Testing theories of vowel inherent spectral change

Three competing accounts of vowel inherent spectral change in English all agree on the importance of initial formant frequencies; however, they disagree about the nature of the perceptually relevant aspects of formant change. The onset+offset hypothesis claims that the final formant values themselves matter. The onset+slope hypothesis claims that only the rate of change counts. The onset+direction hypothesis claims that only the general direction of change in formant frequencies is important. A synthetic-vowel perception experiment was designed to differentiate among the three. Results provide support for the superiority of the onset+offset hypothesis.     

Sidelobe contrast reduction for optical vortex beams using a helical axicon

We present a new approach for generating an optical vortex pattern with reduced sidelobes without increasing the radius of the vortex and without excessive energy loss. Our technique combines the spiral phase plate with a weak axicon to form a helical axicon. Experimental results using a liquid crystal display agree with theory.     

In situ Raman spectroscopy of low-temperature/high-pressure transformations of H2O

In situ Raman spectra of transformations of H2O as functions of pressure and temperature have been measured starting from high-density amorphous ice (HDA). Changes above Tx, the crystallization temperature of HDA, were observed. The spectra provide evidence for an abrupt, first-order-like, structural change that appears to be distinct from those associated with the transformation between low-density amorphous ice (LDA) and HDA. In separate experiments, in situ Raman spectra of ice XII transformed from HDA have been measured at various P-T regions, in order to improve the understanding of the stability limits of ice XII. The spectra of ices VI and XII differ in shape, but the vibrational frequencies are very close in the same P-T regimes. A metastable phase of ice found to form within the stability field of ice VI appears to be distinct from ice XII.     

Microwave spectra and ab initio studies of Ar-propane and Ne-propane complexes: structure and dynamics

Microwave spectra in the 7-26 MHz region have been measured for the van der Waals complexes, Ar-CH3CH2CH3, Ar-(13)CH3CH2CH3, 20Ne-CH3CH2CH3, and 22Ne-CH3CH2CH3. Both a- and c-type transitions are observed for the Ar-propane complex. The c-type transitions are much stronger indicating that the small dipole moment of the propane (0.0848 D) is aligned perpendicular to the van der Waals bond axis. While the 42 transition lines observed for the primary argon complex are well fitted to a semirigid rotor Hamiltonian, the neon complexes exhibit splittings in the rotational transitions which we attribute to an internal rotation of the propane around its a inertial axis. Only c-type transitions are observed for both neon complexes, and these are found to occur between the tunneling states, indicating that internal motion involves an inversion of the dipole moment of the propane. The difference in energy between the two tunneling states within the ground vibrational state is 48.52 MHz for 20Ne-CH3CH2CH3 and 42.09 MHz for 22Ne-CH3CH2CH3. The Kraitchman substitution coordinates of the complexes show that the rare gas is oriented above the plane of the propane carbons, but shifted away from the methylene carbon, more so in Ne propane than in Ar propane. The distance between the rare gas atom and the center of mass of the propane, Rcm, is 3.823 A for Ar-propane and 3.696 A for Ne-propane. Ab initio calculations are done to map out segments of the intermolecular potential. The global minimum has the rare gas almost directly above the center of mass of the propane, and there are three local minima with the rare gas in the plane of the carbon atoms. Barriers between the minima are also calculated and support the experimental results which suggest that the tunneling path involves a rotation of the propane subunit. The path with the lowest effective barrier is through a C2v symmetric configuration in which the methyl groups are oriented toward the rare gas. Calculating the potential curve for this one-dimensional model and then calculating the energy levels for this potential roughly reproduces the spectral splittings in Ne-propane and explains the lack of splittings in Ar-propane.     

A practical synthesis of a gamma-secretase inhibitor

A practical and scaleable synthesis of the gamma-secretase inhibitor 1 is reported. The inhibitor consists of a central trisubstituted cyclohexane core with appended propionic acid, 2,5-difluorophenyl, and 4-chlorophenylsulfonyl moieties. Two alternative synthetic strategies, proceeding by way of a common disubstituted cyclohexanone derivative 5, were studied. In the preferred route, conjugate reduction of acrylonitrile derivative 4 with L-Selectride configures the desired relative stereochemistry of the cyclohexane core with >99.9:0.1 dr. A second strategy, based on catalyst-controlled hydrogenation of racemic cyclohexene derivative 2, is more convergent but less diastereoselective (up to 75:25 dr). The common cyclohexanone intermediate 5 was constructed by a regioselective Diels-Alder condensation of a 1,1-disubstituted vinyl sulfone 6 with 2-trimethylsiloxybutadiene.     

