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1.
Bull Environ Contam Toxicol ; 112(5): 74, 2024 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-38733375

RESUMO

Polycyclic aromatic hydrocarbons (PAHs), dust, and wax were measured in pine needles, and PAHs were also measured in surface soil. Pearson correlation analysis was performed between the analytical values. The main compounds responsible for the increase in total PAHs were non-carcinogenic phenanthrene and fluoranthene. Therefore, the % content of carcinogenic PAHs decreased with a slope = -0.037 (r = 0.47, p < 0.01), as the total PAH concentration in pine needles increased. Correlations between individual PAHs in pine needles and surface soil were very high when only low-number ring PAHs (2R- and 3R-PAHs) were statistically analyzed and significant when only high-number ring PAHs were statistically analyzed. Low-number ring PAH mainly moves in the gas phase and diffuses into the wax layer, so it was found to be statistically significant with the wax content of pine needles. High-number ring PAHs showed a high correlation with the amount of dust in pine needles because they mainly attached to dust particles and accumulated on the surface of pine needles. The ratios of fluoranthene/pyrene and methylphenanthrene/phenanthrene for predicting the origin of atmospheric PAHs have also been proven valid for pine needles.


Assuntos
Monitoramento Ambiental , Pinus , Hidrocarbonetos Policíclicos Aromáticos , Hidrocarbonetos Policíclicos Aromáticos/análise , Pinus/química , República da Coreia , Folhas de Planta/química , Fenantrenos/análise , Poluentes do Solo/análise , Poluentes Atmosféricos/análise
2.
Anal Bioanal Chem ; 416(6): 1363-1374, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38285226

RESUMO

Several countries have exempted synthetic nicotine from existing regulatory frameworks, resulting in the widespread substitution of synthetic nicotine (SN) in almost all e-cigarette products available. However, it remains uncertain whether the purported synthetic nicotine is indeed genuine SN. There is a need to develop biological indicators and an analytical method that more clearly distinguishes between the two sources. Impurities in neat tobacco-derived nicotine (TDN) were characterized and identified through non-targeted and targeted analysis. Gas chromatography-tandem mass spectrometry (GC-MS/MS) conditions were optimized for detecting biological indicators in e-cigarette products. Nine tobacco-related alkaloids were identified and selected as biological indicators for TDN. A liquid-liquid extraction and GC-MS/MS quantitative method were developed to detect nine biological indicators in e-cigarette products with the limit of quantification ranging from 0.2 to 4.2 µg L-1 using 0.5 mL of e-liquid. This method was applied to 50 e-cigarette brands purchased in the Korean market. The developed method was able to easily and accurately identify the origin of nicotine even using a small amount of e-liquid sample. It is expected that effective e-cigarette regulation will be possible if the nicotine biological indicator and high-sensitivity analysis method developed in this study are used.


Assuntos
Sistemas Eletrônicos de Liberação de Nicotina , Nicotina , Nicotina/análise , Biomarcadores Ambientais , Espectrometria de Massas em Tandem/métodos , Cromatografia Gasosa-Espectrometria de Massas
3.
Biomed Chromatogr ; 36(6): e5360, 2022 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-35261063

RESUMO

A method to determine 8 polychlorinated biphenyls (PCBs), 23 organochlorine pesticides (OCPs) and 16 polycyclic aromatic hydrocarbons (PAHs) was described using dispersive liquid-liquid microextraction (DLLME) of a small amount of plasma or serum sample and gas chromatography-tandem mass spectrometry (GC-MS/MS). The appropriate selection of the extraction solvent and dispersing solvent contributes to a high extraction yield and a clean extract. To verify the developed method, the interference, linearity of the calibration curve, detection limit, precision and accuracy were evaluated. The calibration curves were linear by 2-3 orders of magnitude with correlation coefficients above 0.997 in all cases. The LODs of PCBs, OCPs and PAHs were measured in the ranges of 0.0006-0.0029, 0.001-0.029 and 0.0002-0.012 ng/mL. The intraday precision achieved by this method was 2.19-10.3% (PCBs), 1.65-14.3% (OCPs) and 0.91-12.8% (PAHs), and the intraday accuracy 1.56-7.37% (PCBs), 2.34-19.6% (OCPs) and 1.49-15.7% (PAHs). The advantage of this method is that the analysis of PCBs, OCPs, and PAHs can be performed in a single chromatographic run, and the low detection limit enables monitoring of target substances in low exposure general public samples, and the analysis procedure is relatively simple and fast.


