Magnetic Fe3O4@SiO2 core shell nanoparticles containing diphenylcarbazide in the shell were utilized for solid phase extraction of Hg(II) from aqueous solutions. The Hg(II) loaded nanoparticles were then separated by applying an external magnetic field. Adsorbed Hg(II) was desorbed and its concentration determined with a rhodamine-based fluorescent probe. The calibration graph for Hg(II) is linear in the 60 nM to 7.0 μM concentration range, and the detection limit is at 23 nM. The method was applied, with satisfying results, to the determination of Hg(II) in industrial waste water.
Platinum nanoparticles (Pt-NPs) with sizes in the range from 10 to 30 nm were synthesized using protein-directed one-pot reduction. The model globular protein bovine serum albumin (BSA) was exploited as the template, and the resulting BSA/Pt-NPs were studied by transmission electron microscopy, energy dispersive X-ray spectroscopy, and resonance Rayleigh scattering spectroscopy. The modified nanoparticles display a peroxidase-like activity that was exploited in a rapid method for the colorimetric determination of hydrogen peroxide which can be detected in the 50 μM to 3 mM concentration range. The limit of detection is 7.9 μM, and the lowest concentration that can be visually detected is 200 μM.
Pt-NPs were synthesized using BSA-directed one-pot reduction and BSA/Pt-NPs composite can effectively catalyze the oxidation of TMB producing blue solution in the presence of H2O2.
A label-free and single-step method is reported for rapid and highly sensitive detection of bisphenol A (BPA) in aqueous samples. It utilizes an aptamer acting as a probe molecule immobilized on a commercially available array of interdigitated aluminum microelectrodes. BPA was quantified by measuring the interfacial capacitance change rate caused by the specific binding between bisphenol A and the immobilized aptamer. The AC signal also induces an AC electrokinetic effect to generate microfluidic motion for enhanced binding. The capacitive aptasensor achieves a limit of detection as low as 10 fM(2.8 fg ⋅ mL − 1) with a 20 s response time. The method is inexpensive, highly sensitive, rapid and therefore provides a promising technology for on-site detection of BPA in food and water samples.
A. AC electrokinetics effect plays a vital role in BPA detection by introducing microfluidic movement to accelerate the molecular transport to the electrode surface.
B. The ACEK capacitive aptasensor has a limit of detection as low as 10 fM (2.8 fg ⋅ mL − 1) with a 20-s response time.
A molecularly imprinted polymer (MIP) for the specific retention of neopterin has been developed. A set of 6 polymers was prepared by radical polymerization under different experimental condition using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker, with the aim to understand their influence on the efficiency of the MIP. The performance of each MIP was tested in batch experiments via their binding capacity. The MIP prepared in the presence of nickel ions in dimethylsulfoxide-acetonitrile mixture (P4) exhibited the highest binding capacity for neopterin (260 μmol per gram of polymer). A selectivity study with two other pteridines demonstrated the polymer P4 also to possess the best selectivity.
A molecularly imprinted polymer for the specific retention of neopterin was developed. A set of 6 polymers was prepared under different experimental condition. The performance of each MIP was tested through their binding capacity. The MIP P4 prepared in the presence of nickel ions exhibited the highest binding capacity
We report on an ultrasensitive fluorescence immunoassay for human chorionic gonadotrophin antigen (hCG). It is based on the use of silica nanoparticles coated with a copolymer (prepared from a fluorene, a phenylenediamine, and divinylbenzene; PF@SiO2) that acts as a fluorescent label for the secondary monoclonal antibody to β-hCG antigen. In parallel, Fe3O4 nanoparticles were coated with polyaniline, and these magnetic particles (Fe3O4@PANI) served as a solid support for the primary monoclonal antibody to β-hCG antigen. The PF@SiO2 exhibited strong fluorescence and good dispersibility in water. A fluorescence sandwich immunoassay was developed that enables hCG concentrations to be determined in the 0.01–100 ng·mL−1 concentration range, with a detection limit of 3 pg·mL−1.
