Water: a responsive small molecule

Unique among small molecules, water forms a nearly tetrahedral yet flexible hydrogen-bond network. In addition to its flexibility, this network is dynamic: bonds are formed or broken on a picosecond time scale. These unique features make probing the local structure of water challenging. Despite the challenges, there is intense interest in developing a picture of the local water structure due to water's fundamental importance in many fields of chemistry. Understanding changes in the local network structure of water near solutes likely holds the key to unlock problems from analyzing parameters that determine the three dimensional structure of proteins to modeling the fate of volatile materials released into the atmosphere. Pictures of the local structure of water are heavily influenced by what is known about the structure of ice. In hexagonal I(h) ice, the most stable form of solid water under ordinary conditions, water has an equal number of donor and acceptor bonds; a kind of symmetry. This symmetric tetrahedral coordination is only approximately preserved in the liquid. The most obvious manifestation of this altered tetrahedral bonding is the greater density in the liquid compared with the solid. Formation of an interface or addition of solutes further modifies the local bonding in water. Because the O-H stretching frequency is sensitive to the environment, vibrational spectroscopy provides an excellent probe for the hydrogen-bond structure in water. In this Account, we examine both local interactions between water and small solutes and longer range interactions at the aqueous surface. Locally, the results suggest that water is not a symmetric donor or acceptor, but rather has a propensity to act as an acceptor. In interactions with hydrocarbons, action is centered at the water oxygen. For soluble inorganic salts, interaction is greater with the cation than the anion. The vibrational spectrum of the surface of salt solutions is altered compared with that of neat water. Studies of local salt-water interactions suggest that the picture of the local water structure and the ion distribution at the surface deduced from the surface vibrational spectrum should encompass both ions of the salt.     

Estimating stimuli from contrasting categories: Truncation due to boundaries.

In this article, the authors present and test a formal model that holds that people use information about category boundaries in estimating inexactly represented stimuli. Boundaries restrict stimuli that are category members to fall within a particular range. This model posits that people increase the average accuracy of stimulus estimates by integrating fine-grain values with boundary information, eliminating extreme responses. The authors present 4 experiments in which people estimated sizes of squares from 2 adjacent or partially overlapping stimulus sets. When stimuli from the 2 sets were paired in presentation, people formed relative size categories, truncating their estimates at the boundaries of these categories. Truncation at the boundary of separation between the categories led to exaggeration of differences between stimuli that cross categories. Yet truncated values are shown to be more accurate on average than unadjusted values. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

MASS TRANSFER EFFECTS ON THE ETCH RATE OF GAAS IN FLOW SYSTEMS

In industrial wet etching reactors, the fluid contacts the substrate surface as a spray of flowing stream, thus introducing mass-transfer resistances to the reaction rate. The etching of gallium arsenide in H₂O₂-NH₄OH-H₂O solutions was studied using an open-channel flow reactor to simulate the industrial conditions. The etch rate was always lower than that obtained under kinetic control, and the dependence of etch rate on H₂O₂ concentration shifted closer to first order. From the calculation of the ratio of rate constant to mass-transfer coefficient, the reaction-rate and mass-transfer resistances were both significant in this system. When the mass-transfer coefficient was calculated from equations for flow past a flat plate, the prediction of etch rate was good, particularly when the starting length for velocity boundary layer development ahead of concentration boundary layer development was taken into account. Another approach for the calculation of mass-transfer coefficient, based on the assumptions for flow between parallel plates, best represented the relative insensitivity of etch rate to fluid velocity.     

High aspect ratio meso-scale parts enabled by wire micro-EDM

Micro-electro discharge machining (EDM) is a subtractive meso-scale machining process. The Agie Excellence 2F wire micro EDM is capable of machining with a 25 micron diameter wire electrode and positioning the work piece to within ±1.5 microns. The over-burn gap can be controlled to within 3 microns to obtain a minimum feature radius of about 16 microns while achieving submicron surface finish and an imperceptible recast layer. For example, meso-scale gears that require vertical sidewalls and contour tolerances to within 3 microns can be wire EDMed into a variety of conductive materials. Material instabilities can affect the dimensional precision of machined meso-scale parts by material relaxation during the machining process. A study is done to investigate the machining performance of the wire micro EDM process by machining a high aspect ratio meso-scale part into a variety of metals (e.g. 304L stainless steel, Nitronic 60 Austentic Stainless, Beryllium Copper, and Titanium). Machining performance parameters such as, profile tolerance, perpendicularity, and repeatability are compared for the different materials. Pertinent inspection methods desirable for meso-scale quality assurance tasks are also evaluated. Sandia National Laboratories is developing meso-scale electro-mechanical components and has an interest in the assembly implications of piece parts fabricated by various meso-scale manufacturing processes. Although the wire EDM process is typically used to fabricate 2½ dimensional features, these features can be machined into a 3 dimensional part having other features such as hubs and chamfers to facilitate assembly.     