Assuntos
Hidrocarbonetos Clorados , Microextração em Fase Líquida , Praguicidas , Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Humanos , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Solventes/análise , Espectrometria de Massas em Tandem
4.
J Mass Spectrom ; 57(2): e4811, 2022 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-35088484

RESUMO

Tobacco flavors increase the attractiveness of a tobacco brand and ultimately promote addiction. Information about what flavor and how much flavor is in flavor capsules can provide an effective way to regulate tobacco flavor. In this study, 128 flavor chemicals were identified and quantified by gas chromatography-mass spectrometry using libraries and authentic standards. Validation of the developed method was performed for interference, detection limits, calibration curves, accuracy, and precision. Menthol was the main ingredient in all capsules, and the carcinogenic pulegone was detected. Detected menthofuran, benzyl alcohol, geraniol, and eugenol cause toxic or severe irritation, and detected lactones can increase nicotine addiction by inhibiting nicotine metabolism in smokers. Margin of exposures for carcinogenic pulegone and non-carcinogenic menthol were well below safety thresholds, indicating a significant risk of inhalation exposure. It is desirable to prohibit the use of flavor capsules in consideration of human risk.

5.
J Pharm Biomed Anal ; 207: 114397, 2022 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-34626940

RESUMO

A gas chromatography-mass spectrometric (GC-MS) method was developed for the qualitative and quantitative analysis of flavor chemicals in tobacco heating products (THPs), traditional tobacco products (TTPs) and their flavoring capsules. A total of 283 compounds were identified through non-target analysis, and the final 302 compounds were selected to develop an analytical method. The lower limits of detection (LOD) of analytes were 0.00074-12 mg/kg and their LOD range was wide depending on the presence or absence in the reference cigarette. The precision of the 302 compounds was less than 24.5%, and the accuracy ranged from 80.0% to 120%. A total of 190 flavors and 5 contaminants were determined in 21 THP, 10 TTP, 8 THP capsules and 11 TTP capsules. When comparing the total flavor content of flavors per cigarette, it was in the order of THP capsule> TTP capsule ≫ THP ≫ TTP. The correlations between the 53 cigarette products and 190 flavor chemicals were analyzed using PCA. It has been demonstrated that PCA results can be a useful tool in differentiating brands and manufacturers of tobacco products.


Assuntos
Sistemas Eletrônicos de Liberação de Nicotina , Produtos do Tabaco , Cápsulas , Aromatizantes , Calefação , Nicotiana
6.
Artigo em Inglês | MEDLINE | ID: mdl-32811350

RESUMO

A method for the simultaneous determination in mussel of 8 polychlorinated biphenyls (PCBs), 23 organochlorine pesticides (OCPs), and 35 polycyclic aromatic hydrocarbons (PAHs), including alkyl-PAHs, was optimised using ultrasound-assisted cloudy extraction and gas chromatography-tandem mass spectrometry (GC-MS/MS). Optimal selection of the extraction solvent and the dispersing solvent contributed to a high extraction yield and a clean extract. The ranges of the lower limits of detection of PCBs, OCPs and PAHs were 0.012-0.058, 0.01-0.29 and 0.01-0.5 µg kg-1, respectively. The feasibility of the proposed method was validated by analysing standard reference materials of mussel with satisfactory results. The precision achieved by this method was in the range of 0.677-2.69% (PCBs), 1.14-6.60% (OCPs) and 0.694-7.46% (PAHs), and its accuracy was in the range of 101-104% (PCBs), 99.6-106% (OCPs) and 101-110% (PAHs). The advantages of the method include the simultaneous measurement of 66 analytes and the simplicity, low cost and high sensitivity of the procedure. When the proposed method was used to analyse the target compounds in 11 mussel samples, the analytical results displayed a concentration range of 0.41-0.45 µg kg-1 for PCBs, 0.26-6.49 µg kg-1 for OCPs, and 3.48-30.69 µg kg-1 for PAHs.


