Cellulose-based materials are produced industrially in countless varieties via top-down processing of natural lignocellulose substrates. By contrast, cellulosic materials are only rarely prepared via bottom up synthesis and oligomerization-induced self-assembly of cellulose chains. Building up a cellulose chain via precision polymerization is promising, however, for it offers tunability and control of the final chemical structure. Synthetic cellulose derivatives with programmable material properties might thus be obtained. Cellodextrin phosphorylase (CdP; EC 2.4.1.49) catalyzes iterative β-1,4-glycosylation from α-d-glucose 1-phosphate, with the ability to elongate a diversity of acceptor substrates, including cellobiose, d-glucose and a range of synthetic glycosides having non-sugar aglycons. Depending on the reaction conditions leading to different degrees of polymerization (DP), short-chain soluble cello-oligosaccharides (COS) or insoluble cellulosic materials are formed. Here, we review the characteristics of CdP as bio-catalyst for synthetic applications and show advances in the enzymatic production of COS and reducing end-modified, tailored cellulose materials. Recent studies reveal COS as interesting dietary fibers that could provide a selective prebiotic effect. The bottom-up synthesized celluloses involve chains of DP ≥ 9, as precipitated in solution, and they form ~5 nm thick sheet-like crystalline structures of cellulose allomorph II. Solvent conditions and aglycon structures can direct the cellulose chain self-assembly towards a range of material architectures, including hierarchically organized networks of nanoribbons, or nanorods as well as distorted nanosheets. Composite materials are also formed. The resulting materials can be useful as property-tunable hydrogels and feature site-specific introduction of functional and chemically reactive groups. Therefore, COS and cellulose obtained via bottom-up synthesis can expand cellulose applications towards product classes that are difficult to access via top-down processing of natural materials.

通过对天然木质纤维素基质进行自上而下的加工，纤维素基材料在工业上以无数种方式生产。相比之下，纤维素材料很少通过自下而上的合成和低聚诱导的纤维素链自组装来制备。然而，通过精确聚合建立纤维素链很有前景，因为它提供了对最终化学结构的可调性和控制。因此可以获得具有可编程材料特性的合成纤维素衍生物。纤维糊精磷酸化酶 (CdP; EC 2.4.1.49) 催化 α- d-葡萄糖 1-磷酸的迭代 β-1,4-糖基化，能够延长多种受体底物，包括纤维二糖、d-葡萄糖和一系列具有非糖苷元的合成糖苷。根据导致不同聚合度 (DP) 的反应条件，会形成短链可溶性纤维寡糖 (COS) 或不溶性纤维素材料。在这里，我们回顾了 CdP 作为合成应用生物催化剂的特性，并展示了 COS 的酶促生产和还原末端改性的定制纤维素材料的进展。最近的研究表明，COS 是一种有趣的膳食纤维，可以提供选择性的益生元效应。自下而上合成的纤维素涉及 DP ≥ 9 的链，如在溶液中沉淀，它们形成~5 nm 厚的片状纤维素异形体 II 晶体结构。溶剂条件和苷元结构可以将纤维素链自组装导向一系列材料结构，包括分层组织的纳米带或纳米棒以及扭曲的纳米片网络。也形成复合材料。所得材料可用作性能可调的水凝胶，并具有功能性和化学反应性基团的位点特异性引入。因此，通过自下而上合成获得的 COS 和纤维素可以将纤维素应用扩展到难以通过天然材料自上而下加工获得的产品类别。所得材料可用作性能可调的水凝胶，并具有功能性和化学反应性基团的位点特异性引入。因此，通过自下而上合成获得的 COS 和纤维素可以将纤维素应用扩展到难以通过天然材料自上而下加工获得的产品类别。所得材料可用作性能可调的水凝胶，并具有功能性和化学反应性基团的位点特异性引入。因此，通过自下而上合成获得的 COS 和纤维素可以将纤维素应用扩展到难以通过天然材料自上而下加工获得的产品类别。