Metal-Free Organocatalyzed Atom Transfer Radical Polymerization: Synthesis, Applications, and Future Perspectives.

Reversible deactivation radical polymerization (RDRP) is a class of powerful techniques capable of synthesizing polymers with a well-defined structure, properties, and functionalities. Among the available RDRPs, ATRP is the most investigated. However, the necessity of a metal catalyst represents a drawback and limits its use for some applications. O-ATRP emerged as an alternative to traditional ATRP that uses organic compounds that catalyze polymerization under light irradiation instead of metal. The friendly nature and the robustness of O-ATRP allow its use in the synthesis of tailorable advanced materials with unique properties. In this review, the fundamental aspects of the reductive and oxidative quenching mechanism of O-ATRP are provided, as well as insights into each component and its role in the reaction. Besides, the breakthrough recent studies that applied O-ATRP for the synthesis of functional materials are presented, which illustrate the significant potential and impact of this technique across diverse fields.

Synthesis of thermally and pH-responsive poly(2-(dimethylamino)ethyl methacrylate)-based hydrogel reinforced with cellulose nanocrystals for sustained drug release.

Hydrogels are widely employed in biomedical applications due to their high swelling potential, tailored mechanical properties, biocompatibility, and ability to incorporate drugs to modify their release behavior. This study explored the synthesis of dual stimuli-responsive composite hydrogels by combining poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) with 4, 8, and 12 % (w/w) of cellulose nanocrystals (CNC) through in-situ free-radical polymerization, modifying their properties for topical anti-inflammatory release. Although PDMAEMA-based hydrogels have been known for their responsiveness to pH and temperature stimuli, which are useful for modulating the release profile of drugs, their use as a matrix for anti-inflammatory topical applications remains unexplored. Thus, a comprehensive analysis of CNC concentration's impact on PDMAEMA-based hydrogel structure and physicochemical properties is provided. The incorporation of ibuprofen as an anti-inflammatory model was assessed, providing insights into the potential of these composite hydrogels for sustained drug delivery applications. Overall, the hydrogels exhibited homogenous CNC dispersion, with gel fraction higher than 70 % and ibuprofen load higher than 90 %. The rise in CNC concentration led to an increase hydrogel stiffness. Finally, the CNC incorporation also modified the ibuprofen release to a more sustained profile, following the Peppas-Sahlin model, which may be attractive for developing pharmaceutical devices for different therapeutical scenarios.

A review of starch-based biocomposites reinforced with plant fibers.

Renewable and biodegradable resources have gained increasing attention as promising alternatives to synthetic plastics. Among the diverse raw materials employed in bioplastics production, starch emerges as an attractive, low-cost, and largely available source. However, the inherent properties of starch-based materials often limit their utility across various applications, necessitating strategic modifications to enhance their performance. A common approach to boost these materials involves incorporating natural fillers into biopolymer matrices. Incorporating natural fibers within starch matrices enables the development of biocomposites with improved properties while retaining their renewable and biodegradable characteristics. This review briefly addresses fundamental aspects of starch structure, obtention, and processing, as well as the main pre-treatments of natural fibers and processing methods currently applied to produce starch-based composites. It also highlights the most recent advances in this field, elucidates the effect of the incorporation of fibers on the biocomposite properties, and discusses the critical parameters affecting the synergic combination between starch and fibers.