Ultrasound and surfactant-assisted dispersive liquid-liquid microextraction prior to poly(ethylene oxide)-mediated stacking in CE for highly sensitive determination of barbiturates in human fluids.

This study developed a facile, highly sensitive technique for extracting and quantifying barbiturates in serum samples. This method combined ultrasound and surfactant-assisted dispersive liquid-liquid microextraction with poly(ethylene oxide)-mediated stacking in capillary electrophoresis. Factors influencing the extraction and stacking performance, such as the type and volume of extraction solvents, the type and concentration of surfactant, extraction time, salt additives, sample matrix, solution pH, and composition of the background electrolyte, were carefully studied and optimized to achieve the optimal detection sensitivity. Under the optimized extraction (injecting 140 µL C2 H4 Cl2 into 1 mL of sample with pH 4 (5 mM sodium phosphate containing 0.05 mM Tween 20 and sonication for 1 min) and separation conditions (150 mM tris(hydroxymethyl)aminomethane-borate with pH 8.5 containing 0.5% (m/v) poly(ethylene oxide)), the limits of detection (signal-to-noise ratio = 3) of five barbiturates ranged from 0.20 to 0.33 ng/mL, and the calculated sensitivity improvement ranged from 868- to 1700-fold. The experimental results revealed excellent linearity (R2  > 0.99), with relative standard deviations of 2.1%-3.4% for the migration time and 4.3%-5.7% for the peak area. The recoveries of the spiked serum samples were 97.1% -110.3%. Our proposed approach offers a rapid and practical method for quantifying barbiturates in biological fluids.

Synthesis of Fluorescent Carbon Dots as Selective and Sensitive Probes for Cupric Ions and Cell Imaging.

A novel sensing system has been designed for the detection of cupric ions. It is based on the quenched fluorescence signal of carbon dots (CDs), which were carbonized from poly(vinylpyrrolidone) (PVP) and L-Cysteine (CYS). Cupric ions interact with the nitrogen and sulfur atoms on surface of the CDs to form an absorbed complex; this results in strong quenching of the fluorescence of the CDs via a fast metal-to-ligand binding affinity. The synthesized water-soluble CDs also exhibited a quantum yield of 7.6%, with favorable photoluminescent properties and good photostability. The fluorescence intensity of the CDs was very stable in high ionic strength (up to 1.0 M NaCl) and over a wide range of pH levels (2.0-12.0). This facile method can therefore develop a sensor that offers reliable, fast, and selective detection of cupric ions with a detection limit down to 0.15 µM and a linear range from 0.5 to 7.0 µM (R2 = 0.980). The CDs were used for cell imaging, observed that they were low toxicity to Tramp C1 cells and exhibited blue and green and red fluorescence under a fluorescence microscope. In summary, the CDs exhibited excellent fluorescence properties, and could be applied to the selective and sensitive detection of cupric ion and multicolor cell imaging.

One-pot green hydrothermal synthesis of fluorescent nitrogen-doped carbon nanodots for in vivo bioimaging.

One-pot green synthesis of fluorescent nitrogen-doped carbon nanodots (CNDs) was developed by hydrothermal treatments of biocompatible polyvinylpyrrolidone (PVP) and glycine. The fluorescent nitrogen-doped CNDs exhibited excellent water solubility, low cytotoxicity, and good salt stability for biological imaging. UV-vis spectroscopy, fluorescence spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) spectroscopy, and Raman spectroscopy were applied to confirm the optical and structural characteristics of the CNDs. Fluorescence of the CNDs was tunable from 417 to 450 nm adjusted by different excitation energy. Fluorescent quantum yield of the CNDs (21.43%) was significantly increased ~47.59% in comparison to that of the CNDs (14.52%) without nitrogen doping by glycine. In the in vivo imaging system (IVIS), fluorescence signal of the nitrogen-doped CNDs was obviously observed in the lungs at 12- and 24-h post-injection. Our work has shown the potential applications of the nitrogen-doped CNDs in fluorescence imaging in vivo.

