Lewis acidic zeolites are silica-based, crystalline microporous materials containing tetravalent heteroatoms (M4+=Ti, Sn, Zr, Hf) substituted in framework locations, and have been reported to catalyze a wide range of reactions involving oxygenates and hydrocarbons. The synthetic protocols used to prepare Lewis acid zeolites determine the structures of the active sites and the reaction pockets that confine them, which in turn influences reactivity, product selectivity, and catalyst stability. Specifically, aqueous-phase reactions of biomass-derived molecules, such as glucose isomerization, are sensitive to the hydrophobicity of confining environments, leading to changes in turnover rates. As a result, precise evaluation of the structure and behavior of reaction environments and confined active sites among catalysts of varying provenance or treatment history requires quantitative descriptions of active Lewis acid site densities, of densities of surface functional groups that determine the polarity of microporous confining environments, and of the kinetic behavior of these catalytic materials.<div><br></div><div>Methods for quantifying Lewis acid sites and silanol defects are developed here by analyzing infrared (IR) spectra collected after Lewis base (CD3CN, pyridine) titrations of Lewis acidic zeolite surfaces and are compared to vapor-phase methanol and water adsorption isotherms. Additionally, IR spectra collected under ex situ (flowing vapor-phase water) and in situ (aqueous-phase, 373 K, 0-50 wt% glucose) conditions are used to compare co-adsorbed water densities and structures within hydrophobic (low silanol density) and hydrophilic (high silanol density) confining environments within M-Beta zeolites. Under reaction conditions relevant for sugar conversion in aqueous media (353-398 K, 1-50 wt% glucose), hydrophilic reaction pockets stabilize liquid-like extended water structures within microporous environments, while hydrophobic channels stabilize vapor-phase water at lower intraporous water densities. Higher aqueous-phase glucose isomerization rates (368-383 K, 1-50 wt% glucose, per kinetically relevant active site) are observed on hydrophobic Ti-Beta (~6-12x, per Lewis acidic Ti) and Sn-Beta (~50x, per Lewis acidic Sn in open configuration) zeolites over their hydrophilic analogs. Higher turnover rates on hydrophobic M-Beta zeolites reflect the absence of an extended, hydrogen-bonded network of waters, which entropically destabilizes kinetically relevant hydride shift transition states by reducing the flexibility of their primary solvation spheres. These findings suggest catalyst design strategies to minimize the generation of silanol groups within confining reaction environments would lead to increases in turnover rates.<br></div><div><br></div><div>The methods derived herein can be applied to understanding the role of the confining environment and the associated co-adsorbed water on zeolitic materials of different topology and Lewis acid site identity. For example, the transient formation of silanol defects under aqueous-phase operating conditions is primarily responsible for the deactivation of Sn-Beta catalysts observed during aqueous-phase glucose isomerization. Further, quantifying the role of the confining environment geometry and hydrophobicity on aqueous-phase glucose isomerization rates can be used as guidance for catalyst design to increase reaction rates and selectivities toward specific isomerization products. These findings show that both the active site identity and its confining environment, which vary with zeolite topology and micropore polarity, combine to influence reactivity, selectivity and stability for aqueous-phase glucose isomerization catalysis.<br></div>

For years, the alloy of choice for electroplating electronic components has been tin-lead (Sn-Pb) alloy. However, the legislation established in Europe on July 1, 2006, required significant lead (Pb) content reductions from electronic hardware due to its toxic nature. A popular alternative for coating electronic components is pure tin (Sn). However, pure tin has the tendency to spontaneously grow electrically conductive Sn whisker during storage. Sn whisker is usually a pure single crystal tin with filament or hair-like structures grown directly from the electroplated surfaces. Sn whisker is highly conductive, and can cause short circuits in electronic components, which is a very significant reliability problem. The damages caused by Sn whisker growth are reported in very critical applications such as aircraft, spacecraft, satellites, and military weapons systems. They are also naturally very strong and are believed to grow from compressive stresses developed in the Sn coating during deposition or over time. The new directive, even though environmentally friendly, has placed all lead-free electronic devices at risk because of whisker growth in pure tin. Additionally, interest has occurred about studying the nature of other metal whiskers such as zinc (Zn) whiskers and comparing their behavior to that of Sn whiskers. Zn whiskers can be found in flooring of data centers which can get inside electronic systems during equipment reorganization and movement and can also cause systems failure.Even though the topic of metal whiskers as reliability failure has been around for several decades to date, there is no successful method that can eliminate their growth. This thesis will give further insights towards the nature and behavior of Sn and Zn whiskers growth, and recommend a novel manufacturing technique that has potential to mitigate metal whiskers growth and extend life of many electronic devices.

