As one of the natural polyphenols, resveratrol possesses hydroxyl substituted trans-stilbene structure and exerts impact on health by inhibiting multiple human enzymes, such as cyclooxygenase, F1 ATPase, and tyrosinase. Resveratrol has to be bound by human serum albumin (HSA) to keep a high concentration in serum, since its solubility is low in water. To improve water solubility and bioavailability, two resveratrol aliphatic acids and their esters have been designed and synthesized. The solubilities of the resveratrol and its derivatives have been measured using a standard procedure. The two aliphatic acids showed better solubilities in pure water and phosphate buffer (pH 7). The binding affinities of resveratrol derivatives for HSA were also measured, and the drug-protein interaction mechanism was investigated using fluorescence, UV-vis, and NMR spectroscopies. Interestingly, resveratrol hexanoic acid (5) was found to be a much better ligand (Ka = (6.70 ± 0.10) × 106 M-1) for HSA than resveratrol (Ka = (1.64 ± 0.07) × 105 M-1), and there was 41-fold improvement for the binding affinity. It was the first time that the increase of fluorescence of resveratrol moiety was observed during the binding to HSA, suggesting that 5 should be bound tightly by HSA. The UV-vis absorption spectroscopy revealed a maximum absorption shift from 318 to 311 nm with decreasing intensity by 20% upon complexation, suggesting that the π-π conjugation of the stilbene structure was impaired during the binding. Although HSA was reported to have only one binding site for resveratrol, the Job's and molar ratio plots suggested that HSA should bind two molecules of 5. NMR study suggested that phenyl group (B ring) in the center of the molecule of 5 should be involved in the π-π stacking interactions with HSA aromatic amino acid residues. Molecular geometry calculation of 5 with Spartan software showed that the stilbene structure had two conformers, orthogonal and planar ones. The former (E = -1.432 KJ/mol) was more stable than the latter (E = -0.128 KJ/mol), suggesting that the former should be the conformer of 5 in the complexation with HSA.

Membrane processes have received growing attention due to their low energy consumption and ease of operation. Thin-film composite reverse osmosis membranes based on polyamides are the most widely applied commercial membranes, because of their high flux and selectivity. However, their application for gas separation processes is still limited. This is the due to the presence of defects in the membrane when in the dry state. Traditionally, thin-film composite membranes are made by interfacial polymerization between a polar (aqueous) phase and a non-polar (organic) phase. The most commonly applied thin-film composite membranes are made by dissolving m-phenylene diamine in the aqueous phase and trimesoyl chloride in the organic phase. This work investigated the possibility of fabricating thin-film composite membranes when an aliphatic alcohol (methanol, ethanol or isopropanol) is used as the polar phase. This is further extended to examining the ability of a PDMS coating to plug the defects in such layers. The effects of temperature and support type on the membrane performance were also studied. Solubility tests were conducted to determine the solubility limit of commercial and in-house fabricated amine monomers in water, methanol, ethanol and isopropanol. Water-insoluble monomers were found to be soluble in ethanol and methanol. Gas permeation tests were conducted on membranes made using water, methanol, ethanol and isopropanol as the polar phase. The results showed that the membranes produced by aliphatic alcohols had higher selectivities. The highest H2/CO2 selectivity of ~ 26 was observed in the ethanol-based membranes when they were coated with PDMS and tested at 80 C. It was confirmed that PDMS is able to plug the defects in the membrane. Membranes made on the polysulfone support were found to have higher permeance and comparable selectivity relative to the membranes made on the polyacrylonitrile supports. It was also found that a change in the polar phase solvent is able to alter the morphology of the membranes. SEM micrographs showed clear differences in the surface structure of each membrane. The average thickness values obtained from ellipsometry measurements showed a correlation with the interface miscibility. The thickest membrane corresponded to the most miscible interface (IPA/Isopar).

No description available.

