Enhancing Bremsstrahlung production from ultraintense laser-solid interactions with front surface structures

A new type of a coaxial multi-layer plasmonic waveguide is proposed. The mode propagation properties are analyzed at the communication working wavelength. Theoretical investigations reveal that the enhanced optical confinement can be achieved in the two low-index dielectric media layers. The mode size can be sub- or deep sub-wavelength scale. The mode propagation loss can be well compensated by replacing the high-index dielectric media with gain material to achieve longer propagation length with better mode confinement. The comparisons of the mode properties between the proposed waveguide and waveguides studied in the published literatures are also considered. These investigations potentially lay the groundwork for the further applications of nanowire type multilayer hybrid structures. This structure could also enable various applications such asnanophotonic waveguides, high-quality nanolasers, and optical trapping and biosensors.     

Microwave measurements of proton tunneling and structural parameters for the propiolic acid-formic acid dimer

Microwave spectra of the propiolic acid-formic acid doubly hydrogen bonded complex were measured in the 1 GHz to 21 GHz range using four different Fourier transform spectrometers. Rotational spectra for seven isotopologues were obtained. For the parent isotopologue, a total of 138 a-dipole transitions and 28 b-dipole transitions were measured for which the a-dipole transitions exhibited splittings of a few MHz into pairs of lines and the b-type dipole transitions were split by ~580 MHz. The transitions assigned to this complex were fit to obtain rotational and distortion constants for both tunneling levels: A(0+) = 6005.289(8), B(0+) = 930.553(8), C(0+) = 803.9948(6) MHz, Δ(0+)(J) = 0.075(1), Δ(0+)(JK) = 0.71(1), and δ(0+)(j) = -0.010(1) kHz and A(0-) = 6005.275(8), B(0-) = 930.546(8), C(0-) = 803.9907(5) MHz, Δ(0-)(J) = 0.076(1), Δ(0-)(JK) = 0.70(2), and δ(0-)(j) = -0.008(1) kHz. Double resonance experiments were used on some transitions to verify assignments and to obtain splittings for cases when the b-dipole transitions were difficult to measure. The experimental difference in energy between the two tunneling states is 291.428(5) MHz for proton-proton exchange and 3.35(2) MHz for the deuterium-deuterium exchange. The vibration-rotation coupling constant between the two levels, F(ab), is 120.7(2) MHz for the proton-proton exchange. With one deuterium atom substituted in either of the hydrogen-bonding protons, the tunneling splittings were not observed for a-dipole transitions, supporting the assignment of the splitting to the concerted proton tunneling motion. The spectra were obtained using three Flygare-Balle type spectrometers and one chirped-pulse machine at the University of Virginia. Rotational constants and centrifugal distortion constants were obtained for HCOOH···HOOCCCH, H(13)COOH···HOOCCCH, HCOOD···HOOCCCH, HCOOH···DOOCCCH, HCOOD···DOOCCCH, DCOOH···HOOCCCH, and DCOOD···HOOCCCH. High-level ab initio calculations provided initial rotational constants for the complex, structural parameters, and some details of the proton tunneling potential energy surface. A least squares fit to the isotopic data reveals a planar structure that is slightly asymmetric in the OH distances. The formic OH···O propiolic hydrogen bond length is 1.8 ? and the propiolic OH···O formic hydrogen bond length is 1.6 ?, for the equilibrium configuration. The magnitude of the dipole moment was experimentally determined to be 1.95(3) × 10(-30) C m (0.584(8) D) for the 0(+) states and 1.92(5) × 10(-30) C m (0.576(14) D) for the 0(-) states.     

