Coumarin Linked Cyanine Dye for the Selective Detection of Cyanide Ion in Environmental Water Sample.

A benzoxazole-coumarin-based probe BOC, was synthesized and validated for its anion sensing ability and found to be effective in recognizing cyanide ions. Upon addition of cyanide, a spontaneous color change was observed that was visible to the naked eye. The sensitization process takes place with nucleophilic addition, and the cyanide ion added to the probe disrupts the intra molecular charge transfer transition (ICT) between the donor and acceptor units, causing the pink colored probe to become yellow. Ultraviolet and fluorescence methods were applied to measure the detection limits of probes with added cyanide ions, which were found to be 3.47 µM and 2.48 nM. The stoichiometry of the probe with the cyanide ion was determined by the Job's method, NMR titration, and mass spectrometry and was found to be in a 1:1 ratio. The results obtained from the visual and UV-visible spectral studies are justified by theoretical calculations. The cyanide-loaded probe induced visual changes, which enabled the development of a test strip for field application, and the prepared strip can be used to detect the ppm level of cyanide in water samples. The developed probe, BOC, can be used to detect cyanide ions in various water samples.

In-syringe homogeneous liquid-phase microextraction followed by filtration-based phase separation for on-site extraction of chloroanilines from water samples.

This study introduces a new in-syringe homogeneous liquid-phase microextraction method for the rapid on-site extraction of chloroanilines from water samples. Extraction was performed using a plastic syringe, eliminating the use of any electrical power source. Di-(2-ethylhexyl) phosphoric acid (DEHPA) served as the extractant. The process initially involved dissolving DEHPA in an alkaline solution to obtain a homogeneous solution. Subsequently, the sodium salt of DEHPA was precipitated by salting-out, and the resulting heterogeneous mixture was filtered using a syringe filter. The precipitate containing the analytes was then dissolved in methanol for analysis by high-performance liquid chromatography. Under optimal conditions, extraction recovery for chloroanilines ranged from 26% to 71%. Method linearity was evaluated within a concentration range of 1.0-100 µg/L, resulting in coefficients of determination exceeding 0.9987 for all analytes. Method detection limits ranged from 0.28 to 0.41 µg/L. Intra and inter-day precision values were below 9.5% and 10.8%, respectively. The developed method was applied to determine chloroanilines in real waters, yielding acceptable recoveries ranging from 80% to 109% for spiked tap, rain, and stream waters. Additionally, the method was successfully employed for on-site extraction of target contaminants, demonstrating no statistically significant differences compared to laboratory results.

Zinc nitride quantum dots as an efficient probe for simultaneous fluorescence detection of Cu2+ and Mn2+ ions in water samples.

The exceptional ascending heights of graphene (carbon) and boron nitride nanostructures have invited scientists to explore metal nitride nanomaterials. Herein, Zn3N2 quantum dots (QDs) were prepared via a simple hydrothermal route from the reaction between zinc nitrate hexahydrate and ammonia solution that possess efficient strength towards sensing applications of metal ions (Cu2+ and Mn2+). The as-prepared Zn3N2 QDs show bright fluorescence, displaying an emission peak at 408 nm upon excitation at 320 nm, with a quantum yield (QY) of 29.56%. It was noticed that the fluorescence intensity of Zn3N2 QDs linearly decreases with the independent addition of Cu2+ and Mn2+ ions, displaying good linearity in the ranges 2.5-50 µM and 0.05-5 µM with detection limits of 21.77 nM and of 63.82 nM for Cu2+ and Mn2+ ions, respectively. The probe was successfully tested for quantifying Cu2+ and Mn2+ in real samples including river, canal, and tap water, providing good recoveries with a relative standard deviation < 2%. Furthermore, the masking proposition can successfully eliminate the interference if the two metal ions exist together. It was found that thiourea is efficiently able to mask Cu2+ and selectively quenches Mn2+, and L-cysteine is able to halt the quenching potential of Mn2+ and is selectively able to sense Cu2+. The Zn3N2 QDs provide a simple way for the simultaneous detection of both Cu2+ and Mn2+ ions in environmental samples at low sample preparations requirements.

