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UNLABELLED: Stoddard solvent (white spirit/mineral spirit) is the most widely used solvent in the paint industry. It is used as a dry cleaning agent; as an extraction, cleaning, and degreasing solvent; and as a solvent in aerosols, paints, wood preservatives, asphalt products, lacquers, and varnishes. Stoddard solvent IIC was nominated by the International Union, United Auto Workers, for carcinogenicity testing because of the large volume used in industrial and other settings. Male and female F344/N rats and B6C3F1 mice were exposed to Stoddard solvent IIC (greater than 99% pure) by inhalation for 2 weeks, 3 months, or 2 years. Genetic toxicology studies were conducted in Salmonella typhimurium and mouse peripheral blood erythrocytes. 2-WEEK STUDY IN RATS: Groups of five male and five female rats were exposed to Stoddard solvent IIC by inhalation at concentrations of 0, 138, 275, 550, 1,100, or 2,200 mg/m3, 6 hours per day, 5 days per week for 16 days. All rats survived to the end of the study, and mean body weights of all exposed groups were similar to those of the chamber controls. Liver weights of males exposed to 550 mg/m3 or greater and of females exposed to 275 mg/m3 or greater were increased. Minimal diffuse cytoplasmic vacuolization of hepatocytes of the liver occurred in all females exposed to 2,200 mg/m3. 2-WEEK STUDY IN MICE: Groups of five male and five female mice were exposed to Stoddard solvent IIC by inhalation at concentrations of 0, 138, 275, 550, 1,100, or 2,200 mg/m3, 6 hours per day, 5 days per week for 17 days. All mice survived to the end of the study, and mean body weights of all exposed groups were similar to those of the chamber controls. Liver weights of males and females exposed to 275 mg/m3 or greater were significantly increased. Cytomegaly of the liver occurred in all males and females exposed to 2,200 mg/m3. 3-MONTH STUDY IN RATS: Groups of 10 male and 10 female rats were exposed to Stoddard solvent IIC by inhalation at concentrations of 0, 138, 275, 550, 1,100, or 2,200 mg/m3, 6 hours per day, 5 days per week for 14 weeks. All rats survived to the end of the study, and the final mean body weight of females exposed to 275 mg/m3 was greater than that of the chamber controls. The relative kidney, liver, and testis weights of all exposed groups of males and the absolute kidney weights of males exposed to 550 mg/m3 or greater were increased. The sperm motility of 550 mg/m3 or greater males was significantly decreased. The incidences of renal tubule granular casts were significantly increased in males exposed to 550 mg/m3 or greater, and the severities of renal tubule hyaline droplet accumulation, granular casts, and regeneration increased with increasing exposure concentration in males. The incidences of goblet cell hypertrophy of the nasal respiratory epithelium in males and females exposed to 2,200 mg/m3 were significantly increased. Sperm motility was decreased in males exposed to 550 mg/m3 or greater. 3-MONTH STUDY IN MICE: Groups of 10 male and 10 female mice were exposed to Stoddard solvent IIC by inhalation at concentrations of 0, 138, 275, 550, 1,100, or 2,200 mg/m3, 6 hours per day, 5 days per week for 14 weeks. Mean body weights of exposed groups were similar to those of the chamber controls, but liver weights of males exposed to 2,200 mg/m3 were significantly increased. The sperm motility of 2,200 mg/m3 males was significantly decreased. This reduction in sperm motility, while statistically significant, is probably of modest importance as studies in mice have found that fertility is unaffected by motility decreases of less than 40%. The incidences of hematopoietic cell proliferation of the spleen in all exposed groups of females were greater than that in the chamber controls. 2-YEAR STUDY IN RATS: Groups of 50 male and 50 female rats were exposed to Stoddard solvent IIC by inhalation at concentrations of 0, 138 (males), 550, 1,100, or 2,200 (females) mg/m3, 6 hours per day, 5 days per week for 104 to 105 weeks. Additional groups of 10 males and 10 females were exposed to the same concentrations for 3 months for renal toxicity analyses. Survival in the top exposure concentration groups of males and females was significantly less than that of the chamber controls. Mean body weights of exposed males and females were similar to those of the chamber controls. Cell proliferation analyses were performed in the left kidney of males and females after 3 months of exposure. The mean numbers of labeled cells and the labeling indices in males exposed to 550 and 1,100 mg/m3 were significantly increased. The amount of alpha2u-globulin in the right kidney of males increased with increasing exposure concentration. Also, the incidences of granular casts and cortical tubule degeneration and regeneration were generally increased in exposed males, as was the severity of hyaline droplets. These effects did not occur in females. At 2 years, the incidences of benign and benign or malignant pheochromocytoma (combined) of the adrenal medulla occurred with positive trends in males, and the incidences in the 550 and 1,100 mg/m3 groups were significantly increased. Due to increased incidences of renal tubule hyperplasia in males at 2 years, extended kidney evaluations were conducted; a slightly increased incidence of renal tubule adenoma occurred in the 1,100 mg/m3 group. Nonneoplastic lesions related to Stoddard solvent IIC exposure occurred in the kidney of males. 