Covalent organic framework-functionalized magnetic MXene nanocomposite for efficient pre-concentration and detection of organophosphorus and organochlorine pesticides in tea samples before gas chromatography-triple quadrupole mass spectrometry analysis.

In this study, a hydrophobic covalent organic framework-functionalized magnetic composite (CoFe2O4@Ti3C2@TAPB-TFTA) with a high specific area with 1,3,5-tris(4-aminophenyl)benzene (TAPB) and 2,3,5,6-tetrafluoroterephthalaldehyde (TFTA) was designed and synthesized through Schiff base reaction. An efficient magnetic solid-phase extraction method was established and combined with gas chromatography-triple quadrupole mass spectrometry to sensitively determine 10 organochlorine and organophosphorus pesticides in tea samples. The established method exhibited good linearity in the range of 0.05-120 µg/L and had low limits of detection (0.013-0.018 µg/L). The method was evaluated with tea samples, and the spiked recoveries of pesticides in different tea samples reached satisfactory values of 85.7-96.8%. Moreover, the adsorption of pesticides was spontaneous and followed Redlich-Peterson isotherm and pseudo-second-order kinetic models. These results demonstrate the sensitivity, effectiveness, and reliability of the proposed method for monitoring organochlorine and organophosphorus pesticides in tea samples, providing a preliminary basis for researchers to reasonably design adsorbents for the efficient extraction of pesticides.

Simultaneous estimation of total phenolic and alkaloid contents in the tea samples by utilizing the catechin and caffeine oxidation signals through the square-wave voltammetry technique.

This work outlines the simultaneous estimation of the total phenolic and alkaloid contents in the tea samples by using catechin (C) and caffeine (CAF) oxidation signals at a non-modified boron-doped diamond (BDD) electrode. Two irreversible oxidation peaks, about + 1.03 (for C) and + 1.45 V (for CAF) vs Ag/AgCl in acetate buffer solution at pH 4.7, were seen in the cyclic voltammetric profile of the binary mixtures of C and CAF. In optimal conditions and utilizing the square-wave mode, the BDD electrode allows for simultaneous quantification of C and CAF within the concentration ranges of 5.0-100.0 µg mL-1 (1.72 × 10-5 - 3.45 × 10-3 mol/L) and 1.0-50.0 µg mL-1 (5.15 × 10-6 - 2.57 × 10-4 mol/L) respectively. The corresponding detection limits are 1.22 µg mL-1 (4.21 × 10-6 mol/L) for C and 0.11 µg mL-1 (5.66 × 10-7 mol/L) for CAF. Other phenolic compounds (like tannic acid, gallic acid, epicatechin, and epigallocatechin gallate) and other alkaloids (theophylline and theobromine) present in tea samples were examined for selectivity assessment. Ultimately, the applicability of the proposed approach was demonstrated by estimating the total phenolic and alkaloid contents in the black and green tea samples, expressed as C and CAF equivalents. The results obtained were contrasted against those acquired using UV-Vis spectrometry.

Facile analysis of mycotoxin in coffee and tea samples using a novel semi-automated in-syringe based fast mycotoxin extraction (FaMEx) technique coupled with direct-injection ESI-MS/MS analysis.

Identifying the risk of ochratoxin A in our daily food has become fundamental because of its toxicity. In this work, we report a novel semi-automated in-syringe-based fast mycotoxin extraction (IS-FaMEx) technique coupled with direct-injection electrospray-ionization tandem mass spectrometer (ESI-MS/MS) detection for the quantification of ochratoxin A in coffee and tea samples. Under the optimized conditions, the results reveal that the developed method's linearity was more remarkable, with a correlation coefficient of > 0.999 and > 92% extraction recovery with a precision of 6%. The detection and quantification limits for ochratoxin A were 0.2 and 0.8 ng g-1 for the developed method, respectively, which is lower than the European Union regulatory limit of toxicity for ochratoxin-A (5 ng g-1) in coffee. Furthermore, the newly developed modified IS-FaMEx-ESI-MS/MS exhibited lower signal suppression of 8% with a good green metric score of 0.64. In addition, the IS-FaMEx-ESI-MS/MS showed good extraction recovery, matrix elimination, good detection, and quantification limits with high accuracy and precision due to the fewer extraction steps with semi-automation. Therefore, the presented method can be applied as a potential methodology for the detection of mycotoxins in food products for food safety and quality control purposes. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-023-05733-z.