Assuntos
Bivalves/química , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Animais , Cromatografia Gasosa , Espectrometria de Massas em Tandem , Ondas Ultrassônicas
7.
J Pharm Biomed Anal ; 189: 113460, 2020 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-32663759

RESUMO

N-Nitrosodimethylamine (NDMA) has been detected in some drug substance and drug products containing sartans, ranitidine and metformin. N-nitrosodiethylamine (NDEA) has also been found to be present in some sartan medications. A method for the simultaneous detection of NDMA and NDEA in drug substances and finished products of sartans, metformin and ranitidine has been optimized using isotope dilution, clean-up procedure and gas chromatography-tandem mass spectrometry (GC-MS/MS). The purification of drug substances and excipients was efficient when utilizing precipitation and activated charcoal cartridges. Most of irbesartan, pimasartan, olmesartan, and candesartan were removed by precipitation using solubility difference, while valsartan, rosartan, metformin and ranitidine were completely removed after activated charcoal purification. Even when the extracts were injected in GC-MS/MS more than 100 times, the peak shape and sensitivity did not change, and no peak interference occurred. When a 0.10 g sample was used, the range of the lower limit of detection was 0.07-0.3 µg/kg, and the range of the lower limit of quantification was 0.3-0.9 µg/kg. The precision was in the range of 0.4-2.7 % for NDMA and 0.4-4.2 % for NDEA, and the accuracy was in the range of 95.0-105 % for NDMA and 93.6-104 % for NDEA. NDMA was detected with a concentration of 0.004 mg/kg in a valsartan and 0.012 mg/kg in a ranitidine, and NDEA was detected at concentrations of 0.009 and 0.008 mg/kg in irbesartan and rosartan. Otherwise, NDMA was detected at a concentration of 0.062 mg/kg in a fimasartan product and 0.009 mg/kg in a ranitidine product. This method is available for all drug substances and finished products of sartans; metformin and ranitidine.


Assuntos
Metformina , Preparações Farmacêuticas , Bloqueadores do Receptor Tipo 1 de Angiotensina II , Dimetilnitrosamina/análogos & derivados , Dimetilnitrosamina/análise , Cromatografia Gasosa-Espectrometria de Massas , Ranitidina , Extração em Fase Sólida , Espectrometria de Massas em Tandem
8.
J Expo Sci Environ Epidemiol ; 30(5): 888-897, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-31300710

RESUMO

Mold stain remover (MSR) is used to clean mold and mildew spots from surfaces and contains a variety of chemical substances. In this study, we estimated the inhalation and dermal exposures associated with the use of trigger spray MSRs, and performed screening-level risk assessments for the use of this type of product in Korea. Inhalation and dermal exposures were estimated using exposure algorithms based on exposure factors obtained from a nationwide survey of 10,000 participants and chemical analyses of the four most popular trigger spray MSRs. The hazard quotients (HQs) for noncancer risk and excess cancer risk (ECR) were calculated for each chemical. The mean inhalation exposure estimates for formaldehyde, benzene, chloroform, and carbon tetrachloride were 6.9 × 10-7, 1.7 × 10-7, 5.4 × 10-6, and 2.7 × 10-5 mg/kg/day, respectively. Dermal exposures of the chemicals were 5.7-6.5 times higher than inhalation exposures. The HQs for total exposure were all below 1, which indicated little noncancer risk from the use of MSRs. The safe ECR value of 1 × 10-6, was exceed in one subject for inhalation exposure of benzene and four subjects for dermal exposure of formaldehyde, while 19.8% for dermal exposure of benzene were above this value. Therefore, use of trigger spray MSRs in Korea should require more detailed exposure and risk assessment, especially for benzene.