2-YEAR STUDY IN MICE: Groups of 50 male and 50 female mice were exposed to Stoddard solvent IIC by inhalation at concentrations of 0, 550, 1,100, or 2,200 mg/m3, 6 hours per day, 5 days per week for 105 weeks. Survival of exposed mice was similar to that of the chamber controls. Mean body weights of exposed females were greater than those of the chamber controls. The incidences of hepatocellular adenoma occurred with a positive trend in females, and the incidence of multiple hepatocellular adenoma in females exposed to 2,200 mg/m3 was significantly increased. However, the incidences of hepatocellular adenoma or carcinoma (combined) and hepatocellular carcinoma alone in exposed males and females were not significantly increased. GENETIC TOXICOLOGY: Stoddard solvent IIC was tested for mutagenicity in Salmonella typhimurium strains TA97, TA98, TA100, and TA1535, with and without S9 metabolic activation enzymes; all results were negative. In vivo, the frequency of micronucleated erythrocytes was assessed in peripheral blood samples from male and female B6C3F1 mice after 3 months of inhalation exposure to Stoddard solvent IIC, and results were negative. CONCLUSIONS: Under the conditions of these 2-year inhalation studies, there was some evidence of carcinogenic activity of Stoddard solvent IIC in male F344/N rats based on increased incidences of adrenal medulla neoplasms; the slightly increased incidences of renal tubule adenoma may have been related to Stoddard solvent IIC exposure. There was no evidence of carcinogenic activity of Stoddard solvent IIC in female F344/N rats exposed to 550, 1,100, or 2,200 mg/m3. There was no evidence of carcinogenic activity of Stoddard solvent IIC in male B6C3F1 mice exposed to 550, 1,100, or 2,200 mg/m3. There was equivocal evidence of carcinogenic activity of Stoddard solvent IIC in female B6C3F1 mice based on increased incidences of hepatocellular adenoma; this slight increase was associated with increased body weight in exposed females. Exposure of male rats to Stoddard solvent IIC resulted in nonneoplastic lesions of the kidney characteristic of alpha2u-globulin accumulation.
The present paper deals with the application of fluctuation theory of solutions to the solubility of poorly soluble substances of environmental significance in aqueous mixed solvents. The fluctuation theory of ternary solutions was first used to derive an expression for the activity coefficient of a solute at infinite dilution in a binary mixed solvent. This equation contains the activity coefficients of the constituents of the solute-free mixed solvent and the molar volume of the solute-free mixed solvent. Further, the derived expression for the activity coefficient of a solute at infinite dilution was used to generate a number of expressions for the solubility of solids in aqueous mixed solvents. Several expressions for the activity coefficients of the components were considered: first, the mixed solvent was considered an ideal mixture; second, the activity coefficients of the constituents of the binary solvent were expressed using the two-suffix Margules equations; third, the activity coefficients of the constituents of the binary solvent were expressed using the Wilson equations. The obtained expressions were applied to 25 experimental data sets pertaining to the solubilities of hydrophobic organic pollutants (HOP) in aqueous mixed solvents. It was found that the suggested equations can be used for an accurate and reliable correlation of the solubilities in aqueous mixed binary solvents. The best results were obtained by combining our expression for the activity coefficient of a solute at infinite dilution in a mixed solvent with the Wilson equations for the activity coefficients of the constituents of a solute-free mixed solvent. The derived equations can also be used for predicting the solubilities of poorly soluble environmentally important compounds in aqueous mixed solvents using for the Wilson parameters those obtained from vapor-liquid equilibrium data. A similar methodology was applied to the solubility of poorly soluble substances of environmental significance in multicomponent (ternary and higher) aqueous mixed solvents. The expression for the activity coefficient of a solute in an ideal multicomponent mixed solvent was used to derive an equation for the solubility of a poorly soluble solute in an ideal multicomponent mixed solvent in terms of its solubilities in two subsystems of the multicomponent solvent and their molar volumes. Ultimately the solubility could be expressed in terms of those in binary or even in the individual constituents of the solvent and their molar volumes. The computational method was applied to predict the solubilities of naphthalene and anthracene in ternary, quaternary and quinary aqueous mixed solvents. The results were compared with experiment and good agreement was obtained.
