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Injectable, self-healing hydrogels with enhanced solubilization of hydrophobic drugs are urgently needed for antimicrobial intravaginal therapies. Here, we report the first hydrogel systems constructed of dynamic boronic esters cross-linking unimolecular micelles, which are a reservoir of antifungal hydrophobic drug molecules. The selective hydrophobization of hyperbranched polyglycidol with phenyl units in the core via ester or urethane bonds enabled the solubilization of clotrimazole, a water-insoluble drug of broad antifungal properties. The encapsulation efficiency of clotrimazole increases with the degree of the HbPGL core modification; however, the encapsulation is more favorable in the case of urethane derivatives. In addition, the rate of clotrimazole release was lower from HbPGL hydrophobized via urethane bonds than with ester linkages. In this work, we also revealed that the hydrophobization degree of HbPGL significantly influences the rheological properties of its hydrogels with poly(acrylamide

Supramolecular motifs showing chemoresponsive properties toward organic molecules are sought after. Their selectivity, however, may depend even on a small structural change. Here, we demonstrate th...

An efficient method was developed enabling the synthesis of spheroidal polymer microparticles. Thorough physicochemical characteristics of the particles were acquired comprising the size, shape, electrophoretic mobility, and the diffusion coefficient. The particles were monodisperse, and their shape was well-fitted by prolate spheroids having the axis ratio equal to 4.17. Knowing the diffusion coefficient, their hydrodynamic diameter of 449 nm was calculated, which matched the value derived from Brenner's analytical expression. Particle deposition kinetics on mica and silicon/silica substrates, modified by poly(allylamine hydrochloride) (PAH) adsorption, was studied by optical microscopy and AFM imaging. The validity of the random sequential adsorption model was confirmed. Additionally, monolayers of the particles on these substrates were thoroughly characterized in situ by the streaming potential measurements for different ionic strengths. These measurements confirmed that the ζ potential change with the spheroidal particle coverage is less abrupt than for spheres and agrees with theoretical predictions. Exploiting these results, a useful analytical expression was derived that allows one to calculate the spheroidal particle coverage in situ via the streaming potential measurements. This expression, especially accurate for low coverage range, can be used for a quantitative interpretation of adsorption and desorption kinetics of anisotropic macromolecules, e.g., proteins on solid substrates.

We present biocompatible hydrogel systems suitable for biomineralization processes based on hyperbranched polyglycidol cross-linked with acrylamide copolymer bearing carbonyl-coordinated boronic acid. At neutral pH, diol functional groups of HbPGL react with boronic acid of polyacrylamide to generate 3D network in water by the formation of boronic ester cross-links. The dynamic associative/dissociative characteristics of the cross-links makes the network reversible. The presented hydrogels display self-healing properties and are injectable, facilitating gap filing of bone tissue. The 1H HR MAS DOSY NMR studies reveal that acrylamide copolymer plays the role of the network framework, whereas HbPGL macromolecules, due to their compact structure, move between reactive sites of the copolymer. The influence of the copolymer macromolecules entanglements and overall polymer concentrations on macromolecules mobility and stress relaxation processes is investigated. The process of hydrogel biomineralization results...

Stable three-dimensional colloidal crystals were fabricated in an aqueous suspension of Tris buffer at pH > 8. The basic building blocks of the crystals were submicron-sized polystyrene–polyglycidol core–shell particles (Dn(SEM) = 270 ± 18 nm) with covalently bound 3,4-dihydroxyphenylalanine (l-DOPA). The growth of the crystals was triggered by a thermodynamically favorable arrangement of particles leading to their close packing and by the formation of covalent cross-links between the individual particles. Under alkaline conditions, molecules of l-DOPA are oxidized, which allows their participation in cross-linking, necessary for the stabilization of the formed colloidal crystals. The average size of the fabricated colloidal crystals is determined by their weight, density of the suspending medium, and the energy of their Brownian motion. Crystals generated during the suspension of particles fall down after reaching the critical weight. Therefore, crystals of similar dimensions are deposited at the bottom ...

Solid-state boron nuclear magnetic resonance (11B NMR) and positron annihilation lifetime spectroscopies (PALS) were used to study the molecular structure of self-healing hydrogels based on cross-linked hyperbranched polyglycidol (HbPGL) with borax at basic pH. The lifetime and intensity of orthopositronium allowed characterizing the micro- and nanostucture of hydrogels at various thermal conditions. Stepwise changes in the free volume parameters were found in pure HbPGL as well as in hydrogels based on this polymer. However, the shift in the phase transition temperature suggests that the important properties of the hydrogel arise from the water building these systems. Rheological measurements demonstrated the subsequent reduction of the average cross-link lifetime within the polymer network under heating. Composition of boronic species within hydrogel systems also diverged upon change in temperature range from −10 °C to +70 °C. The reduced fraction of boronic diester upon heating was quantitatively rebui...

Gradient copolymer grafts of styrene and α-tert-butoxy-ω-vinylbenzyl-poly(glycidol ethoxyethyl ether) (PGLet), a precursor of α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (PGL), were prepared on silicon wafers via a surface-initiated activator generated by electron transfer radical polymerization (AGET ATRP). Silicon plates with previously attached 2-bromoisobutyrate served as a macroinitiator for the AGET ATRP (activator generated by electron transfer) of styrene and PGLet. The copolymers' gradient P(S-co-PPGL) of composition and thickness was obtained by a simple method where the plates were slowly removed from reaction mixture using a step motor. PGLet was added continuously (dropwise) into the reactor during withdrawal of the plates from solution in order to increase the relative concentration of PGLet in polymerization mixture. A range of strategies of making grafts was tested. The plates with copolymers grafts were analyzed by various techniques, like XPS, ellipsometry, and FTIR spectroscopy. The results indicate that the AGET ATRP process is dependent on the styrene/PGLet macromonomer ratio in the polymerization mixture. Under optimal conditions, the addition of PGLet during polymerization and subsequent deprotection of hydroxyl groups of PGLet permit to obtain plates with a novel copolymer layer with composition, thickness, and wettability gradient. Plates with chemical composition of copolymer grafts gradient served as versatile supports with controlled hydrophilic/hydrophobic area and were suitable for tailored deposition of particles.