Linear alkylbenzenes (LAB) are key intermediates in the synthesis of linear alkylbenzene sulfonate surfactants that are used in the manufacture of detergents. Production of LAB with traditional Lewis acids as catalysts, such as hydrofluoric acid, results in the formation of large amounts of toxic wastes and corrosion of industrial equipment. Phosphotungstic acid (PTA) has gained much attention in recent years as a solid catalyst for various alkylation reactions. This research work aims to develop a novel material based on PTA-containing silica gel, which can effectively catalyze LAB synthesis. Sol-gel synthesis of silica gel in the presence of PTA and tetraethyl orthosilicate as precursors produced a mesoporous aterial containing covalently embedded PTA clusters. Obtained superacidic catalyst demonstrated high catalytic activity in liquid-phase alkylation of benzene by various alkenes. Covalent embedding of catalytically active HPA clusters prevents their leaching from the catalyst surface, which enabled its excellent catalytic properties.

Linear alkylbenzenes (LAB) are semi-products in the manufacture of linear alkylbenzene sulfonate surfactants that are active ingredients of various detergents. The use of traditional soluble acids (e.g. hydrofluoric acid or aluminum chloride) as catalysts for production of LAB results in the formation of large amounts of acidic toxic wastes. In this work, an efficient heterogeneous catalyst containing immobilized phosphotungstic acid (PTA) was synthesized and tested in the alkylation of benzene by higher alkenes. Sol–gel synthesis of silica gel from tetraethyl orthosilicate and PTA, as precursors, produced a mesoporous material containing covalently embedded PTA clusters. Obtained superacidic catalyst demonstrated high catalytic activity in liquid-phase alkylation of benzene by higher alkenes. Conversion of alkenes to corresponding phenylalkanes on this catalyst was significantly higher than on pure PTA. Covalent embedding of catalytically active HPA clusters prevented their leaching from the catalyst surface, which enabled its excellent catalytic properties.

Existing viscosity prediction methods and relevant literature are reviewed. An exhaustive review of group contribution, corresponding states, and interpolative prediction methods finds that even the best of these models produces large prediction errors and often require significant experimental data. Molecular dynamics simulation techniques for viscosity prediction are evaluated and compared to one another to determine the best choice for this work. A thorough investigation finds that Equilibrium Molecular Dynamics (EMD) simulations are the best option for reproducible and reliable liquid viscosity predictions. The many tuning parameters available in molecular dynamics simulations are investigated for their effects on prediction uncertainty and accuracy. Challenges associated with molecular dynamics predictions are discussed and a rigorous simulation and data analysis methodology is developed which addresses these issues. The TLVMie force field is developed to describe linear alkanes, branched alkanes, alkylbenzenes, and cycloalkanes. The method is developed with a "training set" of compounds and the transferability is evaluated with a completely different "test set" of compounds. Predictive capability with mixture viscosities is evaluated next without any re-fitting of the parameters determined from pure-component data. The TLVMie potential is shown to be significantly more accurate for both pure-components and mixtures, more reliable for compounds that differ greatly from the training set, and predictions are made without the experimental data requirements of other methods.

Superacidic mesoporous materials containing covalently embedded PTA were synthesized by sol-gel method. Tetraethyl orthosilicate (TEOS) and phosphotungstic acid (PTA) were used as precursors in the synthesis, ionic and nonionic surfactants were used as pore-forming agents, the reaction proceeded in acidic media. TEM images revealed mesoporous structure with embedded PTA clusters. FT-IR spectra of obtained materials contained characteristic bands of PTA at 957 cm-1. Synthesized catalysts had high BET surface area and high concentration of acidic sites. Alkylation of 1,3,5-trimethylbenzene by 1-decene demonstrated high catalytic activity. The catalyst obtained with Pluronic P123 as a template was the most effective and resulted in highest conversion of 1-decene into alkylated products. Covalent embedding of PTA clusters in addition to thermal and chemical stability of synthesized catalysts enabled their recyclability. Catalysts remained active during subsequent cycles of alkylation.

Long-chain alkylbenzenes are industrially synthesized precursors to commercial surfactants such as laundry detergent. The currently used catalysts in the processes of their synthesis are corrosive and harmful to the environment. These problems can be avoided utilizing heterogeneous highly acidic catalysts. Solid catalysts do not corrode equipment and are relatively simple to remove from the post-reaction mixture. Phosphotungstic acid (PTA) supported on silica gel could be a possible catalyst due to its high acidity with an estimated pKa ≈ -13. The catalyst PTA-SiO2 was prepared via the sol-gel method to covalently embed it in a silica support. The catalyst was granulated with γ-alumina for use in a fixed bed flow reactor during the alkylation of benzene with long chain alkenes. The isomerization of 1-octene, 1-decene, and 1-octadecene as well as the conversion of 1-decene in the alkylation of benzene were studied under varying conditions. During these reactions, the catalyst demonstrated good catalytic activity at temperatures above 200 °C with an optimal temperature of 250 °C. Of all three alkenes, 1-octadecene showed the highest conversion into respective isomers. The alkylation of benzene with 1-decene experiments showed decreasing of flow rate and increasing the ratio of benzene to 1-decene lead to higher conversions of 1-decene. Characterization of the catalyst after the reaction showed little changes in porosity and particle size. No leaching of PTA was observed. However, carbon deposits were found on the catalyst that requires regeneration before next use in catalysis.

