本体聚合法制备2-氯酚分子印迹聚合物及其性能评价

采用本体聚合法,以2-氯酚为模板分子,4-乙烯吡啶为功能单体,三羟甲基丙烷三甲基丙烯酸酯为交联剂合成了一系列分子印迹聚合物,并通过选择性实验和静态吸附实验对聚合物的选择性及吸附性能进行评价.结果显示:当以甲苯作为致孔剂,功能单体与模板分子的摩尔比为2:1时,聚合物对模板分子的印迹因子为1.71,亲和位点总数Bmax为0.1137 mmol/g,具有最优的选择性和吸附能力.     

分子印迹纳米胶体阵列检测爆炸物的研究

以三硝基甲苯(TNT)为模板,丙烯酰胺为功能单体,采用乳液聚合法制备具有单分散性的TNT分子印迹胶体小球.通过垂直沉降法自组装,并用胶带将得到的具有蛋白石结构的分子印迹胶体阵列(MICA)固化.研究其在不同比例的甲醇/水溶液中的光学响应,并在最优检测环境下进行特异性吸附实验.实验表明,当甲醇/水的体积比为7∶3,TNT浓度为20 mmol/L时,反射峰红移近24 nm,为非印迹胶体阵列红移量的1.4倍,为TNT结构类似物的23倍.MICA在实现对光子晶体传感器制备简化的同时,提供了对TNT进行快速裸眼检测的可能性.     

吡哌酸分子印迹聚合物的分子识别

采用分子印迹技术合成了吡哌酸分子印迹聚合物。运用平衡结合实验研究了聚合物的吸附特性和选择性识别能力。Scatchard分析表明,在本文所研究的浓度范围内,聚合物中形成了两类不同的结合位点。吡哌酸分子印迹聚合物对吡哌酸呈现较高的选择识别特性,可作为固相萃取剂,在人血清吡哌酸的分析中对样品进行了有效的提取和净化。     

香草醛系列化合物分子印迹聚合物膜的渗透特性

以香草醛(Van)或邻香草醛(o-Van)为模板分子, 用紫外光引发原位聚合, 分别制备了以尼龙和聚偏氟乙烯微孔滤膜为支撑材料的分子印迹复合膜, 并用紫外分光光度法研究了模板分子与功能单体之间的相互作用. 模板分子及竞争物的混合溶液渗透实验结果表明, 支撑材料对膜选择性传输趋势基本没有影响, 但选用合适的支撑材料会得到更理想的分离效果; 当竞争物尺寸小于模板分子时, 尺寸效应起主要作用, 竞争物优先传输; 当模板分子与竞争物尺寸相近时, 尺寸效应不起作用, 模板分子的选择性识别位点及与其相匹配的孔穴起主要作用, 模板分子优先传输; 当竞争物尺寸大于模板分子时, 则尺寸效应和模板分子的选择性识别位点及与其相匹配的孔穴同时起作用, 故模板分子优先传输.     

RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials （i. e., molecularly imprinted polymers, MIPs） with tailor-made recognition sites for certain target molecules. The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation. Recent years have witnessed significant progress in the synthesis and applications of MIPs. This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.     

分子烙印聚合物为固定相分离和识别磺胺类药物

以磺胺甲噁唑为模板分子,采用原位聚合法制备了具有特定识别性能的棒状分子烙印聚合物。作为高效液相色谱的固定相实现了磺胺甲噁唑与其结构类似物的分离。磺胺甲噁唑烙印聚合物和目标分子之间的相互作用除了特异性的氢键作用外,也存在着疏水作用。同时考察含水量、流速对分离的影响,论证了分子烙印聚合物选择性专一的作用原理。结果表明,这种棒状聚合物对模板分子及其类似物有很好的分离能力。     

Molecularly Imprinted Polymers for Stir Bar Sorptive Extraction: Synthesis,Characterization, and Application

Stir bar sorptive extraction is widely used for the preconcentration of organic and inorganic compounds due to its simplicity and versatility. However, commercially available devices are based on nonselective sorbents. Molecularly imprinted polymers provide selective recognition abilities from the template employed during their preparation. In this review, strategies employed for recent for molecularly imprinted polymers employed in stir bar sorptive extraction are described. The advantages and disadvantages are described, as well as future trends involving this preconcentration methodology.     

