Preferential solvation in urea solutions at different concentrations: properties from simulation studies

We performed molecular dynamics simulations of urea solutions at different concentrations with two urea models (OPLS and KBFF) to examine the structures responsible for the thermodynamic solution properties. Our simulation results showed that hydrogen-bonding properties such as the average number of hydrogen bonds and their lifetime distributions were nearly constant at all concentrations between infinite dilution and the solubility limit. This implies that the characterization of urea-water solutions in the molarity concentration scale as nearly ideal is a result of facile local hydrogen bonding rather than a global property. Thus, urea concentration does not influence the local propensity for hydrogen bonds, only how they are satisfied. By comparison, the KBFF model of urea donated fewer hydrogen bonds than OPLS. We found that the KBFF urea model in TIP3P water better reproduced the experimental density and diffusion constant data. Preferential solvation analysis showed that there were weak urea-urea and water-water associations in OPLS solution at short distances, but there were no strong associations. We divided urea molecules into large, medium, and small clusters to examine fluctuation properties and found that any particular urea molecule did not stay in the same cluster for a long time. We found neither persistent nor large clusters.     

Reactions of polymerization-resistant 1,2-dithiolanes with lithiated oxygen heterocycles

Lithiated furans have been found to cleave the S–S bond of polymerization-resistant 1,2-dithiolanes to give the ring opened products in good yields. In the case of lithiated benzofuran, the excess reagent reacted with the normal product to give a mixture. Lithiated dihydrofuran and dihydropyran gave the corresponding ring-opened products that rearranged to spiro-1,3-dithianes during acidic workup. The reaction was applied to the selective synthesis of substrates for intramolecular Diels-Alder reactions. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:281–287, 1998     

Simultaneous optical second harmonic and sum frequency intensity image observation of hydrogen deficiency on a H-Si(1 1 1) 1 × 1 surface after IR light pulse irradiation

In this study, we developed a microscope for the simultaneous acquisition of optical sum frequency (SF) and second harmonic (SH) intensity images in UHV conditions, and observed resonant electronic and vibrational images of the H-Si(1 1 1) surface after IR light irradiation of pulse width ∼6 μs. The SH intensity images showed a spatial distribution of resonant electronic states, associated with the dangling bonds formed after hydrogen desorption induced by the IR light pulses. This result indicates that the hydrogen coverage decreased to less than ∼0.6 ML in the irradiated area. The SF intensity images before the IR light pulse irradiation showed signals attributed to Si-H stretching vibration on the H-Si(1 1 1) surface. After the IR light pulse irradiation, non-resonant SF signals appeared in the irradiated area. The non-resonant SF signals may originate from a nonlinear optical transition involving the surface electronic levels in the dangling bonds. We also found an unidentified bonding state on the edges of the irradiated area in some light conditions. Both the resonant and non-resonant signals were very weak in this area.     

A synthesis of di- and tri-substituted β,γ-unsaturated esters from aldehydes by the magnesium carbenoid 1,2-CH and 1,2-CC insertion as the key reaction

Addition reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from aldehydes, with lithium enolate of tert-butyl acetate at −78 °C in THF gave adducts in high yields. Treatment of these adducts with Grignard reagents resulted in the formation of magnesium carbenoids via the sulfoxide-magnesium exchange reaction. When the adducts were derived from alkyl aldehydes or electron-deficient aromatic aldehydes, carbenoid 1,2-CH insertion reaction took place from the magnesium carbenoids to afford β,γ-unsaturated butyric esters having a substituent at the β-position. On the other hand, when the adducts were derived from electron-rich aromatic aldehydes, carbenoid 1,2-CC insertion reaction took place from the magnesium carbenoids to give β,γ-unsaturated butyric esters having the aromatic group at the γ-position. Highly stereospecific 1,2-CC insertion reactions were observed in the latter reactions. When the addition reactions were quenched with iodoalkanes, the alkylated adducts were obtained in quantitative yields. Tri-substituted β,γ-unsaturated esters, or in some case γ,δ-unsaturated esters, were obtained by the treatment of the alkylated adducts with EtMgCl. These procedures provide a good way for a new synthesis of di- and tri-substituted β,γ-unsaturated esters from aldehydes with two or three carbon-carbon bond-formations.     