Cloreto estanoso (SnCl2.2H2O) é o composto mais utilizado na redução do íon pertecnetato (TcO4-), obtido pela eluição do gerador, para a marcação de reagentes liofilizados para radiodiagnóstico. Estes reagentes liofilizados contêm um ligante, cloreto estanoso, e diferentes excipientes. Muitos métodos analíticos para a determinação de estanho não conseguem distinguir entre os íons estanoso (Sn(II)) e estânico (Sn(IV)) em soluções. Os dois métodos, descritos na literatura, para determinação seletiva de Sn(II) são análise titrimétrica e polarografia. O método mais confiável descrito para a quantificação do íon estanoso é a polarografia (voltametria) e pode ser utilizado para a determinação em concentrações de mg e g de Sn(II) e Sn(IV) (0,06-1,0 mg), com boa seletividade. Foi realizada análise titrimétrica, para quantificação de Sn(II), na matéria-prima e em 3 lotes consecutivos de 9 reagentes liofilizados produzidos pelo IPEN-CNEN/SP, utilizando-se sulfato cérico 0,1 mol L-1, diluído 10 vezes e iodo 0,05 mol L-1, diluído 10 vezes, como soluções titulantes. Polarografia por pulso diferencial foi utilizada com configuração convencional composta por três eletrodos: eletrodo de trabalho de gota de mercúrio, eletrodo referência de Ag/AgCl (saturado com KCl) e eletrodo auxiliar de platina. O intervalo de potencial analisado foi de -250 a -800 mV e o pico atribuído à redução de Sn(II) foi encontrado em -370 mV em eletrólito suporte de H2SO4 3 mol L-1 e, para Sn(IV), -470 mV, em eletrólito suporte de HCl 3 mol L-1. Para retirada do oxigênio da solução na cela polarográfica utilizou-se nitrogênio 5.0 por 5 minutos, antes e após cada introdução de amostra. Para determinação de Sn(IV) foi feita a oxidação do Sn(II), por adição de peróxido de hidrogênio, em 37 ± 5 ºC, por 5 minutos, seguida de purga com nitrogênio, e análise. A análise polarográfica desenvolvida mostrou-se adequada para a determinação de Sn(II), na presença de Sn(IV), e de estanho total nos kits radiofarmacêuticos estudados. / Stannous chloride (SnCl2.2H2O) is the major compound used for reduction of generator-derived 99mTc-pertechnetate in cold kits for on site preparation of 99mTc-radiopharmaceuticals. These cold kits usually contain a ligand, stannous chloride, and different additives. Various techniques were described for tin determination, but they cannot distinguish between stannous (Sn(II)) and stannic (Sn(IV)) ions in solutions. The two methods described in literature for selective determination of Sn(II) are polarography and mass analysis (redox-titration). Polarography is a good selective method in the mg range as well as in the g range for Sn(II) and Sn(IV) (0.06-1,0mg). Titrimetric analysis was performed for quantification of Sn(II) in Sn(II) reagents and in 3 consecutive lots of 9 radiopharmaceutical cold kits produced by IPEN-CNEN/SP, using Ce(SO4)2.4H2O 0.1 mol L-1, diluted 10 times and, I2 0.05 mol L-1, diluted 10, as a titrant solution. Differential pulse polarography was chosen with a conventional three-electrode configuration consisting of a static mercury drop electrode, an AgCl/Ag (saturated KCl) reference electrode and a platinum wire auxiliary electrode. The potential was swept from 250 to 800 mV and the current (A) was measured at 370 mV and 470 mV potentials for Sn(II) in H2SO4 3 mol L-1 and Sn(IV) in HCl 3 mol L-1, respectively. The supporting electrolytes were deaerated during 5 min with 5.0 nitrogen gas before and after each sample addition. For total tin determination the oxidation of tin (II) was carried out in the same vial, by adding H2O2 at 37 ± 5 ºC, for 5 min to quantify tin (IV). The developed polarographic method showed to be adequate to quantify tin (II), in the presence of tin (IV), in analyzed radiopharmaceutical cold kits.

