Benzoxaborole-grafted high molecular weight chitosan from prawn: Synthesis, characterization, target recognition and antibacterial properties.

Boronated polymers are in the focus of dynamic functional materials due to the versatility of the B-O interactions and accessibility of precursors. Polysaccharides are highly biocompatible, and therefore, an attractive platform for anchoring boronic acid groups for further bioconjugation of cis-diol containing molecules. We report for the first time the introduction of benzoxaborole by amidation of the amino groups of chitosan improving solubility and introducing cis-diol recognition at physiological pH. The chemical structures and physical properties of the novel chitosan-benzoxaborole (CS-Bx) as well as two phenylboronic derivatives synthesized for comparison, were characterized by nuclear magnetic resonance (NMR), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic light scattering (DLS), rheology and optical spectroscopic methods. The novel benzoxaborole grafted chitosan was perfectly solubilized in an aqueous buffer at physiological pH, extending the possibilities of boronated materials derived from polysaccharides. The dynamic covalent interaction between boronated chitosan and model affinity ligands, was studied by means of spectroscopy methods. A glycopolymer derived from poly(isobutylene-alt-anhydride) was also synthesized to study the formation of dynamic assemblies with benzoxaborole-grafted chitosan. A first approximation to apply fluorescence microscale thermophoresis for the interactions of the modified polysaccharide is also discussed. Additionally, the activity of CSBx against bacterial adhesion was studied.

Revisiting carboxylic group functionalization of silica sol-gel materials.

The carboxylic chemical group is a ubiquitous moiety present in amino acids, a ligand for transition metals, a colloidal stabilizer, and a weak acidic ion-exchanger in polymeric resins and given this property, it is attractive for responsive materials or nanopore-based gating applications. As the number of uses increases, subtle requirements are imposed on this molecular group when anchored to various platforms for the functioning of an integrated chemical system. In this context, silica stands as an inert and multipurpose platform that enables the anchoring of multiple chemical entities combined through several orthogonal synthesis methods on the interface. Surface chemical modification relies on the use of organoalkoxysilanes that must meet the demand of tuned chemical properties; this, in turn, urges for innovative approaches for having an improved, but simple, organic toolbox. Starting from commonly available molecular precursors, several approaches have emerged: hydrosilylation, click thiol-ene additions, the use of carbodiimides or the reaction between cyclic anhydrides and anchored amines. In this review, we analyze the importance of the COOH groups in the area of materials science and the commercial availability of COOH-based silanes and present new approaches for obtaining COOH-based organoalkoxide precursors. Undoubtedly, this will attract widespread interest for the ultimate design of highly integrated chemical platforms.

Carbohydrate-Derived Polytriazole Nanoparticles Enhance the Anti-Inflammatory Activity of Cilostazol.

Poly(amide-triazole) and poly(ester-triazole) synthesized from d-galactose as a renewable resource were applied for the synthesis of nanoparticles (NPs) by the emulsification/solvent evaporation method. The NPs were characterized as stable, spherical particles, and none of their components, including the stabilizer poly(vinyl alcohol), were cytotoxic for normal rat kidney cells. These NPs proved to be useful for the efficient encapsulation of cilostazol (CLZ), an antiplatelet and vasodilator drug currently used for the treatment of intermittent claudication, which is associated with undesired side-effects. In this context, the nanoencapsulation of CLZ was expected to improve its therapeutic administration. The carbohydrate-derived polymeric NPs were designed taking into account that the triazole rings of the polymer backbone could have attractive interactions with the tetrazole ring of CLZ. The activity of the nanoencapsulated CLZ was measured using a matrix metalloproteinase model in a lipopolysaccharide-induced inflammation system. Interestingly, the encapsulated drug exhibited enhanced anti-inflammatory activity in comparison with the free drug. The results are very promising since the stable, noncytotoxic NP systems efficiently reduced the inflammation response at low CLZ doses. In summary, the NPs were obtained through an innovative methodology that combines a carbohydrate-derived synthetic polymer, designed to interact with the drug, ease of preparation, adequate biological performance, and environmentally friendly production.

Synthesis, characterization and chemical degradation of poly(ester-triazole)s derived from d-galactose.

α-Azide-ω-alkynyl ester monomers were designed and synthesized in order to obtain hydrolytically degradable polymers. The monomers were prepared from d-galactose, as a renewable resource. Environmentally benign azido-alkyne cycloaddition polymerizations were conducted to afford poly(ester-triazole)s, with complete atom economy. Although polymer formation prevailed under optimized polymerization conditions, variable proportions of cyclic oligomer byproducts were detected. The Cu-catalyzed click polymerization led regioselectively to 1,4-disubstituted triazole linkages, while the thermal, metal-free polymerization produced a random distribution of 1,4- and 1,5-disubstituted triazoles in the polymer backbone. The poly(ester-triazole)s exhibited high molecular weights (M w in the range 35-85 kDa). They were soluble in organic solvents but highly insoluble in water, thus removal of the Cu(i) catalyst was simplified. The polymers were stable up to 300 °C, and had T g values in the range 90-100 °C. The materials were hydrolysed under either basic or strong acid conditions, and the degradation products have been characterized.

Self-assembled monolayers of disulfide Cu porphyrins on Au surfaces: adsorption induced reduction and demetalation.

Metalloporphyrin molecules have a wide range of potential applications in diverse technological areas ranging from electronics to optoelectronics, electrochemistry, photophysics, chemical sensors, and catalysis. In particular, self-assembled monolayers of porphyrin molecules have recently attracted considerable interest. In this work we have studied for the first time the self-assembly of a novel Cu deutero porphyrin functionalized with disulfide moieties using electrochemical techniques, UV-vis absorption spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and photoelectron spectroscopies (XPS and UPS). Experimental results indicate that the molecule adsorbs retaining its molecular integrity without forming molecular aggregates via the formation of Au-S covalent bonds. Furthermore, the monolayer consists of a packed array of molecules adsorbed with the plane of the porphyrin molecule at an angle of around 30° with respect to the surface normal. Interestingly, adsorption induces reduction of the Cu center and its consequent removal from the center of the porphyrin ring resulting in porphyrin demetalation. Our results are important in the design of self-assembled monolayers of metallo porphyrins where not only blocking of the metal center by the functional groups that drive the self-assembly should be considered but also possible adsorption induced demetalation with the consequent loss in the properties imparted by the metal center.