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1.
Anal Bioanal Chem ; 416(14): 3459-3471, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38727737

ABSTRACT

Concerns regarding microplastic (MP) contamination in aquatic ecosystems and its impact on seafood require a better understanding of human dietary MP exposure including extensive monitoring. While conventional techniques for MP analysis like infrared or Raman microspectroscopy provide detailed particle information, they are limited by low sample throughput, particularly when dealing with high particle numbers in seafood due to matrix-related residues. Consequently, more rapid techniques need to be developed to meet the requirements of large-scale monitoring. This study focused on semi-automated fluorescence imaging analysis after Nile red staining for rapid MP screening in seafood. By implementing RGB-based fluorescence threshold values, the need for high operator expertise to prevent misclassification was addressed. Food-relevant MP was identified with over 95% probability and differentiated from natural polymers with a 1% error rate. Comparison with laser direct infrared imaging (LDIR), a state-of-the-art method for rapid MP analysis, showed similar particle counts, indicating plausible results. However, highly variable recovery rates attributed to inhomogeneous particle spiking experiments highlight the need for future development of certified reference material including sample preparation. The proposed method demonstrated suitability of high throughput analysis for seafood samples, requiring 0.02-0.06 h/cm2 filter surface compared to 4.5-14.7 h/cm with LDIR analysis. Overall, the method holds promise as a screening tool for more accurate yet resource-intensive MP analysis methods such as spectroscopic or thermoanalytical techniques.


Subject(s)
Oxazines , Seafood , Seafood/analysis , Oxazines/analysis , Food Contamination/analysis , Microplastics/analysis , Animals , Water Pollutants, Chemical/analysis , Staining and Labeling/methods , Plastics/analysis , Humans , Fluorescent Dyes/chemistry
2.
Ecotoxicol Environ Saf ; 259: 115065, 2023 Jul 01.
Article in English | MEDLINE | ID: mdl-37245243

ABSTRACT

Agrochemical indoxacarb is an important tool for selective pest control in radish that be consumed globally. A rapid and sensitive analytical method UHPLC-MS/MS was developed for tracing indoxacarb in radish leaves and roots with LOQ of 0.001 mg/kg and RT within 2 min, which were confirmed the satisfied storage stability of indoxacarb in radish matrixes with degradation rates less than 30 %. The occurrence, pharmacokinetics dissipation and concentration variation of indoxacarb were reflected by the original deposition of 2.23-4.12 mg/kg, half-lives of 2.6-8.0 d and terminal magnitude of 0.17 × 10-2-25.46 mg/kg in radish, and the influencing factors were further illustrated in terms of climate factors, crop cultivars and soil properties. The highest residues of indoxacarb were 25.46 mg/kg in leaves and 0.12 mg/kg in roots, which were higher than international maximum residue limits. A probabilistic model, as well as deterministic model, were introduced to evaluated the health risks of indoxacarb offering a better description for uncertainty. The total chronic dietary risk values of indoxacarb were 146.961-482.065 % in 12 registered crops, of which ADI % in radish was accounted for 19.8 % with risk dilution effects. The unacceptable acute dietary risks of 121.358-220.331 % were observed at 99.9th percentile, whereas the high-potential non-carcinogenic effects were observed over 90th percentile (105.035-1121.943 %). The health risks should be continuously emphasized given the increasing applications and persistent characteristics of indoxacarb, which is vital to protect the human population from hazardous effects, particularly for vulnerable children.


Subject(s)
Pesticide Residues , Raphanus , Child , Humans , Raphanus/metabolism , Tandem Mass Spectrometry , Pesticide Residues/analysis , Oxazines/analysis , Risk Assessment
3.
Integr Environ Assess Manag ; 18(3): 709-721, 2022 May.
Article in English | MEDLINE | ID: mdl-34292667

