RESUMEN
Henna is a plant-based dye obtained from the powdered leaf of the pigmented plant Lawsonia inermis, and has often been used for grey hair dyeing, treatment, and body painting. As a henna product, the leaves of Indigofera tinctoria and Cassia auriculata can be blended to produce different colour variations. Although allergy from henna products attributed to p-phenylenediamine, which is added to enhance the dye, is reported occasionally, raw material plants of henna products could also contribute to the allergy. In this study, we reported that raw material plants of commercial henna products distributed in Japan can be estimated by LC-high resolution MS (LC-HRMS) and multivariate analysis. Principal Component Analysis (PCA) score plot clearly separated 17 samples into three groups [I; henna, II; blended henna primarily comprising Indigofera tinctoria, III; Cassia auriculata]. This grouping was consistent with the ingredient lists of products except that one sample listed as henna was classified as Group III, indicating that its ingredient label may differ from the actual formulation. The ingredients characteristic to Groups I, II, and III by PCA were lawsone (1), indirubin (2), and rutin (3), respectively, which were reported to be contained in each plant as ingredients. Therefore, henna products can be considered to have been manufactured from these plants. This study is the first to estimate raw material plants used in commercial plant-based dye by LC-HRMS and multivariate analysis.
Asunto(s)
Espectrometría de Masas , Análisis Multivariante , Hojas de la Planta/química , Lawsonia (Planta)/química , Indigofera/química , Colorantes/química , Colorantes/análisis , Cassia/química , Cromatografía Liquida , Cromatografía Líquida de Alta Presión , Análisis de Componente Principal , Naftoquinonas/química , Naftoquinonas/análisis , Estructura MolecularRESUMEN
In Japan, the use of frame retardants [tris(2,3-dibromopropyl)phosphate: TDBPP and bis(2,3-dibromopropyl)phosphate: BDBPP] in several household textile products is banned under the "Act on the Control of Household Products Containing Harmful Substances." As the official analytical methods for testing these substances have not been revised for over 42 years, several issues such as the using of harmful reagents, have been pointed out. Therefore, we developed a new method to revise the official method in our previous study. In this study, the validity of the developed test method is evaluated at six laboratories using two types of textile samples spiked with TDBPP and BDBPP at three concentrations (4, 8, and 20 µg/g). TDBPP and BDBPP are extracted under reflux using methanol containing hydrochloric acid. TDBPP is analyzed using GC-MS, and BDBPP is also analyzed using GC-MS after methylation with trimethylsilyl diazomethane. Although the accuracy (70-120%), repeatability (<10%), and reproducibility (<15%) of a few samples, mainly low concentration samples, are out of range, overall, the concentration level of detection limits of TDBPP and BDBPP (8 and 10 µg/g) in official analytical methods are quantifiable with sufficient precision using the proposed method. Furthermore, harmful reagents are not used in this method. Thus, the method validated in this study is effective as a revised method for the testing of TDBPP and BDBPP in household textile products.
Asunto(s)
Organofosfatos , Fosfatos , Reproducibilidad de los Resultados , Productos DomésticosRESUMEN
BACKGROUND: In recent years, due to the global shortage of helium gas, the development of gas chromatography (GC) analytical methods using alternatives to helium carrier gases is necessary. OBJECTIVE: The objective of this study was to examine the applicability of hydrogen and nitrogen as alternative carrier gases using the test method for azo compounds in the Act on Control of Household Products Containing Harmful Substances of Japan. METHOD: The gas chromatograph mass spectrometer (GC-MS) analytical method using hydrogen and nitrogen as alternative carrier gases was compared with a method using helium for 26 primary aromatic amines (PAAs) originated from azo dyes. RESULTS: When hydrogen and nitrogen were used as carrier gases under the same conditions used during analysis using helium (same column, gas flow rate, oven temperature conditions, etc.), sufficient peak separation of 26 PAAs was obtained. The sensitivities of the methods using helium and hydrogen were comparable, whereas the sensitivity was lower when nitrogen was used, with the detection limits ranging from 1/220 to 1/25. However, all carrier gases achieved quantification at concentrations below the standard value (30 µg/g) of the Act on Control of Household Products Containing Harmful Substances, and the results were in agreement with the standard value for the target product. CONCLUSIONS: Our results indicated that hydrogen or nitrogen can be used as alternative carrier gases to helium for GC-MS analysis of azo compounds producing specific aromatic amines. HIGHLIGHTS: Using hydrogen or nitrogen as an alternative carrier gas to helium, azo compounds could be quantified with excellent accuracy.
