approach to better control cell-material interactions. The aim of this research is to use collagen, a major component of the ECM, to elaborate nanostructured biointerfaces. Different strategies were implemented and are reviewed here. First, chemically patterned substrates were used to confine collagen assembly in given domains. Then, layer-by-layer (LbL) assembly was used to incorporate collagen in thin multilayered films, using assembly with either poly(styrene sulfonate) or fibronectin, another ECM component involved in cell adhesion. Finally, collagen-based nanotubes were synthesized using LbL assembly within the pores of a membrane. Electrophoretic deposition was used to immobilize these nanotubes at the surface of indium-tin oxide-coated glass, and preosteoblast cells were shown to interact with the nanotubes. Taken together, these methods improve our ability to direct collagen adsorption, thereby producing tailored biointerfaces for applications in biomaterials science and tissue engineering.

tSorption of fluids during typical wetting experiments on natural fibers produces a zero receding contactangle situation, leading to an incomplete analysis of their wetting behavior. An acoustic vibration methodwas used to measure “equilibrium” contact angles on natural bamboo fibers. The correctness of the tech-nique is verified by performing the experiment with polyethylene terephthalate (PET) fibers and films,and comparing these results with the average of the cosine functions of the advancing and receding anglesfor a given system. Surface energies and components of the surface energies of bamboo and PET fiberswere estimated using the “equilibrium” contact angle data of various test liquids by using the acid–baseapproach. The results are in general agreement with X-ray photoelectron spectroscopy (XPS) analysis ofthe fiber’s surface. The findings contribute to a better understanding of the complex phenomena occur-ring during wetting of natural fibers and suggest that the contact angle obtained by forcing relaxationthrough acoustic vibration is a reliable method for study the wetting behavior of natural fibers.

Development of microfabrication technologies allowed creating surfaces with subcellular topographic and chemical features, which led to an improved control of cell reaction in contact with biomaterials. More recently, it was discovered that cells were also sensitive to mechanical properties of their substrate. This study aims at evaluating cell behavior in contact with surfaces presenting mechanical cues at the nanometer scale. However, control of the mechanical properties of such surface remains challenging. The adopted strategy consists in creating rigid topographic features prepared by colloidal lithography of 500 nm silica particles on a glass substrate, and covering it with a soft layer of polydimethylsiloxane (PDMS) by spin-coating. X-ray photoelectron spectroscopy analysis shows that the PDMS layer ensures a homogeneous surface chemistry, while spin-coating parameters can be adjusted to obtain a limited topography. Presence of mechanical contrast is confirmed by force–distance measurements obtained by atomic force microscopy. Finally, morphology and proliferation of MC3T3 preosteoblasts cultured during 3 days on the obtained substrates is shown to be influenced by the presence of mechanical heterogeneities at the subcellular level.

Biomolecule adsorption is the first stage of biofouling. The aim of this work was to reduce the adsorption of proteins on stainless steel (SS) and titanium surfaces by modifying them with a poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-PEO triblock copolymer. Anchoring of the central PPO block of the copolymer is known to be favoured by hydrophobic interaction with the substratum. Therefore, the surfaces of metal oxides were first modified by self-assembly of octadecylphosphonic acid. PEO-PPO-PEO preadsorbed on the hydrophobized surfaces of titanium or SS was shown to prevent the adsorption of bovine serum albumin (BSA), fibrinogen and cytochrome C, as monitored by quartz crystal microbalance (QCM). Moreover, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry were used to characterize the surfaces of the SS and titanium after competitive adsorption of PEO-PPO-PEO and BSA. The results show that the adsorption of BSA is well prevented on hydrophobized surfaces, in contrast to the surfaces of native metal oxides.

