分子印迹胶体阵列检测对硝基苯酚

以对硝基苯酚(p-NP)为印迹模板,丙烯酰胺为功能单体,制备单分散的对硝基苯酚分子印迹胶体微球。通过垂直沉降法将分子印迹胶体微球自组装为分子印迹胶体阵列,采用胶带将分子印迹胶体阵列粘贴固定。固定于胶带上的分子印迹胶体阵列膜显示出良好的稳定性,而且对目标分子p-NP具有明显的光学响应。分子印迹微球吸附目标分子发生溶胀,引起胶体阵列溶涨,分子印迹胶体阵列(MICA)反射峰位置发生移动。实验结果显示,MICA随着p-NP浓度增加,反射峰红移近60 nm,MICA表面颜色由红色逐渐变为蓝紫色;而非印迹胶体阵列红移量只约40 nm。MICA简化了光子晶体凝胶传感材料的制备步骤,为开发新型高性能生化传感器材料提供了新思路。     

TNT分子印迹聚合物微球的合成与性能研究

以三硝基甲苯(TNT)为模板分子,EDMA为交联剂,采用沉淀聚合法制备了TNT分子印迹微球.讨论了溶剂用量、模板分子用量、功能单体种类等对分子印迹微球的形貌及吸附性能的影响;利用紫外吸收光谱和BET表征了印迹聚合物微球的结合位点相互作用与印迹孔穴结构;通过平衡吸附和选择性吸附实验,研究了印迹聚合物微球的吸附性能和选择性识别性能.结果表明,以丙烯酰胺为功能单体制备的分子印迹聚合物为规则的球形,内部含有分子印迹孔穴,微球的粒径为1～2μm.印迹聚合物微球可在30 min内达到吸附平衡,在1 mmol/L的TNT乙醇溶液中,印迹聚合物微球的平衡吸附量为32.5 mmol/kg,对TNT分离系数为25.19,具有较好的特异性吸附能力,并可选择性识别TNT分子.     

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.     

沉淀聚合法制备TNT分子印迹聚合物微球

以TNT为模板分子,丙烯酰胺为功能单体,二甲基丙烯酸乙二醇酯为交联剂,乙腈为溶剂,用沉淀聚合法制备了TNT分子印迹微球.紫外吸收光谱证实TNT与丙烯酰胺之间存在相互作用;平衡吸附实验结果表明,制备的分子印迹聚合物微球对TNT分子有较好的特异性吸附能力,能够选择性识别TNT分子.     

苏丹红I分子印迹聚合物的制备及其性能评价

以苏丹红I为模板分子,通过沉淀聚合法制备了一种对苏丹红I具有特异性吸附的分子印迹聚合物。通过选择性评价和前沿色谱实验,评价了致孔剂的选择和用量、功能单体和模板分子的物质的量比对分子印迹聚合物识别性能的影响。实验结果表明: 当以甲醇和乙腈的混合液(体积比为30:10)为致孔剂,甲基丙烯酸(MAA)为功能单体,且功能单体和模板分子的物质的量比为8:1时,分子印迹聚合物的印迹因子为2.32,亲和位点总数(Bt)为0.50 μmol/g;将其作为固相萃取柱填料用于辣椒粉样品中痕量苏丹红I的净化和富集,结果表明: 苏丹红I浓度在10～500 μmol/L范围内时,呈现良好的线性关系(r=0.999);检出限为3.3 μmol/L,加标回收率为95.87%～98.41%,相对标准偏差低于3.1%。该方法有望用于辣椒粉样品中苏丹红I添加剂的常规检测。     

分子印迹光子晶体传感芯片的制备及对邻苯二甲酸酯类化合物的检测

将光子晶体与分子印迹技术相结合,制备了一种反蛋白石结构的分子印迹光子晶体传感芯片,并将其应用于4种邻苯二甲酸酯类化合物的检测效果研究.分子印迹光子晶体传感芯片的制备过程包含3个步骤.首先,通过垂直沉降自组装方法制备SiO2蛋白石结构模版;随后,向蛋白石结构模板空隙中填充含有印迹分子邻苯二甲酸二异壬酯(DINP)的预聚液,引发光聚合;最后,移除SiO2结构模版及印迹分子,得到对邻苯二甲酸酯类化合物具有特异性识别功能的分子印迹光子晶体传感芯片.结果表明,传感芯片对待测物分子的识别过程可通过布拉格方程转换为可读的光学信号,当4种待测物浓度从1×10-5 mol/L增大到1 mol/L时,最大衍射峰位置发生20～40 nm的红移,且检测过程仅需6 min.检测芯片高度交联的聚合物结构令其具有较高的稳定性和重复利用性,5次检测后,芯片仍保持较好的传感性能.     

