Pervaporation with a "reverse-selective" (hydrophobic) membrane is a promising technology for the energy-efficient separation of alcohols from dilute alcohol-water streams, such as those formed in the production of biofuels. Pervaporation depends on the selectivity and throughput of the membrane, which in turn is highly dependent on the membrane material. A nanocomposite approach to membrane design is desirable in order to combine the advantages and eliminate the individual limitations of previously-reported polymeric and zeolitic membranes. In this work, a hollow-fiber membrane composed of a thin layer of polymer/zeolite nanocomposite material on a porous polymeric hollow fiber support is developed. The hollow fiber geometry offers considerable advantages in membrane surface area per unit volume, allowing for easier scaling and higher throughput than flat-film membranes. Poly(dimethyl siloxane) (PDMS) and pure-silica MFI zeolite (silicalite-1) were investigated for these membranes. Iso-octane was used to dilute the dope solution to provide thinner coatings. Previously-spun non-selective Torlon hollow fibers were used as the support layer for the nanocomposite coatings. To determine an acceptable method for coating fibers with uniform, defect-free coatings, flat-film membranes (0 to 60 wt% MFI on a solvent-free basis) and hollow-fiber membranes (0 and 20 wt% MFI) were fabricated using different procedures. Pervaporation experiments were run for all membranes at 65C with a 5 wt% ethanol feed. The effects of membrane thickness, fiber pretreatment, coating method, zeolite loading, and zeolite surface treatment on membrane pervaporation performance were investigated.

No description available.

<p>Molecular recognition is arguably the most elementary physical process essential for life that arises at the molecular scale. Molecular recognition drives events across virtually all length scales, from the folding of proteins and binding of ligands, to the organization of membranes and the function of muscles. Understanding such events at the molecular level is massively complicated by the unique medium in which life occurs: water. In contrast to recognition in non-aqueous solvents, which are driven largely by attractive interactions between binding partners, binding reactions in water are driven in large measure by the properties of the medium itself. Aqueous binding involves the loss of solute-solvent interactions (desolvation) and the concomitant formation of solute-solute interactions. Despite decades of research, aqueous binding remains poorly understood, a deficit that profoundly limits our ability to design effective pharmaceuticals and new enzymes. Particularly problematic is understanding the energetic consequences of aqueous desolvation, an area the Toone and Beratan groups have considered for many years.</p><p> In this dissertation, we embark on a quest to shed new light on aqueous desolvation from two perspectives. In one component of this research, we improve current computational tools to study aqueous desolvation, employing quantum mechanics (QM), molecular dynamics (MD) and Monte Carlo (MC) simulations to better understand the behavior of water near molecular surfaces. In the other, we use a synthetic host, cucurbit[7]uril (CB[7]), in conjunction with a de novo series of ligands to study the structure and thermodynamics of aqueous desolvation in the context of ligand binding with atomic precision, a feat hitherto impossible. A simple and rigid macrocycle, CB[7] alleviates the drawbacks of protein systems for the study of aqueous ligand binding, that arise from conformational heterogeneity and prohibitive computational costs to model.</p><p> </p><p> We first constructed a novel host-guest system that facilitates internalization of the trimethylammonium (methonium) group from bulk water to the hydrophobic cavity of CB[7] with precise (atomic-scale) control over the position of the ligand with respect to the cavity. The process of internalization was investigated energetically using isothermal titration microcalorimetry and structurally by nuclear magnetic resonance (NMR) spectroscopy. We show that the transfer of methonium from bulk water to the CB[7] cavity is accompanied by an unfavorable desolvation enthalpy of just 0.49±0.27 kcal*mol-1, a value significantly less endothermic than those values suggested from previous gas-phase model studies. Our results offer a rationale for the wide distribution of methonium in biology and demonstrate important limitations to computational estimates of binding affinities based on simple solvent-accessible surface area approaches.</p><p> To better understand our experimental results, we developed a two-dimensional lattice model of water based on random cluster structures that successfully reproduces the temperature-density anomaly of water with minimum computational cost. Using reported well-characterized ligands of CB[7], we probed water structure within the CB[7] cavity and identified an energetically perturbed cluster of water. We offer both experimental and computational evidence that this unstable water cluster provides a significant portion of the driving force for encapsulation of hydrophobic guests.</p><p> The studies reported herein shed important light on the thermodynamic and structural nature of aqueous desolvation, and bring our previous understanding of the hydrophobic effect based on ordered water and buried surface area into question. Our approach provides new tools to quantify the thermodynamics of functional group desolvation in the context of ligand binding, which will be of tremendous value for future research on ligand/drug design.</p> / Dissertation