Asunto(s)
Compuestos Azo , Helio , Cromatografía de Gases y Espectrometría de Masas/métodos , Helio/química , Compuestos Azo/análisis , Cromatografía de Gases , Aminas/análisis , Textiles/análisis , Hidrógeno/química , NitrógenoRESUMEN
Polycyclic aromatic hydrocarbons (PAHs) in creosote products used for wood preservation are regulated in Japan. Although the analytical method for this regulation has been stipulated by law, two main problems have been highlighted, namely the use of dichloromethane, a potential carcinogen, as a solvent and inadequate purification. Therefore, an analytical method to solve these problems was developed in this study. Actual creosote-treated wood samples were examined, and it was found that acetone could be used as an alternative solvent. Purification methods using centrifugation, silica gel cartridges, and strong anion exchange (SAX) cartridges were also developed. It was found that the SAX cartridges strongly retained PAHs, and an effective purification method was developed using this phenomenon, in which contaminants were removed by washing with diethyl ether/hexane (1/9 v/v), which could not be achieved with a silica gel cartridge. This strong retention was attributed to cation-π interactions. The analytical method developed in this study yielded good recoveries (81.4-113.0%) with low relative standard deviations (<6.8%), and the limit of quantification (0.02-0.29 µg/g) was significantly lower than the current creosote product regulation. Therefore, this method can safely and effectively extract and purify PAHs from creosote products.
Asunto(s)
Creosota , Hidrocarburos Policíclicos Aromáticos , Gel de Sílice , Madera , SolventesRESUMEN
The objectives of this study were to develop a novel analytical method for quantifying vinyl chloride (VC) emitted from aerosol products, to provide analytical data on VC in aerosol products, and to evaluate consumer VC exposure by aerosol products. Our quantitative method involves absorbing VC into dimethyl sulfoxide and analyzing it using headspace gas chromatography/mass spectrometry. The correlation coefficients of the VC calibration curves were ≥ 0.9994 in the range of 0.16-80 µg/mL VC standard gases, which were prepared under either nitrogen or emission gases containing dimethyl ether or liquid petroleum gas. VC concentrations in these emission gases were calculated using a VC calibration curve from standard gases prepared under nitrogen; they were within ± 10% of the actual concentrations. We analyzed 39 household aerosol products; VC concentrations of 0.095, 0.098, and 0.28 µg/L were detected in three polyvinyl chloride spray paints. Consumer VC inhalation exposure level was estimated through an exposure scenario, and the hazard quotient was confirmed to be very low when comparing the exposure level with a cancer risk level of 10-5 for inhaled VC. These results suggest that the human health risk from VC in spray paint was low.