An integrated physical–chemical–micromechanicalapproach is implemented to investigate the fibre–matrix interfacial compatibility and adhesion of natural coir fibre composites. Wetting measurements of the fibres and the matrices are carried out to obtain their static equilibrium contact angles in various liquids, and these are used to estimate the surface energies comprising of different components. The work of adhesion is calculated for each composite system, accordingly. Also, fibre surface chemistry is examined by X-ray photoelectron spectroscopy (XPS)to have more information about functional groups at the fibre surface, which assists in adeeper understand ing of the interactions at the composite interfaces. Single fibre pull-out tests and transverse three point bending tests are performed on UD composites to measure interfacial shear strength and interfacial tensile strength respectively. The results suggest that the higher interfacial adhesion of coir fibreswith polyvinyliden efluoridecompared with polypropylene can be attributed to higher fibre–matrix physico-chemical interaction corresponding with the work of adhesion. Whilst the improvement of interfacial adhesion for coir fibreswith maleic anhydride grafted polypropylene compared with polypropylene can probably be attributed to achemical adhesion mechanism. In agreement with the interface evaluations, the flexural strength in longitudinal direction of the composites is largely correlated with their interfacial adhesion.

Chitosan (Cs) and hydroxyapatite (Ha) were analysed by X-ray photoelectron spectroscopy (XPS). Phosphorylated Cs microparticles and hybrid Cs/Ha microparticles were prepared and analysed by XPS before and after immersion in a solution 1.5 times more concentrated than a simulated body fluid (SBF). The accuracy of spectrum recording, peak decomposition and peak component assignment was insured by a post-control of charge stabilization, and by the examination of correlations between spectral data guided by stoichiometry and charge balance. The concentration of organic oxygen was determined from the concentrations of the oxidized forms of carbon, allowing a sharper insight into speciation and O 1s peak shape. This indicated that the hydroxide ion of Ha, and hydrogenophosphate if present, give a contribution near 532.4 eV, which overlaps with organic oxygen. As a result of immersion in the 1.5*SBF solution, the formation of CaCO3 and of Ha material occurred. A quantification could be made for the constituents of biomaterial interest, contaminating salts and paraffin oil residues from the microparticle manufacturing process. The uncertainties regarding the nature of the model calcium phosphate used and the best marker for calcium carbonate were addressed by comparing the possible effect on the output, which was facilitated by using ternary composition diagrams. Whatever their formulation, the native microparticles were found to be coated by a thick layer of paraffin oil. The induction of calcium carbonate and phosphate precipitation or the retention of precipitates by the microparticles was favored by the presence of phosphate in the initial formulation either by phosphorylation or by incorporation of Ha.

Systematic experimental results describing the dynamic wetting properties of bamboo fibres were analysed by applying the molecular-kinetic theory of wetting. Results suggest that the bamboo fibre surface represents a well-defined system for wetting analysis. The surface free energy components were calculated according to the acid–base theory. These values were then used to calculate the theoretical work of adhesion, spreading coefficient, wetting tension, and interfacial energy. The wetting behaviour of various thermoplastic matrices (polypropylene, maleic anhydride-grafted polypropylene,polyvinylidene-fluoride, and polyethylene-terephthalate) was characterized. Surface chemical components were identified using XPS. Additionally,transverse 3-point bending tests and single fibre pull-out tests were performed. This integrated physical–chemical–mechanical approach was used to study the effect of adhesion on the mechanical strength of thermoplastic composites reinforced with bamboo,showing that increase in physical adhesion can explain the improved interfacial and longitudinal strength in bamboo polyvinylidene-fluoride (PVDF) composites compared to the other thermoplastic matrices used in this study. Surface energy components of bamboo fibres and PVDF were matched, resulting in an improvement of the physical adhesion.

The influence of moisture content in the environment during manufacture of a novel cobalt-free UP matrix reinforced with flax fibres, on the fibre–matrix adhesion was studied. Flax surface energy was experimentally determined by measuring contact angles on technical fibres, using the Wilhelmy technique and the acid–base theory. The mechanical strength of the interface under different humidity conditions was characterized by the critical local value of interfacial shear stress, τd, at the moment of crack initiation, which was assessed by single-fibre pull-out tests. Differential scanning calorimetry and X-ray photoelectron spectroscopy analysis gave further insight into the topic. The results suggest that the effect of humidity during manufacturing on the composite interface might be limited. However, longitudinal composite strength decreased somewhat for composites produced in humid conditions, showing that there is some detrimental effect of high levels of moisture during cure on the fibre mechanical performance, likely caused by some fibre degradation. ispartof: Composites A, Applied Science and Manufacturing vol:84 pages:209-2015 status: published

