化学学报 ›› 2017, Vol. 75 ›› Issue (10): 1010-1016.DOI: 10.6023/A17050236 上一篇    

研究论文

二元共组装法制备无裂痕反蛋白石结构薄膜的研究

罗文昊a, 朱水洪a, 林友辉a, 刘向阳a,b   

  1. a 厦门大学材料学院 物理科学与技术学院 生物仿生及软物质研究院 福建省柔性功能材料重点实验室 厦门 361005;
    b 新加坡国立大学物理系 新加坡 117542
  • 投稿日期:2017-05-31 发布日期:2017-09-04
  • 通讯作者: 林友辉,E-mail:linyouhui@xmu.edu.cn;刘向阳,E-mail:phyliuxy@nus.edu.sg E-mail:linyouhui@xmu.edu.cn;phyliuxy@nus.edu.sg
  • 基金资助:

    国家自然科学基金(Nos.21401154,U1405226)、111计划(No.B16029)、广东省自然科学基金(No.2014A030310005)及厦门大学校长基金(No.20720170011)资助.

Preparation of Crack-free Inverse-opal Films by Template/Matrix Co-assembly

Luo Wenhaoa, Zhu Shuihonga, Lin Youhuia, Liu Xiang Yanga,b   

  1. a College of Materials & College of Physical Science and Technology, Research Institute for Biomimetics and Soft Matter, Fujian Provincial Key Laboratory for Soft Functional Materials Research, Xiamen University, Xiamen 361005;
    b Department of Physics, National University of Singapore, Singapore 117542
  • Received:2017-05-31 Published:2017-09-04
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21401154, U1405226), the 111 Project (No. B16029), the Natural Science Foundation of Guangdong Province (2014A030310005) and the Fundamental Research Funds for the Central Universities of China (No. 20720170011).

近年来,由于在光学、电学和生化等领域具有广泛的潜在应用,有序多孔反蛋白石结构薄膜的研究引起了人们的广泛关注.但是其在制备过程中常常会形成一些无法控制的缺陷,限制了这类材料的普及和实际应用.通过使用两种基质前驱体(正硅酸乙酯或丝素蛋白)与胶体小球混合共组装,探究了二元体系共组装法制备无裂痕反蛋白石结构薄膜的可行性.并用扫描电镜和可见光谱对薄膜结构进行了表征.结果表明,对于正硅酸乙酯体系,在不影响胶体小球有序排列的条件下,正硅酸乙酯在小球间的空隙中发生溶胶凝胶转变,与微球共同组装成有序致密的整体,去除微球模板后,可以得到大规模(>200 μm)无缺陷有序的反蛋白石结构薄膜.而对于大分子丝素蛋白体系,由于它和胶体小球有较强的相互作用力,会抑制胶体小球的有序组装,导致无法形成有序结构薄膜.对两种二元共组装体系进行了实验探索,实验结果不仅有助于人们了解共组装方式的适用范围,而且为设计和制备无缺陷反蛋白石薄膜提供了新的途径.

关键词: 共组装, 反蛋白石结构, 无裂痕, 胶体小球

Recently, there has been a significant interest in utilizing well-ordered, porous inverse-opal films for applications in optical, electronic and (bio)chemical fields. However, uncontrolled defects are always formed during their preparation process, which limit their practical applications. In this work, we examine the feasibility of using template/matrix co-assembly strategies to fabricate crack-free inverse opal thin films. Polystyrene spheres (PS) are chosen as a colloidal template, and two matrix precursors[tetraethoxysilane (TEOS) precursor and regenerated silk fibroin solution] are used for the current study. Our scanning electron microscope (SEM) and optical spectrum results show that, for the TEOS-based system, the resulting silica gel due to the sol-gel transition of TEOS can effectively fill the gap between particles, but cannot affect the self-assembly of PS colloidal particles. After selective removal of the PS template, centimeter-scale crack-free and well-ordered inverse opal films can be obtained. In addition, for a constant concentration of TEOS, the film thickness and order degree of structure can be simply tuned by adjusting the concentrations of colloidal spheres. In comparison with indirect approach through template self-assembly and liquid infiltration, such a co-assembly approach can effectively minimize the associated cracking and avoid the need for matrix infiltration into the preassembled colloidal spheres. On the other hand, macro-molecule silk fibroin has a relatively strong interaction with PS colloidal particles, which is demonstrated by SEM and confocal images. Due to their interaction, silk fibroin molecules are preferably adsorbed on the surface of PS spheres, which can restrain the self-assembly of colloidal particles. As a result, it cannot form well-ordered silk film based on such co-assembly strategy. That is to say, the co-assembly approach is not suitable for systems that matrices have strong interactions with templates. These findings pave the way to use the template/matrix co-assembly strategy for rationally designing and developing crack-free inverse opal films and to apply such well-ordered and porous materials in a variety of fields.

Key words: co-assembly, inverse-opal structure, crack-free, colloidal spheres