Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 31
Filtrar
1.
Sci Total Environ ; 857(Pt 2): 159485, 2023 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-36257444

RESUMO

Recycled tire crumb rubber (RTCR) surfaces contain harmful and carcinogenic substances, which can be ingested by the users of these facilities, mainly athletes and children. In this work, the potential in-vitro oral bioaccessibility of eighteen polycyclic aromatic hydrocarbons (PAHs) from RTCR employed as infill in synthetic football fields was studied in human synthetic body fluids (saliva, gastric, duodenal and bile), prepared according the Unified Bioaccessibility Method. Solid-phase extraction (SPE) using commercial sorbents and a new green material based on cork (cork industry by-product) were used to isolate the bioaccessible PAHs before gas chromatography-tandem mass spectrometry analysis. The method was optimized and validated attending the analytical figures of merit. The feasibility of cork biosorbent for the extraction of the compounds was demonstrated, as well as the suitability of the UBM method to perform the digestion with good precision. The application to real samples collected from football fields demonstrated the presence of 17 of the 18 target PAHs in the biofluids. Most volatile PAHs such as NAP, ACY, ACE, FLU, PHN and ANC, achieved the highest bioaccessibility percentage levels. The carcinogenic B[a]P was detected in 75 % of the samples at concentrations up to 2.5 ng g-1 (bioaccessible fraction). Children exposure assessment was carried out to identify potential risk. Other hazardous and environmentally problematic compounds such as N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-quinone), recently related with the dead of coho salmon, and hexamethoxymethylmelamine (HMMM), among others, were also detected. This is the first study in which the bioaccesibility from real crumb rubber samples of 15 out of the 16 PAHs considered as priority pollutants by the United States Environmental Protection Agency (EPA) and the presence of 6PPD-quinone and HMMM in the bioaccessible fractions is reported.


Assuntos
Benzoquinonas , Carcinógenos , Exposição Ambiental , Futebol Americano , Fenilenodiaminas , Hidrocarbonetos Policíclicos Aromáticos , Borracha , Triazinas , Criança , Humanos , Carcinógenos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Policíclicos Aromáticos/análise , Borracha/química , Fenilenodiaminas/análise , Benzoquinonas/análise , Triazinas/análise , Líquidos Corporais
2.
J Food Drug Anal ; 27(3): 825-831, 2019 07.
Artigo em Inglês | MEDLINE | ID: mdl-31324298

RESUMO

Phenylenediamines (PDs), which are reported to cause allergic dermatitis and possess genotoxicity and carcinogenicity, are the ingredients used in permanent hair dyes. The fluorescent derivatization strategy coupled with micellar electrokinetic chromatography (MEKC) were established to analyze four PDs, including o-phenylenediamine (OPD), m-phenylenediamine (MPD), p-phenylenediamine (PPD) and toluene-2,5-diamine (PTD). Additionally, 5-(4, 6-dichlorotriazinyl) aminofluorescein (DTAF) was used as a fluorescent reagent derived at amino groups of PDs and underwent nucleophilic substitution reaction to improve the detection sensitivity. The derivatization condition reacted at 90 °C for 10 min in alkaline conditions. The optimized separation conditions were 20 mM borate (pH 8.0) containing 10 mM Brij 35 and 35% (v/v) methanol. The limits of detection (S/N = 3) for MPD, PTD, PPD and OPD were 25, 25, 50 and 100 nM, respectively. Compared to MEKC-UV, the sensitivity enhancements were 30- to 81-fold when PDs were derived with DTAF. The high-sensitivity MEKC-LIF method was successfully established and applied to determine PDs in commercial hair colors for quality control and in real hair samples for evaluating the location of PDs in dyed hair samples, as well as in percutaneous absorption samples for evaluating the ability of PDs to penetrate skin.


