Di-(2-ethylhexyl)-phthalate (DEHP), an ubiquitous environmental contaminant, has been shown to cause adverse effects on glucose homeostasis and insulin sensitivity in epidemiological studies, but the underlying mechanisms are still unknown. We therefore tested the hypothesis that chronic DEHP exposure causes impaired insulin sensitivity, affects body weight, adipose tissue (AT) function and circulating metabolic parameters of obesity resistant 129S6 mice in vivo. An obesity-resistant mouse model was chosen to reduce a potential obesity bias of DEHP effects on metabolic parameters and AT function. The metabolic effects of 10-weeks exposure to DEHP were tested by insulin tolerance tests and quantitative assessment of 183 metabolites in mice. Furthermore, 3T3-L1 cells were cultured with DEHP for two days, differentiated into mature adipocytes in which the effects on insulin stimulated glucose and palmitate uptake, lipid content as well as on mRNA/protein expression of key adipocyte genes were investigated.We observed in female mice that DEHP treatment causes enhanced weight gain, fat mass, impaired insulin tolerance, changes in circulating adiponectin and adipose tissue Pparg, adiponectin and estrogen expression. Serum metabolomics indicated a general increase in phospholipid and carnitine concentrations. In vitro, DEHP treatment increases the proliferation rate and alters glucose uptake in adipocytes. Taken together, DEHP has significant effects on adipose tissue (AT) function and alters specific serum metabolites. Although, DEHP treatment led to significantly impaired insulin tolerance, it did not affect glucose tolerance, HOMA-IR, fasting glucose, insulin or triglyceride serum concentrations. This may suggest that DEHP treatment does not cause impaired glucose metabolism at the whole body level.

O poli(cloreto de vinila) - PVC é considerado um polímero muito versátil devido à possibilidade deste ser formulado mediante a incorporação de aditivos, alterando suas características originais. Plastificantes a base de ftalatos, como o di(2-etilhexil) ftalato (DOP) são os mais utilizados, porém, existem regulamentações que estão restringindo a sua utilização, intensificando-se os estudos com possíveis alternativos. Desta forma, este trabalho visa avaliar a influência de plastificantes de diferentes naturezas nas propriedades físicas, mecânicas, térmicas e reológicas do PVC plastificado. Para formulação dos compostos foi utilizado a resina Norvic SP1000 produzida via suspensão, com VK65 e portanto, propícia para aplicações de materiais flexíveis, além disso, para cada composto utilizou-se uma dosagem de 60 pcr de sete diferentes plastificantes: DOP, considerado como referência para comparação dos resultados, diisononil ciclohexano (DINCH), di(2-etilhexil) ciclohexanoato (DOCH), di(2-etilhexil) adipato (DOA), di(2-etilhexil) tereftalato (DOTP), óleo de soja epoxidado (OSE) e plastificante de óleos vegetais (DIMIT) Neste estudo foram efetuadas avaliações nos compostos como, gelificação e fusão, reologia via reômetro de placas paralelas, densidade, índice de fluidez entre outras para compreender a influência de cada plastificante no processamento do composto e várias caracterizações no produto final como estabilidade térmica dos compostos via TGA, Metrastat, propriedades óticas, propriedades mecânicas como dureza Shore A, tração, resistência a abrasão, resiliência, envelhecimento em câmara UV assim como ensaios de exsudação dos plastificantes. Os resultados indicam comportamentos distintos do PVC em função da natureza química do plastificante utilizado. O plastificante DIMIT possui boa estabilidade térmica, porém os resultados de cor e parâmetros de processamento foram insatisfatórios quando comparados ao DOP, já os plastificantes OSE e DOA apresentaram bons resultados para as propriedades avaliadas. Conclui-se que dentre os plastificantes analisados não foi possível determinar qual seria o melhor para substituição direta do DOP considerando toda a gama de produtos flexíveis de PVC, contudo esse trabalho colabora para a avaliação e seleção do melhor plastificante com base nos requisitos de cada aplicação do produto. / The poly (vinyl chloride) - PVC is a very versatile polymer due to the possibility of being formulated by incorporating additives, which can change the resin characteristics. Plasticizers composed of phthalates, such as di(2-ethylhexyl) phthalate (DOP), are the most used, however, there are regulations restricting the use of this kind of plasticizers, intensifying studies with possible replacement alternatives. In this way, the objective of this work is