Protein analysis by desorption electrospray ionization mass spectrometry and related methods

Desorption electrospray ionization mass spectrometry (DESI‐MS) requires little to no sample preparation and has been successfully applied to the study of biologically significant macromolecules such as proteins. However, DESI‐MS and other ambient methods that use spray desorption to process samples during ionization appear limited to smaller proteins with molecular masses of 25 kDa or less, and a decreasing instrumental response with increasing protein size has often been reported. It has been proposed that this limit results from the inability of some proteins to easily desorb from the surface during DESI sampling. The present study investigates the apparent mass dependence of the instrumental response observed during the DESI‐MS analysis of proteins using spray desorption collection and reflective electrospray ionization. Proteins, as large as 66 kDa, are shown to be quantitatively removed from surfaces by using spray desorption collection. However, incomplete dissolution and the formation of protein–protein and protein–contaminant clusters appear to be responsible for the mass‐dependent loss in sensitivity for protein analysis. Alternative ambient mass spectrometry approaches that address some of the problems encountered by spray desorption techniques for protein analysis are also discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

-NH- termination of the Si(111) surface by wet chemistry

For over a quarter of a century the hydrogen-terminated Si(111) single-crystalline surface has been the gold standard as a starting point for silicon surface modification chemistry. However, creating a well-defined and stable interface based on Si-N bonds has remained elusive. Despite the fact that azides, nitro compounds, and amines do lead to the formation of surface Si-N, each of these modification schemes produces additional carbon- or oxygen-containing functional groups that in turn react with the surface itself, leaving contaminants that affect the interface properties for any further modification protocols. We describe the preparation of a Si(111) surface functionalized predominantly with Si-NH-Si species based on chlorination followed by the room temperature ammonia treatment utilizing NH(3)-saturated tetrahydrofuran (THF). The obtained surface has been characterized by infrared spectroscopy and X-ray photoelectron spectroscopy. This analysis was supplemented with DFT calculations. This newly characterized surface will join the previously established H-Si(111) and Cl-Si(111) surfaces as a general starting point for the preparation of oxygen- and carbon-free interfaces, with numerous potential applications.     

An enhanced odd-even effect of liquid crystal dimers Orientational order in the α,ω-bis(4'-cyanobiphenyl-4-yl)alkanes

The odd-even behaviour observed for liquid crystal dimers has been predicted to be a sensitive function of the geometry of the link joining the mesogenic groups to the flexible spacer. Here we report the synthesis of two cyanobiphenyl dimers with methylene links, together with a determination of their transitional properties. In particular we have probed their orientational order via the major and biaxial orientational order parameters of a solute molecule, anthracene-d₁₀, using NMR spectroscopy. For comparison we have also determined the corresponding quantities for the cyanobiphenyl dimers with ether links. The enhanced odd-even effect observed for the methylene linked dimers relative to those with ether links is in good accord with theory.     

A convenient reagent for aldehyde to alkyne homologation

A convenient reagent for the one-carbon homologation of an aldehyde to the corresponding alkyne is reported. This reagent allows this conversion to conveniently be carried out on a large scale under ambient conditions.     

Homology of generalized Steinberg varieties and Weyl group invariants

Let be a complex, connected, reductive algebraic group. In this paper we show analogues of the computations by Borho and MacPherson of the invariants and anti-invariants of the cohomology of the Springer fibres of the cone of nilpotent elements, , of for the Steinberg variety of triples.

Using a general specialization argument we show that for a parabolic subgroup of the space of -invariants and the space of -anti-invariants of are isomorphic to the top Borel-Moore homology groups of certain generalized Steinberg varieties introduced by Douglass and Röhrle (2004).

The rational group algebra of the Weyl group of is isomorphic to the opposite of the top Borel-Moore homology of , where . Suppose is a parabolic subgroup of . We show that the space of -invariants of is , where is the idempotent in the group algebra of affording the trivial representation of and is defined similarly. We also show that the space of -anti-invariants of is , where is the idempotent in the group algebra of affording the sign representation of and is defined similarly.

     

Synthesis of Bis-18,18'-desmethyl Ritterazine N

Bis-18,18'-desmethyl ritterazine N has been prepared in enantiomerically pure form. The synthetic alkaloid, lacking only two of the 52 carbon atoms of the natural product, shows selective activity in the NIH 60 cell panel.     

A three-step route to a tricyclic steroid precursor

2-Alkyl cyclohexenones are useful intermediates for organic synthesis. The Wittig reaction of a series of aldehydes with (cyclopropylmethyl)triphenylphosphonium bromide delivered the corresponding alkenyl cyclopropanes. UV irradiation in the presence of Fe(CO)5 converted the alkenyl cyclopropanes to the 2-substituted cyclohexenones. This approach enabled a three-step synthesis of the tricyclic core of estrone methyl ether.