ABSTRACT

The ban imposed by the European Union on the use of neonicotinoids as sugar beet seed treatments was based on the exposure of bees to residues of neonicotinoids in pollen and nectar of succeeding crops. To address this concern, residues of thiamethoxam (TMX) and clothianidin (CTD) were analyzed in soil collected from fields planted in at least the previous year with thiamethoxam-treated sugar beet seed. This soil monitoring program was conducted at 94 sites across Germany in two separate years. In addition, a succeeding crop study assessed residues in soil, guttation fluid, pollen, and nectar sampled from untreated succeeding crops planted in the season after thiamethoxam seed-treated sugar beet at eight field sites across five countries. The overall mean residues observed in soil monitoring were 8.0 ± 0.5 µg TMX + CTD/kg in the season after the use of treated sugar beet seed. Residue values decreased with increasing time interval between the latest thiamethoxam or clothianidin application before sugar beet drilling and with lower application frequency. Residues were detected in guttation fluid (2.0-37.7 µg TMX/L); however, the risk to pollinators from this route of exposure is likely to be low, based on the reported levels of consumption. Residues of thiamethoxam and clothianidin in pollen and nectar sampled from the succeeding crops were detected at or below the limit of quantification (0.5-1 µg a.i./kg) in 86.7% of pollen and 98.6% of nectar samples and, unlike guttation fluid residues, were not correlated with measured soil residues. Residues in pollen and nectar are lower than reported sublethal adverse effect concentrations in studies with honeybee and bumble bee individuals and colonies fed only thiamethoxam-treated sucrose, and are lower than those reported to result in no effects in honeybees, bumble bees, and solitary bees foraging on seed-treated crops. Integr Environ Assess Manag 2022;18:709-721. © 2021 SYNGENTA. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).


Subject(s)
Beta vulgaris , Insecticides , Animals , Bees , Crops, Agricultural , Insecticides/analysis , Insecticides/toxicity , Neonicotinoids/toxicity , Nitro Compounds/toxicity , Oxazines/analysis , Oxazines/toxicity , Plant Nectar/analysis , Plant Nectar/chemistry , Seeds/chemistry , Soil , Sugars/analysis , Thiamethoxam/analysis , Vegetables
4.
J Sep Sci ; 44(15): 2917-2931, 2021 Aug.
Article in English | MEDLINE | ID: mdl-34076952

ABSTRACT

A stability-indicating reversed-phase high-performance liquid chromatography method for simultaneous estimation of dolutegravir sodium and lamivudine encapsulated in the nanoliposomal formulation was developed. The chromatographic parameters namely, organic phase ratio, flow rate, and sample injection volume were selected as independent factors and were optimized by multivariate Box-Behnken design. Responses analyzed were retention time, peak area, and resolution. The optimized chromatographic method with Hypersil BDS C8 CN column as stationary phase and methanol and acetonitrile mixture and acidified Milli-Q water (pH 2.8, adjusted with 0.02% v/v orthophosphoric acid) as the mobile phase in an isocratic elution mode was validated according to parameters of International Conference on Harmonization Q1(R2) guidelines. The validated reversed-phase high-performance liquid chromatography method exhibited specificity for both dolutegravir sodium and lamivudine in the presence of degradation products as well as the liposomal matrix. This method was effectively utilized to determine the amount of drug entrapped and drug loading efficiency of dolutegravir sodium and lamivudine in a nano-liposomal formulation.


Subject(s)
Chromatography, High Pressure Liquid/methods , Chromatography, Reverse-Phase/methods , Drug Carriers , HIV Integrase Inhibitors/analysis , Heterocyclic Compounds, 3-Ring/analysis , Lamivudine/analysis , Liposomes , Nanoparticles , Oxazines/analysis , Piperazines/analysis , Pyridones/analysis , Reverse Transcriptase Inhibitors/analysis , Drug Compounding , Limit of Detection
5.
Sci Rep ; 11(1): 5831, 2021 03 12.
Article in English | MEDLINE | ID: mdl-33712666

ABSTRACT

This report suggests a method of enhancing the sensitivity of chemifluorescence-based ELISA, using photooxidation-induced fluorescence amplification (PIFA). The PIFA utilized autocatalytic photooxidation of the chemifluorescent substrate, 10-acetyl 3,7-dihydroxyphenoxazine (ADHP, Amplex Red) to amplify the fluorescent product resorufin, initially oxidized by horse radish peroxidase (HRP). As the amplification rate is proportional to the initial level of resorufin, the level of antigen labeled by HRP is quantified by analyzing the profile of fluorescence intensity. The normalized profile was interpolated into an autocatalysis model, and the rate of increase at half-maximum time was quantified by the use of an amplification index (AI). The lower limit of detection, for resorufin or HRP, was less than one-tenth that of the plate reader. It requires only slight modification of the fluorescence reader and is fully compatible with conventional or commercial ELISA. When it is applied to a commercial ELISA kit for the detection of amyloid beta, it is verified that the PIFA assay enhanced the detection sensitivity by more than a factor of 10 and was compatible with a conventional 96-well ELISA assay kit. We anticipate this PIFA assay to be used in research for the detection of low levels of proteins and for the early diagnosis of various diseases with rare protein biomarkers, at ultra-low (pg/mL) concentrations.


