High-temperature protonic motion and low-temperature lattice deformation in one-dimensional hydrogen-bonded molecular chain in tetramethylpyrazine–chloranilic acid (1:1)

Recent theoretical advances have identified several computational algorithms that can be implemented utilizing quantum information processing (QIP), which gives an exponential speedup over the corresponding (known) algorithms on conventional computers. QIP makes use of the counter-intuitive properties of quantum mechanics, such as entanglement and the superposition principle. Unfortunately it has so far been impossible to build a practical QIP system that outperforms conventional computers. Atomic ions confined in an array of interconnected traps represent a potentially scalable approach to QIP. All basic requirements have been experimentally demonstrated in one and two qubit experiments. The remaining task is to scale the system to many qubits while minimizing and correcting errors in the system. While this requires extremely challenging technological improvements, no fundamental roadblocks are currently foreseen.     

Qβ measurements of 158, 159Pm , 159, 161Sm , 160-165Eu , 163Gd and 166Tb using a total absorption BGO detector

Q _β values of the neutron-rich isotopes of ^160-165Eu and ¹⁶³Gd were measured for the first time using a total absorption bismuth germanate (BGO) detector, and previously obtained data on ^{158, 159}Pm , ^{159, 161}Sm and ¹⁶⁶Tb were re-analyzed. These radioactive sources were prepared by an on-line mass separator (Tokai-ISOL) following the ²³⁸U (p,f reaction. The deduced Q _β values are the following: 6085(80)keV for ¹⁵⁸Pm , 3805(65)keV for ¹⁵⁹Sm , 5460(140)keV for ¹⁵⁹Pm , 4705(60)keV for ¹⁶⁰Eu , 5065(130)keV for ¹⁶¹Sm , 3705(60)keV for ¹⁶¹Eu , 5575(60)keV for ¹⁶²Eu , 4690(70)keV for ¹⁶³Eu , 3170(70)keV for ¹⁶³Gd , 6430(70)keV for ¹⁶⁴Eu , 5800(120)keV for ¹⁶⁵Eu , and 4695(70)keV for ¹⁶⁶Tb . Moreover, the deduced mass excesses and two-neutron separation energies ( S _2n values) were compared with those of the atomic mass evaluations and theoretical predictions.     

Correlation between proton transfer and 35Cl NQR frequency as well as molecular geometry of chloranilic acid in co‐crystals with some organic bases

Proton transfer in hydrogen‐bonded organic co‐crystals of chloranilic acid with some organic bases was investigated by nuclear quadrupole resonance (NQR) spectroscopy. The ³⁵Cl NQR frequencies of chloranilic acid molecule as well as ¹⁴N NQR frequencies of the organic base molecule were measured with the conventional pulse methods as well as double‐resonance methods, respectively. The extent of proton transfer in the O···H···N hydrogen bond was estimated from Townes–Dailey analysis of the ¹⁴N NQR parameters. The ³⁵Cl NQR frequency and molecular geometry of chloranilic acid are correlated to the extent of proton transfer in the protonation process of the organic base molecule. It is shown that the hydrogen bond affects the π‐electron system of chloranilic acid. Geometry dependence of the O···H···N hydrogen bond, i.e. the H? N valence bond order versus the hydrogen‐bond geometry correlation is also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Acoustic effects in chromatography

An acoustic field effectively affects chromatographic retention in some separation modes and, thus, can be a novel factor controlling retention. After being transmitted into the column, ultrasound energy is mostly converted into heat as a result of absorption by stationary and mobile phases. Thus, ultrasound brings about temperature increases. However, actual temperature increases measured by thermosensors are smaller than those calculated from chromatographic retention changes. In addition, larger ultrasound effects are observed in chromatographic modes involving ionic interactions. These results possibly imply that ultrasound directly influences ionic interactions involved in retention mechanisms.     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

Long-lived polymer radicals. VIII. Easy formation of long-lived propagating radicals of vinyl monomers at room temperature

