Ultrafast Ratiometric Detection of Aflatoxin B1 Based on Fluorescent ß-CD@Cu Nanoparticles and Pt2+ Ions.

Rapid detection of aflatoxin B1 (AFB1) is a very important task in food safety monitoring. However, it is still challenging to achieve highly sensitive detection without antibody or aptamer biomolecules. In this work, a rapid detection of aflatoxin B1 was achieved using a ratiometric fluorescence probe without antibody or aptamer for the first time. In the ratiometric fluorescence system, the fluorescence emission of AFB1 at 433 nm was significantly enhanced due to the ß-cyclodextrin-AFB1 host-guest interaction and the complexation of AFB1 and Pt2+. Meanwhile, the inclusion of aflatoxin B1 also quenched the fluorescence emission of ß-CD@Cu nanoparticles (NPs) at 650 nm based on inner filter effect mechanism. On the basis of the above effects, the ratiometric detection of aflatoxin B1 was achieved in the range of 0.03-10 ng/mL with a low detection limit of 0.012 ng/mL (3σ/s). In addition, the ß-CD@Cu NPs based nanoprobe could achieve stable response within 1 min to AFB1. The above ratiometric detection also demonstrated excellent application potential in the rapid on-site detection of AFB1 in food due to the advantages of convenience, rapidness, and high accuracy.

Mesoporous silica-loaded gold nanocluster with enhanced fluorescence and ratiometric fluorescent detection of thiram in foods.

A core-shell QDs@mSiO2@y-AuNCs nanoprobe was prepared, and a new ratiometric fluorescent sensor for thiram detection was developed. The mechanism of thiram sensing was investigated using FTIR, surface-enhanced Raman, XPS spectra, etc. The sensing of thiram was mainly ascribed to the formation of Au-S bonds between thiram and Au atoms on y-AuNCs surface, resulting in the dissociation of 11-MUA ligand from the y-AuNCs surface and the charge transfer between thiram and y-AuNCs. In the ratiometric fluorescence detection of thiram based on QDs@mSiO2@y-AuNCs, a linear range of 0.5-60 ng/mL was obtained with a LOD of 0.19 ng/mL. Compared with the fluorescence detection based on y-AuNCs, the ratiometric fluorescence detection of thiram demonstrated 3-fold enhanced sensitivity. The improvement was ascribed to two aspects: the fluorescence emission of y-AuNCs was enhanced after they were loaded onto the QDs@mSiO2 nanoparticles; the ratiometric detection mode provided more precise sensing. The detection of thiram can be completed immediately after mixing the nanoprobe with thiram. Good recoveries of thiram in apple and pear samples were achieved. All the above results demonstrated the high potential of this method in practical applications.

DNA dendrimer-templated copper nanoparticles: self-assembly, aggregation-induced emission enhancement and sensing of lead ions.

Copper nanomaterials based on DNA scaffold (DNA-Cu NMs) are becoming a novel fluorescent material, but it is still challenging to obtain highly fluorescent DNA-Cu NMs with excellent stability. In this work, we report a kind of copper nano-assemblies (Cu NASs) with aggregation-induced emission enhancement (AIEE) property using DNA dendrimers with sticky end as template. The sticky end of the DNA dendrimers induced the formation of much bigger Cu NASs with average size ranging from 131 to 264 nm, depending on the length of the DNA dendrimer sticky end from 6 bases to 27 bases. Compared with complete complementary DNA dendrimer, nearly 6-fold fluorescence enhancement was achieved using DNA dendrimer with 27 bases sticky end. Moreover, the DNA dendrimer-Cu NASs demonstrated excellent stability in serum and could be rapidly quenched by Pb2+ ions. Based on the above property, highly sensitive and selective fluorescent detection of Pb2+ ions was possible with a linear range of 2.0-100 nM and a detection limit of 0.75 nM. Due to the sensitive and rapid response to Pb2+ as well as excellent stability in complex matrix, the proposed fluorescent Cu NASs demonstrated high potential as an excellent fluorescent probe for Pb2+ in complex matrix.

A Fluorescent Detection for Paraquat Based on ß-CDs-Enhanced Fluorescent Gold Nanoclusters.

