From Glucose to Polymers: A Continuous Chemoenzymatic Process

Abstract

Efforts to synthesize degradable polymers from renewable resources are deterred by technical and economic challenges; especially, the conversion of natural building blocks into polymerizable monomers is inefficient, requiring multistep synthesis and chromatographic purification. Herein we report a chemoenzymatic process to address these challenges. An enzymatic reaction system was designed that allows for regioselective functional group transformation, efficiently converting glucose into a polymerizable monomer in quantitative yield, thus removing the need for chromatographic purification. With this key success, we further designed a continuous, three‐step process, which enabled the synthesis of a sugar polymer, sugar poly(orthoester), directly from glucose in high yield (73 % from glucose). This work may provide a proof‐of‐concept in developing technically and economically viable approaches to address the many issues associated with current petroleum‐based polymers.

Synthesis and Biopharmaceutical Applications of Sugar-Based Polymers: New Advances and Future Prospects

“…Enzymatic or chemoenzymatic synthesis of carbohydrate polymers is an important green method for obtaining products with well-defined and uniform chain lengths; however, technical hurdles need to be solved mainly due to issues of scale-up to kilograms. Recently, a continuous process has been developed to synthesize sugar polymers with high efficiency . Regarding the hard-to-define structure–property relationships of heterogeneous glycosaminoglycans, such as natural chondroitin sulfate, Ji et al proposed that the use of homogeneous chondroitin sulfate can clarify structure–activity relationships .…”

“…Recently, a continuous process has been developed to synthesize sugar polymers with high efficiency. 50 Regarding the hard-to-define structure−property relationships of heterogeneous glycosaminoglycans, such as natural chondroitin sulfate, Ji et al proposed that the use of homogeneous chondroitin sulfate can clarify structure−activity relationships. 51 Synthesis of chondroitin sulfate with well-defined and uniform chain lengths and the related problems in enzymatic or chemoenzymatic synthesis have been reviewed by Ji et al 51 More well-defined polysaccharides have been prepared by step-growth approaches, using monosaccharide directly or oligosaccharide building blocks, with such enzymes as glycosynthases, sucrases, glycosyltransferases, and phosphorylases.…”

Synthesis and melt-spinning of partly bio-based thermoplastic poly(cycloacetal-urethane)s toward sustainable textiles

“…PlantBottle TM by Coca Cola), polylactic acid (PLA), 54,55 as well as many other sugar-based new polymers. 38,52,[56][57][58][59][60][61][62][63][64][65][66][67][68] Recently, a sugar-based platform molecule, 5-hydroxymethylfurfural (HMF), 69,70 was used to fabricate PAUs toward coating applications. 47 However, these PAUs were not readily suitable for textile investigations due to the relatively low thermal stability of the monomer, the presence of crosslinking, and the lack of flexible segments (as in Elastane fibres).…”