Assuntos
Cromatografia Capilar Eletrocinética Micelar , Fluoresceínas/análise , Tinturas para Cabelo/análise , Cabelo/química , Fenilenodiaminas/análise , Voluntários Saudáveis , Humanos
3.
Contact Dermatitis ; 81(3): 194-209, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31006869

RESUMO

BACKGROUND: Allergic contact dermatitis caused by henna-based hair-colouring products has been associated with adulteration of henna with p-phenylenediamine (PPD). OBJECTIVES: To develop a testing approach based on in vitro techniques that address key events within the skin sensitization adverse outcome pathway in order to evaluate the allergenic potential of hair-colouring products. METHODS: The following in vitro assays were used to test the sensitizing capacity of hair dye ingredients: the micro-direct peptide reactivity assay (mDPRA); the HaCaT keratinocyte-associated interleukin (IL)-18 assay; the U937 cell line activation test (U-SENS)/IL-8 levels; the blood monocyte-derived dendritic cell test; and genomic allergen rapid detection (GARD skin). Those techniques with better human concordance were selected to evaluate the allergenic potential of 10 hair-colouring products. RESULTS: In contrast to the information on the label, chromatographic analyses identified PPD in all products. The main henna biomarker, lawsone, was not detected in one of the 10 products. Among the techniques evaluated by testing hair dye ingredients, the mDPRA, the IL-18 assay, GARD skin and the U-SENS correlated better with human classification (concordances of 91.7%-100%) and were superior to the animal testing (concordance of 78.5%). Thus, these assays were used to evaluate hair-colouring products, which were classified as skin sensitizers by the use of different two-of-three approaches. CONCLUSIONS: Our findings highlight the toxicological consequences of, and risks associated with, the undisclosed use of PPD in henna-based "natural" "real-life" products.


Assuntos
Tinturas para Cabelo/efeitos adversos , Naftoquinonas/efeitos adversos , Fenilenodiaminas/efeitos adversos , Antígeno B7-2/metabolismo , Bioensaio/métodos , Linhagem Celular Tumoral , Cromatografia Líquida de Alta Pressão , Células Dendríticas/metabolismo , Dermatite Alérgica de Contato/etiologia , Tinturas para Cabelo/química , Humanos , Técnicas In Vitro , Interleucina-18/metabolismo , Interleucina-8/metabolismo , Queratinócitos/metabolismo , Naftoquinonas/análise , Fenilenodiaminas/análise
4.
Environ Sci Pollut Res Int ; 25(18): 17830-17841, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29679271

RESUMO

Magnetic chitosan particles (MCS) were chemically grafted by m-phenylenediamine (mPD) forming a distinctive shell layer with abundant nitrogenous functional groups and used as an adsorbent for the effective removal of Cr(VI) from aqueous solution. By interaction among functional groups in the facile oxidative polymerization process, the grafting of mPD and its polymers on MCS surface was innovatively realized. Through Fourier-transformed infrared spectroscopy, energy dispersive spectrometer, X-ray photoelectron spectroscopy, etc., the chemical properties of MCS before and after modification were characterized and the concurrent reduction-adsorption mechanism in Cr(VI) adsorption by mPD-MCS was carefully analyzed. The maximal Cr(VI) removal performance of mPD-MCS reached 227.27 mg/g, which was significantly better than that of the original MCS. The analysis indicated that Cr(VI) could be efficiently reduced to Cr(III) and the removal of Cr(VI) and Cr(III) was through adsorption and chelation simultaneously by mPD-MCS. Results also indicated that the concurrent reduction-adsorption was enhanced by protonation of nitrogenous functional groups under low pH. The obtained results suggest that mPD-MCS has a good potential in removal and detoxication of Cr(VI) from aqueous solutions.


Assuntos
Quitosana/química , Cromo/análise , Fenilenodiaminas/análise , Polímeros/química , Adsorção , Quelantes/química , Cromo/química , Cinética , Magnetismo , Oxirredução , Fenilenodiaminas/química , Espectroscopia Fotoeletrônica , Espectroscopia de Infravermelho com Transformada de Fourier
5.
Regul Toxicol Pharmacol ; 95: 124-132, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29530615

RESUMO

Occupational exposure of hairdressers to hair dyes has been associated with the development of allergic contact dermatitis (ACD) involving the hands. p-Phenylenediamine (PPD) and toluene-2,5-diamine (PTD) have been implicated as important occupational contact allergens. To conduct a quantitative risk assessment for the induction of contact sensitization to hair dyes in hairdressers, available data from hand rinsing studies following typical occupational exposure conditions to PPD, PTD and resorcinol were assessed. By accounting for wet work, uneven exposure and inter-individual variability for professionals, daily hand exposure concentrations were derived. Secondly, daily hand exposure was compared with the sensitization induction potency of the individual hair dye defined as the No Expected Sensitization Induction Levels (NESIL). For PPD and PTD hairdresser hand exposure levels were 2.7 and 5.9 fold below the individual NESIL. In contrast, hand exposure to resorcinol was 50 fold below the NESIL. Correspondingly, the risk assessment for PPD and PTD indicates that contact sensitization may occur, when skin protection and skin care are not rigorously applied. We conclude that awareness of health risks associated with occupational exposure to hair dyes, and of the importance of adequate protective measures, should be emphasized more fully during hairdresser education and training.