Ultra-sensitive determination of Ochratoxin A in coffee and tea samples using a novel semi-automated in-syringe based coagulant-assisted fast mycotoxin extraction (FaMEx) technique coupled with UHPLC-MS/MS.

In this study, we demonstrated a novel semi-automated in-syringe-based coagulant-assisted liquid-liquid microextraction (IS-CGA-LLME) as fast mycotoxin extraction (FaMEx) technique coupled with ultra-high-performance liquid chromatography connected with a tandem-mass spectrometer (UHPLC-MS/MS) for the quantification of mycotoxin (Ochratoxin A, OT-A) in coffee and tea samples. IS-CGA-LLME is a three-step extraction process that includes extraction of OT-A from sample matrix using low-volume solvent extraction, then the extractant was cleaned-up using a coagulation process, and finally, the decolorized/matrix removed sample solution was processed for LLME for target analyte's pre-concentration. The final extractant was analyzed using UHPLC-MS/MS for OT-A quantification. Under the optimized experimental conditions, highly sensitive detection and quantification limits were obtained at 0.001 and 0.003 ng g-1 for OT-A with excellent extraction recovery (93-111%) and precision <10%. These results proved that the developed method is a simple, highly sensitive, semi-automated, low-matrix effect and efficient procedure for the determination of mycotoxins in food samples.

Discovery of a triphenylamine-benzofuran derivative as fluorescent probe for hydrogen polysulfide in tea samples.

In this work, a novel triphenylamine-benzofuran derived fluorescent probe, TBF-SS, was developed for detecting hydrogen polysulfide in tea samples and intracellular imaging. TBF-SS showed the practical advantages including high sensitivity (LOD = 0.01 µM), high selectivity, rapid response (within 15 min), and steadiness in various environmental conditions. The detecting system was steady within pH range of 6.0-11.0 and temperature range of 20-55 °C. The probe TBF-SS could guarantee the stable detection of H2Sn for 7 d in storage of either solid or solution. In particular, in the application of various tea samples with different brewing times and testing temperatures, the recovery percentages varied in the range of 95.22 % to 105.0 %. Therefore accurate monitoring of H2Sn could be achieved by using the probe TBF-SS. In addition, TBF-SS could monitor the exogenous level, the ß-lapachone-induced generation and the tea-sample-treated introduction of H2Sn in living MCF-7 cells. This work might inspire the improvement of the serviceability of fluorescent implements.

AuNPs-based lateral flow immunoassay for point-of-needs analysis of four neonicotinoids in tea samples: Effects of grinding degrees, solvent types and contents on extraction efficiency.

The higher extraction efficiency of analytes is crucial for developing immunoassays with high accuracy. Here, we evaluated the extraction efficiency of neonicotinoids in tea samples in terms of grinding degrees, extraction solvents types and contents. Fragments for fresh tea leaves (1 g, 5-10 mm2) or tea powder (1 g, 35 mesh) for commercial tea was extracted with 100 % methanol. The extraction (1 mL) was diluted 10-fold with buffer solution, and then submitted to gold nanoparticles-based lateral flow immunoassay. This optimal extraction protocol exhibited a higher extraction efficiency (72.4-99.3 %) for the positive neonicotinoids samples. The cut-off values of lateral flow immunoassay were 0.325 or 0.65 µg/g, 0.3 or 0.45 µg/g, 0.3 or 0.45 µg/g, 0.03 or 0.06 µg/g for thiamethoxami, clothianidin, acetamiprid and midacloprid in fresh tea leaves and commercial tea. In summary, this proposed lateral flow immunoassay can be used as the point-of-needs analysis method for four neonicotinoids in tea.

