Highly Sensitive Fluorometric Assay Method for Acetylcholinesterase Inhibitor Based on Nile Red‐Adsorbed Gold Nanoparticles

A new sensitive fluorometric assay method for acetylcholinesterase (AChE) and its inhibitor was developed using a fluorescent dye, nile red (NR). Due to the fluorescence resonance energy transfer between the NR and the gold nanoparticle (AuNPs), the fluorescence was quenched. AChE can break down acetylthiocholine to produce a thiol‐bearing compound, thiocholine. In the presence of thiocholine, the nile red is replaced from the AuNPs surfaces and simultaneously transformed to a derivative of nile red. The fluorescence intensity of the derivative is much stronger than that of the native nile red with the same concentration and its maximum emission wavelength has a blue shift so that the sensor achieves a good signal‐to‐background ratio. In addition, when organophosphate pesticide (OPs) exists, the activity of AChE can be inhibited, the generation of thiocholine will be prevented and no fluorescence enhancement occurs. The results show that the method is sensitive to AChE and paraoxon with the detection limits of 0.2 mU/mL and 0.05 ng/mL, respectively.     

Synthesis,characterization, and application of silver nanoparticle‐thiophenol nanocomposite film on the glassy carbon surface

In this study, 4‐thiophenol modified glassy carbon electrode was prepared by the reduction of 4‐diazothiophenol tetrafluoroborate salt. Silver nanoparticles were attached to the thiophenol modified surface to prepare a thiophenol‐silver nanoparticle composite film. 4‐Aminothiopenol molecules were deposited by self‐assembling technique to form multi‐layered nanofilms of TP/SNP/PhNH₂ on glassy carbon substrate. These surfaces were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy, reflectance‐absorption infrared spectroscopy, and ellipsometry at each multilayer film growth process. Atomic force microscopic images of GC/TP/SNP/PhNH₂ surfaces were also acquired. The characterization methods show that the amine group containing surface permits the subsequent modification by a variety of coupling reactions for the immobilization of more complex systems. An application of the electrode modification for the determination of uric acid with a significantly lower detection limit is described. Copyright © 2013 John Wiley & Sons, Ltd.     

Visible Light Photocatalytic Activity of Porphyrin Tin(IV) Sensitized TiO2 Nanoparticles for the Degradation of 4-Nitrophenol and Methyl Orange

A stable metalloporphyrin sensitized TiO₂ (Degussa P25) photocatalyst was prepared by using trans-dihydroxo[5,10,15,20-tetraphenylporphyrin]tin(IV) (SnP) as a sensitizer in a simple impregnation process. The solid diffuse reflectance ultraviolet-visible (UV-vis) spectrum of the SnP sensitized TiO₂ photocatalyst (SnP-TiO₂) indicated that there existed interaction between SnP and TiO₂. It was found that SnP-TiO₂ exhibited an enhanced visible light photocatalytic activity as compared with that over P25 for the degradation of 4-nitrophenol (4-NP) and methyl orange (MO) in aqueous solutions. The mechanism exploration showed that the degradation of MO and 4-NP experienced two different ways, that is, MO was photodegraded by reactive oxygen species and 4-NP was directly photodegraded by the excited state of SnP. Furthermore, it was found that the loading content of SnP had an important influence on the photocatalytic activity of TiO₂. The maximum photocatalytic efficiency was achieved when the contents of SnP were 25 mg and 30 mg per gram TiO₂ for MO and 4-NP, respectively. Importantly, SnP-TiO₂ was particularly stable and the photocatalytic activity was hardly decreased after being recycled seven times in the presence of oxygen, which could be attributed to the easy reductive regeneration of SnP.     

Magnetic solid-phase extraction using Schiff base ligand supported on magnetic nanoparticles as sorbent combined with dispersive liquid-liquid microextraction for the extraction of phenols from water samples

ABSTRACT

In this work, the magnetic sorbent was developed by covalent binding of a Schiff base ligand, N,N’-bis(3-salicyliden aminopropyl)amine (salpr), on the surface of silica coated magnetic nanoparticles (Salpr@SCMNPs). The core-shell nanoparticle was applied for the magnetic solid-phase extraction (MSPE) combined with dispersive liquid-liquid microextraction (DLLME) of phenolic compounds from water samples prior to gas chromatography-flame ionisation detector (GC?FID). Characterisation of the Salpr@SCMNPs was performed with different physicochemical methods such as Fourier transform infrared (FT-IR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). Variables affecting the performance of both extraction steps such as pH of the water sample, the sorbent amount, the desorption conditions, the extraction time; and extraction solvent were studied. Under the optimised conditions, the analytical performances were determined with a linear range of 0.01–100 ng mL^?1 and a limit of detection at 0.003–0.02 ng mL^?1 for all of the analytes studied. The intra-day (n = 5) and inter-day (n = 3) relative standard deviations (RSD%) of three replicates were each demonstrated in the range of 6.9–8.9% and 7.3–10.1%, respectively. The proposed method was executed for the analysis of real water samples, whereby recoveries in the range of 92.9–99.0% and RSD% lower than 6.1% were attained.     

