A density-functional study for the liquid-vapor coexistence curve of nitrogen fluid

We have used a density-functional theory based on the interaction site model to predict the liquid-vapor coexistence curve of nitrogen fluid. The pressure and chemical potential were calculated from thermodynamic integrations. The different paths of thermodynamic integration provide slightly different predictions for the liquid-vapor coexistence curve. However, these critical points and coexistence curves evaluated by the theory are in qualitative agreement with the experimental data. The theoretical coexistence curves scaled to critical constants agree with the experimental data quantitatively.     

STM-based molecular detection of "catch-and-release" of protons for bipyridine bound to phenylene-ethynylene thiol

The protonation/deprotonation response of a novel bipyridine containing (phenylene-ethynylene) thiol adsorbed to a Au surface was investigated with scanning tunneling microscopy (STM), showing reversible changes in the average heights (approximately 50 spots) and the height distribution arising from protonation/deprotonation.     

Electron localization and a confined electron gas in nanoporous inorganic electrides

The nanoporous main group oxide 12CaO.7Al(2)O3 (C12A7) can be transformed from a wide-gap insulator to an electride where electrons substitute anions in cages constituting a positive frame. Our ab initio calculations of the electronic structure of this novel material give a consistent explanation of its high conductivity and optical properties. They show that the electrons confined in the inert positive frame are localized in cages and undergo hopping between neighboring cages. The results are useful for the understanding of behavior of confined electron gas of different topology and electron-phonon coupling, and for designing new transparent conductors, electron emitters, and electrides.     

Gluonic excitation of the three-quark system in SU(3) lattice QCD

We present the first study of the gluonic excitation in the three-quark (3Q) system in SU(3) lattice QCD with beta=5.8 and 16(3) x 32 at the quenched level. For the spatially fixed 3Q system, we measure the gluonic excited-state potential, which is responsible for the properties of hybrid baryons. The lowest gluonic-excitation energy in the 3Q system is found to be about 1 GeV in the hadronic scale. This large gluonic-excitation energy is expected to bring about the success of the simple quark model without gluonic modes.     

Band-selective recoupling of homonuclear double-quantum dipolar interaction with a generalized composite 0 degrees pulse: application to 13C aliphatic region-selective magnetization transfer in solids

Recoupling of homonuclear double quantum (DQ)-dipolar interactions is a useful technique for the structural analysis of molecules in solids. We have designed a series of elemental 0 degrees pulses for the recoupling sequences with the rf phase rotation about the z-axis, known as CN. The proposed 0 degrees pulses whose total flip angle >/=360 degrees provide spin rotation vectors in the xy-plane. Thus, the residual spin rotation can be canceled by rf phase rotation about the z-axis. An analysis by the coherent averaging theory showed that effective bandwidths of the recoupling sequences are limited not by the reduction in the dipolar scaling factor but by the increase in the residual spin rotation due to offset. A CN sequence with these elemental pulses provides an effective bandwidth of DQ-dipolar recoupling from ca. 0.5nu(R) to 4nu(R) for numerical simulations. Here, nu(R) is the sample spinning frequency. The 0 degrees pulses were applied to band-selective recoupling for the magnetization transfer in uniformly 13C-labeled molecules. Narrow-band recoupling enhances the magnetization transfer between spins within the effective range by decoupling the dipolar interactions between spins one of which is outside the range. The narrow band operation reduces rf field strength, which improves the CH decoupling. Increases in signal intensities by the use of the proposed 0 degrees pulses are experimentally shown for 13C-labeled amino acids.     

Photolysis of regioisomeric diazides of 1,2-diphenylacetylenes studies by matrix-isolation spectroscopy and DFT calculations

A series of diazides of 1,2-diphenylacetylenes was photolyzed in matrices at low temperature and transient photoproducts were characterized by using IR, UV/vis methods combined with ESR studies. Theoretical calculations were also used to understand the experimental findings. The introduction of phenylethynyl groups on phenyl azides has little effect on the photochemical pathway. Thus, upon photoexcitation, (phenylethynyl)phenyl azides afforded the corresponding triplet nitrene, which is in photoequilibrium with the corresponding azacycloheptatetraene. In marked contrast, azidophenylethynyl groups exhibited a dramatic effect not only on the photochemical pathway of phenyl azides but also on the electronic and molecular structure of the photoproducts. The patterns of the effect depended upon the relative position of azide groups in the diphenylacetylene unit. Whenever two azide groups were situated in a conjugating position with respect to each other, as in p,p'-, o,o'-, and p,o'-bis(azides), the azides always resulted in the formation of a quinoidal diimine diradical in which unpaired electrons were extensively delocalizedin the pi-conjugation. The situation changed rather dramatically when azide groups were introduced in the meta position. Thus, the formation of azacycloheptatetraene was noted in the photolysis of the m.m'-isomer. ESR studies indicated the generation of a quintet state that was shown to be a thermally populated state with a very small energy gap of ca. 100 cal mol(-1). The m,p'-isomer was shown to be an excellent precursor for the high-spin quintet dinitrene. The IR spectra of the photoproduct showed no bands ascribable to azacycloheptatetraene. The observed spectra were in good agreement with that calculated for the quintet state. Strong EPR signals assignable to the quintet state were observed, along with rather weak signals due to mononitrenes. Moreover, the quintet bis(nitrene) was rather photostable under these conditions.     

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.     

A convenient synthesis of the beraprost intermediate: a useful method for introducing a C3 unit at the benzyl position

[reaction: see text] The Heck reaction is a more efficient and reliable method than previous ones for introducing a C3 unit at the benzyl position for the synthesis of Beraprost. Especially, trialkylated long-chain amines such as (n-C(8)H(17))(3)N and (n-C(12)H(25))(3)N resulted in good yields. This development will be used for the industrial synthesis of Beraprost.     

NaI闪烁探测器测量感生放射性及其蒙特卡罗模拟

描述了如何使用蒙特卡罗方法评估产生在加速器屏蔽混凝土中的感生放射性. 使用EGS4程序模拟了NaI闪烁探测器测量屏蔽混凝土块表面剂量率时, 对于半径和厚度的响应. 结果发现,在屏蔽混凝土块半径和厚度分别达到40cm和30cm时, 表面剂量率达到饱和. 研究了东京大学SF回旋加速器北墙位置8和位置9的表面剂量率, 并和使用NaI闪烁探测器的测量结果进行了对比, 发现模拟和实验结果符合很好. 并且, 获得了表面剂量和表面感生放射性之间的转换系数, 对于⁶⁰Co转换系数为0.90(Bq·g^－1)·(μSv·h^－1)^－1, 对于¹⁵²Eu转换系数为1.26(Bq·g^－1)·(μSv·h^－1)^－1. 这样, 就可以通过NaI闪烁探测器表面剂量的测量结果简单评估加速器设备屏蔽混凝土中的感生放射性.