Novel Glutathione-Capped Cadmium Telluride Quantum Dots-Based Off–On Fluorescence Sensor for Highly Sensitive and Selective Monitoring of Histidine

A novel glutathione-capped cadmium telluride quantum dots-based fluorescence “off–on” sensor was designed and applied for highly sensitive and selective monitoring of histidine in aqueous solution. To provide a platform for histidine detection, manganese ion was first employed as an effective quencher to decrease the fluorescence of glutathione-capped cadmium telluride quantum dots because of the binding of manganese ion to glutathione on the surface of quantum dots and the electron transfer from the photoexcited glutathione-capped cadmium telluride quantum dots to manganese ion. Due to its high binding affinity with manganese ion, histidine can make the manganese ion to be dissociated from the surface of glutathione-capped cadmium telluride quantum dots to form more stable complex with histidine in solution, and set free the luminescent glutathione-capped cadmium telluride quantum dots, thereby recovering the fluorescence of glutathione-capped cadmium telluride quantum dots. Experimental results showed that the recovered fluorescence intensity was directly proportional to the concentration of histidine in the range of 0.006 to 465.0 µg mL^?1 with a correlation coefficient (R) of 0.9977, and the detection limit (3σ/K) was 1.82 ng mL^?1. Relevant experiments also revealed that the fluorescence sensor gives excellent selectivity for histidine over other common amino acids. To further investigate perfect analysis performance, this sensor was utilized to determine histidine in synthetic samples with satisfactory results.     

Cyclodextrin-functionalized magnetic graphene as solid-phase extraction absorbent coupled with flame atomic absorption spectrophotometry for determination of cadmium in water and food samples

A magnetic hydroxypropyl-β-cyclodextrin-functionalized reduced graphene oxide was synthesized and used as a magnetic solid-phase extraction adsorbent for the enrichment of cadmium from water and food samples before its determination by flame atomic absorption spectrometry. The effects of pH, amount of adsorbent, extraction time, desorption condition, and coexisting ions on the extraction efficiency were investigated and optimized. Under the optimal conditions, the limit of detection was 0.23?µg?L^?1 for water samples and 0.015?µg?g^?1 for food samples, respectively. The linear range was between 0.50 and 100.0?µg?L^?1 with a good correlation coefficient of 0.9986 in water samples, and between 0.050 and 5.0?µg?g^?1 with a correlation coefficient of 0.9975 in food samples. The method recoveries for the spiked samples were in the range of 87.5–102.4%, with the relative standard deviations ranging from 4.7% to 6.2% and enrichment factors ranging from 38 to 41, respectively. The adsorbent could be reused over 50 times without a significant change of extraction capability. The established method provides a promising environmentally friendly alternative for the determination of cadmium in complex matrix samples with no need of additional chelating reagents during the extraction process.     

A Novel Pyrene Fluorescent Sensor Based on the π–π Interaction Between Pyrene and Graphene of Graphene–Cadmium Telluride Quantum Dot Nanocomposites

In this article, water-soluble graphene–cadmium telluride quantum dot nanocomposites were fabricated through the synthesis of cadmium telluride quantum dots in the presence of graphene aqueous dispersion. It was found that pyrene could remarkably quench fluorescence of graphene–cadmium telluride quantum dot nanocomposites. On this basis, a novel method for the determination of pyrene was developed. Factors affecting the pyrene detection were investigated, and the optimum conditions were determined. Under the optimum conditions, a linear relationship could be established between the quenching of fluorescence intensity of graphene–cadmium telluride quantum dot nanocomposites and the pyrene concentration in the range of 6.00 × 10^?8–2.00 × 10^?6 mol L^?1 with a correlation coefficient of 0.9959. The detection limit was 4.02 × 10^?8 mol L^?1. Furthermore, the nanocomposites were applied to practical determination of pyrene in different water samples with satisfactory results.     

Quantum Dots (QDs) Based Fluorescent Sensor for the Selective Determination of Nimesulide

Fluorescent PET (Photoinduced Electron Transfer) has been of particular growth in recent times. A novel PET based fluorescent sensor using unmodified CdSe quantum dots (QDs) has been developed for the trace determination of Nimesulide (NIM). The sensor is based on the selective fluorescence quenching of quantum dots by NIM in presence of other NSAIDs and is found that intensity of quenching is linearly related to NIM concentration in the range 8.2?×?10^?7 – 4.01?×?10^?5?M. The mechanism of interaction is discussed. Finally, the potential application of the proposed method for the trace determination of NIM in pharmaceutical formulation is demonstrated.     

