Vanillin crosslinked 3D porous chitosan hydrogel for biomedicine applications: Preparation and characterization.

Crosslinked chitosan (CS) is one of the most useable hydrogels in biomedicine and tissue engineering. Unlike most chitosan crosslinkers that are toxic, such as glutaraldehyde, vanillin is a natural, biocompatible, and antimicrobial alternative. The crosslinking of chitosan and vanillin consists of Schiff base bonds between the amines of chitosan and the aldehydes of vanillin, in addition to hydrogen bonds formed across the network. In most studies, the combination of chitosan and vanillin has been investigated in small sizes (micro/nanoscale and biofilms). In this study, a chitosan-vanillin (CV) hydrogel was studied on a macroscale with a three-dimensional porous structure, and it was compared with chitosan crosslinked with glutaraldehyde (CG) on the same scale. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (FE-SEM) used to identify the bonds formed and examine the morphology of the hydrogels. The gel content, swelling, porosity, mechanical properties, cell viability (on L929 and mesenchymal cells), and antibacterial activity (against Escherichia coli and Staphylococcus aureus) of the samples were investigated. The results showed that the CV had both gel content and high porosity (>90%), with an interconnected porous network of uniform pore size. The CV hydrogel exhibited good antibacterial activity and cell viability. In terms of mechanical properties, CV has weaker mechanical properties compared to CG in the dry state, while the mechanical properties of CV have more improved in the swollen state compared to CG.

Solvent-controlled formation of alkali and alkali-earth-secured cucurbituril/guest trimers.

Cucurbit[7]uril (CB[7]) encapsulates adamantyl and trimethylsilyl substituents of positively charged guests in dimethyl sulfoxide (DMSO). Unlike in water or deuterium oxide, addition of a selection of alkali and alkali-earth cations with van der Waals radii between 1.0 and 1.4 Å (Na+, K+, Ca2+, Sr2+, Ba2+ and Eu3+) to the CB[7]/guest complexes triggers their cation-mediated trimerization, a process that is very slow on the nuclear magnetic resonance (NMR) time scale. Smaller (Li+, Mg2+) or larger cations (Rb+, Cs+ or NH4+) are inert. The trimers display extensive CH-O interactions between the equatorial and pseudo-equatorial hydrogens of CB[7] and the carbonyl rim of the neighboring CB[7] unit in the trimer, and a deeply nested cation between the three interacting carbonylated CB[7] rims; a counteranion is likely perched in the shallow cavity formed by the three outer walls of CB[7] in the trimer. Remarkably, a guest must occupy the cavity of CB[7] for trimerization to take place. Using a combination of semi-empirical and density functional theory techniques in conjunction with continuum solvation models, we showed that trimerization is favored in DMSO, and not in water, because the penalty for the partial desolvation of three of the six CB[7] portals upon aggregation into a trimer is less unfavorable in DMSO compared to water.

Atomically precise control of rotational dynamics in charged rare-earth complexes on a metal surface.

Complexes containing rare-earth ions attract great attention for their technological applications ranging from spintronic devices to quantum information science. While charged rare-earth coordination complexes are ubiquitous in solution, they are challenging to form on materials surfaces that would allow investigations for potential solid-state applications. Here we report formation and atomically precise manipulation of rare-earth complexes on a gold surface. Although they are composed of multiple units held together by electrostatic interactions, the entire complex rotates as a single unit when electrical energy is supplied from a scanning tunneling microscope tip. Despite the hexagonal symmetry of the gold surface, a counterion at the side of the complex guides precise three-fold rotations and 100% control of their rotational directions is achieved using a negative electric field from the scanning probe tip. This work demonstrates that counterions can be used to control dynamics of rare-earth complexes on materials surfaces for quantum and nanomechanical applications.