铽荧光纳米配合物的制备及其潜血手印显现应用

以铽离子为发光中心、对苯二甲酸为第一配体、菲咯啉为第二配体,采用化学方法一步制备出表面羧基修饰的铽荧光纳米配合物。使用活化剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐配合稳定剂N-羟基琥珀酰亚胺对配合物表面的羧基进行活化,促使活化羧基与潜血手印中的胺基在温和条件下迅速发生酰胺反应,成功实现了潜血手印的靶向显现。优化了潜血手印显现的最佳条件,显现悬浮液中配合物与水的质量比推荐为1∶35,显现浸泡时间推荐为20 s。并深入探究了手印显现的对比度、灵敏度、选择性、适用性。实验结果表明,制备的表面活化羧基修饰的铽荧光纳米配合物适用于光滑非渗透性及半渗透性客体表面潜血手印的高质量与高效率显现。     

基于聚硫堇/亚甲基蓝和纳米金放大的免疫传感器检测贝类毒素大田软海绵酸

采用聚硫堇(PTH)修饰电极为传感界面提供一个生物修饰功能基质膜,借助纳米金(GNPs)的导电性、生物相容性与高比表面积特性实现抗体的有效固定,并以亚甲基蓝(MB)为电子媒介加速电极表面电化学反应的电子传递,构建了一种高灵敏的非标记电化学免疫传感器,用于贝类毒素大田软海绵酸(OA)的检测。当分子结构中含有羧基和酚基的OA与其抗体特异性结合后,生成以阴离子形式存在的抗原-抗体复合物,阻碍了传感器表面电子的传递,导致峰电流下降。利用免疫反应前后峰电流的变化,可对OA进行特异性识别和准确定量。在优化实验条件下,OA浓度的对数在0.2~100 μg/L范围内与其峰电流的变化值(ΔI)呈线性相关,线性方程为ΔI=1.721 7+1.083 6lgρ,相关系数为0.992 0,检出限为0.1 μg/L。该免疫传感器重现性好、特异性强,用于实际贝类样品的测定,回收率为85.3%~112%。     

负载型纳米金催化葡萄糖氧化研究进展

负载型金催化剂的制备具有重要的理论和应用价值。葡萄糖作为一种可再生资源已用于合成具有应用价值的葡萄糖酸。作为“绿色化学”反应过程,负载型金催化剂催化葡萄糖氧化已经成为热门的研究领域。负载型金催化剂具有产物专一性强、催化活性高、反应条件温和、长期催化稳定性等优点。本文主要对负载型金催化剂制备方法及其催化葡萄糖氧化方面近年来的进展进行综述。     

Ag修饰的Fe_3O_4/TiO_2复合磁性纳米纤维的制备及光催化性能

通过静电纺丝法制备了含有Fe3O4纳米粒子的TiO2纳米纤维,采用水热法对该纤维表面进行纳米Ag修饰,制备出具有较强磁性和较好光催化性能的复合纤维.采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和紫外-可见光谱(UV-Vis)等对样品的结构和形貌进行表征,并以罗丹明B(Rh B)水溶液降解为模型反应,考察样品在紫外光照射下的光催化性能.结果表明,所制备的TiO2为锐钛矿结构,Fe3O4纳米粒子均匀分布在TiO2纤维中,Ag纳米颗粒比较均匀地分散在磁性TiO2纤维表面.经过纳米Ag修饰后,材料的光吸收能力大为增强,吸收带红移并扩展到可见光区.在紫外光照射40 min后,合成样品对Rh B的降解率达到99.5%.此外,Fe3O4纳米粒子的存在使该材料具有较强的磁性,可通过外加磁场将其分离回收.     

SiO2/Co3O4核壳催化剂对AP热分解的催化性能研究

采用改良的Stöber法制备粒径约为200 nm的单分散球形SiO₂颗粒,以此为内核,分别通过液相沉淀法和尿素均匀沉淀法制备包覆形式不同的新型SiO₂/Co₃O₄核壳式纳米催化剂。采用X-射线衍射分析(XRD)、透射电子显微镜(TEM)、红外光谱分析(IR)、拉曼光谱分析(Raman)、BET比表面积测试等手段对产物进行表征,利用差式扫描量热仪(DSC)考察SiO₂/Co₃O₄复合物对高氯酸铵(AP)热分解反应的催化作用,探讨不同包覆形式对其催化活性的影响。结果表明,两种方法制备得到的SiO₂/Co₃O₄复合物分别为层包覆和粒子包覆,比表面积大,具有明显的核壳结构,且粒子包覆形式的SiO₂/Co₃O₄对AP热分解反应的催化效果最好,使AP的高温分解温度降低了110 ℃,放热量增加了662 J·g^-1。     

纳米金颗粒增强信号的电化学生物传感器用于谷胱甘肽和半胱氨酸的检测

构建了一种高灵敏检测谷胱甘肽(GSH)和半胱氨酸(Cys)的新型电化学生物传感器. 先将富含T碱基的DNA1和DNA2探针分别修饰在金电极和纳米金颗粒(AuNPs)上, 再加入Hg²⁺, 通过形成T-Hg²⁺-T结构使AuNPs结合到金电极表面. 当加入GSH(或Cys)后, GSH(或Cys)可以竞争结合T-Hg²⁺-T结构中的Hg²⁺, 使AuNPs离开电极表面. 由于AuNPs上修饰的DNA探针能够静电吸附大量电活性物质六氨合钌(RuHex), 因此该过程可引起计时电量信号的显著变化, 据此实现了GSH(或Cys)的高灵敏检测. 该传感器的检出限达10 pmol/L, 比荧光法或比色法降低了2~3个数量级. 实验结果表明, 该传感器具有较好的选择性.