基于巯基嘌呤/多肽修饰的金纳米粒子的比色方法检测溶液中的镉离子

研究了一种基于双配体（巯基嘌呤（MP）和多肽CALNN）修饰金纳米粒子（AuNPs）的比色方法,用于快速、选择性地检测水溶液中的Cd2+。 其中,MP作为功能配体通过N原子与Cd2+发生配合作用,从而引起AuNPs聚集;CALNN配体有助于提高体系的稳定性和选择性。 当体系中无Cd2+时,溶液呈红色,随着Cd2+浓度的增加,溶液颜色逐渐由红色变为蓝紫色,这种颜色变化可以通过光谱测定还可以用肉眼直接观察。 该方法操作简便,具有较好的选择性和较快的响应速度（＜5 min）,其检测限达到350 nmol/L。     

Sensitive and selective detection of glutathione based on anti-catalytical growth of gold nanoparticles colorimetric sensor

Gold nanoparticles (AuNps) are often employed in different detection paths based on the catalytic growth mechanism; AuNps could act as catalyst for the reduction of AuCl₄^? and result in the enlargement of the original AuNps. However, there are few probes based on the anti-catalytical growth of AuNps in previous studies. In this article, we proposed a simple colorimetric sensor for the detection of glutathione (GSH) based on the anti-catalytical growth of AuNps, the strong affinity of GSH make it readily combine with AuNps or metal ions (AuCl₄^?), and thus inhibit the catalytical growth of AuNps through the specific property of GSH. Therefore, the UV absorbance of detection system could be used to estimate the concentration of GSH, and the probe exhibits highly sensitive and selective detection of the concentration of GSH with a wide linear from 13 to 800 nM within 20 min. Meanwhile, a good linear relationship with correlation coefficient of R² = 0.9795 was obtained. It is believed that this research could broaden the choices of GSH detection methods.     

Spectrophotometric and colorimetric determination of gallium (III) with p-aminohippuric acid-functionalized citrate capped gold nanoparticles

A new technique for sensing Ga(III) concentration based on polyvinyl alcohol-citrate capped gold nanoparticle– p- aminohippuric acid hybrid (or three-layer core-shell configurations) has been demonstrated. The p- aminohippuric acid capped citrate-gold nanoparticles were comfortably agglomerated in the presence of Ga(III), and the color of the reaction quickly turned from red to violet or blue. Under the detection conditions, a good linear relationship was ideally obtained between the ratio of the absorbance intensity at 620 nm to that at 520 nm (A₆₂₀/A₅₂₀). The linear response range, the detection, and quantification limit was 34.9–418.3 μg/L and 7.6 μg/L, and 25 μg/L, respectively. To reflect the accuracy, the developed sensing approach was evaluated against certified reference materials (TMDA 51.3 fortified water and TMDA 28.3 fortified water). This colorimetric strategy was displayed excellent selectivity for Ga(III) over other examined ions. Additionally, the colorimetric method was properly used to detect the concentrations of Ga in tap water and certified reference material samples with recoveries ranging from 95.4 to 102.0%, displaying that the colorimetric procedure could be safely used for a realistic application.     

基于磁性分子印迹聚合物的电化学传感器的研究进展

分子印迹聚合物与磁性纳米材料结合,制备成磁性分子印迹纳米敏感膜,这样做不仅可以发挥分子印迹聚合材料的优势,而且磁性纳米粒子可有效提高电化学传感器的灵敏度、稳定性以及生物相容性等.近年来将磁性分子印迹纳米敏感膜应用于电化学传感器制备成的磁性分子印迹电化学传感器得到了较快的发展.本文就近5年来磁性分子印迹电化学传感器敏感膜...     