to evaluate the influence of plasticizers from different sources in PVC, mainly physical, mechanical thermal stability, and rheological properties in the plasticized PVC. In the formulation of the compounds it was used the resin Norvic SP1000, product with VK65 and produced by suspension, suitable for flexible materials applications. In addition, it was used 60 phr of seven different plasticizers for each compound: DOP, considered as reference for all results, cyclohexane diisononyl (DINCH), di(2-ethylhexyl) cyclohexanoate (DOCH), di(2-ethylhexyl) adipate (DOA), di(2-ethylhexyl) terephthalate (DOTP), epoxidized soybean oil (OSE) and plasticizer produced from vegetable oils (DIMIT). In this study, the compounds were evaluated with many characterization analyzes, such as gelling and melting point in a torque rheometer, rheology by parallel plate rheometer, density, melt flow index in order to understand the influence of each plasticizer on the material processing Some characterizations in the final product as thermal stability through TGA, Metrastat, optical and mechanical properties such as hardness Shore A, tensile strength, abrasion resistance, resilience, aging in UV chamber as well as exudation tests. The results indicate different behaviors of PVC depending on the chemical nature of the plasticizer used. Results indicate that the DIMIT plasticizer had good thermal stability, but the color and processability results were unsatisfactory when compared to the DOP. In the other hand, the OSE and DOA presented good results for the evaluated properties. It can be concluded that among the plasticizers analyzed it wasn´t possible to determine the best for direct DOP replacement considering the entire range of flexible PVC products. However, this work contributes to the evaluation and selection of the best plasticizer based on the requirements of each application.

The fate and transformation of laboratory-prepared nano-ZnO, nano-Ag and nano-CeO2 in three aqueous solutions under different environmental conditions were investigated in this work. Over the past decades nanomaterials have been widely used in different technical fields and consumer goods. As a result, nanomaterials might enter the environmental media via different routes and then posed potential hazards to the environment and human health. Researches in this regard have received much attention worldwide. In this work it was found that the solubility of each nanomaterial was highly influenced by the solution pH, but not by the solution temperature. The maximal solubility for the tested nanomaterials was obtained at pH 3, namely about 100% for nano-ZnO and lower than 2% for both nano-Ag and nano-CeO2. The solution pH and ionic strength were found to affect the stability of nanoparticles in different aquatic environments. For the solution pH of higher than the isoelectric point of the concerned nanomaterial, the higher the solution pH is, the greater the degree of stabilization of nanoparticles would be. On the contrary, nanoparticles aggregated as the ionic strength of the solution exceeded its critical aggregation concentration (CAC). CAC for each concerned nanomaterial could also be graphically determined as the attachment efficiency (£\) of nanoparticles increased with increasing ionic strength of the solution and then leveled off after reaching CAC. Experimental results also showed that Zn(OH)2(s) would form when nano-ZnO was in the solution of pH 10. The crystalline structure of the said precipitates was confirmed by X-ray diffraction. Likewise, Ce4+ dissolved from nano-CeO2 reacted with SO42- in aqueous solution yielding Ce(SO4)2(s). Clearly, transformation of nanomaterials might take place when they are in contact with various species in different aquatic environments. Humic acid in aqueous solution was found to be beneficial to the stability of nanomaterial of concern. Efforts have also been made to study the reaction behaviors among di(2-ethylhexyl)phthalate, erythromycin, and selected nanomaterials when they co-existed in the same solution. Their interactions, however, seemed to be unobvious. In this work it was found that under sunlight irradiation nano-ZnO did show its antibiotic effect due to photocatalysis. Nano-Ag was proven to have a strong antibacterial ability even in natural aquatic environments. It yielded the total bacteria survival ratio of less than 2% within one hour of reaction. In summary, the findings of this study showed that the behaviors of nano-ZnO, nano-Ag, and nano-CeO2 in aqueous solutions could be greatly influenced by different factors in different reaction systems.

