磺胺二甲嘧啶分子印迹二维光子晶体水凝胶传感器的研究

以聚苯乙烯二维光子晶体为模板,磺胺二甲嘧啶为印迹分子,甲醇为溶剂,甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂,2,2-二乙氧基苯乙酮为引发剂,经紫外光引发低温聚合反应,用甲醇/乙酸(体积比9∶1)混合液洗脱除去印迹分子,制备得到能够特异性识别磺胺二甲嘧啶的分子印迹二维光子晶体水凝胶(MIPH).通过测试该水凝胶传感器在不同浓度的磺胺二甲嘧啶溶液中德拜环直径的变化,考察了其响应性能.实验结果表明,当磺胺二甲嘧啶的浓度从0增加到1×10~(-6)mol/L时,德拜环直径增加0.9 cm,相应的晶格间距减小46 nm.研究发现,当MIPH的交联度为10%,印迹分子与功能单体摩尔比为1∶75时,德拜环直径变化量最大.此外,该水凝胶传感器在浓度为10-6mol/L的磺胺二甲嘧啶类似物磺胺嘧啶(SDZ)、磺胺异噁唑(SIZ)及其它抗生素四环素(TE)、罗红霉素(RM)溶液中,德拜环直径变化量分别为0.4,0.3,0.25和0.2 cm,可见该传感器具有良好的特异性识别功能.将该传感器用于模拟水样及兽用药片中磺胺二甲嘧啶的测定,均具有良好的响应性.     

壬基酚分子印迹二维光子晶体水凝胶传感器

以聚苯乙烯二维光子晶体为模板,壬基酚(NP)为印迹分子,甲醇为溶剂,甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂(EGDMA),2,2-二乙氧基苯乙酮(DEAP)为引发剂,经紫外光引发聚合,得到了可特异性识别壬基酚的分子印迹二维光子水凝胶传感器.通过测量德拜衍射环直径(D)的变化(ΔD)来判断传感器的响应性能.实验结果表明,在壬基酚溶液中,水凝胶的体积膨胀导致凝胶中光子晶体的粒子间距增大,德拜衍射环直径减小.随着溶液中NP的浓度从0增加到1×10^?5 mol/L,德拜衍射环的直径减小了8.0 mm,相应的光子晶体的颗粒间距增加了25.1 nm.在1×10^-13～1×10^-8 mol/L范围内,德拜衍射环直径的变化与壬基酚浓度的对数值(lgc)呈线性关系,制备的传感器检出限低至1×10^?13 mol/L,具有较高的灵敏度、良好的特异性识别能力和稳定的可重复利用性,并且可以实现对壬基酚的可视化检测.     

红霉素分子印迹二维光子晶体水凝胶传感器的研究

以红霉素为印迹分子,聚苯乙烯二维光子晶体为模板,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸甲酯为交联剂,2,2-二乙氧基苯乙酮为引发剂,紫外光引发聚合,在甲醇-乙酸(9∶1, V/V)中洗脱印迹分子,得到能够特异性识别红霉素的分子印迹二维光子晶体水凝胶.通过测试德拜环直径变化,研究了此水凝胶在红霉素溶液中的响应性能.实验结果表明,当红霉素的浓度从0增加到1×10-6 mol/L时,德拜环直径增加6 mm, 相应的晶格间距减小30 nm.此外,水凝胶在1×10-6 mol/L红霉素的类似物罗红霉素、琥乙红霉素溶液中,德拜环直径仅分别增加1.5和2.0 mm,表明此光子晶体水凝胶具有良好的选择性,有望用于红霉素低成本的简易检测.     

高灵敏度二维光子晶体水凝胶Cu~(2+)传感器

以聚苯乙烯二维光子晶体阵列为模板,戊二醛为交联剂,制备了聚乙烯醇二维光子晶体水凝胶(PVA 2DPCH),再以巯基乙酸为酯化剂,通过聚乙烯醇(PVA)的巯基化改性,得到巯基化聚乙烯醇二维光子晶体水凝胶(PVA-SH 2DPCH).利用德拜环法,研究了PVA-SH 2DPCH对Cu~(2+)的响应行为.结果表明,PVA-SH 2DPCH对Cu~(2+)具有超灵敏响应,在Cu~(2+)溶液中,凝胶收缩,其德拜环直径(D)随Cu~(2+)浓度的增大而增大,当Cu~(2+)浓度由0增加至10-15 mol/L时,其德拜环直径即可增加0.45 cm,当浓度继续增大到10~(-7) mol/L时,其德拜环直径(ΔD)可增加0.85 cm.当Cu~(2+)浓度在10~(-15)～10~(-7) mol/L范围内时,PVA-SH2DPCH的德拜环直径变化(ΔD)与Cu~(2+)浓度(c)呈线性关系,其线性回归方程为ΔD=1.195+0.0493×logc,(ΔD, cm;c, mol/L),R~2=0.99899.以制备的PVA-SH 2DPCH为Cu~(2+)传感器,利用德拜环法表征溶液中Cu~(2+)的浓度,方法简单快速兼具无标记、可视化检测的特点,为现场实时检测Cu~(2+)提供了可能.     