Assuntos
Dermatite Alérgica de Contato/etiologia , Tinturas para Cabelo/toxicidade , Exposição Ocupacional/efeitos adversos , Fenilenodiaminas/toxicidade , Indústria da Beleza , Feminino , Tinturas para Cabelo/análise , Mãos , Humanos , Masculino , Exposição Ocupacional/análise , Fenilenodiaminas/análise , Medição de Risco , Absorção Cutânea
6.
Water Sci Technol ; 78(12): 2481-2488, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30767913

RESUMO

Water pollution due to industrial processes has necessitated and spurred robust research into the development of adsorbent materials for remediation. Polyphenylenediamines (PPD) have attracted significant attention because of their dual cationic and redox properties. They are able to reduce Cr(VI) to Cr(III) in solution. Interrogation of the chemical processes involved in the Cr(VI) adsorption on para-PPD was primarily by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectroscopy. It was confirmed that the underlying oxidation of the amino groups to imines during the reduction of Cr(VI) to Cr(III) was irreversible. This process occurred at both acidic and alkaline conditions. Reduction was accompanied by Cr(III) chelation on the adsorbent surface. Further, regeneration with dilute aqueous NaOH and HCl extended the polymer's adsorptive capacity beyond exhaustion of its redox potentials.


Assuntos
Cromo/química , Fenilenodiaminas/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Adsorção , Cromo/análise , Concentração de Íons de Hidrogênio , Fenilenodiaminas/análise , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/análise
7.
Med Pr ; 68(4): 497-505, 2017 Jun 27.
Artigo em Polonês | MEDLINE | ID: mdl-28584339

RESUMO

BACKGROUND: Toluenediamines are harmful substances. Toluene-2,4-diamine has been assigned to Carcinogen 1B hazard class, pursuant to Regulation (European Community - EC) No. 1272/2008 of the European Parliament and of the Council, and toluene- 2,6-diamine to Mutagen 2 hazard class. The main routes of exposure to toluene-2,4-diamine and toluene-2,6-diamine are via the respiratory tract and the skin. Toluene-2,4-diamine and toluene-2,6-diamine occur in the work environment in Poland. The aim of this study was to develop and validate a method for the determination of toluene-2,4-diamine and toluene-2,6-diamine that allows the simultaneous determination of their concentrations in the workplace air by personal sampling. MATERIAL AND METHODS: Determination of toluene-2,4-diamine and toluene-2,6-diamine derivatives in acetonitrile were carried out by means of liquid chromatography with a diode assay detector. The method involves passing amine-containing air through sulfuric acidtreated glass fiber filter, washing out the substance settled on the filter, using water and solution of sodium hydroxide, followed by the extraction with toluene, reaction with 3,5-dinitobenzoyl chloride, replacement of dissolvent with acetonitrile and analysis of obtained solution. RESULTS: The method developed in this study enables the researcher to determine the content of toluene-2,4-diamine and toluene-2,6-diamine in the presence of other hazardous substances. In the specified measuring range (2.88-57.6 µg/ml) calibration curves are linear. Under the optimized conditions of determination, the limit of detection (LOD) values achieved: 51.36 ng/ml for toluene-2,4-diamine and 52.93 ng/ml for toluene-2,6-diamine. CONCLUSIONS: This method makes it possible to determine the concentration of toluene-2,4-diamine and toluene-2,6-diamine in the workplace air within the specified measuring range of 0.004-0.08 mg/m3 (for air sample volume of 720 l). Med Pr 2017;68(4):497-505.


