Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures

A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003     

Heterocyclic compounds from 3-(4-phenyl) benzoyl propionic acid

3-(4-Phenyl) benzoyl propionic acid was used as the starting material for the synthesisof furanones (2), pyrrolinones (5), pyridazinones (7), benzoxazinones (8) and quinazolinones (9-11). The behaviour of the derivatives of furanones and benzoxazinones toward different nucleophiles is reported.     

Optical spectroscopy of RuC: 18,000-24,000 cm(-1)

The optical spectrum of diatomic RuC has been recorded from 17 800 to 24 200 cm(-1). Three previously unidentified excited electronic states were analyzed and identified as having Omega' = 0, Omega' = 2, and Omega' = 3. The Omega' = 3 state was determined to be a 3Delta3 state that is suggested to arise from a mixture of the 10sigma(2)11sigma(2)5pi(3)2delta(3)12sigma(1)6pi(1) and 10sigma(2)11sigma(1)5pi(3)2delta(3)12sigma(2)6pi(1) electronic configurations. Three additional bands belonging to the previously observed [18.1] (1)Pi<--X (1)Sigma(+) system were analyzed to obtain B(e) (')=0.558 244(48) cm(-1), alpha(e) (')=0.004 655(27) cm(-1), omegae' = 887.201(37) cm(-1), and omega(e) 'xe' = 5.589(7) cm(-1) for the 102Ru 12C isotopomer (1sigma error limits). A Rydberg-Klein-Rees analysis was then performed using the determined spectroscopic constants of the [18.1] 1Pi state, and similar analyses were performed for the previously observed states. The resulting potential energy curves are provided for the 100Ru 12C, 101Ru 12C, 102Ru 12C, and 104Ru 12C isotopic species.     

Influence of vanadium doping on the behavior of YBa_2Cu_3O_7-y

YBa2Cu3-xVxO7-y(x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) superconductors have been prepared. X-ray diffraction shows that the system remains orthorhombic for all compositions studied, but for x > 0.4 V2O5 was detected as an impurity phase. Substitution of V5+ for Cu2+ occurs in the Cu(2) sites on the Cu(2)-O planes. The introduction of the high valence element, vanadium, produces the extra free-electrons. These electrons recombine with the positive carrier of the system. It makes depression of the mobility and the Hall number of YBa2Cu3-xVxO7-v and also results in a depression of TC.     

CHEMILUMINESCENCE AND FLUORESCENCE OF THE EUROPIUM IONS-ADENINE NUCLEOTIDES SYSTEM AND ITS POSSIBLE BIOLOGICAL SIGNIFICANCE

Abstract— Chemiluminescence of the Eu(II)/Eu(III)-adenine nucleotide-H₂O₂ system and fluorescence of the Eu(III)-adenosine triphosphate system have been investigated. The spectral distribution of the chemiluminescence emission has shown an occurrence of three main bands (Λ=470–480,590–620 and ca. 700 nm). The energy transfer process from the adenosine triphosphate molecules to the Eu(III) ions has been observed in the fluorescence spectrum. The examined chemiluminescence and fluorescence spectra show that these both kinds of emission originate from the ⁵ D _***τ⁷F_*** ( n =1–4) transitions in the Eu(III) ions.     

The temperature dependence of nematic liquid crystalline polymer melt diffusion

Abstract

Polymer chain diffusion in the nematic mesophase was studied using a model main chain liquid crystalline (LC) polyether based on 2,2′-dimethyl-4,4′-dihydroxyazoxybenzene and mixed alkane spacers. A side chain LC polymethacrylate containing an azobenzene mesogenic group was also investigated. Tracer diffusion coefficients were determined as a function of temperature by an ion-beam depth profiling technique, forward recoil spectrometry. The results confirm that main chain LC polymer chain dynamics are dramatically affected by phase transitions and sample geometry. This behaviour is in marked contrast to the side chain LC polymer which exhibited no phase dependence on the part of the tracer diffusion coefficient.     

微米铜丝的低温力学性能测试

针对纤维材料变温环境力学性能测试的需要,在华中科技大学研制的纤维材料试验机的基础上引入了温控装置,从而实现纤维材料在高低温环境下的力学性能测试。采用该装置对不同直径微米铜丝在不同温度、不同拉伸速率条件下的力学性能开展实验研究,测试结果表明弹性模量和抗拉强度随温度的降低而线性增加,屈服强度的变化不太明显。另外,低温环境下微米铜丝的力学性能表现出与其直径相关的尺度效应,而这一现象在常温下一直没有观测到。最后,还研究了拉伸速率对微米铜丝的力学性能影响,结果表明,在现有装置的许用范围之内,拉伸速率对其力学性能的影响不大。     

Achievable accuracy of parameter estimation for multidimensional NMR experiments

A fundamental issue in NMR spectroscopy is the estimation of parameters such as the Larmor frequencies of nuclei, J coupling constants, and relaxation rates. The Cramer-Rao lower bound provides a method to assess the best achievable accuracy of parameter estimates resulting from an unbiased estimation procedure. We show how the Cramer-Rao lower bound can be calculated for data obtained from multidimensional NMR experiments. The Cramer-Rao lower bound is compared to the variance of parameter estimates for simulated data using a least-squares estimation procedure. It is also shown how our results on the Cramer-Rao lower bound can be used to analyze whether an experimental design can be improved to provide experimental data which can result in parameter estimates with higher accuracy. The concept of nonuniform averaging in the indirect dimension is introduced and studied in connection with nonuniform sampling of the data.