Fabrication and Optical Properties of Periodic Ag Nano‐Pore and Nano‐Particle Arrays with Controlled Shape and Size over Macroscopic Length Scales

A facile and economical route to preparation of highly ordered sliver pore or particle arrays with controlled pore‐shape and size extended over cm² areas is described. The substrates are prepared at planar and curved surfaces via sphere‐imprinted polymer (PDMS) templating using polystyrene spheres with diameters of 820, 600, or 430 nm. Nano‐pore arrays are created by sputtering 80 nm of Ag directly onto the templates and nano‐particle arrays are prepared by electrode‐less deposition of Ag from Tollen's reagent. The shape of the nano‐pore or particles in the array conformed to that of the imprint of the sphere on the template. Stretching the flexible template enable creation of cuboid shaped nano‐voids and nano‐particles following Ag deposition. Diffuse reflectance from the spherical Ag nano‐cavity arrays showed absorbance maxima at wavelengths comparable similar to the diameter of the templating sphere, whereas reflectance from the cuboid arrays, showed little correlation with the sphere diameter. The cuboid nano‐particle arrays showed the most intense visible absorption which is red‐shifted compared to the spherical arrays. White light diffraction from the arrays, observed by rotating 1 cm² substrates relative to a fixed light source, reflected exactly the symmetry axes of the periodic nano‐features in the arrays demonstrating the remarkable macroscopic order of the periodic structures. Raman spectra of 1‐benzenethiol adsorbed at the arrays indicated SERS enhancements from the substrates are attributed mainly to surface nano‐roughness with only moderate contributions from the periodically corrugated structures. Despite excitation at the major resonance dip in the reflectance spectrum, a weak, localized rim dipole mode is found to elicit a small increase in the SERS enhancement factor for the 430 nm diameter spherical arrays. FDTD studies of nano‐void arrays provided insights into v arious factors affecting the SERS experiment and confirmed the array's plasmonic spectra are dominated by propagating plasmon modes under microscope excitation/collection angles.     

Ascorbic acid imprinted polymer-modified graphite electrode: A diagnostic sensor for hypovitaminosis C at ultra trace ascorbic acid level

A new kind of molecularly imprinted polymer-modified graphite electrode was fabricated by “grafting-to” approach, incorporating sol–gel technique, for the detection of acute deficiency in serum ascorbic acid level (SAAL), manifesting hypovitaminosis C. The modified electrode exhibited ascorbic acid (AA) oxidation at less positive potential (0.0 V) than the earlier reported methods, resulting in a limit of detection as low as 6.13 ng mL⁻¹ (RSD = 1.2%, S/N = 3). The diffusion coefficient (1.096 × 10⁻⁵ cm² s⁻¹), rate constant (7.308 s⁻¹), and Gibb's free energy change (−12.59 kJ mol⁻¹) due to analyte adsorption, were also calculated to explore the kinetics of AA oxidation. The proposed sensor was found to enhance sensitivity substantially so as to detect ultra trace level of AA in the presence of other biologically important compounds (dopamine, uric acid, etc.), without any cross interference and matrix complications from biological fluids and pharmaceutical samples.     

Designing of MIP-based QCM sensor for the determination of Cu(II) ions in solution

A novel quartz crystal microbalance (QCM) sensor with a high selectivity and sensitivity has been developed for the determination of Cu(II) ions, based on the modification of Cu(II) ion-imprinted polymer (Cu(II)-IIP) film onto a quartz crystal. The performance of the developed MIP-QCM sensor was evaluated and the results indicated that a sensitive MIP-QCM sensor could be fabricated. The obtained MIP-QCM sensor presents high-selectivity monitoring of Cu(II) ions, better reproducibility, shorter response time (6 min), wider linear range (0.001–50 μM) and lower detection limit (8 × 10⁻⁴ μM). The practical analysis of the MIP-QCM sensor confirms the feasibility of Cu(II) determination in wastewater.     

中空纤维分子印迹复合膜选择性分离萘普生对映体

以聚偏氟乙烯(PVDF)中空纤维超滤膜为支撑膜,S-(+)-萘普生为模板分子,4-乙烯基吡啶为功能单体,制备了分子印迹复合膜。通过紫外光谱法研究了模板分子与功能单体之间的相互作用,比较了热聚合和光聚合两种引发方式对膜形貌和性能的影响。试验结果表明,分子印迹聚合物膜中存在着三维空间结构和功能基均与模板分子互补的孔穴组成的通道,该通道可选择性地透过S-(+)-萘普生,在压力和亲和力的协同作用下,最大分离因子可达6.19。     

微囊藻毒素分子印迹聚合物的制备及性能研究

以微囊藻毒素MC-LR为模板,采用本体聚合法制备微囊藻毒素分子印迹聚合物,优化制备过程.通过电子显微镜、孔隙度分析、红外吸收等对其进行表征,并研究其反应机理和吸附性能.结果表明,单体∶模板∶交联剂配比为0.9×106∶1∶1.2×106,洗脱时间25 min时为优选条件,最大吸附量为153.7μg/g,此分子印迹聚合物对MC-LR具有显著的特异性吸附作用.     

酞酸二丁酯表面印迹聚合物的合成及其吸附性能

以酞酸二丁酯(DBP)作为模板分子,甲基丙烯酸作为功能单体,乙二醇二甲基丙烯酸酯(EDMA)作为交联剂,在硅胶表面合成分子印迹聚合物(MIPs)。通过红外、热重分析、比表面积测定等对聚合物进行分析和表征;采用静态吸附法对水相中的印迹聚合物的吸附性能进行考察.红外结果表明硅胶表面存在对模板分子具有识别功能的官能团;热重分析证明其良好的热稳定性;通过测定计算印迹膜厚度;静态吸附实验说明印迹聚合物具有良好的吸附性能.     

