Substituent effect on electron affinity,gas‐phase basicity,and structure of monosubstituted propargyl radicals and their anions: a theoretical study

The substituent effect of electron‐withdrawing groups on electron affinity and gas‐phase basicity has been investigated for substituted propargyl radicals and their corresponding anions. It is shown that when a hydrogen of the α‐CH₂ group or acetylenic CH in the propargyl system is substituted by an electron‐withdrawing substituent, electron affinity increases, whereas gas‐phase basicity decreases. The calculated electron affinities are 0.95 eV (CH?C? CH₂?), 1.15 eV (CH?C? CHF?), 1.38 eV (CH?C? CHCl?), 1.48 eV (CH?C? CHBr?) for the isomers with terminal CH and 1.66 eV (CF?C? CH₂?), 1.70 eV (CCl?C? CH₂?), 1.86 eV (CBr?C? CH₂?) for the isomers with terminal CX at B3LYP level. The calculated gas‐phase basicities for their anions are 378.4 kcal/mol (CH?C? CH₂:^?), 371.6 kcal/mol (CH?C? CHF:^?), 365.1 kcal/mol (CH?C? CHCl:^?), 363.5 kcal/mol (CH?C? CHBr:^?) for the isomers with terminal CH and 362.6 kcal/mol (CF?C? CH₂:^?), 360.4 kcal/mol (CCl?C? CH₂:^?), 356.3 kcal/mol (CBr?C? CH₂:^?) for the isomers with terminal CX at B3LYP level. It is concluded that the larger the magnitude of electron‐withdrawing, the greater is the electron affinity of radical and the smaller is the gas‐phase basicity of its anion. This tendency of the electron affinities and gas‐phase bacisities is greater in isomers with the terminal CX than isomers with the terminal CH. Copyright © 2009 John Wiley & Sons, Ltd.     

Dinuclear Zn(II) catalysts as biomimics of RNA and DNA phosphoryl transfer enzymes: changing the medium from water to alcohol provides enzyme‐like rate enhancements

Phosphodiesters are notoriously hydrolytically inert compounds that are demonstrated to have large accelerations of P‐OR cleavage promoted by transition and lanthanide metal ions in methanol and ethanol media. This review commentary describes recent findings of how a simple mononuclear and a dinuclear Zn(II) complex promote the cleavage of a series of RNA models and DNA models in alcohol media. The discussion centers on the analysis of the mechanisms of cleavage, energetics of the catalytic process, on recent findings of electrophilic assistance of leaving group departure, and the observation of a rapid hydrolytic reaction of a DNA model promoted by the dinuclear Zn(II) complex in ethanol containing less than 2% water. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of substituent groups of porphyrins on the electroluminescent properties of porphyrin‐doped OLED devices

Six tetraphenylporphyrins (TRPPH₂) with different horizontal substituents R (R = H, CH₃, OH, F, Cl, Br) were synthesized, and the organic light‐emitting diode (OLED) devices with a general configuration of ITO/TPD/Alq₃:2%TRPPH₂/Alq₃/Al were prepared. The substituted TRPPH₂ was used as the host dopant, 4,4‐bis‐(m‐tolyphenylamino)biphenyl (TPD) was used as a hole‐transporting material, and aluminum tris(8‐quinolinolato) (Alq₃) was used as an electron‐transporting material. The electroluminescent (EL) properties of these devices were studied to understand the light emitting properties of the substituted TRPPH₂. Previous studies have found that the color emitted by the devices was dependent on the TRPPH₂ dye concentration. The electronic effect of the horizontal substituents R of TRPPH₂ influenced the turn‐on voltage, brightness, and power efficiency of the devices. Also, the electroluminescence performance of the porphyrin‐doped OLED devices depended on the effectual overlaps between the emission of electron‐transporting material and the absorption of the dopants. This means that it is possible to evaluate the electroluminescence performance of the porphyrin‐doped OLED devices based on the emission of electron‐transporting material and the absorption of the dopants. Copyright © 2009 John Wiley & Sons, Ltd.     

Intramolecular Diels–Alder reaction in enyne–allenes: a computational investigation and comparison with the Myers–Saito and Schmittel reactions

The reaction mechanisms as well as substituted effect and solvent effect of the enyne–allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers–Saito and Schmittel reactions. The Myers–Saito reaction of non‐substituted enyne–allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C₂? C₇ cyclization and more exothermic (Δ_RE = ?69.38 kcal/mol). For R₁ = CH₃ and t‐Bu, the increasing barrier of the C₂? C₇ cyclization is higher than that for the C₂? C₆ cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron‐releasing group. Moreover, the strong steric effect of R₁ = t‐Bu would shift the C₂? C₇ cyclization to the [4 + 2] cycloaddition. On the other hand, for R₁ = Ph, NH₂, O^?, NO₂, and CN substituents, the barrier of the C₂? C₆ cyclization would be more diminished than the C₂? C₇ cyclization due to strong mesomeric effect; the reaction path of C₂? C₇ cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential‐energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water. Copyright © 2009 John Wiley & Sons, Ltd.     