Dispersive liquid-liquid microextraction combined with acetonitrile stacking through capillary electrophoresis for the determination of three selective serotonin reuptake inhibitor drugs in body fluids.

Dispersive liquid-liquid microextraction was combined with acetonitrile stacking in capillary electrophoresis for the identification of three selective serotonin reuptake inhibitors (citalopram, fluoxetine, and fluvoxamine) in human fluids such as urine and plasma. Parameters that affect the extraction and stacking efficiency, such as the type and volume of the extraction and disperser solvent, extraction time, salt addition for dispersive liquid-liquid microextraction, and sample matrices, pH, and concentration of the separation buffer for stacking, were investigated and optimized. Under optimum conditions, the enrichment factors were in the range of 1195-1441. Limits of detection ranged from 1.4 to 1.7 nM for the target analytes. Calibration graphs displayed satisfied linearity with R2 greater than or equal to 0.9978, and relative standard deviations of the peak area analysis were in the range of 2.9-5.0% (n = 3). The recoveries of all tricyclic antidepressant drugs from urine and plasma were in the range of 77-117 and 79-106%, respectively. The findings of this study show that dispersive liquid-liquid microextraction acetonitrile-stacking capillary electrophoresis is a rapid and convenient method for identifying tricyclic antidepressant drugs in urine and plasma.

Online dynamic pH junction-sweeping for the determination of benzoic and sorbic acids in food products by capillary electrophoresis.

A simple, low-cost, and efficient online focusing method that combines a dynamic pH junction and sweeping by capillary electrophoresis with polymer solutions was developed and optimized for the simultaneous determination of benzoic acid (BA) and sorbic acid (SA). A sample solution consisting of 2.5 mM phosphate at pH 3.0 and a buffer solution containing 15 mM tetraborate (pH 9.2), 40 mM sodium dodecyl sulfate, and 0.100 % (w/v) poly(ethylene oxide) were utilized to realize dynamic pH junction-sweeping for BA and SA. Under the optimized conditions, the entire analysis process was completed in 7 min, and a 900-fold sensitivity enhancement was achieved with limits of detection (S/N = 3) as low as 8.2 and 6.1 nM for BA and SA, respectively. The linear ranges were between 20 nM and 20 µM for BA and 20 nM and 10 µM for SA, with correlation coefficients greater than 0.992. The recoveries of the proposed method ranged from 90 to 113 %. These satisfactory results indicate that this method has the potential to be an effective analytical tool for the rapid screening of BA and SA in different food products.

Recent advances in bacteria identification by matrix-assisted laser desorption/ionization mass spectrometry using nanomaterials as affinity probes.

Identifying trace amounts of bacteria rapidly, accurately, selectively, and with high sensitivity is important to ensuring the safety of food and diagnosing infectious bacterial diseases. Microbial diseases constitute the major cause of death in many developing and developed countries of the world. The early detection of pathogenic bacteria is crucial in preventing, treating, and containing the spread of infections, and there is an urgent requirement for sensitive, specific, and accurate diagnostic tests. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is an extremely selective and sensitive analytical tool that can be used to characterize different species of pathogenic bacteria. Various functionalized or unmodified nanomaterials can be used as affinity probes to capture and concentrate microorganisms. Recent developments in bacterial detection using nanomaterials-assisted MALDI-MS approaches are highlighted in this article. A comprehensive table listing MALDI-MS approaches for identifying pathogenic bacteria, categorized by the nanomaterials used, is provided.

Tannic Acid-Decorated Bimetallic Copper-Gold Nanoparticles with High Catalytic Activity for the Degradation of 4-Nitrophenol and Rhodamine B.

