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Imparting hydrophobicity to solid acid catalysts is critical to regulating their performances by allowing the creation of a less polar environment and improved partitioning of the reactants. Here we present different approaches for the preparation of silica-based catalysts comprising sulfonic acid (-SO3H) sites and hydrophobic decyl (-C10) chains by either simultaneous or sequential postfunctionalization of an azide-functionalized mesoporous silica platform. This set of hybrid bifunctional catalysts is compared in the model esterification of octanol with acetic acid, and the influence of the preparation methods together with the resulting site spatial distribution is discussed. In parallel, we show that pairing the two functional groups affords a maximum synergistic effect compared to more traditional mixed catalysts with random distributions of acid and hydrophobic functions.

The temperature-dependence of the volume and surface hydrophilicity of a series of water-swollen dense polymer brushes is measured by contact angle measurements in the captive bubble configuration, by ellipsometry, and by quartz crystal microbalance with dissipation monitoring (QCM-D). Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and poly(di(methoxyethoxy)ethyl methacrylate) (PMEO2MA), strongly hydrophilic poly(N,N-dimethylacrylamide) (PDMA) and poly(oligo(ethylene glycol) methacrylate) (POEGMA), and weakly hydrophilic poly(2-hydroxyethyl methacrylate) (PHEMA) brushes were synthesized by surface-initiated atom-transfer radical polymerization (SI-ATRP). Conditions leading to reproducible measurements of the contact angle are first provided, giving access to the surface hydrophilicity. Volume hydrophilicity is quantified by measuring the swelling of the brushes, either by QCM-D or by ellipsometry. A model-free methodology is proposed to analyze the QCM-D data. Comparison between the acoustic and optical swelling coefficients shows that QCM-D is sensitive to the maximal thickness of swollen brushes, while ellipsometry provides an integral thickness. Diagrams of surface versus volume hydrophilicity of the brushes finally lead to identify two types of behavior: strongly water-swollen brushes exhibit a progressive decrease of volume hydrophilicity with temperature, while surface hydrophilicity changes moderately; weakly water-swollen brushes have a close-to-constant volume hydrophilicity, while surface hydrophilicity decreases with temperature. Thermoresponsive brushes abruptly switch from one behavior to the other, and do not exhibit an abrupt change of surface hydrophilicity across their collapse transition contrarily to a common erroneous belief. In general, there is no direct correlation between surface and volume hydrophilicity, because surface properties are dependent on the details of conformation and composition at the surface, whereas volume properties are averaged over a finite region within the brush.

A wide range of nano-objects are synthesized by combining template synthesis, using polycarbonate membrane as template, with different material deposition methods. The resulting nanostructures varied from robust inorganic gold nanowires grown by electrodeposition to rigid polypyrrole nanotubes synthesized by chemical polymerization and softer nanotubes made of different combinations of synthetic and natural polyelectrolytes fabricated by layer-by-layer (LbL) assembly. The morphology of these various nano-objects is characterized prior to and after their immersion in water, revealing that the rigidity degree of LbL nanotubes strongly decreases after being in contact with water, leading to highly swollen and flexible nanotubes in aqueous solution that tend to stick to any surface and are very difficult to collect and disperse quantitatively in aqueous solution. Different processes to collect these nano-objects and disperse them in aqueous medium for further analysis and application were then studied. Among them, a method based on simple filtration of nanotubes in the presence of a powdered dextran adjuvant leads to the quantitative collection and dispersion in water of all types of tested cylindrical nano-objects. This universal method to efficiently collect membrane templated nano-objects paves the way to further characterization of a large variety of nanotubes in aqueous solution and to their potential use as cargo nanocarriers or as nanoreactors.