The pulsed field gradient fourier transform nuclear magnetic resonance (PFG-FTNMR) method to measure translational diffusion coefficients in multicomponent systems has been applied to amphiphilic molecules forming liquid crystalline phases. By analyzing the concentration dependence of the diffusion coefficients of water and amphiphile in a micellar system of N,N-dimethyldodecy lamine oxide (DDAO) in water it was possible to conclude that the micelles formed were polydisperse in size and shape. It was also shown that solubilization of small amounts of hydrophobic molecules into the micelles induces spherical micelles of a narrow size distribution. From the magnitude of the lateral diffusion coefficient in the cubic phase of DDAO/water it was concluded that this phase is built up of bicontinous aggregates. The lipid lateral diffusion in the cubic phase of monooleoylglycerol (MO)/water has been measured. The decrease in the lateral diffusion of MO in this phase, when the water was replaced by glycerol, was ascribed to changes in viscosity in the polar region. Measurements by electron spin resonance and time-resolved fluorescence spectroscopy showed that changes in viscosity of the solvent also affected the motions in the hydrocarbon region. The diffusion coefficients of all three components in the cubic phase located in the lowwater region of the ternary system of diacylglycerol (DAG)/soybean phosphatidylcholine (SPC)/water have been determined. Conclusive evidence was provided for that this cubic phase is built up of reversed micelles containing mainly SPC in a continous matrix of mainly DAG. The effect on the phase properties of DDAO upon incorporation of the peptide gramicidin D has been investigated. It was shown that gramicidin D induces a lamellar phase at all water contents. The change in the order parameter profile of the C-2H bonds in perdeuterated DDAO upon incorporation of gramicidin D is compatible with theoretical calculations for proteins exhibiting a positive hydrophobic mismatch. A method for using the PFG FTNMR technique in measurements of the transmembrane exchange rate of small molecules in vesicular suspensions is discussed and some preliminary data is shown. / <p>Diss. (sammanfattning) Umeå : Umeå universitet, 1994, härtill 4 uppsatser</p> / digitalisering@umu

Most of the processes in a living cell are carried out by proteins. Depending on the needs of the cell, different proteins will interact and form the molecular machines demanded for the moment. A subset of proteins called integral membrane proteins are responsible for the interchange of matter and information across the biological membrane, the lipid bilayer enveloping and defining the cell. Most of these proteins are co-translationally integrated into the membrane by the Sec translocation machinery. This thesis addresses two questions that have emerged during the last decade. The first concerns membrane proteins: a number of α-helices have been observed to span the membrane in the obtained three-dimensional structures even though these helices are predicted not to be hydrophobic enough to be recognized by the translocon for integration. We show for a number of these marginally hydrophobic protein segments that they indeed do not insert well outside of their native context, but that their local sequence context can improve the level of integration mediated by the translocon. We also find that many of these helices are overlapped by more hydrophobic segments. We propose, supported by experimental results, that the latter are initially integrated into the membrane, followed by post-translational structural rearrangements. Finally, we investigate whether the integration of the marginally hydrophobic TMHs of the lactose permease of Escherichia coli is facilitated by the formation of hairpin structures. However our combined efforts of computational simulations and experimental investigations find no evidence for this. The second question addressed in this thesis is that of the interpretation of the large datasets on which proteins that interact with each other in a cell. We have analyzed the results from several large-scale investigations concerning protein interactions in yeast and draw conclusions regarding the biases, strengths and weaknesses of these datasets and the methods used to obtain them. / At the time of the doctoral defense the following publications were not published and had a status as follows: Paper 2: In press; Paper 4 Manuscript.