Assuntos
Benzeno , Exposição por Inalação , Humanos , Exposição por Inalação/efeitos adversos , Exposição por Inalação/análise , República da Coreia , Medição de Risco
9.
J Pharm Biomed Anal ; 174: 115-122, 2019 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-31163345

RESUMO

Benzene (B), toluene (T), ethylbenzene (E), o-, m- and p-xylene (o-, m-, p-X) are ubiquitous and frequently exposed to human throughout the environment. Previously published test methods for phenolic biomarkers are not sensitive enough to be detected in most general population groups and require a lot of labor. A simple and convenient headspace solid-phase microextraction (HS-SPME) gas chromatography-mass spectrometry method was described for the simultaneous determination of 15 hydroxyl biomarkers of BTEX in urine. Hydroxyl biomarkers in urine were vaporized and adsorbed onto a selected fiber after enzyme hydrolysis with ß-glucuronidase/arylsulfatase. The optimal HS-SPME conditions were achieved with an 85-µm-carboxen-polydimethylsiloxane fiber, an extraction temperature of 70 °C, a heating time of 30 min, and a pH of 4.0. The desorption was performed for 1 min at 250 °C. Under the established conditions, the lowest limits of detection were from 0.02 to 0.15 µg/L in 5.0 mL of urine, and the intra- and inter-day relative standard deviations were less than 12.7% at 0.5, 2.0, 50, and 200 µg/L. The calibration curve demonstrated good linearity with greater than r2 = 0.99 in synthetic urine. This method is convenient, simple, environmentally friendly, and amenable to automation.


Assuntos
Derivados de Benzeno/urina , Benzeno/química , Biomarcadores/urina , Tolueno/urina , Xilenos/urina , Adolescente , Calibragem , Criança , Pré-Escolar , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Concentração de Íons de Hidrogênio , Íons , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes , Microextração em Fase Sólida , Temperatura , Urinálise
10.
Anal Chim Acta ; 950: 57-63, 2017 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-27916130

RESUMO

A headspace solid-phase micro extraction (HS-SPME) and gas chromatography-tandem mass spectrometric (GC-MS/MS) method is described to detect hydrazine after derivatization with 1,1,1-trifluoro-2,4-pentanedione (1,1,1-TFPD) to 3-methyl-5-(trifluoromethyl) pyrazole in industrial waste water. The following optimal HS-SPME conditions were used: 85 µm-carboxen-polydimethylsiloxane fibre, 100 mg L-1 TFPD, saturated NaCl, an extraction/derivatization temperature of 80 °C, a heating time of 40 min, and a pH of 9.5. Under the established conditions, the detection and quantification limits were 0.002 µg L-1 and 0.007 µg L-1 by using 5 mL of waste water and the intra- and inter-day relative standard deviations were less than 10.2% at concentrations of 0.02 and 0.1 µg L-1. The calibration curve showed good linearity, with r2 = 0.998; the accuracy was in the range of 98.0-103%; and the precision of the assay was less than 10.2% in industrial waste water. Hydrazine was detected over a concentration range of 0.011-0.074 µg L-1 in 5 of 20 waste water samples.

11.
Anal Bioanal Chem ; 409(5): 1247-1256, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-27826631

RESUMO

An analytical method for the detection of 14 volatile organic compounds (VOCs) was developed to investigate VOCs in refill fluids and cartridges of electronic cigarettes (EC) using headspace solid-phase micro extraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). In total, 14 VOCs were identified and quantified in 283 flavored liquids, 21 nicotine liquids, and 12 disposable cartridges. The detected concentration ranges of the VOCs are as follows: benzene (0.008-2.28 mg L-1), toluene (0.006-0.687 mg L-1), ethylbenzene (0.01-1.21 mg L-1), m-xylene (0.002-1.13 mg L-1), p-xylene (0.007-2.8 mg L-1), o-xylene (0.004-2.27 mg L-1), styrene (0.011-0.339 mg L-1), ethyl acetate (0.3-669.9 mg L-1), ethanol (16-38,742 mg L-1), methanol (66-3375 mg L-1), pyridine (0.077-99.7 mg L-1), acetylpyrazine (0.077-147 mg L-1), 2,3,5-trimethylpyrazine (0.008-96.8 mg L-1), and octamethylcyclotetrasiloxane (0.1-57.2 mg L-1). Benzene, toluene, ethylbenzene, m-xylene, p-xylene, and o-xylene coexisted in samples, which may have originated from the use of petrogenic hydrocarbons as an extraction solvent for flavor and nicotine from natural plants. The maximum detected concentrations of benzene, methanol, and ethanol in liquid samples were found in quantities higher than their authorized maximum limits as residual solvents in pharmaceutical products.