Fabrication of Nitrogen Based Magnetic Conjugated Microporous Polymer for Efficient Extraction of Neonicotinoids in Water Samples.

Facile and sensitive methods for detecting neonicotinoids (NEOs) in aquatic environments are crucial because they are found in extremely low concentrations in complex matrices. Herein, nitrogen-based magnetic conjugated microporous polymers (Fe3O4@N-CMP) with quaternary ammonium groups were synthesized for efficient magnetic solid-phase extraction (MSPE) of NEOs from tap water, rainwater, and lake water. Fe3O4@N-CMP possessed a suitable specific surface area, extended π-conjugated system, and numerous cationic groups. These properties endow Fe3O4@N-CMP with superior extraction efficiency toward NEOs. The excellent adsorption capacity of Fe3O4@N-CMP toward NEOs was attributed to its π-π stacking, Lewis acid-base, and electrostatic interactions. The proposed MSPE-HPLC-DAD approach based on Fe3O4@N-CMP exhibited a wide linear range (0.1-200 µg/L), low detection limits (0.3-0.5 µg/L), satisfactory precision, and acceptable reproducibility under optimal conditions. In addition, the established method was effectively utilized for the analysis of NEOs in tap water, rainwater, and lake water. Excellent recoveries of NEOs at three spiked levels were in the range of 70.4 to 122.7%, with RSDs less than 10%. This study provides a reliable pretreatment method for monitoring NEOs in environmental water samples.

A Commercially Available 2-aminoanthracene Fluorescent Probe for Rapid and Sensitive Detection of Hypochlorite in 100% Buffer Solution and its Application in Complex Water Samples.

Hypochlorite (ClO-), a crucial chemical in the living organism, engages in various physiological activities. However, high amounts of ClO- result in oxidative damage. In this work, a commercially available 2-aminoanthracene (AA) was used to detect ClO-. AA demonstrated distinct properties such as superior selectivity and rapid response (< 30 s) with a low detection limit (140 nM) towards ClO- in 100% buffer solution. Furthermore, the probe exhibited a notable achievement by effectively identifying the presence of ClO- in complicated water samples. In conclusion, AA offers an easy-to-use and accurate method for quantifying ClO- in complex water samples.

A strategy for As(III) determination based on ultrafine gold nanoparticles decorated on magnetic graphene oxide.

In this work, a new dendrimer modified magnetic graphene oxide (GO) was used as a substrate for electrodeposition of Au nanoparticles. The modified magnetic electrode was employed for sensitive measuring of As(III) ion as a well-established human carcinogen. The prepared electrochemical device exhibits excellent activity towards As(III) detection using the square wave anodic stripping voltammetry (SWASV) protocol. At optimum conditions (deposition potential at -0.5 V for 100 s in 0.1 M acetate buffer with pH 5.0), a linear range from 1.0 to 125.0 µgL-1 with a low detection limit (calculated by S/N = 3) of 0.47 µg L-1 was obtained. In addition to the simplicity and sensitivity of the proposed sensor, its high selectivity against some major interfering agents, such as Cu(II) and Hg(II) makes it an appreciable sensing tool for the screening of As(III). In addition, the sensor revealed satisfactory results for detection of As(III) in different water samples, and the accuracy of obtained data were confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) setup. Accounting for the high sensitivity, remarkable selectivity and good reproducibility, the established electrochemical strategy has great potential for analysis of As(III) in environmental matrices.

Design and synthesis of nickel-doped cobalt molybdate microrods: An effective electrocatalyst for the determination of antibiotic drug ronidazole.

