In situ photopolymerized hydrogel dressings create minimally invasive methods that offer advantages over the use of preformed dressings such as conformability in any wound bed, convenience of application, and improved patient compliance and comfort. Here, we report an in situ-formed hydrogel membrane through ultraviolet cross-linking of a photocross-linkable azidobenzoic hydroxypropyl chitosan aqueous solution. The hydrogel membrane is stable, flexible, and transparent, with a bulk network structure of smoothness, integrity, and density. Fluid uptake ability, water vapor transmission rate, water retention, and bioadhesion of the thus resulted hydrogel membranes (0.1 mm thick) were determined to range from 97.0–96.3%, 2,934–2,561 g/m2/day, 36.69–22.94% (after 6 days), and 4.8–12.3 N/cm2, respectively. These data indicate that the hydrogel membrane can maintain a long period of moist environment over the wound bed for enhancing reepithelialization. Specifically, these properties of the hydrogel membrane were controllable to some extent, by adjusting the substitution degree of the photoreactive azide groups. The hydrogel membrane also exhibited barrier function, as it was impermeable to bacteria but permeable to oxygen. In vitro experiments using two major skin cell types (dermal fibroblast and epidermal keratinocyte) revealed the hydrogel membrane have neither cytotoxicity nor an effect on cell proliferation. Taken together, the in situ photocross-linked azidobenzoic hydroxypropyl chitosan hydrogel membrane has a great potential in the management of wound healing and skin burn.
A gold nanoparticle (AuNP)-based colorimetric method was developed for the molecular weight (MW) determination of polyethylene glycol (PEG), a commonly used hydrophilic polymer. Addition of a salt solution to PEG-coated AuNP solutions helps in screening the electrostatic repulsion between nanoparticles and generating a color change of the solutions from wine red to blue in 10 min in accordance with the MW of PEG, which illustrates the different stability degrees (SDs) of the AuNPs. The SDs are calculated by the absorbance ratios of the stable to the aggregated AuNPs in the solution. The root mean square end-to-end length (〈h2〉1/2) of PEG molecules shows a linear fit to the SDs of the PEG-coated AuNPs in a range of 1.938 ± 0.156 to 10.151 ± 0.176 nm. According to the Derjaguin-Landau-Verwey-Overbeek theory, the reason for this linear relationship is that the thickness of the PEG adlayer is roughly equivalent to the 〈h2〉1/2 of the PEG molecules in solution, which determines the SDs of the AuNPs. Subsequently, the MW of the PEG can be obtained from its 〈h2〉1/2 using a mathematical relationship between 〈h2〉1/2 and MW of PEG molecule. Applying this approach, we determined the 〈h2〉1/2 and the MW of four PEG samples according to their absorbance values from the ordinary ultraviolet–visible spectrophotometric measurements. Therefore, the MW of PEG can be distinguished straightforwardly by visual inspection and determined by spectrophotometry. This novel approach is simple, rapid, and sensitive.
We prepared two types of cholesterol hydrophobically modified pullulan nanoparticles (CHP) and carboxyethyl hydrophobically modified pullulan nanoparticles (CHCP) substituted with various degrees of cholesterol, including 3.11, 6.03, 6.91 and 3.46 per polymer, and named CHP−3.11, CHP−6.03, CHP−6.91 and CHCP−3.46. Dynamic laser light scattering (DLS) showed that the pullulan nanoparticles were 80–120 nm depending on the degree of cholesterol substitution. The mean size of CHCP nanoparticles was about 160 nm, with zeta potential −19.9 mV, larger than CHP because of the carboxyethyl group. A greater degree of cholesterol substitution conferred greater nanoparticle hydrophobicity. Drug-loading efficiency depended on nanoparticle hydrophobicity, that is, nanoparticles with the greatest degree of cholesterol substitution (6.91) showed the most drug encapsulation efficiency (90.2%). The amount of drug loading increased and that of drug release decreased with enhanced nanoparticle hydrophobicity. Nanoparticle surface-negative charge disturbed the amount of drug loading and drug release, for an opposite effect relative to nanoparticle hydrophobicity. The drug release in pullulan nanoparticles was higher pH 4.0 than pH 6.8 media. However, the changed drug release amount was not larger for negative-surface nanoparticles than CHP nanoparticles in the acid release media. Drug release of pullulan nanoparticles was further slowed with human serum albumin complexation and was little affected by nanoparticle hydrophobicity and surface negative charge.