Subject(s)
Enzyme-Linked Immunosorbent Assay/methods , Amyloid beta-Peptides/analysis , Fluorescence , Horseradish Peroxidase/chemistry , Humans , Oxazines/analysis , Oxazines/chemistry , Oxidation-Reduction
6.
Food Chem ; 339: 127920, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-32877812

ABSTRACT

Rapid and efficient detection of indoxacarb (IXC), a common chemical contaminant, in environmental and biological samples is necessary. In this work, a modern optical sensor was developed for IXC, based on environmentally friendly molecularly imprinted polymer (MIP) coated on silica-carbon quantum dots (SiCQDs). A hydrothermal method was used to prepare highly fluorescence SiCQDs and, subsequently, MIP formed on surface (MIP@SiCQDs) using a sol-gel method. A linear relationship between the fluorescence quenching effect and increased IXC concentration was found for the range of 4-102 nM, under the optimal conditions, with a 1 nM detection limit. Precisions was of 4.5 and 2.3% for five replicate detections at 21 and 60 nM IXC, respectively. Applicability of the sensor for IXC quantification in environmental and biological samples was verified with recoveries in the range 95-106% with a relative standard deviation of <6.0%.


Subject(s)
Oxazines/analysis , Quantum Dots/chemistry , Carbon/chemistry , Hydrogen-Ion Concentration , Limit of Detection , Molecularly Imprinted Polymers/chemistry , Reproducibility of Results , Silicon Dioxide/chemistry , Spectrometry, Fluorescence , Temperature
7.
J Biomed Mater Res B Appl Biomater ; 109(4): 527-537, 2021 04.
Article in English | MEDLINE | ID: mdl-32945122

ABSTRACT

Presently, most of anticancer drugs are high toxic for normal cells and, and as a result, they have severe side effects. Moreover, most of the formulations are lipophilic and have poor selectivity. To overcome these limitations, various drug delivery systems could be proposed. The aim of the current study was to fabricate novel polysaccharide nanocontainers (NC) by one-step ultrasonication technique and to evaluate their accumulation efficacy and cytotoxicity in 2D (monolayer culture) and 3D (tumor spheroids) in vitro models. NC with mean sizes in a range of 340-420 nm with the core-shell structure are synthetized and characterized. The NC shell is composed from diethylaminoethyl dextran/xanthan gum polyelectrolyte complex, while the hydrophobic core was loaded with the lipophilic anticancer drug thymoquinone. To enhance NC accumulation in human breast adenocarcinoma MCF-7 cells, the NC surface was modified with poly-L-lysine (PLL) or polyethylene glycol. Cell uptake of the NC loaded with Nile Red into the tumor cells was investigated by laser scanning confocal microscopy, fluorescent flow cytometry and fluorimetry. Modification of the NC with PLL allowed to obtain the optimal drug delivery system with maximal cytotoxicity, which was tested by MTT-test. The developed NC are promising for lipophilic anticancer drug delivery.


Subject(s)
Antineoplastic Agents, Phytogenic/administration & dosage , Benzoquinones/administration & dosage , Drug Packaging/instrumentation , Nanoparticle Drug Delivery System , Antineoplastic Agents, Phytogenic/chemistry , Benzoquinones/chemistry , Cell Culture Techniques, Three Dimensional , DEAE-Dextran , Emulsions , Female , Flow Cytometry , Fluorometry , Humans , Hydrophobic and Hydrophilic Interactions , In Vitro Techniques , MCF-7 Cells , Microscopy, Confocal , Oxazines/analysis , Polyethylene Glycols , Polylysine , Polysaccharides, Bacterial , Sonication , Spheroids, Cellular/drug effects
8.
J Mater Chem B ; 9(1): 53-79, 2021 01 07.
Article in English | MEDLINE | ID: mdl-33226060

