新型表面印迹聚合物的制备及其在样品前处理和传感中的应用
文献类型：学位论文
| 作者 | 学位论文
|
| 学位类别 | 博士 |
| 答辩日期 | 2015-05-29 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 北京 |
| 导师 | 陈令新 |
| 关键词 | 分子印迹聚合物 表面印迹 藻蓝蛋白 汞形态分析 传感 |
| 中文摘要 | 样品前处理技术在污染物分析方面一直起着不可替代的重要作用，越是高灵敏的仪器，它对样品的纯度状态要求也越高。分子印迹技术依靠其良好的选择性，在样品前处理、传感、酶模拟等方面取得了快速的发展。本文针对传统分子印迹聚合物存在模板分子洗脱困难、印迹容量低，传递速率慢等缺点，利用一些新型的制备技术和材料，将其与表面印迹技术相结合，开发了一系列新型表面印迹聚合物，并将其运用到环境和生物样品的分析检测和传感中，主要的研究内容和结果如下： （1）均匀核壳印迹聚合物：壳层厚度与吸附容量关系的研究 通过核壳乳液聚合法制备了苏丹红核壳印迹聚合物，建立了壳层厚度与吸附容量之间的关系模型。分别采用了三种方法：调节预聚溶液的量、调整SDS的用量和两步升温法对壳层厚度进行可控调节。当壳层厚度为2.60 μm时，核壳印迹聚合物具有最高的吸附容量为30.1 μmol/g。通过模型拟合，发现静态吸附过程符合Langmuir-Freundlich方程，吸附动力过程符合伪二阶方程。对4种苏丹红样品进行测定，对苏丹红I具有良好的选择性，印迹因子为2.69。建立的核壳厚度与印迹容量之间的模型为制备核壳印迹聚合物和分子识别的理论探索提供了基础。 （2）磁性印迹微球的制备及识别检测藻蓝蛋白 以藻蓝蛋白为模板，在磁性纳米粒子表面进行氨基修饰、醛基改性，结合细乳液聚合开发了一种简单、高效制备蛋白质磁性核壳印迹微球的方法。得到的印迹微球吸附容量为10.53 mg/g，对藻蓝蛋白具有明显的选择吸附能力，印迹因子为2.41。此外，印迹微球不仅能在宽pH范围内灵敏荧光检测藻蓝蛋白，而且能通过磁场快速分离。印迹微球作为吸附剂也成功应用到电泳预处理中，用于蛋白质的分离提纯。结合表面印迹和磁响应的优点，该方法在未来对细胞中特定蛋白进行特异吸附有巨大发展潜力。 （3）磁性印迹微马达的合成及选择性识别和去除海水中的藻蓝蛋白 将藻蓝蛋白作为模板分子，用掺杂聚苯乙烯磺酸的聚-乙烯二氧噻吩作为电化学选择性材料，以镍作为磁导航材料，金属铂作为固体支架和催化双氧水水解的催化剂，以多孔模板辅助化学电沉积法形成管状结构，得到了磁性印迹微马达。通过共焦显微镜观察，微马达呈现两种不同的运动轨迹，运动速度也可以通过模型进行计算，表明速度和过氧化氢浓度有线性关系。磁性微马达对藻蓝蛋白具有特异性识别与吸附能力，在海水样品中对分析没有干扰，并能实现对蛋白的吸附、运输可视化。该方法不仅丰富了蛋白质印迹的研究内容，而且为催化微马达多功能、智能化提供了行之有效的思路，具有广泛的应用前景。 （4）基于量子点的蛋白质介孔印迹微球的合成及用于荧光检测藻蓝蛋白 基于量子点和介孔硅结构，以藻蓝蛋白为模板，采用溶胶–凝胶法制备了一种新型荧光印迹微球，用于特异识别和灵敏检测藻蓝蛋白，其荧光变化服从电子转移引发的荧光猝灭机理。在藻蓝蛋白的存在下，藻蓝蛋白和氨基形成复合物，然后量子点的能量将转移到复合物上，使得量子点的荧光减弱。据此可实现对藻蓝蛋白的高效识别与荧光灵敏检测，在0.02–0.8 µM的浓度范围有令人满意的线性，最低检测限达到5.9 nM。此外，以三个浓度水平检测海水和湖水中的藻蓝蛋白，回收率为94.0–105.0%。本研究提供了一种方便、快速识别和检测复杂基质中的痕量蛋白质的有效方法，丰富了蛋白质印迹的相关研究。 （5）基于双硫腙螯合作用的汞离子印迹聚合物的制备及在环境和生物样品中的汞形态分析 将双硫腙和汞的螯合物为模板分子，用APTES作为功能单体，TEOS作为交联剂，采用溶胶–凝胶法制备汞离子印迹聚合物，用于生物样品中汞的形态分析。所得聚合物对汞离子具有吸附容量高、传质速率快、识别选择性强和抗干扰能力强等优点。该聚合物作为固相萃取吸附剂，实现了高选择性富集环境和生物样品中的汞离子，进而将汞离子分离去除。此外，借助双硫腙的螯合原理，实现了生物样品中汞的形态分析。采用两种法定标准材料对该方法进行验证，具有良好的一致性。证明该方法可以应用于快速、高效去除、浓缩和测定复杂基质中痕量的不同形态汞。 |
| 英文摘要 | Sample pretreatment techniques have still played important and irreplaceable roles in the environmental pollutants analysis. As for the high sensitive instrument, it requires high purity of the sample. Molecular imprinting technology due to its good selectivity has been rapidly developed in sample pretreatment, sensing, enzymes simulation. MIPs still face severe challenges, involving low binding capacity, template leakage and slow transfer rate. In the present thesis, some new technologies and materials were introduced to combine with surface molecular imprinting and a series of surface imprinting polymers were developed and applied to the environment and biological samples, and the research contents and results are as follows: (1) Uniform core-shell molecularly imprinted polymers: A correlation study between shell thickness and binding capacity Herein, we purpose to explore the correlation between shell thickness and binding capacity to prepare different CS-MIPs at the surface of carboxyl polystyrene through emulsion polymerization. Main factors were studied such as the amount of prepolymer solution, the amount of SDS and the temperature step. Consequently, the CS-MIPs with 2.60 μm of shell thickness presented the highest binding capacity of 30.1μmol/g and the most rapid mass transfer rate. The static adsorption isotherm followed the Langmuir-Freundlich adsorption model, and the kinetics obeyed the pseudo-second-order kinetics model. Recognition specificity for Sudan I with respect to its analogues was well displayed, with a high imprinting factor of 2.69. The establishment of critical value of shell thickness provides new insights into the preparation methodology and molecular recognition mechanism of core-shell imprinted polymers. (2) Magnetic coreshell imprinting microspheres strategy for recognition and detection of phycocyanin By using phycocyanin as a model, we developed a facile and highly efficient approach to obtain magnetic coreshell imprinting microspheres. Miniemulsion polymerization was employed, based on surface immobilization of phycocyanin with aminolysis and aldehyde modification on magnetic support particles. The imprinting microspheres exhibited high adsorption capacity of 10.53 mg/g, excellent binding selectivity toward phycocyanin with a high imprinting factor of 2.41. Furthermore, fast magnetic separation and sensitive fluorescent detection in a wide pH range was offered for