手性药物(S)-布洛芬氢键自组装印迹聚合物识别机理

以含有单一结合基团的手性药物(S)-布洛芬作为模板分子,制备了系列印迹聚合物.采用紫外-可见光谱和红外光谱对印迹及识别机理进行了研究.结果表明,模板分子与功能单体分别通过形成蓝移氢键和红移氢键完成预组装过程和再识别吸附过程,且形成了主客体配比为1∶1的配合物.等温吸附实验结果表明,印迹聚合物对模板分子表现出明显的选择性吸附,特异性吸附容量为37.92μmol/g,印迹指数为3.06,且印迹聚合物内特定的三维空间结构对其特异性吸附性能具有显著影响.由手性分离实验考察了印迹聚合物的拆分性能,其对(R)-布洛芬的分离因子为1.79.     

基于葡聚糖自组装胶体粒子的分子印迹传感器的制备及电化学性能

首先,以光敏小分子肉桂酸(CINN)为疏水基元,通过酯化反应对葡聚糖(Dex)进行疏水改性,制备双亲性大分子Dex-CINN;然后,利用选择性溶剂法诱导Dex-CINN与模板分子葡萄糖(Glu)共组装,制备分子印迹胶体粒子(MINPs)。通过红外光谱(FT-IR)和核磁共振氢谱(1 HNMR)确定Dex-CINN的化学结构及改性率。利用Zeta电位及纳米粒度仪和透射电子电镜(TEM)对MINPs的粒径、电位及形貌进行表征。利用滴涂或电泳沉积的方法使MINPs在电极表面二次组装构建MINPs涂层,通过光交联固定涂层结构,再洗脱除去模板分子后得到分子印迹传感涂层。通过扫描电子显微镜(SEM)对两种分子印迹传感涂层的形貌进行表征,并进一步利用循环伏安法(CV)、差分脉冲溶出伏安法(DPSV)对比研究两种分子印迹传感涂层的分析检测性能。研究结果表明:通过滴涂或电泳沉积的方法均能在电极表面制备分子印迹传感涂层;相比于滴涂法,电泳沉积法所制备的分子印迹传感涂层连续均匀,所形成的传感器对Glu具有更好的响应性以及识别能力,检测下限更低。     

对羟基苯甲酸分子印迹传感器的制备及其性能研究

采用简单高效的分子印迹膜技术,制备了对羟基苯甲酸(PHA)分子印迹传感器。敏感膜采用循环伏安法(CV)在玻碳电极表面合成,采用CV、微分脉冲伏安法、线性扫描伏安法和电化学交流阻抗法在K3[Fe(CN)6]/K4[Fe(CN)6]溶液中测试此分子印迹传感器的性能。在最优条件下,PHA检测线性范围为0.6～8.0μmol/L,检测限(S/N=3)为0.2μmol/L。实验结果表明:该分子印迹传感器灵敏度高、选择性好并且具有良好的再生性能,传感器对与PHA结构相似的分子有较强的抗干扰能力,可望用于植物体分泌化感物质PHA的实时监测。     

表面定向磁性印迹聚合物的制备及对槲皮素的选择性识别

利用硼酸功能化的磁性碳纳米管作为反应基质, 采用一种简便、 绿色的硼酸亲和表面定向印迹法制备了槲皮素磁性分子印迹聚合物, 并将其应用于银杏叶提取物中槲皮素的特异性识别. 透射电子显微镜、 X射线光电子能谱仪、 X射线衍射及振动样品磁强计测试结果表明, 制备的分子印迹聚合物具有良好的形貌和晶型结构. 吸附实验结果表明, 该分子印迹聚合物对模板分子槲皮素具有较好的吸附容量(4.57 μg/mg)、 良好的印迹效果(IF=8.44)和再生能力. 对实际中药样品银杏叶提取物的吸附实验结果表明, 所建立的方法能达到预期的槲皮素检测效果, 可作为中药有效成分槲皮素的特异性识别工具.     