ABSTRACT

The fluorescence imaging technique has attracted increasing attention in the detection of various biological molecules in situ and in real-time owing to its inherent advantages including high selectivity and sensitivity, outstanding spatiotemporal resolution and fast feedback. In the past few decades, a number of fluorescent probes have been developed for bioassays and imaging by exploiting different fluorophores. Among various fluorophores, resorufin exhibits a high fluorescence quantum yield, long excitation/emission wavelength and pronounced ability in both fluorescence and colorimetric analysis. This fluorophore has been widely utilized in the design of responsive probes specific for various bioactive species. In this review, we summarize the advances in the development of resorufin-based fluorescent probes for detecting various analytes, such as cations, anions, reactive (redox-active) sulfur species, small molecules and biological macromolecules. The chemical structures of probes, response mechanisms, detection limits and practical applications are investigated, which is followed by the discussion of recent challenges and future research perspectives. This review article is expected to promote the further development of resorufin-based responsive fluorescent probes and their biological applications.


Subject(s)
Fluorescent Dyes/metabolism , Optical Imaging/methods , Oxazines/metabolism , Animals , Colorimetry/methods , Fluorescent Dyes/analysis , Humans , Oxazines/analysis
9.
Article in English | MEDLINE | ID: mdl-32738524

ABSTRACT

Ethoxyresorufin (ER)-O-deethylation (EROD) activity has been widely used to assess cytochrome P450 1A (CYP1A) activity. The kinetics of CYP1A activity have been well characterized in the liver microsomes. However, studies in kidney microsomes are limited due to the much lower EROD activity in this organ. Here, we developed and validated a sensitive UPLC-MS/MS assay for the characterization of the EROD activity in the rat kidney microsomes. In a 50 µL reaction mixture, rat kidney microsomes (0.25 mg/mL) were incubated with ER (0.1-5 µM) and NADPH (1 mM) for 10 min. Acidic solvents, such as trichloroacetic acid or formic acid, used for quenching of the metabolic reactions and precipitation of the proteins, unexpectedly caused a spontaneous formation of resorufin (RES) from ER. Therefore, the metabolic reactions were terminated by adding acetonitrile, containing a deuterated internal standard (IS). Chromatographic separation was achieved on a C18 UPLC column, and the MS/MS ion transitions were 213.9/185.9 for RES and 220.0/192.0 for IS. The assay was validated in the linear range of 0.5 nM to 75 nM of RES and had a lower limit of quantitation of 0.5 nM. The overall recoveries of RES (90%-99%) and IS (85%-103%) were relatively high, with minimal matrix effect. The assay was successfully applied to the estimation of the Michaelis-Menten (MM) kinetics of EROD activity in the rat kidney microsomes (n = 3), which showed a maximum velocity of 2.68 ± 0.17 pmol/min/mg and a MM constant of 1.72 ± 0.24 µM (mean ± SD). It is concluded that our sensitive and specific analytical method, coupled with the optimized microsomal incubation conditions, provides a robust platform for further investigations of the effects of xenobiotics, environmental factors, or pathophysiologic conditions on the kinetics of EROD activity in the kidney microsomes.


Subject(s)
Chromatography, High Pressure Liquid/methods , Cytochrome P-450 CYP1A1/analysis , Kidney/metabolism , Microsomes/metabolism , Tandem Mass Spectrometry/methods , Animals , Cytochrome P-450 CYP1A1/metabolism , Kidney/cytology , Kinetics , Limit of Detection , Linear Models , Male , Microsomes/enzymology , Oxazines/analysis , Oxazines/metabolism , Rats , Rats, Sprague-Dawley , Reproducibility of Results
10.
Chem Commun (Camb) ; 56(65): 9296-9299, 2020 Aug 13.
Article in English | MEDLINE | ID: mdl-32666982

ABSTRACT

A tetralactam macrocycle acts as a novel supramolecular adjuvant to capture a released resorufin dye and create a higher contrasting yellow/blue color change for enhanced naked eye interpretation of a colorimetric indicator assay.