Assuntos
Poluentes Ocupacionais do Ar/análise , Cromatografia Líquida/métodos , Fenilenodiaminas/análise , Limite de Detecção
8.
Sensors (Basel) ; 17(1)2016 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-28042814

RESUMO

Changes in the structure and function of the hippocampus contribute to epilepsy, schizophrenia and other neurological or mental disorders of the brain. Since the function of the hippocampus depends heavily on the glutamate (Glu) signaling pathways, in situ real-time detection of Glu neurotransmitter release and electrophysiological signals in hippocampus is of great significance. To achieve the dual-mode detection in mouse hippocampus in vivo, a 16-channel implantable microelectrode array (MEA) was fabricated by micro-electromechanical system (MEMS) technology. Twelve microelectrode sites were modified with platinum black for electrophysiological recording and four sites were modified with glutamate oxidase (GluOx) and 1,3-phenylenediamine (mPD) for selective electrochemical detection of Glu. The MEA was implanted from cortex to hippocampus in mouse brain for in situ real-time monitoring of Glu and electrophysiological signals. It was found that the Glu concentration in hippocampus was roughly 50 µM higher than that in the cortex, and the firing rate of concurrently recorded spikes declined from 6.32 ± 4.35 spikes/s in cortex to 0.09 ± 0.06 spikes/s in hippocampus. The present results demonstrated that the dual-mode MEA probe was capable in neurological detections in vivo with high spatial resolution and dynamical response, which lays the foundation for further pathology studies in the hippocampus of mouse models with nervous or mental disorders.


Assuntos
Eletrofisiologia/instrumentação , Eletrofisiologia/métodos , Ácido Glutâmico/análise , Sistemas Microeletromecânicos/instrumentação , Sistemas Microeletromecânicos/métodos , Animais , Técnicas Biossensoriais/instrumentação , Técnicas Biossensoriais/métodos , Hipocampo/metabolismo , Camundongos , Microeletrodos , Fenilenodiaminas/análise
9.
Environ Sci Pollut Res Int ; 22(13): 9932-42, 2015 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-25663339

RESUMO

Scrap Cu-modified cast iron (CMCI) is a potent material for the reduction of 2,4-dinitrotoluene (2,4-DNT) by a surface-mediated reaction. However, the effects of operational parameters and common ions on its reduction and final rate are unknown. Results show that the 2,4-DNT reduction was significantly affected by Cu:Fe mass ratio and the optimum m(Cu:Fe) was 0.25%. The slight pH-dependent trend of 2,4-DNT reduction by CMCI was observed at pH 3 to 11, and the maximum end product, 2,4-diaminotoluene (2,4-DAT), was generated at pH 7. Dissolved oxygen (DO) in the water reduced the 2,4-DNT degradation and the formation of 2,4-DAT. CMCI effectively treated high concentrations of 2,4-DNT (60 to 150 mg L(-1)). In addition, varying the concentration of (NH4)2SO4 from 0.001 to 0.1 mol L(-1) improved the efficiency of the reduction process. The green rust-like corrosion products (GR-SO4 (2-)) were also effective for 2,4-DNT reduction, in which Na2CO3 (0.01 to 0.2 mol L(-1)) significantly inhibited this reduction. The repeated-use efficiency of CMCI was also inhibited. Moreover, 2,4-DNT and its products, such as 4A2NT, 2A4NT, and 2,4-DAT, produced mass imbalance (<35%). Hydrolysis of Fe(3+) and CO3 (2-) leading to the generation of Fe(OH)3 and conversion to FeOOH that precipitated on the surface and strongly adsorbed the products of reduction caused the inhibition of CO3 (2-). The 2,4-DNT reduction by CMCI could be described by pseudo-first-order kinetics. The operational conditions and common ions affected the 2,4-DNT reduction and its products by enhancing the corrosion of iron or accumulating a passive oxide film on the reactivity sites.


Assuntos
Cobre/química , Dinitrobenzenos/química , Ferro/química , Poluentes Químicos da Água/química , Dinitrobenzenos/análise , Recuperação e Remediação Ambiental , Cinética , Oxirredução , Fenilenodiaminas/análise , Fenilenodiaminas/química , Águas Residuárias/química , Poluentes Químicos da Água/análise , Purificação da Água
10.
J Agric Food Chem ; 61(22): 5260-70, 2013 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-23647382

RESUMO

Although both antioxidant capacity and oxidative conversion (hazard) are important in food and bioanalytical chemistry, there is considerable confusion in the literature between the results of these two types of assays. After the generation of ROS in the medium via Fe(III)-H2O2 reaction, attenuation of total oxidative conversion (TOC; as measured by thiobarbituric acid-reactive substances (TBARS) and N,N-dimethyl-p-phenylenediamine (DMPD) assays) was tested for possible correlation with the total antioxidant capacity (TAC; as measured by cupric reducing antioxidant capacity (CUPRAC) and trolox equivalent antioxidant capacity (ABTS/TEAC) assays) of the introduced antioxidant sample. The inverse relationship between oxidative conversion and antioxidant capacity was processed to establish a curvilinear relationship between the absolute values of TAC increments and TOC decrements as a function of added antioxidant concentration. This simple relationship may form a bridge between the two diverse disciplines of medical biochemistry and food analytical chemistry mainly using TOC and TAC results, respectively.