Asunto(s)
Cloruro de Vinilo , Humanos , Cloruro de Vinilo/análisis , Cloruro de Polivinilo , Aerosoles , Gases/química , Nitrógeno/análisis , Medición de RiesgoRESUMEN
Transient Receptor Potential Ankyrin 1 (TRPA1), which is expressed in the airways, has causative and exacerbating roles in respiratory diseases. TRPA1 is known as a target of sick building syndrome-related air pollutants, such as formaldehyde. Thus, an in vitro TRPA1 activation assay would be useful for predicting the potential risk of air pollution. In this study, we used human TRPA1 (hTRPA1)- and mouse TRPA1 (mTRPA1)-expressing cell lines to measure TRPA1 activation by the emerging indoor air pollutants 2-ethyl-1-hexanol (2-EH), a mixture of 2,2,4-trimethyl-1,3-pentanediol 1- and 3-monoisobutyrate (Texanol), and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB). The results indicated that 2-EH activated both hTRPA1 and mTRPA1 in a concentration-dependent manner, whereas TXIB did not activate hTRPA1 or mTRPA1. Texanol also activated hTRPA1 in a concentration-dependent manner. In contrast, a bell-shaped concentration-dependent curve was observed for mouse TRPA1 activation by Texanol, indicating inhibitory effects at a higher concentration range, which was also reported for menthol, a typical TRPA1 modulator. To further elucidate the mechanism underlying the species difference in TRPA1 activation by Texanol, V875G and G878V mutations were introduced into hTRPA1 and mTRPA1, respectively, which were reported to be key mutations for the inhibitory effect of menthol. These mutations switched the inhibitory effects of Texanol; thus, hTRPA1/V875G, but not mTRPA1/G878V, was inhibited at higher concentrations of Texanol. These results indicate that Texanol shares an interaction site with menthol. Overall, these findings suggest that careful interpretation is necessary when extrapolating rodent TRPA1-dependent toxicological effects to humans, especially with respect to the risk assessment of indoor air pollutants.
Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire Interior , Humanos , Ratones , Animales , Contaminación del Aire Interior/efectos adversos , Contaminación del Aire Interior/análisis , Mentol , Especificidad de la Especie , Contaminantes Atmosféricos/toxicidad , Canal Catiónico TRPA1/genéticaRESUMEN
BACKGROUND: Several primary aromatic amines (PAAs) have been designated carcinogenic or suspected of carcinogenicity. Several kinds of PAAs may occur either via the reduction of azo compounds or as impurities in azo colorants or other agents. OBJECTIVE: An analytical method was developed and applied to determine whether certain PAAs are present as impurities in synthetic organic colorants. METHOD: Target chemicals were analyzed by the ultrasound extraction of the synthetic organic colorant with a hydrochloric acid solution containing 20% methanol, followed by conversion from an acidic to alkaline solution, and then extraction using a diatomaceous earth column. RESULTS: We analyzed certain PAAs in 38 synthetic organic colorants, resulting in the detection of 2,4-dimethylaniline in four samples at 1.2 to 19 µg/g, o-toluidine in three samples at 1.0 to 3.4 µg/g, p-phenylazoaniline in two samples at 74 to 305 µg/g, and, in one sample each, 2,4,5-trimethylaniline (13 µg/g), 5-nitro-o-toluidine (12 µg/g), and 2-methyl-4-(2-tolylazo)aniline (13 µg/g). Nearly all PAAs were determined to be starting materials for colorant synthesis, although p-phenylazoaniline in Yellow No. 407 was apparently a byproduct formed during synthesis. For Red No. 225, in which high concentrations of p-phenylazoaniline were detected, additional samples were purchased from five companies, and p-phenylazoaniline was detected at concentrations of 88 to 370 µg/g in all samples. CONCLUSIONS: A method to analyze certain PAAs contained as impurities in synthetic organic colorants was developed, and the actual status of them in colorants was clarified. HIGHLIGHTS: The analytical method developed in this study for the determination of certain PAAs contained as impurities in synthetic organic colorants may be used to improve the safety of colorants.