Subject(s)
Colorimetry , Fluorescent Dyes/analysis , Lactams/chemistry , Oxazines/analysis , Macromolecular Substances/chemistry , Molecular Structure
11.
Food Chem ; 328: 127134, 2020 Oct 30.
Article in English | MEDLINE | ID: mdl-32473493

ABSTRACT

An efficient single quadrupole gas chromatography with mass spectrometry method was developed and validated for the determination of indoxacarb residues in tomato and soil. Residues were extracted from the samples using acetonitrile as extracting solvent and the extracts were purified through primary secondary amine and graphitized carbon black. Recoveries were obtained in the range of 92.12-110.51% with the relative standard deviation of 1.32-4.32%. Indoxacarb dissipated with half-life of 3.12-3.21 and 1.24-1.35d for tomato and soil, respectively following doses of indoxacarb 14.5% SC at 60, 90 and 120 g.a.i./ha. Safe waiting periods were found to be 1-3d. The residues were removed from tomato fruit was in the range of 16.73 to 54.32% using simple decontamination approaches. The present study suggest that the use of indoxacarb in tomato at recommended dose, does not seem to pose any dietary risk to the consumers. The soil RQ values indicated low level of risk to earthworms and arthropods.


Subject(s)
Food Contamination/analysis , Oxazines/analysis , Pesticide Residues/analysis , Soil Pollutants/analysis , Solanum lycopersicum/chemistry , Acetonitriles/chemistry , Dietary Exposure , Food Analysis/methods , Gas Chromatography-Mass Spectrometry , Half-Life , Humans , India , Oxazines/metabolism , Risk Assessment , Soil Pollutants/metabolism , Solvents/chemistry , Time Factors
12.
Sensors (Basel) ; 20(5)2020 Mar 10.
Article in English | MEDLINE | ID: mdl-32164236

ABSTRACT

Accurate analysis of pesticide residue in real samples is essential for food safety and environmental protection. However, a traditional electrochemical sensor based on single-signal output is easily affected by background noise, environmental conditions, electrode diversity, and a complex matrix of samples, leading to extremely low accuracy. Hence, in this paper, a ratiometric strategy based on dual-signal output was adopted to build inner correction for sensing of widely-used carbaryl (CBL) for the first time. By comparison, Nile blue A (NB) was selected as reference probe, due to its well-defined peak, few effects on the target peak of CBL, and excellent stability. The effects of a derivatization method, technique mode, and pH were also investigated. Then the performance of the proposed ratiometric sensor was assessed in terms of three aspects including the elimination of system noise, electrode deviation and matrix effect. Compared with traditional single-signal sensor, the ratiometric sensor showed a much better linear correlation coefficient (r > 0.99), reproducibility (RSD < 10%), and limit of detection (LOD = 1.0 µM). The results indicated the introduction of proper reference probe could ensure the interdependence of target and reference signal on the same sensing environment, thus inner correction was fulfilled, which provided a promising tool for accurate analysis.


Subject(s)
Carbaryl/analysis , Electrochemistry/methods , Food Analysis/methods , Vegetables , Water/chemistry , Biosensing Techniques , Brassica , Calibration , Chromatography, High Pressure Liquid , Electrodes , Hydrogen-Ion Concentration , Limit of Detection , Linear Models , Solanum lycopersicum , Oxazines/analysis , Reproducibility of Results , Signal Processing, Computer-Assisted
13.
Methods Mol Biol ; 1995: 33-50, 2019.
Article in English | MEDLINE | ID: mdl-31148120

ABSTRACT

Oleaginous microbes, which contain over 20% intracellular lipid, predominantly triacylglycerols (TG), by dry weight, have been discovered to have high oil content by many different protocols, ranging from simple staining to more complex chromatographic methods. In our laboratory, a methodical process was implemented to identify high oil yeasts, designed to minimize labor while optimizing success in identifying high oil strains among thousands of candidates. First, criteria were developed to select candidate yeast strains for analysis. These included observation of buoyancy of the yeast cell mass in 20% glycerol, and phylogenetic placement near known oleaginous species. A low-labor, semiquantitative Nile red staining protocol was implemented to screen numerous yeast cultures for high oil content in 96-well plates. Then, promising candidates were selected for more quantitative analysis. A more labor-intensive and quantitative gravimetric assay was implemented that gave consistent values for intracellular oil content for a broad range of yeast species. Finally, an LC-MS protocol was utilized to quantify and identify yeast triacylglycerols. This progressive approach was successful in identifying 30 new oleaginous yeast species, out of over 1000 species represented in the Phaff Yeast Culture Collection.