Submitted by Cleide Dantas (cleidedantas@ufpa.br) on 2014-04-10T14:42:57Z No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaConveccaoTermossolutal.pdf: 2004245 bytes, checksum: ffa9b9a4cf0968080a0cf43f957949cf (MD5) / Approved for entry into archive by Ana Rosa Silva (arosa@ufpa.br) on 2014-08-29T16:35:23Z (GMT) No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaConveccaoTermossolutal.pdf: 2004245 bytes, checksum: ffa9b9a4cf0968080a0cf43f957949cf (MD5) / Made available in DSpace on 2014-08-29T16:35:23Z (GMT). No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaConveccaoTermossolutal.pdf: 2004245 bytes, checksum: ffa9b9a4cf0968080a0cf43f957949cf (MD5) Previous issue date: 2011 / Este trabalho apresenta um estudo teórico-experimental sobre os efeitos da convecção termossolutal sobre os espaçamentos dendríticos primários de ligas hipoeutéticas Sn-Pb. Assim, um dispositivo experimental de configuração horizontal refrigerado a água foi construído e amostras do referido sistema de ligas foram solidificadas direcionalmente sob condições transientes de extração de calor. Um método teórico-experimental é aplicado para determinar as velocidades de deslocamento da isoterma liquidus, os gradientes térmicos e as taxas de resfriamento. São também apresentados resultados para os respectivos coeficientes de transferência de calor na interface metal/molde os quais foram calculados a partir de uma análise comparativa realizada entre os perfis experimentais de temperatura e valores teóricos fornecidos por um método numérico baseado em volumes finitos. Alguns modelos teóricos para a previsão dos espaçamentos dendríticos primários são comparados com os resultados experimentais obtidos. Finalmente, um estudo comparativo é realizado entre resultados encontrados neste trabalho e aqueles apresentados na literatura para os espaçamentos dendríticos primários das ligas Sn-Pb investigadas quando solidificadas direcionalmente nos sistemas verticais ascendente e descendente, sob as mesmas condições. A análise das microestruturas indica que os espaçamentos dendríticos primários são bastante influenciados pela direção de crescimento do sólido. / In order to investigate the effect of thermosolutal convection on the primary dendritic spacings of Pb–Sn hypoeutectic alloys, horizontal directional solidification experiments have been carried out. For this purpose, a water-cooled solidification experimental apparatus was developed and specimens were solidified in unsteady state heat flow conditions. A combined theoretical and experimental approach is developed to quantitatively determine the solidification thermal parameters: tip growth rates, thermal gradients and cooling rates. The results also include transient metal/mold heat transfer coefficients, determined from comparisons between the experimental thermal profiles in castings and the simulations provided by a finite difference heat flow program. A comparison between theoretical models that predict primary dendritic spacings with the experimental results generated in this study is conducted. A comparative study between some experimental data of this work and those from the literature proposed to predict the primary dendritic spacings during upward and downward vertical unsteady-state directional solidification of Sn–Pb alloys have is presented. The observation of the microstructures has indicated that the primary dendritic spacings have been affected by the direction of growth, increasing in conditions of horizontal solidification when compared with those obtained during upward and downward vertical solidification of Sn–Pb hypoeutectic alloys analyzed.

Submitted by Cleide Dantas (cleidedantas@ufpa.br) on 2014-04-11T12:08:27Z No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaParametrosTermicos.pdf: 3274679 bytes, checksum: 67a56351708ea6a0728c738561741289 (MD5) / Approved for entry into archive by Ana Rosa Silva (arosa@ufpa.br) on 2014-08-29T17:08:58Z (GMT) No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaParametrosTermicos.pdf: 3274679 bytes, checksum: 67a56351708ea6a0728c738561741289 (MD5) / Made available in DSpace on 2014-08-29T17:08:58Z (GMT). No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InfluenciaParametrosTermicos.pdf: 3274679 bytes, checksum: 67a56351708ea6a0728c738561741289 (MD5) Previous issue date: 2007 / CEFET/PA - Centro Federal de Educação Tecnológica do Pará / O principal objetivo deste trabalho é desenvolver um estudo teórico/experimental sobre a influência dos parâmetros térmicos de solidificação (V L e T) na transição colunar/equiaxial das ligas Sn 5%Pb, Sn 15%Pb, Sn 20%Pb e Sn 25%Pb sob condições de solidificação unidirecional horizontal refrigerada à água. Inicialmente, são calculadas experimentalmente as velocidades da isoterma líquidus e as taxas de resfriamento das ligas em questão cujos resultados são comparados com as previsões teóricas de um modelo numérico. Em seguida, a posição da transição colunar/equiaxial é determinada por meio da análise macroestrutural assim como são avaliados os efeitos impostos por correntes convectivas devido ao efeito do soluto no comportamento da transição colunar/equiaxial das referidas ligas. Finalmente, é realizado um estudo experimental comparativo para as ligas estudadas quando solidificadas unidirecionalmente em diferentes sistemas refrigerados à água. / This work carry out a theoretical experimental study about the influence of solidification thermal parameters on the columnar to equiaxed transition of Sn 5%Pb, Sn 15%Pb, and Sn 20% Pb and Sn 25% Pb alloys during the horizontal unidirectional solidification process cooled by water which considers the solute convection effects. The tip growth rates and cooling rates have been experimentally calculated and the obtained results are compared with those of a numerical model. The columnar to equiaxed transition position is determined through the macrostructure characterization of the studied alloys. The experimental results have shown that the thermosolutal convection influences the CET occurrence. Finally, a comparative experimental study is done for the studied alloys when directionally solidified in different water-cooled systems.