Preparation and Adsorption Characteristics of Cordycepin Molecularly Imprinted Polymers

The separation of a molecularly imprinted polymer for cordycepin was investigated. The synthesis employed cordycepin as the molecular template, alpha-methylacrylic acid as the functional monomer, glycol dimethyl acrylate as the cross-linking agent, azobisisobutyronitrile as the initiator, and tetrahydrofuran as the solvent and pore-foaming agent. The interaction between cordycepin and the functional monomer was investigated by ultraviolet-visible and infrared spectroscopy. The properties of the molecularly imprinted polymer were analyzed by scanning electron microscopy, equilibrium adsorption experiments, and the Scatchard equation. Static adsorption, solid phase extraction, and high-performance liquid chromatography experiments were employed to evaluate the adsorption properties and selective recognition characteristics. The results showed that the molecularly imprinted polymer had specific adsorption with cordycepin, and the maximum absorption capacity was 1920 µg/g. Scatchard analysis suggested that high affinity and low affinity binding sites were present. For the high affinity case, the dissociation constant and apparent maximum numbers of the binding sites were 0.0089 mmol/L and 4.78 µmol/g, respectively. The dissociation constant and apparent numbers of binding sites were 0.035 mmol/L and 6.047 µmol/g for the low affinity sites. Compared with the corresponding nonimprinted polymer, the cordycepin molecularly imprinted polymer exhibited higher adsorption and selectivity for cordycepin than structural analogs.     

分子印迹微凝胶模拟酶的研究

采用油包水反相乳液法, 以马来酸酐酯化葡聚糖-氨基吡啶偶联物(Dex-MA-AP)为功能大单体、过渡态类似物p-硝基苯磷酸酯(NPP)为模板分子、Co2+为中心离子, 制得分子印迹微凝胶模拟酶(MIGs). 用紫外光谱研究了Dex-MA-AP上吡啶功能基团与NPP之间的相互作用. 用SEM观察了MIGs的形貌和大小. 研究发现, MIGs催化活性受模板分子和交联剂用量的影响,MIGs催化p-硝基乙酸苯酯(NPA)水解反应行为可用Michaelis-Menten方程进行描述, 其最大催化水解反应速率(Vm)和Michaelis-Menten常数(Km)分别为25.1 nmol/h和0.030 mmol/L, 且具有较好的催化选择性.     

Synthesis and characterization of a novel molecularly imprinted polymer for simultaneous extraction and determination of water-soluble and fat-soluble synthetic colorants in chilli products by solid phase extraction and high performance liquid chromatography

A sorbent was synthesized and investigated for molecularly imprinted solid phase extraction (MISPE). Molecularly imprinted polymers (MIP) were synthesized via precipitation polymerization procedure, where 4-vinyl pyridine (4-VP) was used as functional monomer and ethylene glycol dimethacrylate (EDMA) as cross-linking agent. The imprinting effect of the MISPE was evaluated by elution experiments. The resulting MISPE showed high extraction selectivity to water-soluble and fat-soluble synthetic colorants. The determination of multi-residue for three kinds of water-soluble and six kinds of fat-soluble synthetic colorants in chilli products was also investigated by HPLC coupled with MISPE. The mean recoveries calculated by solvent calibration curve for water-soluble and fat-soluble synthetic colorants were from 72.1% to 95.6% for chilli spice and 72.1% to 92.3% for chilli powder. The decision limit (CCα) and the detection capability (CCβ) obtained for water-soluble and fat-soluble synthetic colorants were in the range of 1.2–1.6 and 1.9–2.4 μg kg⁻¹ in chilli spice and chilli powder. The resulting MISPE was successfully used off-line for the determination of nine kinds of synthetic colorants in chilli products.     

