分子印迹聚合物因其构效预订性、特异识别性和广泛适用性，在过去的三十年中得到了快速发展，成为人们普遍关注的热点。本文主要针对分子印迹聚合物存在的模板分子难以洗脱，印迹聚合物结合容量低、质量传递慢，应用于分子印迹的功能单体种类较少等问题，提出了几种新型分子印迹聚合物的制备方法。具体内容如下：

1活性沉淀聚合制备莠去津印迹聚合物用于食品中莠去津的浓缩富集.将活性聚合中应用广泛的可逆加成断裂链转移聚合与分子印迹聚合物制备中的沉淀聚合相结合，通过活性沉淀聚合制备具有规则球形形貌、表面粗糙多孔的莠去津分子印迹聚合物，提高了分子印迹聚合物的结合容量和质量传递速率。该印迹聚合物理论最大结合容量为2.89 mg/g，而传统沉淀聚合法制备的印迹聚合物最大结合容量仅为 1.53 mg/g。将所制备的新型莠去津分子印迹聚合物用于生菜、玉米加标样品中莠去津的浓缩富集，加标回收率在81.5%–100.9%。

2 活性沉淀表面印迹制备莠去津纳米印迹聚合物粒子.将活性沉淀聚合与二氧化硅表面印迹技术相结合，提出一种简单有效的表面印迹新方法：首先进行简单的一步表面修饰，将乙烯基双键引入到纳米二氧化硅表面，然后通过活性沉淀聚合，辅助两步升温法，制备壳层厚度可控的莠去津表面印迹聚合物。由于活性聚合物结构、分子量的可控性，制备的印迹聚合物形貌规则，粒径具有单分散性，其结合容量高于传统沉淀聚合物。将其用于生菜、玉米加标样品中莠去津的选择性浓缩富集，回收率在79.8%–93.4%。

3 多孔莠去津分子印迹聚合物的制备及其用于固相萃取土壤样品中三嗪类除草剂.将多孔聚合物与分子印迹相结合，制备多孔中空、单孔中空和多孔实心三种多孔结构莠去津印迹聚合物。由于多孔聚合物具有可控孔结构，有利于质量传递，所制备的多孔印迹聚合物在结合容量和质量传递速率上得到大幅度提高。将单孔中空结构莠去津印迹聚合物作为固相萃取填料用于土壤加标样品中五种三嗪类除草剂的高选择性浓缩富集，得到了理想的结果：对 10 μg L-1 的加标样品，加标回收率为 94.5–106%，相对标准偏差 RSD1.17–4.24%。多孔分子印迹聚合物的制备，为复杂样品基质中三嗪类除草剂的分离富集提

供一种有效方法。

4 基于T-Hg2+-T特异结合制备新型汞离子印迹聚合物用于水体中汞离子浓缩富集.基于胸腺嘧啶 T 与汞离子的 T-Hg2+-T 特异结合，设计合成含有 T 基团的新型单体T-IPTS，采用溶胶–凝胶法制备汞离子印迹聚合物，首次将 T-Hg2+-T 特异结合用于汞离子印迹聚合物的制备。鉴于 T-Hg2+-T的高亲和性特异结合，所制备的汞离子印迹聚合物具有较高的选择性，其对 Hg2+的结合容量远高于 Co2+、Mn

2+、Cd2+、Mg2+、Ca2+、Zn2+、Pb2+等。将所制备的新型汞离子印迹聚合物作为固相萃取填料用于水体中汞离子的浓缩富集，加标回收率在95.2%–116.3%。结果表明设计合成新型单体是提高印迹聚合物选择性，开拓分子印迹技术应用范围的有效途径。

5 磁、光双重响应分子印迹聚合物的制备及其在咖啡因浓缩富集中的应用.将刺激响应聚合物制备技术与分子印迹技术相结合，制备具有磁、光双重响应的咖啡因分子印迹聚合物。这种新型印迹材料具有磁性的核和光响应的壳，其光响应性的壳可以在光控下对模板分子咖啡因进行选择性控释。将双重响应印迹聚合物用于复杂样品中咖啡因的浓缩富集，磁性的核为快速分离提供基础，而其光响应的壳为模板分子的洗脱提供了有利条件。在对实际水样、茶水样品和可乐样品进行加标回收实验时，加标回收率在89.5–117.6%。这种磁、光双重响应分子印迹材料为发展简单高效的萃取方法提供了有利的支持。

Molecularly imprinted polymers (MIPs) are becoming increasing recognized as a powerful material that contain tail-made recognition sites for certain molecules, and hence have attracted extensive  research interest due to  the potential application in separation, chemical sensor, environment detection. At present, MIPs still faces severe challenges, involving template leakage, low binding capacity,  and  the rare of  functional monomer.  In this present thesis, several novel MIPs were prepared in order to improve the performances of MIPs, and  the contents of this thesis are as follows: 

1  Molecularly imprinted polymers by reversible addition-fragmentation chain transfer precipitation polymerization for preconcentration of atrazine in food matrices