甲基丙烯酸/丙烯酰胺双单体共聚反蛋白石光子晶体的制备

以烧结后的二氧化硅光子晶体为模板,采用溶胶凝胶法向模板间隙填充以甲基丙烯酸(MAA)和丙烯酰胺(AM)为双功能单体,N,N’-亚甲基双丙烯酰胺(BIS)为交联剂的聚合物前驱液,制备了甲基丙烯酸/丙烯酰胺共聚(PMAM)双单体反蛋白石凝胶光子晶体.通过紫外可见光谱分析表明,反蛋白石结构的凝胶膜对pH响应范围在4.0～7.0之间.由于其不受离子强度的影响,除了可以作为pH传感器外,还可以作为金属离子及生物小分子等分子印迹光子晶体传感器的基体膜.     

苯胺分子印迹光子晶体水凝胶传感器的研究

基于分子印迹与光子晶体技术,制备了一种高灵敏、特异性好的苯胺水凝胶光学传感器。以Stober法制作的SiO_2微球作为三维光子晶体模板,苯胺为印迹分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸甲酯为交联剂,2,2-偶氮二异丁腈为光引发剂,在紫外光下引发聚合,并在三氯甲烷(加入适量乙醇)中洗脱印迹分子,最终得到具有对苯胺分子有传感功能的分子印迹光子晶体水凝胶传感器。实验结果表明,该传感器对苯胺分子具有良好的识别能力,当苯胺的浓度从0增加到1×10~(-4)mol/L时,通过光谱仪检测出的吸收峰偏移了42 nm。此外,该传感器在苯胺的结构类似物甲基苯胺的缓冲液的响应位移明显较小,表明该传感器具有良好的选择性。     

水相分子印迹光子晶体水凝胶传感器检测尿液中的痕量吗啡

结合水相分子印迹和光子晶体技术构建了吗啡分子印迹光子晶体水凝胶传感器,并成功用于生物样品中痕量吗啡的筛查.以吗啡为印迹模板,甲基丙烯酸为单体,乙二醇二甲基丙烯酸甲酯为交联剂,填充至二氧化硅光子晶体模板孔隙中进行共价型分子印迹聚合,在1％ HF溶液中除去光子晶体模板,并洗脱印迹模板分子,即可得到具有目标分子传感功能的分子印迹光子晶体水凝胶传感器.此传感器在水相环境中对吗啡分子的识别能力良好,可以在不需要标记的情况下,将目标分子的识别转变为衍射峰的位移,该光学信号通过传感器颜色的变化表现出来,吗啡浓度由10 pg/mL增加到1μg/mL过程中,衍射峰最大偏移达到38 nm,并且抗干扰能力强,检出限为0.1 μg/L,响应时间为40 s,可以重复使用.此检测平台不需要对样品进行处理,便可准确、灵敏、快速地检测复杂样品中的目标分析物.     

基于聚丙烯酸二维光子晶体水凝胶的阳离子表面活性剂传感器

以聚苯乙烯二维光子晶体为模板,丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,2,2-二乙氧基苯乙酮为引发剂,紫外光引发聚合,制备聚丙烯酸二维光子晶体水凝胶(PAA 2D-PCH),利用德拜环法研究了其对阳离子表面活性剂的刺激响应行为.实验结果表明,在pH=7.4的磷酸盐缓冲溶液中,PAA 2D-PCH对阳离子表面活性剂有灵敏的响应,凝胶体积收缩,引起颗粒间距减小,德拜环直径增大,衍射波长蓝移,当氯化十六烷基吡啶(CPC)、溴化十六烷基吡啶(CPB)、十六烷基三甲基溴化铵(CTAB)浓度由0增加到4×10~(-3) mol/L时,德拜环直径分别增加了5.95、5.50、5.05 cm,颗粒间距分别减小了380、364、341 nm;而在阴离子表面活性剂、非离子表面活性剂和两性离子表面活性剂溶液中,PAA 2D-PCH的德拜环直径基本保持不变,表明其对阴离子型、非离子型和两性离子表面活性剂均无响应.该PAA 2D-PCH制备简单,有望作为传感器用于水体中阳离子表面活性剂的检测,无需复杂的仪器设备,操作方便、可重复利用,兼具可视化的特点.     