In this study, tannic acid (TA) was applied as a stabilizing agent for synthesizing bimetallic copper-gold (CuAu) nanoparticles. Cu(NO3)2 and NaAuCl4 were used as the sources of copper and gold ions, respectively, and NaBH4 was employed as a reducing agent. The prepared TA-CuAu nanoparticles were extensively characterized via ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, X-ray diffraction, and zeta potential analyses. To evaluate their catalytic activity, the TA-CuAu nanoparticles and NaBH4 were applied in the degradation of 4-nitrophenol (4-NP) and rhodamine B (RB) individually and in a mixture. The individual degradation of 4-NP and RB was completed within 10 min, and the apparent rate constants were calculated as 0.3046 and 0.2628 min-1, respectively, emphasizing the efficient catalytic activity of the TA-CuAu nanoparticles. Additionally, controlled experiments were performed for the degradation of 4-NP and RB in the absence of catalysts or NaBH4 to investigate the kinetic feasibility of the catalytic reactions. A mixture of 4-NP and RB was successfully degraded within 10 min using the TA-CuAu nanoparticles as catalysts. Furthermore, the reuse of the catalysts after five successive cycles demonstrates an outstanding performance with no significant loss in the catalytic activity. Finally, the successful treatment of the tap and lake water samples spiked with 4-NP and RB using the TA-CuAu nanoparticles further confirmed their application potential as catalysts in environmental water remediation.

A Ratiometric Fluorescent Sensor for Penicillin G Based on Color-Tunable Gold-Silver Nanoclusters.

Excessive administration of penicillin G and improper disposal of its residues pose a serious risk to human health; therefore, the development of convenient methods for monitoring penicillin G levels in products is essential. Herein, novel gold-silver nanoclusters (AuAgNCs) were synthesized using chicken egg white and 6-aza-2-thiothymine as dual ligands with strong yellow fluorescence at 509 and 689 nm for the highly selective detection of penicillin G. The AuAgNCs were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible absorption spectrophotometry, and fluorescence spectrophotometry. Under optimum conditions, the fluorescence intensity decreased linearly with the concentration of penicillin G from 0.2 to 6 µM, with a low detection limit of 18 nM. Real sample analyses indicated that a sensor developed using the AuAgNCs could detect penicillin G in urine and water samples within 10 min, with the recoveries ranging from 99.7 to 104.0%. The particle size of the AuAgNCs increased from 1.80 to 9.06 nm in the presence of penicillin G. We believe the aggregation-induced quenching of the fluorescence of the AuAgNCs was the main mechanism for the detection of penicillin G. These results demonstrate the ability of our sensor for monitoring penicillin G levels in environmental and clinic samples.

Recent advances in on-line concentration and separation of amino acids using capillary electrophoresis.

This article highlights recent methodological developments in the on-line concentration and separation of amino acids and their enantiomers using capillary electrophoresis. Sections are dedicated to recent contributions to on-line concentration strategies such as field-amplified sample stacking, large-volume sample stacking, dynamic pH junction, transient isotachophoresis, sweeping, and the combination of two methods. The main applications, advantages, and limitations of these procedures in the biological, food, and pharmaceutical fields are addressed. Comprehensive tables listing on-line techniques for the concentration and separation of amino acids and their enantiomers, categorized by the stacking strategies used, background electrolytes, sample matrix, limit of detection, and enhancement factor, are provided.

Determination of seven preservatives in cosmetic products by micellar electrokinetic chromatography.

A micellar electrokinetic chromatography method using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, coupled with UV-Vis detection, was developed for the simultaneous determination of seven preservatives, including methyl-, ethyl-, propyl- and butyl-paraben and phenol, phenoxyethanol and resorcinol. The method involved optimizing the pH of the phosphate buffer and concentrations of CTAB, ethanol and 2-hydroxypropyl-ß-cyclodextrin (HP-ß-CD). The preservatives were well separated using optimum conditions and separated within 10 min at a separation voltage of -12.5 kV with the 1.0 mM phosphate buffer (pH 7.0) containing 90 mM CTAB, 25 mM HP-ß-CD and 10% (v/v) ethanol. Satisfactory recoveries (84.1-103.0%), migration time (RSD < 3.1%) and peak area (RSD < 4.5%) repeatabilities were achieved. Detection limits of the preservatives were between 0.31 and 1.52 µg mL(-1) (S/N = 3, n = 5). The optimized method was successfully applied to the simultaneous determination of these preservatives in 10 commercial cosmetic products.

