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131.
Reactivities of homogeneous series of ethylenic compounds R1CHCH21, trans R1CHCHMe 2, R1MeCCH23 and R1CHCMe24 have been measured in methanol at 25°C (R1 Me, Et, n-Pr, -CH2C6H5-CH2OCOCH3, -CH2Cl). The criterion developed to decide between a bridged and a carbonium ion-like transition state is based on an internal comparison of the series and avoids resorting to external structural scales. Even in the case of alkenes 3 and 4 which are very dissymmetric with respect to polarity, the sensitivity to polar effects remains constant and the transition state behaves like a symmetric entity; only a slight secondary effect, attributed to hyperconjugation, is detectable. 相似文献
132.
133.
In this study, the Schiff base ligands H2L1–H2L3 and their CuII, CoII, NiII, FeIII RuIII and VOIV complexes have been prepared and characterized by spectroscopic and analytical techniques. All the complexes are mononuclear.
Keto-enol tautomeric forms of the ligands have been investigated in polar and apolar solvents. The ligands favor the keto-form
in the C7H8 and C6H14. The C–C coupling reaction of the 2,6-di-t-butylphenol has been investigated by the CoII and CuII complexes. Thermal properties of the complexes have been assessed using thermal techniques and similar properties were found.
In the FeIII and RuIII complexes, firstly, the coordinated water molecule is lost from the complex; in the second step, the chloride ion leaves
the molecule in the 300–350 °C temperature range. Finally, the complexes decompose to the appropriate metal oxide at the higher
temperature ranges. The electrochemical properties of the complexes have been studied in the two different solvents (DMF and
CH3CN). 相似文献
134.
E. Czárán O. V. Bragin M. Dobrovolszky Z. Karpinskii Z. Paál P. Tétényi 《Reaction Kinetics and Catalysis Letters》1977,7(2):211-218
Electron microscopic studies reveal that repeated air/hydrogen regeneration cycles cause irreversible structural changes of a Pt/C catalyst involving sintering and migration of the platinum over the support. This is reflected by a serious decrease of the catalytic activity. With hydrogen treatment only, these effects are less significant.
, / Pt/C, . . .相似文献
135.
Aguilar CN Favela-Torres E Viniegra-González G Augur C 《Applied biochemistry and biotechnology》2002,102(1-6):407-414
Undesirable protease production by Aspergillus niger Aa-20 in submerged culture and solid-state culture was evaluated using different concentrations of tannic acid as sole carbon
source in a model system designed for tannase production. Protease production was found to be dependent on the culture system
used (submerged culture or solid-state culture) and on the initial tannic acid concentration. Expression of protease activity
in submerged culture was higher (up to 10 times) than activity obtained in solid-state culture, using identical culture medium
composition. In submerged culture, the lowest final protease activity (0.13 IU) was obtained with the highest tannic acid
concentration, while in solid-state culture protease activity was not affected by changes in initial substrate concentration.
Absence of detectable proteolytic activity in solid-state culture is related to high production of tannase enzyme. Hence,
the use of solid-state culture for fungal enzyme production may allow for higher and more stable enzyme titers present in
culture extracts. 相似文献
136.
Voszka I Szabó Z Csík G Maillard P Gróf P 《Journal of photochemistry and photobiology. B, Biology》2005,79(2):83-88
The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane. 相似文献
137.
Dénes Szabó István Kapovits Árpád Kucsman Mátyás Czugler Vilmos Fülöp Alajos Kálmán 《Structural chemistry》1991,2(5):529-535
1-[2-(N-methylcarbamoyl)phenyl]-3H-2,1-naphto-(1,8-d,e)-oxathiin-1-ium chloride (2), 1-[2-(N-methylcarbamoyl)-phenyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (3), 1-[8-(N-methylcarbamoyl)naphtyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (4) and 1-(8-carboxylatonaphtyl)-2-methyl-3-oxo-3H-1,2-naphto-(1,8-d,e)-thiazin-1-ium dipolar ion (5) cyclic sulfonium salts were prepared and their chemical properties investigated (spirosulfurane-formation, hydrolysis). The molecular structures obtained from x-ray diffraction can be described with a considerably distorted trigonal bipyramidal arrangement of the ligands about the sulfonium center, with O/N—S ... O=apical angles of 173.9, 164.9, 156.6, and 159.0°, as well as with S—O/N apical bond lengths of 1.648, 1.671, 1.664, and 1.682 Å. The structures exhibit relatively short S ... O close contacts with interatomic distances of 2.253, 2.448, 2.795, and 2.619 Å. 相似文献
138.
139.
Melinda Fekete Pál Kolonits Ngo Thi Hien Lajos Novák 《Central European Journal of Chemistry》2005,3(4):792-802
New tryptamine 5, 7 and β-carboline derivatives 3 were preparated by palladium-catalyzed coupling reaction of 5-bromotryptamine 1 with aryl boronic acids.
Dedicated to Professor András Lipták on his 70th birthday. 相似文献
140.
[reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction. 相似文献