Aromatic polyimides have found widespread applicability which can be partially attributed to their thermal stability, chemical resistance, and high glass transition temperature. However, deficiencies in their processability, solubility, transparency, and relatively high dielectric constants do not always provide the optimum properties for many specialty microelectronics applications. The incorporation of aliphatic segments to form partially aliphatic polyimides, has been used to counteract these shortcomings. Many of the potential uses of partially aliphatic polyimides require them to adhere to ceramic substrates, a main topic of this research. Polyimides and copolyimides that varied in chemical composition by their aliphatic content were characterized by their molecular weight, glass transition temperature, thermal stability, coefficient of thermal expansion, refractive index, dielectric behavior, and mechanical properties. Structure-property relationships were established. The gamma and beta sub-Tg viscoelastic relaxations were investigated to understand their molecular origins. The adhesion performance of a selected series of partially aliphatic polyimides to SiO2/Si was examined using a shaft loaded blister test, which was designed and instrumented for use in a dynamic mechanical analysis instrument. The adhesion was studied at high and low percent relative humidities and for several temperatures to examine if adhesion strength is influenced by polymer chemical composition. The adhesion energy could not be quantified for the entire series of polyimides. It was possible to interpret the quantitative adhesive fracture energies along with the qualitative adhesion strength behaviors, the failure surface analyses, and to offer an understanding of the adhesive chemical structure-physical property relationships. These understandings provide a conclusion that the incorporation of aliphatic segments into the polyimide chemical structure improves the durability of the adhesive bond to SiO2/Si under high percent relative humidities. / Ph. D.

Dimethacrylate oligomers diluted with styrene reactive diluents (so-called vinyl ester resins) are becoming increasingly important for composites in applications such as transportation vehicles, printed wiring boards and civil infrastructure. This research has focused on the generation and comparative analysis of glassy dimethacrylate networks as a function of oligomer structure, the type of reactive diluent, composition and curing conditions. A novel cycloaliphatic dimethacrylate was synthesized and its networks were compared to oligomeric structures containing dimethacrylates derived from epoxy terminated oligomers (from bisphenol-A and epichlorohydrin). Both types of dimethacrylates co-cured with methyl methacrylate exhibited increases in Mc and fracture toughness as the concentration of methyl methacrylate was increased. By contrast, networks prepared with a styrene diluent displayed reduced toughness with increasing styrene and Mc. Due to the need for long-term composite environmental durability, the effects of moisture and exposure to sunlight are important. Thus, these materials were exposed to ultraviolet light on a rotating drum for 225 days and the exposure was carefully monitored. Initial results from this study suggest that both the networks comprising the aromatic dimethacrylate/styrene structures as well as the cycloaliphatic analogues cured with methyl methacrylate undergo reductions in rubbery moduli upon aging under these conditions. X-Ray photoelectron spectroscopy shows higher levels of oxidation on the bisphenol-A vinyl ester networks cured with styrene, especially those containing dimethylaniline and cobalt naphthenate as accelerators. Scanning electron microscopy indicates a smooth surface for the cycloaliphatic networks cured with methyl methacrylate and a pitted surface for the aromatic networks cured with styrene. Water absorption is also higher for the cycloaliphatic vinyl ester; however, curing with a longer alkyl chain methacrylate (butyl methacrylate) decreases the water absorption to levels comparable to those cured with styrene. / Ph. D.

No / Aliphatic aldehydes have a high affinity toward aldehyde dehydrogenase activity but are relatively poor substrates of aldehyde oxidase and xanthine oxidase. In addition, the oxidation of xenobiotic-derived aromatic aldehydes by the latter enzymes has not been studied to any great extent. The present investigation compares the relative contribution of aldehyde dehydrogenase, aldehyde oxidase, and xanthine oxidase activities in the oxidation of substituted benzaldehydes in separate preparations. The incubation of vanillin, isovanillin, and protocatechuic aldehyde with either guinea pig liver aldehyde oxidase, bovine milk xanthine oxidase, or guinea pig liver aldehyde dehydrogenase demonstrated that the three aldehyde oxidizing enzymes had a complementary substrate specificity. Incubations were also performed with specific inhibitors of each enzyme (isovanillin for aldehyde oxidase, allopurinol for xanthine oxidase, and disulfiram for aldehyde dehydrogenase) to determine the relative contribution of each enzyme in the oxidation of these aldehydes. Under these conditions, vanillin was rapidly oxidized by aldehyde oxidase, isovanillin was predominantly metabolized by aldehyde dehydrogenase activity, and protocatechuic aldehyde was slowly oxidized, possibly by all three enzymes. Thus, aldehyde oxidase activity may be a significant factor in the oxidation of aromatic aldehydes generated from amines and alkyl benzenes during drug metabolism. In addition, this enzyme may also have a role in the catabolism of biogenic amines such as dopamine and noradrenaline where 3-methoxyphenylacetic acids are major metabolites.

