Chemo‐enzymatic Assembly of Clickable Cellulose Surfaces via Multivalent Polysaccharides

Abstract

The chemist's guide to the galactosyl unit: A chemo-enzymatic process is developed for the multivalent functionalization of cellulose surfaces via regioselective oxidation of heteropolysaccharides with galactose 6-oxidase. Reductive amination, surface sorption, and click chemistry enable the assembly of (bio)chemically active cellulose surfaces for applications ranging from functional biocomposites to in vitro diagnostics.

A review of bioactive plant polysaccharides: Biological activities, functionalization, and biomedical applications

“…Judicious choices of the functional group allow further in situ surface modification. For example, Xu et al (2012) attached propargylamino groups to yield multialkynylated conjugates, which are clickable by "click chemistry" for desired applications, such as in vitro diagnostics, (bio) molecular capture, and detection as illustrated in Fig. 3. …”

Oxidation with galactose oxidase: Multifunctional enzymatic catalysis

“…In this case, the polymeric product reduced with NaBD 4 is enzymatically hydrolyzed prior analysis by ESI-MS. This technique was especially feasible in the case of galactoxyloglucan, which forms few and well characterized oligosaccharide fragments that are M a n u s c r i p t 8 easily recognized in ESI-MS spectra [41,43]. A similar approach was used to analyze modified galactoxyloglucan by matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF-MS) [44].…”

“…The so-called click chemistry technique has also been adopted to modify cellulose surfaces using GAO oxidized hemicelluloses [43]. Specially, spruce galactoglucomannan and tamarind galactoxyloglucan were first oxidized with GAO, and then reductively aminated with…”

“…The potential of the products to modify cellulosic surfaces was investigated using filter paper as a model. The uniform distribution of the polysaccharides onto the paper surface was visualized by reacting the products with fluorescent or colored azides (Scheme 3, B) [43].…”

Biocatalytic Production of Amino Carbohydrates through Oxidoreductase and Transaminase Cascades

“…[1][2][3][4][5] Bifunc-tional molecules containing at erminal acid and an amine functionality are among the desired products, because they are key building blocks in the synthesis of different types of polymers. [14][15][16][17] Bifunctional carbohydrates (e.g.,d iacids, diamines, or AB monomers) from native carbohydrate structures are among the desired products. [9][10][11][12][13] An emerging area of research aims to utilize the versatility and ensuingu seful properties of native structures present in plant carbohydrates instead of degrading the structurest o monomers.…”