Elemental Composition of Commercial Herbal Tea Plants and Respective Infusions.

This study evaluated the elemental composition of 25 herbal tea plants commonly used in infusions by Portuguese consumers and the contribution to the elemental daily intake of some essential elements. Hydrocotyle asiatica (L.), Matricaria chamomilla (L.), and Melissa officinalis (L.) samples are a rich source of K with around 6.0 mg g-1 while the Asteraceae Silybum marianum (L.) and Echinacea angustifolia (DC.) exhibited 4.9 and 5.6 mg g-1 Ca, respectively. The highest concentrations of S and Zn were noted in Hydrocotyle asiatica (L.), while the highest concentration of Sr was found in Cassia angustifolia (Vahl.). In general, a large variability in the concentrations among different families and plant organs had been observed, except Cu with levels around 30 µg g-1. The principal component analysis (PCA) showed positive correlations between Zn and S and Sr and Ca, also revealing that Hydrocotyle asiatica (L.), Echinacea angustifolia (DC.), Silybum marianum (L.), and Cassia angustifolia (Vahl.) samples, stands out about all other samples regarding the enrichment of macro and micronutrients. The elemental solubility of macronutrients in the infusion is greater than the micronutrient solubility, despite the contribution to the recommended daily intake was weak. As a whole, Cynara scolymus (L.) and Hibiscus sabdariffa (L.) are the species with the best elemental solubilities, followed by Hydrocotyle asiatica (L.). No harmful elements, such as As and Pb, were observed in both the raw material and the infusions.

An ultralow concentration of Al-MOFs for turn-on fluorescence detection of aflatoxin B1 in tea samples.

A turn-on fluorescent sensing platform based on an ultralow concentration of Al-metal organic frameworks for the detection of aflatoxin B1 has been developed for the first time. This fluorescence turn-on sensor exhibits the largest fluorescence enhancement (or quenching) constant value of 179404 M-1 among all luminescence-based chemical sensors reported till date. Moreover, the sensor afforded a rapid detection of aflatoxin B1, with a linear response in the concentration range of 0.05-9.61 µM and a low detection limit of 11.67 ppb. Additionally, the fabricated sensor showed good repeatability, reproducibility, stability, and selectivity. Most importantly, the practical application of this sensor has been demonstrated by detecting aflatoxin B1 in complex tea samples with low relative standard deviation (≤7.72%; n = 3) and satisfactory recoveries. In summary, the proposed method has great potential as a simple, sensitive and selective strategy for monitoring aflatoxin B1 in food samples.

Electrochemically activated pencil lead electrode as a sensitive voltammetric sensor to determine gallic acid.

An electrochemical sensor for the determination of some polyphenolic compounds such as Gallic acid (GA) and Galloyl esters was developed using the activated pencil lead electrode (APLE). At first, a study has been made of the optimum conditions for electrochemical activation of the pencil lead electrode. Potentiodynamic and potentiostatic strategies were investigated for activation of the pencil lead electrode and the results show that the potentiodynamic pretreatment gives better performance toward measurement of the polyphenolic compounds. Electrochemical properties of GA were investigated using chronoamperometry and cyclic voltammetry; and some thermodynamic and kinetic variables such as α, n α, and D were calculated. Sensitive differential pulse voltammetry (DPV) technique was applied for the determination of Gallic acid and Galloyl esters in different samples. Enhanced oxidation peak currents of Gallic acid were observed at APLE when compared with non-activated PLE. The calibration graph has two linear ranges of 0.49-24.3 µM and 0.07-0.83 mM, and the obtained limit of detection for S/N = 3 was 0.25 µM. Adsorptive stripping differential pulse voltammetry (AdSDPV) was also conducted to determine Gallic acid and Galloyl esters in sub-micromolar concentration range. Using the AdSDPV method, the limit of detection was improved and calculated to be 5.2 nM. The proposed method was successfully applied for quantification of the total concentration of Gallic acid and Galloyl esters in a variety of real samples such as black and green tea, and mango juice samples, and desirable recovery values indicated the good accuracy of the developed sensor.