O poli(cloreto de vinila) - PVC é considerado um polímero muito versátil devido à possibilidade deste ser formulado mediante a incorporação de aditivos, alterando suas características originais. Plastificantes a base de ftalatos, como o di(2-etilhexil) ftalato (DOP) são os mais utilizados, porém, existem regulamentações que estão restringindo a sua utilização, intensificando-se os estudos com possíveis alternativos. Desta forma, este trabalho visa avaliar a influência de plastificantes de diferentes naturezas nas propriedades físicas, mecânicas, térmicas e reológicas do PVC plastificado. Para formulação dos compostos foi utilizado a resina Norvic SP1000 produzida via suspensão, com VK65 e portanto, propícia para aplicações de materiais flexíveis, além disso, para cada composto utilizou-se uma dosagem de 60 pcr de sete diferentes plastificantes: DOP, considerado como referência para comparação dos resultados, diisononil ciclohexano (DINCH), di(2-etilhexil) ciclohexanoato (DOCH), di(2-etilhexil) adipato (DOA), di(2-etilhexil) tereftalato (DOTP), óleo de soja epoxidado (OSE) e plastificante de óleos vegetais (DIMIT) Neste estudo foram efetuadas avaliações nos compostos como, gelificação e fusão, reologia via reômetro de placas paralelas, densidade, índice de fluidez entre outras para compreender a influência de cada plastificante no processamento do composto e várias caracterizações no produto final como estabilidade térmica dos compostos via TGA, Metrastat, propriedades óticas, propriedades mecânicas como dureza Shore A, tração, resistência a abrasão, resiliência, envelhecimento em câmara UV assim como ensaios de exsudação dos plastificantes. Os resultados indicam comportamentos distintos do PVC em função da natureza química do plastificante utilizado. O plastificante DIMIT possui boa estabilidade térmica, porém os resultados de cor e parâmetros de processamento foram insatisfatórios quando comparados ao DOP, já os plastificantes OSE e DOA apresentaram bons resultados para as propriedades avaliadas. Conclui-se que dentre os plastificantes analisados não foi possível determinar qual seria o melhor para substituição direta do DOP considerando toda a gama de produtos flexíveis de PVC, contudo esse trabalho colabora para a avaliação e seleção do melhor plastificante com base nos requisitos de cada aplicação do produto. / The poly (vinyl chloride) - PVC is a very versatile polymer due to the possibility of being formulated by incorporating additives, which can change the resin characteristics. Plasticizers composed of phthalates, such as di(2-ethylhexyl) phthalate (DOP), are the most used, however, there are regulations restricting the use of this kind of plasticizers, intensifying studies with possible replacement alternatives. In this way, the objective of this work is to evaluate the influence of plasticizers from different sources in PVC, mainly physical, mechanical thermal stability, and rheological properties in the plasticized PVC. In the formulation of the compounds it was used the resin Norvic SP1000, product with VK65 and produced by suspension, suitable for flexible materials applications. In addition, it was used 60 phr of seven different plasticizers for each compound: DOP, considered as reference for all results, cyclohexane diisononyl (DINCH), di(2-ethylhexyl) cyclohexanoate (DOCH), di(2-ethylhexyl) adipate (DOA), di(2-ethylhexyl) terephthalate (DOTP), epoxidized soybean oil (OSE) and plasticizer produced from vegetable oils (DIMIT). In this study, the compounds were evaluated with many characterization analyzes, such as gelling and melting point in a torque rheometer, rheology by parallel plate rheometer, density, melt flow index in order to understand the influence of each plasticizer on the material processing Some characterizations in the final product as thermal stability through TGA, Metrastat, optical and mechanical properties such as hardness Shore A, tensile strength, abrasion resistance, resilience, aging in UV chamber as well as exudation tests. The results indicate different behaviors of PVC depending on the chemical nature of the plasticizer used. Results indicate that the DIMIT plasticizer had good thermal stability, but the color and processability results were unsatisfactory when compared to the DOP. In the other hand, the OSE and DOA presented good results for the evaluated properties. It can be concluded that among the plasticizers analyzed it wasn´t possible to determine the best for direct DOP replacement considering the entire range of flexible PVC products. However, this work contributes to the evaluation and selection of the best plasticizer based on the requirements of each application.