The chemical compositions of the surface conditioning layers formed by different types of solutions (from isolated EPS to whole culture media), involving different bacterial strains relevant for biocorrosion were compared, as they may influence the initial step in biofilm formation. Different substrata (polystyrene, glass, steel) were conditioned and analyzed by X-ray photoelectron spectroscopy. Peak decomposition and assignment were validated by correlations between independent spectral data and the ubiquitous presence of organic contaminants on inorganic substrata was taken into account. Proteins or peptides were found to be a major constituent of all conditioning layers and polysaccharides were not present in appreciable concentrations; the proportion of nitrogen which may be due to DNA was lower than 15%. There was no significant difference between the compositions of the adlayers formed from different conditioning solutions, except for the adlayers produced with tightly bound EPS extracted from D. alaskensis.

A growing number of nano-objects such as nanotubes, capsules or beads are being developed for various biological and medical applications. In particular, the use of polymer templates for the synthesis of nanomaterials, using layer-by-layer assembly, has become a method of choice due to its simplicity and versatility in shapes and dimensions. However, chemical characterisation of these nano-objects still remains challenging. Here, we report the use of ToF-SIMS, especially in the imaging mode, for the characterisation of collagen-based nano- and microtubes deposited on surfaces, with a view to applications in biomaterials science. The classical univariate or multivariate Principal Component Analysis (PCA) spectral data treatments do not display any significant differences between the nanotubes with different layer sequences (protein-polymer or polymer-protein). However, the layer sequences are clearly differentiated by the ToF-SIMS images acquired at high lateral resolution (0.3 µm), combined with high mass resolution (m/Δm > 5000 @ 29 m/z), because of the complexity of the protein spectral pattern. These results highlight the importance of imaging for chemical analysis of nanoparticles-coated samples. This study has particular relevance for nanoscale imaging of biointerfaces.

The water-induced surface reorganization of a thin film of a block copolymer [polystyrene-b-poly(ethylene oxide), PS-PEO], was studied by cryogenic X-ray photoelectron spectroscopy (cryo-XPS). Experimental parameters were examined with a view to optimize the analysis. The absence of artifacts due to the low temperature of analysis was checked, and the influence of the procedure used for sample hydration before analysis was investigated. Adequate timing of the different steps of the analysis and temperature program was also established. With this optimized protocol, an important reorganization of the block copolymer was detected, showing more pronounced exposure of the PEO block at the outermost surface in hydrated compared to dry environment. As this type of polymer surface is prone to be used for biomedical applications, an accurate knowledge of the chemical composition of the outermost surface in aqueous environments is crucial. The development of this technique is therefore promising for related systems.

Bamboo fibres recently attracted interest as a sustainable reinforcement fibre in (polymer) composite materials, due to specific mechanical properties which are comparable to glass fibres. To achieve good wetting and adhesion of the bamboo fibre with different polymers, the fibre surface needs to be characterized. The wetting behaviour of technical bamboo fibres is studied experimentally by using the Wilhelmy technique, and the results are modelled using the molecular-kinetic theory. A novel procedure, based on an autoclave treatment, allows stable and reproducible advancing contact angles to be measured. In this way, meaningful information on interfacial interactions can be obtained, allowing improvement of the bamboo-polymer interface. Additionally, for comparison, the wetting behaviour of synthetic poly(ethylene terephthalate) (PET) fibre is studied. This article aims at contributing to a better understanding of the complex phenomena occurring during wetting of natural fibres. The results indicate that the high concentration of lignin on the surface of bamboo fibres is responsible for their wetting properties, whereas typical phenomena affecting wetting experiments on plant fibres can be minimized. (C) 2011 Elsevier B.V. All rights reserved.

