Imprinted Polymeric Film-Based Sensor for the Detection of Dopamine Using Cyclic Voltammetry

The imprinted polymeric film was synthesized on the glass-carbon electrodes dlrectly. The response to the template molecule-dopamine and other molecules with similar structure was measured by cyclic voltammetry. The response of dopamine on imprinted electrode was much higher than that of other molecules,because of the existing of micro-cavities in polymeric rdm fitting with the size and shape of dopamine in the imprinted polymer.Experimental results showed that dopamlne can be enriched by the imprinted film, therefore increasing the sensitivity of the sensor. The imprinted film could also efface the interference of ascorbic acid, indicating that dopamine can be determined with a large excess of ascorbic acid.     

L-色氨酸分子印迹传感器敏感膜的制备与性能

以L-色氨酸(L-Trp)为模板分子, 邻苯二胺(o-PD)为功能单体, 在金电极表面原位合成了分子印迹聚合物敏感膜; 通过循环伏安法(CV)、 差示脉冲伏安法(DPV)和电化学阻抗谱法(EIS)考察了该电极的性能. DPV测试结果表明, 在1×10^-8~2×10^-7 mol/L范围内, 峰电流与L-Trp的浓度呈线性关系, 检出限为0.3×10^-8 mol/L; 选择识别性实验结果表明, L-Trp印迹敏感膜的印迹因子达到3.72, 相对于干扰物的选择因子均大于1, 对与L-Trp结构相似的L-酪氨酸(L-Tyr)的选择因子也达到2.30, 说明该印迹膜对L-Trp具有良好的选择性; 识别过程动力学研究结果表明, 印迹膜对L-Trp的识别是一个两步连续发生的过程, 即快结合过程和慢吸附过程.     

Design of EGDMA‐Crosslinked Theophylline Imprinted Polymer with High Specificity and Selectivity

An attempt has been made to design theophylline selective polymers with maximum selectivity and specificity, and to relate the rebinding capacity of the polymers with the degree of crosslinking, as well as with the template‐monomer ratio. The theophylline imprinted and non‐imprinted polymers based on methacrylic acid as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent (35–80 mol%) were prepared. The developed imprinted polymers were characterized by FT‐IR, ¹H and ¹³C‐NMR spectra. Equilibrium binding of theophylline by the imprinted and non‐imprinted polymers were investigated and optimized the conditions. Imprinted polymers showed specific binding of the template theophylline. Selectivity of the imprinted polymers was investigated towards caffeine and nicotine. Imprinted polymers showed specific and selective binding of theophylline, which varied with the degree of EGDMA crosslinking. Equilibrium rebinding experiments proved that imprinted polymer with moderate (70%) crosslinking with 1∶2 template‐functional monomer ratio is ideal with maximum specificity and selectivity.     

Preparation of Surface Molecularly Imprinted Poly(dopamine) Film for 4-Hydroxybenzoic Acid (4-BA) Recognition by One-Step Method

In this paper, we present a one-step aqueous self-polymerization strategy to prepare surface molecularly imprinted poly(dopamine) (PDA) film. The method is simple and convenient compared with the “template-guided” surface molecularly imprinted synthesis method and the layer-by-layer self-assembly and the surface-grafted molecularly imprinted synthesis methods. The molecularly imprinted PDA films could selectively bind the template molecules (4-Hydroxybenzoic acid as a model), and bisphenol A (BPA) imprinted PDA films were also investigated. Meanwhile, the 2-dimension imprinted film material was used very conveniently.     