In this report, a fluorescent sensing method for paraquat based on gold nanoclusters (AuNCs) is proposed. It was found that paraquat could quench both glutathione-capped AuNCs (GSH-AuNCs) and ß-cyclodextrin-modified GSH-AuNCs (GSH/ß-CDs-AuNCs). The modification of ß-CDs on the surface of GSH-AuNCs obviously enhanced the fluorescence intensity of GSH-AuNCs and improved the sensitivity of paraquat sensing more than 4-fold. This sensibilization was ascribed to the obvious fluorescence intensity enhancement of GSH-AuNCs by ß-CDs and the "host-guest" interaction between paraquat and ß-CDs. The fluorescence quenching was mainly due to the photoinduced energy transfer (PET) between GSH/ß-CDs-AuNCs and paraquat. With the optimized ß-CDs modification of the GSH-AuNC surfaces and under buffer conditions, the fluorescent detection for paraquat demonstrated a linear response in the range of 5.0-350 ng/mL with a detection limit of 1.2 ng/mL. The fluorescent method also showed high selectivity toward common pesticides. The interference from metal ions could be easily masked by ethylene diamine tetraacetic acid (EDTA). This method was applied to the measurement of paraquat-spiked water samples and good recoveries (93.6-103.8%) were obtained. The above results indicate that host molecule modification of fluorescent metal NC surfaces has high potential in the development of robust fluorescent sensors.

DNA-Gold Nanozyme-Modified Paper Device for Enhanced Colorimetric Detection of Mercury Ions.

In this work, a paper device consisted of a patterned paper chip, wicking pads, and a base was fabricated. On the paper chip, DNA-gold nanoparticles (DNA-AuNPs) were deposited and Hg2+ ions could be adsorbed by the DNA-AuNPs. The formed DNA-AuNP/Hg2+ nanozyme could catalyze the tetramethylbenzidine (TMB)-H2O2 chromogenic reaction. Due to the wicking pads, a larger volume of Hg2+ sample could be applied to the paper device for Hg2+ detection and therefore the color response could be enhanced. The paper device achieved a cut-off value of 50 nM by the naked eye for Hg2+ under optimized conditions. Moreover, quantitative measurements could be implemented by using a desktop scanner and extracting grayscale values. A linear range of 50-2000 nM Hg2+ was obtained with a detection limit of 10 nM. In addition, the paper device could be applied in the detection of environmental water samples with high recoveries ranging from 85.7% to 105.6%. The paper-device-based colorimetric detection was low-cost, simple, and demonstrated high potential in real-sample applications.

Colorimetric determination of Pb2+ ions based on surface leaching of Au@Pt nanoparticles as peroxidase mimic.

We report the first use of metallic nanozyme as colorimetric probe for Pb2+ determination. The method is based on the surface leaching of Au@PtNP nanozyme by Pb2+-S2O32- ions, accompanied by a decreased catalytic activity of the metallic nanozyme. To construct this colorimetric determination, the Pt deposition onto the AuNPs was carefully investigated and other experimental factors including kind of substrate and buffer were optimized. With increasing Pb2+ concentration, the catalytic activity of the Au@PtNPs decreased gradually. As a result, the blue color at 650 nm from the oxidation of 3,3',5,5'-tetramethylbenzidine by H2O2 faded gradually. A determination limit of 3.0 nM Pb2+ with a linear range from 20 to 800 nM was obtained. The assay demonstrated negligible response to common metal ions even at elevated concentrations. This colorimetric method was applied to the determination of Pb2+ ions spiked in lake water samples, and good recoveries (96.8-105.2%) were obtained. The above results indicate the potential application of metallic nanozymes in developing robust colorimetric assays. Graphical abstract Schematic representation of the surface leaching of Au@PtNP nanozyme by Pb2+-S2O32- ions, accompanying the decreased catalytic activity of the metallic nanozyme.

Green Phosphors Based on 9,10-bis((4-((3,7-dimethyloctyl)oxy) phenyl) ethynyl) Anthracene for LED.

An anthracene aromatic unit was introduced into the phenylethynyl structure by a rigid acetylene linkage at the C-9 and C-10 positions via Sonogashira coupling reactions, resulting in a planar and straight-backbone molecule (9,10-bis((4-((3,7-dimethyloctyl)oxy) phenyl) ethynyl) anthracene) (BPEA). Thermogravimetric analysis demonstrated the good thermal stability of the BPEA. Photoluminescence analysis showed that a suitable expanded π-conjugation in the BPEA made its excitation band extend into the visible region, and an intense green emission was observed under blue-light excitation. A bright green light-emitting diode with an efficiency of 18.22 lm/w was fabricated by coating the organic phosphor onto a 460 nm-emitting InGaN chip. All the results indicate that BPEA is a useful green-emitting material which is efficiently excited by blue light, and therefore, that it could be applied in many fields without UV radiation.