Ronidazole (RDZ) is a veterinary antibiotic drug that has been used in animal husbandry as feed. However, improper disposal and illegal use of pharmaceuticals have severely polluted water resources. Doping/substitution of metal ions is an effective strategy to change the material's crystal phase, morphology, and electrocatalytic activity. In this work, nickel (Ni2+)-doped cobalt molybdate microrods (NCMO MRs) were prepared for the electrochemical detection of RDZ. The catalyst was prepared by reflux method followed by calcination at 500 °C. The prepared catalyst was confirmed by various spectroscopic and microscopic analyses. XRD and Raman spectroscopy demonstrated that the phase transition from ß-CoMoO4 to α-CoMoO4 was achieved by Ni2+ doping. The SEM analysis showed that cobalt molybdate (CMO) microrods were self-assembled during Ni2+ doping and formed an urchin-like structure, and the average diameter of the MRs was ±50 nm. The electrocatalytic activity of the catalysts was analyzed using the CV technique. The NCMO MRs/GCE exhibited the higher current response than the pristine CMO. The electron transfer coefficient (α = 0.56) and heterogeneous rate constant (ks = 0.32 s-1) of NCMO MRs/GCE were evaluated by kinetic studies. In addition, the diffusion coefficient of RDZ was determined to be 2.32 × 10-5 cm2/s. Moreover, NCMO MRs/GCE exhibits a low detection limit for RDZ (15 nM) as well as a higher sensitivity (1.57 µA µM-1 cm-2). The fabricated RDZ sensor was successfully applied to analysis of lake and tap water samples. Based on the results, we believe that the as-prepared NCMO MRs/GCE is a viable electrode material for RDZ sensors in environmental monitoring.

Assessing the pollution level of a subtropical lake by using a novel hydrogen sulfide fluorescence technology.

Hydrogen sulfide (H2S) is an important environmental toxin with bi-directional biological effects on organisms. In natural waters, H2S complexes with heavy metal ions in an anaerobic environment influence heavy metals' bioavailability and induce phosphorus release and eutrophication in water columns. Traditional detection techniques, such as colorimetric, electrochemical, and chromatographic, cannot simultaneously detect H2S and pollution assessment of subtropical lakes. To address these technical defects, we developed small-molecule fluorescent probes to evaluate the pollution level in natural water bodies. This method relies on the combination of the probes' response signals to raw water and the water quality index, thereby enhancing the accuracy and reliability of water quality assessments. Furthermore, this novel material has a large Stokes shift. It can detect complex levels of H2S concentrations in natural water bodies by correlating the degree of contamination and fluorescence signals. The development of this visual research tool for detecting environmental H2S levels in natural water bodies is expected to have meaningful, practical applications.

Temperature-induced dispersive solid-phase extraction as a new approach for preconcentration of Sudan dyes in water and food samples prior to the determination by high-performance liquid chromatography.

This study introduced a new microextraction method named temperature-induced dispersive solid-phase extraction. The performance of the method was demonstrated with the determination of Sudan dyes in food and natural water samples. In this method, a low quantity of sorbent was added to the aqueous solution and the mixture was shaken manually for about one minute. Then, the solution was heated in an ultrasonic water bath, and the sorbent was dissolved. Subsequently, the solution was cooled down with ice water, and consequently, the solubility of the sorbent was reduced in the sample solution and became cloudy. The phase separation was accelerated by centrifugation. The upper liquid phase was picked up using a syringe, and the remainder was solved in methanol and introduced into the HPLC for analysis. Various parameters affecting the extraction yield were evaluated. Analytical parameters, including limits of detection (0.011-0.016 µg/L) and quantification (0.038-0.055 µg/L), relative standard deviations (2.3%-3.1%), and preconcentration factor (40) proved the high efficiency of the developed method for the analysis of Sudan dyes. The proposed method was used to measure Sudan dyes in water and food samples and showed good extraction recoveries (95.0%-103.5%).

Fabrication of highly crystalline covalent organic framework for solid-phase extraction of three dyes from food and water samples.