In the present study, both in vitro and in vivo experiments were performed to investigate modes of action of selected EDCs including mercury chloride (HgCl2), bisphenol A (BPA), vinclozolin (VZ) and Di-(2-ethylhexyl)-phthalate (DEHP) on male reproductive physiology in fish. Results obtained from in vitro studies showed that EDCs decrease sperm motility via disruption in energetics and damage to spermatozoa; however the effective doses are higher than reported in the environmentally relevant concentrations. In contrast, in vivo studies showed adverse effects of BPA, VZ, and DEHP on sperm quality at environmentally relevant concentrations. Decrease in sperm quality is associated with disruption in testicular steroidogenesis, particularly inhibition of androgens. Only BPA induced vitellogenin production, associated with increase in transcripts of estrogen receptor, androgen receptor and cytochrome P450 mRNA at the high dose approaching environmental level. Inhibition of androgen production is due to disruption in transfer of cholesterol into the steroidogenesis pathway, because transcript of steroidogenic acute regulatory protein mRNA was decreased. In addition, BPA acts through sex steroid-mediated mechanism while DEHP mode of action is sex-steroid independent mechanism.

O poli(cloreto de vinila) - PVC é considerado um polímero muito versátil devido à possibilidade deste ser formulado mediante a incorporação de aditivos, alterando suas características originais. Plastificantes a base de ftalatos, como o di(2-etilhexil) ftalato (DOP) são os mais utilizados, porém, existem regulamentações que estão restringindo a sua utilização, intensificando-se os estudos com possíveis alternativos. Desta forma, este trabalho visa avaliar a influência de plastificantes de diferentes naturezas nas propriedades físicas, mecânicas, térmicas e reológicas do PVC plastificado. Para formulação dos compostos foi utilizado a resina Norvic SP1000 produzida via suspensão, com VK65 e portanto, propícia para aplicações de materiais flexíveis, além disso, para cada composto utilizou-se uma dosagem de 60 pcr de sete diferentes plastificantes: DOP, considerado como referência para comparação dos resultados, diisononil ciclohexano (DINCH), di(2-etilhexil) ciclohexanoato (DOCH), di(2-etilhexil) adipato (DOA), di(2-etilhexil) tereftalato (DOTP), óleo de soja epoxidado (OSE) e plastificante de óleos vegetais (DIMIT) Neste estudo foram efetuadas avaliações nos compostos como, gelificação e fusão, reologia via reômetro de placas paralelas, densidade, índice de fluidez entre outras para compreender a influência de cada plastificante no processamento do composto e várias caracterizações no produto final como estabilidade térmica dos compostos via TGA, Metrastat, propriedades óticas, propriedades mecânicas como dureza Shore A, tração, resistência a abrasão, resiliência, envelhecimento em câmara UV assim como ensaios de exsudação dos plastificantes. Os resultados indicam comportamentos distintos do PVC em função da natureza química do plastificante utilizado. O plastificante DIMIT possui boa estabilidade térmica, porém os resultados de cor e parâmetros de processamento foram insatisfatórios quando comparados ao DOP, já os plastificantes OSE e DOA apresentaram bons resultados para as propriedades avaliadas. Conclui-se que dentre os plastificantes analisados não foi possível determinar qual seria o melhor para substituição direta do DOP considerando toda a gama de produtos flexíveis de PVC, contudo esse trabalho colabora para a avaliação e seleção do melhor plastificante com base nos requisitos de cada aplicação do produto. / The poly (vinyl chloride) - PVC is a very versatile polymer due to the possibility of being formulated by incorporating additives, which can change the resin characteristics. Plasticizers composed of phthalates, such as di(2-ethylhexyl) phthalate (DOP), are the most used, however, there are regulations restricting the use of this kind of plasticizers, intensifying studies with possible replacement alternatives. In this way, the objective of this work is to evaluate the influence of plasticizers from different sources in PVC, mainly physical, mechanical thermal stability, and rheological properties in the plasticized PVC. In the formulation of the compounds it was used the resin Norvic SP1000, product with VK65 and produced by suspension, suitable for flexible materials applications. In addition, it was used 60 phr of seven different plasticizers for each compound: DOP, considered as reference for all results, cyclohexane diisononyl (DINCH), di(2-ethylhexyl) cyclohexanoate (DOCH), di(2-ethylhexyl) adipate (DOA), di(2-ethylhexyl) terephthalate (DOTP), epoxidized soybean oil (OSE) and plasticizer produced from vegetable oils (DIMIT). In this study, the compounds were evaluated with many characterization analyzes, such as gelling and melting point in a torque rheometer, rheology by parallel plate rheometer, density, melt flow index in order to understand the influence of each plasticizer on the material processing Some characterizations in the final product as thermal stability through TGA, Metrastat, optical and mechanical properties such as hardness Shore A, tensile strength, abrasion resistance, resilience, aging in UV chamber as well as exudation tests. The results indicate different behaviors of PVC depending on the chemical nature of the plasticizer used. Results indicate that the DIMIT plasticizer had good thermal stability, but the color and processability results were unsatisfactory when compared to the DOP. In the other hand, the OSE and DOA presented good results for the evaluated properties. It can be concluded that among the plasticizers analyzed it wasn´t possible to determine the best for direct DOP replacement considering the entire range of flexible PVC products. However, this work contributes to the evaluation and selection of the best plasticizer based on the requirements of each application.