The functionalization of poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) polyelectrolyte multilayers by silanes reacted from the gas phase is studied depending on reaction time and temperature, pH of multilayer assembly, and nature of the reacting silane group. Whereas monochlorosilanes only diffuse in the multilayer and graft in limited amount, trichloro- and triethoxysilanes form rapidly a continuous gel layer on the surface of the multilayer, with a thickness of ca. 10-20 nm. The reactivity is lower in the strongly paired regime of the multilayers (neutral assembly conditions) but otherwise is not affected by the pH of multilayer assembly. Silanization considerably broadens the range of possible functionalities for (PAH/PAA) multilayers: hydrophobicity, surface-initiated polymerization, and grafting of fluorescent probes by the formation of disulfide bridges are demonstrated. Conversely, our results also broaden the range of substrates that can be functionalized by silanes, using (PAH/PAA) multilayers as ubiquitous anchoring layers.

Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance.

We compare two routes for creating protein adsorption-resistant self-assembled monolayers (SAMs) by chemical modification of silicon surfaces with poly(ethylene oxide) (PEO) oligomeric derivatives. The first route involves the assembly of 2-methyl[(polyethyleneoxy)propyl]trichlorosilane (Cl3SiMPEO) films onto oxidized silicon surfaces (OH-SiO(x)) either by a liquid-phase process at room temperature or by a gas-phase process at 423 K, producing Si-O-Si bonds between the substrate and the organic layer. The second pathway makes use of the assembly of poly(ethylene glycol methyl ether) (MPEG) films onto hydrogen-passivated silicon surfaces (H-Si) using a liquid-phase process at 353 or 423 K, leading to the formation of Si-O-C bonds between the substrate and the organic layer. Structural investigation by X-ray reflectometry (XRR) reveals that the thickness and surface densities of the grafted PEO monolayers strongly depend on experimental conditions such as temperature and grafting time. Atomic force microscopy (AFM) shows that very smooth and homogeneous monolayers can be obtained with average roughnesses close to those measured on the corresponding bare substrates. Finally, the antifouling properties of the modified silicon surfaces were evaluated by X-ray photoelectron spectroscopy (XPS), using a membrane protein (P.69 antigen) as model protein. Both types of PEO monolayers exhibit excellent protein repellency, as soon as the grafting density is equal to or higher than 1.7 chains/nm2.

The effect of roughness on the dewetting behavior of polyethylene thin films on silicon dioxide substrates is presented. Smooth and rough silicon dioxide substrates of 0.3 and 3.2-3.9 nm root-mean-square roughness were prepared by thermal oxidation of silicon wafers and plasma-enhanced chemical vapor deposition on silicon wafers, respectively. Polymer thin films of approximately 80 nm thickness were deposited by spin-coating on these substrates. Subsequent dewetting and crystallization of the polyethylene were observed by hot-stage optical microscopy in reflection mode. During heating, the polymer films melt and dewet on both substrates. Further observations after cooling indicate that, whereas complete dewetting occurs on the smooth substrate surface, partial dewetting occurs for the polymer film on the rough surface. The average thickness of the residual film on the rough surface was determined by ellipsometry to be a few nanometers, and the spatial distribution of the polymer in the cavities of the rough surface could be obtained by X-ray reflectometry. The residual film originates from the impregnation of the porous surface by the polymer fluid, leading to the observed partial dewetting behavior. This new type of partial dewetting should have important practical consequences, as most real surfaces exhibit significant roughness.

We report on the exchange between a hydrophilic thiol (11-mercapto-1-undecanol) in a liquid or gas phase and a hydrophobic thiol (dodecanethiol) of similar length self-assembled on a polycrystalline gold surface for a wide range of temperatures and times. The molecular composition of the mixed monolayers is determined by the static water contact angle and X-ray photoelectron spectroscopy measurements. Atomic force microscopy in lateral force mode is used to characterize the molecular domains at the nanometer level. The exchange first occurs rapidly at the gold grain boundaries, with an activation energy of about 66 +/- 4 kJ/mol. Then, boundaries of ordered thiol domains are progressively replaced, and the exchange is slowed because only regions of increasing perfection are left untouched. Higher temperatures lead to faster kinetics of replacement and the removal of larger amounts of the original thiol. No significant difference could be detected between exchange occurring in an ethanol solution or in the gas phase, and the initial rate of exchange was found to be similar for the displacement of dodecanethiol by 11-mercapto-1-undecanol molecules and for the converse displacement.