Assuntos
Álcoois/análise , Sistemas Eletrônicos de Liberação de Nicotina , Cromatografia Gasosa-Espectrometria de Massas/métodos , Microextração em Fase Sólida/métodos , Compostos Orgânicos Voláteis/análise
12.
J Cancer Prev ; 21(3): 187-193, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-27722145

RESUMO

BACKGROUND: Despite major advances in lung cancer treatment, early detection remains the most promising way of improving outcomes. To detect lung cancer in earlier stages, many serum biomarkers have been tested. Unfortunately, no single biomarker can reliably detect lung cancer. We combined a set of 2 tumor markers and 4 inflammatory or metabolic markers and tried to validate the diagnostic performance in lung cancer. METHODS: We collected serum samples from 355 lung cancer patients and 590 control subjects and divided them into training and validation datasets. After measuring serum levels of 6 biomarkers (human epididymis secretory protein 4 [HE4], carcinoembryonic antigen [CEA], regulated on activation, normal T cell expressed and secreted [RANTES], apolipoprotein A2 [ApoA2], transthyretin [TTR], and secretory vascular cell adhesion molecule-1 [sVCAM-1]), we tested various sets of biomarkers for their diagnostic performance in lung cancer. RESULTS: In a training dataset, the area under the curve (AUC) values were 0.821 for HE4, 0.753 for CEA, 0.858 for RANTES, 0.867 for ApoA2, 0.830 for TTR, and 0.552 for sVCAM-1. A model using all 6 biomarkers and age yielded an AUC value of 0.986 and sensitivity of 93.2% (cutoff at specificity 94%). Applying this model to the validation dataset showed similar results. The AUC value of the model was 0.988, with sensitivity of 93.33% and specificity of 92.00% at the same cutoff point used in the validation dataset. Analyses by stages and histologic subtypes all yielded similar results. CONCLUSIONS: Combining multiple tumor and systemic inflammatory markers proved to be a valid strategy in the diagnosis of lung cancer.

13.
J Chromatogr A ; 1448: 115-120, 2016 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-27130584

RESUMO

A simple and convenient headspace solid-phase microextraction (HS-SPME) gas chromatography mass spectrometry (GC-MS) method was described for the determination of glutaraldehyde in water. Glutaraldehyde in water reacted with 2,2,2-trifluoroethylhydrazine (TFEH) in a headspace vial and the formed TFEH derivatives were vaporized and adsorbed onto a fiber. The optimal HS-SPME conditions were achieved with a 50/30µm-divinylbenzene-carboxen-polydimethylsiloxane fiber, 0.06% 2,2,2-TFEH, 25% salt, an extraction/derivatization temperature of 80°C, a heating time of 30min, and a pH of 6.5. The desorption was performed for 1min at 240°C. Under the established conditions, the lowest limits of detection were 0.3µg/L and 0.1µg/L in 6.0mL of surface water and drinking water, respectively, and the intra- and inter-day relative standard deviation was less than 9.1% at concentrations of 50, 100 and 500µg/L. The calibration curve showed good linearity with R=0.9995 and R=0.9993 in surface water and drinking water, respectively. This method is simple, amenable to automation and environmentally friendly.


Assuntos
Glutaral/análise , Hidrazinas/química , Poluentes Químicos da Água/análise , Dimetilpolisiloxanos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Indicadores e Reagentes , Polivinil , Microextração em Fase Sólida/métodos , Temperatura
14.
15.
J Chromatogr A ; 1407: 216-21, 2015 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-26162669

RESUMO

A simple and convenient method to detect fluoride in biological samples was developed. This method was based on derivatization with 2-(bromomethyl)naphthalene, headspace solid phase microextraction (HS-SPME) in a vial, and gas chromatography-tandem mass spectrometric detection. The HS-SPME parameters were optimized as follows: selection of CAR/PDMS fiber, 0.5% 2-(bromomethyl)naphthalene, 250 mg/L 15-crown-5-ether as a phase transfer catalyst, extraction and derivatization temperature of 95 °C, heating time of 20 min and pH of 7.0. Under the established conditions, the lowest limits of detection were 9 and 11 µg/L in 1.0 ml of plasma and urine, respectively, and the intra- and inter-day relative standard deviation was less than 7.7% at concentrations of 0.1 and 1.0 mg/L. The calibration curve showed good linearity of plasma and urine with r=0.9990 and r=0.9992, respectively. This method is simple, amenable to automation and environmentally friendly.


