用于检测水产品中汞离子的纤维素基凝胶光化学传感器基础研究

There are many problems existed in traditional detection methods of Hg(II) in aquatic products, such as complexity, consuming time, and disturbances of inorganic salt and other factors. To overcome the problems mentioned above, this project aims to design and synthesize Hg(II) stimuli-responsive cellulose-based responsive polymer crystalline colloidal array optical chemosensors, cellulose-based derivatives of which use hydroxyethyl celluloses as the backbone grafted with alkyl glycidyl ether and thioether oligomer. The Hg(II) stimuli-responsive cellulose-based hydrogels with large swelling volume and fast swelling ratio are synthesized by crosslink reactions, and the swelling ratio of hydrogels is almost not influenced by inorganic salt and other factors. These brilliant properties of cellulose-based hydrogels provided the feasibility for hydrogels applied to optical chemosensors. Through the coupling between Hg(II) stimuli-responsive cellulose-based hydrogels and three dimensional photonic crystals into cellulose-based responsive polymer crystalline colloidal arrays, the volume change of hydrogels induced by the Hg(II) recognition signal of recognition group can be transformed into color change, and cellulose-based responsive polymer crystalline colloidal arrays with high responsive rate, obvious responsive color change and high sensitivity will be developed. The film of the cellulose-based responsive polymer crystalline colloidal arrays will be applied to detecting Hg(II) in aquatic products, and the color of film was determined under different concentration ranges of Hg(II). The novel optical chemosensors which can quickly and conveniently recognize Hg(II) and confirm its concentrations in aquatic products by naked-eye will be developed. Thus, this optical chemosensors will supply the new method to detect Hg(II) in aquatic products sensitively, conveniently, and accurately.

针对水产品中汞离子传统检测方法具有复杂、费时、检测结果易受无机盐及其他因素干扰等问题。本项研究首先以具有资源、结构和性能优势的纤维素为凝胶骨架，接枝短链烷烃、硫醚齐聚物等作为功能型分子，设计合成溶胀体积大、溶胀速率快且溶胀率受无机盐及其它因素影响弱的汞离子刺激响应纤维素基凝胶；然后通过汞离子刺激响应纤维素基凝胶与三维光子晶体阵列的耦合，将识别基团识别汞离子后产生的识别信号所引起的凝胶体积变化转化为裸眼可视的颜色变化，研究设计出响应速率快、响应前后颜色变化明显、灵敏度高、选择识别能力强、裸眼可视的响应聚合物胶体晶体阵列光化学传感器。将刺激响应纤维素基聚合物胶体晶体阵列薄膜应用于水产品中汞离子的检测，并确定在不同汞离子浓度范围内薄膜的颜色，研制出裸眼可视、方便快速识别水产品中汞离子并确定其浓度的光化学传感器，从而为水产品中汞离子的检测提供全新且灵敏、便捷、准确的方法。

本项目研究由具有资源和结构优势的纤维素为原料制备了纤维素基刺激响应聚合物胶体晶体阵列。采用醚化反应、点击化学反应，设计合成了一系列含烷基、硫醚键的纤维素衍生物，并以乙二醇二缩水甘油醚，聚乙二醇二缩水甘油醚或乙烯砜为交联剂应制备了上述一系列纤维素基刺激响应凝胶。研究了纤维素基凝胶的汞离子和温度刺激响应性能。研究结果表明，根据纤维素衍生物的化学结构不同，制得纤维素基凝胶具有良好的汞离子和温度刺激响应性能。将温度或汞离子刺激响凝胶与聚苯乙烯微球三维光子晶体阵列耦合，研制出纤维素基刺激响应聚合物胶体晶体阵列薄膜，并研究了金属离子种类和温度等外部刺激的变化对聚合物胶体晶体阵列颜色的影响。研究结果表明，汞离子刺激响应纤维素基聚合物胶体晶体阵可高度选择性的识别汞离子，并产生裸眼可视的颜色变化，同时温度刺激响应纤维素基聚合物胶体晶体阵可准确的识别温度的变化。本项目研究研发了一系列汞离子和温度响应的纤维素基刺激响应聚合物，目的是实现可快速、便捷、实时地检测汞离子和温度。此外，这种检测方法具有很强的普适性，通过设计不同的重金属离子专属识别基团，可制备一系列用于检测重金属离子的裸眼可视的纤维素基凝胶光化学传感器，具有理论和实际双重意义。