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1.
Vishal Sipani Ann Kirsch Alec B. Scranton 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4409-4416
The effective propagation rate constant (kp; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the kp as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the kp values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004 相似文献
2.
Vishal A. Mahajan 《Tetrahedron》2006,62(6):1258-1272
A short synthetic strategy for synthesis of lignan analogues involving 5-methylene-4-substituted-2(5H)-furanones as the key intermediates has been developed. Various lignans including the natural product solafuranone and analogues of dihydrotaiwanin C and deoxydehydropodophyllotoxin were synthesized in good yields. 相似文献
3.
The kinetics of the direct synthesis reaction (Si + 2CH3Cl → (CH3)2SiCl2) were measured on a Cu3Si alloy containing 1.2 atom % Zn. Reaction was carried out in a differential reactor (520–595 K, 1 atm) attached to an ultrahigh vacuum (UHV) system. Auger spectroscopy was used to characterize the surface before and after reaction. Zinc does not significantly change the overall rate of reaction, but it changes selectivity to dimethyldichlorosilane (the desired product), surface composition, activation energies, and induction times. The rate of silicon diffusion to the surface is not limiting in the presence of zinc. Zinc is found to be a promoter for improved selectivity only in low concentrations, and only a fraction of the surface appears to be active for reaction. The kinetics appear relatively insensitive to the surface composition or the form of surface carbon. A Cu3Si surface with Zn is shown to be a good model catalyst for the direct synthesis reaction. 相似文献
4.
Summary The complexes Pd(PTH)2Cl2 · 3.5 H2O, Pd(PTH)3(PPh3), Ru(PTH)2(PPh3)Cl2, Ru(PTH)2(PPh3)Cl3, Rh(PTH)2(PPh3)Cl and Rh(PT)Cl2 · 0.5 H2O, where PTH isN-phenylcarbamoylpyrrole-2-thiocarboxamide, have been prepared and characterised by magnetic and spectral (i.r., u.v. and visible) studies. 相似文献
5.
Birendra K. Agrawal Madhup Chandra Badri V. Agarwala Arun K. Dey 《Transition Metal Chemistry》1978,3(1):243-246
Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO4], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present. 相似文献
6.
Zhou S Xu C Wang J Gao W Akhverdiyeva R Shah V Gross R 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):7926-7932
Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees. 相似文献
7.
A visible light promoted, photoredox catalysed, green one-pot approach for the alkylation of amine substrates with sp2 carbon has been developed. This eosin Y based organic transformations, can behave as an effective direct hydrogen-atom transfer catalyst for coupling reaction. The proposed strategy includes simple procedure which can make adduct product with sp2 carbon. This eosin Y based photocatalytic hydrogen-atom transfer strategy may hold great potential for diverse functionalization of a wide range of native CH bonds in an economical and sustainable manner. 相似文献
8.
Proline-catalyzed enantioselective direct intermolecular aldol reactions of tetrahydro-4H-thiopyran-4-one with various aldehydes give anti adducts with high diastereo- and enantioselectivities in moderate to excellent yields. With the aromatic aldehydes best results were obtained in wet DMF whereas dry DMSO generally was superior with the aliphatic aldehydes. Desulfurization of the adducts with Raney Ni provides products equivalent to aldols from 3-pentanone with potential applications in polypropionate synthesis. 相似文献
9.
Paul N Nashine VC Hoops G Zhang P Zhou J Bergstrom DE Davisson VJ 《Chemistry & biology》2003,10(9):815-825
The development of novel artificial nucleobases and detailed X-ray crystal structures for primer/template/DNA polymerase complexes provide opportunities to assess DNA-protein interactions that dictate specificity. Recent results have shown that base pair shape recognition in the context of DNA polymerase must be considered a significant component. The isosteric azole carboxamide nucleobases (compounds 1-5; ) differ only in the number and placement of nitrogen atoms within a common shape and therefore present unique electronic distributions that are shown to dictate the selectivity of template-directed nucleotide incorporation by DNA polymerases. The results demonstrate how nucleoside triphosphate substrate selection by DNA polymerase is a complex phenomenon involving electrostatic interactions in addition to hydrogen bonding and shape recognition. These azole nucleobase analogs offer unique molecular tools for probing nonbonded interactions dictating substrate selection and fidelity of DNA polymerases. 相似文献
10.
It was predicted that the folding space for various protein sequences is restricted and a maximum of 1000 protein folds could be expected. Although, there were about 648 folds identified, general functional features of individual folds is not thoroughly studied. We selected OB-fold, which is supposed to be an oligonucleotide and oligosaccharide binding fold to study the general functional features. OB-fold is a small beta-barrel fold formed from 5 strands connected by modulating loops. We observed consistently 2 or 3 loops on the same face of barrel acting as clamps to bind to their ligands. Depending on the ligand, which could be a single or double stranded DNA/RNA or an oligosaccharide, and their conformational properties the loops change in length and sequence to accommodate various ligands. Different classes of OB-folded proteins were analyzed and found that the functional features are retained in spite of negligible sequence homology among various proteins studied. 相似文献