No description available.

Prenatal alcohol exposure (Fetal Alcohol Syndrome [FAS] and Fetal Alcohol Spectrum Disorders [FASD’s]) represents the leading preventable cause of intellectual disabilities in the western world, with FASDs estimated to affect approximately 2-5% of live births in the United States at an approximate annual cost of $3.6 billion (CDC, 2015; May et al., 2009). Ethanol (ETOH) exposure during development can lead to a variety of long-term behavioral impairments including problems with executive functioning, motor coordination, spatial learning, attention, and hyperactivity (Jones, 2011; Mattson & Riley, 1998). Much research has been conducted to develop pharmacological and/or environmental interventions to reduce these deficits, however, there are currently no clinically approved medications to treat the deficits related to fetal ETOH exposure. The current study used a developmental “3rd trimester” ETOH exposure model in neonatal rats to test the hypothesis that compounds targeting the nicotinic system will reduce deficits associated with ETOH exposure. Both compounds demonstrated promise in reducing some of the effects of developmental ethanol exposure, with DMXB-A treatment after ethanol exposure reducing balance deficits in females and spatial memory deficits in males. Solidago nemoralis treatment after ETOH exposure reduced learning and memory deficits in males and balance and executive functioning deficits in both sexes. With these results and previous work in this lab and others there appears to be ample evidence for their usefulness in reducing various forms of neurotoxicity. The long-term goal of this research is to evaluate the usefulness of both DMXB-A & Solidago nemoralis (SN) in treating deficits related to developmental ETOH exposure in humans and hopefully develop a treatment for these disorders.

Staphylococcal nuclease and tudor-domain containing 1 (SND1) is an oncogene for a wide variety of cancers, including hepatocellular carcinoma (HCC). SND1 is a multifunctional protein regulating gene expression of proto-oncogenes and tumor suppressor genes, making SND1 a prime target for developing cancer therapeutics. This notion is especially attributed to HCC as most patients are diagnosed in advanced stages and the therapeutic options available for these patients are severely limited. In this study, we evaluated the therapeutic potential of a replication-defective adenovirus vector delivering SND1 shRNA (Ad.SND1sh) to human HCC cell lines, HepG3, HuH-7, and Hep3B. Adenovirus infection in HCC cells was confirmed by Western blotting and immunofluorescence. The efficacy of Ad.SND1sh to knockdown SND1 expression was confirmed via Western blot, qRT-PCR, and immunofluorescence. Ad.SND1sh did not significantly affect proliferation of the three human HCC cells but significantly inhibited their invasive and migratory capacities, as determined by wound healing and Matrigel invasion assays, respectively. As a corollary, Ad.SND1sh treatment resulted in a decrease in mesenchymal markers, such as N-cadherin, Twist, Snail, and Slug, without affecting levels of epithelial marker E-Cadherin, indicating that SND1 knockdown induces mesenchymal conversion in HCC cells. Additionally, reductions in liver cancer stem cell marker CD133 and HCC marker α-fetoprotein (AFP) were observed with SND1 knockdown. HCC cells with aberrant expression of these markers are associated with tumor initiation, recurrence, and multi-drug resistance. Our findings indicate that Ad.SND1sh may potentially be an effective therapy for advanced HCC and needs to be studied further for its clinical application.