2,4,6-三氯酚分子印迹光子晶体水凝胶传感器的研究

以SiO2三维光子晶体为模板,2,4,6-三氯酚为印迹分子,甲醇为溶剂,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸甲酯为交联剂,通过紫外光引发聚合,在2%氢氟酸溶液中去除光子晶体模板,0.015 mol/L NaOH溶液中洗脱印迹分子,制得2,4,6-三氯酚检测用分子印迹光子晶体水凝胶传感器。结果表明,传感器对2,4,6-三氯酚具有良好的响应与识别能力,在2,4,6-三氯酚浓度由0增加到6×10-4 mol/L过程中,吸收峰红移31 nm;浓度继续增加,吸收峰开始发生蓝移;当浓度增加到1×10-3 mol/L时,吸收峰蓝移56 nm,响应时间仅需要30 min。2,4,6-三氯酚分子印迹光子晶体水凝胶传感器具有高灵敏、高选择、易操作等优点,可实现对2,4,6-三氯酚的裸眼检测。     

葡萄糖检测用分子印迹光子晶体的研究

基于快速、持续、无创检测技术在血糖监测领域的重要性,以聚甲基丙烯酸甲酯微球阵列为光子晶体制孔模板,以葡萄糖为印迹模板,N-异丙基丙烯酰胺和甲基丙烯酸羟乙酯为混合单体,4-乙烯基苯硼酸为识别基,N,N-亚甲基双丙烯酰胺为交联剂,在制孔模板间隙进行共价型分子印迹聚合,除去制孔模板后,制得具有规整孔结构的新型光学凝胶材料--...     

MOLECULAR IMPRINTED POLYMERS—Novel Polymer Adsorbents

Molecular imprinted polymers(MIPs) are novel functional polymer materials and known as specific adsorbents for the template molecules,These novel functional polymers have promised potential applications in racemic resolution,sensor,chromatography,adsorptive separation and other fields.This review exhibits the approach for preparing MIPs,the features of MIPs obtained by different routes and the characteristics of adsorptive separations with MIPs.The molecular recognition mechanism and the idea of the present possibilities and limitations of molecular imprinting polymerization are discussed as well.     

MOLECULAR IMPRINTED POLYMERS——Novel Polymer Adsorbents

1. INTRODUCTIONMolecular imprinted polymers (MIPs) have attracted wide attention for its molecular recognition properties. More and more publications involved in the area of adsorption and separation with MIPs. As early as in 1931, Poljacov [1] found that the pore structure of silica gel was influenced by the size and shape of the molecules in the gas atmosphere when he removed water from the gel under the atmosphere of benzene, toluene and xylene. The gel dried in benzene atmosphere a…     

基于分子印迹技术的丙溴磷压电石英晶体微天平研制

介绍了一种用于检测丙溴磷农药的分子印迹压电生物传感器的构建方法。采用沉淀聚合法合成了农药丙溴磷的分子印迹聚合物,将其固定于石英晶体微天平电极表面构建传感器;采用环境扫描电镜以及原子力显微镜对聚合物形貌、传感器电极表面形貌特征进行分析,并利用传感器对丙溴磷农药进行检测分析,其质量浓度在10~1000 ng/mL范围内,传感器频率改变与丙溴磷浓度之间的响应呈线性关系,线性方程为y=0.139ρ+2.26(r=0.9984)。结果表明,构建的分子印迹压电生物传感器能够对农药进行初步检测,具有较高的灵敏性和较好的特异识别能力。     

A molecularly imprinted photonic polymer sensor with high selectivity for tetracyclines analysis in food

A molecularly imprinted photonic polymer (MIPP) sensor for respective detection of tetracycline, oxytetracycline and chlortetracycline is developed based on the combination of a colloidal crystal templating method and a molecular imprinting technique. Colloidal crystal templates are prepared from monodisperse polystyrene colloids. The molecularly imprinted polymer, which is embodied in the colloidal crystal templates, is synthesized with acrylic acid and acrylamide as monomers, N,N'-methylene bisacrylamide as a cross-linker and tetracyclines (TCs) as imprinting template molecules. After removal of the colloidal crystal template and the molecularly imprinted template, the resulted MIPP consists of a three-dimensional, highly ordered and interconnected macroporous array with a thin hydrogel wall, where nanocavities complementary to analytes in shape and binding sites are distributed. The response of MIPP to TCs stimulants in aqueous solution is detected through a readable Bragg diffraction red-shift, which is due to the lattice change of MIPP structures responding to their rebinding to the target TCs molecules. A linear relationship was found between the Δλ and the concentration of TCs in the range from 0.04 μM to 0.24 μM. With this sensory system, direct and selective detection of TCs has been achieved without using label techniques and expensive instruments. The developed method has been applied successfully to detect tetracycline in milk and honey samples.     

