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Abstract: A novel lipase-catalyzed synthesis of aliphatic polyesters has been achieved successfully by using Candida sp.99-125 with diethyl sebacate and 1,4-butanediol as starting substrates in absence of organic solvents. The lipase from Candida sp.99-125 was employed for the first time to catalyze synthesis of poly(butylene sebacate) and showed high catalytic activity for bulkpolymerization under mild reaction conditions. The eco-friendly processes, without any environmental pollution, avoided both phase separation of the reactants and the use of toxic solvents effectively. The polycondensation reactions were performed in two stages: first stage reaction under atmospheric pressure to convert the monomers to oligomers followed by second stage reaction under vacuum process, with a highest molecular weight of 15,800 obtained in molar ratio of 1:1 at 70°C. The corresponding polyesters determined by thermogravimetric analysis (TGA) were much thermally stable up to 300°C. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXS) analysis demonstrated the polymers had a strong ability to crystallize with the degree of crystallinity up to 66%. [Copyright &y& Elsevier]

Glycerol waste from the biodiesel production can be used as a carbon source in the production of 1,3-propanediol (1,3-PD) through microbial fermentation. However, downstream processing is a major bottleneck that restricts its biological production. Here, we investigated an environmentally-friendly method to enzymatically separate 1,3-PD. The transformation of 1,3-PD to an ester was achieved by exploiting the esterification reaction with fatty acids under lipase catalysis. The reaction efficiency was optimized using different poly-alcohols that were existed in the fermentation broth reacted with a fatty acid. Whereas the 1,3-PD conversion reached 62%, only a 0.06% and 0.08% conversion was reached for 2,3-butanediol and glycerol, illustrating the former’s more efficient separation. The recovery efficiency of 1,3-PD was 96%. Finally, 1,3-PD was obtained by lipase-directed ester hydrolysis. Taken together, the bio-catalyzed separation process presented here is a novel and promising method for recovering 1,3-PD. [ABSTRACT FROM AUTHOR]

Due to the poor biodegradability and toxicity of mineral-based lubricants, the development and application of plant-based biolubricants are increasing. However, low stability and poor low temperature performance restrict plant oils to use as lubricants directly. Hence, the paper tried to find an efficient and green way to modify the plant oil derivate oleic acid and obtained high-performance biolubricants. This study demonstrated that modification of oleic acid through epoxidation combined with ring opening reaction, and further esterification, was an efficient strategy for modifying unsaturated fatty acids for the biolubricant production. Meanwhile, catalytic effects of ionic liquids were compared with other catalysts. The results indicated that ionic liquid [HMIm][PF6] is an efficient catalyst for the ring opening and esterification for the synthesis of biolubricants with different kinds of fatty acids. Modified biolubricants from this research exhibited excellent viscosity index (>116) and low temperature performance (pour point < −48 °C). The results of high frequency reciprocating friction experiments exhibited superior lubrication performance of the lubricant. These findings provide a new green and efficient method for improving plant oils as biolubricants. Image 1 • Green way to produce high-performance biolubricant from oleic acid was developed. • Esterification after epoxide ring-opening is efficient for lubricant production. • Catalytic effects of ionic liquids were compared with other reported catalysts. • Biolubricant from this research exhibited excellent low temperature performance. [ABSTRACT FROM AUTHOR]

Due to the poor biodegradability and toxicity of mineral-based lubricants, the development and application of plant-based biolubricants are increasing. However, low stability and poor low temperature performance restrict plant oils to use as lubricants directly. Hence, the paper tried to find an efficient and green way to modify the plant oil derivate oleic acid and obtained high-performance biolubricants. This study demonstrated that modification of oleic acid through epoxidation combined with ring opening reaction, and further esterification, was an efficient strategy for modifying unsaturated fatty acids for the biolubricant production. Meanwhile, catalytic effects of ionic liquids were compared with other catalysts. The results indicated that ionic liquid [HMIm][PF6] is an efficient catalyst for the ring opening and esterification for the synthesis of biolubricants with different kinds of fatty acids. Modified biolubricants from this research exhibited excellent viscosity index (>116) and low temperature performance (pour point < −48 °C). The results of high frequency reciprocating friction experiments exhibited superior lubrication performance of the lubricant. These findings provide a new green and efficient method for improving plant oils as biolubricants. Image 1 • Green way to produce high-performance biolubricant from oleic acid was developed. • Esterification after epoxide ring-opening is efficient for lubricant production. • Catalytic effects of ionic liquids were compared with other reported catalysts. • Biolubricant from this research exhibited excellent low temperature performance. [ABSTRACT FROM AUTHOR]

Abstract: Diesters and diols were successfully converted into aliphatic polyesters by enzymatic lipase Candida sp.99-125 catalysis, with β-cyclodextrin acting as supporting architecture (in a similar way as chaperone proteins). No organic solvents were used. The polytransesterification was a much greener process, being solvent-free and without metal residues. Lipase Candida sp.99-125 showed a high catalytic activity for bulkpolymerization of diesters and diols with various numbers of methylene groups in their chains. β-Cyclodextrin encircled the linear polymer chain and maintained the chain in a proper configuration to avoid its coagulation. Lipase initiated the polymerization and β-cyclodextrin threaded onto the polymer chain to control the structure for producing high molecular weight polyesters. From a combination of diesters and diols, polyesters with a high molecular weight of 62,100Da were obtained at 70°C. The corresponding polyesters showed an excellent thermal stability till 350°C and had a strong ability to crystallize with up to 72% crystallinity, contributing to their high storage modulus. [Copyright &y& Elsevier]