Fluorescence detection of prepared immune reagent nano-composites using the fluorescence cell
The replacement of antibodies by molecularly imprinted polymers (MIPs) has been investigated for many decades. However, indirect protocols (including natural primary and secondary antibodies) are still utilized to evaluate the ability of MIP thin films to recognize target molecules. MIPs can be prepared as either a thin film or as particles, and cavities that are complementary to the template can be generated on their surfaces. We have prepared thin film MIPs and particle MIPs prepared by solvent evaporation and phase inversion, respectively, from solutions of poly(ethylene-co-vinyl alcohol) (pEVAL) in the presence of the target analytes amylase, lysozyme, and lipase. These were first adsorbed on MIP thin films and by MIP particles that contain fluorescent quantum dots. Sandwich fluoroimmunoassays were then conducted to quantify them in MIP-coated 96-well microplates. The method was applied to determine amylase in saliva, and results were compared with a commercial analytical system.
We describe an electrochemical sensor for nitric oxide that was obtained by modifying the surface of a nanofiber carbon paste microelectrode with a film composed of hexadecyl trimethylammonium bromide and nafion. The modified microelectrode displays excellent catalytic activity in the electrochemical oxidation of nitric oxide. The mechanism was studied by scanning electron microscopy and cyclic voltammetry. Under optimal conditions, the oxidation peak current at a working voltage of 0.75 V (vs. SCE) is related to the concentration of nitric oxide in the 2 nM to 0.2 mM range, and the detection limit is as low as 2 nM (at an S/N ratio of 3). The sensor was successfully applied to the determination of nitric oxide released from mouse hepatocytes.
NO electrochemical sensor based on CTAB-Nafion/CNFPME was fabricated through a simple method and applied to detect NO released from mouse hepatocytes successfully.
We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of −0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N = 3) and a repeatability of 3.4 % (n = 5).
A facile method was developed for in situ construction of a porous network-like Ag film on a glassy carbon electrode by a galvanic replacement reaction, where a layer of Cu nanoparticles previously electrodeposited as a sacrificial template. Thus-formed Ag film displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward nitrate reduction.
The food antioxidant quercetin was used as a template in an ultrathin molecularly imprinted polymer (MIP) film prepared by photopolymerization. Indium tin oxide (ITO) plates were electrografted with aryl layers via a diazonium salt precursor bearing two terminal hydroxyethyl groups. The latter act as hydrogen donors for the photosensitizer isopropylthioxanthone and enabled the preparation of MIP grafts through radical photopolymerization of methacrylic acid (the functional monomer) and ethylene glycol dimethacrylate (the crosslinker) in the presence of quercetin (the template) on the ITO. The template was extracted, and the remaining ITO electrode used for the amperometric determination of quercetin at a working potential of 0.26 V (vs. SCE). The analytical range is from 5.10−8 to 10−4 mol L−1, and the detection limit is 5.10−8 mol L−1.
This work describes the grafting of a molecularly imprinted polymer (MIP) film by combining diazonium surface chemistry and surface-initiated photopolymerization. The MIP grafts specifically and selectively recognize quercetin in pure solution in THF and in real green tea infusion.
We have prepared a surface imprinted polymer (SIP) film for label-free recognition of immunoglobulin G (IgG). The IgG-SIPs were obtained by covalent immobilization of IgG via a cleavable covalent bond and a suitable spacer unit to a gold electrode, followed by electrodepostion of a nm-thin film of polydopamine (PDA). The IgG was then removed by destruction of the cleavable bond so that complementary binding sites were created on the surface of the film. IgG-SIPs with various thicknesses of the PDA films were compared with respect to their affinity to IgG using a quartz crystal microbalance combined with flow injection analysis. The films were also characterized by cyclic voltammetry and scanning electron microscopy. The IgG-SIPs with a film thickness of around 17 nm showed the most pronounced imprinting effect (IF 1.66) and a binding constant of 296 nM.
A strategy for preparation of the IgG-Surface Imprinted Polymeric (IgG-SIP) thin films was developed. IgG was covalently immobilized via a cleavable cross-linker to a gold electrode surface followed by electrochemical deposition of a nanometer thin PDA film. After cleaving S-S bond in the linker the IgG was removed leaving behind the complementary binding sites confined in the surface of the polymer film. The prepared IgG-SIPs were applied for IgG recognition.