Electrochemically synthesized green fluorescent carbon dots for quantitation of hypochlorite and carbendazim.

Green emission carbon dots (CDs) electrochemically prepared from 2,6-pyridinedicarboxylic acid and o-phenyl-enediamine were applied separately for the quantitation of hypochlorite and carbendazim. The characteristic and optical properties of the CDs were studied through fluorescence, UV-vis absorption, X-ray photoelectron spectroscopy, and transmission electron microscopy. The synthesized CDs were mainly 0.8-2.2 nm in size, with an average size of 1.5 nm. The CDs exhibited green luminescence centered at 520 nm when excited by 420 nm light. The green emission of the CDs is quenched after the addition of hypochlorite, mainly through the redox reaction between hypochlorite and hydroxyl groups on the CDs surface. Furthermore, the hypochlorite-induced fluorescence quenched can be prevented in the presence of carbendazim. The sensing approaches exhibit good linear ranges of 1-50 µM and 0.05-5 µM for hypochlorite and carbendazim, respectively, with low detection limits of 0.096 and 0.005 µM, respectively. Practicalities of the luminescent probes were separately validated by the quantitation of the two analytes in real sample matrix with recoveries ranging from 96.3 to 108.9% and the relative standard deviation values below 5.51%. Our results show the potential of the sensitive, selective, and simple CD probe for water and food quality control.

Selective detection of tricyclazole by optical technique using thiomalic acid-modified Au and Ag nanoparticle mixtures.

This study proposes the use of thiomalic acid-modified Au and Ag nanoparticle mixtures (TMA-Au/AgNP mixes) for the selective detection of tricyclazole. Upon the addition of tricyclazole, the color of TMA-Au/AgNP mixes solution changes from orange-red to lavender (red-shift). According to the density-functional theory calculations, tricyclazole-induced aggregation of TMA-Au/AgNP mixes through electron donor-acceptor interactions was proved. The sensitivity and selectivity of the proposed method are affected by the amount of TMA, volume ratio of TMA-AuNPs to TMA-AgNPs, pH value, and buffer concentration. The ratio of absorbance (A654/A520) of TMA-Au/AgNP mixes solution is proportional to the concentration of tricyclazole over the range 0.1-0.5 ppm with a linear correlation (R2 = 0.948). Moreover, the limit of detection was estimated at 0.028 ppm. The practicality of TMA-Au/AgNP mixes was validated for the determination of tricyclazole concentration in real samples (spiked recovery was 97.5%-105.2%), demonstrating its advantages of simplicity, selectivity, and sensitivity.

Analysis of carbofuran, carbosulfan, isoprocarb, 3-hydroxycarbofuran, and 3-ketocarbofuran by micellar electrokinetic chromatography.

We developed an analytical method for the detection and quantitation of five pesticides and some of their metabolites - 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, carbosulfan, and isoprocarb - using micellar electrokinetic chromatography coupled with a UV-Vis detector. The optimum separation conditions were 20 mM phosphate buffer (pH 8.0) containing 15 mM sodium dodecyl sulfate. The detection wavelength was set at 200 nm and the applied voltage was 12.5 kV. Under these conditions, baseline separation of five pesticides was achieved in 15 min, and the detection limits (S/N = 3) of 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, carbosulfan, and isoprocarb were 0.3, 0.3, 0.3, 4.0, and 0.3 µM, respectively. The linear ranges for 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, and isoprocarb were between 1.0 and 50.0 µM and that for carbosulfan was between 10.0 and 100.0 µM, with R(2) larger than 0.995. When applied to the analysis of a carbofuran-spiked rice sample, this approach yielded results with excellent repeatability (3.3%, n = 5), reproducibility (4.5%, n = 5), separation efficiency (>2.1 × 10(4) theoretical plates), and recovery (95.5 ± 1.4%, n = 5).

Sodium-Alginate-Functionalized Silver Nanoparticles for Colorimetric Detection of Dimethoate.

