Microchimica Acta

Tang, Juan; Tang, Dianping

doi: 10.1007/s00604-015-1567-8pmid: N/A

Electrochemical immunodetection has attracted considerable attention due to its high sensitivity, low cost and simplicity. Large efforts have recently made in order to design ultrasensitive assays. Noble metal nanoparticles (NM-NPs) offer advantages such as high conductivity and large surface-to-volume ratio. NM-NPs therefore are excellent candidates for developing electrochemical platforms for immunodetection and as signal tags. The use of biofunctionalized NM-NPs often results in amplified recognition via stronger loading of signal tags, and also in enhanced signal. This review (with 87 references) gives an overview on the current state in the use of NM-NPs in Non-enzymatic electrochemical immunosensing. We discuss the application of NM-NPs as electrode matrices and as electroactive labels (either as a carrier or as electrocatalytic labels), and compare the materials (mainly nanoparticles of gold, platinum, or of bimetallic materials) in terms of performance (for example by increasing sensitivity via label amplification or via high densities of capture molecules). A conclusion covers current challenges and gives an outlook. Rather than being exhaustive, the review focuses on representative examples that illustrate novel concepts and promising applications. NM-NPs based immunosensing opens a series of concepts for basic research and offers new tools for determination of trace amounts of protein-related analytes in environment and clinical applications.

Yusoff, Norazriena; Pandikumar, Alagarsamy; Ramaraj, Ramasamy; Lim, Hong; Huang, Nay

doi: 10.1007/s00604-015-1609-2pmid: N/A

This review (with 110 refs.) gives an overview on the progress that has been made in the past few years on the use of gold nanoparticles (AuNPs) for use in sensors and analytical tools for the determination of dopamine (DA). Both AuNPs and their composites with other organic and inorganic materials including noble metals are treated. Following an overview on the clinical significance of DA, we discuss the various analytical methods that are (a) electrochemiluminescence (ECL); (b) surface enhanced Raman scattering (SERS); (c) colorimetric probing and visual detection; and (d) the large class of electrochemical sensors. Subsections cover sensors based on plain AuNPs, bimetallic NPs, AuNP-metal@metal oxide nanocomposites, AuNP nanocomposites with organic polymers, AuNP nanocomposites with carbon nanotubes or with graphene, and finally sensors based on ternary materials containing AuNPs. The review ends with a conclusion on current challenges of sensors for DA and an outlook on future trends.

Xu, Wailan; He, Junlin; Gao, Liuliu; Zhang, Jing; Yu, Chao

doi: 10.1007/s00604-015-1551-3pmid: N/A

We describe a nanostructured immunosensor for the cardiovascular biomarker netrin 1. A glassy carbon electrode was consecutively modified with multi-walled carbon nanotubes (MWCNTs), nafion (to retain the MWCNTs), thionine-coated gold nanoparticles (Thi@AuNPs), and monoclonal antibodies against netrin 1. The modified electrode was characterized by transmission electron microscopy, cyclic voltammetry, differential pulse voltammetry, UV-visible spectrophotometry and X-ray diffraction. The presence of Thi@AuNPs warrants direct and convenient immobilization of the antibody. This immunoelectrode enables netrin 1 to be determined, best at a voltage of −300 mV (vs. SCE), with a limit of detection of 30 fg mL−1 (at an S/N ratio of 3) after a 50 min incubation time. The detection range extends from 0.09 to 1800 pg∙mL−1. The method is simple, sensitive, specific and reproducible. We presume this stable and reproducible biosensor to be useful for the early detection of cardiovascular diseases.