Vietnam grown coir fibres have been studied for use in composite materials. In order to understand the fibre-matrix interfacial compatibility, it is necessary to investigate the wetting behaviour and surface chemistry of the fibres. The aim of this paper is to develop a wetting measurement procedure to determine stable and reproducible advancing static contact angles, and estimate the fibre surface energy. Dynamic contact angles are measured using the Wilhelmy technique. The experiments are carried out by considering the effects on the contact angle results of irregular wetted perimeter along the fibre and liquid absorption, which commonly appear with natural fibres. Dynamic wetting of coir fibres is then modelled using the Molecular-kinetic theory from which the advancing static contact angle can be approximated by fitting dynamic data. Besides, advancing static contact angle was determined experimentally using an approach derived from the Wilhelmy technique, in which the relaxation of the liquid meniscus was monitored after stopping the fibre movement. There is a good agreement between advancing static angles from the experimental and modelling method. The fibre surface energy comprising polar and dispersive components is estimated following the Owens/Wendt approach using the advancing static contact angle of various test liquids. The fibre surface chemistry examined by XPS shows a carbon rich surface consisting of waxes and a low proportion of lignin and fatty substances. From the results of the wetting measurements and surface characterisation, the coir fibre surface seems to be hydrophobic.

Plasma enhanced chemical vapor deposition has been tested for the formation of hydrophobic perfluorinated coating on the surface of hydrophilic poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) [poly(HEMA-co-MMA)] substrates, used for the fabrication of intraocular lenses (IOLs). The properties of the dry and hydrated surface modified by two plasma techniques, Radiofrequency (RF) and Microwave (MW), were investigated in parallel by contact angle measurements in the dry and hydrated state, X-ray photoelectron spectroscopy, and atomic force microscopy. The coating stability and hydrophobicity were challenged by swelling and sterilizing the samples in water. Investigation of the optical performances of the modified samples was performed by ultraviolet spectroscopy and diopter measurements. Since materials with biomedical application are considered, the performances of their surface in contact with lens epithelial cells were tested at in vitro conditions, and repulsion was not found to be enhanced upon modification. Generally, the results showed poor stability of the coating and bring in question its covalent grafting to the surface.

Understanding the behavior of enzymes at solid surfaces requires coping with the complexity of the interfaces. Examples are given to illustrate key considerations: (i) influence of the adventitious contamination; the amount of glucose oxidase adsorbed on stainless steel in conditions producing an electrochemical effect is very low compared to the amount of organic contaminants; (ii) structure (multilayered, random) of an adsorbed phase containing an enzyme and other organic constituents (self-assembled monolayer, adventitious contaminants); (iii) competition between proteins for adsorption and influence of the adsorption procedure (simultaneous or sequential) and (iv) reality vs. expectation in enzyme (glucose oxidase) immobilization by tentative covalent grafting. The study of enzyme adsorption in several model systems (catalase on surface-modified carbon blacks, beta-glucosidase on clay at different pHs, beta-glucosidase on sand and surface-modified sand) showed that a strong adsorption, whether by electrostatic or hydrophobic interactions, provokes an extensive deactivation. After adsorption, which is a quick process, the enzyme activity may continue to decrease both in the adsorbed phase and in the solution owing to dynamic processes which involve the adsorbed enzyme and exchanges between the adsorbed phase and the liquid phase. (c) 2008 Elsevier Ltd. All rights reserved.

Given the relevance of principal component analysis (PCA) to the treatment of spectrometric data, we have evaluated potentialities and limitations of such useful statistical approach for the harvesting of information in large sets of X-ray photoelectron spectroscopy (XPS) spectra. Examples allowed highlighting the contribution of PCA to data treatment by comparing the results of this data analysis with those obtained by the usual XPS quantification methods. PCA was shown to improve the identification of chemical shifts of interest and to reveal correlations between peak components. First attempts to use the method led to poor results, which showed mainly the distance between series of samples analyzed at different moments. To weaken the effect of variations of minor interest, a data normalization strategy was developed and tested. A second issue was encountered with spectra suffering of an even slightly inaccurate binding energy scale correction. Indeed, minor shifts of energy channels lead to the PCA being performed on incorrect variables and consequently to misleading information. In order to improve the energy scale correction and to speed up this step of data pretreatment, a data processing method based on PCA was used. Finally, the overlap of different sources of variation was studied. Since the intensity of a given energy channel consists of electrons from several origins, having suffered inelastic collisions (background) or not (peaks), the PCA approach cannot compare them separately, which may lead to confusion or loss of information. By extracting the peaks from the background and considering them as new variables, the effect of the elemental composition could be taken into account in the case of spectra with very different backgrounds. In conclusion, PCA is a very useful diagnostic tool for the interpretation of XPS spectra, but it requires a careful and appropriate data pretreatment.