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化学进展 2019, Vol. 31 Issue (10): 1425-1439 DOI: 10.7536/PC190409 前一篇   后一篇

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光化学反应在生物材料表面修饰中的应用

刘萍, 汪璟, 郝鸿业, 薛云帆, 黄俊杰, 计剑**()   

  1. 浙江大学高分子科学与工程学系 高分子合成与功能构造教育部重点实验室 杭州 310027
  • 收稿日期:2019-04-08 出版日期:2019-10-15 发布日期:2019-08-05
  • 通讯作者: 计剑
  • 基金资助:
    国家重点研发计划重点专项(2017YFB0702500)
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Photochemical Surface Modification of Biomedical Materials

Ping Liu, Jing Wang, Hongye Hao, Yunfan Xue, Junjie Huang, Jian Ji**()   

  1. Key Laboratory of Macromolecular Synthesis and Functionalization,Ministry of Education,Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2019-04-08 Online:2019-10-15 Published:2019-08-05
  • Contact: Jian Ji
  • About author:
    ** E-mail:
  • Supported by:
    National Key Research and Development Program of China(2017YFB0702500)

生物医用材料的表界面设计在组织工程、生物医疗器械、生物传感与检测、生物芯片等领域越来越重要,深入理解材料性质,尤其是表界面性质,对生物材料研发具有一定指导作用。在生物材料表界面修饰的各种方法中,光化学修饰方法简单高效,且具有时空可控性和非侵入性等优点,已成为生物材料表界面修饰中的热点研究领域之一。本综述在介绍近年来发展的生物材料表面光化学修饰方法的基础上,集中介绍其在组织再生材料(仿细胞外基质界面、硬度调控薄膜凝胶、图案化和梯度表面、光响应动态表面)、微液滴阵列表面、高通量生物芯片等领域的应用,并进一步展望了光化学表面修饰在生物医用界面研究中的关键挑战和发展方向。

关键词： 表面修饰, 光化学, 点击化学, 图案化, 梯度, 高通量

The surface design of biomedical materials is becoming more and more important in the fields of tissue engineering, biomedical devices, biosensing and detection, and biochips. In-depth understanding of the properties of materials, especially the surface properties, has a certain guiding role in the development of biomedical materials. Among various methods of surface modification based on biomaterials, photochemical modification is very simple and efficient, and has the advantages of spatiotemporal controllability and non-invasiveness. Based on this, in recent years, photochemical modification has become one of the hot research fields in the interface modification of biomaterials. This review first simply introduces the recent development of photochemical modification methods on biochemical surface, then mainly focuses on tissue regeneration materials(extracellular matrix biomimetic surfaces, stiffness-controllable hydrogel films, patterning and gradient surfaces, photo-responsive smart surfaces), 2D droplet microarrays surfaces, high-throughput biochip and other applications. Finally, this article points out the current shortcomings of photochemical surface modification and the future development trend of this field is also proposed.

Key words: surface modification, photochemical, click chemistry, pattern, gradient, high-throughput
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图1 巯基-烯烃在光引发剂和紫外光条件下的反应机理[13]
Fig. 1 Reaction mechanism of thiol-ene reaction under photoinitiator and ultraviolet light[13]
图2 (A)光引发的叠氮-炔烃环加成反应[27]; (B)无催化剂的叠氮-炔烃环加成反应[31]
Fig. 2 (A) Photoinduced CuAAC click reactions[27]; (B) Photoactivated copper-free azide-alkyne cycloaddition reaction[31]
图3 (A)四唑-烯烃反应机理;(B)将四唑分子分别引入到硅片和纤维素膜表面,再进行后修饰[36]
Fig. 3 (A)Tetrazole-olefin reaction mechanism;(B)Introduction of tetrazole molecules onto the silicon wafer and the cellulose film followed by post-modification[36]
图4 二苯甲酮在表面上进行光接枝聚合的机理[4]
Fig. 4 Proposed mechanism of photografting polymerization on a surface derived from benzophenone[4]
图5 (A)铱作为光氧化还原催化剂的光控表面活性聚合反应;(B)图案化聚合物刷和(C)聚合物接枝梯度表面[47]
Fig. 5 (A) Photo-controlled surface-active polymerization reaction using Ir-based photoredox catalyst;(B) Patterned polymer brush and(C) polymer gradient surface[47]
图6 邻硝基苄基光不稳定反应。(A,B)两种形式的光引发肟化反应;(C)光激活RGD多肽促使细胞黏附[58]
Fig. 6 O-nitrobenzyl photolabile reaction. (A,B) Two forms of oxime ligation reactions;(C) Light-triggered activation of cell adhesion activity of caged RGD peptide[58]
图7 润滑油灌注图案化的多孔表面制备微液滴阵列[70,73]
Fig. 7 The patterned lubricant-infused porous surfaces for creating droplet microarrays by liquid sliding[70,73]
图8 (A)改变光照时间制备硬度梯度凝胶的示意图;(B)无掩模光刻方法制备“星空“硬度图案[93]
Fig. 8 (A) Schematic diagram of preparing gradient hardness gel by changing the illumination time;(B) Maskless lithography method for preparing “the Starry Night” hardness pattern[93]
图9 基于聚电解质涂层内多孔结构的形成及消失实现功能客体在膜内的区域化包埋过程[107]
Fig. 9 The embedding process of functional objects in the patterned film based on the formation and disappearance of the porous structure in the polyelectrolyte coating[107]
图10 (A)制备动态图案和梯度化表面的流程;(B)电化学和光化学方法共同在表面固定配体[110]; (C)细胞在RGD梯度表面的黏附和迁移图片[111]
Fig. 10 (A) Flow diagram for preparing dynamic patterns and gradient surfaces;(B)Combined electroactive and photochemical strategy for chemoselective immobilization of ligands[110];(C) Representative images for cell attachment and migration on RGD defined gradients[111]
图11 使用UCNPs吸收近红外光控制细胞在涂层的黏附[116]
Fig. 11 The using of UCNPs to absorb near-infrared light for controlling cell adhesion on the surface[116]
图12 微液滴阵列细胞筛选平台[132]。(A) 不同尺寸大小的超亲水和超疏水区域设计;(B)微液滴阵列照片;(C)微液滴阵列用于细胞筛选的工作流程图(比例尺1 mm)
Fig. 12 Droplet-microarray(DMA) cell screening platform[132].(A) Different sizes of the super-hydrophilic spots and super-hydrophobic borders;(B) Photographs of droplet microarrays;(C)Schematic diagram of cell screening using a DMA platform(scale=1 mm)
图13 (A)硬度-配体浓度正交高通量凝胶制备原理图;(B)正交梯度凝胶表面U373-MG细胞miR18a表达情况分布;(C)巨噬细胞分泌的外源可溶性因子对U373-MG细胞miR18a表达影响[144]
Fig. 13 (A)Preparation schematic of matrix stiffness and fibronectin density orthogonal high-throughput gel;(B) The distribution of miR18a expression in U373-MG cells on orthogonal gradient gel;(C) The effect of exogenous macrophage-derived soluble factors on ECM-sensitive regulation of miR18a[144]
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