Poly[acryloyl-L-valine (ALV)] microspheres containing peroxy ester groups were prepared by radical copolymerization of ALV with a small amount of di-tert-butyl peroxyfumarate. When the microspheres were irradiated in the presence of second vinyl monomers, long-lived propagating radicals of the second monomers were formed in the microspheres by the reaction of microsphere polymer radicals with the monomers. The presence of a minute quantity of ethyl alcohol served to soften the microspheres and made the polymer radicals more mobile in the microspheres. As a result, sharper ESR spectra of the propagating radicals were observed although their lifetimes became shorter. This microsphere method also yielded easily the stable propagating radicals of a-methylstyrene and 1,1-diphenylethylene which have no homopolymerizability in usual radical polymerization. When N-n-propyldimethacroylamide and N,N′-dimethyl-N,N′-dimethacroylhydrazine, which undergo cyclopolymerization, were used as second monomer, uncyclized polymer radicals were only observed. Some discussions were given on the propagation mechanism of the cyclopolymerization.     

Synthesis of proton conductive inorganic–organic hybrid membranes through copolymerization of dimethylethoxyvinylsilane with vinylphosphonic acid

Proton conductive inorganic–organic hybrid membranes were synthesized from dimethylethoxyvinylsilane (DMEVS), vinylphosphonic acid (VPA) and 3-glycidoxypropyltrimethoxysilane (GPTMS) through copolymerization followed by sol–gel process. The ratio of phosphorus to silicon in the copolymer almost corresponded to the charged molar ratio of VPA to DMEVS when the ratio of VPA to DMEVS was below 1/2. Self-standing, homogeneous, highly transparent membranes were synthesized from DMEVS–VPA copolymer and GPTMS via sol–gel condensation. Differential thermal analysis-thermogravimetry analyses indicated that these membranes were thermally stable up to 200 °C. The results of Fourier transform infrared and ¹³C NMR revealed that phosphonic acid groups of VPA were chemically bound to organosiloxane network. The copolymerization and condensation of (DMEVS–VPA)/GPTMS were confirmed by ³¹P and ²⁹Si NMR spectra. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The membrane of (DMEVS–VPA)/GPTMS showed a remarkable conductivity of 6.3 × 10⁻² S cm⁻¹ at 130 °C and 100% relative humidity.     

Regio-selective cyanation of (Z)-(1,2-dibromo-2-arylvinyl)triisopropylsilane with suppression of halogen elimination

Highly regio-selective cyanation of vicinal (Z)-dibromoalkenyl silanes was achieved by a vinylic Rosenmund-von Braun reaction, significantly suppressing side-production of alkyne. The alkyne was generated by a halogen elimination side-reaction that is an intrinsic problem in metal-activation of vicinal dihaloalkenes. We have studied to overcome the problem, and finally found the combination of CuCN and O = PPh₃ in toluene solvent effectively controlled the production of byproducts. The resultant single isomer has significance in potentially application as a multi-tunable synthetic scaffold.     

Analytical investigations of the behavior of silole-core dendrimers with peripheral globotriaose in water and acetone/water mixed solvent

A new compound having a 2,3,4,5-tetraphenylsilole derivative on the center silicon of Dumbbell(1)6Gb3; Silole-Dumbbell(1)6Gb3 (1) was previously reported. It was found that 1 exhibited strongly increased fluorescence both in water and in a 96% acetone/water mixed solvent. The physical behavior of 1 in water and in the 96% acetone/water mixed solvent was investigated, and analyses including fluorescence quantum yields, dynamic-light-scattering (DLS), atomic-force-microscopy (AFM), and fluorescence microscopy were carried out. It was clarified that 1 dynamically formed different types of aggregates in water and in higher acetone concentrations to yield high aggregation-induced emission (AIE) effects due to the formation of micelle-like particles in water and inversion-type micelles in the acetone/water mixed solvent, respectively.     

A≈110质量区奇A核形状演化研究

应用E-GOS（E-Gamma Over Spin）曲线方法研究了A≈110质量区奇A核结构随角动量增加的演化, 发现随着角动量的增加原子核的激发特性从振动逐渐演化为转动。 The E-GOS（E-Gamma Over Spin）curves were used to investigate the structure evolution in the odd A nuclei around A≈110 as a function of spin. The result shows that there is a clear transition from vibration to rotation while increasing spin.