Thermocapillary Flows In Liquid Bridges Of Molten Tin With Small Aspect Ratios

Numerical simulations were conducted to study thermocapillary flows in short half-zone liquid bridges of molten tin with Prandtl number Pr = 0.009, under ramped temperature difference. The spatio-temporal structures in the thermocapillary flows in short half-zone liquid bridges with aspect ratios As = 0.6, 0.8, and 1.0 were investigated. The first critical Marangoni numbers were compared with those predicted by linear stability analyses (LSA). The second critical Marangoni numbers for As = 0.6 and 0.8 were found to be larger than that for As = 1.0. The time evolutions of the thermocapillary flows exhibited unusual features such as a change in the azimuthal wave number during the three-dimensional stationary (non-oscillating) flow regime, a change in the oscillation mode during the three-dimensional oscillatory flow regime, and the decreasing and then increasing of amplitudes in a single oscillation mode. The effects of the ramping rate of the temperature difference on the flow modes and critical conditions were studied as well. In this paper, the experimental observability of the critical conditions was also discussed. (C) 2008 Elsevier Inc. All rights reserved.

过滤电弧沉积的TiN/TiCrN/CrN/CrTiN多层膜

用过滤电弧技术在高速钢表面沉积了TiN/TiCrN/CrN/CrTiN多层膜 ,用扫描电镜 (SEM )观察了截面和断口形貌及划痕后的形貌。使用俄歇电子谱仪进行剥层成分分析 ,用纳米压痕仪测试了多层膜和单层膜的显微硬度和弹性模量。结果表明 ,在调制周期大于 10 0nm时 ,多层膜的显微硬度符合Hall Petch关系 ,在 80nm时 ,则脱离线性关系。划痕法测试多层膜的结合力达到 80N。

过滤电弧沉积TiN、ZrN和TiN／CrN多层纳米薄膜的性能比较

用过滤电弧离子镀(FAMIP)技术在高速钢基体上沉积了TiN、ZrN单层薄膜和TiN／CrN多层纳米薄膜。利用扫描电子显微镜(SEM)观察了薄膜及其划痕的表面形貌;用X射线衍射仪(XRD)分析了薄膜的相组成,结合显微探针仪、划痕试验机、金相显微镜和钻床,研究了金属陶瓷单层和多层纳米薄膜的性能并进行比较。研究结果表明:3种薄膜的临界载荷值均大于80N,多层纳米薄膜的耐磨性明显优于2种单层薄膜。

电弧离子镀中脉冲偏压对TiN,CrN薄膜性能的影响

在电弧离子镀技术中使用脉冲偏压电源是近年来发展起来的一项新技术。研究表明，在薄膜沉积过程中，以直流偏压为基础，迭加一个高脉冲电压，有助于改善薄膜的性能，并且能够在较低的沉积温度下获得结合力较强、内应力较小、表面光洁度也比较好的薄膜。通过正交设计和方差分析，本文首次研究了在电弧离子镀技术中使用脉冲偏压电源， 在高速钢和不锈钢基体上沉积TiN和CrN的过程中，对薄膜的表面粗糙度、表面形貌、结合力、显微硬度、沉积速率等性能的影响，发现：（1） 在考虑气氛、弧电流和脉冲电源的各种参数的情况下，气氛和频率是影响薄膜性能的主要因素；（2）在气氛、弧电流不变的条件下，脉冲电源的频率和占空比是影响薄膜粗糙度的主要因素；（3）在比较了直流偏压和脉冲偏压的实验结果之后，认为利用直流迭加脉冲的偏压方式，经过优化参数，能够比较显著地 降低薄膜的表面粗糙度，提高沉积速率。

Reactivity of titanocene methylidene with metal halides, alkene sulfides, and alkene oxides

Titanocene metallacyclobutanes show a wide variety of reactivites with organic and inorganic reagents. Their reactions include methylene transfer to organic carbonyls, formation of enolates, electron transfer from activated alkyl chlorides, olefin metathesis, ring opening polymerization. Recently, preparations of heterobinuclear µ-methylene complexes were reported. In this thesis, mechanistic, synthetic, and structural studies of the heterobinuclear µ-methylene complexes will be described. Also, the reaction of titanocene methylidene trimethylphosphine complex with alkene sulfide and styrene sulfide will be presented.

Heterobinuclear µ-methylene-µ-methyl complexes C_(p2)Ti(µ-CH_2)( µ-CH_3)M(1,5-COD) have been prepared (M = Rh, Ir). X-ray crystallography showed that the methyl group of the complex was bonded to the rhodium and bridges to the titanium through an agostic bond. The ^(1)H,^(13)CNMR, IR spectra along with partial deuteration studies supported the structure in both solution and solid state. Activation of the agostic bond is demonstrated by the equilibration of the µ-CH_3 and µ-CH_2 groups. A nonlinear Arrhenius plot, an unusually large kinetic isotope effect (24(5)), and a large negative activation entropy (-64(3)eu) can be explained by the quantum-mechanical tunneling. Calculated rate constants with Bell-type barrier fitted well with the observed one. This equilibration was best explained by a 4e-4c mechanism (or σ bond metathesis) with the character of quantum-mechanical tunneling.