Determination of Protoporphyrin IX Disodium Salt Based on Fluorescence Quenching of Glutathione-Capped Cadmium/Tellurium Quantum Dots

ABSTRACT

Aqueous glutathione-capped cadmium/tellurium quantum dots with a diameter of about 3 nm were synthesized. The fluorescence was quenched in the presence of protoporphyrin IX disodium salt, with the excitation wavelength at 320 nm. Under the optimal conditions, the quenched fluorescence intensity was linear in the range of 0.096–16 µg · mL^?1 with a concentration of protoporphyrin IX disodium salt, and the detection limit (3σ) was 2.8 × 10^?2 µg · mL^?1. The proposed method has been applied to the determination of protoporphyrin in serum samples with satisfactory results. The interaction mechanism was investigated.     

Comparison of Carbon Dots Prepared in Deep Eutectic Solvent and Water/Deep Eutectic Solvent: Study of Fluorescent Detection of Fe3+ and Cetirizine and their Photocatalytic Antibacterial Activity

In this study, two solvents (deep eutectic and water/deep eutectic solvents) were used for N-doped carbon dots (N-CDs) preparation by microwave irradiation. The solvent can influence surface chemical composition, quantum yield, morphology, and fluorescence of CDs. N-CDs synthesized in water/deep eutectic solvent (DES) had better quantum yield (24.5%) with respect to N-CDs synthesized in deep eutectic solvent (17.4%). These carbon dots were used as a rapid and high sensitive “off–on” fluorescent probe for the determination of Fe³⁺ ion and cetirizine. Morphology and structure of the N-CDs were characterized by FT-IR, UV–Vis, XRD and TEM. Linear range and detection limit for N-CDs synthesis in deep eutectic solvent for cetirizine were 0.08–48 µM and 15 nM, respectively and for N-CDs synthesis in water/deep eutectic solvent were 0.03–50 µM and 10 nM, respectively. Applicability of this nanoprobe was tested in cetirizine determination in serum sample. Antibacterial activities of the two synthesized N-CDs were also investigated using agar disk diffusion method.

     

Dispersive liquid–liquid microextraction based on solidification of floating organic drop for separation and preconcentration of malachite green before its determination by flow injection spectrophotometry

ABSTRACT

A simple and fast dispersive liquid–liquid microextraction based on solidification of floating organic drop has been developed for the separation and preconcentration of malachite green in water samples prior to its determination by flow injection spectrophotometry. Sodium lauryl sulfate, an anionic surfactant, was used for the ion-pair formation with malachite green. The factors affecting the ion-pair formation and extraction were optimized. Under the optimized conditions (volume of 1-undecanol as the extraction solvent, 40 μL; the volume of ethanol as the disperser solvent, 100 μL; sodium lauryl sulfate concentration, 7.5 × 10^?7 mol L^?1, and the pH of the sample, ～3.0), the calibration graph was linear over the range of 0.8–25 µg L^?1 with the detection limit of 0.3 µg L^?1 and the preconcentration factor of 750. The relative standard deviation at 7 µg L^?1 (n = 6) was found to be 2.1%. The developed method was successfully applied to the determination of malachite green in river water and fish farming water samples.     

Online Copper Removal for Selenium Determination by Hydride Generation–Inductively Coupled Plasma Optical Emission Spectrometry

Abstract

Selenium determination in samples with a high copper content by hydride generation–inductively coupled plasma optical emission spectrometry (HG‐ICP‐OES) after online copper removal and selenium (VI) reduction is described. An activated carbon minicolumn was used for the retention of copper and its subsequent separation of Se. Se(VI) was then online reduced by heating into a PTFE coiled reactor with 12 M HCl. The analyte was introduced into a water stream containing sodium tetrahydroborate (NaBH₄) in order to generate selenium hydride (H₂Se). The detection limit (DL) obtained was 0.8 µg L^?1, and the precision, expressed by the relative standard deviation (RSD), was 2.5% (n=10; 10 µg L^?1 selenium level). The current method was applied to the Se determination in two copper reference materials, MBH‐39DK 3601 (with a Se content of 90 mg kg^?1) and MBH‐39 DK 3604 (with a Se content of 15 mg kg^?1).     