Chiral electrochemical recognition by very thin molecularly imprinted sol-gel films

Thin films with enantioselective properties for electrochemically active chiral probes were developed. Enantioselectivity was accomplished via molecular imprinting. The films were fabricated through the sol-gel technique and were spin-coated on ITO electrodes. The chiral selectivity recognition was detected using two enantiomer pairs: D- and L-3,4-dihydroxyphenylalanine (D- and L-dopa) and (R)- and (S)-N,N'-dimethylferrocenylethylamine [(R)-Fc and (S)-Fc]. A defined chiral cavity was obtained by selection of functional monomers that interact with the template molecule, followed by its removal. Chiral selection properties were measured by cyclic voltammetry and square wave voltammetry. For both template molecules, very good chiral recognition was revealed by electrochemical measurement. The nonspecific adsorption measured for reference nonimprinted films was negligible (less than 5%). Dopa imprinted films revealed both high sensitivity, by the detection of 1 nM (0.2 ppb) concentration, and excellent selectivity, when challenged with a series of catechol derivatives. Fc-imprinted films were able to detect ca. 2 ppm of the target molecule, with very good enantioselectivity and low nonspecific adsorption. To our knowledge, this is the first report of successful molecular imprinting of a ferrocene derivative.     

水杨酸分子印迹膜电化学传感器的制备

以水杨酸为模板分子,采用循环伏安法电聚合形成聚吡咯膜,以固定电位过氧化法去除印迹分子,制备了水杨酸分子印迹膜电极.本印迹电极能促进水杨酸电氧化过程,有效地避免结构类似物(如苯甲酸)对其测定的干扰.循环伏安法用于电化学检测,当富集时间为10 min,磷酸盐缓冲溶液的pH=6.86 时,在1.0×10-6～2.0×10-3 mol/L浓度范围内,水杨酸氧化峰电流与其浓度呈良好的线性关系,检出限为0.8 μmol/L, 用分子印迹膜电极对加标样品进行分析,回收率为94.6%～103.4%.     

Preparation of Z-L-Phe-OH-NBD imprinted microchannel and its molecular recognition study

An integrated microchip was presented for selective recognition of Z-L-Phe-OH-NBD, using molecular imprinting technique. Molecularly imprinted polymer (MIP) were prepared by copolymerization in the presence of template molecule Z-L-Phe-OH-NBD, in which methacrylic acid and 4-vinylpyridine were used as functional monomers and ethylene dimethacrylate used as crosslinker. Imprinted polymer particles were introduced into a microchannel fabricated with a new material i.e. poly(methylvinylsiloxane) by simply rapid prototyping method. Imprinted effects were evaluated by laser-induced fluorescence (LIF) detection where the results indicated that good selective recognition for Z-L-Phe-OH-NBD in the imprinted polymer was obtained; the adsorption percentage of Z-L-Phe-OH-NBD was 61%. In contrast to conventional molecular imprinting analysis, integration shortened overall analysis time from 4h to 10 min.     

磁性石墨烯修饰辛基酚印迹传感器制备及应用研究

以辛基酚(4-OP)为模板分子,多巴胺为功能单体,采用电聚合技术在磁性石墨烯修饰碳电极表面制备对辛基酚具有高选择性与灵敏性的印迹电化学传感器。采用循环伏安法(CV)和差分脉冲伏安法(DPV)对此印迹传感器的电化学性能进行详细表征;采用扫描电子显微技术对修饰电极的形貌进行表征。结果表明,此印迹电化学传感器对辛基酚具有良好的特异识别性能。采用 DPV 法考察了孵化时间和洗脱溶剂对印迹传感器性能影响,结果表明,最佳孵化时间为14 min。此印迹电化学传感器的响应电流(△IR )与辛基酚在5.0×10-6~5.0×10-9 mol/ L 范围内浓度的负对数(-lgC)呈良好的线性关系,线性方程为△IR ( mA)=-0.25lgC(mol/ L)+2.35,检出限为3.64×10-10 mol/ L (S/ N=3)。此印迹电化学传感器对辛基酚具有良好的选择性和灵敏性,成功用于实际水样中辛基酚的检测,回收率为96.0%~104.0%。     