Erratum: Xie, Z.-J.; Bao, X.-Y.; Peng, C.-F. Highly Sensitive and Selective Colorimetric Detection of Methylmercury Based on DNA-Functionalized Gold Nanoparticles. Sensors 2018, 18, 2679.

The authors wish to make the following corrections to their paper [...].

Highly Sensitive and Selective Colorimetric Detection of Methylmercury Based on DNA Functionalized Gold Nanoparticles.

A new colorimetric detection of methylmercury (CH3Hg⁺) was developed, which was based on the surface deposition of Hg enhancing the catalytic activity of gold nanoparticles (AuNPs). The AuNPs were functionalized with a specific DNA strand (HT7) recognizing CH3Hg⁺, which was used to capture and separate CH3Hg⁺ by centrifugation. It was found that the CH3Hg⁺ reduction resulted in the deposition of Hg onto the surface of AuNPs. As a result, the catalytic activity of the AuNPs toward the chromogenic reaction of 3,3,5,5-tetramethylbenzidine (TMB)-H2O2 was remarkably enhanced. Under optimal conditions, a limit of detection of 5.0 nM was obtained for CH3Hg⁺ with a linear range of 10⁻200 nM. We demonstrated that the colorimetric method was fairly simple with a low cost and can be conveniently applied to CH3Hg⁺ detection in environmental samples.

Colorimetric detection of thiocyanate based on inhibiting the catalytic activity of cystine-capped core-shell Au@Pt nanocatalysts.

In this work, core-shell Au@Pt nanocatalysts (Au@Pt NCs) with ultrathin Pt shell were synthesized and demonstrated high peroxidase-like activity. Thiocyanate ions (SCN-) were found to effectively inhibit the peroxidase-like activity of Au@Pt NCs, and the mechanism was discussed by the characterization of TEM, DLS, EPR and XPS, etc. The inhibition of the catalytic activity of Au@Pt NCs by SCN- was mainly due to the decreased ability of the Au@Pt NCs for capturing •OH radicals and the increased ratio of Pt2+ to Pt° on the surface of the Au@Pt NCs. A sensitive colorimetric detection of thiocyanate (SCN-) was developed, based on the activity inhibition of Au@Pt NCs by SCN-. Interestingly, cystine modification of Au@Pt NCs was found to significantly improve the selectivity of SCN- recognition. After optimization, a colorimetric assay for SCN- was established with a detection limit of 5.0nM and a broad linear calibration over the range of 20nM to 40µM. This assay has the advantages of highly sensitive, selective and low-cost. Moreover, this assay demonstrated highly potential application in the quantitative determination of SCN- in water and raw milk samples.

A Highly Sensitive Colorimetric Method for Copper Ions Detection Based on Controlling the Peroxidase-like Activity of Au@Pt Nanocatalysts.

In this study, a sensitive colorimetric method for the detection of copper ion (Cu2+) was developed based on controlling the peroxidase-like activity of (gold core)@(ultrathin platinum shell) nanocatalysts (Au@Pt-NCs). It was found that D-penicillamine can effectively inhibit the activity of Au@Pt-NCs. After being incubated with Cu2+, D-penicillamine lost inhibition toward the catalytic ability of Au@Pt-NCs. Based on the above interaction, a colorimetric detection of Cu2+ was develop by measuring the colorimetric signal variation of the H2O2-3,3',5,5'-tetramethylbenzidine (TMB) reaction. This method exhibited high sensitivity and selectivity toward Cu2+ over a panel of other metal ions. The detection limit of this method was 3.7 nM and the linear range was 20 - 300 nM. Moreover, 20 nM Cu2+ can be distinguished directly by the naked eye. Furthermore, this method was applied to the analysis of water samples with good accuracy. These results demonstrated the excellent application potential of the method.

Rapid determination of clenbuterol in urine by a competitive bead immunoassay based on Luminex technology.

A new competitive bead immunoassay (CBIA) based on Luminex technology for detecting clenbuterol in urine was reported. The carboxylated fluorescent beads were directly coated with clenbuterol derivatives without carrier protein spacer. Clenbuterol antibody was biotinylated, which was used for clenbuterol detection in combination with the functionalized bead and streptavidin-phycoerythrin (SAPE). The effects of spacer on the CBIA method were investigated. The results indicated that the presence of small molecular spacer between bead and hapten improved the assay sensitivity and the hydrophilic spacer (glycine) was better than the hydrophobic spacer (m-aminobenzoic acid) for this CBIA method. The study affirms the importance of the judicious choice of hapten derivatives in the CBIA method for detecting small molecule drug based on Luminex technology. The method could be used for clenbuterol detection in livestock urine and possible for the simultaneous detection of multiple veterinary drugs.

