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In view of intrinsic challenges encountered in surface patterning on actual biomaterials such as the ones based on biodegradable polymers, we have demonstrated an innovative strategy to create micro-patterns on the surface of tartaric acid based aliphatic polyester P (poly(hexamethylene 2,3--isoprpylidentartarate)) without significant loss of its molecular weight. Around 10 wt% PAG (photoacid generator, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine) was purposefully encapsulated in a polyester matrix comprising of P and PLA (polylactide) at a ratio of 5 : 95. With the help of a photomask, selective areas of the matrix were exposed to UV radiation at 395 nm for 25 min to trigger the acid release from PAG entrapped unmasked areas for generating hydroxyl functionality that was later converted to an ATRP (atom transfer radical polymerization) initiating moiety on the irradiated domain of P. In subsequent steps, spatio-selective surface modification by surface initiated ATRP was carried out to generate an alternate pattern of polyPEGMA (poly(ethylene glycol)methyl ether methacrylate) and polyDMAPS (poly(3-dimethyl-(methacryloyloxyethyl)ammonium propane sulfonate)) brushes on the matrix. The patterned surface modified with dual brushes was found to be antifouling in nature (rejection of >97% of proteins). Strikingly, an alternate pattern of live bacterial cells ( and ) was evident and a relatively high population of bacteria was found on the polyPEGMA brush modified domain. However, a complete reverse pattern was visible in the case of L929 mouse fibroblast cells, , cells were found to predominantly adhere to and proliferate on the zwitterionic brush modified surface. An attempt was made to discuss a plausible mechanism of selective cell adhesion on the zwitterionic brush domain. This novel strategy employed on the biodegradable polymer surface provides an easy and straightforward way to micro-pattern various cells, bacteria, on biodegradable substrates which hold great potential to function as biochips, diagnostics, bacteria/cell microarrays,
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http://dx.doi.org/10.1039/d2tb01477g | DOI Listing |
Chemistry
September 2025
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Sequence-controlled polyester-based alternating copolymers have attracted significant interest due to their biocompatibility, biodegradability, closed-loop recyclability, and hydrolytic degradability, offering broad potential in biomedical and sustainable materials. Among the available strategies, regioselective ring-opening polymerization (ROP) of asymmetric cyclic di(thio)esters and cyclic(ester-amide)s has emerged as a promising approach for constructing alternating copolymers with precise sequence- and stereo-control, structural diversity, and tunable properties. This review classifies asymmetric cyclic monomers into two categories: (1) monomers with two aliphatic ester bonds, where regioselectivity is mainly dictated by steric differences and typically requires tailored metal catalysts; and (2) monomers with chemically distinct reactive sites (e.
View Article and Find Full Text PDFCatal Sci Technol
September 2025
EaStCHEM School of Chemistry, University of Edinburgh EH9 3FJ UK
The ring-opening polymerisation (ROP) of lactide (LA) is an attractive route to produce aliphatic polyesters, with bimetallic catalysts displaying some of the highest catalyst activities to date. While a range of heterometallic catalysts have been reported to outperform their homometallic analogues, the origins of cooperativity are not always well understood. Previous studies indicate that the reaction pathways may differ for different metal heterocombinations, especially when an alkali metal is combined with zinc or aluminium.
View Article and Find Full Text PDFBiomacromolecules
September 2025
Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan.
Biobased polyesters, recyclable sustainable polymers derived from renewable feedstock, are promising alternatives to petroleum-based polymers. The crystallization behavior, crystal structure, and supramolecular structures of a series of biobased long-chain aliphatic polyesters, consisting of a diester of 10-undecenoic acid with isosorbide (IS), isomannide (IM), and butanediol (BD) as the midsegments, were studied by various scattering methods and Raman spectroscopy. Polyesters containing butanediol-type midsegments (CBD) participated in the crystallization by being incorporated into the orthorhombic polyethylene crystal lamellae.
View Article and Find Full Text PDFMaterials (Basel)
August 2025
Department of Mechanics and Applied Computer Science, Faculty of Mechanical Engineering, Bialystok University of Technology, 45C Wiejska St, 15-351 Bialystok, Poland.
Novel polyester-polyurethane polymeric materials were formulated by combining a natural aliphatic polyester, poly(3-hydroxybutyrate) (P3HB), with a synthetic aliphatic polyurethane via melt blending. The resulting fully biodegradable compositions were functionally modified through the incorporation of urea, with the aim of enabling post-consumer utilization of the material residues as nitrogen-rich fertilizers. The fabrication process was systematically established and optimized, focusing on homogeneous blending and processability.
View Article and Find Full Text PDFBioresour Technol
August 2025
BOKU University, Institute of Environmental Biotechnology, Department of Agricultural Sciences, Tulln an Der Donau, Austria. Electronic address:
This study investigates enzymatic hydrolysis of four novel polyesters (REPolymers) with different structures based on terephthalic acid, ethylene glycol, glutaric acid, and decanediol. These polyesters were synthesized from PET building blocks and bio-based monomers. A hydrolase from Rhizobacter sp.
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