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991.
Preparation, 19F NMR Spectroscopic Evidence and Study of the Formation of Metal-Mixed Cluster Anions [(Mo6?nWnCl )F ]2?, n = 0?6 The complete system of metal-mixed octahedral cluster ions [(Mo6?nWnCl)F]2?, n = 0?6, is prepared by tempering Mo powder with WCl6 at 600°C. A mixture containing inclusively the geometric isomers (n = 2, 3, 4) all ten possible species is transferred into the tetra-n-butylammonium salts (TBA)2[(Mo6?nWnCl)F]. In the 19F nmr spectrum the 24 expected signals are observed, assigned on the basis of their chemical shifts, multiplicities and intensities, and confirmed by a 2D-19F-19F COSY spectrum. From the integrated intensities the distribution of the different components is derived revealing a non-statistical formation, in that isomers with Mo…?Mo or W…?W atoms in trans-positions in comparision to those with mixed Mo…?W axes are favoured, and that especially the homoleptic compounds Mo6 and W6 are present to an over-average extent. Evaluation of 19F chemical shifts reveals that F bound to W which is in antipodal position to Mo resonates at higher field compared to F bound to W in a W…?W arrangement, caused by an increased shielding, which is synonymous to a positive antipodal-effect by Mo. Vice versa F bound to Mo with an antipodal W resonates at lower field compared with F bound to Mo in an Mo…?Mo arrangement caused by an increased deshielding and synonymous a negative antipodal-effect by W. The chemical shifts, resulting from antipodal-effects, are different for the compounds within the [(Mo6?nWnCl)F]2? - system. The difference of the antipodal effect of successive substitution products results in characteristic values designated as antipodal shift constants, depending on the kind of substituents, which is valid for other cluster systems, too. 相似文献
992.
The First Titanate with ?Stuffed Pyrgoms”?: RbNa3Li12[TiO4]4 = RbNa3Li8{Li[TiO4]}4 By heating a well grounded mixture of the binary oxides Rb2O, Na2O, Li2O, and TiO2 [Rb:Na:Li:Ti = 1.1:3.1:12.5:4.0; 780°C, 41 d] we obtained RbNa3Li8{Li[TiO4]}4 as colourless platelike crystals. This first titanate with ?stuffed pyrgoms”? is isostructural with RbNa3Li8{Li[SiO4]}4, CsKNa2Li8{Li[SiO4]}4 and CsKNaLi9{Li[SiO4]}4 [2]. The compound crystallizes tetragonal I4/m with a = 1 125.8(1) pm and c = 652.4(1) pm (Guinier-Simon-Data, Z = 2). The structure was determined by four-cyrcle-data (Siemens AED2, MoK) and leds to the residual values R = 3.7% and Rw = 3.1% (additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Raddii (MEFIR) and the Charge Distribution in Solids (CHARDI) are calculated and discussed. 相似文献
993.
Linjing Yang Xizeng Feng Imshik Lee Chunli Bai 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(3):197-204
Rhodamine B-ethylenediamine--cyclodextrins (RhB--CDen) and rhodamine B--cyclodextrins (RhB--CD) can form inclusive complexes with many guest molecules, a reaction which can be used as a nucleic acid probe. In this paper, the most stable conformations of RhB--CDen and RhB--CD have been determined by fluorescence experiments and analyzed by molecular modeling simulation. The interaction between RhB--CDen and two guest molecules, 1-borneol and cyclohexanol, has also been investigated. The results showed that RhB--CDen has a stronger interaction with 1-borneol than with cyclohexanol. Borneol could push the three aromatic-rings of rhodamine B out of the CD cavity, while the cyclohexanol could not. The interactive sites of host and guest are also presented. 相似文献
994.
4,4-Difluoro-5-trifluoromethyl-2-(2,2,2-trifluoro-1-trifluoromethylethyl)-4H-1,3-dioxine andcis/trans-3-dimethylamino-2-trifluoromethacryloyl fluoride were obtained by reaction ofN-(3,3,3-trifluoro-2-trifluoromethylprop-1-enyl)dimethylamine with MgSO4·7H2O.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1069–1071, May, 1997. 相似文献
995.
Summary A cerebroside fraction was obtained from the fruit bodies offomitopsis pinicola using column chromatography and then separated into six compounds by reversed-phase HPLC. The sugar component of all cerebrosides wasD-glucose. The major fatty acids were 2-hydroxyfatty acids (C14–C18), the long chain base was identified as 9-methyl-C18-4,8-sphingadienine which is widely distributed in fungi and reported to be essential for the fruit-inducing activity of fungi. Based on degradation studies, fast atom bombardment mass spectrometry, and different1H and13C NMR investigations, the structure of the main cerebroside (1) was determined to be (4E,8E,2S,3R,2R)-N-2-hydroxypalmityl-1-O--D-glucopyranosyl-9-methyl-4,8-sphingadienine.
