Molecular Recognition by Pillar[5]arenes: Evidence for Simultaneous Electrostatic and Hydrophobic Interactions

The formation of inclusion complexes between alkylsulfonate guests and a cationic pillar[5]arene receptor in water was investigated by NMR and ITC techniques. The results show the formation of host-guest complexes stabilized by electrostatic interactions and hydrophobic effects with binding constants of up to 107 M−1 for the guest with higher hydrophobic character. Structurally, the alkyl chain of the guest is included in the hydrophobic aromatic cavity of the macrocycle while the sulfonate groups are held in the multicationic portal by ionic interactions.

Molecular Recognition by Pillar[5]arenes: Balance Between Hydrophobic and Electrostatic Interactions

The formation of inclusion complexes between alkylsulfonate guests and a cationic pillar[5]arene receptor in water was investigated by NMR and ITC techniques. The results show the formation of host-guest complexes stabilized by electrostatic interactions and hydrophobics effects with binding constants of up to 107 M-1 for the guest with higher hydrophobic character. Structurally, the alkyl chain of the guest is included in the hydrophobic aromatic cavity of the macrocycle while the sulfonate groups are hold in the multicationic portal by ionic interactions.

The fatty acids based organofunctional silane protective coatings for concrete

The possibility of using free fatty acids for the synthesis of new organofunctional silanes is shown. In nature, fatty acids occur in the form of esters with glycerin (fats) and are widely used for production of soap, oil paints, medicines and cosmetics. Of particular interest in this study was the application of organosilicon derivatives of oleic acid for production of coating that would cover the surface of concrete and protect it from water permeation. As a result of proposed silanization, the concrete surface acquired hydrophobic character with the wetting angles up to 115°, and the concrete absorbability was reduced by up to 93%.

Chitosan Films Incorporated with Exopolysaccharides from Deep Seawater Alteromonas sp.

Two Alteromonas sp. strains isolated from deep seawater were grown to promote the production of exopolysaccharides (EPS, E611 and E805), which were incorporated into chitosan solutions to develop films. The combination of the major marine polysaccharides (chitosan and the isolated bacterial EPS) resulted in the formation of homogenous, transparent, colorless films, suggesting good compatibility between the two components of the film-forming formulation. With regards to optical properties, the films showed low values of gloss, in the range of 5–10 GU, indicating the formation of non-glossy and rough surfaces. In addition to the film surface, both showed hydrophobic character, with water contact angles higher than 100 º, regardless of EPS addition. Among the two EPS under analysis, chitosan films with E805 showed better mechanical performance, leading to resistant, flexible, easy to handle films.

Acetonitrile Synthesis via Ammoxidation: Mo/zeolites Catalysts Screening

Mo/zeolites catalysts were investigated in ethane and ethylene ammoxidation into acetonitrile. The catalysts were prepared either in solid‒solid or liquid‒solid interface after varying different parameters. The stabilization of Mo species upon the exchange is dependent on the hydrophilic/hydrophobic character of the zeolite and the type of Mo precursor. In fact, zeolites with low Si/Al molar ratios should be avoided due to their higher dehydration enthalpy values (Δdehyd.H). On the other hand, the use of MoOCl4, Mo(CO)6 and MoCl3 precursors and zeolites with high Si/Al ratios led to inefficient [Mo7O24]6‒ species and amorphous MoO3 which catalyzes the combustion reaction. Nevertheless, the use of MoCl5, MoO3 and MoO2(C5H7O2)2 led to promising activities. In catalysis, [MoO4]2‒ species are required to activate C2H6 into C2H4, while [MoxO3x+1]2‒ (x =1, 2) species catalyze the ammoniation of C2H4 and the ethylamine dehydrogenation into CH3CN. Interestingly, active catalysts could be obtained by humid impregnation and a simultaneous oxidative treatment. Such a treatment improves the dispersion state of crystalline MoO3, which activate ethane molecules. It is judicious to perform C2H6 oxidative dehydrogenation before ammoxidation since the interference between the different investigated parameters could be noted.

Diazonium Salts: Versatile Molecular Glues for Sticking Conductive Polymers to Flexible Electrodes

Adhesion of polymers to surfaces is of the upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO2H), 4-sulfonicbenzenediazonium (ITO-SO3H), 4-N,N-dimethylbenzenediazonium (ITO-N(CH3)2), 4-aminobenzenediazonium (ITO-NH2), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to all aryl-modified surfaces, whereas adhesive failure was noted for bare ITO following simple solvent washing or sonication. Adhesion of polypyrrole was investigated in terms of hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid-doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers and permit to tune their interfacial properties. With robust, diazonium-based architectured interfaces, one can design high performance materials for e.g., sensors, printed soft electronics and flexible thermoelectrics.

Diazonium Salts: Versatile Molecular Glues for Sticking Conductive Polymers to Flexible Electrodes

Adhesion of polymers to surfaces is of upmost importance in timely applications such as protective coatings, biomaterials, sensors, new power sources and soft electronics. In this context, this work examines the role of molecular interactions in the adhesion of polypyrrole thin films to flexible Indium Tin Oxide (ITO) electrodes grafted with aryl layers from various diazonium salts, namely 4-carboxybenzenediazonium (ITO-CO2H), 4-sulfonicbenzenediazonium (ITO-SO3H), 4-N,N dimethylbenzenediazonium (ITO-N(CH3)2), 4-aminobenzenediazonium (ITO-NH2), 4-cyanobenzenediazonium (ITO-CN) and 4-N-phenylbenzenediazonium (ITO-NHPh). It was demonstrated that PPy thin layers were adherent to these surfaces, whereas adhesion failure was noted on bare ITO, following simple solvent washing or sonication. Adhesion of the polypyrrole was investigated in terms of the hydrophilic/hydrophobic character of the underlying aryl layer as probed by contact angle measurements. It was found that sulfonic acid doped polypyrrole (PPy-BSA) thin films were preferably deposited on the most hydrophobic surfaces. More importantly, the redox properties and electrochemical impedance of PPy were closely related to the hydrophobic character of the aryl layers. This work demonstrates that diazonium compounds are unique molecular glues for conductive polymers, and permit to tune their interfacial properties. With diazonium-based robust, architectured interfaces, one can design high performance materials for e.g.sensors, printed soft electronics and flexible thermoelectrics.