Assuntos
Antioxidantes/análise , Análise de Alimentos , Sequestradores de Radicais Livres/análise , Modelos Químicos , Espécies Reativas de Oxigênio/antagonistas & inibidores , Antioxidantes/química , Quelantes/química , Cromanos/química , Sequestradores de Radicais Livres/química , Indicadores e Reagentes/química , Cinética , Oxirredução , Fenantrolinas/química , Fenilenodiaminas/análise , Fenilenodiaminas/química , Espécies Reativas de Oxigênio/química , Substâncias Reativas com Ácido Tiobarbitúrico/análise
11.
J Chromatogr B Analyt Technol Biomed Life Sci ; 879(20): 1795-801, 2011 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-21606006

RESUMO

A rapid method for the determination of para-phenylenediamine (PPD) in cosmetic products, such as henna tattoos has been developed and evaluated. This analytical procedure involved extracting a 10mg test portion of cosmetic product in 10 mL of ethyl acetate, followed by determination by gas chromatography-mass spectrometry in the selected ion monitoring mode (GC/MS-SIM). 1,4-Phenylenediamine-2,3,5,6-d(4) was selected as an internal standard that was added at the beginning of the extraction procedure and used to correct for recovery and matrix effects. The linearity ranged from 1.0 to 1275 µg/mL with a coefficient of determination (r(2)) greater than 0.999. LOQ and LOD were 1.0 and 0.10 µg/mL, respectively. The recovery in a tattoo product containing PPD was 94% and that for a tattoo product containing no PPD reached 105%. Extraction efficiency of 98% was obtained. This method has been successfully applied to henna temporary tattoo and other henna-related cosmetic products for the determination and quantitation of PPD.


Assuntos
Cosméticos/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Naftoquinonas/química , Fenilenodiaminas/análise , Estabilidade de Medicamentos , Análise dos Mínimos Quadrados , Fenilenodiaminas/química , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
12.
Artigo em Inglês | MEDLINE | ID: mdl-21482181

RESUMO

Tridentate triazole based Schiff base 4-salicylideneamino-3-methyl-1,2,4-triazole-5-thione has been found to selectively detect toxic aromatic amines such as aniline and benzene-1,4-diamine by simple titration techniques like UV-visible, fluorescence spectral studies (PL) and 1H NMR titrations. The Schiff base receptor utilizes, thione sulfur, NH-thione and the phenolic hydroxyl group to form hydrogen bonded adduct of aniline and benzene-1,4-diamine with high binding affinity, followed by a slow removal of the corresponding hydrogens thus providing a promising candidate and an unique receptor for toxic aromatic amines.


Assuntos
Compostos de Anilina/análise , Carcinógenos/análise , Tionas/química , Triazóis/química , Cromatografia Líquida de Alta Pressão , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética/métodos , Modelos Moleculares , Fenilenodiaminas/análise , Bases de Schiff/química , Sensibilidade e Especificidade , Espectrometria de Fluorescência/métodos , Espectrofotometria Ultravioleta/métodos , Titulometria/métodos
13.
Ann Occup Hyg ; 53(3): 289-96, 2009 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-19279162