Synergistic in-situ growth of silver nanoparticles with nanozyme activity for dual-mode biosensing and cancer theranostics

A multifunctional nanocomposite of AgNPs@GQDs is prepared by synergistic in-situ growth of silver nanoparticles (AgNPs) on the complex of tannic acid (TA) and graphene quantum dots (GQDs) for the construction of dual-mode biosensing platform and cancer theranostics. The nanocomposite exhibits a hydrogen peroxide (H₂O₂)-responsive degradation, in which Ag⁰ is oxidized to Ag⁺ along with the release of oxidized TA and GQDs. The degradation induces the decreased absorbance and enhanced fluorescence (FL) intensity due to the suppression of Förster resonance energy transfer (FRET) in AgNPs@GQDs, which is employed for colorimetric/fluorescence dual-mode sensing of H₂O₂. The intrinsic peroxidase-like activity of GQDs nanozyme can effectively catalyze the oxidation reaction, enhancing the detection sensitivity significantly. Based on the generation of H₂O₂ from the oxidation of glucose with the catalysis of glucose oxidase (GOx), this nanoprobe is versatilely used for the determination of glucose in human serum. Further, through combining the H₂O₂-responsive degradation of AgNPs@GQDs with high H₂O₂ level in cancer cells, the nanocomposites exhibit good performance in cancer cell recognition and therapy, in which the synergistic anticancer effect of Ag⁺ and oxidized TA contribute to effective cell death, and the liberated GQDs are used to monitor the therapeutic effect by cell imaging.     

TGA and magnetization measurements for determination of composition and polymer conversion of magnetic hybrid particles

Magnetic hybrid colloidal particles can be characterized using various techniques and numerous tools leading generally to particles size, size distribution, and electrokinetic properties. However, the chemical composition of these hybrid particles can be estimated using thermal gravimetric analysis (TGA). More interestingly, the combination of this quantitative technique with the magnetization measurement leads not only to chemical composition but also to the overall polymerization conversion and more precisely to the polymerization conversion on the seed particles. In fact, the TGA performed on dried magnetic particles leads to exact organic/inorganic chemical composition. Regarding the magnetization, the amount of magnetic material can be deduced, and consequently, the amount of non‐magnetic material can be also estimated. Thus, TGA and magnetization measurements are considered as complementary techniques for characterization of magnetic hybrid colloidal particles. Copyright © 2015 John Wiley & Sons, Ltd.     

基于金纳米粒子及石墨烯量子点的四环素分子印迹电化学传感器研究

该文以四环素为模板分子,4-氨基苯硫酚(4-ATP)为功能单体,采用循环伏安法在金纳米粒子和石墨烯量子点复合材料修饰的玻碳电极表面电聚合分子印迹膜,制备四环素(TC)分子印迹传感器(MIPs/GQDs-AuNPs/GCE),并通过循环伏安法(CV)、电化学交流阻抗法(EIS)和线性扫描伏安法(LSV)等研究了其电化学响应性能。结果表明,该传感器对四环素具有良好的电流响应。在最佳实验条件下,TC氧化峰电流值与其浓度在2.0×10^-8～3.0×10^-5 mol/L范围内呈良好的线性关系,相关系数为0.999 4,检出限为1.5×10^-9 mol/L,加标回收率为97.9%～106%。该传感器稳定性好、响应灵敏、选择性高,具有良好的应用前景。     

Potentiometric detection of polyions based on functionalized magnetic nanoparticles

A novel potentiometric detection strategy based on functionalized magnetic nanoparticles has been developed for rapid and sensitive sensing of polyions. Highly dispersed magnetic nanoparticles coated with ion exchanger and plasticizer could promote an in situ cooperative ion-pairing interaction between the ion exchanger and the polyion analyte in sample solution by dramatically reducing the mass-transfer distance. With applying a magnetic field, the nanoparticles can be attached to the surface of ion exchanger free polymeric membrane. The observed potential signals are related to the polyion concentrations. The proposed polymeric membrane electrode exhibits a linear relationship between the greatest potential response slope (dE/dt) and the logarithm of protamine concentration in the range of 0.05−5 μg/mL with a lower detection limit of 0.033 μg/mL.     