Herein, a covalent organic framework, which was fabricated at room temperature by using 1,3,5-tris(p-formylphenyl) benzene and 1,3,5-tris(4-aminophenyl)benzene as building blocks, was employed as an adsorbent for solid-phase extraction of dyes including congo red, methyl blue and direct red 80 for the first time. The prepared covalent organic framework was properly characterized by different techniques and the results revealed that it had a uniform spherical structure, high crystallinity, satisfactory surface area, and good thermal stability. Moreover, the adsorption performance of the material was explored by using static and dynamic adsorption experiments and the results indicated that the material showed good adsorption capacities for three dyes with adsorption capacities in the range of 55.25-284.10 mg/g and the adsorption equilibrium can be achieved in 15 min. Further, to achieve the best adsorption effects of the material, the influence parameters such as pH, ionic strength, type of desorption solvent, and the material dosage in the solid-phase extraction column, were optimized in turn. Finally, under optimal conditions, the solid-phase extraction coupled with HPLC was applied to the analysis of dyes in food and water samples. The recoveries of dyes in actual samples were satisfactory, revealing the unique applicability of the material in the sample pretreatment field.

Separation and quantification of diazinon in water samples using liquid-phase microextraction-based effervescent tablet-assisted switchable solvent method coupled to gas chromatography-flame ionization detection.

This study used a liquid-phase microextraction-based effervescent tablet-assisted switchable solvent method coupled to gas chromatography-flame ionization detection as an eco-efficient, convenient-to-use, cost-effective, sensitive, rapid, and efficient method for extracting, preconcentrating, and quantifying trace amounts of diazinon in river water samples. As a switchable solvent, triethylamine (TEA) was used. In situ generation of CO2 using effervescent tablet containing Na2 CO3 and citric acid changed the hydrophobic TEA to the hydrophilic protonated triethylamine carbonate (P-TEA-C). CO2 removal from the specimen solution using NaOH caused P-TEA-C to be converted into TEA and led to phase separation, during which diazinon was extracted into the TEA phase. The salting-out process was helpful in enhancing extraction efficiency. In addition, a number of significant parameters that affect extraction recovery were examined. Under optimum conditions, the limit of detection and limit of quantitation were 0.06 and 0.2 ng/ml, respectively. The extraction recovery percentage and pre-concentration factor were obtained at 95 and 190%, respectively, and the precision (inter- and intra-day, relative standard deviation %, n = 5) was <5%.

Waste toner-derived micro-materials as low-cost magnetic solid-phase extraction adsorbent for the analysis of trace Pb in environmental and biological samples.

Lead (Pb) is a toxic heavy metal and is commonly used in industrial applications. Thus, Pb poisoning is a concerning public health issue worldwide. The amounts of lead in natural water, urine, and blood can serve as significant indicators for monitoring the exposure of Pb poisoning. Waste toner has the characteristics of both "waste" and "resource," as it is a "resource in the wrong place." Here, a low-cost carboxylate-functionalized magnetic adsorbent was first synthesized from waste toner by a simple thermal treatment and served as a novel adsorbent with a flexible multidentate O-donor for pre-concentration of trace Pb. The characterization, adsorption behavior, and various factors of adsorption and desorption were adequately optimized, and prior to graphite furnace atomic absorption spectrometry (GFAAS) detection, a new magnetic solid-phase extraction method was proposed for the analysis of Pb in real environmental water and biological samples. The developed method exhibited a low detection limit (0.003 µg L-1), high enrichment factor (88.6-fold), good linearity (0.01-0.3 µg L-1), satisfactory precision with relative standard deviations of 7.9% (n = 7, CPb = 0.02 µg L-1), fast adsorption kinetics (5 min), and strong ability to overcome matrix interference. Validation was also performed by analyzing a certified standard reference material, and the method was successfully applied to real tap water, lake water, human urine, and human blood serum with satisfactory recoveries of 92.6-109%.

Evaluation of three sorbent-phase extraction techniques based on hyper-crosslinked polymer for the extraction of five endocrine disrupters in water.