牛血清白蛋白在超薄纳米二氧化钛膜表面的印迹与吸附

基于溶胶凝胶分子印迹方法,以溶胶二氧化钛TiO2为基质印迹了牛血清白蛋白分子。用1%的NaOH溶液可有效地除去纳米TiO2印迹膜中的模板分子。采用石英晶体微天平现场技术,研究了牛血清白蛋白在超薄纳米TiO2膜表面的吸附行为。研究表明,牛血清白蛋白在印迹膜和非印迹膜上的吸附量都随溶液浓度增加而增大,印迹膜具有吸附的特异性和可再生性,其吸附量是非印迹膜的3~5倍;在非印迹膜上的吸附符合Langmuir吸附模型,而在印迹膜上的吸附符合allosteric吸附模型;牛血清白蛋白在非印迹膜上的吸附量先随pH升高而增大,当pH为5左右时达到最大值,随后吸附量又随pH的增大而减小;而在印迹膜上其吸附量仅随pH增大而增大。     

多巴胺有序介孔硅表面分子印迹传感器的研制

以多巴胺(DA)为模板,氨基修饰的介孔硅为载体,制得对多巴胺具有特异选择性的表面分子印迹聚合物(MIP)。将所得的MIP制成碳糊电极,用循环伏安法对多巴胺进行检测。在优化实验条件下,传感器的氧化峰电流与多巴胺浓度在1.0×10-7～2.0×10-6mol/L和2.0×10-6～1.0×10-4mol/L范围内呈良好的线性关系,相关系数分别为0.992 5和0.996 9,检出限为1.3×10-9mol/L。该传感器对DA具有较高的灵敏度和选择性,将其用于实际样品检测,结果满意。     

Remarkable enantioselectivity of molecularly imprinted TiO2 nano-thin films

TiO(2) nano-thin films with imprinted (R)- and (S)-enantiomers of propranolol, 1,1'-bi-naphthol, and 2-(4-isobutylphenyl)-propionic acid were fabricated on quartz plates by spin-coating their solutions with Ti(O-(n)Bu)(4) in a toluene-ethanol mixture (1:1, v/v). After template removal, the imprinted films showed better binding for original templates than to the corresponding enantiomers. The assessment of template incorporation, template removal, and re-binding was conducted through UV-vis measurements. Significant enhancement of enantioselectivity was achieved by optimization of the film thickness and by heat-treatment of the imprinted films. After subtraction of non-specific binding, the optimized films provided chiral recognition with the enantioselectivity of almost 100% for (R)-propranolol and 95% for (S)-propranolol.     

The Syntheses and Characterization of Molecularly Imprinted Polymers for the Controlled Release of Bromhexine

Imprinted polymers are now being increasingly considered for active biomedical uses such as drug delivery. In this work, the use of molecularly imprinted polymers (MIPs) in designing new drug delivery devices was studied. Imprinted polymers were prepared from methacrylic acid (functional monomer), ethylene glycol dimethacrylate (cross-linker), and bromhexine (as a drug template) using bulk polymerization method. The influence of the template/functional monomer proportion and pH on the achievement of MIPs with pore cavities with a high enough affinity for the drug was investigated. The polymeric devices were further characterized by FT-IR, thermogravimetric analysis, scanning electron microscopy, and binding experiments. The imprinted polymers showed a higher affinity for bromhexine and a slower release rate than the non-imprinted polymers. The controlled release of bromhexine from the prepared imprinted polymers was investigated through in vitro dissolution tests by measuring absorbance at λ _max of 310 nm by HPLC-UV. The dissolution media employed were hydrochloric acid at the pH level of 3.0 and phosphate buffers, at pH levels of 6.0 and 8.0, maintained at 37.0 and 25.0 ± 0.5 °C. Results from the analyses showed the ability of MIP polymers to control the release of bromhexine In all cases The imprinted polymers showed a higher affinity for bromhexine and a slower release rate than the non-imprinted polymers. At the pH level of 3.0 and at the temperature of 25 °C, slower release of bromhexine imprinted polymer occurred.     