L-色氨酸在金纳米粒子修饰电极上的电化学行为及其分析研究

制备了金纳米粒子修饰玻碳电极(Au/GCE),用循环伏安法研究L-色氨酸(L-Trp)在修饰电极上的电化学行为,以及支持电解质、溶液p H、扫描速率等对L-Trp伏安响应的影响。实验表明:在p H=3.5的HAcNa Ac支持电解质中,L-Trp在Au/GCE上有一灵敏的氧化峰(Epa=0.93)。氧化峰电流与L-Trp浓度在5.0×10-7~1.0×10-4mol·L-1范围内呈良好的线性关系,相关系数为0.9990,检出限1.6×10-7mol·L-1。测得L-Trp样品平均回收率为98%。     

基于相转移技术的劣质食用油快速可视化检测方法

近年来,劣质油流入成品食用油市场引起的地沟油事件,导致了严重的食品安全隐患和社会负面反响.本研究结合可视化和相转移技术,建立了以铜离子和聚二烯丙基二甲基氯化铵（PDDA）修饰的阳离子纳米金为探针的两种简单、准确、灵敏的劣质食用油现场快速检测方法.结果表明,两种方法均可检测到合格食用油中掺入2.8%的劣质油含量,大于5%掺入量可明确测定.将上述方法分别应用于共235个样品的盲测,结果显示,总准确率达95.7%.本工作为劣质食用油的快速现场检测提供了有益的参考方法.     

Construction of a novel electrochemical sensor based on molecularly imprinted polymers for the selective determination of chlorpyrifos in real samples

We present a novel electrochemical sensor based on an electrode modified with molecularly imprinted polymers for the detection of chlorpyrifos. The modified electrode was constructed by the synthesis of molecularly imprinted polymers by a precipitation method then coated on a glassy carbon electrode. The surface morphology of the modified electrode was characterized by using field‐emission scanning electron microscopy and transmission electron microscopy. The performance of the imprinted sensor was thoroughly investigated by using cyclic voltammetry and differential pulse voltammetry. The imprinted electrochemical sensor displayed high repeatability, stability, and selectivity towards the template molecules. Under the optimal experimental conditions, the peak current response of the imprinted electrochemical sensor was linearly related to the concentration of chlorpyrifos over the range 1 × 10⁻¹⁰–1 × 10⁻⁵ mol/L with a limit of detection of 4.08 × 10⁻⁹ mol/L (signal‐to‐noise ratio = 3). Furthermore, the proposed molecularly imprinted electrochemical sensor was applied to the determination of chlorpyrifos in the complicated matrixes of real samples with satisfactory results. Therefore, the molecularly imprinted polymers based electrochemical sensor might provide a highly selective, rapid, and cost‐effective method for chlorpyrifos determination and related analysis.     

Application of new sol-gel electrochemical sensors to the determination of trace mercury

The aim of this work was the synthesis and characterization of new modified sol-gel carbon composite electrodes and their application to the determination of trace mercury species with positive charge. Two types of modified electrodes were synthesized, sol-gel and sol-gel-PVSA carbon composite electrodes. In the last ones, poly(vinylsulfonic acid) (PVSA) was used as a functional polymer entrapped within the sol-gel material due to its cationic exchange properties. In a first stage, parameters affecting both, the sol-gel process and the electrode preparation were optimized. In a second stage, usefulness of developed electrodes applied to the determination of cationic mercury species was evaluated, optimizing the activation, preconcentration, measurement and regeneration steps. Developed electrodes showed very favourable electroanalytical properties for their use as amperometric sensors, such as small size, low cost, simple fabrication and handling, renewability and reusability. By means of an easy and low-cost methodology, satisfactory experimental results were obtained in Hg²⁺ determination. In this sense, developed analytical methodology showed adequate response times, linear concentration range up to three orders of magnitude (from 5.0 × 10⁻⁸ to 5.0 × 10⁻⁵ M) and detection limits of 1.5 × 10⁻⁸ M (3.0 μg L⁻¹). These results suggest that the incorporation of different receptor molecules at the sol-gel carbon composite material in combination with a selected electrochemical reaction could improve the detection limit achieved and obtain electrochemical sensors adapted to the determination of different species of mercury and other heavy metals.     