OBJECTIVE: To examine (1) common types of organic solvent work and prevalent types of solvent used, and (2) possible association of high solvent concentration with types of solvent work and with enterprise size. METHODS: The present survey was conducted in Kyoto, Japan, in April 2004 to March 2005. Air samples were collected in 1,010 solvent workplaces (SWPs) (>or=5 samples/SWP) in 156 enterprises of various sizes, and analyzed for 47 legally designated organic solvents by flame-ionization detector-equipped gas-liquid chromatography. The geometric mean value of the concentrations (after summation by use of the additiveness formula) in the >or=5 samples were taken as a representative value for the SWP. Solvent works were classified into 11 categories according to the Japanese regulation. Enterprises were classified in terms of number of employees. RESULTS: Degreasing (including cleaning and wiping) was the most common type of solvent work, followed by painting and printing, and toluene was the most often detected solvent (i.e., in 42% of the 1,010 SWPs). Further observation by types of solvent work disclosed that toluene was most common in printing (61%), painting (78%), and adhesive spreading/adhesion SWPs (47%), whereas isopropyl alcohol was the leading solvent in cases of surface coating (51%) and degreasing/cleaning/wiping SWPs (42%). Use of methyl alcohol was also high (36% of all cases). In contrast, use of hexane in adhesives was limited (12%). There was a reverse size-dependency in solvent concentrations in air of SWPs, being five times higher in enterprises with or=501 employees. Among SWPs, concentrations tended to be high in printing workplaces especially in small enterprises. In contrast, the levels were much lower in testing and research laboratories irrespective of enterprise size. Comparison with the results in a previous survey in 1996 (Ukai et al. 1997) showed that use of toluene and xylenes was reduced and use of isopropyl alcohol and methyl alcohol was increased. The need of continuous updating of the target analyte list was stressed in relation to the limitation of the present study. CONCLUSIONS: Solvent levels were about five times higher in small enterprises as compared with the levels in large enterprises. There was a gradual shift in solvent use from aromatics to other solvents, typically alcohols. The use of hexane in adhesives was reduced. Solvent levels were relatively high in solvent-drying and printing workplaces and low in degreasing/cleaning/wiping workplaces and testing/research laboratories.
The importance of good solvent concentration in the non-solvent mixture and the non-solvent viscosity on the ability to form microspheres using solvent removal process was investigated. The higher the viscosity of the polymer solutions, the higher the concentration of good solvent needed in the nonsolvent mixture to produce microspheres. This finding was due to faster precipitation of the polymer phase. Also, the addition of a model drug, fluorescein isothiocyanate conjugated-labelled bovine serum albumin, to the polymer solution (10% poly-L-lactic acid:poly(fumaric-co-sebacic) anhydride in methylene chloride) resulted in an overall lower polymer solution viscosity (15.5 cP with fluorescein isothiocyanate conjugated-labelled bovine serum albumin as compared with 18.25 cP for blank polymer at 25 degrees C). Additionally, the effect of good solvent concentration on non-solvent viscosity was evaluated, and the viscosity decreased as the concentration of good solvent increased. The effect of good solvent concentration on the non-solvent mixture on sphere formation was of great importance. Microspheres would not form when the good polymer solvent (methylene chloride) in the non-solvent phase was too low (below 175 ml for poly-L-lactic acid or 150 ml for poly(D,L-lactidco-glycolid)) or was replaced by another good solvent such as ethyl acetate, even though the same viscosity was achieved. It was shown that the concentration of the good solvent in the non-solvent mixture was more of a controlling factor than the viscosity of the non-solvent mixture in microsphere formation and the findings support the conclusion that diffusion is the main controlling parameter in solvent removal.