FT-NIRS Coupled with PLS Regression as a Complement to HPLC Routine Analysis of Caffeine in Tea Samples.

Daily consumption of caffeine in coffee, tea, chocolate, cocoa, and soft drinks has gained wide and plentiful public and scientific attention over the past few decades. The concentration of caffeine in vivo is a crucial indicator of some disorders-for example, kidney malfunction, heart disease, increase of blood pressure and alertness-and can cause some severe diseases including type 2 diabetes mellitus (DM), stroke risk, liver disease, and some cancers. In the present study, near-infrared spectroscopy (NIRS) coupled with partial least-squares regression (PLSR) was proposed as an alternative method for the quantification of caffeine in 25 commercially available tea samples consumed in Oman. This method is a fast, complementary technique to wet chemistry procedures as well as to high-performance liquid chromatography (HPLC) methods for the quantitative analysis of caffeine in tea samples because it is reagent-less and needs little or no pre-treatment of samples. In the current study, the partial least-squares (PLS) algorithm was built by using the near-infrared NIR spectra of caffeine standards prepared in tea samples scanned by a Frontier NIR spectrophotometer (L1280034) by PerkinElmer. Spectra were collected in the absorption mode in the wavenumber range of 10,000-4000 cm-1, using a 0.2 mm path length and CaF2 sealed cells with a resolution of 2 cm-1. The NIR results for the contents of caffeine in tea samples were also compared with results obtained by HPLC analysis. Both techniques provided good results for predicting the caffeine contents in commercially available tea samples. The results of the proposed study show that the suggested FT-NIRS coupled with PLS regression algorithun has a high potential to be routinely used for the quick and reproducible analysis of caffeine contents in tea samples. For the NIR method, the limit of quantification (LOQ) was estimated as 10 times the error of calibration (root mean square error of calibration (RMSECV)) of the model; thus, RMSEC was calculated as 0.03 ppm and the LOQ as 0.3 ppm.

Tea geographical origin explained by LIBS elemental profile combined to isotopic information.

The combined LIBS and ICP HRMS analysis of 13 tea samples are studied in view of identification of tea geographical origin. The elemental signature provided by LIBS spectra is treated by principal component analysis followed by partial least square discriminant analysis and factorial discriminant analysis. Selected element lines are found efficient to discriminate most sample groups. Data analysis model is improved by variable selection and the isotopic ratio 11B/10B was employed to improve the prediction capacity of the model. The alkaline earth: Ba, Ca, Mg, Sr and alkaline Rb, Na are easily detected by the LIBS system and these elements are important to classify sample according to their geographical origin. Minor elements like P, S, Fe, B … also bring discriminant information. A five clusters model gave best correct identification in a cross validation test (94.2%). This method also allowed to identify the origin of four unknown teas. In this study the use of FDA or PLS DA after the PCA examination of the LIBS/ICP MS data led to similar conclusions for fast classification of the tea samples and identification of the geographical origin of the four unknown teas.

Rapid Analysis in Continuous-Flow Electrochemical Paper-Based Analytical Devices.