Assuntos
Análise Química do Sangue/métodos , Fluoretos/análise , Cromatografia Gasosa-Espectrometria de Massas , Microextração em Fase Sólida , Urinálise/métodos , Calibragem , Fluoretos/sangue , Humanos , Limite de Detecção , Temperatura
16.
J Chromatogr Sci ; 53(6): 841-8, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-25404560

RESUMO

Electronic cigarettes (E-cigarettes) are devices that are refilled with replacement liquids, which normally contain propylene glycol, nicotine and the desired flavor blend. Many consumers suspect that hazardous substances are present in addition to nicotine content. In this study, eight contaminated compounds in 105 replacement liquids from 11 types of E-cigarettes sold in the Republic of Korea were identified and quantified by gas chromatography-mass spectrometry. Diethyl phthalate and diethylhexyl phthalate were detected in concentration ranges of 0.01-1745.20 mg/L (47.6% detection frequency) and 0.06-81.89 mg/L (79.1% detection frequency) in the replacement liquids. Triethylene glycol, tetraethylene glycol and pentaethylene glycol were quantified in concentration ranges of 0.1-19.3 mg/L (10.5% detection frequency), 0.1-30.1 mg/L (12.4% detection frequency) and 0.1-24.9 mg/L (6.7% detection frequency) in the same samples. cis-3-Hexene-1-ol, methyl cinnamate and dodecane were quantified in concentration ranges of 0.03-3267.46 mg/L (70.5% detection frequency), 4.41-637.54 mg/L (6.7% detection frequency) and 0.01-639.96 mg/L (47.6% detection frequency) in the samples.


Assuntos
Contaminação de Medicamentos , Sistemas Eletrônicos de Liberação de Nicotina , Substâncias Perigosas/análise , Nicotina/química , Ácidos Ftálicos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Substâncias Perigosas/química , Substâncias Perigosas/isolamento & purificação , Limite de Detecção , Modelos Lineares , Ácidos Ftálicos/química , Ácidos Ftálicos/isolamento & purificação , Reprodutibilidade dos Testes
17.
Anal Chem ; 87(2): 975-81, 2015 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-25486065

RESUMO

A novel derivatization method of free cyanide (HCN + CN(-)) including cyanogen chloride in chlorinated drinking water was developed with d-cysteine and hypochlorite. The optimum conditions (0.5 mM D-cysteine, 0.5 mM hypochlorite, pH 4.5, and a reaction time of 10 min at room temperature) were established by the variation of parameters. Cyanide (C(13)N(15)) was chosen as an internal standard. The formed ß-thiocyanoalanine was directly injected into a liquid chromatography-tandem mass spectrometer without any additional extraction or purification procedures. Under the established conditions, the limits of detection and the limits of quantification were 0.07 and 0.2 µg/L, respectively, and the interday relative standard deviation was less than 4% at concentrations of 4.0, 20.0, and 100.0 µg/L. The method was successfully applied to determine CN(-) in chlorinated water samples. The detected concentration range and detection frequency of CN(-) were 0.20-8.42 µg/L (14/24) in source drinking water and 0.21-1.03 µg/L (18/24) in chlorinated drinking water.