Radiation dose-dependent risk on individuals due to ingestion of uranium and radon concentration in drinking water samples of four districts of Haryana,India

Uranium gets into drinking water when the minerals containing uranium are dissolved in groundwater. Uranium and radon concentrations have been measured in drinking water samples from different water sources such as hand pumps, tube wells and bore wells at different depths from various locations of four districts (Jind, Rohtak, Panipat and Sonipat) of Haryana, India, using the LED flourimetry technique and RAD7, electronic silicon solid state detector. The uranium (²³⁸U) and radon (²²²Rn) concentrations in water samples have been found to vary from 1.07 to 40.25?µg?L^?1 with an average of 17.91?µg?L^?1 and 16.06?±?0.97 to 57.35?±?1.28?Bq?L^?1 with an average of 32.98?±?2.45?Bq?L^?1, respectively. The observed value of radon concentration in 43 samples exceeded the recommended limits of 11?Bq?L^?1 (USEPA) and all the values are within the European Commission recommended limit of 100?Bq?L^?1. The average value of uranium concentration is observed to be within the safe limit recommended by World Health Organization (WHO) and Atomic Energy Regulatory Board. The annual effective dose has also been measured in all the water samples and is found to be below the prescribed dose limit of 100?µSv?y^?1 recommended by WHO. Risk assessment of uranium in water is also calculated using life time cancer risk, life time average daily dose and hazard quotient. The high uranium concentration observed in certain areas is due to interaction of ground water with the soil formation of this region and the local subsurface geology of the region.     

A Novel Method for the Assessment of Cortisol Hormone in Different Body Fluids Using A New Photo Probe Thiazole Derivative

A low cost and accurate method for the detection and analytical determination of the cortisol in pharmaceutical preparation, blood serum and urine was developed. The method was based upon the enhancement of fluorescence intensity of the band at 424 nm of the photo probe by different cortisol concentrations in acetonitrile at (pH 5.7, λ_ex?=?320 nm). The influence of the different parameters, e.g. pH, solvent, cortisol concentration and foreign ions concentrations that control the enhancement process of fluorescence intensity of the band of photo probe was critically investigated. The remarkable enhancement of the fluorescence intensity at 424 nm in acetonitrile by various concentrations of cortisol was successfully used as a photo- probe for the assessment of cortisol concentration. The calibration plot was achieved over the concentration range 8.0?×?10^?6–5.5?×?10^?9 mol L^?1 cortisol with a correlation coefficient of 0.998 and a detection limit of 4.7?×?10^?9 mol L^?1. The developed method is simple and proceeds without practical artifacts compared to the other determination methods.     

Effect of sodium citrate as complexing on electrochemical behavior and speciation diagrams of CoFeNiCu baths

In this study, the effects of addition of sodium citrate dosages and different pH levels on the electrochemical behavior of CoFeNiCu alloy baths (electrolytes containing metal ions) were investigated. Stability (Pourbiax) diagrams and also speciation diagrams of cobalt, iron, nickel and copper, in conventional and citrate-added CoFeNiCu bath, were calculated by ChemEQL V.3.0 software. Stability diagrams showed that addition of 20 g?L^?1 sodium citrate to the bath increased the pH of formed detrimental metal hydroxides (especially Fe(OH)₃ from pH 3.4 to pH?~?6.9) through forming stable complexed species that were more stable than metal hydroxides at low pH levels (< ~3). According to the speciation diagrams, both pH level and sodium citrate dosage had noticeable effect on the distribution of species in the baths. Generally, at low pH level and/or sodium citrate dosage, Co⁺⁺, Fe⁺⁺, Ni⁺⁺, and Cu⁺⁺ species were dominant. The concentration of complexed species of Co(C₆H₅O₇)^? ( at pH?>?~ 7.5 or sodium citrate dosage?>?~ 30 g?L^?1), Fe(C₆H₅O₇)^? (at pH?>?~ 5.5 or sodium citrate dosage?>?~ 25 g?L^?1), Ni(C₆H₅O₇)^? (at pH?>?~ 6 or sodium citrate dosage?>?~ 30 g?L^?1), and Cu(OHC₆H₅O₇)^2? ( at pH?>?~ 8 or sodium citrate dosage?>?~ 20 g?L^?1) became significant. The effects of sodium citrate and reverse potential (E _λ) on cyclic voltammetry curves were also studied. The addition of sodium citrate in the bath shifted the reduction potential of metals towards more negative potentials. Moreover, in order to deposit cobalt, iron, and nickel simultaneously with copper, it was necessary to increase E _λ value gradually with sodium citrate dosage; otherwise, only copper would have deposited from citrate-added CoFeNiCu bath. The study of speciation diagrams showed that reduction of metals from CoFeNiCu bath with natural pH (no acid or base is added to adjust pH and it was?~?5.2) and containing 20 g?L^?1 of sodium citrate mainly occurred directly from complexed species.     

