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71.
Summary: Linear poly (ethylene-co-1-butene) was produced through two-step polymerization in one reactor using a Ziegler-Natta catalyst, where in the first step, low molecular weight homopolymer of ethylene in the presence of hydrogen and in the next step, high molecular weight copolymer of ethylene with 1-butene in the absence of hydrogen were produced. Molecular weight distribution of bimodal polyethylene was tailored through adjustment of polymerization time of each stage and hydrogen concentration of the first stage. Increasing hydrogen concentration shifted the molecular weight distribution curve to the lower molecular weights and broadened molecular weight distribution while interestingly increased high molecular weight incorporation of copolymer produced in the second stage due to increasing of reaction rate in the second step. To achieve bimodal molecular weight distribution, the polymerization times of the first and the second steps, which are highly dependent on the amount of hydrogen, were adjusted properly. The effects of the mentioned parameters on the processability as well as rheological properties of some samples were investigated. The rheological results showed shear thinning behavior of all specimens and confirmed the changes in molecular weight and molecular weight distribution. It was also demonstrated that the melt miscibility between low molecular weight and high molecular weight fractions improved with increasing of chains having very low molecular weight. 相似文献
72.
EDTA forms stable complexes with plutonium that are integral to nuclear material processing, radionuclide decontamination, and the potentially enhanced transport of environmental contamination. To characterize the aqueous Pu(4+/3+)EDTA species formed under the wide range of conditions of these processes, potentiometry, spectrophotometry, and cyclic voltammetry were used to measure solution equilibria. The results reveal new EDTA and mixed-ligand complexes and provide more accurate stability constants for previously identified species. In acidic solution (pH < 4) and at 1:1 ligand to metal ratio, PuY (where Y4- is the tetra-anion of EDTA) is the predominant species, with an overall formation constant of log beta110 = 26.44. At higher pH, the hydrolysis species, PuY(OH)- and PuY(OH)(2)2-, form with the corresponding overall stability constants log beta(11 - 1) = 21.95 and log beta(11 - 2) = 15.29. The redox potential of the complex PuY at pH = 2.3 was determined to be E(1/2) = 342 mV. The correlation between redox potential, pH, and the protonation state of PuY- was derived to estimate the redox potential of the Pu(4+/3+)Y complex as a function of pH. Under conditions of neutral pH and excess EDTA relative to Pu4+, PuY(2)4- forms with an overall formation constant of log beta120 = 35.39. In the presence of ancillary ligands, mixed-ligand complexes form, as exemplified by the citrate and carbonate complexes PuY(citrate)3- (log beta1101 = 33.45) and PuY(carbonate)2- (log beta1101 = 35.51). Cyclic voltammetry shows irreversible electrochemical behavior for these coordinatively saturated Pu4+ complexes: The reduction wave is shifted approximately -400 mV from the reduction wave of the complex PuY, while the oxidation wave is invariant. 相似文献
73.
Dimakis N Iddir H Díaz-Morales RR Liu R Bunker G Chung EH Smotkin ES 《The journal of physical chemistry. B》2005,109(5):1839-1848
The C-O stretching frequency (nu(CO)) of atop CO/Pt in PtRu alloys is compositionally tuned in proportion to the Pt mole percent. The application of a Blyholder-Bagus type mechanism (i.e., increased back-donation from the metal d-band to the hybridized 2pi CO molecular orbitals (MOs)) to compositional tuning has been paradoxical because (1) a Pt-C bond contraction, expected with increased back-donation as the Pt mole percent is reduced, is not observed (i.e., calculated Pt-C bond is either elongated or insensitive to alloying and the binding energies of CO/Pt decrease with alloying) and (2) the lowering d-band center and increased d-band vacancies upon alloying (suggesting less back-donation to the higher energy metal hybridized 2pi CO MOs) must be reconciled with the alloy-induced red shift of the nu(CO). A library of spin-optimized Pt and Pt alloy clusters was the basis of density functional theory (DFT) calculations of CO binding energies, nu(CO) values, shifts, and broadening of 5sigma/2pi CO MO upon hybridization with the alloy orbitals and a DFT derived Mulliken electron population analysis. The DFT results, combined with FEFF8 local density of states (LDOS) calculations, validate a 5sigma donation-2pi back-donation mechanism, reconciling the direction of alloy compositional tuning with the lowering of the d-band center and increased vacancies. Although the d-band center decreases in energy with alloying, an asymmetric increase in the dispersion of the d-band is accompanied by an upshift of the metal cluster HOMO level. Concomitantly, the hybridization and renormalization of the CO 5sigma/2pi states results in a broadening of the 5sigma/2pi manifold with additional lower energy states closer to the upshifted (with respect to the pure Pt cluster) HOMO of the alloy cluster. The dispersion toward higher energies of the alloy d-density of states results in more 5sigma/2pi CO filled states (i.e., enhanced 2pi-back-donation). Finally, Mulliken and FEFF8 electron population analysis shows that the increase of the average d-band vacancies upon alloying and additional 2pi back-donation are not mutually exclusive. The d-electron density of the CO-adsorbed Pt atom increases with alloying while the average d-electron density throughout the cluster is reduced. The localized electron density is manifested as an electrostatic wall effect, preventing the Pt-C bond contractions expected with increased back-donation to the 2pi CO MOs. 相似文献
74.
75.
76.
DECPO, a new analogue of EMPO was synthesized through a two-step synthetic pathway. Its structure and its application to trap superoxide were investigated. The ESR detection of the DECPO-OOH spin adduct is easy even at low concentration of superoxide. In comparison with DEPMPO, the trapping of superoxide with DECPO is faster and the detection of DECPO-OOH can be performed using a very low nitrone concentration (0.5 mM). 相似文献
77.
G L Biagi A M Barbaro M C Guerra G Hakim G C Solaini P A Borea 《Journal of chromatography. A》1979,177(1):35-39
The RM values of naphthols obtained in a chromatographic system where the stationary phase consisted of a silica gel G layer impregnated with silicone oil are much more closely related to the log P values in an octanol-water system than the RM values determined on polyamide layers. Similarly, the RM values of a series of acetophenones in the silicone system are closely related to their log P values. The equations describing the structure-activity relationship indicate the importance of lipophilic character and halogen substitution in determining the hemolytic activity and the acute toxicity of compounds. 相似文献
78.
Eckelbarger JD Wilmot JT Epperson MT Thakur CS Shum D Antczak C Tarassishin L Djaballah H Gin DY 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(14):4293-4306
Deoxyharringtonine (2), homoharringtonine (3), homodeoxyharringtonine (4), and anhydroharringtonine (5) are reported to be among the most potent members of the antileukemia alkaloids isolated from the Cephalotaxus genus. Convergent syntheses of these four natural products are described, each involving novel synthetic methods and strategies. These syntheses enabled evaluation of several advanced natural and non-natural compounds against an array of human hematopoietic and solid tumor cells. Potent cytotoxicity was observed in several cell lines previously not challenged with these alkaloids. Variations in the structure of the ester chain within this family of alkaloids confer differing activity profiles against vincristine-resistant HL-60/RV+, signalling new avenues for molecular design of these natural products to combat multi-drug resistance. 相似文献
79.
Mohamed Alahyane Abdelilah Hakim Amine Laghrib Said Raghay 《Mathematical Methods in the Applied Sciences》2019,42(18):7059-7075
In this paper, we present a fast algorithm of the nonparametric elastic image registration using a simple implementation of the Range Restricted GMRES (RRGMRES) method. This approach differs from the others in the fact that it is specified to the tridiagonal block matrix type to resolve a nonsymmetric linear system. In what follows, we prove existence and uniqueness of minimizer of the elastic registration problem and present the corresponding discrete problem by employing a finite difference scheme. The accuracy of the proposed method is demonstrated on different image registration examples; we also show the speedup of the proposed approach by calculating the corresponding CPU time and compared it with the classical elastic registration method. 相似文献
80.