18.
Anal Chim Acta ; 852: 168-73, 2014 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-25441894

RESUMO

A gas chromatography-tandem mass spectrometric (GC-MS/MS) method has been established for the determination of cyanide in surface water. This method is based on the derivatization of cyanide with 2-(dimethylamino)ethanethiol in surface water. The following optimum reaction conditions were established: reagent dosage, 0.7 g L(-1) of 2-(dimethylamino)ethanethiol; pH 6; reaction carried out for 20 min at 60°C. The organic derivative was extracted with 3 mL of ethyl acetate, and then measured by using GC-MS/MS. Under the established conditions, the detection and quantification limits were 0.02 µg L(-1) and 0.07 µg L(-1) in 10-mL of surface water, respectively. The calibration curve had a linear relationship relationship with y=0.7140x+0.1997 and r(2)=0.9963 (for a working range of 0.07-10 µg L(-1)) and the accuracy was in a range of 98-102%; the precision of the assay was less than 7% in surface water. The common ions Cl(-), F(-), Br(-), NO3(-), SO4(2-), PO4(3-), K(+), Na(+), NH4(+), Ca(2+), Mg(2+), Ba(2+), Mn(4+), Mn(2+), Fe(3+), Fe(2+) and sea water did not interfere in cyanide detection, even when present in 1000-fold excess over the species. Cyanide was detected in a concentration range of 0.07-0.11 µg L(-1) in 6 of 10 surface water samples.

19.
Anal Chim Acta ; 852: 162-7, 2014 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-25441893

RESUMO

A gas chromatography-mass spectrometric method was developed in this study in order to determine fluoride in plasma and urine after derivatization with 2-(bromomethyl)naphthalene. 2-Fluoronaphthalene was chosen as the internal standard. The derivatization of fluoride was performed in the biological sample and the best reaction conditions (10.0 mg mL(-1) of 2-(bromomethyl)naphthalene, 1.0 mg mL(-1) of 15-crown-5-ether as a phase transfer catalyst, pH of 7.0, reaction temperature of 70°C, and heating time of 70 min) were established. The organic derivative was extracted with dichloromethane and then measured by a gas chromatography-mass spectrometry. Under the established condition, the detection limits were 11 µg L(-1) and 7 µg L(-1) by using 0.2 mL of plasma or urine, respectively. The accuracy was in a range of 100.8-107.6%, and the precision of the assay was less than 4.3% in plasma or urine. Fluoride was detected in a concentration range of 0.12-0.53 mg L(-1) in six urine samples after intake of natural mineral water containing 0.7 mg L(-1) of fluoride.


Assuntos
Fluoretos/sangue , Fluoretos/urina , Cromatografia Gasosa-Espectrometria de Massas/métodos , Calibragem , Fluoretos/isolamento & purificação , Humanos , Limite de Detecção , Naftalenos/química
20.
J Chromatogr A ; 1361: 117-24, 2014 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-25130090

RESUMO

A liquid chromatography-tandem mass spectrometry method (LC-MS/MS) was developed in order to determine the amount of acrylamide in foods after derivatization with d-cysteine. The sulfhydryl group of d-cysteine was added at the ß-site double bond of acrylamide to form 2-amino-3-(3-amino-3-oxo-propyl)sulfanyl-propanoic acid. Deuterated acrylamide (acrylamide-d3) was chosen as the internal standard (IS) for analyzing the food samples. Acrylamide was extracted from 2.0 g of food sample with 6 mL of methylene chloride, and the organic extract was diluted with 3 mL of hexane, and then the analyte was back-extracted with 0.5 mL of pure water. The derivatization of acrylamide was performed in the water extract. The best reaction conditions (3.0mg of d-cysteine, a pH 6.5, a reaction temperature of 90°C, and a heating time of 50 min) were established by the variation of parameters. The formed derivative was injected into the LC-MS/MS without further extraction or purification procedures. Separation and detection were improved with the use of an ion-pairing reagent of perfluorooctanoic acid. Under the established conditions, the limits of detection and the limits of quantification were 0.04 µg/kg and 0.14 µg/kg, respectively, and the inter-day relative standard deviation was less than 8% at concentrations of 20 and 100 µg/kg. The method was successfully applied to determine the amount of acrylamide in potato chips, French fries, and coffee.


Assuntos
Acrilamida/análise , Cromatografia Líquida de Alta Pressão/métodos , Cisteína/análogos & derivados , Análise de Alimentos/métodos , Espectrometria de Massas em Tandem/métodos , Café/química , Concentração de Íons de Hidrogênio , Limite de Detecção , Solanum tuberosum/química , Temperatura
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