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This work investigated the effect of glyco-regioisomerism of glycopolymers on their dynamic interaction with benzoxaborole-containing polymers. Two kinds of glycopolymers, P-1-Gal and P-6-Gal, i.e. galactoside pendant group linked to the identical main chain through its anomeric (C1) and C6-hydroxyl group position, respectively, were studied. We found that P-6-Gal showed stronger binding strength to the PNIPAM- co-PBOB polymer than P-1-Gal did, which controlled the macroscopic property of the resultant hydrogels at a molecular level. [ABSTRACT FROM AUTHOR]

A biomimetic conical submicrochannel (tip side ca. 400 nm) with functions of continuously tunable ion rectification and conductance based on thermoresponsive polymer layer-by-layer (LbL) self-assembly is presented. These self-assembled polymers with different layers exhibited a capability to regulate the effective channel diameter, and different ion rectifications/conductance were achieved. By controlling temperature, the conformation and wettability of the assembled polymers were reversibly transformed, thus the ion rectification/conductance could be further adjusted subtly. Owing to the synergistic effect, the ion conductance could be tuned over a wide range spanning three orders of magnitude. Moreover, the proposed system can be applied for on-demand on-off molecule delivery, which was important for disease therapy. This study opens a new door for regulating channel size according to actual demand and sensing big targets with different size with one channel., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this work, peptide amphiphile (PA) with benzoboroxole (BOB) group at the hydrophilic end was prepared and assembled into fibers (PAA) with BOB group on the fiber surface. Then glycopolymer with mannopyranoside as pendent group interacted with the PAA via dynamic covalent bond between sugar and BOB. By combining the results from 2D 1 H NMR spectroscopy, the exact binding mode of mannopyranoside pendent group and BOB, i.e., mannopyranoside participated by its diol on 2,3-position instead of that on 4,6-position, which was clearly observed on the fiber surface. The success in determining this binding mode in macroscopic material was due to the high density of BOB on PAA and the multivalent effect between the multiple BOB moieties on fiber surface and repeating mannopyranoside groups of the glycopolymer.

Sugar regioisomerism (glycosidic linkage on different hydroxyl groups of the same sugar) widely exists in various polysaccharides and glycans with a significant contribution to their biological functions. However, the effects of this regioisomersim in glycopolymers and their self-assembled nanoparticles on such functions were almost not investigated previously. In this paper, this regioisomersim effect is studied for self-assembled nanoparticles NP-1-Gal and NP-6-Gal from triblock copolymers carrying different constitutional isomers of the pendent sugar species (1 and 6 denote the glycosidic linkage from the anomeric position and 6 position of the galactose unit, respectively). NP-1-Gal shows strong binding to lectins of Peanut ( Arachis hypogea ) agglutinin (PNA) and Erythrina cristagalli agglutinin (ECA), while NP-6-Gal does not. More importantly, they show binding behavior similar to the asialoglycoprotein receptor (ASGPR) but different internalization pathways in the Hep G2 cell after ASGPR-mediated endocytosis; i.e., NP-1-Gal can reach the early endosome, late endosome, as well as lysosome, while NP-6-Gal enters the early endosome only but not the others.