No description available.

Di-(2-ethylhexyl)-phthalate (DEHP), an ubiquitous environmental contaminant, has been shown to cause adverse effects on glucose homeostasis and insulin sensitivity in epidemiological studies, but the underlying mechanisms are still unknown. We therefore tested the hypothesis that chronic DEHP exposure causes impaired insulin sensitivity, affects body weight, adipose tissue (AT) function and circulating metabolic parameters of obesity resistant 129S6 mice in vivo. An obesity-resistant mouse model was chosen to reduce a potential obesity bias of DEHP effects on metabolic parameters and AT function. The metabolic effects of 10-weeks exposure to DEHP were tested by insulin tolerance tests and quantitative assessment of 183 metabolites in mice. Furthermore, 3T3-L1 cells were cultured with DEHP for two days, differentiated into mature adipocytes in which the effects on insulin stimulated glucose and palmitate uptake, lipid content as well as on mRNA/protein expression of key adipocyte genes were investigated.We observed in female mice that DEHP treatment causes enhanced weight gain, fat mass, impaired insulin tolerance, changes in circulating adiponectin and adipose tissue Pparg, adiponectin and estrogen expression. Serum metabolomics indicated a general increase in phospholipid and carnitine concentrations. In vitro, DEHP treatment increases the proliferation rate and alters glucose uptake in adipocytes. Taken together, DEHP has significant effects on adipose tissue (AT) function and alters specific serum metabolites. Although, DEHP treatment led to significantly impaired insulin tolerance, it did not affect glucose tolerance, HOMA-IR, fasting glucose, insulin or triglyceride serum concentrations. This may suggest that DEHP treatment does not cause impaired glucose metabolism at the whole body level.