A Dihomooxacalix[4]arene-gold nanohybrid based colorimetric sensor for sensitive and selective detection of iodide

Bidentate ureido-dihomooxacalix[4]arene based supramolecular hosts (n-propyl 1 and tert-butyl 2) were processed into organic nanoparticles via a bottom up approach in which a single step of re-precipitation was employed. These organic nanoparticles were then coupled with gold nanoparticles on the surface, resulting in an organic – inorganic hybrid framework (n-propyl H1 and tert-butyl H2). Photophysical studies of the organic nanoparticles and of the hybrid material were performed. The size and morphology were determined by TEM and DLS analysis. Moreover, the prepared hybrid frameworks were screened against various anions using UV-Visible absorption and fluorescence spectrophotometry. H1 exhibited ratiometric response towards iodide ion in aqueous medium, and colour change of the solution from pink to light blue was observed. This hybrid material selectively and sensitively detected iodide ion with detection limit of 8.3 nM and with almost no interference from other anions. H1 sensor ability was also tested with artificial and real urine samples. H2 showed different responses and no selectivity to any anion.     

A new strategy based on cholesterol-functionalized iron oxide magnetic nanoparticles for determination of polycyclic aromatic hydrocarbons by high-performance liquid chromatography with cholesterol column

This study reported for the first time the use of cholesterol-functionalized magnetic nanoparticles (Fe₃O₄@SiO₂@Chol) for the determination of polycyclic aromatic hydrocarbons (PAHs) in traditional Chinese medicine samples (TCMs) by high performance liquid chromatography (HPLC) coupled with fluorescence detection. The method was efficient, environmentally friendly, and fast. The solvent consumption of the proposed column is only half of the conventional column but with higher efficiency. Influencing factors, including sorbent amount, desorption solvent, sample volume and extraction time, were investigated in detail. Under the optimum conditions, good linearity (R² > 0.991) was obtained over the range of 5–400 ng g⁻¹, with limits of detection (LOD) 0.75, 0.50, 1.0, 0.56, 0.60, 0.84 and 0.80 ng g⁻¹ for anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene, respectively.     

2-硫代巴比妥酸修饰金纳米探针高灵敏比色检测三聚氰胺

以2-硫代巴比妥酸(TBA)修饰金纳米粒子为探针,TBA与三聚氰胺通过氢键作用诱导金纳米探针团聚,进而使金纳米胶体颜色由酒红色变为蓝色。 实验优化得最佳反应条件为在乙酸缓冲溶液（pH=7.0）介质中,室温反应15 min。 对不同浓度三聚氰胺进行检测时发现,在0.062~0.18 μmol/L和0.18~6.0 μmol/L之间,A660/A520吸收比率与三聚氰胺浓度呈现良好的线性关系,检出限为0.043 μmol/L。 该方法用于检测牛奶样品中的三聚氰胺的加标回收率为102.8%～105.3%。     

基于未修饰纳米金及无标记单链DNA的Pb~(2+)比色测定

根据纳米金对ss DNA和G-四联体结构的DNA的不同吸附能力,设计了一种简单的Pb2+比色传感器。富含G的无标记ss DNA可以通过静电作用吸附于Au NPs表面,保护Au NPs在高盐浓度溶液中仍呈分散态;当Pb2+存在时,DNA与Pb2+结合形成Pb2+-G-四联体结构,使得Au NPs失去DNA的保护而发生聚集,溶液颜色由红色变成蓝色,最大吸收峰发生红移。通过优化条件,得到溶液吸光度比值(A630/A520)与Pb2+浓度在0.1~10μmol/L范围内呈良好的线性关系,检出限可达50 nmol/L。其他金属离子对Pb2+的检测几乎无干扰。该方法灵敏度高,选择性好,且无需复杂的Au NPs表面修饰过程及DNA标记,制备和操作简便、成本低、响应快(1 min),非常适合于现场实时应用。     

Polythionine-decorated magnetic nanoparticles as a robust and highly effective sorbent for mercury determination in environmental water samples