<p>Chlorinated aliphatic hydrocarbons (CAH´s) were used widely within dry cleaning facilities and for metal degreasing until their toxicity was discovered. PCE is still used as dry cleaning liquid. Today CAH´s are found in soil environment at places where they have been used in the past. The CAH-concentration in trees growing on contaminated land has quite recently received attention as a cheap and effective way of assessing the extent of a CAH-contamination. The method has however, not been put into use in Sweden.</p><p>The aim of the study has been to investigate whether the CAH-concentration in tree cores could be used to delineate the spread of CAH in a soil environment under Swedish conditions in different seasons. The aim has also been to gain an understanding of the uptake process, as well as to identify the limitations of the method and important issues to consider when sampling.</p><p>Trees were sampled in March and June on Helgö 1:25, 1:26 in Växjö, Småland. Metal degreasing earlier conducted at this site has lead to the CAH contamination of soil and groundwater (PCE, TEC c-DACE). Mostly PCE, TCE, and chloroform were detected in tree cores. The CAH concentration was higher in June. Using the sum of PCE+TCE+c-DCE in trees to delineate the spread gave a result that was quite consistent with a delination done based on groundwater sampling.</p><p>The uptake of CAH by trees is governed by the uptake of water at the root. The water usage, together with the origin of the water used is important for the ability of the tree to take up CAH. The CAH concentration within trees is also dependent on the chemical properties of the compound (Log kow, solubility etc), the concentration of the compound in the soil as well as degradation processeses. The position and height of sampling in the trees, tree species as well as tree size are important factors to consider when sampling. Sampling during summer is preferred when the concentration of CAH in trees is likely to be higher.</p><p>The analysis of CAH in tree cores has potential to be used as a screening tool in soil investigations under Swedish conditions. It is a cheap and easy to use method, which would be a good complement to other investigative measures. However, an increased understanding of the processes involved, together with more analysis are needed., as this is a new method.</p> / <p>Klorerade lösningsmedel (CAH) användes i stor omfattning som bl a kemtvättmedel och avfettningsmedel tills dess att deras toxiska egenskaper blev kända. Perkloretylen (PCE) används än idag som kemtvättmedel. CAH återfinns ofta i markmiljö på de platser där de tidigare använts. Analys av CAH-koncentration i trädkärnor har uppmärksammats som en billig och effektiv metod för att översiktligt bedöma utbredningen av dessa föroreningar. Metoden har inte tidigare använts i Sverige.</p><p>Syftet med detta examensarbete är att undersöka om trädprovtagning kan användas för att bedöma utbredningen av föroreningar i markmiljö under svenska förhållanden vid olika årstider.</p><p>Analyserade CAH-halter i träd har jämförts med tidigare registrerade halter av CAH i grundvatten. Syftet har också varit att beskriva CAH-upptaget i träd, undersöka metodens begränsningar samt att sammanfatta viktiga aspekter vid provtagning.</p><p>Provtagningar av träd har genomförts under mars och juni på fastigheterna Helgö 1:25 och 1:26 i Växjö, där tidigare metallavfettning har medfört att mark och grundvattnet förorenats av CAH; perkloretylen (PCE), trikloretylen (TCE) och nedbrytningsprodukten dikloretylen (c1,2-DCE). Vid analys av trädkärnor detekterades främst PCE, TCE samt TCM (kloroform). Koncentrationen av CAH var högre i juni. Halten PCE+TCE+c-DCE i trädproverna gav en översiktlig bild av föroreningssituationen som överensstämde väl med de grundvattenprover som tidigare tagits på fastigheten.</p><p>CAH tas upp i vattenlöst fas vid trädens rötter. Trädets vattenbehov och vilket vatten det utnyttjar är därför viktigt för dess möjlighet att ta upp CAH. Ämnets kemiska egenskaper (log kow, flyktighet, mm.), samt förekomst och nedbrytning påverkar den halt som registreras i trädet. Vid provtagning bör provtagningspunkternas höjd över marken och position, trädart samt trädstorlek beaktas. Provtagning under sommaren är att föredra eftersom halterna då är högre.</p><p>Jämförelsen med grundvattenprovtagning visar att metoden har potential att användas i Sverige för att bedöma utbredningen av en CAH-förorening i markmiljö. Den är enkel att använda och kan vara ett alternativ på platser där konventionella metoder är svåra att genomföra. En ökad förståelse för involverade processer, samt utökade undersökningar av metoden är nödvändiga då metoden är ny.</p>