Heterobinuclear µ-methylene-µ-phenyl complexes were synthesized. Structural study of C_(p2)Ti(µ-CH_(2))(µ-p-Me_(2)NC_(6)H_(4))Rh(l,5-COD) showed that the two metal atoms are bridged by the methylene carbon and the ipso carbon of the p-N,N-dimethylarninophenyl group. The analogous structure of C_(p2))Ti(µ-CH_(2))(µ-o-MeOC_(6)H_(4))Rh(1,5-COD) has been verified by the differential NOE. The aromaticity of the phenyl group observed by ^(1)H NMR, was confirmed by the comparison of the C-C bond lengths in the crystallographic structure. The unusual downfield shifts of the ipso carbon in the ^(13)C NMR are assumed to be an indication of the interaction between the ipso carbon and electron-deficient titanium.

Titanium-platinum heterobinuclear µ-methylene complexes C_(p2)Ti(µ-CH_(2))(µ -X)Pt(Me)(PM_(2)Ph) have been prepared (X= Cl, Me). Structural studies indicate the following:(1) the Ti-CH2 bond possesses residual double bond character, (2) there is a dative Pt→Ti interaction which may be regarded as a π back donation from the platinum atom to the 'Ti=CH_(2)'' group, and (3) the µ-CH_3 group is bound to the titanium atom through a three-center, two-electron agostic bond.

Titanocene (η^(2)-thioformaldehyde)•PMe_3 was prepared from C_(p2)Ti=CH_(2)•PMe_3 and sulfur-containing organic compounds (e.g. alkene sulfide, triphenylphosphine sulfide) including elemental sulfur. Mechanistic studies utilizing trans-styrene sulfide-d_1 suggested the stepwise reaction to explain equimolar mixture of trans- and cis-styrene-d_1 as by-products. The product reacted with methyl iodide to produce cationic titanocene (η_(2)-thiomethoxymethyl) complex. Complexes having less coordinating anion like BF_4 or BPh_4 could be obtained through metathesis. Together with structural analyses, the further reactivities of the complexes have been explored.

The complex C_(p2)TiOCH_(2)CH(Ph)CH_2 was prepared from the compound C_(p2)Ti=CH_(2)-PMe_3 and styrene oxide. The product was characterized with ^(1)H-^(1)H correlated 2-dimensional NMR, selective decoupling of ^(1)H NMR, and differential NOE. Stereospecificity of deuterium in the product was lost when trans-styrene oxide-d_1 was allowed to react. Relative rates of the reaction were measured with varying substituents on the phenyl ring. Better linearity (r = -0.98, p^(+) = -0.79) was observed with σ_(p)^(+)than σ(r = -0.87, p = -1.26). The small magnitude of p^+ value and stereospecificity loss during the formation of product were best explained by the generation of biradicals, but partial generation of charge cannot be excluded. Carbonylation of the product followed by exposure to iodine yields the corresponding β-phenyl γ-lactone.

Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

Structural Characterizations of the Dimeric Anti-HIV Antibody 2G12 and the HIV-2 Envelope Glycoprotein

More than thirty years after the discovery that Human Immunodeficiency Virus (HIV) was the causative agent of Acquired Immunodeficiency Syndrome (AIDS), the disease remains pandemic as long as no effective universal vaccine is found. Over 34 million individuals in the world are infected with the virus, and the vast majority of them have no access to the antiretroviral therapies that have largely reduced HIV to a chronic disease in the developed world. The first chapter of this thesis introduces the history of the virus. The key to the infectious mechanism of the virus lies in its envelope glycoprotein (Env), a trimeric spike on the viral surface that utilizes host T cell receptors for entry. Though HIV-1 Env is immunogenic, most infected patients do not mount an effective neutralizing antibody response against it. Broadly-neutralizing anti-Env antibodies (bNAbs) present in the serum of a minority of infected individuals are usually sufficient to prevent the progression to full blown AIDS. Thus, the molecular details of these bNAbs as well as the antibody-antigen interface are of prime interest for structural studies, as insight gained would contribute to the design of a more effective immunogen and potential vaccine candidate. The second chapter of this thesis describes the low-resolution crystal structure of one such antibody, 2G12 dimer, which targets a high mannose epitope on the surface of Env. Patients infected with HIV-2, a related virus with ~35% sequence identity in the Env region, can generally mount a robust antibody response sufficient for viral control for reasons still unknown. The final two chapters of this thesis focus on the first reported structural studies of HIV-2 Env, the molecular details of which may inform HIV-1 therapy and immunogen design.

Formation and characterization of tin oxide aerogel derived from sol-gel process based on tetra(n-butoxy)tin(IV)

Transparent and translucent SnO2 aerogels with high specific surface area (>300m(2)/g) have been prepared by sol-gel process using tetra(n-butoxy)tin(IV) as a starting compound, and supercritical drying technique for solvent extraction. Light scattering measurements reveal that the polymeric cluster size distribution in sol system is gradually broadened during sol-gel transition. SEM images show that the aerogels are made up of the cottonlike oxide agglomerates with a large number of Pores. TEM images show that these aerogels seem to be self-similar at different magnifications. Their pore size distribution is pretty wide ranging, from mesopore to macropore especially for that of translucent aerogel. (C) 2004 Elsevier B.V. All rights reserved.

Vanadyl arsenates as catalysts for selective oxidation of organic sulfides and alkenes

artículo científico (postprint)