Supernovae are some of the most energetic phenomena in the Universe and they have throughout history fascinated people as they appeared as new stars in the sky. Supernova (SN) 1987A exploded in the nearby satellite galaxy, the Large Magellanic Cloud (LMC), at a distance of only 168,000 light years. The proximity of SN 1987A offers a unique opportunity to study the medium surrounding the supernova in great detail. Powered by the dynamical interaction of the ejecta with the inner circumstellar ring, SN 1987A is dramatically evolving at all wavelengths on time scales less than a year. This makes SN 1987A a great ``laboratory'' for studies of shock physics. Repeated observations of the ejecta-ring collision have been carried out using the UVES echelle spectrograph at VLT. This thesis covers seven epochs of high resolution spectra taken between October 1999 and November 2007. Three different emission line components are identified from the spectra. A narrow (~10 km/s) velocity component emerges from the unshocked ring. An intermediate (~250 km/s) component arises in the shocked ring, and a broad component extending to ~15,000 km/s comes from the reverse shock. Thanks to the high spectral resolution of UVES, it has been possible to separate the shocked from the unshocked ring emission. For the unshocked gas, ionization stages from neutral up to Ne V and Fe VII were found. The line fluxes of the low-ionization lines decline during the period of the observations. However, the fluxes of the [O III] and [Ne III] lines appear to increase and this is found to be consistent with the heating of the pre-shock gas by X-rays from the shock interactions. The line emission from the ejecta-ring collision increases rapidly as more gas is swept up by the shocks. This emission comes from ions with a range of ionization stages (e.g., Fe II-XIV). The low-ionization lines show an increase in their line widths which is consistent with that these lines originate from radiative shocks. The high-ionization line profiles (Fe X-XIV) initially show larger spectral widths, which indicates that at least a fraction of the emission comes from non-radiative shocks.

Joining of electronic components onto the circuit boards is done by soldering operation, during production of all electronic devices. In many countries, including Turkey, traditionally used tin-lead (Sn-Pb) solder alloys have been restricted to be used in consumer electronics appliances because of the toxic effects of lead (Pb) within these alloys. Tin-silver-copper (Sn-Ag-Cu) based alloys have been developed as the most promising candidate that can replace the Sn-Pb alloys. However, various problems have emerged with the increasing trend in use of Sn-Ag-Cu solder alloys in electronics industry, namely large intermetallic compound formation, low wettability and thermal shock resistance. Many researches have been done in the past decade to overcome these problems. The solutions are based on changing the undercooling of the solder alloy / which was determined to be done by either changing the composition of the solder alloy by micro-alloying or changing the cooling rate during soldering operation. In this thesis study Sn-3.5Ag-0.9Cu (wt. %) lead-free solder having the eutectic composition, was micro-alloyed with additions of aluminum (Al), iron (Fe) and titanium (Ti). Experimental results were compared with commercially available near-eutectic Sn-40Pb (wt. %) solder, a commercially available Sn-3.0Ag-0.5Cu (wt. %) solder and also eutectic Sn-3.5Ag.0.9Cu (wt. %) and near-eutectic Sn-3.7Ag-0.9Cu (wt. %) solders that were produced for this thesis study. In the first stage of the study, the effects of 0.05 wt. % of Al, Fe and Ti micro-alloying were investigated. When preliminary results of mechanical and thermal test were compared, Fe was found to make positive effect on shear strength and undercooling. Further research was carried out to establish a relationship between the Fe compositions and solder properties. Therefore, 0.01, 0.03, 0.07 and 0.1 wt. % Fe additions were also studied and results were reported. 0.01 wt. % and 0.07 wt. % Fe added solders were found to have a smaller undercooling, resulting with dispersed intermetallic compound (IMC) and thus has highest shear strength. Different cooling rates / 0.017, 0.17 and 1.7 &deg / C/sec were applied to solder-copper joints and microstructures were investigated. Large IMC-free microstructure was achieved by 0.01 wt. % Fe micro-alloyed solder, which was cooled with 1.7 &deg / C/sec rate. Wetting of copper substrate was found to be improved by additions of Al, Fe and Ti compared to alloy with eutectic composition of Sn-Ag-Cu alloy. Selected SAC+X alloys have been subjected to thermal shock experiments for crack formation analysis on the copper substrate-solder joints. The results showed that SAC+0.05Al solder has the higher thermal shock resistance, which no cracks were observed after 1500 cycles of thermal shock. In order to understand the insights of SAC performance, some of the lead-free solders were applied onto printed circuit boards for thermal shock resistance test. These results have indicate that the cracking may occur after thermal shock cycles due to process conditions of soldering operation (i.e. cooing rate), independent of the solder alloy composition.