For many years the problem of separating aliphatic and aromatic compounds has been at the forefront of the petroleum and oil refining industries. This separation is often effected using liquid-liquid extraction or extractive distillation. Both of these processes require the addition of a solvent to bring about separation. The aims of this work were to investigate the use of "mixed" solvents, such as those used in the Arosolvan process, for their application in liquid-liquid extraction and extractive distillation as well as to provide related thelmodynamic data for systems containing mixed solvents. In the last part of this work, a computer program was developed to theoretically predict the effectiveness of a number of solvents on a user-defined separation. The solvents used for liquid-liquid extraction were chosen based on their similarities to those in the Arosolvan process and were of the form, {N-methyl-2-pyrollidone (NMP) + glycerol, a glycol or water} where the glycol was either monoethylene glycol (MEG), diethylene glycol (DEG) or triethylene glycol (TEG). The additives were combined in various mixing ratios to NMP to determine a mixing ratio for which the effect of the solvent is possibly optimized (a list of all solvents and mixing ratios used are presented in this work). Solvent selectivity and the range of compositions over which separation could occur determined the effectiveness of the solvents. This work dealt with the separation of n-hexane and toluene. In order to determine the selectivity and range of compositions, the liquid-liquid equilibria (LLE) of systems containing n-hexane + toluene + solvent had to be determined. LLE was measured using a simple equilibrium cell at 298 K and 1 atm. The phase separation boundaries (binodal curves) were determined using a titration method. The results obtained in this work showed an increase in the range of compositions over which the mixture of n-hexane and toluene could be separated (i.e a larger range of mixing ratios over which these components could be separated from each other) from the pure NMP solvent to the mixed solvent cases. This implies that there is a The range of compositions over which separation could be affected is given (for the solvents) in descending order: NMP + 50% glycerol> NMP + 10% water > NMP + 30% MEG > NMP + 5% water > NMP + 30% glycerol> NMP + 10% glycerol > NMP + 10% MEG > NMP + 10% DEG > NMP + 10% TEG > NMP + 5% DEG > 100% NMP. The selectivities of the solvents showed a remarkable increase from the pure NMP case to the mixed solvent cases. The maximum selectivity obtained for the NMP + 10% DEG system was over 1200 compared to a maximum selectivity of just 6 for the pure NMP system. The maximum selectivities obtained in descending order were as follows: NMP + 10% DEG > NMP + 10% TEG > NMP + 10% glycerol > NMP + 10% MEG > NMP + 30% MEG > NMP + 50% glycerol > NMP + 10% water > NMP + 5% water > NMP + 30% glycerol > NMP + 5% DEG > 100% NMP. The binodal curves were modelled using the Hlavaty, ,8-density and log-y functions. The maximum standard deviations obtained were 0.075, 0.078 and 0.05 for each of the functions respectively. The equilibrium data was modelled using the UNIQUAC and NRTL thermodynamic models and showed excellent agreement. This work showed better agreement to the NRTL functions due to the fact that the non-randomness parameter, a ij , may be chosen arbitrarily. The results obtained in this work indicate that the use of mixed solvents greatly increases the effectiveness ofNMP used for the separation of n-hexane and toluene. It is suggested that further studies be performed on a wider range of aliphatic and aromatic compounds in order to determine whether this is a generic behaviour or just true for n-hexane and toluene. The effectiveness of each solvent for extractive distillation was determined by its separation factor. In order to determine separation factors, the activity coefficients at infinite dilution (IDACs) had to be measured. This was done using a gas-liquid chromatography technique. The solvents employed in this study were NMP, Glycerol, MEG, TEG, NMP + 10% glycerol, NMP + 10% MEG, NMP + 10% DEG, NMP + 10% TEG. The solutes used were: pentane, heptane, hexane, toluene and benzene. The separation factors