A disposição de esgoto em áreas costeiras pode causar impactos para a vida marinha, alterando a biodiversidade e o equilíbrio do ecossistema chegando a causar graves doenças nos seres humanos. Neste estudo, determinou-se a concentração de um conjunto de marcadores orgânicos moleculares de introdução de esgoto no ambiente marinho: alquilbenzeno lineares (LABs) em amostras de sedimento, ostras (Crassostrea brasiliana), mexilhões (Mytella charruana e Mytella guyanensis) e peixes (Mugil curema) (Valenciennes, 1836) nos Estuário de Cananéia - Iguape e Santos - São Vicente, SP, Brasil. As concentrações de LABs (peso seco) encontradas em amostras de sedimento de Cananéia variaram de <1,0 a 80,6 ng g-1 e em Santos variaram de 6,7 a 1234,0 ng g-1. Em moluscos bivalves as concentrações detectadas em Cananéia encontravam-se na faixa de 90 a 1849 ng g-1(peso seco) e em Santos as concentrações variaram de 110 a 50495 ng g-1(peso seco). Os estudos em peixes de Cananéia apresentaram os seguintes valores médios (ng g-1 em peso seco): músculo (64,7 ± 22,6), pele (124,0 ± 60,1), fígado (164,0 ± 79,2) e rim (9,1 ± 9,9). No estuário de Santos, os tecidos de peixes apresentaram os seguintes valores médios (ng g-1 em peso seco): músculo (95,0 ± 90,1), pele (438,0 ± 437,0), fígado (274,0 ±147,0) e rim (60,7 ± 35,6). Houve diferença significativa entre as amostras analisadas nos tecidos de peixes de Cananéia e Santos evidenciando diferenças de acúmulo de LABs de acordo com o nível de antropização. A detecção de LABs nestas matrizes evidenciou a sua capacidade de acúmulo e reflete a exposição ao esgoto e portanto pode ser utilizadas no monitoramento ambiental. / The sewage disposal in coastal areas can cause impacts to marine life, altering the balance of the ecosystem and biodiversity and causing serious diseases in humans. In this study, the concentration of a set of molecular markers for the introduction of organic sewage into the marine environment: linear alkylbenzene (LAB), in samples of sediment, oysters (Crassostrea brasiliana), mussels (Mytella charruana and Mytella guyanensis) and fish (Mugil curema) (Valenciennes, 1836) from Cananéia - Iguape and Santos - São Vicente estuaries, located in Sao Paulo State, Brazil. LABs concentrations (dry weight) found in sediment samples from Cananéia ranged from <1.0 to 80.6 ng g-1 and from Santos ranged from 6.7 to 1234.0 ng g-1. In bivalve molluscs of Cananéia, the concentrations were in the range 90 to 1849 ng g-1 (dry weight) and in Santos, the concentrations ranged from 110 to 50495 ng g-1 (dry weight). Studies in fish from Cananéia showed the following average values (ng g-1 - dry weight): muscle (64.7 ± 22.6), skin (124.0 ± 60.1), liver (164.0 ± 79.2) and kidney (9.1 ± 9.9). In the Santos estuary, the fish tissue showed the following average values (ng g-1 - dry weight): muscle (95,0 ± 90.1), skin (438 ± 437), liver (274 ± 147) and kidney (60.7 ± 35.6). There were significant differences between the samples of tissues of fish from Cananéia and Santos showing differences in accumulation of LABs according to the level of anthropogenic occupation. The LABs detection in these matrices demonstrated their ability to accumulate and reflects the exposure to sewage and therefore can be used in environmental monitoring.