Laser-Patterned Carbon-Supported Graphitic Carbon Nitride Quantum Dots for Flexible Nanozyme-Based Fluoride Sensor

Graphitic carbon nitride quantum dots (g-CNQDs)-based colorimetric sensors are typically solution-based and hence incompatible with wearable electronics. Today's competitive technology demands safe and reliable, high-performance sensors suitable for integration with sophisticated electronics—all at a low cost. Herein, a flexible and reusable solid-state fluoride ion sensor manufactured by combining the intriguing surface properties of laser-patterned carbon (LP-C) with the sensitivity of g-CNQDs is reported. LP-C is obtained by direct IR-laser writing onto polyimide films, and g-CNQDs are synthesized via a solvent-free and zero-waste green process. The hybrid of LP-C and g-CNQDs (g-CNQDs/LP-C), mimics the natural enzyme horseradish peroxidase and oxidizes the chromogenic substrate 3,3’,5,5’-tetramethylbenzidine in the presence of H₂O₂ in acidic media. The highly selective and user-friendly nanozyme sensors feature a lower limit of detection of 0.568 ± 0.006  × 10⁻⁶ m (23.8 ± 1.5 µg L⁻¹) with linearity in the range of 0.5 × 10⁻⁶ to 100  × 10⁻⁶ m . A sensing mechanism based on the electronic transitions of g-CNQDs and LP-C, the two variants of nitrogen-containing carbon used in this work, is established. Finally, the device is tested for fluoride ion sensing in natural water samples collected from the Uhl river in Mandi, India.     

Determination of Epinephrine in Pharmaceutical Formulation by an Optimized Novel Luminescence Method Using CdS Quantum Dots as Sensitizer

In this article, a novel chemiluminescence method using water-soluble CdS quantum dots (QDs) as sensitizers is proposed for the chemiluminometric determination of epinephrine. The method is based on the quenching effect of epinephrine on the chemiluminescence emission generated by the mixing of CdS quantum dots (QDs) with hydrogen carbonate (HCO₃ ^-) in the presence of hydrogen peroxide (H₂O₂) in an alkaline medium. The optimization of variables influencing the chemiluminescence response of the method has been carried out by using experimental design. Under the optimal conditions, there is good linear relationship between the relative chemiluminescence intensity and the concentration of epinephrine over the range of 5?×?10^?9–1?×?10^?6?molL^?1 with a 3σ detection limit of 5?×?10^?11?molL^?1. The method has been successfully applied to the determination of epinephrine in pharmaceutical formulation and the recovery test was done in human urine.     

Study on the Interaction of the CpG Alternating DNA with CdTe Quantum Dots

A novel sensitive method for detection of DNA methylation was developed with thioglycollic acid (TGA)-capped CdTe quantum dots (QDs) as fluorescence probes. Recognition of methylated DNA sites would be useful strategy due to the important roles of methylation in disease occurrence and developmental processes. DNA methylation occurs most often at cytosine-guanine sites (CpG dinucleotides) of gene promoters. The QDs significantly interacted with hybridized unmethylated and methylated DNA. The interaction of CpG rich methylated and unmethylated DNA hybrid with quantum dots as an optical probe has been investigated by fluorescence spectroscopy and electrophoresis assay. The fluorescence intensity of QDs was highly dependent to unmethylated and methylated DNA. Specific site of CpG islands of Adenomatous polyposis coli (APC), a well-studied tumor suppressor gene, was used as the detection target. Under optimum conditions, upon the addition of unmethylated dsDNA, the fluorescence intensity increased in linear range from 1.0?×?10^??10 to 1.0?×?10^??6M with detection limit of 6.2?×?10^??11 M and on the other hand, the intensity of QDs showed no changes with addition of methylated dsDNA. We also demonstrated that the unmethylated and methylated DNA and QDs complexes showed different mobility in electrophoresis assay. This easy and reliable method could distinguish between methylated and unmethylated DNA sequences.     

