Direct-Ink Write 3D Printing Multistimuli-Responsive Hydrogels and Post-Functionalization Via Disulfide Exchange
Direct-Ink Write 3D Printing Multistimuli-Responsive Hydrogels and Post-Functionalization Via Disulfide Exchange
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DOI：
10.1021/acsapm.1c01538
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发表时间：
2022-01-06
影响因子：
5
通讯作者：
Nelson, Alshakim
中科院分区：
文献类型：
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作者：
Fellin, Christopher R.;Nelson, Alshakim
在此，我们描述了一种多刺激响应水凝胶，它可以通过直接墨水写入过程进行 3D 打印，以提供可以用带有硫醇的分子进行后功能化的交联水凝胶网络。合成了末端带有甲基丙烯酸酯基团的聚（烷基缩水甘油醚），并自组装成水凝胶，该水凝胶具有基于挤出的 3D 打印所需的三种关键刺激响应行为：溶胶-凝胶温度响应、剪切稀化行为和光化学交联能力。此外，化学交联的水凝胶表现出与 LCST 行为一致的温度依赖性膨胀。将吡啶基二硫化物聚氨酯甲基丙烯酸酯（PDS-UM）单体引入网络中作为水凝胶后功能化的硫醇反应手柄。使用谷胱甘肽作为反应探针，研究了这些水凝胶在不同温度（5、25 和 37 摄氏度）和膨胀状态（固化/预膨胀）下的反应性。为了说明该平台的多功能性，我们在不同的温度、pH 值和浓度下将许多额外的含硫醇探针（例如蛋白质、聚合物和小分子）缀合到水凝胶网络上。在多重刺激响应水凝胶平台的最终演示中，使用定制的 DIW 3D 打印机来制造打印物体，该物体随后与荧光标签结合，并显示出尺寸随环境温度变化的能力。
Herein, we describe a multistimuli-responsive hydrogel that can be 3D printed via a direct-ink write process to afford cross-linked hydrogel networks that can be postfunctionalized with thiol-bearing molecules. Poly(alkyl glycidyl ether)s with methacrylate groups at their termini were synthesized and self-assembled into hydrogels with three key stimuli-responsive behaviors necessary for extrusion-based 3D printing: a sol-gel temperature response, shear-thinning behavior, and the ability to be photochemically cross-linked. In addition, the chemically cross-linked hydrogels demonstrated a temperature-dependent swelling consistent with an LCST behavior. Pyridyl disulfide urethane methacrylate (PDS-UM) monomers were introduced into the network as a thiol-reactive handle for postfunctionalization of the hydrogel. The reactivities of these hydrogels were investigated at different temperatures (5, 25, and 37 degrees C) and swelling statuses (as-cured/preswollen) using glutathione as a reactive probe. To illustrate the versatility of the platform, we conjugated a number of additional thiol-containing probes such as proteins, polymers, and small molecules to the hydrogel network at different temperatures, pH values, and concentrations. In a final demonstration of the multistimuli-responsive hydrogel platform, a customized DIW 3D printer was used to fabricate a printed object that was subsequently conjugated with a fluorescent tag and displayed the ability to change in size with environmental temperature.