We report on a method for the determination of the herbicide atrazine in tap water samples using melamine-modified gold nanoparticles (Mel-AuNPs). If a solution containing atrazine is added to a solution of such NPs, a color change occurs from wine-red to blue. This is due to a transition from monodisperse to aggregated Mel-AuNPs and caused by strong hydrogen bonding between atrazine and melamine. The color change can be monitored by a UV–vis spectrophotometer or with bare eyes. The ratio of the absorbances at 640 and 523 nm is linearly related to the logarithm of the atrazine concentration in the 0.165 to 16.5 μM range, and (with different slope) in the 16.5 μM to 330 μM range. The detection limit of atrazine is as low as 16.5 nM (S/N = 3). The method was successfully applied to the determination of atrazine in spiked tap water and gave recoveries that ranged from 72.5 % to 102.3 %.
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This article describes an electrochemical sensor for the dye additive Sunset Yellow (SY). It consists of a carbon paste electrode modified with nanostructured resorcinol-formaldehyde (RF) resin. The RF resin warrants strong signal enhancement and a strongly increased oxidation peak currents of SY at 0.66 V (vs. SCE). The effects of pH value, amount of RF polymer, accumulation potential and time were optimized. The sensor has a linear response to SY in the 0.3 to 125 nM concentration range, and the limit of detection is 0.09 nM after a 2-min accumulation time. The electrode was applied to the analysis of samples of wastewater and drinks, and the results are consistent with those obtained by HPLC.
Nanostructured resorcinol-formaldehyde (RF) resin was prepared and used as a material for electrochemical determination of Sunset Yellow.
We have investigated the gas sensing properties of ZnO thin films (100 to 200 nm thickness) deposited by room-temperature radio frequency magnetron sputtering. The sensitivity of the films to ethanol vapor was measured in the 10 to 50 ppm concentration range at operating temperatures between 200 and 400 °C. A synergetic effect of decreasing grain size and increasing operating temperature was observed towards the improvement of the sensitivity, reaching a value of 54 and a limit of detection as low as 0.61 ppm. The decrease in the grain size resulted in prolonged response time but faster recovery. In any case, both response time and recovery time are < 400 s. The results demonstrate that room-temperature magnetron sputtering is a viable approach to enhance the performances of ZnO films in sensors for ethanol vapor.
Sensor response for ZnO films in presence of 50 ppm ethanol as a function grain size and temperature
We have prepared molecularly imprinted beads with molecular recognition capability for target molecules containing the penicillanic acid substructure. They were prepared by (a) grafting mesoporous silica beads with 6-aminopenicillanic acid as the mimic template, (b) filling the pores with a polymerized mixture of methacrylic acid and trimethylolpropane trimethacrylate, and (c) removing the silica support with ammonium fluoride. The resulting imprinted beads showed good molecular recognition capability for various penicillanic species, while antibiotics such as cephalosporins or chloramphenicol were poorly recognized. The imprinted beads were used to extract penicillin V, nafcillin, oxacillin, cloxacillin and dicloxacillin from skimmed and deproteinized milk in the concentration range of 5–100 μg·L−1. The extracts were then analyzed by micellar electrokinetic chromatography by applying reverse polarity staking as an in-capillary preconcentration step, and this resulted in a fast and affordable method within the MRL levels, characterized by minimal pretreatment steps and recoveries of 64–90 %.
Penicillanic acid-imprinted beads prepared in preformed porous silica by an imprinting &; etching approach show selectivity towards β-lactams antibiotics. Molecularly imprinted solid phase extraction/micellar electrokinetic chromatography coupled with in-capillary preconcentration resulted in a fast and affordable method for penicillins in milk at MRL levels.
We demonstrate the application of an ionic liquid-based ferrofluid to the dispersive solid phase extraction of lead(II) using PAN as the chelator. The ionic liquid contains silica nanoparticles with a magnetic core as the dispersion medium, and its use results in improved stability of the colloidal dispersion and a complete extraction of lead(II) within a few seconds. In addition, there is no need for centrifugation. Specifically, the effect of different variables on the extraction of lead(II) was studied using an experimental design. Lead(II) was quantified by AAS. Under optimized conditions, the calibration graph for lead(II) is linear in the range from 5 to 372 μg L−1, the relative standard deviation is 1.34 % (for n = 7), the limit of detection is 1.66 μg L−1, and the enrichment factor is 200. The maximum adsorption capacity of sorbent was calculated to be 10.7 mg g−1, and adsorption follows a Langmuir isotherm.