Rapid voltammetric determination of nitroaromatic explosives at electrochemically activated carbon-fibre electrodes

The electrochemical behaviour of some nitroaromatic explosives (2,4,6-trinitrotoluene, TNT; 2,6-dinitrotoluene, 2,6-DNT; 2-nitrotoluene, 2-NT; 2-amino-4,6-dinitrotoluene, 2-A-4,6-DNT; 3,5-dinitroaniline, 3,5-DNA; and nitrobenzene, NB) at electrochemically activated carbon-fibre microelectrodes is reported. Electrochemical activation of such electrode material by repeated square-wave (SW) voltammetric scans between 0.0 and +2.6 V versus Ag/AgCl, produced a dramatic increase in the cathodic response from these compounds. This is attributed to the increase of the carbon-fibre surface area, because of its fracture, and the appearance of deep fissures along the main fibre axis into which the nitroaromatic compounds penetrate. Based on the important contribution of adsorption and/or thin layer electrolysis to the total voltammetric response, a SW voltammetric method for rapid detection of nitroaromatic explosives was developed. No interference was found from compounds such as hydrazine, phenolic compounds, carbamates, triazines or surfactants. The limits of detection obtained are approximately 0.03 g mL^–1 for all the nitroaromatic compounds tested. The method was applied for the determination of TNT in water and soil spiked samples; recoveries were higher than 95% in all cases.     

Facile fabrication of free-standing colloidal-crystal films by interfacial self-assembly

This paper reports a rapid and facile method of preparing free-standing colloidal crystals from monodisperse charged polystyrene (PS) microspheres. Mixed solvents (ethanol/water) were used as the dispersion medium in the self-assembly process of colloidal crystals. By a simple "floating self-assembly" method, PS microspheres floated on the surface of liquid and self-assembled into large area of three-dimensional (3D) ordered colloidal crystals within 15 min. Then epichlorohydrin was added in as a cross-linking agent to strengthen the colloidal-crystal film. After cross-linking reactions between the microspheres, the obtained colloidal-crystal film was free-standing and could be easily transferred to other substrates. Using tetrabutyl titanate as a titania precursor, 3D porous TiO(2) materials with rodlike skeletal structure were fabricated from the prepared free-standing colloidal crystal. This work provides a facile method to fabricate free-standing colloidal-crystal film, which can be used as an ideal template for the preparation of porous materials.     

Detection of chlorinated quinones using interdigitated electrodes coupled with capillary electrophoresis

An array of eight interdigitated microband gold electrodes (IDEs) has been developed together with electrophoretic separation for analysis of chlorinated hydroquinones (ClHQs) and benzoquinones (ClBQs). The IDE chip positioned very close to the separation capillary outlet served as an amplification/detection system without the requirement for frequent "capillary-electrode" alignment. ClHQs, electrophoretically migrating to the IDE surface, were oxidized at +1.1 V by seven electrodes of the array and then detected by the remaining electrode, poised at -0.1 V. Conversely, ClBQs were detected at +1.1 V by the detecting electrode after having been reduced at the 7 adjacent electrodes poised at -0.1 V. There was an amplification effect on both the detecting electrode as well as the adjacent electrodes because of the recycle between ClHQs and ClBQs. The detecting "amplification" current response was dependent on the potentials applied, the position of the detecting electrode on the array, the number of adjacent electrodes being used for recycling and the distance between the oxidative and reductive electrodes. Micellar electrokinetic chromatography (MEKC) separation of the analytes was achieved using 30 mM sodium dodecyl sulfate (SDS) with a detection limit in the range of 2-20 micro M. In addition to a facile "capillary-electrode" alignment, the important aspect described here was the capability of detecting through recycling a reduced compound (in the case of ClHQs) at a negative potential to circumvent fouling and electroactive interferences. An appealing feature was also the concurrent oxidation/reduction detection for each compound to ascertain peak assignment, as interfering compounds are less likely to exhibit the same oxidative/reductive characteristics and electrophoretic mobilities as the target analytes.     

Ultrasensitive detection of TNT in soil, water, using enhanced electrogenerated chemiluminescence