Cerebroside ausFomitopsis pinicola (Sw. Ex Fr.) Karst.
Zusammenfassung Aus den Fruchtkörpern vonfomitopsis pinicola wurde ein Cerebrosidgemisch erhalten und durch Säulenchromatographie und HPLC in sechs Verbindungen aufgetrennt. Der Zuckerbaustein aller Cerebroside warD-Glucose. Die Fettsäurekomponenten waren 2-Hydroxyfettsäuren mit einer Kettenlänge zwische C14 und C18. Der Basenteil konnte als 9-Methyl-C18-4,8-sphingadienin identifiziert werden. Diese Verbindung ist in Pilzen weit verbreitet und für die Fruchtbildung verantwortlich. Aus Abbaustudien, FAB-MS und verschiedenen1H- und13C-NMR-Messungen wurde die Struktur des Hauptcerebrosids (1) als (4E,8E,2S,3R,2R)-N-2-hydroxypalmityl-1-O--D-glucopyranosyl-9-methyl-4,8-sphingadienin ermittelt.相似文献
996.
L. G. Voskressensky T. N. Borisova T. A. Vorob’eva A. I. Chernyshev A. V. Varlamov 《Russian Chemical Bulletin》2005,54(11):2594-2601
Reactions of substituted tetrahydropyrrolo[3,2-c]pyridines with dimethyl acetylenedicarboxylate in protic and aprotic solvents were studied. A novel single-step method for
the synthesis of pyrrolo[2,3-d]azocine derivatives was developed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2513–2519, November, 2005. 相似文献
997.
H. N. Altshuler L. P. Abramova N. V. Malyshenko G. Yu. Shkurenko E. V. Ostapova 《Russian Chemical Bulletin》2005,54(8):1978-1981
The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na+, K+, and Ba2+ as matrices was studied. The selectivity coefficients of ion exchanges Ba2+-H+, Na+-H+, K+-H+, Na+-K+, and Na+-NH4
+ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol−1.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005. 相似文献
998.
Xiao‐Yan Chen Peng Cheng Shi‐Ping Yan Dai‐Zheng Liao Zong‐Hui Jiang 《无机化学与普通化学杂志》2005,631(15):3104-3107
A novel two‐dimensional cobalt complex, [Co(btrm)2(dca)]ClO4 ( 1 , btrm = 1,2‐bis(1,2,4‐triazole‐1‐yl)methane, dca = dicyanamide), was synthesized and characterized. X‐ray diffraction analyses reveal that the title complex crystallizes in the monoclinic space group C2/m with a = 29.507(13)Å, b = 17.804(8) Å, c = 14.709(7) Å, β = 119.916(7)°, Z = 12, and R1 = 0.0784, wR2 = 0.2041. The cobalt atom involves a six‐coordinated CoN6 environment, with a distorted octahedral coordination. Two btrm ligands connect the CoII atoms with the exodentate nitrogen atoms on the 4‐position of triazole rings to form a sixteen‐membered rhombic grid. The unprecedented double btrm bridges and μ1,5‐dca bridge connect the cobalt atoms to form a two‐dimensional grid‐like layered structure. The spectroscopic and magnetic properties have also been investigated. 相似文献
999.
1000.
The activity of enzyme I (EI), the first protein in the bacterial PEP:sugar phosphotransferase system, is regulated by a monomer–dimer equilibrium where a Mg2+-dependent autophosphorylation by PEP requires the homodimer. Using inactive EI(H189A), in which alanine is substituted for the active-site His189, substrate binding effects can be separated from those of phosphorylation. Whereas 1 mM PEP (with 2 mM Mg2+) strongly promotes dimerization of EI(H189A) at pH 7.5 and 20 °C, 5 mM pyruvate (with 2 mM Mg2+) has the opposite effect. A correlation between the coupling of N- and C-terminal domain unfolding, measured by differential scanning calorimetry, and the dimerization constant for EI, determined by sedimentation equilibrium, is observed. That is, when the coupling between N- and C-terminal domain unfolding produced by 0.2 or 1.0 mM PEP and 2 mM Mg2+ is inhibited by 5 mM pyruvate, the dimerization constant for EI(H189A) decreases from >108 to <5 × 105 or 3 × 107 M−1, respectively. With 2 mM Mg2+ at 15–25 °C and pH 7.5, PEP has been found to bind to one site/monomer of EI(H189A) with KA′106 M−1 (ΔG′=−33.7±0.2 kJ mol−1 and ΔH=+16.3 kJ mol−1 at 20 °C with ΔCp=−1.4 kJ K−1 mol−1). The binding of PEP to EI(H189A) is synergistic with that of Mg2+. Thus, physiological concentrations of PEP and Mg2+ increase, whereas pyruvate and Mg2+ decrease the amount of dimeric, active, dephospho-enzyme I. 相似文献