A series of low-cost hyper-crosslinked polymers were prepared by an easy one-step Friedel-Crafts reaction. The synthesized hyper-crosslinked polymers exhibited remarkably porous structure, large surface area, and hydroxyl groups, which can be employed as an ideal adsorbent material for novel sorbent-phase extraction techniques. Based on this, using hyper-crosslinked polymers as sorbent and coating, three novel extraction methods, including micro-solid-phase extraction, dispersive solid-phase extraction, and solid-phase microextraction, were explored and evaluated for simultaneous measurement of five endocrine-disrupting compounds (triclosan and bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A bisallylether, and tetrabromobisphenol A bis(2,3-dibromopropyl ether)) in environment water prior to high-performance liquid chromatography-ultraviolet. The influence of experimental parameters on three extraction techniques such as extraction time, the amount of hyper-crosslinked polymers, extraction temperature, ionic strength, and desorption conditions were optimized. Three previously mentioned methods provided limits of detection ranging from 0.01 to 0.05 µg/L, and high recoveries (85-99%) with relative standard deviations of 1.7-5.6%. This study presented the merits and disadvantages of three proposed extraction methods and their potential for effective monitoring of hazardous pollutants in real water samples.

Potentiometric Electronic Tongue for Quantitative Ion Analysis in Natural Mineral Waters.

The present paper addresses the development and use of a new potentiometric electronic tongue for both qualitative and quantitative characterization of natural mineral waters. The electronic tongue is particularly related to the conductivity and ion content of/in the water sample. The analytical system is based on six ion-selective electrodes whose membranes are formulated to provide either cationic or anionic response and considering plasticizers with different dielectric constants (bis(2-ethylhexyl) sebacate, 2-nitrophenyl octyl ether or tricresylphosphate), while keeping the polymeric matrix, i.e., poly(vinyl chloride). Notably, the absence of any ionophore in the membrane provides a general response profile, i.e., no selectivity toward any special ion, which is convenient for the realization of an effective electronic tongue. The dynamic response of the tongue toward water samples of different chemical compositions and geographical locations has been obtained. At the optimized experimental conditions, the tongue presents acceptable repeatability and reproducibility (absence of hysteresis). The principal component analysis of the final potential values observed with the six electrodes allows for the differentiation and classification of the samples according to their conductivity, which is somehow related to the mineralization. Moreover, quantitative determination of the six main ions in the water samples (i.e., chloride, nitrate, hydrogen carbonate, sulfate, sodium, calcium, and magnesium) is possible by means of a simple linear calibration (and cross-validation) model.

Characterizing spatiotemporal variations of polycyclic aromatic hydrocarbons in Taihu Lake, China.

In this study, we analyzed the concentration distributions of 20 polycyclic aromatic hydrocarbons (PAHs) in 41 water samples which were collected from the northern part of Taihu Lake during 4 field campaigns (201511, 201606, 201702 and 201709). The concentrations were determined with GC-MS, and their spatial and seasonal distribution characteristics were interpreted. The results show that 2-ring PAHs present considerably higher concentrations in warm seasons than cold seasons, but the concentrations of the other higher-ring PAHs are rather stable in warm and cold seasons. The distribution patterns of these PAHs might be mainly attributed to ambient temperature effects on the PAH solubility in the water body. Meanwhile, the spatial distributions of the PAH concentrations in cold seasons were rather various in the sampling area, while the distributions in the warm seasons were homogeneous. The different distributions could result from the water recharge from the Yangtze River during cold seasons, which diluted PAH concentrations in the northeastern part of the lake. Furthermore, via literature review on PAH concentrations in water body, PAHs are in a wide range of levels and their patterns are different among the studies, which should be more effected by local factors instead of general PAH properties. The results from this study also present special characteristics of PAHs in Taihu Lake, which exhibit more insight on PAHs existence in water bodies.

A Highly Selective Turn-on Fluorescent and Naked-eye Colourimetric Dual-channel Probe for Cyanide Anions Detection in Water Samples.