A simple and low-cost continuous-flow (CF) electrochemical paper-based analytical device (ePAD) coupled with thermoplastic electrodes (TPEs) was developed. The fast, continuous flow combined with flow injection analysis was made possible by adding two inlet reservoirs to the same paper-based hollow channel flowing over detection electrodes, terminating in a fan-shaped pumping reservoir. The upstream inlet reservoir was filled with buffer and provided constant flow through the device. Sample injections were performed by adding 2 µL of the sample to the downstream sample inlet. Differences in flow resistance resulted in sample plugs displacing buffer as the solution flowed over the working electrodes. The electrodes were fabricated by mixing carbon black and polycaprolactone (50% w/w). CF-TPE-ePADs were characterized with chronoamperometry using ferrocenylmethyl trimethylammonium as the electrochemical probe. Optimized flow rates and injection volumes gave analysis times roughly an order of magnitude faster than those of previously reported flow injection analysis ePADs. To demonstrate applicability, the CF-TPE-ePADs were used to quantify caffeic acid in three different tea samples. The proposed method had a linear range from 10 to 500 µmol L-1 and limits of detection and quantification of 2.5 and 8.3 µmol L-1, respectively. Our approach is promising for fabricating simple, inexpensive, yet high-performance, flow injection analysis devices using paper substrates and easy-to-make electrodes that do not require external mechanical pumping systems or complicated valves.

Fluorescent sensing platform for low-cost detection of Cu2+ by coumarin derivative: DFT calculation and practical application in herbal and black tea samples.

A fluorogenic probe based on a coumarin-derivative for Cu2+ sensing in CH3CN/H2O media (v/v, 95/5, 5.0 µM) was developed and applied in real samples. 3-(4-chlorophenyl)-6,7-dihydroxy-coumarin (MCPC) probe was obtained by synthetic methodologies and identified by spectral techniques. The probe MCPC showed remarkable changes with a "turn-off" fluorogenic sensing approach for the monitoring of Cu2+ at 456 nm under an excitation wavelength of 366 nm. The response time of the probe MCPC was founded as only 1 min. The detection limit of the probe MCPC was recorded to be 1.47 nM. The binding constant and possible stoichiometric ratio (1:1) values were determined by Benesi-Hildebrand and Job's plot systems, respectively. The mechanism of the probe MCPC with Cu2+ was further confirmed by ESI-MS and FT-IR analyses, as well as supported by theoretical calculations. Furthermore, the probe MCPC was successfully employed for the practical applications to sense Cu2+ in different herbal and black tea samples. The proposed sensing method was also verified by ICP-OES method.

Rhodol-based fluorescent probes for the detection of fluoride ion and its application in water, tea and live animal imaging.

Herein, we presented two novel turn-on colorimetric and fluorescent probes based on a F- triggered SiO bond cleavage reaction, which displayed several desired properties for the quantitative detection for F-, such as high specificity, rapid response time (within 3 min) and naked-eye visualization. The fluorescence intensity at 574 nm (absorbance at 544 nm) of the solution was found to increase linearly with the concentration of F- (0.00-30.0 µM) with the detection limit was estimated to be 0.47 µM/0.48 µM. Based on these excellent optical properties, the probes were employed to monitor F- in real water samples and tea samples with satisfactory. Furthermore, it was successfully applied for fluorescent imaging of F- in living nude mice, suggesting that it could be used as a powerful tool to predict and explore the biological functions of F- in physiological and pathological processes.

Magnetic solid-phase extraction of benzoylurea insecticides in tea samples with Fe3 O4 -hyperbranched polyester magnetic composite as sorbent.

In this work, a method for the analysis of benzoylurea insecticides, including hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron, in tea samples by high-performance liquid chromatography with Fe3 O4 -hyperbranched polyester nanocomposite as the adsorbent for magnetic solid-phase extraction was developed. The magnetic nanocomposite was prepared and characterized by infrared spectroscopy, vibrating sample magnetometry, and scanning electron microscopy. The as-prepared nanocomposite was used as a sorbent for the extraction and preconcentration of pesticide residues in tea samples. The extraction and desorption conditions, including mass ratios of raw materials, amount of sorbent, pH value, extraction time, and desorption time, were investigated. Under the final conditions chosen for the analysis, good linearity was obtained for all the tested compounds, with R2 values of at least 0.9979. The limits of detection were determined in the range of 0.15-0.3 µg/L. The recovery obtained from the analysis of tea samples with various spiked concentrations was between 90.7 and 98.4%, with relative standard deviations (n = 4) lower than 4.1%. Furthermore, the present approach was successfully applied to the quantitative determination of residues of benzoylurea insecticides in real samples.