A disposição de esgoto em áreas costeiras pode causar impactos para a vida marinha, alterando a biodiversidade e o equilíbrio do ecossistema chegando a causar graves doenças nos seres humanos. Neste estudo, determinou-se a concentração de um conjunto de marcadores orgânicos moleculares de introdução de esgoto no ambiente marinho: alquilbenzeno lineares (LABs) em amostras de sedimento, ostras (Crassostrea brasiliana), mexilhões (Mytella charruana e Mytella guyanensis) e peixes (Mugil curema) (Valenciennes, 1836) nos Estuário de Cananéia - Iguape e Santos - São Vicente, SP, Brasil. As concentrações de LABs (peso seco) encontradas em amostras de sedimento de Cananéia variaram de <1,0 a 80,6 ng g-1 e em Santos variaram de 6,7 a 1234,0 ng g-1. Em moluscos bivalves as concentrações detectadas em Cananéia encontravam-se na faixa de 90 a 1849 ng g-1(peso seco) e em Santos as concentrações variaram de 110 a 50495 ng g-1(peso seco). Os estudos em peixes de Cananéia apresentaram os seguintes valores médios (ng g-1 em peso seco): músculo (64,7 ± 22,6), pele (124,0 ± 60,1), fígado (164,0 ± 79,2) e rim (9,1 ± 9,9). No estuário de Santos, os tecidos de peixes apresentaram os seguintes valores médios (ng g-1 em peso seco): músculo (95,0 ± 90,1), pele (438,0 ± 437,0), fígado (274,0 ±147,0) e rim (60,7 ± 35,6). Houve diferença significativa entre as amostras analisadas nos tecidos de peixes de Cananéia e Santos evidenciando diferenças de acúmulo de LABs de acordo com o nível de antropização. A detecção de LABs nestas matrizes evidenciou a sua capacidade de acúmulo e reflete a exposição ao esgoto e portanto pode ser utilizadas no monitoramento ambiental. / The sewage disposal in coastal areas can cause impacts to marine life, altering the balance of the ecosystem and biodiversity and causing serious diseases in humans. In this study, the concentration of a set of molecular markers for the introduction of organic sewage into the marine environment: linear alkylbenzene (LAB), in samples of sediment, oysters (Crassostrea brasiliana), mussels (Mytella charruana and Mytella guyanensis) and fish (Mugil curema) (Valenciennes, 1836) from Cananéia - Iguape and Santos - São Vicente estuaries, located in Sao Paulo State, Brazil. LABs concentrations (dry weight) found in sediment samples from Cananéia ranged from <1.0 to 80.6 ng g-1 and from Santos ranged from 6.7 to 1234.0 ng g-1. In bivalve molluscs of Cananéia, the concentrations were in the range 90 to 1849 ng g-1 (dry weight) and in Santos, the concentrations ranged from 110 to 50495 ng g-1 (dry weight). Studies in fish from Cananéia showed the following average values (ng g-1 - dry weight): muscle (64.7 ± 22.6), skin (124.0 ± 60.1), liver (164.0 ± 79.2) and kidney (9.1 ± 9.9). In the Santos estuary, the fish tissue showed the following average values (ng g-1 - dry weight): muscle (95,0 ± 90.1), skin (438 ± 437), liver (274 ± 147) and kidney (60.7 ± 35.6). There were significant differences between the samples of tissues of fish from Cananéia and Santos showing differences in accumulation of LABs according to the level of anthropogenic occupation. The LABs detection in these matrices demonstrated their ability to accumulate and reflects the exposure to sewage and therefore can be used in environmental monitoring.

Novel sol-gel titania-poly(dimethylsiloxane) (TiO2-PDMS) and titania-silica-N-(triethoxysilylpropyl)-O-polyethylene oxide urethane (TiO2-SiO2-TESP-PEO) coatings were developed for capillary microextraction (CME) to perform on-line preconcentration and HPLC analysis of trace impurities in aqueous samples. Due to chemical inertness of titania, effective covalent binding of a suitable organic ligand to its surface is difficult via conventional surface modification methods. In this research, sol-gel chemistry was employed to chemically bind hydroxy-terminated poly(dimethylsiloxane) (PDMS) and N-(triethoxysilylpropyl)-O-polyethylene oxide urethane (TESP-PEO) to sol-gel titania and sol-gel titania-silica network, respectively. A method is presented describing in situ preparation of the titania-based sol-gel PDMS and TESP-PEO coatings and their immobilization on the inner surface of a fused-silica microextraction capillary. To perform on-line CME-HPLC, the sol-gel TiO2-PDMS or TiO2-SiO2-TESP-PEO capillarywas installed in the HPLC injection port as an external sampling loop, and a conventionalHPLC separation column was used for the liquid chromatographic separation. The sol-gel TiO2-PDMS-coated microextraction capillary was used for on-line CME-HPLC analysis of non-polar and moderately polar analytes, and the sol-gel coatings showed excellent pH (1-13), and solvent (acetonitrile and methanol) stabilities under elevated temperatures (150 C) over analogous non-sol-gel silica-based coatings. Extraction of highly polar analytes, especially from aqueous phases is not an easy task. However, the sol-gel TiO2-SiO2-TESP-PEO-coated capillaries showed excellent capability of extracting underivatized highly polar analytes from aqueous samples. This opens the possibility to employ sol-gel titania-based polar coatings for solvent-free extraction and trace analysis of target analytes in environmental and biomedical matrices. To our knowledge, this is the first research on the use of sol-gel titania (or titania-silica)-based organic-inorganic materials as a sorbent in capillary microextraction. The newly developed sol-gel titania (or titania-silica)-based organic-inorganic hybrid extraction media provides an effective solution to coupling CME with HPLC (CME-HPLC), and this can be expected to become a powerful analytical tool in environmental investigations, proteomic research, early disease diagnosis and biomarker research. Being a combination of a highly efficient solvent free sample preconcentration technique (CME) and a powerful separation method (HPLC), CME-HPLC poses to become a key analytical tool in solving complex chemical, environmental, and biomedical problems involving complex matrices.