Subject(s)
Lipids/analysis , Yeasts/chemistry , Chromatography, Liquid/methods , Fluorescent Dyes/analysis , Lipidomics/methods , Mass Spectrometry/methods , Microscopy, Fluorescence/methods , Oxazines/analysis , Staining and Labeling/methods , Triglycerides/analysis
14.
Methods Mol Biol ; 1995: 395-403, 2019.
Article in English | MEDLINE | ID: mdl-31148141

ABSTRACT

Over the last decade, finding bacterial strains with ability to accumulate high concentrations of lipids has gained increasing interest, since these lipids may be used in different industries. Here we describe two methods for evaluation of lipid accumulation in cyanobacteria, following by our personal reflection on issues surrounding the use of these methods. First, we present the Bligh and Dyer protocol as a traditional extraction method using organic solvents for quantitative determination of lipids and next Nile red, a selective fluorescent stain, that has been used as a rapid approach for both qualitative and quantitative measurement of lipids.


Subject(s)
Cyanobacteria/metabolism , Lipid Metabolism , Lipids/analysis , Cyanobacteria/chemistry , Fluorescent Dyes/analysis , Lipids/isolation & purification , Oxazines/analysis , Spectrometry, Fluorescence/methods , Staining and Labeling/methods
15.
Environ Sci Pollut Res Int ; 26(19): 19523-19539, 2019 Jul.
Article in English | MEDLINE | ID: mdl-31077043

ABSTRACT

The present paper describes the sono-assisted adsorption (sono-adsorption) of methylene blue (MB), methyl violet (MV), and Nile blue (NB) from aqueous solution by AC/CoFe2O4 magnetic composite. FT-IR, TGA-DTG, VSM, XRD, TEM, SEM, EDX, Map, and Raman analysis were used to characterize the magnetic composite. The magnetization saturation value of AC/CoFe2O4 magnetic composite was determined to be 53.06 emu/g. Dye sono-adsorption efficiency was increased by increasing adsorbent dose, pH value, and contact time, but not dye concentration. Pseudo-first-order, pseudo-second-order, and intra-particle diffusion models were used to study the kinetic behavior of the cationic dye sono-adsorption. The sono-adsorption kinetics was reasonably followed by pseudo-second-order model (R2 > 0.998). The results showed that the Freundlich model (R2 > 0.976) was more able to describe the sono-adsorption equilibrium behavior than Langmuir, D-R, and Scatchard models. The maximum sono-adsorption capacity of NB, MV, and MB was determined as 86.24, 83.90, and 87.48 mg/g, respectively. Based on the parameters derived from isotherm modeling (RL, n, and E), the sono-adsorption process of cationic dyes is desirable and physical. An increase in NaCl concentration reduced the sono-adsorption efficiency for all dyes. Also, the adsorption-desorption of AC/CoFe2O4 magnetic was studied up to 10 stages, and it was confirmed that the sono-adsorption efficiency is acceptable up to the eight stage. AC/CoFe2O4 magnetic composite is, therefore, an affordable and recyclable adsorbent to remove the molecule of NB, MV, and MB dyes from aqueous media.


Subject(s)
Charcoal/chemistry , Cobalt/chemistry , Coloring Agents/analysis , Ferric Compounds/chemistry , Magnetite Nanoparticles/chemistry , Water Pollutants, Chemical/analysis , Water Purification/methods , Adsorption , Diffusion , Gentian Violet/analysis , Hydrogen-Ion Concentration , Kinetics , Methylene Blue/analysis , Oxazines/analysis
16.
Biomed Chromatogr ; 33(7): e4522, 2019 Jul.
Article in English | MEDLINE | ID: mdl-30821836

ABSTRACT

We developed an analytical method using liquid-liquid extraction (LLE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) to detect and quantify tebufenozide (TEB) and indoxacarb (IND) residues in animal and aquatic products (chicken muscle, milk, egg, eel, flatfish, and shrimp). The target compounds were extracted using 1% acetic acid (0.1% acetic acid for egg only) in acetonitrile and purified using n-hexane. The analytes were separated on a Gemini-NX C18 column using (a) distilled water with 0.1% formic acid and 5 mm ammonium acetate and (b) methanol with 0.1% formic acid as the mobile phase. All six-point matrix-matched calibration curves showed good linearity with coefficients of determination (R2 ) ≥0.9864 over a concentration range of 5-50 µg/kg. Intra- and inter-day accuracy was expressed as the recovery rate at three spiking levels and ranged between 73.22 and 114.93% in all matrices, with a relative standard deviation (RSD, corresponding to precision) ≤13.87%. The limits of quantification (LOQ) of all target analytes ranged from 2 to 20 µg/kg, which were substantially lower than the maximum residue limits (MRLs) specified by the regulatory agencies of different countries. All samples were collected from different markets in Seoul, Republic of Korea, and tested negative for tebufenozide and indoxacarb residues. These results show that the method developed is robust and may be a promising tool to detect trace levels of the target analytes in animal products.