Sodium alginate (SA) was used to functionalize the surfaces of silver nanoparticles (AgNPs) to form SA-AgNPs for sensing dimethoate with a rapid and sensitive visual readout. UV-Vis spectrophotometry, Fourier transform infrared spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and zeta potential measurements were used to characterize SA-AgNPs that were synthesized under the ideal conditions. SA-AgNPs were spherical with an average size of 14.6 nm. The stability of SA-AgNPs was investigated with changes in pH, salinity, and storage time. This colorimetric assay of dimethoate relied on the change in the absorption ratio (A475/A400) of SA-AgNPs, resulting in their aggregation caused by dimethoate, leading to a visual change for SA-AgNPs from yellow to pale yellow. As a result, the absorption ratio (A475/A400) of SA-AgNPs showed good linearity in the range of 0.05 to 2.0 ppm (R2 = 0.9986) with a limit of detection (LOD) of 30 ppb. Adding other pesticides did not significantly change the absorption ratio of SA-AgNPs, indicating its high selectivity as a colorimetric assay. The sensor was successfully used to detect dimethoate in actual water samples.

Quantitation of branched-chain amino acids in ascites by capillary electrophoresis with light-emitting diode-induced fluorescence detection.

Branched-chain amino acids (BCAAs) are one of the important biomarkers for monitoring liver disease such as hepatitis or hepatoma. In this communication, we present the determination of the concentrations of BCAA in ascites by CE light-emitted diode-induced fluorescence (LEDIF) using 1.5% m/v poly(ethylene oxide) (average M(v) : ~8 000 000 g/mol) that was prepared in 10 mM sodium tetraborate solution (pH 9.3). Naphthalene-2,3-dicarboxaldehyde was used to derivatize 15 amino acids (AAs) to form naphthalene-2,3-dicarboxaldehyde (NDA)-AA derivatives prior to CE analysis. The separation of 15 NDA-AA derivatives was accomplished within 15 min, with RSD values of <5.8% (within-day) and 7.4% (between-days) with respect to their migration times. The limits of detection for the tested BCAAs ranged from 10.6 to 10.9 nM. We determined the concentrations of three BCAAs--leucine, isoleucine and valine--in ascites by applying a standard addition method, with recovery percentages ranging from 93.9 to 111%. The results obtained from this CE-LEDIF method is in good agreement with those by a gold standard method using an AA analyzer. We have found that the concentrations of the three BCAAs in ascites obtained from patients suffering from liver diseases were lower than those from healthy individuals. Our approach is highly efficient, sensitive, and cost-effective, which holds great potential for the diagnosis of liver diseases.

Functionalized silver nanoparticles as colorimetric probes for sensing tricyclazole.

A colorimetric assay for highly selective and sensitive detection of tricyclazole using fluorescein-functionalized silver nanoparticles (F-AgNPs) as sensing probes was investigated. As the addition of tricyclazole to F-AgNPs, a drastic decrease in the absorbance at 394 nm was detected, which was accompanied with a noticeable color change from yellow to gray. The sensing mechanism involved an interaction between tricyclazole and F-AgNPs, which led to aggregation of the latter, inducing a color change from yellow to gray. An excellent linear calibration curve (R2 = 0.9994) was achieved between absorbance at 394 nm and the tricyclazole concentration in the range between 0.06 and 1.0 ppm. Moreover, the detection limit was estimated at 0.051 ppm. The developed colorimetric assay also showed good selectivity and was successfully utilized to quantify tricyclazole in rice samples with satisfactory recoveries. The proposed assay has been successfully applied for monitoring tricyclazole in rice samples.

Facile synthesis of dual-emission fluorescent carbon nanodots for a multifunctional probe.

In this study, we developed a facile method for synthesizing dual-emission carbon nanodots (CDs) through trimesic acid and o-phenylenediamine through electrolysis for 2 h. The synthesized CDs were mainly 3-7 nm in size, with an average size of 5.17 nm. The dual-emission fluorescent property of these CDs could be observed under two different excitation wavelengths. The green emission of the CDs could be quenched after the addition of mercury ions or copper ions, and the blue emission of the CDs could be inhibited using hydroxychloroquine (HCQ). Furthermore, the quenched fluorescence of CDs/Cu2+ could be recovered through the addition of glyphosate. We developed a multifunctional chemical sensor by using these special fluorescence materials. Under optimal conditions, the detection limits of mercury ions, glyphosate, and HCQ were 0.42 µM, 1.1 mg L-1, and 0.14 µM, respectively. Moreover, this method can be used to detect mercury ions, glyphosate, and HCQ in environmental water, cereals, and urine samples, respectively.