分子印迹阵列式传感器的研究进展

分子印迹阵列式传感器具有识别率高、选择性好、价格低廉等优点,受到研究者们的极大关注,已经在食品分析、环境分析、药物分析、临床诊断等研究领域中得到应用。分子印迹阵列式传感器是以分子印迹聚合物作为识别元素的集成化传感器,通过各传感单元对分析物响应后产生的特征图谱实现对目标化合物的识别,不仅可用于单一目标化合物的选择性识别,还可以用于多种目标化合物同时存在时的测定。分子印迹阵列式传感器的响应信号机制主要划分为光信号、质量敏感信号和电化学信号等。本文简要介绍了分子印迹技术的产生和发展,重点评述了基于三种信号机制的分子印迹阵列式传感器的研究进展,并展望了分子印迹阵列式传感器的应用前景和研究方向。     

胆固醇分子印迹聚合物的制备及其选择性吸附

随着人们生活水平的逐步提高,因人体内胆固醇过高所产生的疾病呈逐年增加的趋势.近年来的研究表明,胆固醇分子印迹聚合物对胆固醇具有良好的选择性吸附能力.将胆固醇分子印迹聚合物作为胆固醇的识别剂,提取食品中的胆固醇和治疔胆固醇有关的疾病,展现出了良好的应用前景.本文分别从胆固醇分子印迹聚合物的制备方法、识别机理、提高选择性识别途径以及新的印迹方法等方面进行了综述.     

Synthesis and characterisation of molecularly imprinted catalytic microgels for carbonate hydrolysis

Novel molecularly imprinted microgels incorporating arginine and tyrosine side chains as functional monomers have been designed and synthesised with percentages of cross-linker ranging from 70 to 90%. Full chemico-physical characterisation including M_r, coil density and size particle determination concluded that all polymer preparations obtained can be classified as microgels. Molecular imprinting using a phosphate template was used to generate catalytic microgels for the hydrolysis of p-nitrophenyl carbonates. Kinetic characterisation of the catalytic activity of the different preparations indicated that values of critical monomer concentration (C_M) and percentage of cross-linker play an important role in determining the catalytic efficiency of the different preparations. Microgels containing 70% cross-linker were the only ones following the Michaelis-Menten saturation model and kinetic parameters were obtained using 4 mg/ml of M397: V_max = 1.34 × 10⁻⁶ M s⁻¹ (S.E. 1.28 × 10⁻⁷) and K_M = 2.38 × 10⁻³ M (S.E. 3.1 × 10⁻⁴).     

单分散双酚A分子印迹微球的制备及其色谱性能

通过改变块状聚合法的合成条件,使用液体石蜡和甲苯的混合溶剂为致孔剂,发展了一种制备双酚A(BPA)分子印迹微球的简单方法。微球的粒径、分散度可通过液体石蜡和甲苯的比例调节。当液体石蜡和甲苯的体积为5mL、体积比为2∶3,EGDMA的量为24mmol时,可得到直径约为3μm、单分散BPA分子印迹微球。液相色谱评价显示,相比于传统的块状聚合方法,本微球具有良好的印迹效应。本法有望成为制备适合于HPLC填充使用单分散分子印迹微球的一种有效方法。     

纳米结构分子印迹聚合物及其在药物分析中的应用进展

纳米材料是纳米技术发展的重要基础,它具有许多传统材料所不具备的独特的理化性质,因此有着广泛的应用前景.分子印迹技术是一种通过模拟抗体-抗原相互作用原理,制备具有分子识别功能的聚合物的技术.以纳米材料制备的分子印迹聚合物具有较高的结合容量,较大的选择性和较快的结合动力学特性,近年来备受关注.本文简单概述了零维、一维、二维纳米结构分子印迹聚合物的合成、表征方法及研究现状,并对其在手性药物分析、临床药物分析、传感器及药物残留检测中的应用进行了综述.     