Moghaddam, Firouzeh; Taher, Mohammad; Behzadi, Mansoureh; Naghizadeh, Matin

doi: 10.1007/s00604-015-1550-4pmid: N/A

A simple, sensitive and accurate method was developed for solid-phase extraction and preconcentration of trace levels of gold in various samples. It is based on the adsorption of gold on modified oxidized multi-walled carbon nanotubes prior to its determination by graphite furnace atomic absorption spectrometry. The type and volume of eluent solution, sample pH value, flow rates of sample and eluent, sorption capacity and breakthrough volume were optimized. Under these conditions, the method showed linearity in the range of 0.2–6.0 ng L−1 with coefficients of determination of >0.99 in the sample. The relative standard deviation for seven replicate determinations of gold (at a level of 0.6 ng L−1) is ±3.8 %, the detection limit is 31 pg L−1 (in the initial solution and at an S/N ratio of 3; for n = 8), and the enrichment factor is 200. The sorption capacity of the modified MWCNTs for gold(III) is 4.15 mg g−1. The procedure was successfully applied to the determination of gold in (spiked) water samples, human hair, human urine and standard reference material with recoveries ranging from 97.0 to 104.2 %.

Xu, Jingyue; Li, Ying; Bie, Jiaxin; Jiang, Wei; Guo, Jiajia; Luo, Yeli; Shen, Fei; Sun, Chunyan

doi: 10.1007/s00604-015-1547-zpmid: N/A

A sensitive, specific and rapid colorimetric aptasensor for the determination of the plasticizer bisphenol A (BPA) was developed. It is based on the use of gold nanoparticles (AuNPs) that are positively charged due to the modification with cysteamine which is cationic at near-neutral pH values. If aptamers are added to such AuNPs, aggregation occurs due to electrostatic interactions between the negatively-charged aptamers and the positively-charged AuNPs. This results in a color change of the AuNPs from red to blue. If a sample containing BPA is added to the anti-BPA aptamers, the anti-BPA aptamers undergo folding via an induced-fit binding mechanism. This is accompanied by a conformational change, which prevents the aptamer-induced aggregation and color change of AuNPs. The effect was exploited to design a colorimetric assay for BPA. Under optimum conditions, the absorbance ratio of A 527/A 680 is linearly proportional to the BPA concentration in the range from 35 to 140 ng∙mL−1, with a detection limit of 0.11 ng∙mL−1. The method has been successfully applied to the determination of BPA in spiked tap water and gave recoveries between 91 and 106 %. Data were in full accordance with results obtained from HPLC. This assay is selective, easily performed, and in our perception represents a promising alternative to existing methods for rapid quantification of BPA.

Yu, Ningxiang; Peng, Hailong; Xiong, Hua; Wu, Xiaqing; Wang, Xiaoyan; Li, Yanbin; Chen, Lingxin

doi: 10.1007/s00604-015-1548-ypmid: N/A

A fluorescent probe for the sensitive and selective determination of sulfide ions is presented. It is based on the use of graphene quantum dots (GQDs) which emit strong and stable blue fluorescence even at high ionic strength. Copper(II) ions cause aggregation of the GQDs and thereby quench fluorescence. The GQDs-Cu(II) aggregates can be dissociated by adding sulfide ions, and this results in fluorescence turn on. The change of fluorescence intensity is proportional to the concentration of sulfide ions. Under optimal conditions, the increase in fluorescence intensity on addition of sulfide ions is linearly related (r 2 = 0.9943) to the concentration of sulfide ions in the range from 0.20 to 20 μM, and the limit of detection is 0.10 μM (at 3 σ/s). The fluorescent probe is highly selective for sulfide ions over some potentially interfering ions. The method was successfully applied to the determination of sulfide ions in real water samples and gave recoveries between 103.0 and 113.0 %.

Chen, Yinji; Yao, Li; Deng, Yi; Pan, Daodong; Ogabiela, Edward; Cao, Jinxuan; Adeloju, Samuel; Chen, Wei

doi: 10.1007/s00604-015-1538-0pmid: N/A

The article describes a method for rapid and visual determination of Hg(II) ion using unmodified gold nanoparticles (Au-NPs). It involves the addition of Au-NPs to a solution containing Hg(II) ions which, however, does not induce a color change. Next, a solution of lysine is added which induces the aggregation of the Au-NPs and causes the color of the solution to change from wine-red to purple. The whole on-site detection process can be executed in less than 15 min. Other amines (ethylenediamine, arginine, and melamine) were also investigated with respect to their capability to induce aggregation. Notably, only amines containing more than one amino group were found to be effective, but a 0.4 μM and pH 8 solution of lysine was found to give the best results. The detection limits for Hg (II) are 8.4 pM (for instrumental read-out) and 10 pM (for visual read-out). To the best of our knowledge, this LOD is better than those reported for any other existing rapid screening methods. The assay is not interfered by the presence of other common metal ions even if present in 1000-fold excess over Hg(II) concentration. It was successfully applied to the determination of Hg(II) in spiked tap water samples. We perceive that this method provides an excellent tool for rapid and ultrasensitive on-site determination of Hg(II) ions at low cost, with relative ease and minimal operation.