A new fluorescence reagent: Synthesis, characterization and application for speciation of arsenic (III)/(VI) species in tea samples.

A sensitive and selective fluorimetric method for the rapid determination of trace amounts of As(III)/As(V) species in certain tea samples forms the basis of the study. 3',6'-bis(diethylamino)-2-{[(1E)-(4,5-dimethyl-2-furyl)methylene]amino}spiro[isoindole-1,9'-xanthen]-3(2H)-one (DMBD), was synthesized and characterized as a new fluorescence reagent for the speciation of As(III)/As(V) species. As(III) was quantitatively recovered with fluorescence reagent at concentrations between 0.5 and 1.5 mol L-1 of HNO3, while As(V) was not quantitatively recovered at any pH. The optimum conditions for the speciation of As(III)/As(V) species were investigated on certain commonly tested experimental parameters such as acidity and pH of the sample, amount of reagent, effects of temperature, and interfering ions etc. In order to determine trace amounts of total arsenic, KI and l(+) ascorbic acid were used to reduce As(V) to the trivalent state in the sample solution prior to determination. The concentration of As(V) in the sample solution were calculated by the difference in concentration between As(III) and the total arsenic in the sample solution. The study yielded a linear function of the concentration of As(III) in the 0-5 mg L-1 range with a detection limit of 0.22 µg L-1. The relative standard deviation was found to be 0.3% for the 0.5 mg L-1 As(III) level. The proposed method was successfully applied for the determination of trace amounts of As(III) and As(V) in certain tea samples. The results of analysis of the certified reference material (INCT-TL-1 tea sample) was found to be in good agreement with the certified value.

[Simultaneous determination of insecticide in tea samples using QuEChERS-based clean up and ultra-fast liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To develop a method for determination of imidacloprid, acetamiprid, chlorobenzamide and indoxacarb in tea samples using Qu ECh ERS-based pretreatment method and ultra-fast liquid chromatography-tandem mass spectrometry( UFLC-MS/MS). METHODS: Tea samples were firstly extracted by acetonitrile-water solution( 4∶ 1, V/V) by vortex and ultrasound, and then 1 g Na Cl and 4 g Mg SO4 were added into the mixture, following by vortex and centrifugation at 8500 r/min for 5 min. Finally the supernatant was purified by Mg SO4 and PSA power, and then the chromatographic separation process was performed on a Waters ACQUITY UPLC BEH C18 column( 2. 1 mm × 100 mm, 1. 7 µm) with a linear gradient elution procedure ofacetonitrile and 0. 1%( V/V) formic acid-5 mmol/L ammonium acetate in water as elution solvent. The multiple reaction monitoring( MRM) in positive mode was used for quantification by internal standard method. RESULTS: The four insecticides including imidacloprid, acetamiprid, chlorobenzamide, and indoxacarb showed good linearity in the range of 0. 20-50. 0 µg/L with coefficients( r) higher than 0. 9998. The limits of detection( LODs) varied from 0. 1 µg/kg to 0. 3 µg/kg. The recoveries of spiked tea samples in the range of 88. 4%-98. 8% at the three concentrations of 1. 0 µg/kg, 40. 0µg/kg and 80. 0 µg/kg, while the relative standard deviations( RSD) were all less than10%. CONCLUSION: The proposed method is simple, fast, sensitive and accuracy, and can be used for qualitative and quantitative analysis of imidacloprid, acetamiprid, chlorobenzamide, andindoxacarb in tea samples.

A 3D nanoscale polyhedral oligomeric silsesquioxanes network for microextraction of polycyclic aromatic hydrocarbons.