were determined for each alkane/aromatic pair per solvent. The pure solvent cases were then compared to the mixed solvent cases. The mixed solvents did not show results as promising for extractive distillation applications as they did for liquid-liquid extraction. TEG displayed the best selectivities for each of the alkane/aromatic separations except for the heptane/benzene pair, for which NMP + 10% glycerol proved to be the most effective solvent. When compared to the results obtained from the original UNIF AC model, the IDACs obtained in this work showed up to a 99% deviation. This is due to the fact that the model does not work well for all types of molecules and does not predict the equilibrium of "unlike" molecules adequately. It is suggested that other mixing ratios and different solvents be used to further investigate the effectiveness of mixed solvents for extractive distillation applications. It is further recommended that a computer aided data logging system be developed to determine residence times. This would not only provide more accurate results, but also provide a database for future reference. The computer program that was developed using the original UNIF AC method contains a database of 28 commonly used industrial solvents. This program enables the user to compare graphically the effectiveness of each of the solvents on the desired separation. Due to the limitations of the original UNIF AC method, the program does not work well for all types of molecules. However, the model can be changed without altering the prografnming structure to include a modified version of the UNIFAC model depending on the users needs. The program although written from an extractive distillation standpoint can be extended to include liquid-liquid equilibrium predictions. The main benefit of such a program is to eliminate time-consuming experimental work required to narrow down a long list of solvents required for a particular separation by theoretically predicting the best solvents for the job. The solvent database can also be expanded when new solvents become available or the user needs change / Thesis (M.Sc. Eng)-University of Natal, Durban, 2003.

Made available in DSpace on 2015-04-22T22:02:04Z (GMT). No. of bitstreams: 1 Dissertacao Alcinei Pereira Lopes.pdf: 3280697 bytes, checksum: 535d2d7812f1764295a9b8c14b85a386 (MD5) Previous issue date: 2010-09-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The waters of the Rio Negro, in the border city of Manaus, receives large amounts of domestic and industrial waste from its main tributaries (Tarumã-Acu, Sao Raimundo, Pupils and Puraquequara) that may be compromising their natural features (water, plants, sediments and etc.). Due the ability to accumulate organic and inorganic compounds, the bottom sediments are used to assess the contamination levels of aquatic environments. As a result, we determined the concentrations of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAH) and potentially toxic metals (MPT) in ten samples of bottom sediments collected in March 2009 in the confluence between the Rio Negro and major watersheds the city of Manaus. The aim of study was to classify the origin and level of contamination of these compounds. In the determination of hydrocarbons, sediments were freeze dried, extracted with hexane, fractionated by open column liquid chromatography. The determination of aliphatic hydrocarbons was performed by GC-FID and the PAH by GC-MS. After digestion with aqua regia the MPT (Al, Fe, Zn, Cu, Ni, Cr, Pb, Cd and Mn) in total fraction of sediments were determined by ICP-OES. The results showed that concentrations of total aliphatic hydrocarbons were 13.4 to 448 mg g-1, and the sum of 38 PAHs was 58.8 to 6832 ng g-1. These values are considered high for natural aquatic environments that have not suffered oil spill accidents. Among the metals determined Al (32 091 mg kg-1) and Fe (35 474 mg kg-1) were those with the highest concentrations.The sediments that received the largest anthropogenic contribution were those collected at the entrance of the basin of the streams São Raimundo and Educandos. The diagnosis index hydrocarbons the origin of in sediments showed a predominance of mixed sources and petrogenic sources in most seasons / As águas do rio Negro na orla urbana de Manaus recebem grande quantidade de resíduos domésticos e industriais de seus principais afluentes (Tarumã-Açu, São Raimundo, Educandos e Puraquequara) que podem estar comprometendo suas