水溶液微悬浮聚合法制备酸性药物吲哚美辛分子印迹微球及其色谱表征

以带有羧基的酸性药物吲哚美辛为模板分子、碱性的4-乙烯基吡啶为功能单体,采用水溶液微悬浮聚合法制备了用于色谱分离的微米级分子印迹微球.详细讨论了流动相中缓冲溶液的pH值对吲哚美辛在MIMs柱上的容量因子(k′)、分离因子(α)和印迹因子(β)的影响.通过MIMs柱对吲哚美辛和4-氨基吡啶(4-AP)的保留行为的比较,证明以4-乙烯基吡啶为功能单体制得的MIMs对吲哚美辛的识别作用,主要靠吡啶环上氮原子与吲哚美辛羧基之间的离子键相互作用,以及吡啶环与模板分子之间的π-π相互作用.     

Thymopentin Magnetic Molecularly Imprinted Polymers with Room Temperature Ionic Liquids as a Functional Monomer by Surface-Initiated ATRP

Ionic liquids are also called “designer solvents.” In this article, we calculated the interaction energy of four ionic liquids with a template by molecular dynamics simulation. A simple approach was used to prepare biomacromolecule molecularly imprinted polymers for adsorbent and separation thymopentin (Tp5). In order to overcome intrinsic and increase structural selectivity, surface-initiated ATRP and ionic liquids (ILs) as functional monomer were used to prepare Fe3O4 molecularly imprinted polymers. Selective adsorption was applied to investigate the interactions between the polymers and lysine, phenylalanine, glutathione (GSH), and hemoglobin. The results demonstrated that Fe3O4 MIPs with 1-vinyl-3-ethyl acetate imidazolium chloride as functional monomer demonstrated high isolation and recognition of performance to the Tp5.     

分子印迹聚合物的制备及其传感器应用研究

分子印迹技术于近十年内得到了飞速的发展,已经成为当前研究的热点之一.本文主要介绍了分子印迹聚合物的原理以及一些常用制备方法.分子印迹聚合物的一个重要应用是在化学传感器中作为识别元件,研制稳定、低成本的分子印迹传感器.分子印迹聚合物在传感器领域的应用是分子印迹技术的一个重要方面,本文综述了分子印迹聚合物在化学传感器方面的应用研究现状,并对分子印迹传感器的发展前景进行了评述.     

分子印迹聚合物微球的制备及应用研究进展

球形分子印迹聚合物具有制备简单、使用方便；分子识别效率高且便于功能设计等优点，近年来成为分子印迹技术领域研究的热点之一。对球形分子印迹聚合物微球的制备及其应用研究进展作了较为详细的介绍。     

Investigation of protein imprinting in hydrogel-based molecularly imprinted polymers (HydroMIPs)

We have developed a strategy to produce molecularly imprinted polymers based on polyacrylamide hydrogels for the selective imprinting of bovine haemoglobin (BHb). For the first time, we have explored in detail a variety of template removal strategies including varying ratios of sodium dodecylsulphate:acetic acid (SDS:AcOH) and also the use of a trypsin digest. The optimum ratio of SDS:AcOH was found to be a 10% (w/v):10% (v/v) for the most effective template removal. This resulted in >90% (imprinting efficiency) of re-loaded template (protein) molecule being selectively bound within the MIP. At 15%:15% of SDS:AcOH, although there was even more initial template removal, subsequent re-binding studies showed a decrease in imprinting efficiency (67.9%). Trypsin solutions were also used as a method of template removal. Up to 87.4% of template was reproducibly removed initially; however, the imprinting efficiency was only 20.4%. The high selectivity of the BHb HydroMIP to BHb compared with other structural analogues (namely cytochrome C and myoglobin) was successfully demonstrated.