phycocyanin. Consequently, the imprinting microspheres were successfully as sorbents applied for selective isolation of phycocyanin from protein mixtures. Taking advantages of magnetic polymers and surface imprinting, the developed strategy provides great application potentials for convenient, rapid targeting identification/enrichment and separation of proteins. (3) Magnetic molecularly imprinted micromotor for selective recognition and transport of fluorescent phycocyanin in seawater An attractive magnetic micromotor for selective recognition and transport of phycocyanin via a template electrodeposition process was proposed. The MIP-based catalytic micromotor was fabricated using phycocyanin as imprinting molecule, PEDOT as electrochemical selective material, nickel as magnetic navigation material, and metal platinum as solid support and catalyst to facilitate the catalytic micromotor freely move in solutions. The autonomous self-propulsion micromotor presented two different trajectories by confocal microscope. The movement velocity was calculated based on the body-deformation model, suggesting a linear positive correlation between the velocity and hydrogen peroxide concentration. In addition, high efficient targeted identification and enrichment abilities were demonstrated based on the magnetic imprinted layer. No obvious interference was found from complicated matrices such as seawater samples, along with a real-time visualization of the protein loading and transport. Related studies would not only enrich the research connotations of protein imprinting, but also push forwards the development of multi-functionalized intelligent devices and strategy. (4) Quantum dots based mesoporous structured imprinting microspheres for the sensitive fluorescent detection of phycocyanin Herein, using phycocyanin as template via a sol–gel process, we developed a novel fluorescent probe for specific recognition and sensitive detection of phycocyanin by quantum dots based mesoporous structured imprinting microspheres, obeying electron-transfer-induced fluorescence quenching mechanism. In the presence of phycocyanin, a Meisenheimer complex would be formed between phycocyanin and primary amino groups on the surface of the QDs, and then the photoluminescent energy of QDs would be transferred to the complex and then result in QDs fluorescence quenching. The SiO2@QDs@ms-MIPs produced a significantly reduced fluorescent intensity and accordingly presented a satisfactory linearity in the range of 0.02–0.8 µM and a high detectability of 5.9 nM. Moreover, recoveries ranging from 94.0–105.0% were attained for spiked seawater and lake water samples with three concentration levels of phycocyanin. The study provided an effective way to develop fluorescent probes for convenient, rapid recognition and detection of trace proteins from complex matrices, and further pushed forward protein imprinting research. (5) Hg2+ ion-imprinted polymers sorbents based on dithizone-Hg2+ chelation for mercury speciation analysis in environmental and biological samples Novel Hg2+ ion-imprinted polymers were synthesized by sol–gel process, using the chelate of dithizone and Hg2+ as template and APTES as functional monomer, followed by solid-phase extraction and atomic fluorescence spectroscopy detection, for mercury speciation analysis in environmental and biological samples. The resultant Hg-IIPs offered high binding capacity and fast kinetics. The IIPs displayed excellent selectivity toward Hg2+ over its organic forms and other metal ions, as well as high anti-interference ability for Hg2+ confronting with common coexistent ions. Moreover, by virtue of the chelation of dithizone, the IIPs could readily discriminate Hg2+ from organic mercury. The method was validated by using two certified reference materials with very consistent results. The IIPs-SPE-AFS demonstrated great application perspectives for rapid and high-effective cleanup, enrichment and determination of trace mercury species in complicated matrices. |
| 学科主题 | 化学 ; 环境科学 |
| 语种 | 中文 |
| 源URL | [http://ir.yic.ac.cn/handle/133337/8967]  |
| 专题 | 中科院烟台海岸带研究所知识产出_学位论文 |
| 作者单位 | 中国科学院烟台海岸带研究所 |
| 推荐引用方式 GB/T 7714 | 学位论文. 新型表面印迹聚合物的制备及其在样品前处理和传感中的应用[D]. 北京. 中国科学院研究生院. 2015. |
入库方式： OAI收割
来源：烟台海岸带研究所
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