分子印迹纳米管膜的制备及对人体尿液中儿茶酚胺类药物的检测

以多巴胺(DA)为模板, 多孔阳极氧化铝膜(AAO)为反应载体, 合成了多巴胺分子印迹聚合物纳米管膜(AAO@MIP). 利用扫描电子显微镜对分子印迹纳米管膜的形貌进行了表征, 并用高效液相色谱(HPLC)研究了其对儿茶酚胺类(CLs)药物的吸附性能. 实验结果表明, 在最优萃取条件下, AAO@MIP 纳米管膜对多巴胺、 肾上腺素和去甲肾上腺素具有较高的选择性, 3种儿茶酚胺类药物在0.50~300 μmol/L浓度范围内呈良好的线性关系(r²>0.9970); 检出限(S/N=3)分别为15.5, 12.6和22.5 ng/L. AAO@MIP纳米管膜对多巴胺的最大吸附容量可达82.1 μmol/g; 6次吸附-解吸附重复利用后, 吸附容量仅降低3.3%. 将AAO@MIP 纳米管膜应用于萃取人体尿液中3种儿茶酚胺, 样品加标回收率为74.0%~100.4%, 相对标准偏差(RSD)为3.6%~6.8%. 该方法简便、 快速、 选择性高, 适用于检测人体尿液中的儿茶酚胺类药物的含量.     

Capacitive Chemical Sensor for Thiopental Assay Based on Electropolymerized Molecularly Imprinted Polymer

A novel capacitive sensor based on electropolymerized molecularly imprinted polymer (MIP) for thiopental detection is described. The molecularly imprinted film as a recognition element was prepared by electropolymerization of phenol on a gold electrode in the presence of thiopental (template). Cyclic voltammetry and capacitive measurements were used for characterization and evaluation of the polymeric film. The template molecules were removed from the modified electrode surface by washing with an ethanol:water solution. The sensor’s linear response range was between 3 and 20 µM, with a detection limit of 0.6 µM. The proposed sensor exhibited good selectivity, reproducibility. Satisfactory results were obtained in the direct detection of real samples.     

基于纳米金的分子印迹传感器检测果蔬中的氧化乐果和乐果

以甲基丙烯酸为功能单体,氧化乐果为印迹分子,构建了一种可用于检测果蔬中氧化乐果和乐果的分子印迹传感器.在金电极上电沉积金纳米粒子,然后将修饰电极浸入10 mL含有氧化乐果和甲基丙烯酸的聚合物溶液中进行9次循环电聚合(-0.3～0.3 V),无水甲醇/乙酸洗涤除去模板分子.循环伏安法和电化学阻抗谱表征传感器,差分脉冲伏安...     

Recovery and separation of erythromycin from industrial wastewater by imprinted magnetic nanoparticles that exploit β‐cyclodextrin as the functional monomer

A type of surface imprinting over magnetic Fe₃O₄ nanoparticles utilizing erythromycin‐A as a template for use in the separation and recovery of erythromycin was developed and investigated. As the intermolecular forces play a key role in the performance of imprinted materials, differential scanning calorimetry, and ¹H NMR spectroscopy was employed to evaluate the interactions between erythromycin and the functional monomer β‐cyclodextrin. To synthesize the surface imprinted polymers, magnetic Fe₃O₄ nanoparticles, the core materials, were modified with a free radical initiator to initialize polymerization in a “grafting from” manner. Then using acryloyl‐modified β‐cyclodextrin as the functional monomer and ethyleneglycol dimethacrylate as the cross‐linker, thin erythromycin‐imprinted films were fabricated by the radical‐induced graft copolymerization of monomers on the surface of the Fe₃O₄ nanoparticles. Selectivity experiments showed that the erythromycin‐A‐imprinted materials had recognition ability toward erythromycin derivatives. Finally, these magnetic molecularly imprinted particles were successfully used for the separation and enrichment of erythromycin from the mother liquor. The recovery, detected by high‐performance liquid chromatography and differential pulse voltammetry, approached 97%. The combination of the specific selectivity of the imprinted material and the magnetic separation provided a powerful tool that is simple, flexible, and selective for the separation and recovery of erythromycin.     