Abolghasemi, Mir; Yousefi, Vahid; Piryaei, Marzieh

doi: 10.1007/s00604-015-1553-1pmid: N/A

Double-charged diazabicyclo[2.2.2]octane (DABCO) was immobilized on the inner surface of a nanomaterial composed of the layered double hydroxides (LDHs) of Zn(II) and Cr(III). The resulting material was characterized by SEM, FT-IR and XRD techniques. This novel nanocomposite has been used as a highly porous fiber coating for solid-phase microextraction (SPME) of phenol and various chloro-, nitro- and aminophenols. The LDH nanocomposite was deposited on a stainless steel wire and then evaluated with respect to the extraction of phenolic compounds from water samples. The effects of temperature, extraction time, ionic strength, stirring rate, pH, and desorption temperature and time on the extraction were optimized. The compounds were then separated and quantified by GC-MS. Under optimum conditions, the repeatability for a single fiber (for n = 3 and expressed as the relative standard deviation) is between 2.3 and 7.2 %. The detection limits are between 0.02 and 6.3 pg mL−1. The method is simple, rapid, and inexpensive. The fiber is thermally stable and its use gives high recoveries.

Devasenathipathy, Rajkumar; Karthik, Raj; Chen, Shen-Ming; Ali, Mohammad; Mani, Veerappan; Lou, Bih-Show; Al-Hemaid, Fahad

doi: 10.1007/s00604-015-1545-1pmid: N/A

We describe the electrochemical preparation of bismuth nanoribbons (Bi-NRs) with an average length of 100 ± 50 nm and a width of 10 ± 5 μm by a potentiostatic method. The process occurs on the surface of a glassy carbon electrode (GCE) in the presence of disodium ethylene diamine tetraacetate that acts as a scaffold for the growth of the Bi-NRs and also renders them more stable. The method was applied to the preparation of Bi-NRs incorporated into reduced graphene oxide. This nanocomposite was loaded with the enzyme glucose oxidase onto a glassy carbon electrode. The resulting biosensor displays an enhanced redox peak for the enzyme with a peak-to-peak separation of about 28 mV, revealing a fast electron transfer at the modified electrode. The loading of the GCE with electroactive GOx was calculated to be 8.54 × 10−10 mol∙cm−2, and the electron transfer rate constant is 4.40 s−1. Glucose can be determined (in the presence of oxygen) at a relatively working potential of −0.46 V (vs. Ag|AgCl) in the 0.5 to 6 mM concentration range, with a 104 μM lower detection limit. The sensor also displays appreciable repeatability, reproducibility and remarkable stability. It was successfully applied to the determination of glucose in human serum samples.

Bhaisare, Mukesh; Talib, Abou; Khan, M.; Pandey, Sunil; Wu, Hui-Fen

doi: 10.1007/s00604-015-1541-5pmid: N/A

A jelly-like form of carbon dots (C-dots) was prepared by microwave-assisted synthesis from citric acid in the presence of tetraoctylammonium bromide. The effect of the concentration of tetraoctylammonium bromide was examined. The synthesized carbon dots were characterized by UV–vis, XRD, FTIR, fluorescence and HR-TEM. Fluorescence extends from 350 to 600 nm, and the corresponding excitation wavelengths range from 300 to 460 nm. Quantum yields are at around 0.11. A cytotoxicity study showed carbon dots to be cell permeable and biocompatible which renders them appropriate for imaging applications. The dots were used to image HeLa cell lines via the blue fluorescence of the dots.