Subject(s)
Chromatography, High Pressure Liquid/methods , Drug Residues/analysis , Food Analysis/methods , Hydrazines/analysis , Oxazines/analysis , Tandem Mass Spectrometry/methods , Animals , Chickens , Drug Residues/chemistry , Drug Residues/isolation & purification , Food Contamination/analysis , Hydrazines/chemistry , Hydrazines/isolation & purification , Limit of Detection , Linear Models , Liquid-Liquid Extraction , Oxazines/chemistry , Oxazines/isolation & purification , Reproducibility of Results
17.
Ecotoxicol Environ Saf ; 171: 130-137, 2019 Apr 30.
Article in English | MEDLINE | ID: mdl-30599430

ABSTRACT

Neonicotinoid insecticides such as imidacloprid, indoxacarb and thiamethoxam are widely used for control of a large number of insect pests of pomegranate crop. Their residue levels were evaluated on pomegranate fruits over 2 years during the same cropping season. The QuEChERS analytical method in conjunction with LC-MS/MS was validated to analyse the insecticides on pomegranate fruits with peel (whole fruit), without peel (aril) and in the field soil. The method performance was satisfactory with the limit of quantification (LOQ) of 0.005 mg/kg which was below the maximum residue limits (MRLs) in pomegranate for the 3 compounds. A first order reaction kinetics was observed for the three insecticides with the half -life of degradation of 8-11.1 days for imidacloprid; 7.4-8.4 days for indoxacarb and 9.8-14.2 days for thiamethoxam. Though the insecticides are systemic in nature, the residues in the edible pomegranate aril were always < LOQ. The maximum residue levels of imidacloprid on pomegranate was less than its MRL of 1 mg/kg, so the pre-harvest interval (PHI) required was 1 day only. For indoxacarb, 31-42 days PHI was needed for the residues to reduce to its MRL of 0.02 mg/kg. The PHI of thiamethoxam was 46-77 days, the time required for its residues to reduce to its MRL of 0.01 mg/kg. Higher rainfall possibly facilitated faster dissipation of imidacloprid residues from pomegranate whereas indoxacarb and thiamethoxam remained unaffected. The results of the study can be utilized to incorporate these three chemicals in the plant protection program of pomegranate and fixation of MRL in India.


Subject(s)
Fruit/chemistry , Insecticides/analysis , Lythraceae/chemistry , Neonicotinoids/analysis , Nitro Compounds/analysis , Oxazines/analysis , Pesticide Residues/analysis , Thiamethoxam/analysis , Chromatography, Liquid , Environmental Monitoring , India , Tandem Mass Spectrometry
18.
Nat Prod Res ; 33(7): 1040-1051, 2019 Apr.
Article in English | MEDLINE | ID: mdl-28679319

ABSTRACT

In this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865-1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones.


Subject(s)
Coloring Agents/analysis , Complex Mixtures/analysis , Textiles/analysis , Clothing/history , Coloring Agents/history , Complex Mixtures/history , Female , History, 19th Century , Humans , Oxazines/analysis , Sicily , Spectrum Analysis , Textiles/history
19.
Int J Food Microbiol ; 292: 13-20, 2019 Mar 02.
Article in English | MEDLINE | ID: mdl-30553178