基于门控制效应的氯霉素分子印迹传感器研制

研究了分子印迹技术与电化学检测手段相结合的分子印迹电化学传感器,并用于定量分析蜂蜜中的氯霉素含量。以亚甲基蓝为功能单体、氯霉素为模板分子,在pH＝7.0的磷酸盐缓冲溶液中采用循环伏安法在玻碳电极表面电聚合形成分子印迹敏感膜,并以此作为识别元件制备了电流型氯霉素分子印迹电化学传感器。采用铁氰化钾作为探针分子,利用门控制效应对氯霉素进行定量检测。氯霉素浓度在0.323～54.9μg/L范围内与峰电流呈良好的线性关系。检出限（3δ）为0.14μg/L。该传感器具有灵敏度高、选择性好、成本低且容易制备的优势。     

Trichloroacetic acid‐imprinted polypyrrole film and its property in piezoelectric quartz crystal microbalance and electrochemical sensors to application for determination of haloacetic acids disinfection by‐product in drinking water

A molecularly trichloroacetic acid (TCAA) imprinted non‐crosslinked polypyrole (TCAA‐MIPpy) has been successfully prepared and evaluated in its properties for both piezoelectric quartz crystal microbalance (QCM) and electrochemical means of detection, and application of such sensors for determination of haloacetic acid concentrations in water. Haloacetic acid selectivity was demonstrated in gravimetric or in electrochemical sensors via either cyclic voltammetric or inter‐digitated conductometric (IDC) analyses studies upon comparison with nonimprinted polypyrrole and TCAA‐imprinted polypyrrole. The measurement results with all these systems revealed that the prepared molecularly imprinted polymer can recognize TCAA well from structurally similar compounds. The TCAA‐MIPpy incorporated with only the IDC transduction system produced the specific signal for TCAA detection in aqueous environment, which is useful for the quantifying TCAA disinfection by‐product in water. The analytical application for determination of TCAA in real‐life samples was readily achieved with the incorporation of TCAA‐MIPpy in the IDC analysis system, the results revealing the high sensitivity and selectivity of the method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Submicron nanoporous polyacrylamide beads with tunable size for verapamil imprinting

Submicron sized polyacrylamide particles were prepared via modified precipitation polymerization method. Experimental design based on Taguchi approach was employed to study the influence of the polymerization composition including monomer (acrylamide), crosslinker (methylenebisacrylamide), initiator (azobisisobutyronitrile), and modifier (polyvinylpyrrolidone, K-30), on the size and morphology of the particles. Varying the polymerization composition, submicron-particles with sizes ranging between 100 and 600 nm were achieved. In all the cases, polydispersity index (PDI) of the particle size was found to be almost 1 indicating uniformity of the particle size. The concentration of crosslinker was found to be the most influential parameter on the particles size and the modifier concentration as an extra tunable parameter was believed to affect the nucleation mechanism and the viscosity of the medium to help controlling the particle size. To validate the optimization, particles with a preset diameter, i.e., 500 nm, were synthesized based on the composition predicted by the mathematical correlation. The polymer with the preset particle size was also imprinted with verapamil and characterized by FTIR, DSC, SEM, physisorption, elemental analysis, swelling, and batch rebinding experiments. The verapamil imprinted polymers bearing nano-cavities exhibited high affinity with imprinting factor 2.17 towards the target molecule. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Efficient adsorptive extraction materials by surface protein-imprinted polymer over silica gel for selective recognition/separation of human serum albumin from urine

In this study, we report the development of adsorptive extraction materials by surface protein-imprinted polymers (MIPs) over silica gel for selective recognition/separation of human serum albumin (HSA) from urine. The HSA-imprinted polymers prepared on silica particle had at interface between the silica gel and different MIPs greatly produced enrichment for the binding of protein from the urine. The solid-phase extraction of the optimized polymer layer was prepared by copolymerization of methacrylic acid (MAA), acrylamide (AAm), and dimethylaminoethylmethacrylate (DMAEMA) and a crosslinker methylenebisacrylamide (MBA) at the mole ratio of 1:158:88 (T:M:C) and showed moderate affinity (<10⁴ order M⁻¹) toward target protein HSA and selectivity. Four analogues, egg white albumin (EWA), bovine serum albumin (BSA), lysozyme (Lyz), and creatinine (Cre) were selected to study the binding efficiency of MIPs in single and binary protein solutions. We studied the influence on recognition ability for HSA and found that prepolymer mixture and matrix flexibility of the optimized thin polymer layer (35 ± 10 nm) on the submicrosilica particles. The high-binding affinity (Q_MIP, 86.7 mg g⁻¹) and fast kinetics (180 min) were observed for this synthesized HSA-MIP when compared with other reported HSA-MIPs in surface imprinting (5.9 and 11.3 mg g⁻¹) and epitope surface imprinting (46.6 mg g⁻¹) methods. We demonstrated the application in real and synthetic urine samples that the approach allowed the efficient adsorption of HSA in real urine (129.48 mg g⁻¹) is almost double to the binding of HSA in synthetic urine (67.84 mg g⁻¹). Apart from this, only minor interference of Cre (2.74 mg g⁻¹) was observed, eventhough Cre is the final metabolite in urine. These adsorptive submicrosilica materials have potential in the pharmaceutical industry and clinical analysis applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46894.