Asunto(s)
Compuestos de Anilina , Colorantes , AminasRESUMEN
There has been extensive studies on the composition of tires and industrial rubber. However, there is insufficient information on volatile organic compounds (VOCs) emitted from rubber granule products used to fill synthetic turf fields. In this study, we applied a passive sampling method for assessing the VOCs emitted from rubber granule products used for filling synthetic turf fields. We also performed a quantitative component analysis using a gas chromatography-mass spectrometer (GC-MS). The component analysis results of 46 rubber granule-based products showed the predominant presence of benzothiazole and methyl isobutyl ketone. The level of benzene, which the International Agency for Research on Cancer classifies as a substance with sufficient evidence for carcinogenicity to humans, was below the lower quantification limit in the products tested in this study. Our study included most of the rubber granule products used for synthetic turf fields in Japan (>95% of the products in the current domestic market of Japan). Therefore, we obtained a comprehensive overview of the VOCs emitted from the rubber granule-based products used in Japan's synthetic turf fields. Estimating the exposure to these airborne VOCs is essential to evaluate the adverse health effects of the VOCs emitted from these rubber granule-based products. Our sampling method and results can help provide key data for such risk assessment studies in the future.
Asunto(s)
Elastómeros , Compuestos Orgánicos Volátiles , Humanos , Japón , Medición de Riesgo , GomaRESUMEN
Since the Coronavirus Disease 2019 (COVID-19) pandemic began, people have been wearing face masks for many hours every day. As these face masks are in contact with the skin, it is important to pay more attention to their quality and safety. This study examined the concentration of free formaldehyde in 90 non-medical face masks and related products (33 nonwoven, 30 woven cloth, 12 polyurethane, and 15 related products) because formaldehyde is a common contact allergen in textile products. For products consisting of mixed materials, each material was sampled, resulting in 103 samples for analysis. Free formaldehyde (34-239 µg/g) was found in three cloth masks, which consisted of cotton and polyester, with antibacterial and antiviral labeling. It was confirmed that the detected formaldehyde originated from the mask-finishing treatment by a hydrochloric acid extraction discrimination test. These masks may elicit contact dermatitis if the consumers have already been sensitized to formaldehyde. However, the risk of contact dermatitis caused by formaldehyde in masks may be considered low since the frequency of formaldehyde detection in masks in Japan is low.
Asunto(s)
COVID-19 , Dermatitis por Contacto , COVID-19/epidemiología , COVID-19/prevención & control , Dermatitis por Contacto/epidemiología , Formaldehído/toxicidad , Humanos , Japón , Máscaras , Pandemias , SARS-CoV-2RESUMEN
The sensitivity of the 3M TM Molecular Detection Assay 2-STEC Gene Screen (stx) assay (3M MDA2 STEC assay) was evaluated for verotoxin (VT) gene screening from food materials. The pure culture and foods such as sliced beef, tandoori paste, cucumber, etc. were used for this study. The sensitivity was obtained as 3 to 4 log CFU/mL in enrichment broth (BPW and mEC), which was cultured with food matrices. These results showed this detection kit was suitable the notification of standard methods from Ministry of health, which requires 4 log CFU/mL as detection limit in enrichment broth. This assay was useful as a rapid and simple screening method for VT gene from foods.
Asunto(s)
Contaminación de Alimentos , Microbiología de Alimentos , Toxina Shiga , Escherichia coli Shiga-Toxigénica , Animales , Bovinos , Escherichia , Escherichia coli Shiga-Toxigénica/genéticaRESUMEN
In Japan, the use of methanol, trichloroethylene, and tetrachloroethylene in aerosol household products is banned under the Act on the Control of Household Products Containing Harmful Substances. As the official analytical methods for testing for these substances have not been revised for over 35 years, several issues have been pointed out. Thus, we developed a new method to revise the official method in our previous study. In this study, validation of the proposed method for detecting the target substances was conducted using two aerosol-product samples (A and B), which contained methanol, trichloroethylene, and tetrachloroethylene. Sample A comprised regulated values of these compounds, while sample B comprised one-tenth of the regulated amounts. They also contained several volatile compounds that served as interfering substances. Subsequently, the samples were analyzed using head space/gas chromatography-mass spectrometry, and it was confirmed that the three target substances were separated from the other chemicals on chromatograms. Validation tests were conducted at seven laboratories to evaluate the proposed method using the prepared samples. In one laboratory, the recovery of trichloroethylene and tetrachloroethylene in sample B was slightly higher at 120%, while the recoveries obtained from the other tests were between 70% and 120%. Relative standard deviation at each laboratory was less than 10%. Furthermore, the relative standard deviations between the validation tests with respect to each chemical were less than 15%. Therefore, the method validated in this study was considered to be effective as a revised method for testing for methanol, trichloroethylene, and trichloroethylene in household aerosol products.