Most membrane proteins are inserted into the membrane co-translationally utilizing the translocon, which allows a sufficiently long and hydrophobic stretch of amino acids to partition into the membrane. However, X-ray structures of membrane proteins have revealed that some transmembrane helices (TMHs) are surprisingly hydrophilic. These marginally hydrophobic transmembrane helices (mTMH) are not recognized as TMHs by the translocon in the absence of local sequence context. We have studied three native mTMHs, which were previously shown to depend on a subsequent TMH for membrane insertion. Their recognition was not due to specific interactions. Instead, the presence of basic amino acids in their cytoplasmic loop allowed membrane insertion of one of them. In the other two, basic residues are not sufficient unless followed by another, hydrophobic TMH. Post-insertional repositioning are another way to bring hydrophilic residues into the membrane. We show how four long TMHs with hydrophilic residues seen in X-ray structures, are initially inserted as much shorter membrane-embedded segments. Tilting is thus induced after membrane-insertion, probably through tertiary packing interactions within the protein. Aquaporin 1 illustrates how a mTMH can shape membrane protein folding and how repositioning can be important in post-insertional folding. It initially adopts a four-helical intermediate, where mTMH2 and TMH4 are not inserted into the membrane. Consequently, TMH3 is inserted in an inverted orientation. The final conformation with six TMHs is formed by TMH2 and 4 entering the membrane and TMH3 rotating 180°. Based on experimental and computational results, we propose a mechanism for the initial step in the folding of AQP1: A shift of TMH3 out from membrane core allows the preceding regions to enter the membrane, which provides flexibility for TMH3 to re-insert in its correct orientation. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.</p>

Biologically inspired design is used as an approach for sustainable engineering. Taking a biologically inspired approach, one abstracts ideas and principles from nature, an inherently sustainable system, and uses them in engineering applications with the goal of producing environmentally superior designs. One such biological idea with potential environmental benefits for engineering is microscale and nanoscale surface roughness found on the Lotus plant and many other surfaces in nature. These surfaces repel water and aid in contaminant removal; this self-cleaning phenomenon is called the "Lotus Effect," in honor of the plant first observed to exhibit it. The structures responsible for the Lotus Effect inspired research and development of many technologies capable of creating hydrophobic, self-cleaning surfaces, and many potential self-cleaning surface applications exist beyond nature's intended application of cleaning. While statements have been made about the environmental benefits of using a self-cleaning surface, only limited scientific data exist. Artificial self-cleaning surfaces are successfully cleaned using fog or mist. This shows that such surfaces can be cleaned with less energy and water intensive methods than the more conventional methods used to clean regular surfaces, such as spray or solvent cleaning. This research investigates the potential environmental burden reductions associated with using these surfaces on products. A life cycle assessment is performed to determine the environmental burdens associated with manufacturing a self-cleaning surface, for three production methods: a chemical coating, a laser ablated steel template, and an anodized aluminum template. The environmental benefits and burdens are quantified and compared to those of more conventional cleaning methods. The results indicate that self-cleaning surfaces are not necessarily the environmentally superior choice.

In this thesis, a direct method of Atomic Force Microscopy (AFM) technique has been developed to measure the adhesion forces between BSA and two different surfaces: mica (a hydrophilic surface); and polystyrene (a hydrophobic surface); in PBS solution. We have shown possible to measure interactions between proteins and substrate surface directly without any modification to the substrate and the AFM tip; this means protein molecules can keep the natural elastic property within the force measurements. The average measured value of adhesion forces between BSA and mica is 0.036 ± 0.002 nN, and between BSA and polystyrene is 0.066 ± 0.003 nN. The polystyrene surface is more adhesive to BSA than the mica surface. This is consistent with previous research, which assessed that hydrophobic surfaces enhance protein adhesion but hydrophilic surfaces do not.