Creatinine Imprinted Photonic Crystals Hydrogel Sensor

There is a demand for simple, selective, and efficient assays for the determination of clinically important metabolites such as creatinine for healthcare. Creatinine is the by-product of muscle energy metabolism and is excreted by the kidneys. To measure creatinine in the human serum, a creatinine imprinted photonic crystal hydrogel (CIPC hydrogel) for naked-eye detection is developed. CIPC hydrogel utilizes polystyrene-based two-dimensional (2D) photonic crystal colloidal arrays (PCs-array) embedded in the polyacrylamide hydrogel containing methacrylic acid which imprinted the creatinine template. The nanocavities in the hydrogel produced after the removal of the template bind to and recognize creatinine in the serum samples. The binding is selective and specific for creatinine. The binding is observed as shrinkage of the hydrogel volume and a decrease in the particle spacing which is monitored through changes in the Debye diffraction ring diameter and a visible blue-green to blue color shift. The binding event and the mechanism are investigated by molecular dockings. The CIPC sensor demonstrates a limit of detection (LOD) of 2.45 ± 1.6 µM, a linear detection range (25–500 µM), and recovery from 85.6 % to 99.9 % in the serum samples. CIPC hydrogel is available for the rapid and quantitative onsite detection of creatinine in the human serum sample.     

分子印迹光子晶体凝胶传感器检测食品中的防腐剂

将响应性光子晶体与分子印迹技术相结合,建立了一种反蛋白石结构的分子印迹光子晶体凝胶传感器,并成功用于水果罐头中痕量防腐剂尼泊金乙酯的筛查。该传感器对尼泊金乙酯具有良好的识别能力,抗干扰能力强,对待测物的识别过程可通过光纤光谱仪转化成可读的光学信号,其布拉格衍射峰位移值与尼泊金乙酯浓度呈线性相关,定量下限为83 mg/L,且可重复使用。该检测平台具有便携式特征,无需对样品进行前处理,可准确、灵敏、快捷地检测复杂样品中的目标分析物,适于现场快速筛查和检测。     

Hydrogel photonic sensor for the detection of 3-pyridinecarboxamide

Molecular imprinting is recognized as a powerful technique for preparing polymeric structures that contains tailor-made recognition sites for certain molecules. By combining a responsive hydrogel photonic crystal and molecular imprinting of 3-pyridinecarboxamide, polyacrylamide (PAM) imprinted photonic crystals (IPCs) with an inverse opal structure were prepared. They showed a rapid, recoverable, and selective response to 3-pyridinecarboxamide, which was detected by measuring the diffraction peak. The position of the diffraction peak could be tuned by copolymerizing acrylamide (AM) with acrylic acid (AA), by changing the ratio of AM to AA, by adding N,N'-methylene bisacrylamide to the monomers, or by imprinting molecules to monomers. More interestingly, the change in the Bragg diffraction of the IPCs can be directly converted into a readable optical signal that is visible to the naked eye without any labeling treatment.     

乙基膦酸分子印迹光子晶体传感器的研究

本研究结合光子晶体与分子印迹技术,制备了一种新颖有机磷毒剂光学传感器——三维分子印迹光子晶体(3D-MIPCs)凝胶膜.采用聚甲基丙烯酸甲酯胶体小球为光子晶体自组装阵列模板,以甲基丙烯酸羟乙酯和N-异丙基丙烯酰胺为混合单体,乙二醇二甲基丙烯酸酯和N,N-亚甲基双丙烯酰胺为混合交联剂,正辛醇和乙腈混合溶液为溶剂,光聚得到印迹聚合物.该材料对乙基膦酸响应速度快、选择性高,其对目标分子的识别作用会导致衍射光谱图的改变.随着在EPA浓度从0.5 mmol/L增加到1.5 mmol/L的过程中,反射峰强度逐渐降低,降幅达到10％,并伴随明显红移.该材料为乙基膦酸检测提供了新的思路,在神经毒剂检测及监控等领域有应用前景.