A thermal desorption-gas chromatography (GC) system was developed for use with commercial adhesive plasters used for monitoring exposure of hands to common solvents. The efficiency of solvent adsorption on the activated carbon pads located on the plasters was determined for acetone, trichloroethylene, D-limonene, methanol, ethyl methyl ketone, toluene, tetrachloroethylene and m-xylene. The degree of solvent recovery for the system was also investigated for each solvent, as was its sensitivity and reproducibility. All solvents exhibited > 90% adsorption on the pads at spiking levels of 100-200 ng for each solvent, except for m-xylene and d-limonene. Solvent recovery was dependent on the volatility of the solvent at spiking volumes of about 1 microliter per pad with solvents with boiling points above 110 degrees C showing recoveries of < 75%. Increasing primary desorption times and temperatures increased these values. The precision was good with RSD < 5% for all solvents over the range 0.5-5.0 microliters of applied solvent. It was possible to detect 15-60 ng of each solvent component within solvent mixtures on the pads with the exception of D-limonene. It is concluded that all solvents tested except D-limonene can be determined on the pads under the conditions for thermal desorption-GC analysis described. The pads were used under protective gloves with six workers using xylene isomers as solvent in the workplace, when apparent solvent breakthrough through their gloves was observed.
The process of reversible denaturation of several proteins (alpha-chymotrypsin, trypsin, laccase, chymotrypsinogen, cytochrome c and myoglobin) by a broad series of organic solvents of different nature was investigated using both our own and literature data, based on the results of kinetic and spectroscopic measurements. In all systems studied, the denaturation proceeded in a threshold manner, i.e. an abrupt change in catalytic and/or spectroscopic properties of dissolved proteins was observed after a certain threshold concentration of the organic solvent had been reached. To account for the observed features of the denaturation process, a thermodynamic model of the reversible protein denaturation by organic solvents was developed, based on the widely accepted notion that an undisturbed water shell around the protein globule is a prerequisite for the retention of the native state of the protein. The quantitative treatment led to the equation relating the threshold concentration of the organic solvent with its physicochemical characteristics, such as hydrophobicity, solvating ability and molecular geometry. This equation described well the experimental data for all proteins tested. Based on the thermodynamic model of protein denaturation, a novel quantitative parameter characterizing the denaturing strength of organic solvents, called the denaturation capacity (DC), was suggested. Different organic solvents, arranged according to their DC values, form the DC scale of organic solvents which permits theoretical prediction of the threshold concentration of any organic solvent for a given protein. The validity of the DC scale for this kind of prediction was verified for all proteins tested and a large number of organic solvents. The experimental data for a few organic solvents, such as formamide and N-methylformamide, did not comply with equations describing the denaturation model. Such solvents form the group of so-called 'bad' solvents; reasons for the occurrence of 'bad' solvents are not yet clear. The DC scale was further extended to include also highly nonpolar solvents, in order to explain the well-known ability of enzymes to retain catalytic activity and stability in biphasic systems of the type water/water-immiscible organic solvent. It was quantitatively demonstrated that this ability is accounted for by the simple fact that nonpolar solvents are not sufficiently soluble in water to reach the inactivation threshold concentration.