Modern indoor environments contain a vast array of contaminating sources. Emissions from these sources produce contaminant concentrations that are substantially higher indoors than outside. Because we spend most of our time indoors, exposure to indoor pollutants may be orders-of-magnitude greater than that experienced outdoors. Phthalate esters have been recognized as major indoor pollutants. They are mainly used as plasticizers to enhance the flexibility of polyvinylchloride (PVC) products, as well as in humectants, emollients, and antifoaming agents. Phthalates are found in a wide range of consumer products including floor and wall coverings, car interior trim, floor tiles, gloves, footwear, insulation on wiring, and artificial leather. Because these phthalate additives are not chemically bound to the polymer matrix, slow emission from the products to the surrounding air or other media usually occurs. Biomonitoring data suggest that over 75% of the U.S. population is exposed to phthalates. The ubiquitous exposure to phthalates is of concern because toxicological investigations have demonstrated considerable adverse health effects of phthalates and their metabolites. Studies have shown that exposure to phthalates results in profound and irreversible changes in the development of the reproductive tract, especially in males, raising the possibility that phthalate exposures could be the leading cause of reproductive disorders in humans. In addition, effects such as increases in prenatal mortality, reduced growth and birth weight, skeletal, visceral, and external malformations are possibly associated with phthalate exposure. Epidemiologic studies in children also show associations between phthalate exposure in the home and the risk of asthma and allergies. Given the ubiquitous nature of phthalates in the environment and the potential for adverse human health impacts, there is a critical need to understand indoor emissions of phthalates and to identify the most important sources and pathways of exposure. In this study, a model that integrates the fundamental mechanisms governing emissions of semi-volatile organic compounds (SVOCs) from polymeric materials and their subsequent interaction with indoor surfaces and airborne particles was developed. The emissions model is consistent with analogous mechanistic models that predict emission of volatile organic compounds (VOCs) from building materials. Reasonable agreement between model predictions and gas-phase di-2-ethylhexyl phthalate (DEHP) concentrations was achieved for data collected in a previously published experimental study that measured emissions of DEHP from vinyl flooring in two very different chambers. The analysis showed that while emissions of highly volatile VOCs are subject to “internal“ control (through the material-phase diffusion coefficient), emissions of the very low volatility SVOCs are subject to “external“– control (through partitioning into the gas phase, the convective mass transfer coefficient, and adsorption onto interior surfaces). Because of the difficulties associated with sampling and analysis of SVOCs, only a few chamber studies quantifying their emissions from building materials and consumer products are available. To more rigorously validate the SVOCs emission model and more completely understand the mechanisms governing the release of phthalate from polymeric building materials, the emission of DEHP from vinyl flooring was studied for up to 140 days in a specially-designed stainless steel chamber. In the duplicate chamber study, the gas-phase concentration in the chamber increased slowly and reached a steady state level of 0.9 µg/m3 after 30 days. By increasing the area of vinyl flooring and decreasing that of the stainless steel surface in the chamber, the time to reach steady state was significantly reduced, compared to the previous study (1 month vs. 5 months). The adsorption isotherm of DEHP on the interior stainless steel chamber surface was explicitly measured using two different methods (solvent extraction and thermal desorption). Strong adsorption of DEHP onto the stainless steel surface was observed and found to follow a simple linear relationship. In addition, parameters measured in the experiments were then applied in the fundamental SVOCs emission model. Good agreement was obtained between the predictions of the model and the gas-phase DEHP chamber concentrations, without resorting to fitting of model parameters. These chamber studies have shown that the tendency of SVOCs to adsorb strongly to interior surfaces has a very strong influence on the emission rate. Compared to the experimental chamber systems, however, the real indoor environment has many other types of surface that will adsorb phthalates to different extents. The emission rate measured in a test chamber may therefore be quite different to the emission rate from the same material in the indoor environment. For this reason, both a two-room model and a more representative three-compartment model were developed successively to estimate the emission rate of DEHP from vinyl flooring, the evolving gas-phase and adsorbed surface concentrations, and human exposures (via inhalation, dermal absorption and oral ingestion of dust) in a realistic indoor environment. Adsorption isotherms for phthalates and plasticizers on interior surfaces, such as carpet, wood, dust and human skin, were derived from previous field and laboratory studies. A subsequent sensitivity analysis revealed that the vinyl flooring source characteristics, as well as mass-transfer coefficients and ventilation rates, are important variables influencing the steady-state DEHP concentration and resulting exposures. A simple uncertainty analysis suggested that residential exposure to DEHP originating from vinyl flooring may fall somewhere between about 5 µg/kg/d and 180 µg/kg/d. The roughly 40-fold range in exposure reveals the inherent difficulty in using biomonitoring results to identify specific sources of exposure in the general population. This research represents the first attempt to explicitly elucidate the fundamental mechanisms governing the release of phthalates from polymeric building materials as well as their subsequent interaction with interior surfaces. The mechanistic models developed can most likely be extended to predict concentration and exposure arising from other sources of phthalates, other sources of other semi-volatile organic compounds (such as biocides and flame retardants), as well as emissions into other environmental media (food, water, saliva, and even blood). The results will be of value to architects, governments, manufacturers, and engineers who wish to specify low-emitting green materials for healthy buildings. It will permit health professionals to identify and control health risks associated with many of the SVOCs used in indoor materials and consumer products in a relatively inexpensive way. / Ph. D.

No description available.