Polyhedral oligomeric silsesquioxanes are 3D nanoscaled materials with large potential in solid phase microextraction (SPME). Here, as a case study, an octaglycidyldimethylsilyl modified polyhedral oligomeric silsesquioxane network is described. It was deposited on a stainless steel wire via a sol-gel method and used as a fiber coating for SPME of aromatic compounds. The uniform pore structure, high surface area, and hydrophobicity of the network make it susceptible toward isolation of non-polar and semi-polar chemical compounds. The performance of the fiber coating was tested with three classes of environmental pollutants, viz. chlorobenzenes (CBs), benzenes (benzene, toluene, ethylbenzene, xylene; known as BTEX), and polycyclic aromatic hydrocarbons. The effects of various types of sol-gel precursors on the fabrication and performance of fiber coatings were investigated. The extraction capability of the fiber coating was compared with the polydimethyl siloxane/divinylbenzene based commercial fiber. Parameters affecting headspace analysis and gas chromatographic quantitation were optimized. The method was applied to the quantification of PAHs, as model analytes, in tea, coffee and some environmental waters. Linear responses typically cover the 1-200 ng·L-1 concentration range, limits of detection are between 0.1 and 0.3 ng·L-1, intra-day relative standard deviation are <10%, and inter-day RSDs are <12%. The fiber has a long lifespan and can be used >200 times. Graphical abstract Schematic presentation of a headspace solid phase microextraction process which is implemented to the analysis of PAHs in tea and coffee samples. The SEM image of the SPME fiber coating, the 3D nanoscale polyhedral oligomeric silsesquioxane (POSS) network, and the POSS-epoxy molecular structure are shown.

Multivariate curve resolution strategy for non-quadrilinear type 4 third-order/four way liquid chromatography-excitation-emission fluorescence matrix data.

For the first time, a third-order/four-way system having instrumental modes depending on each other was experimentally generated and it was successfully resolved. Non-quadrilinear type 4 data, constituted by liquid chromatographic elution times (LC) and excitation-emission fluorescence matrices (EEFMs), were on-line measured using conventional equipment. Thus, third-order/four-way data, valuable for giving rise to highly sensitive and selective methods, were obtained minimizing significantly the experimental work and time, in comparison with the reported strategies for the acquisition of LC-EEFM data. The usefulness of MCR-ALS (multivariate curve resolution-alternating least square) for attaining reliable results from data with two mutually dependent instrumental modes, namely elution time and excitation wavelength modes, was established through the simultaneous quantitation of benz[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene. Limits of detection in the range 1.0-1.4 ng mL-1 were achieved for the target polycyclic aromatic hydrocarbons, allowing their determination in about 9 min per sample in leaves of different types of tea.

A new turn-on fluorimetric method for the rapid speciation of Cr(III)/Cr(VI) species in tea samples with rhodamine-based fluorescent reagent.

A new fluorimetric method with rhodamine-based fluorescent agent was developed for the rapid speciation of Cr(III)/Cr(VI) in tea, soil and water samples. The system, which utilizes a fluorescent reagent, was used for the first time after synthesis/characterization of 3',6'-bis(diethylamino)-2-{[(1E)-(2,4-dimethoxyphenyl)methylene] amino}spiro[isoindole-1,9'-xanthen]-3(2H)-one (BDAS). The reagent responds instantaneously at room temperature in a 1:1 stoichiometric manner to the amount of Cr(III). The selectivity of this system for Cr(III) over other metal ions is remarkably high, and its sensitivity is below 0.01mgL-1 in aqueous solutions which enables a simplification without any pretreatment of the real sample. The method has a wide linear range of 0.1-10mgL-1 and a detection limit of 0.15µgL-1 for Cr(III) while the relative standard deviation was 0.1% for 0.1mgL-1 Cr(III) concentration. The results of detection and recovery experiments for Cr(III) in tea, soil and water were satisfactory, indicating that the method has better feasibility and application potential in the routine determination and speciation of Cr(III)/Cr(VI). The results of analysis of the certified reference material (INCT-TL-1 tea sample and CWW-TM-D waste water) are in good agreement with the certified value.