Implicit solvent models approximate the effects of solvent through a potential of mean force and therefore make solvated simulations computationally efficient. Yet despite their computational efficiency, the inherent approximations made by implicit solvent models can sometimes lead to inaccurate results. To test the accuracy of a number of popular implicit solvent models, we determined whether implicit solvent simulations can reproduce the set of potential energy minima obtained from explicit solvent simulations. For these studies, we focus on a six-residue amino-acid sequence, referred to as the paired helical filament 6 (PHF6), which may play an important role in the formation of intracellular aggregates in patients with Alzheimer's disease. Several implicit solvent models form the basis of this work--two based on the generalized Born formalism, and one based on a Gaussian solvent-exclusion model. All three implicit solvent models generate minima that are in good agreement with minima obtained from simulations with explicit solvent. Moreover, free-energy profiles generated with each implicit solvent model agree with free-energy profiles obtained with explicit solvent. For the Gaussian solvent-exclusion model, we demonstrate that a straightforward ranking of the relative stability of each minimum suggests that the most stable structure is extended, a result in excellent agreement with the free-energy profiles. Overall, our data demonstrate that for some peptides like PHF6, implicit solvent can accurately reproduce the set of local energy minimum arising from quenched dynamics simulations with explicit solvent. More importantly, all solvent models predict that PHF6 forms extended beta-structures in solution, a finding consistent with the notion that PHF6 initiates neurofibrillary tangle formation in patients with Alzheimer's disease.
The effects of solvents and media on the antioxidant activity of alpha-tocopherol were studied. The antioxidant activities of alpha-tocopherol in different solvents decreased in the order of acetonitrile = hexane > ethanol = methanol, which indicates that the antioxidant activity of alpha-tocopherol is smaller in protic solvent than in aprotic solvent. The antioxidant activity of 2-(4,8,12-trimethyltridecyl)-5-hydroxy-2,4,6,7-tetramethylindan , which has similar structure to alpha-tocopherol but does not have ether oxygen, was also measured in protic and aprotic solvents. Its antioxidant activity was smaller than that of alpha-tocopherol in every solvent, but interestingly, substantially the same solvent effects were observed. These results show that the hydrogen bonding between the protic solvent and either oxygen is not important but that the hydrogen binding between protic solvent and phenolic group reduces the activity of alpha-tocopherol. Antioxidant activities of alpha-tocopherol in micelle system and liposomal membrane were markedly reduced compared with that in homogeneous solution. Solvent effect on the alpha-tocopheroxyl radical was also studied by using electron spin resonance. The hyperfine splitting constants of a5CH3H and a7CH3H were smaller in protic solvent than in aprotic solvent, which shows that lone-pair orbital energy on 5-CH3 and 7-CH3 is smaller in protic solvent. The ESR spectra of alpha-tocopheroxyl radical in liposomal membrane and micelle were similar to those observed in aprotic solvent and in protic solvent, respectively, suggesting that alpha-tocopheroxyl radical is located predominantly in the lipophilic domain of the liposomal membrane but in or closer to water phase of micelle aqueous suspensions.
OBJECTIVE: The purposes of this study were to estimate the prevalence of past solvent abuse among junior high school students in Saitama prefecture and to investigate smoking and drinking as "gateway drugs" for solvent abuse. METHODS: The survey was conducted from Dec 2002 to Jan 2003, in 3 junior high schools in Saitama, using anonymous self-reporting to preserve privacy. A total of 2,049 (93.2%) students responded to our questionnaire. Two groups were categorized and analyzed according to history of solvent abuse in the past. To investigate "gateway effects" of smoking and drinking, we analyzed their relationship with solvent abuse, order of precedence of usage and confounding factors. RESULTS: The prevalence of history of solvent abuse was 1.1% of the total. There were notable differences depending on sex and grade. 1.9% of male students had some experience as compared to only 0.3% of female students. An increase was evident according to grade (grade 1-0.6%, grade 2-0.8%, grade 3-2.1%) and there was a strong association between smoking, drinking and solvent abuse. The order of precedence of solvent abuse could not be established because some users had first experienced smoking, drinking and solvent abuse in the same grade and there was also a high recall bias among the subjects. A number of respondents also reported the reverse order, of experiencing solvent abuse before smoking and drinking. The user group was habitual smokers were recommended to smoke by their parents, spent longer periods in solitude, witnessed solvent abuse and had a friend who abused solvents. After adjusting for confounding factors using multiple logistic regression analysis, a relationship between smoking and solvent abuse remained but not the relationship with drinking. CONCLUSION: The study conformed that there is solvent abuse among junior high school students, even in the lowest grade. Health education must focus on this fact and the finding that the user group reflects peer pressure and is faced with poor communication and advice from their families. Therefore health education focused on life skills and social support considering family ties must be emphasized. It could not be established which was first experienced, but a strong relationship between smoking and solvent abuse was observed even after multivariable analysis. On the other hand, the results suggested that habitual drinking is not a "gateway drug" to solvent abuse.