RESUMO

Skin irritation and contact allergies are skin disorders common to hairdressers. The predominant oxidative hair dye components, such as p-phenylenediamine (PPD) and aminophenol isomers, can cause contact dermatitis. Use of protective gloves can prevent dermal contact with skin irritants. This study investigates the permeation behaviors of p-aminophenol (PAP), m-aminophenol (MAP), o-aminophenol (OAP) and PPD in single and mixed challenge solutions with disposable natural rubber latex (NRL) gloves, disposable polyvinylchloride (PVC) gloves and neoprene (NP) gloves. The challenge solutions were 4% PPD (w/v), 3% OAP (w/v), 2% PAP (w/v) and 2% MAP (w/v) in ethanol or 12% hydrogen peroxide solutions. The cocktail solutions of the four chemicals were also tested. An American Society for Testing and Materials type permeation cell, ethanol liquid collection and gas chromatography-flame ionization detection of samples taken from the collection medium every 10 min facilitated determination of breakthrough times (BTs), cumulative permeated masses and steady-state permeation rates (SSPRs). Experiments were 4 h long for the NRL and PVC gloves and 8 h for NP gloves. No chemicals tested broke through the NP gloves when exposed for 8 h. In the ethanol solution, PPD and OAP started breaking through the PVC gloves at 40 min. The SSPRs of PVC gloves were higher than those for NRL gloves in all challenge conditions for both single chemicals and mixtures. No tested chemicals in hydrogen peroxide solutions permeated the gloves during the 4-h tests. The chemical composition of the challenge solution was a main effecter of BTs and SSPRs for the NRL glove. For disposable PVC gloves, the main factors of BTs were molecular size [molar volume (MV)] and polarity (logK(ow)), and the primary factors of SSPRs were concentration, MV and logK(ow). In conclusion, disposable NRL gloves and disposable PVC gloves should not be used repeatedly for handling the hair dye products. Hydrogen peroxide did not accelerate chemical breakthrough. The compositions of the challenge solutions and physical and chemical properties (MV and logK(ow)) affected permeation behaviors for different gloves.


Assuntos
Aminofenóis/química , Barbearia , Luvas Protetoras , Tinturas para Cabelo/química , Exposição Ocupacional/prevenção & controle , Fenilenodiaminas/química , Aminofenóis/análise , Dermatite de Contato/prevenção & controle , Equipamentos Descartáveis , Humanos , Peróxido de Hidrogênio/química , Teste de Materiais/métodos , Neopreno , Doenças Profissionais/prevenção & controle , Permeabilidade , Fenilenodiaminas/análise , Cloreto de Polivinila , Borracha , Fatores de Tempo
14.
Food Chem Toxicol ; 45(1): 160-9, 2007 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-17030383

RESUMO

We monitored the exposure of hairdressers to oxidative hair dyes for 6 working days under controlled conditions. Eighteen professional hairdressers (3/day) coloured hairdresser's training heads bearing natural human hair (hair length: approximately 30 cm) for 6 h/working day with a dark-shade oxidative hair dye containing 2% [14C]-para-phenylenediamine (PPD). Three separate phases of hair dyeing were monitored: (A) dye preparation/hair dyeing, (B) rinsing/shampooing/conditioning and (C) cutting/drying/styling. Ambient air and personal monitoring samples (vapours and particles), nasal and hand rinses were collected during all study phases. Urine (pre-exposure, quantitative samples for the 0-12, 12-24, 24-48 h periods after start of exposure) and blood samples (blank, 4, 8 or 24 h) were collected from all exposed subjects. Radioactivity was determined in all biological samples and study materials, tools and washing liquids, and a [14C]-mass balance was performed daily. No adverse events were noted during the study. Waste, equipment, gloves and coveralls contained 0.41+/-0.16%, dye mixing bowls 2.88+/-0.54%, hair wash 45.47+/-2.95%, hair+scalp 53.46+/-4.06% of the applied radioactivity, respectively. Plasma levels were below the limit of quantification (10 ng PPDeq/mL). Total urinary 0-48 h excretion of [14C] levels ranged from a total of <2-18 microg PPDeq and was similar in subjects exposed during the different phases of hair dyeing. Minimal air levels at or slightly above the limit of quantification were found in a few personal air monitoring samples during the phases of hair dyeing and hair cutting, but not during the rinsing phase. Air area monitoring samples or nasal rinses contained no measurable radioactivity. Hand residues ranged from 0.006 to 0.15 microg PPDeq/cm2, and were found predominantly after the cutting/drying phase. The mean mass balance of [14C] across the six study days was 102.50+/-2.20%. Overall, the mean, total systemic exposure of hairdressers to oxidative hair dyes during a working day including 6 hair dyeing processes was estimated to be <0.36 microg PPDeq/kg body weight/working day. Our results suggest that (a) current safety precautions for the handling of hair dyes offer sufficient protection against local and systemic exposure and (b) professional exposure to oxidative hair dyes does not pose a risk to human health.


