Classical in-plane negative magnetoresistance and quantum positive magnetoresistance in undoped InSb thin films on GaAs (1 0 0) substrates

Magnetoresistance (MR) effects have been investigated in perpendicular and parallel magnetic fields at 300, 80 K and liquid He temperatures for undoped InSb thin films 0.1–2.3 μm thick grown on GaAs(1 0 0) substrates by MBE. At high temperatures, the intrinsic carriers show the parabolic negative MR observable only in magnetic fields parallel to the film. The skipping-orbit effect due to surface boundary scattering in the classical orbits in the plane vertical to the film has been argued to be responsible for the negative MR. At low temperatures (T=80 K), the transport is dominated by the two-dimensional (2D) electrons in the accumulation layers at the InSb/GaAs(1 0 0) hetero interface; MR is positive and shows a logarithmic increase with anisotropy between parallel and perpendicular field orientation, arising from the 2D weak anti-localization (WAL) that reflects the interplay between the spin-Zeeman effect and strong spin–orbit interaction caused by the asymmetric potential at the interface (Rashba term). The zero-field spin splitting energy of Δ₀13 meV, the electron effective mass of m^*0.10m₀ seven times of the band edge mass in bulk InSb and the effective g-factor of |g^*|15 in the accumulation layer have been inferred from fits of MR for the 0.1 μm thick film to the 2D WL theory.     

On-line cysteine modification for protein analysis: new probes for electrochemical tagging nanospray mass spectrometry

A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules.     

Cationic polymerization of styrene in a neutral ionic liquid

The cationic polymerization of styrene in a neutral ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate, with a 1‐phenetyl chloride/TiCl₄ initiating system is reported. The polymerization proceeds to a high conversion, but an analysis of the matrix‐assisted laser desorption/ionization time‐of‐flight spectra of the polymers indicates that chain transfer is significant, leading to a lack of control over the molecular weight and molecular weight distribution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3230–3235, 2004     

Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004     

Atom transfer radical polymerization of methyl methacrylate by copper(I)‐pyridine‐2‐carboximidate catalysts

Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [k_obs = (1.19 vs 0.56) × 10^?4 s^?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]_o/[ 1d ]_o/[ethyl 2‐bromoisobutyrate]_o/[MMA]_o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr₂. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004     

Soluble,saturated‐red‐light‐emitting poly(p‐phenylenevinylene) containing triphenylamine units and cyano groups

A conjugated poly(p‐CN‐phenylenevinylene) (PCNPV) containing both electron‐donating triphenylamine units and electron‐withdrawing cyano groups was prepared via Knoevenagel condensation in a good yield. Gel permeation chromatography suggested that the soluble polymer had a very high weight‐average molecular weight of 309,000. A bright and saturated red emission was observed under UV excitation in solution and film. Cyclic voltammetry showed that the polymer presented quasi‐reversible oxidation with a relatively low potential because of the triphenylamine unit. A single‐layer indium tin oxide/PCNPV/Mg–Ag device emitted a bright red light (633 nm). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3947–3953, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004     

Yb3+掺杂铝氟磷酸盐玻璃的光谱和激光性能

研究了Yb3 掺杂铝氟磷酸盐 (AFP)玻璃的吸收光谱、荧光光谱 ,测量了Yb3 离子的荧光有效线宽 (Δλeff>5 5nm)以及2 F5 2 能级的荧光寿命 (τmax=2ms)及随掺杂浓度的变化 .应用倒易法计算了Yb3 的发射截面 ,其发射截面可达 0 6 6 82 3pm2 ,且激光增益系数τfσemi达 1 2 89ms.pm2 .评估了Yb3 在AFP玻璃中的激光性能 ,发现其具有较理想的激发态最小粒子数 (0 15 )、饱和抽运强度 (8 3kW cm2 )和最小抽运强度 (1 2 4 5kW cm2 )值及良好的热稳定性 .研究结果表明掺Yb3 氟磷酸盐玻璃是实现高功率超短可调谐激光器的理想增益介质 .     

Cl/HN3/I2全气相化学激光体系的化学动力学模拟计算

 对Cl/HN₃/I₂产生NCl(a)/I激光的过程进行了化学动力学计算，主要考察了Cl,HN₃和I₂的初始粒子数密度及其配比对小信号增益系数的影响。结果发现,当温度为400K, 初始Cl粒子数密度为1×10¹⁵，1×10¹⁶和1×10¹⁷cm^-3时,小信号增益系数分别达到1.6×10^-4,1.1×10^-3和1.1×10^-2cm^-1，获得最佳小信号增益系数的HN₃和I₂的初始粒子数密度分别为初始Cl粒子数密度的1～2倍和2%～4%。同时，对Cl，HN₃和I₂配比对小信号增益系数和增益持续时间的影响进行了讨论。