In  this work, reversible addition-fragmentation chain transfer (RAFT) polymerization, the ideal candidate for controlled/living polymerization, was applied to prepare atrazine molecularly imprinted polymers (MIPs) by precipitation polymerization. The resultant RAFT-MIPs demonstrated  uniform spherical shape with rough surface containing  significant amounts of micropores, leading to an improvement in imprinting efficiency compared with that of the MIPs prepared by traditional precipitation polymerization (TR-MIPs). The maximum binding capacities of the RAFT-MIPs and TR-MIPs were 2.89 mg g-1and 1.53 mg g-1, espectively. The recoveries ranging from 81.5% to  100.9% were achieved by one-step extraction  by using RAFT-MIPs for preconcentration and selective separation of atrazine in spiked lettuce and corn samples. These results provided the possibility for the separation and enrichment of atrazine from complicated matrices by RAFT-MIPs

2  Molecularly  imprinted core-shell nanoparticles for determination of trace atrazine by reversible addition-fragmentation chain transfer surface imprinting

A simple and effective method was proposed to prepare uniform surface imprinted 

nanoparticles. This strategy was carried out by introducing vinyl groups to the surface of silica beads by one-step modification, followed by opolymerization with functional monomers  via reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization. Owing to the intrinsic advantages of controlled/living polymerization and surface imprinting technology, the resultant surface imprinted nano-sized polymers (RAFT-SINPs) demonstrated spherical 

shaped particles with excellent monodispersity, and improvement in imprinting efficiency and mass transfer in comparison to MIPs prepared by traditional precipitation polymerization (TR-MIPs). The recoveries of 93.4% and 79.8% were achieved by one-step extraction when RAFT-SINPs were used for the preconcentration and selective separation of atrazine in spiked corn and lettuce samples, respectively. These results provided the possibility for the separation and enrichment of atrazine from complicated matrices by RAFT-SINPs.

3  Preparation of hollow porous molecularly imprinted polymers and their applications to solid-phase extraction of triazines in soil samples

Porous polymers have aroused increasing interest due to their controllable hole(s) structure in favor of mass transfer.  In this work, three types of porous molecularly imprinted polymers (MIPs) using atrazine as template, namely single-hole hollow molecularly imprinted polymers (s-HMIPs), multihole hollow molecularly imprinted polymers (m-HMIPs) and porous solid molecularly imprinted polymers (ps-MIPs), were prepared, and applied as solid-phase extraction 

(SPE) sorbent for selective preconcentration and specific recognition of triazines in soil samples. For porous MIPs, most of the binding cavities were located in the proximity of the surface, which remarkably  facilitated  template removal and mass transfer. Accordingly, the  s-HMIPs employed as SPE sorbent presented much higher extraction efficiency for several triazines based on the large specific surface area and high adsorption capacity. The validated method was also successfully applied for soil sample analysis, and satisfactory recoveries were attained, such as 94.5–106% with the precision of 1.17–4.24% for three  triazines individual at 10 μg L-1 The .s-HMIPs-SPE proves a high-effective cleanup and enrichment method for simultaneous separation and sensitive determination of triazines in complicated samples.

4 Novel Hg (II) imprinted polymers based on thymine–Hg2+–thymine interaction for high selective preconcentration of Hg (II) in water samples 

A new functional monomer T-IPTS, bearing thymine (T) group, was synthesized for imprinting and specific uptake of Hg2+ Then a novel Hg (II) imprinted olymers based on .thymine–Hg2+–thymine (T-Hg2+-T) interactions (Hg-IIP-T) were prepared by sol-gel process for the first time in this work. Attributed to the specific selective T-Hg2+-T interactions with strong affinity, the obtained Hg-IIP-T displayed high selectivity towards Hg2+over Co2+, Mn2+, Cd2+ ,Mg2+, Ca2+

, Zn2+, Pb2+et al. Accordingly, the IIP-T were used as solid-phase extraction (SPE) sorbent for extraction and enrichment of trace Hg2+in water samples, and satisfactory recoveries ranging from 95.2% to 116.3% were obtained. The IIP-T-SPE proved to be a rapid and high-effective cleanup and enrichment method for trace Hg2+in water samples. More importantly, these results indicated that to design and synthesize new monomers with specific/multi-functional groups would become a general promising way to new imprinted polymers with high selectivity and stability.

5  Photonic  and  magnetic  dual  responsive  molecularly  imprinted  polymers:  preparation, recognition  characteristics and  properties as  novel  sorbent for  uptake and  release  of  trace caffeine in complicated samples

We demonstrated the construction and characteristics of  photonic and magnetic dual responsive molecularly imprinted polymers (DR-MIPs)  prepared by combination of stimuli-responsive polymers  and surface imprinting technique. With the possession of  Fe3O4magnetic core and photoresponsive shell, the resultant DR-MIPs of  Fe3O4@MIPs  exhibited specific affinity to caffeine and  photoisomerization induced  reversible uptake and release of caffeine upon alternate UV and visible light irradiation. The novel DR-MIPs were  used as sorbent for enrichment of caffeine from real water and beverage samples. The recoveries ranging from 89.5–117.6% were achieved. The magnetic core provided fast and simple separation tool while the photonic responsive shell  provided a  simple template eluting method with the assistance of UV-Vis irradiation. The developed method with simplicity, rapidity and reliability proved potentially applicable for trace caffeine analysis in complicated samples.