The results of a quantitative structure-property relationship (QSPR) analysis of 127 different solvent scales and 774 solvents using the CODESSA PRO program are presented. QSPR models for each scale were constructed using only theoretical descriptors. The high quality of the models is reflected by the squared multiple correlation coefficients that range from 0.726 to 0.999; only 18 models have R2< 0.800. This enables direct theoretical calculation of predicted values for any scale and/or for any organic solvent, including those previously unmeasured. The molecular descriptors involved in the models are classified and discussed according to (i) the origin of their calculation (i.e., constitutional, geometric, charge-related, etc.) and (ii) the commonly accepted classification of physical interactions between the solute and solvent molecules in liquid (condensed) media. A reduced matrix 774 (solvents) x 100 (solvent scales) was selected for the principal component analysis (PCA) by taking into account only the solvent scales with more than 20 experimental data points. The first 5 principal components account for 75% of the total variance. The robustness of the PCA model obtained was validated by the comparison models development for restricted submatrices of data and with the results obtained for the full data set. The total variance accounted for by the first three PCs, for the submatrices with the same number of solvent scales but different numbers of solvents, varies from 68.2% to 59.0%. This demonstrates that the total variance described by the first 3 components is essentially stable as the number of solvents involved varies from 100 to 774. Subsequently, a matrix with 703 diverse solvents and 100 solvent scales was selected for the general classification of the solvents and scales according to the scores and loadings obtained from the PCA treatment. Classification of the theoretical molecular descriptors, derived from the chemical structure alone, according to their relevance to specific types of intermolecular interaction (cavity formation, electrostatic polarization, dispersion, and hydrogen bonding) in liquid media enables a more easily comprehensible physical interpretation of the QSPR of molecular properties in liquids and solutions. The reported QSPR models for solvent scales with theoretical molecular descriptors and the results of the PCA analysis are potentially of great practical importance, as they extend the applicability of correlations with empirical solvent scales to many previously unmeasured systems.
OBJECTIVE: The objective of this study was to determine to what extent the substitution of solvent-based paint by water-based paint has reduced potential exposure to organic solvents for spray painters in car repair shops. METHODS: Full-shift personal air sampling (n=79) was carried out over 3 consecutive days in eight car repair shops. Blood samples on the Monday morning (n=26) and at the end of the shift on the Wednesday (n=26), were analysed for organic solvents by headspace techniques. RESULTS: Toluene was the organic solvent detected at the highest geometric mean concentration in air samples when solvent-based paint systems were used (0.8 ppm), whereas xylene was found at the highest level when water-based systems were used (0.25 ppm). Toluene, isopropanol, acetone and butyl acetate were detected at higher concentrations when solvent-based paint was used than when water-based paint was employed. The additive factor, based on Norwegian limit values, was three-times higher for the painters using solvent-based paint (0.15) than for those using water-based paint (0.05). On Wednesday after shift the geometric mean of toluene in blood was significantly higher for the painters using solvent-based paint (0.044 microg/ml) than for the painters using water-based paint (0.007 microg/ml). There was a significant correlation between toluene in personal air samples and toluene in blood samples taken at the end of the shift on the same day. CONCLUSIONS: When solvent-based paint systems were used the additive factor for organic solvent exposure was three-times higher than when water-based systems were employed. The exposure levels of the organic solvents were well below the Norwegian limit values. The significant correlation between the toluene concentration in air and blood samples indicated that the uptake of organic solvents was correspondingly reduced. At the levels of organic solvents presently described the risk of acute and chronic health effects caused by organic solvents is low.