The ultrasensitive detection of 2,4,6-trinitrotoluene (TNT) was accomplished on the basis of sandwich-type TNT immunoassay combined with electrogenerated chemiluminescence (ECL) technology. Biotinylated anti-TNT species were attached to the surface of 1-μm diameter streptavidin-coated magnetic beads (MB) and 10-μm diameter avidin-coated polystyrene microspheres/beads (PSB) pre-loaded with ECL labels (∼7 billion hydrophobic ruthenium(II) tris(2,2′-bipyridine) (Ru^II) molecules per bead) to form anti-TNT ↔ MB and anti-TNT ↔ PSB(Ru^II) conjugates, respectively. Sandwich-type PSB(Ru^II) ↔ anti-TNT < TNT > anti-TNT ↔ MB aggregates were formed when PSB(Ru^II) ↔ anti-TNT was mixed with anti-TNT ↔ MB conjugates in the presence of analyte TNT and 2.0% bovine serum albumin blocking agent. The newly formed aggregates were magnetically separated from the aqueous reaction media and dissolved in acetonitrile containing 0.10 M tri-n-propylamine ECL coreactant-0.055 M trifluoroacetic acid-0.10 M tetrabutylammonium tetrafluoroborate electrolyte. ECL as well as cyclic voltammetric measurements were carried out with a potential scan from 0 to 2.8 V vs Ag/Ag⁺, and the integrated ECL intensity was found to be linearly proportional to the analyte TNT concentration over the range of 0.10-1000 ppt (pg mL⁻¹). The limit of detection (≤0.10 ± 0.01 ppb) is about 600× lower as compared with the most sensitive TNT detection method in the literature, and the absolute detection limit in mass (∼0.1 pg) is only ∼0.5% of that from mass spectroscopy. The approach coupled with the standard addition method was applied to measure the TNT contaminations in soil and creek water samples collected from a military training base.     

Amperometric nitrite sensor based on hemoglobin/colloidal gold nanoparticles immobilized on a glassy carbon electrode by a titania sol-gel film

A novel amperometric nitrite sensor was developed based on the immobilization of hemoglobin/colloidal gold nanoparticles on a glassy carbon electrode by a titania sol-gel film. The sensor shows a pair of well-defined and nearly reversible cyclic voltammogram peaks for Hb Fe(III)/Fe(II) with a formal potential (E°) of –0.370 V, and the peak-to-peak separation at 100 mV s^–1 was 66 mV vs. Ag/AgCl (3.0 M KCl) in a pH 6.9 phosphate buffer solution. The formal potential of the Hb Fe(III)/Fe(II) couple shifted linearly with pH with a slope of –50.0 mV/pH, indicating that electron transfer accompanies single-proton transportation. The sensor exhibited an excellent electrocatalytic response to the reduction of nitrite. The reduction overpotential was 0.45 V below that obtained at a colloidal gold nanoparticles/TiO₂ sol-gel film-modified GCE. The linear range for nitrite determination for the sensor was 4.0×10^–6 to 3.5×10^–4 M, with a detection limit of 1.2×10^–6 M. The stability, repeatability and selectivity of the sensor were also evaluated.     

Multichannel homogeneous immunoassay for detection of 2,4,6-trinitrotoluene (TNT) using a microfabricated capillary array electrophoresis chip

A high-throughput homogeneous immunoassay for the sensitive detection of 2,4,6-trinitrotoluene (TNT) has been developed using radial capillary array electrophoresis microdevices. Samples consisting of equilibrium mixtures of anti-TNT antibody (Ab), fluorescein-labeled TNT, and various concentrations of unlabeled TNT were electrokinetically injected into 48 channels of a radial capillary array electrophoresis microchannel plate. The rapid electrophoretic separation allows us to analyze the equilibrium ratio formed by the competition between the labeled and the unlabeled TNT for Ab binding. The simultaneous parallel TNT separations facilitate determination of a calibration curve for the TNT assay, which has high sensitivity (LOD, 1 ng/mL) and a wide dynamic range (1-300 ng/mL).     

Electrochemical Detection of 2,4,6-Trinitrotoluene Using Interdigitated Array Electrodes

Abstract

We describe the use of interdigitated array gold electrodes (IDAs) for the electrochemical detection of 2,4,6-trinitrotoluene (TNT). Our protocol generates a reversible redox couple (hydroxylamine/nitroso) from the initial reduction of TNT, which can be amplified using redox cycling at IDA electrodes. The IDA electrodes give a limit of detection for TNT at ～6 ng/mL with a linear response (r² = 0.998) between 10 and 10,000 ng/mL for static conditions and between 5 and 200 ng/mL for flow conditions (r² = 0.999).     

Template-directed assembly on an ordered microsphere array

We investigated the capability of an ordered array of microspheres to act as a template for deposition and ordering of a subsequent layer of microspheres. An evaporation-based technique was used to deposit monolayers of large colloidal spheres. A novel technique for selective deposition of polyelectrolyte film was used to stabilize the arrays and optimize the bead-substrate interaction. The template behavior of face-centered cubic and body-centered cubic (bcc) microsphere arrays was studied by optical and scanning electron microscopy, and the packing geometry was found to have a dramatic effect on the arrangement of the subsequent layer. A geometrical interpretation of the experimental data explains why a bcc bead array is well suited to act as a template for an additional layer of microspheres.