Search results for "Active center"
showing 9 items of 9 documents
Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization. 1. Molecular weight distribution
1997
The molecular weight distribution (MWD) and its moments are calculated for hyperbranched polymers formed by self-condensing vinyl polymerization (SCVP) of monomers (“inimers”) with the general structure AB*, where A is a vinyl group and B* is an initiating group. The calculated MWD is extremely broad, the polydispersity index (PDI) being equal to the number-average degree of polymerization: Pw/Pn = Pn. It is twice as broad as that for the polycondensation of AB2 type monomers. If the fraction of unreacted monomer is not taken into account, the MWD becomes somewhat narrower, P‘w/P‘n ≈ 0.40P‘n. The kinetics of the polymerization process are first order with respect to the concentration of vi…
γ-ray-induced bleaching in silica: Conversion from optical to paramagnetic defects
2000
We report experimental results on optical and ESR measurements performed in $\ensuremath{\gamma}$-irradiated natural silica samples having different content of OH groups. A partial bleaching of the optical absorption band ${B}_{2\ensuremath{\beta}}$ at 5.15 eV and the related photoluminescence emissions at 3.1 eV and 4.2 eV is observed together with the growth of an ESR doublet split by 11.8 mT. The kinetics of the two processes as a function of the $\ensuremath{\gamma}$ dose are correlated and depend on the OH content. Our experiments indicate the occurrence of a $\ensuremath{\gamma}$-ray-induced conversion, from optically active centers to paramagnetic ones and vice versa, changing the re…
The active center of superoxide dismutase from Propionibacterium shermanii
1996
A self-consistent description of the EPR spectra and of the Mossbauer spectra of the natural superoxide dismutase from Propionibacterium shermanii with ferric iron as an active centre is presented. The spectra were measured at pH 6.5, 7.8 and 9.4. The theoretical approach is based on the use of the complete crystal field Hamiltonian for the high-spin ferric complexes with due regard for the terms of the fourth power of the electronic spin. It is shown that a SOD molecule can exist in two conformations. The low-pH conformation has predominantly trigonal symmetry, while the high-pH conformation has the symmetry close to the «extreme rhombic». This interpretation is in full agreement with EXAF…
Tri-alkenyl polyhedral oligomeric silsesquioxanes as comonomers and active center modifiers in ethylene copolymerization catalyzed by bis(phenoxy-imi…
2018
Abstract In copolymerization of ethylene (E) with tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) were used bis(phenoxy-imine) titanium, zirconium and vanadium catalysts, as well as salen-type vanadium catalysts. There were obtained copolymers with POSS-R-3 units as side branches of polymer chains. The type of employed bis(phenoxy-imine) titanium, zirconium and vanadium catalysts and salen-type catalyst of vanadium determined the copolymer chain termination reactions, as well as the mechanism of modification of the active species by the POSS-R-3 comonomer. POSS-R-3 comonomers caused selective poisoning of bis(phenoxy-imine) zirconium catalyst and they provided protection against tight …
Kompleksy metali przejściowych z zasadami Lewisa jako prekursory katalizatorów polimeryzacji olefin. Cz. I. Postęp w komputerowym modelowaniu procesu…
2001
A review with 35 references covering molecular modeling in coordination polymerization over homogeneous and heterogeneous Ziegler-Natta catalysts. The study includes supports, cocatalysts, Lewis bases and solvents. Recent progress in elucidating the mechanisrn of elementary polymerization steps is presented against the background of rapidly deveIoping computational methods and available computational power. Theoretical studies on polymerization mcchanisms and structure of active centers are described (egns. 1-4). Authors own calculations are used to compare [MtC14(THF)2] complex-based (Mt = Ti, Hf or Zr) heterogeneous catalysts. The geometrical characteristics of precursors is presented (Ta…
Two Latent and Two Hyperstable Polymeric Forms of Human Neuroserpin
2010
AbstractHuman neuroserpin (hNS) is a serine protease inhibitor that belongs to the serpin superfamily and is expressed in nervous tissues. The serpin fold is generally characterized by a long exposed loop, termed the reactive center loop, that acts as bait for the target protease. Intramolecular insertion of the reactive center loop into the main serpin β-sheet leads to the serpin latent form. As with other known serpins, hNS pathological mutants have been shown to accumulate as polymers composed of quasi-native protein molecules. Although hNS polymerization has been intensely studied, a general agreement about serpin polymer organization is still lacking. Here we report a biophysical chara…
NMR and Quantum-Chemical Study on the Structure of Ester Enolate−Aluminum Alkyl Complexes as Models of the Active Center in the Anionic Polymerizatio…
1999
6Li and 13C NMR on ethyl α-lithioisobutyrate (EiBLi) and quantum-chemical (DFT) calculations on methyl α-lithioisobutyrate (MiBLi) were used to elucidate the structure of the active center in the anionic polymerization of methacrylates in the presence of triethylaluminum (AlEt3) in toluene. This study reveals ester enolate/aluminum alkyl complexes with different degrees of association, (MiBLi·AlEt3)n (n = 1, 2, 4), and different stoichiometries, MiBLi·xAlEt3 (x = 1, 2). In the presence of methyl pivalate (MPiv), which is taken as a model compound for the monomer and polymer, complexes such as (MiBLi·MPiv·AlEt3)n (n = 1, 2) are formed. These complexes can dissociate into MiBLi·2AlEt3 and MPi…
Investigation of polymer organic deposit formed on nickel phosphate in oxidative dehydrogenation of ethylbenzene
1997
Abstract Several polymer organic deposits (PODS) had been obtained by heating of nickel polyphosphate (NiP) at 720 K for 1, 4, or 10 h in a stream of helium (carrier gas) containing 20% of (ethylbenzene : oxygen= 1: 0.5] mixture. The samples were tested in oxidative dehydrogenation (OD) of ethylbenzene (EB) to styrene, before and after their separation from the inorganic part of NiP as catalysts. Some functional groups or bonds, important for enhancement of styrene yield, have been found in the PODS. The POD obtained after 10-h coking of NiP, containing a mixture of both insoluble fused-ring and soluble-in-pyridine macromolecules, provided with at least two types of catalytically active cen…
Cu/P(4-PVP) stereochemistry in tetralin liquid-phase oxidation
2007
Abstract Cu/P(4-PVP) catalyst was used as catalyst for oxidation of tetralin in liquid phase. The catalyst was prepared by reaction of a Cu(II) salt with a 4-vinylpyridine-co-divinylbenzene polymer receptor and characterized by solid 1 H and 13 C NMR, XPS, FTIR, ESR spectroscopies, and by chemical reaction with pure tetralin. That information was used to gain insight into the stereochemistry of the active site needed to orient the reaction toward tetralone production. It was found that the Cu coordination with the pyridine was critical in influencing the peroxy-radical catalytic reaction, and that polyvinylpyridine was able to limit the autothermal oxidation. The active center is postulated…