Extraction, pre-concentration and determination of trace amounts of mercury ions from water samples were investigated by magnetic solid phase extraction (MSPE) method using Fe₃O₄ nanoparticles decorated with polythionine as an adsorbent. A simple chemical synthesis by catalytic reaction of thionine in the presence of FeCl₃ and hydrogen peroxide was used for preparation of the magnetic sorbent. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, vibrating sample magnetometer analysis and Fourier transform infrared spectroscopy were used to characterise the adsorbent. Mercury ions were determined by cold vapour atomic absorption spectrometry. The parameters for MSPE procedure, such as pH of the extraction solution, adsorption time, weight adsorbent, elution conditions (type, concentration and volume of the eluent), volume of the sample solution and effects of coexisting ions were investigated. The obtained optimal conditions were: sample pH of 4; sorbent amount of 4 mg; sorption time of 20 min; elution solvent of HNO₃ (0.3 mol L^?1)/thiourea (2% w/v) with volume of 2 mL, and breakthrough volume of 400 mL. A good linearity in the concentration range of 0.025–40 µg L^?1 (R² > 0.999) with the pre-concentration factor of 198 was obtained. The limits of detection and quantification were achieved as 0.008 and 0.025 µg L^?1, respectively. Furthermore, sea and river water samples were analysed and good recoveries (97.1–99.6%) were obtained.     

Facile and versatile strategy to prepare magnetic molecularly imprinted particles based on the coassembly of magnetic nanoparticles and amphiphilic random copolymers

Magnetic molecularly imprinted polymer nanoparticles for bisphenol A were prepared by coassembling magnetic nanoparticles and amphiphilic random copolymers. Under optimized conditions, bisphenol A as template molecules, magnetic molecularly imprinted polymer particles with regular morphology, small size, good monodispersity, and high content of OA‐Fe₃O₄ were prepared by the coassembly method using P(MMA‐co‐MAA) with monomer ratio of 9:1. These magnetic molecularly imprinted polymer particles could be rapidly collected by an external magnet within 1 min. The saturated adsorption capacity of the magnetic molecularly imprinted polymer for bisphenol A was 201.5 mg/g, and the imprinting factor was 2.5. The separation factors for bisphenol A to β‐estradiol, estriol, and diethylstilbestrol was 3.1, 2.9, and 3.7, respectively. Unlike assembling amphiphilic copolymer in the selective solvent, the coassembly process was simple and rapid. Therefore, the present work provided a facile and versatile approach to construct magnetic molecularly imprinted polymer nanoparticles under mild conditions.     

A fast and sensitive enzyme immunoassay for brain natriuretic peptide based on micro-magnetic probes strategy

In this paper, a simple, rapid and low-cost method for the high-sensitivity detection of brain natriuretic peptide (BNP) was developed, which adopted three amplification steps: (a) biotin-streptavidin amplification; (b) micro-magnetic probe amplification; (c) HRP (horseradish peroxidase) signal amplification. In the present strategy, the streptavidin-coated micro-magnetic particles (MMPs) were first conjugated with biotin-labeled capture antibody via the biotin-streptavidin interaction, which formed bio-functional micro-magnetic probes. Then, the analyte (antigen) is sandwiched by HRP-labeled antibody and capture antibody bound to MMPs. Finally, the HRP at the surface of sandwich structures catalytically oxidized the substrate and generated optical signals that reflected the amount of the target BNP. The influence of some important parameters such as the size of magnetic particles, the working concentration of HRP-labeled BNP antibody, the stability of magnetic probes, and the assay medium of serum BNP, etc. on the detection ability of present method was investigated in details. It is found that the detection limit of the proposed method could reach 10 pg/mL for BNP, which is much lower than that of sandwich-type ELISA. Furthermore, this detection time for the proposed method just takes about 30 min (two reaction steps and one wash step), which is faster than that of conventional sandwich-type ELISA (taking about 4 h, three reaction steps and three wash steps). Inspired by these advantages, it is expected that this method can probably be applicable to the detection of other hormones and tumor markers that are present in only low concentrations within the human body.