Acoustic analysis of the vocal tract during vowel production by finite-difference time-domain method

The vocal tract shape is three-dimensionally complex. For accurate acoustic analysis, a finite-difference time-domain method was introduced in the present study. By this method, transfer functions of the vocal tract for the five Japanese vowels were calculated from three-dimensionally reconstructed magnetic resonance imaging (MRI) data. The calculated transfer functions were compared with those obtained from acoustic measurements of vocal tract physical models precisely constructed from the same MRI data. Calculated transfer functions agreed well with measured ones up to 10 kHz. Acoustic effects of the piriform fossae, epiglottic valleculae, and inter-dental spaces were also examined. They caused spectral changes by generating dips. The amount of change was significant for the piriform fossae, while it was almost negligible for the other two. The piriform fossae and valleculae generated spectral dips for all the vowels. The dip frequencies of the piriform fossae were almost stable, while those of the valleculae varied among vowels. The inter-dental spaces generated very small spectral dips below 2.5 kHz for the high and middle vowels. In addition, transverse resonances within the oral cavity generated small spectral dips above 4 kHz for the low vowels.     

MTV-G experiment: Probing non-standard strong gravitational field at nuclear scale using geodetic precession

A new experiment named MTV-G, probing a large electron spin-precession due to a possible strong gravitational field, which predicted by large extra dimension model, is started at TRIUMF from 2011. In an electron-nuclear scattering experiment, a strong gravitational field is tested as a large spin precession effect caused by geodetic precession predicted by general relativity theory as a result of a warped space-time around nuclei. Experimental design using spin polarized electron source and Mott-spin analyzer, commissioning experiment and the preliminary results are described.     

A narrow process window for the preparation of polytypes of microcrystalline silicon carbide thin films by hot-wire CVD method

Effects of deposition conditions on the structure of microcrystalline silicon carbide (μc-SiC) films prepared by hot-wire chemical vapor deposition (hot-wire CVD) method have been investigated. It is found from X-ray diffraction patterns of the film that a diffraction peak from crystallites from hexagonal polytypes of SiC is observed in addition to those of 3 C-SiC crystallites. This result is obtained in the film under a narrow deposition conditions of SiH₃CH₃ gas pressure of 8 Pa, the H₂ gas pressure of 80–300 Pa and the total gas pressure of 40–300 Pa under fixed substrate and filament temperatures employed in this study. Furthermore, the grain size of hexagonal crystallites (about 20 nm) on c-Si substrates becomes larger than that of 3 C-SiC crystallites (about 10 nm) for the films deposited under the total gas pressure of 36–88 Pa. The fact that microcrystalline hexagonal SiC can be deposited under limited deposition conditions could be interpreted in the context of a result for c-SiC polytypes prepared by thermal CVD method.     

A "zig-zag" naphthodithiophene core for increased efficiency in solution-processed small molecule solar cells

A solution-processed small molecule utilizing a novel 4,9-bis(2-ethylhexyloxy)naphtho[1,2-b:5,6-b']dithiophene "zig-zag" core (zNDT) exhibits high hole mobility, upshifted frontier MO energies, and enhanced photovoltaic cell short-circuit currents, fill-factors, and power conversion efficiencies (4.7%) versus the linear NDT isomer.     

Robust parameter estimation with a small bias against heavy contamination

In this paper we consider robust parameter estimation based on a certain cross entropy and divergence. The robust estimate is defined as the minimizer of the empirically estimated cross entropy. It is shown that the robust estimate can be regarded as a kind of projection from the viewpoint of a Pythagorean relation based on the divergence. This property implies that the bias caused by outliers can become sufficiently small even in the case of heavy contamination. It is seen that the asymptotic variance of the robust estimator is naturally overweighted in proportion to the ratio of contamination. One may surmise that another form of cross entropy can present the same behavior as that discussed above. It can be proved under some conditions that no cross entropy can present the same behavior except for the cross entropy considered here and its monotone transformation.