Easy orientation of diblock copolymers on self-assembled monolayers using UV irradiation

A simple method based on UV/ozone treatment is proposed to control the surface energy of dense grafted silane layers for orientating block copolymer mesophases. Our method allows one to tune the surface energy down to a fraction of a mN/m. We show that related to the surface, perpendicular orientation of a lamellar phase of a PS-PMMA diblock copolymer (neutral surface) is obtained for a critical surface energy of 23.9-25.7 mN/m. Perpendicular cylinders are obtained for 24.6 mN/m and parallel cylinders for 26.8 mN/m.Comment: 3 figures, 1 tabl

Organization of Block Copolymers using NanoImprint Lithography: Comparison of Theory and Experiments

We present NanoImprint lithography experiments and modeling of thin films of block copolymers (BCP). The NanoImprint lithography is used to align perpendicularly lamellar phases, over distances much larger than the natural lamellar periodicity. The modeling relies on self-consistent field calculations done in two- and three-dimensions. We get a good agreement with the NanoImprint lithography setups. We find that, at thermodynamical equilibrium, the ordered BCP lamellae are much better aligned than when the films are deposited on uniform planar surfaces

Investigation of an Allergen Adsorption on Amine- and Acid-Terminated Thiol Layers: Influence on Their Affinity to Specific Antibodies

This work describes the controlled immobilization of a recognized allergen, beta-lactoglobulin, onto gold transducers with the aim of optimizing the elaboration of a biosensor directed against allergen-produced antibodies. This protein was immobilized on both amine- and acid-terminated thiol self-assembled monolayers, and the influence on its affinity to a specific IgG was investigated. For amine-terminated layers, the β-lactoglobulin was immobilized via its surface acid functions implying an activation step with 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride/ester of N-hydroxysuccinimide (EDC-NHS). Conversely, the grafting on acid-terminated layer takes advantage of the accessible amine groups that react with the activated acidalkylthiols. The resulting layers of β-lactoglobulin were then submitted to various concentrations of rabbit serum containing β-lactoglobulin specific rabbit immunoglobulin (rIgG), and the antigen/antibody affinity was evaluated using modulated polarization-infrared absorption spectroscopy (PM-IRRAS) and Fourier transform surface plasmon resonance (FT-SPR). Even though for similar concentration, the amount of adsorbed β-lactoglobulin was identical on both surfaces, atomic force microscopy (AFM) images showed a better dispersion for amine-terminated layers. Moreover, the affinity to specific IgG, estimated under static conditions by PM-IRRAS and under dynamic conditions by SPR, was different. Grafting β-lactoglobulin via its acid groups gave an affinity constant 3 times higher than its immobilization via its amine groups despite the fact that the amount of accessible recognition sites appeared to be similar for both systems. This work underlines the importance of the involved chemical groups upon protein immobilization on their biological activity and will be essential for the construction of nondirect biosensors for detecting specific immunoglobulin E (IgE) of allergens

Two Methods for One-Point Anchoring of a Linear Polysaccharide on a Gold Surface

Two strategies to achieve a one-point anchoring of a hydrolyzed pullulan (P9000) on a gold surface are compared. The first strategy consists of forming a self-assembled monolayer of a 6-amino-1-hexanethiol (AHT) and then achieving reductive amination on the surface between the aminated surface and the aldehyde of the polysaccharide reductive end sugar. The second consists of incorporating a thiol function at the extremity of the pullulan (via the same reductive amination), leading to P9000-AHT and then immobilizing it on gold by a spontaneous reaction between solid gold and thiol. The modified pullulan was characterized by NMR and size-exclusion chromatography coupled to a light-scattering detector. P9000-AHT appears to be in a disulfide dimer form in solution but recovers its unimer form with dithiothreitol (DTT) treatment. The comparison of the two strategies by contact angle and XPS revealed that the second strategy is more efficient for the pullulan one-point anchoring. P9000-AHT even in its dimer form is easily grafted onto the surface. The grafted polymer seems to be more in a coil conformation than in a rigid brush. Furthermore, QCM measurements highlighted that the second strategy leads to a grafting density of around 3.5 × 10¹³ molecules·cm^–2 corresponding to a high surface coverage. The elaboration of a dense and oriented layer of polysaccharides covalently linked to a gold surface might enhance the use of such modified polysaccharides in various fields

Iron and Sulfur Secondary Phases as Proxies of Aqueous Alteration on Chondrite Parent Bodies

Hydrated phases encountered in meteorites are considered as clues of the earliest interactions between their primary components and water in the solar system. We ran hydrothermal experiments associated with thermochemical modeling to constrain the alteration processes, especially the reaction pathways toward hydrated phases on the parent body­(ies) from which the primitive meteorites (chondrites) come from. These parent bodies first accreted rocks and ices. We focused on the early stage after ice melting at moderate temperature and low oxygen fugacity to mimic the alteration conditions present on the CM parent body. Synthetic chondritic mixtures made of olivine (Fo 90), GEMS-like material, pyrite, and α-iron were reacted at T = 80 °C for a time period of 128 days at a water–rock mass ratio of 10. Three kinds of solutions were used in order to investigate the interactions between mineral phases and H2O, NH3, or CO2 ices, respectively. According to scanning electron microscopy (SEM) observations, Raman, X-ray photoelectron spectroscopy (XPS), and X-ray characterizations, secondary phases formed were, respectively, spinel iron oxide, magnetite, magnesium silicate hydroxide, and iron sulfide in the case of saline solution and goethite, sulfur, and ferrotochilinite ± dolomite in the case of ammonia or carbonate solution. Thermochemical calculations, validated by experiments, simulated this complex natural history. These findings help to unravel the pathways of the alteration processes in CM chondrites

Bismuth Nanoparticles Supported on Biobased Chitosan as Sustainable Catalysts for the Selective Hydrogenation of Nitroarenes

The use of chitosan as a support in the field of catalysis has gained tremendous interest because of its abundance and sustainability. We herein disclose a straightforward strategy to trap and stabilize bismuth nanoparticles (BiNPs) on chitosan biopolymer Bi@CS and their use for catalytic applications. Bi@CS was configured as micrometer-thick films, porous beads, and native powders analyzed and next used for the controlled and selective reduction of nitroaromatic compounds to their corresponding anilines and azoarenes, respectively, by varying the concentration medium in reducing NaBH4. A regioselective mechanism has been suggested. Powder nanocomposites CSp-BiNPs exhibited high catalytic capacity, and 10 corresponding anilines and 15 azoarenes were obtained with very high yields. The reductions were achieved under mild and sustainable reaction conditions (water solvent and room temperature) with easy processing and 12 recovery cycles. Shaped catalysts were easily recovered by simple filtration. This catalyst, derived from nontoxic and affordable bismuth metal supported on chitosan ocean waste, presents significant improvements in the realm of sustainable chemistry and could open a new channel of possibilities for green catalysis