将表面模板化的糖聚合物纳米图案转移到水凝胶上，用于设计跨长度尺度的多价碳水化合物-凝集素相互作用,Journal of the American Chemical Society

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将表面模板化的糖聚合物纳米图案转移到水凝胶上，用于设计跨长度尺度的多价碳水化合物-凝集素相互作用
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-14 , DOI: 10.1021/jacs.2c09937
Anamika Singh ₁ , Juan C Arango ₁ , Anni Shi ₁ , Joseph B d'Aliberti ₁ , Shelley A Claridge _{1,

2}

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碳水化合物和蛋白质之间的多价相互作用使广泛的具有关键生物学重要性的选择性化学过程成为可能。这种相互作用可以从大分子尺度（1-10 nm）扩展到更大的细胞或组织尺度，对旨在利用体外类似相互作用的化学图案化材料提出大量要求。在这里，我们展示了具有碳水化合物头基的二炔两亲物可以组装在高度定向的热解石墨 (HOPG) 上，以生成纳米分辨率的碳水化合物图案，具有高达近 1 μm 的单个线性碳水化合物组件和微尺度几何图案。然后将它们光聚合并共价转移到水凝胶的表面。该策略将碳水化合物图案悬浮在相对刚性的聚丁二炔（持久长度 ~ 16 nm）上，暴露在大孔结构上方的水凝胶顶面。适当碳水化合物的转移模式（例如，N -乙酰基-d-葡萄糖胺，GlcNAc) 能够与小麦胚芽凝集素 (WGA) 进行选择性多价相互作用 ( K _{D ∼ 40 nM)，这是一种模型凝集素，与适当间隔的 GlcNAc 部分表现出多价结合。}WGA 结合亲和力可以进一步提高 ( K _D∼ 10 nM) 使用丁二炔使聚合物主链更靠近显示的碳水化合物，表明该策略可用于调节界面处的碳水化合物呈现。相反，GlcNAc 图案化的表面不会诱导刀豆球蛋白 A 的特异性结合，而用葡萄糖醛酸或简单的羧酸或羟基图案化的表面不会诱导 WGA 结合。更广泛地说，这种方法可能有助于设计合成聚糖模拟界面，具有从分子到介观尺度的特征，包括细胞软支架。

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Surface-Templated Glycopolymer Nanopatterns Transferred to Hydrogels for Designed Multivalent Carbohydrate–Lectin Interactions across Length Scales

Multivalent interactions between carbohydrates and proteins enable a broad range of selective chemical processes of critical biological importance. Such interactions can extend from the macromolecular scale (1–10 nm) up to much larger scales across a cell or tissue, placing substantial demands on chemically patterned materials aiming to leverage similar interactions in vitro. Here, we show that diyne amphiphiles with carbohydrate headgroups can be assembled on highly oriented pyrolytic graphite (HOPG) to generate nanometer-resolution carbohydrate patterns, with individual linear carbohydrate assemblies up to nearly 1 μm, and microscale geometric patterns. These are then photopolymerized and covalently transferred to the surfaces of hydrogels. This strategy suspends carbohydrate patterns on a relatively rigid polydiacetylene (persistence length ∼ 16 nm), exposed at the top surface of the hydrogel above the bulk pore structure. Transferred patterns of appropriate carbohydrates (e.g., N-acetyl-d-glucosamine, GlcNAc) enable selective, multivalent interactions (K_D ∼ 40 nM) with wheat germ agglutinin (WGA), a model lectin that exhibits multivalent binding with appropriately spaced GlcNAc moieties. WGA binding affinity can be further improved (K_D ∼ 10 nM) using diacetylenes that shift the polymer backbone closer to the displayed carbohydrate, suggesting that this strategy can be used to modulate carbohydrate presentation at interfaces. Conversely, GlcNAc-patterned surfaces do not induce specific binding of concanavalin A, and surfaces patterned with glucuronic acid, or with simple carboxylic acid or hydroxyl groups, do not induce WGA binding. More broadly, this approach may have utility in designing synthetic glycan–mimetic interfaces with features from molecular to mesoscopic scales, including soft scaffolds for cells.

更新日期：2023-01-14

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