Asunto(s)
Aerosoles/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Cromatografía de Gases y Espectrometría de Masas/estadística & datos numéricos , Productos Domésticos/análisis , Productos Domésticos/normas , Metanol/análisis , Tetracloroetileno/análisis , Tricloroetileno/análisis , Aerosoles/efectos adversos , Productos Domésticos/efectos adversos , Japón , Metanol/efectos adversos , Tetracloroetileno/efectos adversos , Tricloroetileno/efectos adversosRESUMEN
BACKGROUND: The static headspace technique is one of the most popular techniques for residual solvent analysis and dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) are widely use as the dissolution media. OBJECTIVE: This study aims to establish ethyl lactate (EL), a solvent with low toxicity and less environmental impact, as an alternative dissolution medium to DMSO and DMF for the static headspace analysis of toxic residual solvents in food, cosmetics, and similar complex organic matrices. METHODS: Samples (a sample of dietary supplement and two samples each of cosmetics and household products) spiked with benzene, carbon tetrachloride, 1,2-dichloroethane, 1,1-dichloroethene, and 1,1,1-trichloroethane were dissolved in EL, DMSO, and DMF. Static headspace GC/MS and the standard addition method were used to detect and quantify the residual solvents. RESULTS: The dissolution and dispersion of these samples, especially the ones which were water-insoluble, were better than those in DMSO and DMF. The recoveries, except that of benzene in an aerosol spray, in EL ranged from 77 to 110%. The relative SDs in EL ranged from 2.5 to 11% and were better or equivalent to those in DMSO and DMF. CONCLUSIONS: EL was suitable as the dissolution medium for such samples, which may contain large amounts of organic solvents or various ingredients, in static headspace GC/MS analysis of residual solvents.
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Cosméticos , Suplementos Dietéticos , Lactatos , Solubilidad , SolventesRESUMEN
ãCurrently, indoor air quality guidelines for formaldehyde and acetaldehyde are set by the Ministry of Health, Labour and Welfare of Japan. Aldehydes are widely used in adhesives and preservatives, and exposure to these compounds via indoor air is a matter of concern. Considering that contact with indoor air is part of daily life, evaluation of indoor air quality is extremely important. 2,4-Dinitrophenylhydrazine (DNPH) derivatization is widely used for quantitative analysis of aldehydes. A certified reference material with traceability to the International System of Units (SI) is required for this method. However, currently, there are no certified reference materials available for aldehyde-DNPH derivatives, which means that the quantified values obtained by this method are not sufficiently reliable. In this study, we determined the actual content and purity of commercially available aldehyde-DNPH derivatives using 1H-quantitative NMR (qNMR), which can be measured with SI-traceability. Although the commercial DNPH derivatives of formaldehyde and acetaldehyde were low concentration solutions, we were able to determine their purities using 1H-qNMR. Furthermore, we were able to separate and quantify the acetaldehyde isomers generated by the derivatization reaction. In conclusion, it is possible to obtain highly accurate results using 1H-qNMR with commercially available reagents that are not certified metrologically.