Assuntos
Indústria da Beleza , Monitoramento Ambiental/métodos , Tinturas para Cabelo/farmacocinética , Exposição Ocupacional/análise , Fenilenodiaminas/farmacocinética , Adulto , Radioisótopos de Carbono , Feminino , Luvas Protetoras , Tinturas para Cabelo/análise , Desinfecção das Mãos , Humanos , Masculino , Pessoa de Meia-Idade , Fenilenodiaminas/análise
15.
Planta ; 224(1): 222-7, 2006 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-16395581

RESUMO

The long held but challenged view that plants do not synthesize sialic acids was re-evaluated using two different procedures to isolate putative sialic acid containing material from plant tissues and cells. The extracts were reacted with 1,2-diamino-4,5-methylene dioxybenzene and the fluorescently labelled 2-keto sugar acids analysed by reversed phase and normal phase HPLC and by HPLC-electrospray tandem mass spectrometry. No N-glycolylneuraminic acid was found in the protein fraction from Arabidopsis thaliana MM2d cells. However, we did detect 3-deoxy-D: -manno-octulosonic acid and trace amounts (3-18 pmol/g fresh weight) of a compound indistinguishable from N-acetylneuraminic acid by its retention time and its mass spectral fragmentation pattern. Thus, plant cells and tissues contain five orders of magnitude less sialic acid than mammalian tissues such as porcine liver. Similar or lower amounts of N-acetylneuraminic acid were detected in tobacco cells, mung bean sprouts, apple and banana. Yet even yeast and buffer blanks, when subjected to the same isolation procedures, apparently contained the equivalent of 5 pmol of sialic acid per gram of material. Thus, we conclude that it is not possible to demonstrate unequivocally that plants synthesize sialic acids because the amounts of these sugars detected in plant cells and tissues are so small that they may originate from extraneous contaminants.


Assuntos
Arabidopsis/metabolismo , Ácido N-Acetilneuramínico/análise , Ácidos Neuramínicos/análise , Açúcares Ácidos/análise , Animais , Bovinos , Cromatografia Líquida de Alta Pressão , Fígado/química , Espectrometria de Massas , Ácido N-Acetilneuramínico/isolamento & purificação , Fenilenodiaminas/análise , Extratos Vegetais/química , Açúcares Ácidos/isolamento & purificação , Suínos/metabolismo
16.
Photochem Photobiol ; 81(6): 1539-43, 2005.
Artigo em Inglês | MEDLINE | ID: mdl-16149858

RESUMO

This work presents the application of an on-line photoreactor to the detection of 3,5-diamino-trifluoromethyl-benzene (3,5-DABTF) in aqueous solutions. When irradiated at 310 nm, this compound is defluorinated to 3,5-diaminobenzoic acid by a nucleophilic substitution of the fluoride by water. Concomitantly, defluorination intermediates polymerize through amide bonds to give dark-colored compounds. We take advantage of the photocatalyzed defluorination and the subsequent decrease in pH to develop an original and specific photoreactor. Continuous recording of pH and temperature in the outlet of the reactor by a dual electrode gives us an opportunity to optimize the system. In the photoreactor, 3,5-DABTF is immediately and totally transformed as attested by the rapid drop of the flowing solution pH from 6.2 to 3.2 and the chromatographic analysis of the outgoing solutions. The detection remains effective from 1 to 1000 parts per million.


Assuntos
Aminas/química , Hidrocarbonetos Aromáticos/química , Fenilenodiaminas/química , Fotoquímica , Cromatografia Líquida de Alta Pressão , Desenho de Equipamento , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Fenilenodiaminas/análise , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Água/química
17.
J Chromatogr A ; 1066(1-2): 143-8, 2005 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-15794565

RESUMO

In this paper we describe an analytical method for the determination of p-phenylenediamine (PPDA) in hair dyes. In the adopted methodology the analyte is transformed into the corresponding imine derivative by treatment with benzaldehyde, and then analyzed by gas chromatography (GC) combined to mass spectrometry (MS), operating in SIM conditions. The direct and simultaneous chemical derivatization of the two amino functions of the analyte with benzaldehyde enhances the instrumental responses enabling the use of a sensitive and accurate method. Concentrations of PPDA in a set of commercial hair coloring creams are determined making use of N-benzylidene-4-methylbenzene-amine as a very stable internal standard which is easily prepared by condensation of 4-methylbenzene-amine with benzaldehyde. The regression calibration curves for PPDA in hair dyes are linear within 0.1 +/- 25 mg/ml with 0.99 as a typical correlation coefficient.