Specificity of acyl transfer from 2-mercaptobenzamide thioesters to the HIV-1 nucleocapsid protein

The HIV-1 nucleocapsid protein (NCp7) is a small, highly conserved protein with two zinc-binding domains that are essential for the protein's function. Molecules that bind to and inactivate NCp7 are currently being evaluated as new antiviral drugs. In particular, derivatives based on a 2-mercaptobenzamide thioester template have been shown to specifically eject zinc from the C-terminal zinc-binding domain (ZD2) of NCp7 via acyl transfer from the thioester to a cysteine sulfur. In this study, mutational analysis of the NCp7 amino acid sequence has been used to investigate the specificity of the interaction between ZD2 and a 2-mercaptobenzamide thioester compound using UV-vis spectroscopy and mass spectrometry to monitor the rate of metal ejection from NCp7 mutant peptides and sites of acylation, respectively. We were able to extend the previously reported mechanism of action of these thioester compounds to include a secondary S to N intramolecular acyl transfer that occurs after the primary acyl transfer from the thioester to a cysteine side chain in the protein. Structural models of the thioester/ZD2 complex were then examined to identify the most likely binding orientation. We determined that position x+1 (where x is Cys36) needs to be an aromatic residue for reactivity and a hydrogen-bond donor in position x+9 is important for optimal reactivity. A basic residue (lysine or arginine) is required at position x+2 for the correct fold, while a lysine residue is needed for reactivity involving S to N acyl transfer. We report highly specific interactions between 2-mercaptobenzamide thioester compounds and NCp7 that offer a structural basis for refining and designing new antiretroviral therapeutics, directed toward a target that is resistant to viral mutation.     

Vibrational properties of polyanionic hydrides SrAl2H2 and SrAlSiH: new insights into Al-H bonding interactions

The vibrational properties of the recently discovered aluminum hydrides SrAl2H2 and SrAlSiH have been investigated by means of inelastic neutron scattering (INS) and first-principles calculations. Both compounds contain Al-H units being part of a two-dimensional polyanionic layer, [(AlH)(AlH)]2- and [Si(AlH)]2-, respectively. The INS spectrum of SrAlSiH is characterized by very weakly dispersed Al-H modes with well-resolved overtones, while SrAl2H2 yields a solid-state dispersed phonon spectrum. The frequency of the stretching mode of the Al-H unit in SrAlSiH is the hitherto lowest observed for a terminal Al-H bond. At the same time, SrAlSiH displays the highest decomposition temperature known for an aluminum hydride compound. It is proposed that the stability of solid-state aluminum hydrides correlates inversely with the strength of Al-H bonding.     

Influence of the R-substituents on the properties of [Ni(R2pipdt)(dmit)] complexes and crystal structure where R = CH2C6H5

[Ni(R2pipdt)(dmit)], (R2pipdt = 1,4-disubstituted-piperazine-3,2-dithione, R = CH2C6H5; dmit = 1,3-dithiole-2-thione-4,5-dithiolate) (1b) has been prepared and characterised and the properties compared with those of the known complex 2b belonging to the same class where R = Pr i. Cyclic voltammetry of 1b and 2b was carried out and compared with that of the respective R2pipdt ligand precursors (1a and 2a ). The nature of the R-groups of the pipdt ligand exerts an effect on the redox potentials and confirmed the position of the LUMO as mainly on the R2pipdt part of the complex. Accordingly the low frequency absorption, assigned to the HOMO-LUMO transition which has inter-ligand charge-transfer character, is found for 1b at lower frequency when compared to the corresponding transition of 2b. In situ EPR was carried out on electroreduced radical species of the R2pipdt ligand precursors (1a, 2a ) and corresponding complexes (1b, 2b ). This revealed considerable delocalisation of the unpaired electron on the R2pipdt ligand in 1b and 2b with coupling constants to N and H comparable with those of 1a and 2a . Complex 1b crystallised in the space group Pnma and shows an essentially planar complex (with out-of-plane R groups) pi stacked at a distance of 3.65(1) A. Such a one-dimensional structure is not achieved in the case of 2b, where the complex units are almost parallel and head-to-tail with each other forming dimers and this difference in solid-state packing is apparent in the diffuse reflectance spectrum of each. Plane-wave DFT calculations for 1b revealed a highly one-dimensional band structure with considerable band dispersion along the direction of greatest molecular interaction via pi-stacking.     

Introduction of a triazole amino acid into a peptoid oligomer induces turn formation in aqueous solution

Peptoids are a non-natural class of oligomers that are composed of repeating N-substituted glycine units and are capable of folding into helices that mimic peptide structure and function. In this letter, we report the concise synthesis of a 1,5-substituted triazole amino acid (Tzl) and its subsequent incorporation into a short peptoid. The Tzl amino acid was shown to induce turn formation in aqueous solution, thus expanding the structural repertoire available to peptoid chemists.