We present a new way to protect polyelectrolyte multilayers from water, consisting in the adsorption and subsequent fusing of charged wax particles atop a multilayer. The formation of the wax layer is demonstrated by different techniques such as ellipsometry, contact angle measurements, and atomic force microscopy. The diffusion of water in protected and unprotected multilayers is studied by in situ neutron reflectometry. Whereas a top layer of wax crystals already allows substantial reduction of the diffusion, the fusion of this top layer leads to the dominating exclusion of water from the multilayers when dipped in water. This method opens up new interesting avenues for polyelectrolyte multilayers in practical applications where permeability of water, ions, or hydrophilic drugs is an issue.

We report on the introduction of small organic hydrophilic molecules (fluorescein, rhodamine B, and two coumarin-based dyes) in multilayers of strong polyelectrolytes, studied by X-ray reflectometry, UV/visible spectroscopy, and fluorescence measurements. Very low diffusion coefficients (about 10(-17) cm(2.)s(-1)) were found for the inward diffusion of fluorescein in preformed multilayers. In addition, diffusion was accompanied by substantial variations of the thickness of the multilayer (up to 300%), ruling out the practical significance of inward diffusion as a tool to dope multilayers. We then attempted to coadsorb the fluorophores simultaneously with the polyions during the construction of the multilayer. However, displacement of small molecules by polyions of identical charge and outward diffusion of the fluorophores during the rinsing step resulted in very limited inclusion of the dye by this procedure. This issue was solved by introducing the fluorophore in all baths, including the rinsing ones. Then, the concentration of the multilayers in dye is directly related to the concentration of the dipping solutions and is dependent on the nature of the dye and of the multilayer. The outward diffusion of the fluorophores from these multilayers was studied, and very low diffusion coefficients were again determined, depending on the net charge of the dye. The ability to load rapidly polyelectrolyte multilayers with a variety of hydrophilic organic molecules of small molar mass, in tunable concentration, is a major outcome of the present study. It offers new opportunities to use these multilayers as templates for the confinement of active molecules in functional devices.

Electrostatically self-assembled (ESA) polyelectrolyte films show in general no internal structure. The use of special polycations, however, namely of lyotropic ionenes, may give rise to highly ordered coatings. In this article, the influence of the charge density of the polyanion, as well as the distribution of the charged groups within this polymer, is examined, using a series of anionic cellulose derivatives. Various techniques were used to study the films' growth and internal structure. Both showed to be affected in particular by the charge density but also by the substitution pattern.

The influence of the charge density of polyelectrolytes on the growth of polyelectrolyte multilayers via layer-by-layer self-assembly from pure aqueous solutions was studied. Multilayers were built from strong polyanions, namely poly(styrenesulfonate) and an exfoliated synthetic hectorite, and cationic copolymers of diallyldimethylammonium chloride (DADMAC) with N-methyl-N-vinylformamide (NMVF) for which the composition and thus the charge density was varied systematically. The analysis of the system {cationic copolymer/poly(styrenesulfonate)} reveals that a critical linear charge density lambda(c) of 0.036 elementary charge/Angstrom of contour length is necessary to obtain stable multilayer growth in pure water. Above lambda(c) the increment of thickness/deposition cycle varies with the linear charge density of the cationic copolymers, in good agreement with current theories of polyelectrolyte solutions. As linear charge density increases, the system passes successively through a charge-dependent "Debye-Huckel" regime and then through a charge-independent "strong-screening" regime where counterion condensation dominates the behavior. Analogous results were obtained for the variation of the basal spacing of internally structured hybrid multilayers {cationic copolymer/hectorite}. However, by contrast with the first system, no critical linear charge density was found for the hybrid system. This is explained by additional, nonelectrostatic interactions between the clay platelets and the formamide fragment.