Fe valence state at the surface of the Fe0.5Cu0.5Cr2S4 spinel

Here we present X‐ray absorption measurements of a vacuum cleaved Fe_0.5Cu_0.5Cr₂S₄ single crystal. Measurements at different positions on the cleaved sample surface clearly reveal a difference between the valence state of the Fe ions in the sur‐ face layers and the valency of the Fe ions present in the bulk. These results confirm the findings of recent measurements outlined previously. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Accurate standard‐based quantification of X‐ray fluorescence data using metal‐contaminated plant tissue

Quantitative X‐ray fluorescence (XRF) measurements have been conducted on naturally lead‐contaminated samples. The calibration procedure using the ratio of fluorescence to Compton scattered radiation was investigated using Monte Carlo simulation. Experimental results with low‐energy photons (14 keV) and simulations show a very good linearity of the fluorescence to Compton ratio as a function of metal concentration. Lead (Pb), iron (Fe) and zinc (Zn) are measured in samples of Phaseolus vulgaris (bean seeds) that have been grown using a nutritive solution with different Pb dopings. Naturally contaminated samples are thus obtained. The calibration must be done for fixed conditions of X‐ray energy and scattering angle, while X‐ray beam intensity and detector to sample distance can change from one sample to another. Simulation allows to evaluate the matrix effect on the calibration curve, and shows that linearity is preserved even in the presence of other heavy elements in the fluorescence spectrum. However, calibration must be done using samples with similar matrix as it affects the slope of the curve. Copyright © 2010 John Wiley & Sons, Ltd.     

Photoluminescence properties of Y_(0.75-x)Gd_xAl_(0.10)BO_3:Eu_(0.10)~(3+),0.05R~(3+)(R= Sc,Bi) (0.00 ≤ x ≤ 0.45)

Y 0.75 -x Gd x Al 0.10 BO 3 :Eu0.10 3+, 0.05R 3+ (R=Sc, Bi) (0.00 ≤ x ≤ 0.45) powder samples are prepared by solid-state reaction and their luminescence properties are investigated. With the replacement of Y 3+ ions by Sc 3+ (or Bi 3+ ) and Gd 3+ ions in (Y,Al)BO 3 :Eu, the intensities of emission at 254 and 147 nm are remarkably improved, because Sc 3+ ions can absorb UV light and transfer the energy to Eu 3+ ions efficiently. Moreover, Gd 3+ and Bi 3+ ions act as an intermediate "bridge" between the sensitizer and the activator (Eu 3+ ) in energy transfer to produce light in the (Y, Gd)BO 3 :Bi 3+ , Eu 3+ system more effectively. After doping an appropriate concentration of Gd 3+ into Y 0.50 Gd 0.25 Al 0.10 BO 3 :Eu0.01 3+ , Bi0.05 3+ , the emission intensity reaches its maximum, which is nearly 110% compared with the red commercial phosphor (Y,Gd)BO 3 :Eu and better chromaticity coordinates (0.650, 0.350) are obtained.     

CMOS vision sensor with integrated into low fully digital image process power 1/8-inch chip

A digital still camera image processing system on a chip, different from the video camera system, is pre- sented for mobile phone to reduce the power consumption and size. A new color interpolation algorithm is proposed to enhance the image quality. The system can also process fixed patten noise （FPN） reduction, color correction, gamma correction, RGB/YUV space transfer, etc. The chip is controlled by sensor regis- ters by inter-integrated circuit （I2C） interface. The voltage for both the front-end analog and the pad cir- cuits is 2.8 V, and the volatge for the image signal processing is 1.8 V. The chip running under the external 13.5-MHz clock has a video data rate of 30 frames/s and the measured power dissipation is about 75 roW.     

Robust external cavity diode laser system with high frequency stability for Cs atomic clock

<正>A robust external cavity diode laser(ECDL) insensitive to mechanical vibration is built with an interference filter for selecting wavelength and a cat-eye reflector for light feedback.The free-running laser has a linewidth of 72 kHz.The laser frequency stability reaches 3×10~(-12) at 1-s integration time in terms of relative Allan variance based on the saturation absorption spectrum.     

Dissipative Particle Dynamics Simulation of Microscopic Properties in Diblock Copolymer Films

利用耗散粒子动力学模拟方法研究了两嵌段共聚高分子薄膜中的一些微观性质. 结果表明：薄膜中共聚高分子链的均方根末端距2_e>^1/2、均方根回旋半径2_g>^1/2与薄膜厚度l、不同粒子间的相互作用强度a_ij、粒子与薄膜边界间的排斥作用强度a_pb均呈线性关系,而均方键长与a_ij、a_pb呈线性关系,随l增加则呈现出波浪形趋势. 2_e>^1/2与2_g>^1/2的变化趋势可以相互对应. 任一组分在薄膜中的密度分布可以通过其与薄膜边界间的相互作用来有效控制与调节.