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Statistical copolymerization of a monovinyl with a divinylmonomerleads to macroscopic gels, microgels, or soluble branched copolymers,depending on the precise reaction conditions. This approach is widelyused for the manufacture of soft contact lenses and also to preparevarious biomedical hydrogels for the separation and purification ofproteins, DNA, etc. According to Flory–Stockmayer theory, gelationshould occur in such copolymerizations if there is more than 0.50fully reacted divinyl comonomer per primary chain. However, many experimentalstudies indicate significant deviations from this classical theory,which are generally believed to be due to wastage of the divinyl comonomervia intramolecular cyclization. Unfortunately, experimental verificationof this side reaction has proven elusive for the past seven decades.In the present study, we use a disulfide-based cleavable bifunctionalcomonomer to undertake the first experimental quantification of theextent of intramolecular cyclization in nonlinear methacrylic copolymersusing 1H NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Nanogels are nanostructures with dimensions within the nanoscale, composed of crosslinked polymers through their functional groups. Nanogels can display sensitiveness to stimuli, such as pH or temperature. This characteristic has been used in the design of new platforms for the transport and release of active ingredients. Biopolymer‐based nanogels are of great interest due to their biodegradability, biocompatibility, nontoxicity, and among others. In this project, pH‐responsive nanogels are synthesized through a novel methodology, using two polysaccharides classified as safe, biocompatible, and easily accessible materials, i.e., chitosan (CS) and maltodextrin (MD). A reductive amination reaction between CS and partially oxidized MDs allows to synthesized MD/CS nanogels with sizes ranging from 90 ± 5 to 194 ± 40 nm and with a colloidal stability up to 7 weeks. It is found that the variation of nanogels size and charge depends on CS concentration, molecular weight, and pH, as well as on the % oxidation of the MD. As evidence of nanogels pH‐responsiveness, an increase of size and ζ‐potential is observed by decreasing the pH. This size increase is attributed to the swelling of the nanogels upon a change in pH. Finally, doxorubicin is encapsulated in MD/CS nanogels, with a loading capacity up to 57%. [ABSTRACT FROM AUTHOR]

Abstract Polyelectrolyte complexes formed between DNA and chitosan present different and interesting physicochemical properties combined with high biocompatibility; they are very useful for biomedical applications. DNA in its double helical structure is a semi-rigid polyelectrolyte chain. Chitosan, an abundant polysaccharide in nature, is considered as one of the most attractive vectors due to its biocompatibility and biodegradability. Here we study chitosan/DNA polyelectrolyte complex formation mechanism and the key factors of their stability. Compaction process of DNA with chitosan was monitored in terms of the ζ-potential and hydrodynamic radius variation as a function of charge ratios between chitosan and DNA. The influence of chitosan degree of acetylation (DA) and its molecular weight on the stoichiometry of chitosan/DNA complexes characteristics was also studied. It is shown that the isoelectric point of chitosan/DNA complexes, as well as their stability, is directly related to the degree of protonation of chitosan (depending on pH), to the DA and to the external salt concentration. It is demonstrated that DNA compaction process corresponds to an all or nothing like-process. Finally, since an important factor in cell travelling is the buffering effect of the vector used, we demonstrated the essential role of free chitosan on the proton-sponge effect. [ABSTRACT FROM AUTHOR]

Polysaccharide-based nanogels offer a wide range of chemical compositions and are of great interest due to their biodegradability, biocompatibility, non-toxicity, and their ability to display pH, temperature, or enzymatic response. In this work, we synthesized monodisperse and tunable pH-sensitive nanogels by crosslinking, through reductive amination, chitosan and partially oxidized maltodextrins, by keeping the concentration of chitosan close to its overlap concentration, i.e. in the dilute and semi-dilute regime. The chitosan/maltodextrin nanogels presented sizes ranging from 63 ± 9 to 279 ± 16 nm, showed quasi-spherical and cauliflower-like morphology, reached a ζ-potential of +36 ± 2 mV and maintained a colloidal stability for up to 7 weeks. It was found that the size and surface charge of nanogels depended both on the oxidation degree of maltodextrins and chitosan concentration, as well as on its degree of acetylation and protonation, the latter tuned by pH. The pH-responsiveness of the nanogels was evidenced by an increased size, owed to swelling, and ζ-potential when pH was lowered. Finally, maltodextrin-chitosan biocompatible nanogels were assessed by cell viability assay performed using the HEK293T cell line. [ABSTRACT FROM AUTHOR]

Redox-cleavable mikto-arm star polymers are prepared by an 'arm-first' approach involving copolymerization of a dimethacrylate mediated by a mixture of macroRAFT agents. Thus, RAFT copolymerization of the monomers BMA, DMAEMA, and OEGMA, with the disulfide dimethacrylate cross-linker (DSDMA), bis(2-methacryloyl)oxyethyl disulfide, mediated by a 1:1:1 mixture of three macroRAFT agents with markedly different properties [hydrophilic, poly[oligo(ethylene glycol) methacrylate]-P(OEGMA)8-9; cationizable, poly[2-(dimethylamino)ethyl methacrylate]-P(DMAEMA); hydrophobic, poly( n-butyl methacrylate)-P(BMA)] provides low dispersity mikto-arm star polymers. Good control ( Đ < 1.3) is observed for the target P(DMAEMA)/P(OEGMA)/P(BMA) (3:3:1) mikto-arm star, a double hydrophilic P(DMAEMA)/P(OEGMA) (3:3) mikto-arm star and a hydrophobic P(BMA) homo-arm star. However, Đ for the target mikto-arm stars increases with an increase in either the ratio [DSDMA]:[total macroRAFT] or the fraction of hydrophobic P(BMA) macroRAFT agent. The quaternized mikto-arm star in dilute aqueous solution shows a monomodal particle size distribution and an average size of ≈145 nm. [ABSTRACT FROM AUTHOR]