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1.
Andrzej Barszczewicz Michal Jaszuński Krystyna Kamieńska-Trela Trygve Helgaker Poul Jørgensen Olav Vahtras 《Theoretical chemistry accounts》1993,87(1-2):19-28
Summary
Ab initio calculations of parameters which characterize the NMR spectrum are presented for the cyclopropene molecule. The London orbitals CHF (or GIAO-CHF, Gauge-Independent Atomic Orbital Coupled Hartree-Fock) results for the shielding constants are in good agreement with the experimental data, accurately determined, and with otherab initio values. The calculations of the NMR spin-spin coupling constants have been performed using the Multiconfiguration Time-Dependent Hartree-Fock (MC TDHF) approach. Different basis sets and MC SCF wavefunctions were used to estimate the accuracy of the results. Good agreement is obtained with the coupling constants estimated using the available experimental data.Dedicated to Professor Werner Kutzelnigg on the occasion of his 60th birthday 相似文献
2.
Silica xerogels with different structures and morphology, synthesized using a sol-gel procedure, were used as a carrier of vanadium catalysts (VOCl3/AlEt2Cl) for ethylene polymerization. Two techniques of catalyst synthesis were applied: slurry impregnation and gas-phase adsorption and the relevant polymerization methods were then employed. The effect of the carrier structure and morphology on the vanadium loading in the catalysts, the catalyst’s activity and kinetic stability were investigated. 相似文献
3.
Conditions have been found which make possible the determination of thallium and/or lead in cadmium and its salts without preliminary separation. The electrochemical activity of the cadmium, which usually interferes in the determination of thallium, is inhibited by the addition of 0.01% of polyethylene glycol of M.W. 4000. Thallium is determined by electrolysis at ?0.74 V vs. SCE, in 0.1M EDTA solution: 10?1M thallium can be determined in the presence of 0.1M cadmium, while copper and lead at 10?2M and 10?5M respectively do not interfere. Lead is determined in 0.1M acetic acid containing 0.1% cetyltrimethylammonium bromide (CTAB). The addition of CTAB shifts the cadmium peak, as well as the optimum deposition potential for cadmium, to more negative values, making it possible to determine lead in the presence of cadmium as long as the deposition potential lies in the range between ?0.50 and ?0.56 V vs. SCE. Lead can be determined in the presence of ten times as much thallium. 相似文献
4.
The preconcentration and separation of palladium and iridium from base metals is studied with cellulose (Cellex T) and styrene-divinylbenzene (Varion AT 400) anion exchangers. In spite of lower capacity of Cellex T to chloride complexes of Pd and Ir, it allowed to get a higher preconcentration factor. Yields of 92–99% are achieved for Pd and 96–97% for Ir from the solutions containing great excess of base and heavy metals. Graphite furnace atomic absorption spectrometry is used for the final measurements. The procedure has been applied to the determination of palladium in natural samples. 相似文献
5.
Krystyna Cieśla H. Rahier Grażyna Zakrzewska-Trznadel 《Journal of Thermal Analysis and Calorimetry》2004,77(1):279-293
One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated
cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment
and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation
processes. A large amount of non-freezable strongly bounded water was also detected.
Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction
occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module
at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected
during the first, the second and the third heating.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
6.
Gustav Zigeuner W.-Bernd Lintschinger Alfred Fuchsgruber Krystyna Kollmann 《Monatshefte für Chemie / Chemical Monthly》1976,107(1):171-181
2- and 3-aminoalcohols, o-aminobenzylalcohol, o-hydroxybenzylamine and o-amino(thio)-phenol react with 4-isothiocyanato-4-methyl-2-pentanone (1) to yield derivatives of condensed heterocycles (oxazolopyrimidines7, pyrimidooxazine8, pyrimidobenzoxazines9, 10, pyrimidobenzoxazole11 a and pyrimidobenzothiazole11 c respectively). Ethylenediamine or 1,3-diaminopropane react with1 to yield either imidazo-pyrimidine13 and pyrimidopyrimidine14 respectively or the 1,2-ethylene- and trimethylenebisdihydro-2(1H)-pyrimidinethione15 a, b respectively, according to the molar ratio of the reactants. o-Phenylenediamine gives pyrimidobenzimidazole11 d. 11a undergoes ring cleavage in boiling dimethylformamide followed by methylpyrimidine-pyridine rearrangement to dihydrohydroxyphenylamino-2(1H)-pyridinethione12, while15 a is converted into the bis-4-(ethanediimino)-pyridinthione16. 相似文献
7.