características naturais (água, plantas, sedimentos e etc). Por ter a capacidade de acumular compostos orgânicos e inorgânicos, os sedimentos de fundo são utilizados na avaliação dos níveis de contaminação de ambientes aquáticos. Em virtude disso, foram determinados as concentrações de hidrocarbonetos alifáticos, hidrocarbonetos policíclicos aromáticos (HPA) e metais em dez amostras de sedimentos de fundo, coletadas em março de 2009 nas confluências entre o rio Negro e as principais bacias de drenagem da cidade de Manaus. O estudo tem o objetivo de classificar a origem e o nível de contaminação destes compostos. Nas determinações de hidrocarbonetos, os sedimentos foram liofilizados, extraídos em soxhlet, fracionados por cromatografia líquida de coluna aberta. A determinação de hidrocarbonetos alifáticos foi realizada por CG-DIC e os HPA por CG-EM. Apos digestão com água régia, os metais (Al, Fe, Zn, Cu, Ni, Cr, Pb, V, Cd e Mn) presentes na fração total dos sedimentos foram determinados por ICP-OES. Os resultados mostraram que as concentrações dos hidrocarbonetos alifáticos totais foram de 13,4 a 448 μg g-1, e a somatória dos 38 HPA foi de 58,8 a 6832 ng g-1. Esses valores são considerados elevados para ambientes aquáticos naturais que não sofreram acidentes de derrame de óleo. Entre os metais determinados o Al (32091 mg kg-1) e o Fe (35474 mg kg-1) foram os que apresentaram as maiores concentrações. Os sedimentos que receberam a maior contribuição antrópica foram daqueles coletados na entrada da bacia dos igarapés São Raimundo e Educando. Os índices de diagnósticos da origem de ix hidrocarbonetos nos sedimentos mostraram predominância de fontes petrogênica e fontes mistas na maioria das estações.

Macromolecular engineering is one of the most powerful tools to control the molecular parameters, including architecture of polymers, and to improve their performances or to impart them new properties. This contribution aims at reporting on a novel strategy for the macromolecular engineering of poly-ε-caprolactone (PCL) which is based on the use of functional ε-caprolactone, the α-chloro-ε-caprolactone (αClεCL). Indeed, αClεCL is a precursor of polymers and copolymers with εCL that bear pendant activated chlorides well suited to grafting from reaction. These (co)polyesters have been used as macroinitiators for the Atom Transfer Radical Polymerization (ATRP) of methyl methacrylate leading to the corresponding graft copolymer. They have also been involved in an Atom Transfer Radical Addition (ATRA) reaction with a series of olefins bearing different functional groups (hydroxyl, carboxylic acid and epoxy group) in order to functionalize the polyester backbone without deleterious degradation. ATRA of PEO chains with an unsaturation end groups has also been carried out in order to prepare PCL-g-PEO of different compositions to be used as stabilizers of polyester nanoparticles. Combination of ring-opening polymerization of ε-caprolactone and the copper-catalyzed Huisgens [3+2] cycloaddition is a novel strategy for going a step further in the macromolecular engineering of poly-ε-caprolactone (PCL). This click reaction is very well-suited to the chemical modification of aliphatic polyesters because, its implementation under very mild conditions prevents chain degradation from occurring. Indeed, alkynes were cycloadded onto azide containing PCL at low temperature (35°C) in an organic solvent (DMF or THF). Originally, α-chloro-ε-caprolactone and ε-caprolactone were randomly copolymerized in toluene at room temperature followed by reaction of the activated chlorides with sodium azide. In order to make a wide range of functional aliphatic polyesters available, poly(α-azide-ε-caprolactone-co-ε-caprolactone) copolyesters were reacted with a series of alkynes substituted by a functional group, e.g., hydroxyl, acrylate and quaternary ammonium salts, This strategy turned out to be efficient to synthesize for instance hydrophilic, photo-cross-linkable and hydrosoluble PCL. Moreover, a variety of graft copolymers were prepared by both the grafting from and the grafting onto techniques. Indeed, an ATRP initiator was attached onto PCL followed by polymerization of vinyl monomers, whereas alkyne endcapped PEO was cycloadded onto azide-containing PCL with formation of amphiphilic PCL-g-PEO copolymers. Last but not least, the click chemistry was very instrumental in imparting an antimicrobial activity to PCL or for the preparation of new functionalized caprolactones.