OBJECTIVES: To identify the most popular solvent and typical type of solvent work among solvent-using workplaces in Korea. METHODS: In practice, 862 solvent-using workshops in Sinpyeong-Jangrim industrial complex in Pusan were investigated in a 2-year period from March 1995 to February 1997. Solvent vapors in the breathing zone of workers were collected by personal sampling with charcoal tubes. The exposed charcoal was extracted with carbon disulfide, and the solvents in the extract were analyzed by flame ionization detector-equipped gas chromatography (FID-GC). RESULTS: Solvents were used in painting, glue application, cleaning, printing and solvent-mixing workshops in decreasing order of popularity. Toluene was the most frequently measured solvent. In the five types of solvent work, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, tetrachloroethylene, trichloroethylene and xylenes were also used frequently. CONCLUSIONS: Toluene was identified as the most frequently used solvent in solvent works in Korean manufacture industries in the late 1990s. Eight types of solvent were popularly used in five popular types of solvent work. These trends are very similar to the cases reported for industries in Japan.
A total of 1,179 organic solvent products used as thinners, paint, degreasers, inks, adhesive and others, were collected nationwide from factories of various sizes and kinds in Japan, and analyzed by gas chromatography. Solvent components per sample, frequency of each solvent component, and contents of each component were analyzed and classified by use. Paints, inks, and adhesives which contained nonvolatile substances were analyzed by head space techniques. Seventy-seven percent of all samples, 93% of paints, 85% of thinners, 73% of adhesives, and 52% of degreasers contained mixed organic solvents. The average numbers of solvent components per sample were 4.14 (max. 13) in thinner, 3.29 (max. 7) in paint, 2.23 (max. 5) ink, 2.19 (max. 6) in adhesive, 1.71 (max. 6) in degreaser, when gasoline was excluded. Toluene, xylene, methylalcohol, isopropylalcohol, ethylacetate, methylethylketone, industrial gasoline were widely used in the above-mentioned products. Toluene was the most popular component in the solvent products, excluding degreasers. Many kinds of solvent components were used in thinner and paint. However, toluene, xylene and industrial gasoline were their main components and contents per sample were very high. Acetates, alcohols, ketones and glycols were frequently detected in solvent products, but their contents per sample were relatively low, because these solvent components were usually used as subordinate solvents. The chlorinated hydrocarbons such as trichloroethylene, tetrachloroethylene and 1,1,1-trichloroethane, and industrial gasoline were the most popular components in degreasers. 1,4-dioxane was detected in a relatively large number of the samples, but its content per sample was very low, because it is usually used as an additive to 1,1,1-trichloroethane. Toluene was the most popular component in ink solvents, too. In addition, isopropylacohol, methylalcohol, methylethylketone were frequently detected in inks. Toluene was also the most popular component in adhesives, and n-hexane was also frequently detected in them. In order to prevent poisoning by industrial solvents, special attention should be paid to toluene and xylene, which are frequently and largely used for wide purposes, trichloroethylene which is largely used as a degreaser and has a severe toxicity, n-hexane which is frequently used in adhesives and has a high volatility and severe neurotoxicity, and other popular and toxic solvents. The severely toxic solvents such as benzene, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane and carbon disulfide were detected in few samples.(ABSTRACT TRUNCATED AT 250 WORDS)
This review assesses the evidence regarding the effects of occupational exposure to organic solvents on colour discrimination and investigates exposure-response relationships and reversibility. This review also considers the current state of knowledge of the possible mechanisms underlying changes in colour vision, and the human health significance of any reported changes. Among the commonly used organic solvents, styrene has been investigated the most thoroughly. Studies of styrene-exposed workers in Germany, Italy and Japan provide a sufficiently consistent body of evidence to support a robust conclusion that styrene does cause an impairment of colour discrimination relative to age-matched controls. Generally, the impairment of colour discrimination observed in styrene-exposed workers tends to be of the tritan (blue-yellow) type, although some cases of red-green impairment have also been found. The limited information available on exposure-response relationships indicates that the effects on colour discrimination would not be expected at 8-hour time weighted average (8 h TWA) exposures <20 ppm, although a precise threshold cannot be determined. The data on reversibility are limited and inconclusive. The results from the most rigorous study in which