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134.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
135.
高速连续数据记录系统中双页缓存的设计和实现 总被引:2,自引:0,他引:2
在高速连续数据记录系统中,存储设备需要速度匹配单元来实现高速连续数据记录,文章讨论了双页缓存在高速连续记录系统中的作用,并以实际开发的记录系统为例,详细介绍了双页缓存的设计和实现。 相似文献
136.
J.-L. Garden 《Thermochimica Acta》2007,452(2):85-105
What is really measured in dynamic calorimetric experiments is still an open question. This paper is devoted to this question, which can be usefully envisaged by means of macroscopic non-equilibrium thermodynamics. From the pioneer work of De Donder on chemical reactions and with other authors along the 20th century, the question is tackled under an historical point of view. A special attention is paid about the notions of frequency dependent complex heat capacity and entropy production due to irreversible processes occurring during an experiment. This phenomenological approach based on thermodynamics, not widely spread in the literature of calorimetry, could open significant perspectives on the study of macro-systems undergoing physico-chemical transformations probed by dynamic calorimetry. 相似文献
137.
重点介绍了蓄电池电压陡降与容量之间的关系及各操作因素对电压陡降的影响。由此引出一种新的蓄电池容量预测思路,并就如何实现它进行了初步探讨,最后对该思路进行了简要的展望。 相似文献
138.
事物未来的状态仅仅受事物现状的影响,而与过去的状态无关,也就是具有马尔可夫性。用马尔可夫链的理论与方法,对具有马尔可夫性产品的可靠性进行预测,既为产品的可靠性设计和产品售后服务的经济性分析提供了参考,也为马尔可夫模型的实际应用拓广了范围。通过实例说明在数学软件的帮助下这种预测方法的简单可行性。 相似文献
139.
Kan‐Yi Pu Yi Chen Xiao‐Ying Qi Chun‐Yang Qin Qing‐Quan Chen Hong‐Yu Wang Yun Deng Qu‐Li Fan Yan‐Qin Huang Shu‐Juan Liu Wei Wei Bo Peng Wei Huang 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3776-3787
In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007 相似文献
140.
An isothermal equation of state (EOS) for solids, recently suggested by the authors in the realistic form, V/V0=f(P), with relative volume as the dependent and the pressure as the independent variable, was shown to have an advantage for some close-packed materials in that it allows B′∞=(∂Bs/∂P)s(P→∞) to be fitted, and this is where the usual standard equations fail. In the present study, our EOS is applied to a number of inorganic as well as organic solids, including alloys, glasses, rubbers and plastics; varying widely in their bonding and structural characteristics, as well as in their bulk modulus values. A very good agreement is observed between the data and fits. The results obtained are compared with those from two well-known equations, expressible in the realistic form, proposed by Murnaghan and Luban. Further, the results are also compared with those from the widely used two- and three-parameter EOSs, expressible in the unrealistic form only, P=f(V/V0), proposed by Birch—and also with those from the EOS model of Keane in which B′∞ is explicitly expressed as an equation of state parameter. The results obtained from our model compare well to these EOSs. Our EOS, in general, yields the smallest mean-squared deviations between data and fits. The values of B′∞calculated from our EOS are compared with those from Keane's model. Further, we have studied the variation of B′∞with temperature using the experimental isotherms of Mo and W at 10 different temperatures ranging from 100 to 1000 K, and observed that the values of B′∞ yielded by our model and that of Keane vary, as expected, within a narrow range. Furthermore, our EOS is applied to study the stability of the fit parameters with variation in the pressure ranges with reference to the isothermal compression data on Mo and W—and also to study the variation of isothermal bulk modulus with pressure, with reference to the ultrasonic data on NaCl and noted a very good agreement with experiment. In addition, our model is applied, with B0 and B′0 constrained to the theoretical values, to the five theoretical isotherms of MgO at 300, 500, 1000, 1500 and 2000 K obtained on the basis of a first principles approach—a good agreement is observed with the predictions, and the values of B′∞ inferred at different temperatures tend to converge to a constant value. 相似文献