Development of an indirect enzyme-linked immunosorbent assay for the organophosphorus pesticide paraoxon-methyl.

In the present study, the synthesis of hapten for the organophosphorus (OP) pesticide paraoxon-methyl was developed, with a spacer arm (aminocarboxylic acid) attached at the aromatic ring. It was conjugated to bovine serum albumin (BSA) for use as an immunogen and to ovalbumin (OVA) for coating antigen for ELISA testing. Rabbits were immunized with the immunogen and two polyclonal antisera were produced and screened against the coating antigen using competitive indirect enzyme-linked immunosorbent assay (ELISA). For application to textile samples, the influence of several factors such as organic solvent, ionic strength, and pH on the ELISA results were studied. Under optimized conditions, the quantitative working range was 0.012-1.158 microg/mL with a limit of detection (LOD) of 0.005 microg/mL and the IC(50) was 0.115 microg/mL.There was negligible cross reactivity (CR) with other OP pesticides. The recoveries obtained by standard paraoxon-methyl addition to the different textile samples such as cotton, wool and muslin delaine were all from 86.0% to 108.0%. Therefore, the optimized ELISA may become a new convenient and economical analytical tool for monitoring paraoxon-methyl residues in textile samples.

Development of an immunochromatographic assay for rapid detection of 1-Aminohydantoin in urine specimens.

A rapid immunochromatographic assay was developed and validated for detection of 1-aminohydantoin (AHD) in urine specimens. Colloidal gold-labeled polyclonal antibody specific to AHD derivative was used as the marker; based on the competitive reactivity theory, the metabolite of nitrofurantoin after derivatization with benzaldehyde would compete with carboxyphenyl AHD derivative-conjugated ovalbumin. The test strip could efficaciously detect the novel analyte with a visual detection limit of 10 ng mL(-1) and high specificity. The reliability of the assay was determined by testing 80 standard samples comparing with enzyme-linked immunosorbent assay. The semi-quantitative detection was accomplished in less than 15 min with low cost, especially for requirements of rapid and simple screening. This is the first publication of an immunochromatographic assay for detection of nitrofuran residues.

Determination of medroxyprogesterone acetate residues by CE immunoassay with chemiluminescence detection.

A rapid and simple method is developed for the determination of medroxyprogesterone acetate (MPA) by CE immunoassay with chemiluminescence (CL). This method is based on the competitive reactions between horseradish peroxidase (HRP)-labeled MPA (MPA-HRP) and free MPA with anti-MPA antiserum. The influencing factors on the electrophoresis and CL detection were studied completely and the optimal conditions of separation and determination were obtained. The linear range was 2.0-50 nmol/L and the LOD for MPA was 0.9 nmol/L. The present method was applied to the analysis of pork tissues.

Development of a faster determination of 10 anabolic steroids residues in animal muscle tissues by liquid chromatography tandem mass spectrometry.

A method had been developed for determination of residues of 10 anabolic steroids (ASs) in animal muscle tissues by liquid chromatography tandem mass spectrometry (LC/MS/MS). After enzymolysis, the sample was extracted with tert-butyl methyl ether, cleaned up through reverse solid-phase extraction and further determined by LC/MS/MS under multiple reaction monitoring (MRM) mode. The limits of detection (LOD) of LC/MS/MS method used for testing epitestosterone (ETS), nandrolone (17 beta-NT), 17 alpha-methyl-testosterone (MTS), testosterone 17-propionate (PTS), medroxyprogesterone (MED), progesterone (PG), estrone (ESN), 17 beta-estradiol (17 beta-ES), 17alpha-ethynylestradiol (EES) and estriol (EST) in animal muscle ranged from 0.06 to 0.22 microg/kg, and the limits of quantification (LOQ) were from 0.12 to 0.54 microg/kg. Experiments on spiked samples of pork, beef, chicken and fish showed that at addition level of 1.0 microg/kg, the average recoveries of the ASs ranged from 64% to 77%, and coefficients of variation from 7.1% to 20.3%, while at addition level of 2.0 microg/kg, the average recoveries ranged from 70% to 89%, and coefficient of variation from 7.1% to 19.1%.