A longevidade da interface adesiva é afetada pelos efeitos da degradação hidrolítica, cuja ocorrência está associada ao alto conteúdo de água presente no tecido dentinário. A hibridização da dentina com monômeros hidrófobos em um substrato isento de água poderia fazer com que a resistência de união dessas interfaces se mantivesse estável por um período de tempo prolongado. O objetivo deste estudo foi avaliar a resistência de união, através do teste de microtração, da interface adesiva em dentina saturada com etanol, sobre a qual se fez o uso de um adesivo hidrófobo, além de caracterizar a morfologia desta interface. Vinte e oito dentes molares foram cortados para que um flat de dentina do terço médio fosse obtido. Foram estudados quatro grupos experimentais: Grupo controle (Scotchbond MultiUso, 3M ESPE), cuja dentina foi saturada com água, grupo experimental 1, cuja dentina saturada com etanol foi hibridizada com o adesivo hidrófobo puro do sistema Scotchbond e grupos experimentais 2 e 3, cuja dentina saturada com etanol recebeu primers hidrofóbicos dissolvidos em etanol 10% e 30% respectivamente. Após a hibridização da dentina, os dentes foram restaurados de forma incremental com resina composta (Filtek Z350, 3M ESPE). As resistências adesivas imediata (24 horas) e tardia (6 meses) foram avaliadas por -tração (0.5 mm/min) de palitos obtidos por cortes perpendiculares à interface adesiva, com área de seção transversal de 1 mm2. O meio de armazenagem dos palitos foi saliva artificial a 37°C. Amostras dos palitos foram preparadas para caracterização da interface adesiva e avaliação do modo de fratura em microscopia eletrônica de varredura. Os dados foram submetidos à análise de variância de dois fatores, Técnica Adesiva e Tempo de Armazenamento, sendo este último vinculado. Os resultados encontrados não mostraram diferença estatística para todos os grupos estudados após 6 meses de armazenamento quando comparados com os dados obtidos de forma imediata (24 horas). Também não foram encontradas diferenças entre os grupos quando avaliados em 24 horas e em 6 meses separadamente. A camada híbrida formada em dentina saturada por etanol apresentou características similares, em relação à morfologia e dimensão, àquela formada pela técnica convencional. A técnica de substituição de água por etanol produziu interfaces tão resistentes quanto à técnica úmida convencional, pelo menos nos primeiros seis meses. / The longevity of an adhesive interface is affected by the effects of hydrolytic degradation, which is associated with high water content in the dentin tissue. The hybridization of dentin with hydrophobic monomers in a water-free substrate could make the bond strength of these interfaces remain stable for an extended period of time. The aim of this study was to evaluate the bond strength of the adhesive interface in ethanol-saturated dentin using a microtensile test, on which a hydrophobic adhesive was used, and also to characterize the morphology of this interface. Twenty-eight molar teeth were cut to a flat middle third of the dentin was obtained. We studied four experimental groups: control group (Scotchbond MultiPurpose, 3M ESPE), whose dentin was saturated with water; experimental group 1, whose dentin saturated with ethanol was hybridized with the pure hydrophobic adhesive from Scotchbond adhesive system and experimental groups 2 and 3, whose dentin saturated with ethanol received hydrophobic primers dissolved in ethanol 10% and 30%, respectively. After dentin hybridization, teeth were restored with the incremental technique with composite resin (Filtek Z350, 3M ESPE). The immediate (24 hours) and late (6 months) adhesive resistance was determined by - tensile (0.5 mm / min) of \"sticks\" obtained by perpendicular cuts on the adhesive interface, with cross section area of 1 mm2. The sticks storage medium was artificial saliva at 37 °C. Interface samples were prepared to characterize the adhesive interface and to assess the failure mode by scanning electron microscopy. The data were submitted to two factors analysis of variance, adhesive technique and storage time, the latter being dependent. The results showed no statistical differences for all groups after 6 months of storage when compared to data obtained from the immediate group (24 hours). Also, no differences were found between groups evaluated at 24 hours and 6 months separately. The hybrid layer formed in ethanolsaturated dentin had similar characteristics considering the morphology and size formed by conventional technique. The technique of water replacement for ethanol produced interfaces as strong as the conventional wet technique, at least in the first six months.

