Resonance-stabilized phenoxy-like radicals formed by NO-mediated mono-nitration of coumarins containing a hydroxy group

Stable aminoxyls and an iminoxyl were observed by spin trapping and EPR techniques during the nitration of coumarins containing a hydroxy group by nitric oxide. The trapped free radicals are deduced to be the resonance stabilized phenoxy-like radicals. The mechanisms for the nitrations are suggested.     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 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     

Concentrations of hazardous heavy metals in environmental samples collected in Xiamen, China, as determined by vapor generation non-dispersive atomic fluorescence spectrometry.

Non-dispersive atomic fluorescence spectrometry (NDAFS) coupled with vapor generation (VG) sample introduction was applied to the determination of the concentrations of hazardous heavy metals, such as arsenic, cadmium, lead and mercury, in seawater, soils and total airborne particulate matter (PM) collected around the Xiamen area in China. Almost 100% sample introduction efficiency was achieved by using thiourea and ascorbic acid for the pre-reduction of As(V) to As(III), K3Fe(CN)6 and tartaric acid for pre-oxidation of Pb(II) to Pb(IV), and masking the interferences arising from the co-existing transition metals to As, Cd, Hg and Pb during their vapor generation process. Moreover, a novel sample pretreatment device was developed to avoid the loss of mercury, lead, cadmium and arsenic during sample pretreatment. With such methods, the detection limit (DL) of arsenic, cadmium, lead and mercury was down to 0.08, 0.03, 0.05, 0.01 ng mL(-1) (3sigma), respectively. The relative standard deviations (RSD, n = 11) for arsenic, cadmium, lead and mercury at 10 ng mL(-1) were 0.9%, 1.6%, 1.3% and 2.0%, respectively. The concentrations of hazardous heavy metals in the environmental samples collected in Xiamen, China are in the range from 0.02 +/- 0.001 ng mL(-1) in seawater to 15.3 +/- 0.2 microg g(-1) in soils. Besides flame/GF-AAS and ICP-AES/MS, VG-NDAFS should be another choice for the determination of hazardous heavy metals in environmental samples.     

介质靶表面的充电效应对等离子体浸没离子注入过程中鞘层特性的影响

针对等离子体浸没离子注入技术在绝缘体表面制备硅薄膜工艺，采用一维脉冲鞘层模型描述介质靶表面的充电效应对鞘层厚度、注入剂量及靶表面电位等物理量的影响.数值模拟结果表明：随着等离子体密度的增高，表面的充电效应将导致鞘层厚度变薄、表面电位下降以及注入剂量增加，而介质的厚度对鞘层特性的影响则相对较小. 关键词： 等离子体浸没离子注入 脉冲鞘层 绝缘介质 充电效应     

掺杂偶氮苯聚合物光致异构Z扫描测量及其理论解释

用He_Ne激光对掺有偶氮苯聚合物DR 13的PMMA薄膜样品进行Z扫描研究 ,发现其折射率改变量与光强的关系存在着饱和效应 ,且线偏振光引起的折射率改变明显大于圆偏振光引起的折射率改变 .对于这些现象 ,用光致异构的角烧孔机理进行解释     

光纤光栅选频掺Yb3+双包层光纤激光器

利用相位掩模法 ,在D形内包层掺Yb3 双包层光纤一端直接写制出Bragg光栅 ,用作双包层光纤激光器的输出腔镜 .试验得到了线宽为 0 196nm ,波长为 10 5 8 2nm ,最高输出功率为 5 70mW的稳定激光输出 ,解决了激光器中模式竞争造成的输出不稳定现象 .从速率方程出发 ,对激光器的输出功率与抽运功率、光栅反射率的关系以及最佳光纤长度进行了理论分析 ,结果与实验符合很好     

Metabolites of A Novel Antibiotic Bitespiramycin in Rat Urine and Bile

A sensitive analytical method to identify active metabolites of bitespiramycin in rat urine and bile was developed by liquid chromatography-electrospray ionization tandem mass spectrometry(LC/ESI-MS^n).Bitespiramycin and its major active metabolites in rat urine and bile were isolated and identified as M1 serial(spiramycin Ⅰ，Ⅱ，Ⅲ),M2 serial(platenomycin A1,josamycin and leucomycin A1) and M3 serial(deisovalerylplatenomycin A1,deisovaleryljosamycin,deisovalerylleucomycin A1).     

The Isoelectric Point and the Points of Zero Charge of Fe-Al-Mg Hydrotalcite-like Compounds

The relation of the isoelectric point (IEP) and the point of zero net charge (PZNC) of the hydrotalcite-like compounds was discussed. It was found that the IEP does not equal to the PZNC and the IEP is higher than the PZNC. The structural positive charges existing in the HTlc,which cause the difference between the IEP and the PZNC. The effects of the structural positive charges of the HTlc on its IEP and PZNC are the same as the specific adsorption of metal cations.     

Optimality Conditions and Geometric Properties of a Linear Multilevel Programming Problem with Dominated Objective Functions

In this paper, a model of a linear multilevel programming problem with dominated objective functions (LMPPD(l)) is proposed, where multiple reactions of the lower levels do not lead to any uncertainty in the upper-level decision making. Under the assumption that the constrained set is nonempty and bounded, a necessary optimality condition is obtained. Two types of geometric properties of the solution sets are studied. It is demonstrated that the feasible set of LMPPD(l) is neither necessarily composed of faces of the constrained set nor necessarily connected. These properties are different from the existing theoretical results for linear multilevel programming problems.