Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials*.
Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials*.
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DOI：
10.1002/chem.202003604
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发表时间：
2021-01-18
期刊：
影响因子：
--
通讯作者：
Field RA
中科院分区：
文献类型：
--
作者：
de Andrade P;Muñoz-García JC;Pergolizzi G;Gabrielli V;Nepogodiev SA;Iuga D;Fábián L;Nigmatullin R;Johns MA;Harniman R;Eichhorn SJ;Angulo J;Khimyak YZ;Field RA
了解构建块自组装成复杂分层结构的细节是设计和制备具有特定特性的软物质材料的主要挑战。已知酶促合成的纤维糊精具有超过DP 9的有限水溶性，在该点处它们自组装成类似于反平行纤维素II结晶堆积的颗粒。 我们通过化学酶法合成制备并表征了一系列具有不同取代度和取代模式的位点选择性氟化纤维糊精。考虑到纤维素II氢键网络的潜在破坏，我们制备并表征了多6-氟化纤维糊精。 此外，合成了一系列单位点选择性氟化纤维糊精，以评估每条链添加一个氟原子后的结构影响。这些材料在不同长度尺度下的结构表征，结合先进的NMR光谱和显微镜方法，表明6-氟化供体底物产生多个6-氟化纤维糊精链，其组装成颗粒，呈现形态和结晶度特征以及分子间相互作用，这对于纤维素样材料是前所未有的。 生成糖物质：将单氟化和多氟化葡萄糖残基酶促掺入纤维糊精链中产生选择性氟化纤维糊精，其自组装成结晶材料。多重6-氟化纤维糊精产生了纤维素或纤维素样材料之前未报告的同晶型。我们的研究结果突出了化学酶促合成的潜力，产生新的糖材料的控制分子结构和形态。
Understanding the fine details of the self‐assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft‐matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self‐assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site‐selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis. Bearing in mind the potential disruption of the hydrogen‐bond network of cellulose II, we have prepared and characterised a multiply 6‐fluorinated cellodextrin. In addition, a series of single site‐selectively fluorinated cellodextrins was synthesised to assess the structural impact upon the addition of one fluorine atom per chain. The structural characterisation of these materials at different length scales, combining advanced NMR spectroscopy and microscopy methods, showed that a 6‐fluorinated donor substrate yielded multiply 6‐fluorinated cellodextrin chains that assembled into particles presenting morphological and crystallinity features, and intermolecular interactions, that are unprecedented for cellulose‐like materials. Generating glycomaterials: Enzymatic incorporation of singly and multiply fluorinated glucose residues into cellodextrin chains produces selectively fluorinated cellodextrins that self‐assemble into crystalline materials. Multiply 6‐fluorinated cellodextrin gave rise to an allomorph not previously reported for celluloses or cellulose‐like materials. Our findings highlight the potential of chemoenzymatic synthesis for generating novel glycomaterials of controlled molecular structure and morphology.
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DOI：
10.1007/978-3-319-73168-1_4
发表时间：
2018-01-01
期刊：
CELLULOSE DERIVATIVES: SYNTHESIS, STRUCTURE, AND PROPERTIES
影响因子：
--
作者：
Heinze, Thomas;El Seoud, Omar A.;Koschella, Andreas
通讯作者：
Koschella, Andreas
影响因子：
3.1
作者：
Hiraishi, Masao;Igarashi, Kiyohiko;Samejima, Masahiro
通讯作者：
Samejima, Masahiro
影响因子：
--
作者：
French, AD;Johnson, GP;Csonka, GI
通讯作者：
Csonka, GI
影响因子：
11.2
作者：
Lopez Duran, Veronica;Larsson, Per A.;Wagberg, Lars
通讯作者：
Wagberg, Lars
影响因子：
1.6
作者：
Matsuda, T;Makino, M;Murakami, M
通讯作者：
Murakami, M