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Acetaldehído/análisis , Contaminación del Aire Interior/análisis , Exposición a Riesgos Ambientales/análisis , Formaldehído/análisis , Espectroscopía de Resonancia Magnética/métodos , Hidrógeno , FenilhidrazinasRESUMEN
"Licorice oil extract" (LOE) (antioxidant agent) is described in the notice of Japanese food additive regulations as a material obtained from the roots and/or rhizomes of Glycyrrhiza uralensis, G. inflata or G. glabra. In this study, we aimed to identify the original Glycyrrhiza species of eight food additive products using LC/MS. Glabridin, a characteristic compound in G. glabra, was specifically detected in seven products, and licochalcone A, a characteristic compound in G. inflata, was detected in one product. In addition, Principal Component Analysis (PCA) (a kind of multivariate analysis) using the data of LC/MS or (1)H-NMR analysis was performed. The data of thirty-one samples, including LOE products used as food additives, ethanol extracts of various Glycyrrhiza species and commercially available Glycyrrhiza species-derived products were assessed. Based on the PCA results, the majority of LOE products was confirmed to be derived from G. glabra. This study suggests that PCA using (1)H-NMR analysis data is a simple and useful method to identify the plant species of origin of natural food additive products.
Asunto(s)
Aditivos Alimentarios/química , Glycyrrhiza/química , Glycyrrhiza/clasificación , Extractos Vegetales/química , Aceites de Plantas/química , Raíces de Plantas/química , Chalconas/análisis , Cromatografía Liquida , Etanol , Isoflavonas/análisis , Espectroscopía de Resonancia Magnética/métodos , Espectrometría de Masas , Fenoles/análisis , ProtonesRESUMEN
Microcystins, which are cyclic heptapeptides produced by some cyanobacterial species from algal blooms, strongly inhibit serine/threonine protein phosphatase and are known as hepatotoxins. Microcystins have many structural variations, yet insufficient information is available on the differences in the cytotoxic potentials among the structural variants. In this study, the cytotoxicities of 16 microcystin variants at concentrations of 0.03-10 µg/mL to primary cultured rat hepatocytes were determined by measuring cellular ATP content, and subsequently determined by their 50% inhibitory concentration (IC50). Differences in the amino acid constituents were associated with differences in cytotoxic potential. [D-Asp3, Z-Dhb7] microcystin-LR exhibited the strongest cytotoxicity at IC50 of 0.053 µg/mL among the microcystin variants tested. Furthermore, [d-Asp3, Z-Dhb7] microcystin-HtyR was also highly cytotoxic. These results suggest that both D-Asp and Z-Dhb residues are important in determining the cytotoxic potential of microcystin variants.
Asunto(s)
Aminoácidos/química , Hepatocitos/efectos de los fármacos , Microcistinas/toxicidad , Animales , Células Cultivadas , Hepatocitos/metabolismo , Concentración 50 Inhibidora , Toxinas Marinas , Microcistinas/química , Fosfoproteínas Fosfatasas/metabolismo , Ratas , Ratas Sprague-DawleyRESUMEN
Fullerenes C60 have attracted considerable attention in the biomedical field due to their interesting properties. Although there has been a concern that C60 could be metabolized to hydroxylated fullerenes (C60(OH)x) in vivo, there is little information on the effect of hydroxylated C60 on liver cells. In the present study, we evaluated the cytotoxic effects of fullerene C60 and various hydroxylated C60 derivatives, C60(OH)2, C60(OH)6-12, C60(OH)12 and C60(OH)36, with three different types of liver cells, dRLh-84, HepG2 and primary cultured rat hepatocytes. C60, C60(OH)2 and C60(OH)36 exhibited little or no cytotoxicity in all of the cell types, while C60(OH)6-12 and C60(OH)12 induced cytotoxic effects in dRLh-84 cells, accompanied by the appearance of numerous vacuoles around the nucleus. Moreover, mitochondrial activity in liver cells was significantly inhibited by C60(OH)6-12 and C60(OH)12. These results indicate that the number of hydroxyl groups on C60(OH)x contribute to the difference of their cytotoxic potential and mitochondrial damage in liver cells.