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91.
W. Gołkiewicz 《Chromatographia》1986,21(5):259-264
Summary Equations describing multi-step gradient elution with a mobile phase of constant composition in each step were derived. These
equations useful for calculating the retention volumes in both gradient HPLC and TLC were derived on the basis of the relationship
between the isocratic capacity factor and the volume fraction of the organic modifier. The validity of the equations was experimentally
verified in a LiChrosorbRP-18-water/methanol system for 11 methyl- and chlorobenzenes and phenols. A satisfactory agreement
between the theoretical and experimental k′ values was found. 相似文献
92.
Szabó KJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(23):4413-4421
The structure and reactivity of various bis-allylpalladium complexes occurring as catalytic intermediates in important synthetic transformations have been studied by applying density functional theory at the B3PW91(DZ + P) level. It was found that n1,n3 coordinated bis-allylpalladium complexes are readily formed from the corresponding n3,n3 complexes, especially in the presence of pi-acceptor phosphine ligands. The theoretical calculations indicate dsigma-->pi type hyperconjugative interactions occurring in the n1-coordinated allyl moiety of the n3,n3 coordinated complexes. These hyperconjugative interactions influence the structure of the complexes and dramatically increase the reactivity of the double bond in the n1-moiety. The DFT results indicate a remarkably low activation barrier for the electrophilic attack on the n1-allyl functionality. In bridged n1,n3 complexes, the electrophilic attack occurs with a very high regioselectivity, which can be explained on the basis of d-pi type hyperconjugative interactions. 相似文献
93.
Mátyás Milen László Hazai Pál Kolonits György Kalaus Lajos Szabó Ágnes Gömöry Csaba Szántay 《Central European Journal of Chemistry》2005,3(1):118-136
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected.
Dedicated to Professor Károly Lempert on his 80th birthday. 相似文献
94.
Summary The [Rh(acac){P(OPh)3)}2] complex (Hacac = 2,4-pentadione) reacts in solution with gaseous HCN in the presence of P(OPh)3 to give [Rh{P(OPh)3}3CN]. Structural investigations of this complex including its31P n.m.r. spectra are reported. 相似文献
95.
Wójcik A Naumov S Marciniak B Hermann R Brede O 《The journal of physical chemistry. B》2005,109(31):15135-15144
Addition and elimination interaction of thiyl radicals with the C5-C6 double bond in pyrimidines was studied by the pulse radiolysis technique in aqueous solution with the use of different monitoring systems. For this purpose, p-thiocresol, cysteamine hydrochloride, and mercaptoethanol were used. The rate constants of addition and elimination of thiyl radicals were determined by applying the modified version of ACUCHEM (computer program for modeling complex reaction systems). Aliphatic thiyl radicals add to the pyrimidine C5-C6 double bond with k = 1.0-3.0 x 10(7) dm3 mol(-1) s(-1), whereas elimination takes place with k = 0.7-2.0 x 10(5) s(-1). Quantum chemical calculations at the B3LYP/6-31G(d)/PCM level show that the addition should occur at the C6 position of the pyrimidine ring and that the energy of interaction between thiyl radicals and the pyrimidine double bond C5-C6 is low. 相似文献
96.
Berezkin Victor G. Mardanov Robert G. Moiseew Aleksey A. Malinowska Irena Różyło Jan K. 《平面色谱法杂志一现代薄层色谱法》2002,15(5):377-379
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
97.
Kłonkowski Andrzej M. Widernik Teresa Grobelna Beata Jóźwiak Wojciech K. Proga Henryk Szubiakiewicz Ewa 《Journal of Sol-Gel Science and Technology》2001,20(2):161-180
The sol-gel process is a useful method for preparing two series of organically and co-ordinately modified xerogels of the types [CuN
n
]·N
5–n
·5xSiO4/2 (n < 4) and [Cu(N–N)n]·(N–N)2–n
·2x SiO4/2(n 2), where N = NH2(CH2)3 SiO3/2, N–N = NH2(CH2)2NH·(CH2)3SiO3/2 and x = [SiO4/2]/[N] or [SiO4/2]/[N–N]. The amino groups in the materials are coordinately active and participate partly in the coordination sphere of Cu(II) ions. The composition of the coordination sphere can be varied with the SiO4/2 content and also as a result of the thermal decomposition of the organic residues at higher temperatures.Because the xerogel materials are considered to be catalyst precursors, this study is focused on their coordination and thermal properties. The prepared xerogels, such as silica, aminated silicates with N and N–N, as well as those entities complexed with Cu(II), were characterised by FT-IR spectroscopy. During gelation and thermal decomposition the materials were analysed by electron paramagnetic resonance (EPR) spectroscopy. The xerogels were additionally studied by UV-Vis absorption spectroscopy. The gaseous products of the thermal decomposition of these materials in an Ar atmosphere were investigated by the use of FT-IR spectroscopy coupled with TG and DTG thermal analysis. These data were complemented by temperature-programmed decomposition (TPDec) in a 2% O2 + 98% Ar stream coupled with quadrupole mass spectroscopy. 相似文献
98.
