Osteoporosis risk assessment using multilayered gold-nanoparticle thin film via SALDI-MS measurement.

A powerful technique to detect bone biomarkers has been developed for assessment of osteoporosis at the early stage. Two-dimensional multilayered gold-nanoparticle thin film (MTF-AuNPs) was demonstrated as a promising test platform for detection of bone biomarker, hydroxyproline (HYP), measured by surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). With strong surface plasmon resonance and excellent homogeneity, facilely prepared, highly ordered, and large-scale MTF-AuNPs revealed high sensitivity of HYP in the SALDI-MS measurement without additional matrixes, such as α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB). Furthermore, the mass spectrum of HYP with MTF-AuNPs was significantly improved in signal intensity enhancement, background noise reduction, and signal-to-noise ratio amplification. The excellent reproducibility of HYP spectra with only 9.3% relative signal variation could be attributed to MTF-AuNPs' high absorbance at a wavelength of 337 nm, low heat capacity, superior thermal conductivity, and outstanding homogeneity. The calibration curve showed high linear correlation between mass spectrum intensity and HYP concentration in the range of 1 to 100 µM, covering the whole level in healthy people and osteoporosis patients. In particular, the serum sample was directly deposited onto the MTF-AuNP sample substrate without any pretreatment and its HYP concentration was then successfully determined. We believe that the combination of SALDI-MS and MTF-AuNP sample substrates would be a potential approach for bone biomarker detection in the osteoporosis risk assessment. Graphical abstract.

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.

Gold nanoparticles as sensitive optical probes.

Gold nanoparticles (Au NPs) have become one of the most popular materials for sensing of analytes of interest in the last decade, mainly because of their ease in preparation and conjugation, stability, biocompatibility, and size-dependent optical properties. We have witnessed many sensitive and selective Au NP based optical systems for the quantitation of metal ions, anions, proteins, and DNA, based on analyte induced changes in their absorption, fluorescence, and scattering. In this tutorial review, we briefly discuss wet chemical approaches for the preparation of Au NPs. Sensing mechanisms and strategies of Au NP based optical systems are provided to show basic concepts in designing sensitive and selective sensing systems. Strategies for signal amplification applied in Au NP based systems are emphasized for the analysis of trace amounts of analytes in real samples. Many excellent Au NP based optical sensing systems are discussed to highlight their practicality for the analysis of complicated biological and environmental samples. The tutorial review ends with the discussion of the challenges and future trends of Au NP based optical sensing systems.

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.

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.

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.

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.

Establishment of a bioluminescence-based bioassay for the detection of dioxin-like compounds.

Dioxin and dioxin-like compounds are among the most prevalent and toxic environmental pollutants. At present, analytical chemical techniques are considered the gold standard for detection of dioxins. Here, we describe a highly sensitive and cost-effective alternative, based on bioluminescence and bioluminescence resonance energy transfer (BRET). Upon binding to dioxin, aryl hydrocarbon receptor (AHR) dissociates from HSP90 and subsequently translocates to the nucleus, where it interacts with AHR nuclear translocator (ARNT). We generated cell lines that stably co-express a fusion protein of AHR and Renilla luciferase (AHR-RL) and either HSP90 or ARNT tagged with yellow fluorescent protein (HSP90-YFP or ARNT-YFP). The fluorescent signals of YFP are activated by the emission of RL while the interactions between AHR and HSP90 (or ARNT) were monitored. Application of 3-methylcholanthrene, the AHR agonist, enhances BRET signals in cells co-expressing AHR-RL, AIP-His, P23-His and ARNT-YFP (AAPA cells), while suppressing BRET signals in cells co-expressing AHR-RL, AIP-His, P23-His and HSP90-YFP (AAPH cells). In addition, dioxin treatment reduced Renilla luminescence in AAPH cells in a concentration-dependent manner, due to the degradation of AHR. Intriguingly, the detection limit for dioxin in our AHR degradation assay was as low as 10(-17) M. This work highlights the potential of AHR-RL degradation assays to detect dioxin-like pollutants.

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.

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.

Fluorescence-tunable copper nanoclusters and their application in hexavalent chromium sensing.

Generally, metal nanoclusters are synthesized using only a single ligand. Thus, the properties and applications of these nanomaterials are limited by the nature of the ligand used. In this study, we have developed a new synthetic strategy to prepare bi-ligand copper nanoclusters (Cu NCs). These bi-ligand Cu NCs are synthesized from copper ions, thiosalicylic acid, and cysteamine by a simple one-pot method, and they exhibit high quantum yields (>18.9%) and good photostability. Most interestingly, the fluorescence intensities and surface properties of the Cu NCs can be tailored by changing the ratio of the two ligands. Consequently, the bi-ligand Cu NCs show great promise as fluorescent probes. Accordingly, the Cu NCs were applied to the inner-filter-effect-based detection of hexavalent chromium in water. A wide linear range of 0.1-1000 µM and a low detection limit (signal-to-noise ratio = 3) of 0.03 µM was obtained. The recoveries for the real sample analysis were between 98.3 and 105.0% and the relative standard deviations were below 4.54%, demonstrating the repeatability and practical utility of this assay.

Gold-nanoparticle-based fluorescent "turn-on" sensor for selective and sensitive detection of dimethoate.

A simple approach to fabricate a highly selective and sensitive dimethoate probe was developed based on Rhodamine B (RB)-functionalized gold nanoparticles (AuNPs). The quenching of RB fluorescence in the presence of AuNPs in the solution, mediated by fluorescence resonance energy transfer, was observed. In the presence of dimethoate, the fluorescence intensity of the RB-AuNP solution is gradually recovered when dimethoate molecules displace RB molecules on the surface of the AuNPs, which significantly increased the fluorescence intensity of RB. Fluorescence is proportional to the dimethoate concentration in the range of 0.005-1.0 ppm (R2 = 0.989), and the LOD was 0.004 ppm. The recoveries of dimethoate in water and fruit samples were 86-116% with a good RSD (< 9.3%). Because of its high sensitivity, excellent selectivity, and convenient fabrication process, this method is a promising candidate for dimethoate screening.