Rigid nitronyl-nitroxide-labelled anchoring molecules: syntheses, structural and magnetic investigations

The syntheses of two rigid organic molecular rods bearing a nitronyl-nitroxide radical and a terminal nitrogen-based functionality like a pyridine or a cyano group are reported. Both new paramagnetic molecules are fully characterized, including crystal structure analysis. Furthermore their magnetic behaviours in the crystalline state are investigated and their spin concentration corroborate their excellent purity. While the pyridine functionalized rod is synthesized by converting the corresponding benzaldehyde to the phenyl-nitronyl-nitroxide radical, the synthesis of the cyano functionalized rod demonstrates the accessibility of highly sophisticated spin-labelled molecules via cross-coupling reaction with a meta-iodo-phenyl-nitronyl-nitroxide moiety.     

Block copolymers of acrylic acid and butyl acrylate prepared by reversible addition–fragmentation chain transfer polymerization: Synthesis,characterization, and use in emulsion polymerization

Amphiphilic block copolymers of poly(acrylic acid‐b‐butyl acrylate) were prepared by reversible addition–fragmentation chain transfer polymerization in a one‐pot reaction. These copolymers were characterized by NMR, static and dynamic light scattering, tensiometry, and size exclusion chromatography. The aggregation characteristics of the copolymers corresponded to those theoretically predicted for a star micelle. In a butyl acrylate and methyl methacrylate emulsion polymerization, low amounts of these copolymers could stabilize latices with solid contents up to 50%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 684–698, 2003     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003     

First measurement of the helicity-dependent γ p?pη differential cross-section

The helicity dependence of the γ p↦pη reaction has been measured for the first time at a center-of-mass angle θ^* _η = 70^° in the photon energy range from 780 MeV to 790 MeV. The experiment, performed at the Mainz microtron MAMI, used a 4π-detector system, a circularly polarized, tagged photon beam, and a longitudinally polarized frozen-spin target. The helicity 3/2 cross-section is found to be small and the results for helicity 1/2 agree with predictions from the MAID analysis. Received: 19 December 2002 / Accepted: 10 March 2003 / Published online: 20 May 2003     

FREE BOUNDARY PROBLEM ARISING FROM EVAPORATION FROM POROUS MEDIUM

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亚细胞器诱导的2,4,6-三硝基甲苯阴离子自由基的ESR研究

本文在无氧条件下利用ESR分别观察了肝脏和晶状体的微粒体及线粒体酶在NADPH存在下还原三硝基甲苯(TNT)的过程,检测到参数为g=2.0048±0.0005,A_对位~N=1.215mT,A~N=0.800±0.010mT,A~H=0.122±0.0206mT的自由基信号,并通过电子计算机对ESR谱的模拟证明该自由基信号为TNT硝基阴离子自由基,根据其超精细分裂常数认为,其不配对电子的电子云密度主要分布在对位硝基上。     

Mechanism of the thermal decomposition of nitrates from graphite furnace mass spectrometry studies

A basically new mechanism of the thermal decomposition of solids is proposed to explain the mass spectral observations of gaseous molecules of CoO, CuO, Cu₂O, NiO, PbO and Mg(OH)₂ during the low-temperature decomposition of the anhydrous and hydrated nitrates of these metals. The mechanism consists of two stages: congruent gasification of all reaction products irrespective of their saturated vapor pressure and subsequent condensation of the low-volatility species (oxides and hydroxides). The partial pressures of these species at the appearance temperatures calculated from this theory for the first stage of the process (1–50 mPa) are in agreement with the detection limits of the quadrupole mass spectrometers used in these experiments. The proposed mechanism is supported by other available data obtained by thermal analysis.     

Effects of oxygen in gamma irradiated aromatic polyesters in film

The effect of gamma irradiation in air is investigated on four thermoplastic polyesters (PET, PBT, PEN, PCT-co-ET) in films containing aromatic rings, in order to evaluate the influence of aromatic density and the role of oxygen on radiation resistance. Physical-chemical-nuclear analyses were used to this purpose. EPR measurements were carried out to detect radical stability against oxygen permeation. Viscometric investigations reported a very similar trend for all the investigated polyesters: a chain break effect that decreases at the highest doses. FT-IR analyses focused on the formation of oxidized species. Positron annihilation spectra pointed out a decrease of the intensity of ortho-positronium formation, while its lifetime remains unchanged with radiation dose.     

γ辐射引发淀粉目由基衰减的动力学研究

用ESR方法研究了红薯淀粉在γ射线预辐照下,产生的淀粉自由基特性及其室温下的自由基衰减动力学反应。结果表明在室温条件下,淀粉自由基的相对浓度随辐射剂量的增大而增加。自由基相对浓度的室温衰减用二级反应动力学处理,求得了衰减速率常数和淀粉自由基反应的半衰期。