ABSTRACT

Estimations of consumer exposure to mycotoxins through surveillance of mycotoxins in the food trade are well described, but the exposure due to mouldy food in private homes is not known, and may result from removing visible mould on food and eating the rest. In this study, we followed the growth of Penicillium expansum on the surface of apple jam and Penicillium verrucosum on crème fraiche, as well as production and distribution of fungal metabolites throughout the sample (approx. 6 cm high divided into three equal layers), using a multianalyte method, over time (up to 28 days) and at 4, 8 and 15 °C. Growth rates and apparent lag times for P. expansum in apple jam at different temperatures were estimated by fitting to the Baranyi model. The growth rates were 1.7, 2.7 and 4.3 mm day-1 for storage at 4, 8 and 15 °C, respectively; apparent lag times decreased with increasing storage temperature and were 10.6, 7.9 and 2.6 days at corresponding temperatures. Patulin and roquefortine C were identified and quantified, among other fungal metabolites. Patulin was detected in all 2-cm layers of the apple jam at 15 °C. Concentrations in the upper two layers of the jar corresponded to exposures exceeding the health based guidance value (HBGV) for a normal serving size. Consequently, removal of the mouldy part is insufficient to avoid unhealthy exposure. In contrast to patulin, roquefortine C was also produced at 4 °C. The growth of P. verrucosum on crème fraiche was very restricted and could not be modelled. Despite the small colony (8 ±â€¯0.5 mm in diameter), ochratoxin A and citrinin were detected after 21 days at 15 °C in the top 2 cm layer (including the fungal colony), and at concentrations in a normal serving corresponding to an exposure above the HBGV established by EFSA for both mycotoxins. Questiomycin A, an antibiotic, was also produced in crème fraiche but in contrast to the two mycotoxins, was detected throughout all layers of the crème fraiche and was produced also at 4 and 8 °C. As a complement to a previous study, we also present production and the distribution of major fungal metabolites in apple jam and crème fraiche for some additional fungal strains (P. crustosum, P. roqueforti and P. verrucosum on apple jam and P. expansum on crème fraiche). A pilot study investigating the effect of inoculation size on toxin production may have implications for the best inoculum to use in experimental studies.


Subject(s)
Cultured Milk Products/microbiology , Food Contamination/analysis , Indoles/analysis , Malus/microbiology , Mycotoxins/analysis , Oxazines/analysis , Penicillium/growth & development , Citrinin/analysis , Cultured Milk Products/analysis , Heterocyclic Compounds, 4 or More Rings/analysis , Ochratoxins/analysis , Patulin/analysis , Penicillium/metabolism , Pilot Projects , Piperazines/analysis , Temperature
20.
Food Chem ; 268: 264-270, 2018 Dec 01.
Article in English | MEDLINE | ID: mdl-30064756

ABSTRACT

The aim of this study was to determine the insecticide residue processing factor (PF) from plums to prunes and the effect of the industrial processing of prunes residue concentrations. Our results show an increase of insecticide concentrations during plum dehydration that is explained by fruit water loss; however, the normalized insecticide residue concentration, based on plum dry weights to compensate dehydration, was reduced. The water washing and tenderizing of prunes produced insecticide residue reductions of 22.9 ±â€¯4.5% and 21.9 ±â€¯4.2%, respectively. PF were: 1.157, 1.872, 1.316, 0.192, 2.198, 0.775 and 0.156 for buprofezin, l-cyhalothrin, spirodiclofen, indoxacarb, acetamiprid, imidacloprid and emamectin benzoate, respectively, being directly related to water solubility, aqueous hydrolysis and degradation point and inversely related to molecular mass and melting point. In plums for the dehydrated agroindustry the final product is prunes, therefore, it is crucial to consider the PF to determine the specific preharvest interval for this important agroindustry.


Subject(s)
Gas Chromatography-Mass Spectrometry , Pesticide Residues/analysis , Prunus domestica/chemistry , Fruit/chemistry , Fruit/metabolism , Ivermectin/analogs & derivatives , Ivermectin/analysis , Ivermectin/chemistry , Ivermectin/isolation & purification , Neonicotinoids/analysis , Neonicotinoids/chemistry , Neonicotinoids/isolation & purification , Nitriles/analysis , Nitriles/chemistry , Nitriles/isolation & purification , Nitro Compounds/analysis , Nitro Compounds/chemistry , Nitro Compounds/isolation & purification , Oxazines/analysis , Oxazines/chemistry , Oxazines/isolation & purification , Oxidation-Reduction , Pesticide Residues/chemistry , Pesticide Residues/isolation & purification , Prunus domestica/metabolism , Pyrethrins/analysis , Pyrethrins/chemistry , Pyrethrins/isolation & purification , Solid Phase Extraction
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