Krystyna Bogdanowicz-Szwed Regina Gil 《Monatshefte für Chemie / Chemical Monthly》2004,35(12):1415-1425
A convenient method is described for the synthesis of functionalized spiro[cycloalkanono-2,3-thiophenes] by treatment of cyclic 3-oxoacid thioanilides with -nitrostyrenes. Reaction of the obtained products with acetic anhydride yielded the corresponding oxime acetates. 相似文献
8.
Krystyna B. Lesiak Bogdan Uznanski Paul F. Torrence 《Applied biochemistry and biotechnology》1997,67(1-2):33-44
To increase the accessibility of 8-bromo-2′,5′-oligoadenylates, we developed a synthesis of 2′-5′-linked oligoriboadenylates containing varying numbers of 8-bromoadenosine residues based on the use of a CPG-LCA solid support and the phosphoramidite approach. Although N6benzoyl protection was satisfactory for incorporation of nonmodified adenine residues into 2′,5′-oligonucleotides, the effective incorporation of 8-bromoadenine into such 2′,5′-linked oligomers required use of a non acyl protecting group. Amidine protection of the purine exocyclic amino function proved compatible with all aspects of the phophoramidite approach and with the hydroxyl protection groups employed. 相似文献
9.
James P. Kutney Peter Grice Krystyna Piotrowska Steven J. Rettig Jerzy Szykula James Trotter Loc Van Chu 《Helvetica chimica acta》1983,66(6):1820-1826
The thujone-derived enone 1 , upon base-catalyzed reaction with 2-methyl-6-vinylpyridine is converted to the pyridine analogue 5 (Scheme 1). Catalytic reduction of the latter to 6 generates two new centers of chirality which eventually become C(8) and C(14) in the ultimate synthetic steroid analogue 12 . An X-ray analysis of 6 establishes the structure and absolute configuration so as to determine its suitability in subsequent synthetic studies. The acetal derivative 7 , via Birch reduction, hydrolysis, and internal aldol cyclization, is converted into the cyclohexenone analogue 10 (Scheme 2). This ‘one-pot’ process affords an efficient conversion of the pyridine ring into a cyclohexenone system required for A-ring construction of the steroid skeleton. Finally, conversion of 10 , via the unsaturated diketone 11 , provides the chiral steroid analogue 12 . 相似文献
10.
Gustav Zigeuner W.-Bernd Lintschinger Alfred Fuchsgruber Krystyna Kollmann 《Monatshefte für Chemie / Chemical Monthly》1976,107(1):155-170
Heating 1-alkyl- or 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones5, 6 in an inert medium causes rearrangement to 4-alkylamino-(4-arylamino-)-5,6-dihydro-2(1H)-pyridinethiones11, 12, probably via the methylene form29, by thermal heterolysis of the N1/C2 bond and exchange of the alkylamino (arylamino) group 1 through the carbon atom of the methylene group 6. The aminodihydropyridinethiones11, which can be regarded as cyclic derivatives of 3-aminothiocrotonamide, react with bistrichlorophenylmalonate under diacylation, and with formaldehyde and primary amines to yield aminodialkylation products of the enamine system, tetrahydro-4-hydroxy-7,7-dimethyl-5-thioxopyrido[4,3-b]pyridine-2(1H)-ones13, 14 and hexahydro-7,7-dimethylpyrido[4,3-d]pyrimidine-5(6H)-thiones18, 19, 21 respectively. H2O2 converts11 to the corresponding 4-aminodihydro-2(1H)-pyridones22, which can be reconverted into11 with P4S10.11 reacts with alkyl halides to 2-alkylthiodihydropyridines23, 24, 25. The mechanism of the methylpyrimidine-pyridine rearrangement is discussed. 相似文献