High-efficiency 10 J diode pumped cryogenic gas cooled Yb:YAG multislab amplifier

We report on the first demonstration of a diode-pumped, gas cooled, cryogenic multislab Yb:YAG amplifier. The performance was characterized over a temperature range from 88 to 175 K. A maximum small-signal single-pass longitudinal gain of 11.0 was measured at 88 K. When amplifying nanosecond pulses, recorded output energies were 10.1 J at 1 Hz in a four-pass extraction geometry and 6.4 J at 10 Hz in a three-pass setup, corresponding to optical to optical conversion efficiencies of 21% and 16%, respectively. To our knowledge, this represents the highest pulse energy so far obtained from a cryo-cooled Yb-laser and the highest efficiency from a multijoule diode pumped solid-state laser system.     

Widely tunable midinfrared difference frequency generation in orientation-patterned GaAs pumped with a femtosecond Tm-fiber system

We demonstrate a midinfrared source tunable from 6.7 to 12.7 μm via difference frequency generation (DFG) in orientation-patterned GaAs, with 1.3 mW average output power. The input pulses are generated via Raman self-frequency shift of a femtosecond Tm-doped-fiber laser system in a fluoride fiber. We numerically model the DFG process and show good agreement between simulations and experiments. We use this numerical model to show an improved design using longer pump pulses.     

The three-channel model of sound localization mechanisms: interaural level differences

The current understanding of mammalian sound localization is that azimuthal (horizontal) position assignments are dependent upon the relative activation of two populations of broadly-tuned hemifield neurons with overlapping medial borders. Recent psychophysical work has provided evidence for a third channel of low-frequency interaural time difference (ITD)-sensitive neurons tuned to the azimuthal midline. However, the neurophysiological data on free-field azimuth receptive fields, especially of cortical neurons, has primarily studied high-frequency cells whose receptive fields are more likely to have been shaped by interaural level differences (ILDs) than ITDs. In four experiments, a selective adaptation paradigm was used to probe for the existence of a midline channel in the domain of ILDs. If no midline channel exists, symmetrical adaptation of the lateral channels should not result in a shift in the perceived intracranial location of subsequent test tones away from the adaptors because the relative activation of the two channels will remain unchanged. Instead, results indicate a shift in perceived test tone location away from the adaptors, which supports the existence of a midline channel in the domain of ILDs. Interestingly, this shift occurs not only at high frequencies, traditionally associated with ILDs in natural settings, but at low frequencies as well.     

Frequency–rank correlations of rhodopsin mutations with tuned hydropathic roughness based on self-organized criticality

The behavior of disease-linked mutations of membrane proteins is especially simple in rhodopsin, where they are well-studied, as they are responsible for retinitis pigmentosa, RP (retinal degeneration). Here we show that the frequency of occurrence of single RP mutations is strongly influenced by their transportational survival rates, and that this survival correlates well (82%) with a long-range, non-local hydropathic measure of the roughness of the water interfaces of ex-membrane rhodopsin based on self-organized criticality (SOC). It is speculated that this concept may be generally useful in studying survival rates of many mutated proteins.     

Resonance raman excitation profile of a ruthenium(II) complex of dipyrido[2,3-a:3',2'-c]phenazine

The lowest energy transition of [Ru(CN)(4)(ppb)](2-) (ppb = dipyrido[2,3-a:3',2'-c]phenazine), a metal-to-ligand charge transfer, has been probed using resonance Raman spectroscopy with excitation wavelengths (488, 514, 530, and 568 nm) spanning the lowest energy absorption band centered at 522 nm. Wave packet modeling was used to simultaneously model this lowest energy absorption band and the cross sections of the resonance Raman bands at the series of excitation wavelengths across this absorption band. A fit to within +/-20% was obtained for the Raman cross sections, close to the experimental uncertainty which is typically 10-20%. Delta values of 0.1-0.4 were obtained for modes which were either localized on the ppb ligand (345-1599 cm(-1)) or the CN modes (2063 and 2097 cm(-1)). DFT calculations reveal that the resonance Raman bands observed are due to modes delocalized over the entire ppb ligand.     

