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We have previously reported that sequence-controlled copolyesters such as poly((ethylene diglycolate) terephthalate) (poly(GEGT)) showed higher melting temperatures than those of the corresponding random copolymers and high biodegradability in seawater. In this study, to elucidate the effect of the diol component on their properties, a series of new sequence-controlled copolyesters composed of glycolic acid, 1,4-butanediol or 1,3-propanediol, and dicarboxylic acid units was studied. 1,4-Butylene diglycolate (GBG) and 1,3-trimethylene diglycolate (GPG) were prepared by the reactions of 1,4-dibromobutane or 1,3-dibromopropane with potassium glycolate, respectively. Polycondensation of GBG or GPG with various dicarboxylic acid chlorides produced a series of copolyesters. Terephthalic acid, 2,5-furandicarboxylic acid, and adipic acid were used as the dicarboxylic acid units. Among the copolyesters bearing terephthalate or 2,5-furandicarboxylate units, the melting temperatures (Tm) of the copolyesters containing 1,4-butanediol or 1,2-ethanediol units were substantially higher than those of the copolyester containing the 1,3-propanediol unit. Poly((1,4-butylene diglycolate) 2,5-furandicarboxylate) (poly(GBGF)) showed a Tm at 90 °C, while the corresponding random copolymer was reported to be amorphous. The glass-transition temperatures of the copolyesters decreased as the carbon number of the diol component increased. Poly(GBGF) was found to show higher biodegradability in seawater than that of poly(butylene 2,5-furandicarboxylate) (PBF). On the other hand, the hydrolysis of poly(GBGF) was suppressed in comparison with that of poly(glycolic acid). Thus, these sequence-controlled copolyesters have both improved biodegradability compared to PBF and lower hydrolyzability than PGA. [ABSTRACT FROM AUTHOR]

Abstract: Copolyesteramides of 2-pyrrolidone with ε-caprolactone were synthesized by ring-opening copolymerization. The copolymers were random-like and their melting temperature and heat of fusion were dependent on the polymer composition. Biodegradation by a polyamide 4 (PA4) degrading microorganism showed rapid degradation in the region of amide-rich polymer composition. On the contrary, enzymatic hydrolysis using a lipase resulted in a different tendency, that is, ester-rich copolymers hydrolyzed rapidly. Activated sludge makes copolymers degrade to CO2 in wide polymer composition ratio. Copolyesteramides are expected to be applied as an environmentally-friendly plastics or bioabsorbable polymers in medical fields. [Copyright &y& Elsevier]

Abstract: Copolyesters of poly(ε-caprolactone) diol and 1,18-octadecane dicarboxylic acid were synthesized by polyaddition. The copolymers have a "mixed" structure of ’polyester-polyethylene’. Characterization was carried out by using 1H and 13C NMR, FT-IR, viscosities, DSC, and GPC. The tensile strength varied from 11.9 to 19.9 MPa, and elongation at break varied from 370 to 660 %, respectively. Biodegradability was evaluated by enzymatic hydrolysis (lipases from Rhizopus arrhizus and Candida cylindracea and an esterase form hog liver) and by soil burial test. Both tests showed that the copolyesters were characterized by enhanced biodegradability. [Copyright &y& Elsevier]

Abstract: This work studies the enzymatic degradation of polyurethanes (PUs) and segmented polyurethane ureas (SPUUs) derived from lysine diisocyanate (LDI) by various proteases. Thiol proteases, such as papain, bromelain, and ficin, showed high activity on PUs. Protease K and chymotrypsin also hydrolyzed the PUs. For almost all SPUUs, papain showed high activity. For example, LDI/poly(caprolactone) diol (M w =1250)/ethylene diamine (2/1/1) was hydrolyzed to 43% under the same conditions. The water-soluble degradation products of a polyurethane, LDI/BD (1/1), and two model compounds treated with papain were studied with NMR and GPC analysis. From the results, it was evident that the pendant methyl ester group in LDI was rapidly hydrolyzed, followed by slow hydrolysis of urethane bonds in the backbone chain. [Copyright &y& Elsevier]

The selective and efficient production of N-acetyl-d-glucosamine (GlcNAc) was achieved from flake type of α-chitin by using crude enzymes derived from Aeromonas hydrophila H-2330. [Copyright &y& Elsevier]