Submitted by Maria Beatriz Vieira (mbeatriz.vieira@gmail.com) on 2017-03-06T13:55:03Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) dissertacao_mariana_peil_da_rosa.pdf: 780579 bytes, checksum: 32fb27eef72fa6d21ed64bfe1f7c5af1 (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-03-09T20:15:32Z (GMT) No. of bitstreams: 2 dissertacao_mariana_peil_da_rosa.pdf: 780579 bytes, checksum: 32fb27eef72fa6d21ed64bfe1f7c5af1 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-03-09T20:17:03Z (GMT) No. of bitstreams: 2 dissertacao_mariana_peil_da_rosa.pdf: 780579 bytes, checksum: 32fb27eef72fa6d21ed64bfe1f7c5af1 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-03-09T20:17:13Z (GMT). No. of bitstreams: 2 dissertacao_mariana_peil_da_rosa.pdf: 780579 bytes, checksum: 32fb27eef72fa6d21ed64bfe1f7c5af1 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-03-31 / Sem bolsa / O objetivo deste trabalho foi avaliar a expressão do gene HPS no tegumento de quatro genótipos de soja, em épocas distintas de coleta após a antese. O experimento foi conduzido em casa de vegetação da Estação Terras Baixas da Embrapa Clima Temperado e no Laboratório de Sementes e Biotecnologia (UFPel/FAEM), em delineamento completamente casualizado, com três repetições. Utilizou-se duas cultivares de tegumento amarelo, COODETEC 202 e BMX Potência RR (POT) e duas linhagens de tegumento preto, Tegumento Preto (TP) e IAC 222. Efetuou-se sete coletas dos tegumentos, em intervalos de 5 dias cada, durante o desenvolvimento das sementes de soja entre os períodos de 25 a 55 dias após a antese. Procedeu-se a extração de RNA dos tegumentos, seguido da obtenção do cDNA para posterior análise de qRT-PCR, visando quantificar o acúmulo relativo do gene HPS. A cultivar IAC 222 apresentou valores de quantificação relativa superior em todas as épocas avaliadas, sendo o maior valor encontrado na coleta de 35 dias após a antese. O acúmulo relativo de transcritos do gene HPS no tegumento de sementes de soja difere entre as épocas avaliadas, bem como entre os genótipos estudados. / The objective of this study was to evaluate the gene expression of HPS in the seed coat of four soybean genotypes at different sampling times after anthesis. The experiment was conducted in greenhouse at Estação Terras Baixas of Embrapa Clima Temperado and Laboratório de Sementes e Biotecnologia (UFPel / FAEM) in Capão do Leão city - RS, in a randomized complete block design with three replicates, and treatments arranged in a factorial model. Were used four contrasting genotypes, two cultivars of yellow coat (COODETEC 202 and BMX Potência RR) and two genotypes of black coat (Tegumento Preto and IAC). Seed coat samples were collected along the developing soybean seed, intervals for 5 days, between the periods 25-55 days after anthesis. Proceeded the RNA extraction from the seed coats, followed by obtaining the cDNA for further analysis of qRT-PCR, to quantify the relative accumulation of gene transcripts HPS. IAC 222 showed higher values of relative quantification in all periods, with the highest value found in the collection of 35 days after anthesis. The relative accumulation of transcripts of the HPS gene in the seed coat of soybean differs between the periods evaluated, as well as between genotypes.