this aspect was investigated point to a reversibility of effects after a 4-week exposure-free period, whereas results from a study with limitations suggest a persistence of effect. The effects of toluene, tetrachloroethylene or mixed solvent exposure have also been investigated, although the information available is generally less reliable than for styrene. For toluene, it can be confidently concluded that this solvent does not have an acute effect on colour discrimination, even when exposures are relatively high (50-150 ppm 8 h TWA, and 290-360 ppm 30 minutes TWA). However, studies are inconclusive on whether long-term or repeated exposure to toluene can cause a persistent impairment of colour discrimination. There are few studies that have specifically investigated the effects of tetrachloroethylene on colour discrimination. Among these studies, none has examined the potential for any acute effects of this solvent vapour. A large-scale study in Japanese workers showed no effects of long-term exposure to tetrachloroethylene concentrations in the region of 12-13 ppm. However, the test methodology used was relatively insensitive to changes in colour discrimination, hence the results do not provide reassurance for an absence of subtle effects. A study in Italian dry-cleaners suggested a slight impairment of colour discrimination relative to controls, associated with relatively low exposures to tetrachloroethylene (mean 8 h TWA exposure approximately 6 ppm). The studies concerning the effects of mixed solvent exposure on colour discrimination are based on workers exposed to solvents in paints and lacquers, workers from the printing and petrochemical industries, people working in or living near to microelectronics factories and children exposed to solvents prenatally. However, these studies are subject to design limitations or methodological irregularities, such that no conclusions regarding the effects of mixed solvent exposure on colour discrimination can be drawn. Overall, the only credible evidence for an effect of solvents on colour discrimination derives from the studies on styrene. Because of limitations in the data for other solvents it is not possible to determine whether the evidence for styrene reflects a generic property of solvents. The mechanisms of styrene-induced effects on colour discrimination have not been properly investigated and can only be the subject of speculation. One conclusion that can be drawn is that pathological changes to the ocular system, such as changes to the lens, are unlikely to be involved. This is because there is an absence of convincing evidence for such changes from medical examinations conducted in epidemiological studies of solvent-exposed workers. Also, it seems unlikely that effects on colour discrimination are a nonspecific consequence of more generalised CNS depression, given that styrene-induced effects on colour discrimination appear to occur below the threshold for narcotic effects. The effects of styrene on colour discrimination are subtle and involve an impairment of the ability to discriminate accurately between closely related shades of the same colour rather than 'colour blindness'. There is no valid basis for using colour discrimination as a marker for other forms of solvent-induced neurotoxicity.
This paper investigates how solution conditions, especially solvent polarity and hydrogen bonding, affect the fluorescence of ellipticine, a natural plant alkaloid with anticancer activity. A total of 16 solvents that cover a wide range of polarities were tested. The ultraviolet (UV) absorption and fluorescence emission of ellipticine were found to be solvent dependent. The absorption and emission maximum shifted to higher wavelengths (red shift) with increased solvent polarity. The difference in absorption and emission maximum (Stokes' shift) was large, approximately 10,000-11,000 cm-1, in polar solvents (with orientation polarizability Deltaf>0.2) but unusually small, approximately 8900 cm-1, in nonpolar solvents (hexane and cyclohexane). Large Stokes' shifts were due to an intramolecular charge transfer (ICT), which was enabled by large solvent polarity and hydrogen bonding of ellipticine with the solvents. Two transitions were found in the Lippert-Mataga plot between (1) nonpolar and semipolar solvents and between (2) semipolar and polar solvents. The first transition reflected the formation of hydrogen bonds between ellipticine and the solvents whereas the second transition indicated that ellipticine underwent an ICT. In addition, the larger extinction coefficients and the longer lifetime of ellipticine obtained in protic solvents were attributed to the formation of stronger hydrogen bonds. The photophysical response of ellipticine to changes in solvent polarity and hydrogen bond formation could be used to infer the location of ellipticine in a heterogeneous medium, namely liposomes in aqueous solution. A relatively large red shift of emission in liposomes indicated that ellipticine may be in a more polar environment with respect to the lipid bilayer, possibly close to the hydrophilic interface.