A schematic view of D-SPE experimental set up. We demonstrate the application of an ionic liquid-based ferrofluid to the dispersive solid phase extraction of lead(II) using PAN as the chelator. The ionic liquid contains silica nanoparticles with a magnetic core as the dispersion medium
We report on the preparation of fluorescent silica nanoparticles (SiNPs) modified with chitosan and lucigenin by using a reverse microemulsion method. The introduction of chitosan to the lucigenin doped SiNPs is shown to improve the fluorescence quantum yield. The modified SiNPs were used as fluorescent markers in an aptamer-based method for selective determination of thrombin. In this protocol, thrombin was sandwiched between streptavidin-coated magnetic beads and the fluorescent SiNPs modified with a thrombin-binding aptamer. The method was successfully applied to the determination of thrombin in human serum and showed a detection limit as low as 0.02 nM. In our perception, the protocol presented here is promising in that such SiNPs may be applied to the sensitive fluorescent detection of other analytes by changing the corresponding aptamer.
The introduction of chitosan to the lucigenin doped SiNPs is shown to improve the fluorescence quantum yield. The modified SiNPs were used as fluorescent markers in an aptamer-based method for selective determination of thrombin. The effect of chitosan concentration on fluorescence intensity of lucigenin/SiO2 nanoparticles (the volume of chitosan solution is 100 μL)
We describe a nanosensor for sensitive and selective detection of cyanide anions. The Ir(III) chlorine bridge complex [Ir(C^N)2-m-Cl]2 (Irpq, where pq is C^N = 2-phenyl quinoline) was doped into silica nanoparticles (SiNPs) with a typical size of about 30 nm. The intensity of the yellow emission of the doped SiNPs (under 410 nm exCitation) was strongly enhanced on addition of cyanide ions due to the replacement of chloride by cyanide. The method can detect cyanide ions in the 12.5 to 113 μM concentration range, and the limit of detection is 1.66 μM (at an S/N ratio of 3). The method is simple, sensitive and fast, and this makes it a candidate probe for the fast optical determination of cyanide.
The nanosensor is exploiting the cyanide-induced enhancement of the fluorescence of silica nanoparticles doped with an Ir(III) complex which is the result of the replacement of chloride by cyanide.
Hetero-dimeric magnetic nanoparticles of the type Au-Fe3O4 have been synthesised from separately prepared, differently shaped (spheres and cubes), monodisperse nanoparticles. This synthesis was achieved by the following steps: (a) Mono-functionalising each type of nanoparticles with aldehyde functional groups through a solid support approach, where nanoparticle decorated silica nanoparticles were fabricated as an intermediate step; (b) Derivatising the functional faces with complementary functionalities (e.g. amines and carboxylic acids); (c) Dimerising the two types of particles via amide bond formation. The resulting hetero-dimers were characterised by high-resolution TEM, Fourier transform IR spectroscopy and other appropriate methods.
Nano-LEGO: Assembling two types of separately prepared nanoparticles into a hetero-dimer is the first step towards complex nano-architectures. This study shows a solid support approach to combine a gold and a magnetite nanocrystal.
We describe a new chemiluminescence (CL) system based on the oxidation of rhodamine B (RhoB) with alkaline potassium permanganate in the presence of gold nanoparticles (Au-NPs) and anionic detergent sodium dodecyl sulfate. Free RhoB is weakly chemiluminescent when oxidized with permanganate at alkaline pH values. However, a remarkably strong enhancement of CL is observed in the presence of Au-NPs, probably due to a strong interaction between RhoB and the NPs. The possible mechanism was studied via recording the CL emission. It is also found that the intensity of CL gradually decreases in the presence of cyanide due to its interaction with the Au-NPs. The relation between the decreased CL intensity and cyanide concentration was exploited to develop a method for the determination of cyanide in the 0.01–0.5 μM concentration range, with a detection limit of 2.8 nM. The method was used to determine cyanide in spiked water, urine, and serum.
Alkaline permanganate-rhodamine B-SDS CL reaction is dramatically enhanced by gold nanoparticles. Based on the inhibiting effect of cyanide on this system, a sensitive CL method was developed for its determination