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1.
K. C. Kumara Swamy E. Balaraman M. Phani Pavan N. N. Bhuvan Kumar K. Praveen Kumar N. Satish Kumar 《Journal of Chemical Sciences》2006,118(6):495-501
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated
acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature
of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction. 相似文献
2.
This paper investigates regression quantiles (RQ) for unstable autoregressive models. The uniform Bahadur representation of the RQ process is obtained. The joint asymptotic distribution of the RQ process is derived in a unified manner for all types of characteristic roots on or outside the unit circle. It involves stochastic integrals in terms of a sequence of independent and identically distributed multivariate Brownian motions with correlated components. The related L-estimator is also discussed. The asymptotic distributions of the RQ and the L-estimator corresponding to the nonstationary componentwise arguments can be transformed into a function of a normal random variable and a sequence of i.i.d. univariate Brownian motions. This is different from the analysis based on the LSE in the literature. As an auxiliary theorem, a weak convergence of a randomly weighted residual empirical process to the stochastic integral of a Kiefer process is established. The results obtained in this paper provide an asymptotic theory for nonstationary time series processes, which can be used to construct robust unit root tests. 相似文献
3.
低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究 总被引:6,自引:4,他引:2
在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。 相似文献
4.
5.
《Journal of Coordination Chemistry》2012,65(1-3):249-259
Abstract The photochemical insertion of phenylacetylene with the “tied-back” dinuclear complex [(η5-C5H4)2SiMe2]Fe2(CO)2(μ-CO)2 (4) yields, by X-ray structural analysis, a dimetallacyclopentenone product entirely analogous to that obtained from the photochemical reaction of the alkyne with (η5 - C5H5)2Fe2(CO)2(μ-CO)2 (1). This result is interpreted as evidence for an alternative pathway for photochemical alkyne addition to 1. Attempts to identify the photochemical intermediates from 4 have been unsuccessful. A competition study between 1 and 4 indicates that photochemical alkyne insertion into 1 is preferred by approximate ratio of 2:1 over insertion into 4. 相似文献
6.
Lars Müller Santina Hoof Matthias Keck Christian Herwig Prof. Dr. Christian Limberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11851-11861
The design of biomimetic model complexes for the cysteine dioxygenase (CDO) and cysteamine dioxygenase (ADO) is reported, where the 3-His coordination of the iron ion is simulated by three pyrazole donors of a trispyrazolyl borate ligand (Tp) and protected cysteine and cysteamine represent substrate ligands. It is found that the replacement of phenyl groups—attached at the 3-positions of the pyrazole units in a previous model—by mesityl residues has massive consequences, as the latter arrange to a more spacious reaction pocket. Thus, the reaction with O2 proceeds much faster and afterwards the first structural characterization of an iron(II) η2-O,O-sulfinate product became possible. If one of the three Tp-mesityl groups is placed in the 5-position, an even larger reaction pocket results, which leads to yet faster rates and accumulation of a reaction intermediate at low temperatures, as shown by UV/Vis and Mössbauer spectroscopy. After comparison with the results of investigations on the cobalt analogues this intermediate is tentatively assigned to an iron(III) superoxide species. 相似文献
7.
LI Cun-man XIAO Yuan-sheng XUE Xing-ya FENG Jia-tao ZHANG Xiu-li LIANG Xin-miao . Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian P. R. China . Hebei Research Centre of Analysis Testing Hebei University of Science Technology Shijiazhuang 《高等学校化学研究》2011,(3):392-396
An efficient preparative method was successfully developed for isolation and purification of unstable components from medicinal plant extracts, using a combined method of preparative high performance liquid chro-matography(HPLC) and solid-phase extraction(SPE). The aim of this study was to obtain an effective method with high preparative efficiency and importantly to avoid the transformation of unstable compounds. The preparative HPLC system was based on an LC/MS controlled four-channel autopurification sys... 相似文献
8.
Polarization spectroscopy in the mid-infrared (IRPS) has been applied to the detection of acetylene molecules making use of the asymmetric C-H stretching vibration at around 3 μm. The infrared laser pulses were produced through difference frequency generation in a LiNbO3 crystal pumped by a Nd:YAG and dye laser system. By directly probing the ro-vibrational transitions with IRPS, sensitive detection of molecules with otherwise inaccessible electronic states was realized with high temporal and spatial resolution by using a pulsed laser and a cross-beam geometry. Detection sensitivities of 2 × 1013 molecules/cm3 (10 ppm in 70 mbar gas mixture) of C2H2 were achieved using the P(1 1) line of the (0 1 0(1 1)0)-(0 0 0 00 00) band. The dependence of the IRPS signal on the pump laser fluence, acetylene mole fraction, and buffer gas pressure of Ar, N2, H2, and CO2 has been studied experimentally. The investigation demonstrates the quantitative nature of IRPS for sensitive detection of polyatomic IR active molecules. In order to fully demonstrate the technique for combustion applications, nascent acetylene molecules were measured in a low pressure methane/oxygen flame. 相似文献
9.
The pair interaction between bilayer membrane-coated nanosized
particles has been explored by using the self-consistent field (SCF)
theory. The bilayer membranes are composed of amphiphilic polymers.
For different system parameters, the pair-interaction free energies
are obtained. Particular emphasis is placed on the analysis of a
sequence of structural transformations of bilayers on spherical
particles, which occur during their approaching processes. For
different head fractions of amphiphiles, the asymmetrical
morphologies between bilayers on two particles and the inverted
micellar intermediates have been found in the membrane fusion
pathway. These results can benefit the fabrication of vesicles as
encapsulation vectors for drug and gene delivery. 相似文献
10.
非定常空气流场中污染气体的对流与粘性扩散 总被引:1,自引:1,他引:1
基于离散涡方法求得的非定常、不稳定空气流场,数值求解了污染气体在空气中的对流湍流扩散方程.两者在每一个时间步耦合,以求非定常对流项.考虑速度脉动,改进了扩散模式.用SF6作为示踪气体,进行了现场测量实验.测得了各测点的SF6浓度随时间的变化.实验结果与数值仿真进行了对比,两者吻合. 相似文献