Assuntos
Fluoracetatos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Tinturas para Cabelo/química , Iminas/análise , Iminas/química , Fenilenodiaminas/análise , Fenilenodiaminas/química , Anidridos Acéticos , Benzaldeídos/química , Espectroscopia de Ressonância Magnética , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Ácido Trifluoracético/química
18.
Hum Exp Toxicol ; 24(12): 655-62, 2005 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-16408619

RESUMO

Methylene diphenylisocyanate (MDI) and toluene diisocyanate (TDI) are widely used in industry to produce polyurethane foam products. Small amounts of methylenedianiline (MDA) and toluene diamine (TDA) are released during MDI and TDI polymerization and may be present in newly finished polyurethane foam parts. MDA and TDA concentrations in foam decline exponentially within several hours of demolding. MDA and the 2,4-isomer of TDA are known animal carcinogens and, in addition, have significant non-carcinogenic health effects. Our goal was to determine whether worker exposure to MDA or TDA in freshly produced polyurethane foams was associated with unacceptable health risks. Sampling and analysis of the fresh foam indicated that MDA and TDA concentrations varied considerably among products, but concentrations in all materials evaluated declined rapidly over time. We found that, under a worst-case exposure scenario, cancer risks from TDA exposure were approximately 5 x 10(-6), whereas cancer risks from MDA exposure resulted in a tumorigenic margin of exposure (MOE) of 85 000. Non-cancer chronic hazard indices were well below 1.0. Therefore, the potential cancer and non-cancer health risks from MDA or TDA exposure to newly manufactured foam parts appear to fall well within acceptable health risk criteria.


Assuntos
Compostos de Anilina/análise , Indústria Química , Exposição Ocupacional/análise , Fenilenodiaminas/análise , Poliuretanos/química , Compostos de Anilina/efeitos adversos , Monitoramento Ambiental , Humanos , Exposição Ocupacional/efeitos adversos , Fenilenodiaminas/efeitos adversos , Medição de Risco , Absorção Cutânea
19.
Rocz Panstw Zakl Hig ; 55(2): 181-5, 2004.
Artigo em Polonês | MEDLINE | ID: mdl-15493351

RESUMO

The emission of 2,4- and 2,6-diaminotoluene, triethylenediamine, diethanolamine and other volatile organic compounds from polyurethane foams was examined in environmental chamber. Tested materials did not release of amines. The emission of total volatile organic compounds showed differences for polyurethane samples but did not exceed ecological standards.


Assuntos
Poluição do Ar em Ambientes Fechados/análise , Materiais de Construção/análise , Poliuretanos/análise , Poluentes Atmosféricos/análise , Carcinógenos/análise , Etanolaminas/análise , Humanos , Compostos Orgânicos/análise , Fenilenodiaminas/análise , Piperazinas/análise , Polônia , Volatilização
20.
Anal Sci ; 17(12): 1369-74, 2001 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-11783783

RESUMO

2,4-Toluene diamine (TDA), a class A carcinogen, is a major raw material for the production of toluene diisocyanate (TDI), which is one of the precursors for the production of polyurethane foams (PU). This review deals with 2,4-toluene diamine's (TDA) carcinogenicity, analytical techniques, biodegradation and use as a biosensor for biogenic and synthetic amines, emphasizing various carcinogenicity studies by 2,4-TDA on animals and humans. This review reports some publications of the analysis of body fluid samples of workers from a PU producing factory for presence of TDA and TDI, since TDI gets absorbed into the worker's body, getting metabolized into TDA. Biodegradations of 2,4-TDA by various researchers are reported and also our own research experience with biodegradation of 2,4-TDA using Aspergillus nidulans isolated from soil site at a polyurethane foam dumping site have been discussed in this review. Biosensors for various biogenic and synthetic amines are discussed.


Assuntos
Técnicas Biossensoriais , Fenilenodiaminas , Animais , Biodegradação Ambiental , Testes de Carcinogenicidade , Carcinógenos/toxicidade , Humanos , Fenilenodiaminas/análise , Fenilenodiaminas/metabolismo , Fenilenodiaminas/toxicidade
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA