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1.
A. Razavi V. Bellia D. Baekelmans M. Slawinsky S. Sirol L. Peters Ulf Thewalt 《Kinetics and Catalysis》2006,47(2):257-267
In this contribution, the stereochemistry of propylene insertion/propagation reactions with a variety of C
1 symmetric metallocene catalysts, containing bridged cyclopentadienyl-fluorenyl ligand for the preparation of highly stereoregular
polypropylene is presented. The impact of the distal substitutent’s size and composition and changes that the catalytic sites
undergo upon such substitution is elaborated. A comprehensive mechanism is proposed to explain the resulting catalytic changes
that bring about the irreversible C
s/C
1 site transformation and tactic behavior inversion. Furthermore the cyclopentadienyl’s combined distal/proximal and fluorenyl’s
frontal substituent effects on molecular weight, regio-, and stereoregularity of the final polymers are discussed. Finally,
stereoselectivities of C
2 and C
1 symmetric catalyst systems are compared. It is shown that current high performance C
1 symmetric catalyst systems with central site chirality can be isotactic selective as well or even better in certain aspects
than the C
2 symmetric bridged bisindenyl-based metallocene catalysts.
The text was submitted by the authors in English. 相似文献
2.
3.
James C. W. Chien Abbas Razavi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(9):2369-2380
Bis(neomenthyl cyclopentadienyl)zirconium dichloride/methyl aluminoxane (η5-(NMCp)2ZrCl2/MAO) catalyst has been investigated for ethylene polymerization. About 51% of the Zr forms active sites more or less instantaneously according to quenching with tritiated methanol. There is an initial drop of rate of polymerization, Rp, of about 30% which remains constant thereafter. The catalytic activity increases monotonically with temperature; it is proportional to [MAO]1.75 at a constant [Zr] = 1.5 μM and proportional to [Zr]?1.2 at a constant [MAO] = 64.5 mM. At very large [MAO]/[Zr], the catalyst has extremely high activity; κp = 5 × 103 (Ms)?1 at 50°C. There is also facile chain transfer to aluminum, κ = 0.14 s?1 at 50°C. Both κp and κ are about 30 times greater than the corresponding rate constants for MgCl2 supported TiCl3 catalysts. The TiCl3/MgCl2 and (NMCp)2/MAO catalysts have nearly the same activation energy for propagation (ca. 7 kcal/mol?1). The higher activity of the latter is due to its larger preexponential factor in κp. The dependence of catalytic activity on the [MAO]/[Zr] ratio may be explained by rapid association-dissociation equilibria of MAO involving acid-base and/or electron deficient bridge complexation. 相似文献
4.
Sahra Balilehvand Seyed Majid Hashemianzadeh SeyedehSaleheh Razavi Hedayat Karimi 《Adsorption》2012,18(1):13-22
A combination of ab initio quantum mechanical (QM) calculations and canonical Monte Carlo (CMC) simulations are employed to
investigate possible usage of single-walled silicon nanotubes (SWSiNTs) as a novel media for hydrogen and methane adsorption
as well as their separation from each other. By fitting the force field, a Morse potential model is selected as an efficient
potential to describe the binding energies between both hydrogen-SiNTs and methane-SiNTs obtained from ab initio calculations.
Then CMC simulations are performed to evaluate the adsorption and separation behaviors of H2 and CH4 on the three different sizes of SiNTs including (5, 5), (7, 7), and (9, 9) SiNTs at ambient temperatures and pressures from
1 up to 10 MPa. As a comparison, the adsorption and separation of H2 and CH4 on the (8, 8) CNTs which are isodiameter with (5, 5) SiNTs are also simulated. Results are indicative of remarkable enhancement
of H2 and CH4 adsorption capacity on the SiNTs compared to the CNTs, which arise from stronger van der Waals (VDW) attractions. In the
case of methane adsorption on SiNTs, the stored volumetric energy exceeds the goal of the US Freedom CAR Partnership by 2010,
which can not be achieved by methane compression at such low pressures. Moreover, simulation results indicate that SiNTs preferentially
adsorb methane relative to hydrogen in their equimolar mixture, which results in efficient separation of these gases from
each other at 293 K. 相似文献
5.
A new characteristic approach for incompressible thermo‐flow in Cartesian and non‐Cartesian grids
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A virtual‐characteristic approach is developed for thermo‐flow with finite‐volume methodology in which a multidimensional characteristic (MC) scheme is applied along with artificial compressibility. To obtain compatibility equations and pseudo‐characteristics, energy equation is taken into account in the MC scheme. With this inherent upwinding of convective fluxes, no artificial viscosity is required even at high Reynolds numbers. Another remarkable advantage of the MC scheme lies in its faster convergence rate with respect to the averaging scheme that is found to exhibit substantial delays in convergence. As benchmarks, forced and mixed convections in a cavity and in flow over cylinder and between parallel plates are examined for a wide range of Reynolds, Grashof, and Prandtl numbers. The MC and averaging schemes are applied for simulation purposes. Results show the better performance of the MC scheme in forced and mixed convections. Results confirm the robustness of the MC scheme in terms of accuracy and convergence. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
6.
Mohammad Razavi Seyed Majid Saberi Fathi Jack Adam Tuszynski 《Entropy (Basel, Switzerland)》2022,24(1)
The underlying mechanism determining the size of a particular cell is one of the fundamental unknowns in cell biology. Here, using a new approach that could be used for most of unicellular species, we show that the protein synthesis and cell size are interconnected biophysically and that protein synthesis may be the chief mechanism in establishing size limitations of unicellular organisms. This result is obtained based on the free energy balance equation of protein synthesis and the second law of thermodynamics. Our calculations show that protein synthesis involves a considerable amount of entropy reduction due to polymerization of amino acids depending on the cytoplasmic volume of the cell. The amount of entropy reduction will increase with cell growth and eventually makes the free energy variations of the protein synthesis positive (that is, forbidden thermodynamically). Within the limits of the second law of thermodynamics we propose a framework to estimate the optimal cell size at division. 相似文献
7.
We studied the conductivity and superconducting transition temperature Tc of SnAr films. The films were prepared by condensing the SnAr mixture on a sapphire substrate held at 5 K. A plot of the conductivity as a function of Sn concentration shows a metal-insulator transition which agrees with a percolation model consisting of Sn clusters embedded in solid Ar. A drop of Tc is observed below the percolation threshold. 相似文献
8.
Zahedifar Mahboobeh Pouramiri Behjat Ezzati Ghadi Fereshteh Razavi Razieh Ramzani Ghara Abdollah 《Molecular diversity》2021,25(1):29-43
Molecular Diversity - An unexpected regio- and stereoselective [4?+?3] cycloaddition reaction of azomethine ylides with 5-benzylidenethiazolidine-2,4-diones has been successfully... 相似文献
9.
Binary blends of recycled high‐density polyethylene (R‐HDPE) with poly(ethylene terephthalate) (R‐PET) and recycled polystyrene (R‐PS), as well as the ternary blends, i.e. R‐HDPE/R‐PET/R‐PS, with varying amounts of the constituents were prepared by twin screw extruder. The mechanical, rheological, thermal, and scanning electron microscopy (SEM) analyses were utilized to characterize the samples. The results revealed that both R‐HDPE/R‐PET and R‐HDPE/R‐PS blends show phase inversion but at different compositions. The R‐PET was found to have much higher influence on the properties enhancement of the R‐HDPE compared to R‐PS, but at the phase inverted situation, a significant loss in the tensile strength of R‐HDPE/R‐PET blend was observed due to the weak interaction at this morphological state. However, the ternary blends with higher loading of second phase, namely greater than 50 wt% of R‐PET+R‐PS, demonstrated better mechanical properties than the binary blends with the same content of either R‐PET or R‐PS. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
10.
The combination of liquid phase microextraction (LPME) based on a single drop and gas chromatography flame ionization detector (GC-FID) was used for separation and determination of amitriptyline and nortriptyline in human plasma and urine samples. The sample solution was kept alkaline (pH 12), then a microdrop of organic solvent (isooctane) was suspended in the donor solution; after extraction, the organic microdrop was injected into the GC-FID. Experimental LPME conditions were optimized. Finally, the enrichment factors (89.5?C139.0), the relative standard deviation (RSD%, n = 5) 1.1?C8.5, linearity ranges (0.05?C20 ??g mL?1), and the limits of detections (0.01, 0.02 ??g mL?1) for selected drugs were evaluated. 相似文献