Scanning force microscopy study of the morphology of spin‐cast molecular‐imprinted nylon thin films

The morphology of thin, selectively imprinted films of Nylon‐6 was investigated by scanning force microscopy. Four amino acids were used as template molecules in the spin‐cast films. Film thickness ranged from 2 µm to 500 nm, depending on the nylon and template concentration in the casting solution. The thin‐film properties, including the presence of nanometer‐ to micrometer‐sized pores, are clearly associated with the imprinting process. The larger features observed by scanning force microscopy are attributed to amino acid clustering during the casting process. Copyright © 2004 John Wiley & Sons, Ltd.     

Development of a sensitive and selective kojic acid sensor based on molecularly imprinted polymer modified electrode in the lab-on-valve system

In this work, a kojic acid electrochemical sensor, based on a non-covalent molecularly imprinted polymer (MIP) modified electrode, had been fabricated in the lab-on-valve system. The sensitive layer was synthesized by cyclic voltammetry using o-phenylenediamine as the functional monomer and kojic acid as the template. The template molecules were then removed from the modified electrode surface by washing with NaOH solution. Differential pulse voltammetry method using ferricyanide as probe was applied as the analytical technique, after extraction of kojic acid on the electrode. Chemical and flow parameters associated with the extraction process were investigated. The response recorded with the imprinted sensor exhibited a response in a range of 0.01-0.2 μmol L⁻¹ with a detection limit of 3 nmol L⁻¹. The interference studies showed that the MIP modified electrode had excellent selectivity. Furthermore, the proposed MIP electrode exhibited good sensitivity and low sample/reagent consumption, and the sensor could be applied to the determination kojic acid in cosmetics samples.     

Molecularly imprinted TiO2 thin film by liquid phase deposition for the determination of L-glutamic acid

For the first time, the feasibility of a molecularly imprinted liquid phase deposition (LPD) thin film has been demonstrated. Thin films of titanium oxide imprinted with L-glutamic acid were prepared by the LPD method on a gold-coated quartz crystal microbalance. The imprinted molecule could be removed upon treatment with immersion in deionized water. A sensor was developed on the basis of this method and showed good sensitivity, selectivity, and reproducibility to the template molecule. An equation was deduced to characterize the interaction between molecularly imprinted films and the template by virtue of Scatchard analysis. X-ray photoelectron spectroscopy was introduced to show the evidence for the molecular imprinting phenomenon. The linear relationship between the frequency shifts and the concentration of analyte in the range of 10-200 microM was obtained. LPD proves to be a powerful method for imprinting titanium oxide thin films.     

基于磁球表面的抗原决定基印迹法用于选择性识别细胞色素c的研究

本工作合成了一种核壳型的抗原决定基磁性分子印迹聚合物,并用于选择性识别目标蛋白细胞色素c(Cytochrome c,Cyt c)。制备过程中先用溶剂热法合成Fe_3O_4磁性纳米粒子,然后加入Cyt c其C端的九肽作为模板,进行一段时间的预组装,最后加入多巴胺盐酸盐(DA)溶液,调节反应体系的p H使多巴胺聚合在磁球表面。洗脱掉模板后,即得到分子印迹聚合物。优化DA的用量使聚合物达到最佳的吸附效果。在最优条件下,制得的印迹聚合物对目标蛋白有较好的吸附选择性,并且有良好的重复利用性。此外,用抗原决定基做模板制得的聚合物的吸附容量和印迹因子明显优于用相应蛋白质做模板的情况。