M. Czauderna J. Konecki M. Głowacka 《Journal of Radioanalytical and Nuclear Chemistry》1987,109(1):79-88
The incorporation of Se and Te into liver, kidneys, heart, spleen, lung and small intestine after i.p. injections of Balby mice with seleno-cystine (CySe)2 and Na2TeO3 in the presence of Cd (as CdCl2), As (as As2O3) and Zn (as ZnSO4) has been studied. The change of contents of Co, Fe, Rb and Hg were determined in all investigated organs after injections with the above compounds. Instrumental neutron activation analysis was applied as the analytical method. It was found that a competitive interaction occurs between As and Se or Te. Similarly, this interaction has been observed between Se and Cd. The data obtained suggest that Cd has a higher competitive ability to displace Te than Zn and Se. Injection with the above compounds affects the contents of Fe, Co, Rb and Hg in all mice organs. 相似文献
99.
Wiosetek-Reske AM Wysocki S Bak GW 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1172-1178
The absorption and fluorescence spectra of N-nonyl acridine orange are determined at room temperature (298 K) in cyclohexane, benzene, carbon tetrachloride, chloroform, chlorobenzene and dichloromethane. The ground state of dipole moment was obtained by impedance measurements using Guggenheim-Debeye's method. The experimental excited state dipole moment of N-nonyl acridine orange was determined using Bakhshiev's and Kawski-Chamma-Viallet's formulae and solvent polarity parameter proposed by Reichardt. These experimental results were completed with theoretical results using quantum chemical methods. The experimental (muexp=10.76 D) and theoretical (mucal=9.9 D) dipole moments in the ground and excited state (muexp*=14.56 D) were compared. 相似文献
100.
The molecular structure of bis-5-hydroxypentylphthalate (BHPP) is like dihexyl phthalate but having appended to it two hydroxyl end groups, which contribute additional dipole moments and capacity for hydrogen-bond formation. In a previously published dielectric study of the primary and secondary relaxations of BHPP, it was found that all the dynamic properties are normal except for the anomalously large width of the primary relaxation loss peak. There are two secondary relaxations, the relaxation time of the slower one increases with increasing pressure, whereas that of the faster one is practically insensitive to pressure. Hence, the slower secondary relaxation is the "universal" Johari-Goldstein (JG) [J. Chem. Phys. 53, 2372 (1970); 55, 4245 (1971)] relaxation in BHPP. All is well except if the observed large width of the primary relaxation were an indication of a corresponding large coupling parameter n=0.45 in the coupling model. Then the predicted relations between the primary relaxation time tau(alpha) and the JG relaxation time tau(JG) found previously to hold in many glass formers would be violated. It was recognized that this singular behavior of BHPP is likely due to broadening of the primary loss peak by the overlapping contributions of two independent dipole moments present in BHPP, and the actual coupling parameter is smaller. However, at the time of publication of the previous work there were not enough data to support this explanation. By making broadband dielectric measurements of dibutyl phthalate (DBP) and dioctyl phthalate (DOP) that have chemical structures closely related to BHPP but with only one dipole moment, we show that all their dynamic properties are almost the same as BHPP but the widths of their primary relaxation loss peaks are significantly narrower corresponding to a smaller coupling parameter n=0.34. The new data presented here indicate that the coupling parameter of BHPP is about the same as DBP and DOP, and the predicted relations between tau(alpha) and tau(JG) of BHPP are brought back in agreement with the experimental data. 相似文献