A Comparative Study on the Sensitive Detection of Hydroxyl Radical Using Thiol-capped CdTe and CdTe/ZnS Quantum Dots

Four types of water-soluble luminescent quantum dots (QDs) whose surface was functionlaized with thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), or glutathione (GSH), were investigated for the sensitive and selective detection of hydroxyl radical (^●OH) in aqueous media. It was found that the type of capping agent and QD influenced the sensitivity of the probe. The order of sensitivity of the probe was: GSH-CdTe@ZnS > MPA-CdTe@ZnS > TGA-CdTe > MPA-CdTe QDs. Under the optimum conditions, a limit of detection as low as 8.5?×?10^-8?M was obtained using GSH-CdTe@ZnS. The effects of foreign reactive oxygen species and the Fenton reactants and products as possible interferences on the proposed probe were negligible for CdTe@ZnS QDs. Besides, experimental results indicated that CdTe@ZnS QDs were more attractive for the selective recognition of ^●OH than CdTe QDs. The mechanistic reaction pathway between the QDs and ^●OH is proposed.     

Application of experimental design for optimization of erbium determination by high-resolution continuum source electrothermal atomic absorption spectrometry using lanthanum as a chemical modifier

ABSTRACT

In this paper, lanthanum was used as a chemical modifier for the direct determination of erbium by high-resolution continuum source electrothermal atomic absorption spectrometry. A two-step experimental design was used for optimization, first a full factorial design was conducted for identification of significant factors, and then a central composite design was carried out for final optimization of the significant factors. The optimum parameters were obtained as follows: atomization temperature of 2500°C, pyrolysis temperature of 1600°C, and pyrolysis time of 10?s in the presence of lanthanum as a chemical modifier. Under optimum conditions, the characteristic mass, limit of detection, and limit of quantification were 29?pg, 0.71, and 2.4?µg?L^?1, respectively. The precision of the method, estimated as the relative standard deviation for 10 replicate measurements of 50?µg?L^?1 of erbium, was 1.8%. The optimized method was applied to determine erbium content in sediments and rock samples. The determined values of erbium in sediment certified reference materials were in satisfactory agreement with the certified values according to the t-test for a 95% confidence level.     

CdTe quantum dots as fluorescence sensor for the determination of aminophylline in aqueous solution

A novel CdTe quantum dots (QDs) based technology platform was established in aqueous solution. It can perform accurate and simple determination of aminophylline concentration in pharmaceutical samples with satisfactory results. Under optimum conditions, the relative fluorescence intensity of CdTe quantum dots is linearly proportional aminophylline concentration from 2.00 to 80.0 μg mL^?1 with a correlation coefficient of 0.9979 for aminophylline determination and a detection limit of 0.531 μg mL^?1.     

Sensitive and selective electrochemical sensor for magnolol based on the enhancement effect of multiwalled carbon nanotubes

Herein, insoluble multiwalled carbon nanotubes (MWNTs) were dispersed into N,N-dimethylformamide (DMF) via ultrasonication, resulting in a stable and homogeneous MWNTs suspension. After evaporation of DMF, the surface of glassy carbon electrode was successfully coated with MWNTs film, as confirmed from scanning electron microscopy measurements. In pH 7 phosphate buffer, an irreversible oxidation peak was observed for magnolol, and the peak currents greatly increased on MWNTs film surface. The influences of pH value, amount of MWNTs and accumulation conditions were studied. Based on the remarkable enhancement effect of MWNTs, a new electrochemical sensor with high sensitivity was developed for magnolol. The linear range was from 5 μg?L^?1 to 1 mg?L^?1, and the detection limit was 2 μg?L^?1 (7.51?×?10^?9?M) after a 3-min accumulation. This novel sensor was successfully used to detect the content of magnolol in Chinese traditional medicines, and the recovery was over the range from 98.1 to 99.1 %.     

Determination of Selenium (IV) in Natural Waters by HG‐AAS Using an Integrated Reaction Chamber Gas–Liquid Separator

Abstract

A simple online sequential insertion manifold coupled to a hydride generation atomic absorption spectrometer (HG‐AAS) has been developed for selective inorganic Se(IV) determination. The online method is based on the sequential insertion of sample and reagents in the integrated reaction chamber gas–liquid separator (RC‐GLS), which operates initially as reaction chamber for various sample volumes (up to 20 mL) and subsequently as gas–liquid separator with limited dead volume. The generated hydride from a large sample volume is trapped in the RC‐GLS for a short time and then it is flashed in the atomic absorption cell. The HCl and the NaBH₄ concentration was optimized for selective inorganic Se(IV) determination. For 8‐mL and 16‐mL sample consumption, the sampling frequency is 40 h^?1 and 24 h^?1, while the detection limit is 0.04 µg L^?1 and 0.03 µg L^?1, respectively. The precision (relative standard deviation) for 2.0 µg L^?1 Se(IV) (n=10) is 2.6% and 2.8% for 8 mL and 16 mL sample volumes, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1643d, and also by analyzing spiked natural water.