A density functional theory study of the 5-exo cyclization reactions of alpha-substituted 6,6-diphenyl-5-hexenyl radicals

Density functional theory computations were done to study the 5-exo radical cyclization reactions of alpha-substituted 6,6-diphenyl-5-hexenyl radicals. The methoxy electron donor group substitution reduced the barrier to reaction by about 0.5 kcal/mol. On the other hand, the electron acceptor group substitutions (ethoxycarbonyl, carboxylic acid, carboxylate, and cyano) raised the barrier to reaction by varying amounts (0.5-2.1 kcal /mol). The entropic terms of these cyclization reactions are briefly discussed. Solvent effects on these reactions were explored by calculations that included a polarizable continuum model for the solvent. The density functional theory calculated results were found to be in good agreement with the experimental data available in the literature and help to explain some of the observed variation in these types of cyclization reactions with various substitutions. Our results also provide an explanation for why the rate constant for the carboxylate group substituted radical was found to be an order of magnitude smaller than the rate constant for those radicals with carboxylic acid and ethoxycarbonyl substitutions.     

Spin relaxation by transient monopolar and bipolar optical orientation

We have used two-color time-resolved spectroscopy to measure the relaxation of electron spin polarizations in a bulk semiconductor. The circularly polarized pump beam induces a polarization either by direct excitation from the valence band, or by free-carrier (Drude) absorption when tuned to an energy below the band gap. We find that the spin relaxation time, measured with picosecond time resolution by resonant induced Faraday rotation in both cases, increases in the presence of photogenerated holes. In the case of the material chosen, n-InSb, the increase was from 14 to 38 ps.     

Surface plasmon resonance imaging analysis of protein-receptor binding in supported membrane arrays on gold substrates with calcinated silicate films

A new method to fabricate supported bilayer membrane (SBM) arrays for surface plasmon resonance (SPR) imaging analysis is demonstrated in this work. Thin silicate films are produced on gold SPR substrates using layer-by-layer assembly, followed by calcination. Etching into the glassified substrates using photolithographic techniques generates nanowells of desirable size and depth. Atomic force microscopy and SPR imaging analysis show that the features are well-defined, and the etching process appears to have a surface smoothing effect. After the wells are oxidized with strong acid, vesicles spontaneously fuse onto them to form supported membranes with a high degree of lateral mobility. Fluorescence recovery after photobleaching measurements yielded a diffusion coefficient of 1.1 mum2/s. To demonstrate the feasibility for high-throughput receptor-ligand interaction analysis, binding of cholera toxin (CT) to SBM arrays containing 5 mol % ganglioside GM1 receptor was carried out with SPR imaging. The results showed excellent well-to-well reproducibility (8% RSD at 60 nM CT) and marked detection sensitivity.     

Onsager heat of transport for water vapour at the surface of water and ice: thermal accommodation coefficients for water vapour on a stainless-steel surface

The Onsager heat of transport Q* has been measured for water vapour at the surface of water, supercooled water, and ice, over the temperature range -8 to +10 degrees C. For liquid water, Q* is constant at -24.7 +/- 3.6 kJ mol(-1) (two standard deviations) over the pressure range 4-9.5 Torr. Provided the ice is suitably aged, the |Q*| values are very similar for water and ice, a result which is consistent with the presence of a liquid-like layer at the surface of ice. The values are slightly larger for ice, in proportion to the ratio of the heat of sublimation of ice to the heat of vaporization of the liquid. Departures from linearity of plots of P against DeltaT are attributed to temperature jumps at the surface of the dry upper plate. Hence jump coefficients and thermal accommodation coefficients have been derived as a function of temperature for collisions of water molecules with type-304 stainless steel.     

A matrix-assisted laser desorption/ionization compatible reagent for tagging tryptophan residues

Chemical tagging of amino acids is an important tool in proteomics analysis, and has been used to introduce isotope labels and mass defect labels into proteolytic peptides by derivatization of cysteine or lysine residues. Here, we present a new reagent with chemical specificity for tryptophan residues. Previously, 2-nitrobenzenesulfenyl chloride has been used as a highly specific reagent for labeling tryptophan residues. We show that this tag undergoes UV dissociation during matrix assisted laser desorption/ionization (MALDI). The multiplicity of photofragments increases the difficulty of characterizing the derivatization products. To overcome this problem, we have synthesized a new reagent, 2-(trifluoromethyl)benzenesulfenyl chloride, which is shown to react quantitatively with tryptophan in peptides and proteins. Most significantly, it exhibits high photostability in MALDI-Fourier transform mass spectrometry analyses.