A highly selective turn-on fluorescent and naked-eye colourimetric dual-channel probe for cyanide anions (CN-) has been designed and characterized. In the mixed solution (DMSO / H2O, 9:1, v / v), only CN- could cause an increase in the UV absorption intensity and the corresponding fluorescence intensity increased, and other anions had no significant effect on the probe. After treatment with cyanide in the probe solution, the solution showed a noticeable colour change, from light yellow to purple. Moreover, a fluorescence spectrophotometer can be used to observe that the fluorescence intensity of the solution is significantly enhanced. The response of the colourimetric and fluorescent dual-channel probe to CN- was attributed to nucleophilic addition, and the mechanism was determined by 1H NMR spectroscopy. In addition, this probe was used to detect CN- in actual water samples, including river water, drinking water, and tap water. The spiked CN- recovery rate is very high (97.2%-100.06%), and analytical precision is also very high (RSD < 2%), which shows its feasibility and reliability for detecting cyanide ions in actual water samples.

A 2-Hydroxy-1-naphthaldehyde Schiff Base for Turn-on Fluorescence Detection of Zn2+ Based on PET Mechanism.

Zinc ion is closely related to human health. Its content in human body is small, while the effect is large. However, it is not the more the better, must be in a scientific balance. Therefore, it is significant to the rapid detection of Zn2+ in the environment and organism. Herein, a fluorescent probe based on 2-hydroxy-1-naphthalene formaldehyde and furan-2-carbohydrazide was conveniently synthesized via Schiff base reaction. And this probe has been successfully applied to the accurate and quantitative detection of Zn2+ in real samples, showing turn on fluorescence, good selectivity, very low detection limit, real time response and reusability. In addition, this probe has the potential application to trace Zn2+ in living cells with low cytotoxicity.

Fluorescein Based Three-channel Probe for the Selective and Sensitive Detection of CO32- Ions in an Aqueous Environment and Real Water Samples.

We have constructed a novel fluorescein-based fluorescent chemosensor, FL-In, functionalised with an indole moiety and capable of sensing by both the optical "turn-on" and electrochemical detection of carbonate ions (CO32-) in aqueous media. The probe exhibits excellent selectivity and a low detection limit (0.27 µM) regarding carbonate ions by a possible coordination and hydrolysis reaction mechanism. The developed probe successfully detected CO32- ions in different samples of water. Also, in a simple filter paper experiment, we documented its ability to allow the monitoring of CO32- with the naked eye.

Solidified floating organic drop microextraction (SFODME) for the simultaneous analysis of three non-steroidal anti-inflammatory drugs in aqueous samples by HPLC.

In this work, a liquid-liquid microextraction methodology using solidified floating organic drop (SFODME) was combined with liquid chromatography and UV/Vis detection to determine non-steroidal anti-inflammatory drugs (NSAIDs) naproxen (NPX), diclofenac (DCF), and mefenamic acid (MFN) in tap water, surface water, and seawater samples. Parameters that can influence the efficiency of the process were evaluated, such as the type and volume of the extractor and dispersive solvents, effect of pH, agitation type, and ionic strength. The optimized method showed low detection limits (0.09 to 0.25 µg L-1), satisfactory recovery rates (90 to 116%), and enrichment factors in the range between 149 and 199. SFODME showed simplicity, low cost, speed, and high concentration capacity of the analytes under study. Its use in real samples did not demonstrate a matrix effect that would compromise the effectiveness of the method, being possible to apply it successfully in water samples with different characteristics.

A ratiometric fluorescent probe for the rapid and specific detection of HSO3 - in water samples.

Hydrosulphite (HSO3 - ), as a common and important chemical reagent, is widely used in everyday life, however excessive use and abuse of HSO3 - can cause potential harmful effects on the environment and in biological health. In this paper, we describe the design and preparation of a colorimetric and ratiometric fluorescence probe for the visual detection of HSO3 - (excitation wavelengths were, respectively, 336 nm and 520 nm). This method showed some advantages including simple preparation, high selectivity, fast response, and significant colour and fluorescence ratio (F450 /F594 ) changes in the presence of HSO3 - . In addition, this probe was used successfully for the detection of HSO3 - in real water samples and showed a good recovery rate range.