The effects of n-6 polyunsaturated fatty acids on the expression of nm-23 in human cancer cells

Over an interval of approximately six months beginning in October 1993, most haemophilia A patients in Canada were switched from a plasma-derived intermediate-purity factor VIII concentrate (i.p. VIII) to a recombinant factor VIII (rVIII). In order to determine the consequence of this change in therapy on progression of HIV infection, we gathered surveillance data on clinical status and CD4 and CD8 cell counts in those patients who were HIV seropositive at the time of switching concentrates. Data were recorded at the time of switchover, annually for 2 years thereafter, and retrospectively at a point 1 year prior to the switch. CD4 cells fell significantly over the study period. Multiple direct comparisons revealed that this decline was restricted to the time intervals which included the final year in which patients received intermediate-purity factor VIII concentrate (i.p. VIII). In the 2 year interval in which rVIII was used exclusively, there was a nonsignificant fall in CD4 cells. Changes in CD4 cells did not correlate with the intensity of exposure to either i.p.VIII or rVIII. CD8 cells did not fall significantly over the study period. There was no obvious reduction in the incidence of death or clinical progression over the 2 years in which rVIII was used. However, we are hopeful that the stabilizing trend in CD4 cell counts which followed the introduction of rVIII will be predictive of corresponding clinical stabilization over the coming years.     

CW and mode-locked integrated extended cavity lasers fabricatedusing impurity free vacancy disordering

A phosphorus-doped silica (P:SiO₂) cap containing 5 wt% P has been demonstrated to inhibit the bandgap shifts of p-i-n and n-i-p GaAs-AlGaAs quantum-well laser structures during rapid thermal processing. Bandgap shift differences as large as 100 meV have been observed between samples capped with SiO₂ and with P:SiO₂. The technique has been used to fabricate GaAs-AlGaAs ridge lasers with integrated transparent waveguides. With a selective differential blue-shift of 30 nm in the absorption edge, devices with 400 μm/2.73-mm-long active/passive sections exhibited an average threshold current of 9 mA in continuous-wave (CW) operation, only 2.2 mA higher than that of discrete lasers of the same active length and from the same chip. Extended cavity mode-locked lasers were also investigated and compared to all active devices. For the extended cavity device, the threshold current is a factor of 3-5 lower, the pulsewidth is reduced from 10.3 to 3.5 ps and there is a decrease in the free-running jitter level from 15 ps (measurement bandwidth 10 kHz-10 MHz) to 6 ps. In addition, the extended cavity lasers do not exhibit any self-pulsing modulation of the mode-locked pulse train, unlike the all-active lasers, and the optical spectra indicate that the pulses are more linearly chirped     

A computational study of sulfur bridged cyclooctatetraenophanes

Calculations of several thiacyclooctatetraenophanes predicted, as part of their overall geometry, substantial flattening of the cyclooctatetraene (COT) structures relative to the tub conformation generally associated with the COT molecule. The COT structures were approximately parallel to each other and the interplanar distances were predicted to be within 2.787-2.803 angstrom at the DFT/UB3YLP level of calculation. DFT/UB3LYP optimized geometries afforded significant delocalization of the COT structures in each of the thiacyclooctatetraenophanes. Hartree-Fock (HF) methods and the semi-empirical Austin Model 1 (AM1) method deviated significantly from the DFT/UB3LYP optimized geometries. Cyclooctatetraenes can undergo reversible sizing by oxidation and reduction reactions to form the aromatic dication and aromatic dianion, respectively, which could then be used to prepare molecular backbones for polymeric organometallic molecular wires. The number of bridges and the introduction of the sulfur atom have been investigated to provide disparate synthetic routes.     

Processing properties of high- and low-density polyethylenes and their blends

Blends of two characterized linear polyethylenes with a branched polyethylene have been prepared by melt extrusion. It has been found that the linear polyethylenes can be shear modified in a reversible manner similar to branched polymers and that this shear modification and its reversal by re-heating does not change the molecular weight distribution, thereby indicating that the shear modification is a physical rather than chemical change in structure. Because both the high- and low-density polyethylene components of the blends are capable of undergoing reversible shear modification, it is possible to produce blends with either greater or less melt elasticity than the individual components by adjusting the conditions of blending. This demonstrates that the correlation of the properties of blends with the properties of their components should not be attempted without consideration of the effect of the blending process on the properties of the individual components.