One-Pot Hydrothermal Synthesis of Carbon Dots as Fluorescent Probes for the Determination of Mercuric and Hypochlorite Ions.

Nitrogen and sulfur codoped carbon dots (NSCDs) were synthesized via a one-pot hydrothermal method, and citric acid, ethylenediamine, and methyl blue were used as precursors. The obtained NSCDs were spherical with an average size of 1.86 nm. The fluorescence emission spectra of the NSCDs were excitation independent and emitted blue fluorescence at 440 nm with an excitation wavelength at 350 nm. The quantum yield of the NSCDs was calculated to be 68.0%. The NSCDs could be constructed as fluorescent probes for highly selective and sensitive sensing mercuric (Hg2+) and hypochlorite (ClO-) ions. As the addition of Hg2+ or ClO- ions to the NSCDs, the fluorescence intensity was effectively quenched due to dynamic quenching. Under the optimal conditions, the linear response of the fluorescence intensity ranged from 0.7 µM to 15 µM with a detection limit of 0.54 µM and from 0.3 µM to 5.0 µM with a limit of detection of 0.29 µM for Hg2+ and ClO- ions, respectively. Finally, the proposed method was successfully used for quantifying Hg2+ and ClO- ions in spiked tap water samples.

Functionalized gold nanoparticles for sensing of pesticides: A review.

Pesticides are a family of non-biodegradable chemical compounds which widely used in agriculture to control pests and increase yield production. However, overuse or abuse of pesticides and their metabolites may cause potential toxicity for the environment as well as human health and all other living organisms, even at deficient concentrations. Consequently, the development of sensors for monitoring these compounds is significant. Recently, nanoparticles-based sensors have been extensively employed as a potential alternative or complementary analytical tool to conventional detection methods for pesticides. Among them, gold nanoparticles (AuNPs) owing to their unique optical properties have been developed as smart sensors with high selectivity, sensitivity, simplicity, and portability. These comprehensive reviews have summarized various studies performed based on different detection strategies, i.e., colorimetric, fluorescence, surface-enhanced Raman scattering, and electrochemical, using AuNPs as sensing probes for pesticide analysis in various matrices. Additionally, the current challenges and future trends for developing novel AuNPs-based sensors for the detection of pesticides are also discussed.

A sensitive colorimetric probe for detection of the phosphate ion.

In the present article, we report a novel colorimetric probe (TNT@MB) for the detection of the phosphate ion, which is based on the strong binding affinity between the phosphate ion and titanium dioxide nanotubes (TNTs). TNTs were synthesized from TiO2 nanoparticles by hydrothermal treatment. The obtained TNTs had an average length of 200 ± 50 nm and an average width of 12 ± 5 nm. TNT@MB was prepared by adsorbing methyl blue onto TNTs in acidic condition. The optimal synthesis conditions for TNT@MB consisted in having 0.05 g of TNTs react with 1 µmole of methyl blue at pH 2 for 90 min. TNTs and TNT@MB were characterized by UV-vis diffuse reflection spectroscopy, TEM, FTIR, and XPS. The phosphate-ion sensing behavior of TNT@MB was investigated by UV-visible spectroscopy. The phosphate-ion concentration linear range and detection limit of this method based on TNT@MB were 1-40 µM and 0.59 µM, respectively. A sample of lake water was used as a real sample, and analyte recovery rates were measured in the 102.5-103.6% range, with relative standard deviations below 5.6% (n = 3). We also found that this probe could be reused after regeneration in alkaline solution. These results indicate that as a colorimetric probe, TNT@MB has the advantages of being environmentally friendly, inexpensive, and simple to use, as well as giving rise to an easily observable color change.