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41.
An expression for the atom-atom poiarizability between the1s orbitals of geminal or vicinal protons has been derived by perturbation theory using thePople-Santry Theory of electron systems. The coupling constants calculated on this basis agree well with these obtained from full molecular orbital calculations. Expressions have been obtained for the variation of vicinal coupling constants with dihedral angle in ethane and the HCC bond angle and C-C bond length in ethylene, and these agree well with corresponding expressions obtained using the VB method.
Zusammenfassung Es wurde ein Ausdruck für die Atom-Atom-Polarisierbarkeit zwischen den1s Orbitalen geminaler bzw. vicinaler Protonen abgeleitet mittels Störungsrechnung unter Benutzung derPople-Santry-Theorie für-Elektronensysteme. Die auf dieser Basis berechneten Koppelungskonstanten stimmen gut mit denen aus einer vollständigen MO Rechnung überein. Es wurden Ausdrücke erhalten für die Änderung der vicinalen Koppelungskonstanten mit dem Diederwinkel in Äthan sowie dem HOC Bindungswinkel und der C-C Bindungsiänge in Äthylen, die gut mit den entsprechenden Ausdrücken aus der VB Methode übereinstimmen.
Résumé A l'aide de la théorie dePople etSantry sur les systèmes d'électrons, nous dérivons de la théorie des perturbations une expression pour la polarisabiiité atome-atome entre les orbitales1s des protons géminaux ou vicinaux. Les constantes de couplage ici calculées s'accordent bien à celles obtenues des calculs OM complets. Les expressions obtenues pour la variation du couplage vicinal avec l'angle dihédrique dans l'éthane, et l'angle HCC et la distance C-C dans l'éthylène, s'accordent bien aux formules correspondantes de la méthode de la mésomérie.相似文献
42.
Gil Kalai 《Israel Journal of Mathematics》1983,45(4):337-351
Let
(n, k) be the class of all simplicial complexesC over a fixed set ofn vertices (2≦k≦n) such that: (1)C has a complete (k−1)-skeleton, (2)C has precisely (
k
n−1
)k-faces, (3)H
k
(C)=0. We prove that for
,H
k−1(C) is a finite group, and our main result is:
. This formula extends to high dimensions Cayley’s formula for the number of trees onn labelled vertices. Its proof is based on a generalization of the matrix tree theorem. 相似文献
43.
Takehiko Yamato Fumika Kitajima Jeong Tae Gil 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(3):257-262
The lower rim functionalized hexahomotrioxacalix[3]arene triamide 4 with cone-conformation was synthesized from triol 1 by a stepwise reaction. The different extractability for alkali metal ions, transition metal ions, and alkyl ammonium ions from water into dichloromethane is discussed. Due to the strong intramolecular hydrogen bonding between the neighboring NH and CO groups in triamide 4, its affinity to metal cations was weakened. Triamide 4 shows a single selectivity to n-BuNH3+. The anion complexation of triamide 4 was also studied by 1H NMR titration experiments. Triamide 4 binds halides through the intermolecular hydrogen bonding among the NH hydrogens of amide in a 1:1 fashion in CDCl3. The association constants calculated from these changes in chemical shifts of the amide protons are Ka = 223 M−1 for Cl− and Ka = 71.7 M−1 for Br−. Triamide 4 shows a preference for Cl− complexation than Br− complexation. 相似文献
44.
P. J. Mendes J. M. Gil N. Ayres de Campos R. Peichl A. Weidinger 《Hyperfine Interactions》1983,16(1-4):791-794
The perturbation felt by181Hf probes in a181HfTa lattice loaded with 30 at% hydrogen was observed by PAC as a function of temperature. Three different interactions were identified: 1) ΝQ1=433 (6) MHz, η=0.45 2) ΝQ2=142 (9) MHz, η=0.9, and 3) ΝQ?0, σ=4–14 Μ?1 which are attributed to the Β?, ε? and α-phase in TaH system, respectively. 相似文献
45.
In this study, an analytical procedure for the determination in sediment of the most abundant and/or physiological active estrogens (estradiol, estriol, estrone, ethynyl estradiol, and diethylstilbestrol) and progestogens (progesterone, norethindrone. and levonorgestrel) is described. The procedure includes ultrasonic extraction of the lyophilized sediment, clean-up with octadecylsilica cartridges, and analysis by liquid chromatography-diode array detection-mass spectrometry (LC-DAD-MS). MS detection is performed with an electrospray interface in the positive ion mode for determination of the progestogens and in the negative ion mode for determination of the estrogens. The method was applied to the determination of the target compounds in river sediments from the area of Catalonia. Estrogens and progestogens were found at concentrations usually in the low ng g(-1) range. Estriol and norethindrone were the compounds most frequently found whereas maximum concentrations in all sediment samples were obtained for ethynyl estradiol (22.8 ng g(-1)) and estrone (11.9 ng g(-1)). Detection limits were in the range of 0.04-1.00 ng g(-1). Preliminary conjectures with regards to the environmental behavior and impact of estrogens and progestogens in rivers are made. To the authors' knowledge, this is the first work reporting a detailed method for the analysis of estrogens and progestogens in river sediments and data on the environmental occurrence of both groups of compounds. 相似文献
46.
In reactions of (2,3-anti)-3-amino-1,2-diols with diphosgene and phosgene and their conversion into 1,3-oxazolidin-2-ones, some differences in the stereochemistry of the reactions have been found with these two reagents. The reactions with phosgene afforded the expected cis-oxazolidinones, and in the reaction with diphosgene under the same reaction conditions, the trans-oxazolidinones were also obtained. 相似文献
47.
Cornejo A Fraile JM García JI García-Verdugo E Gil MJ Legarreta G Luis SV Martínez-Merino V Mayoral JA 《Organic letters》2002,4(22):3927-3930
[formula: see text] A chiral pyridine-bis(oxazoline) ligand, functionalized with a vinyl group in the pyridine ring, can be polymerized with styrene and divinylbenzene to obtain supported chiral ligands. As proof of the usefulness of this supported ligands, the corresponding ruthenium complexes are catalysts for the cyclopropanation reaction of styrene with ethyl diazoacetate with up to 85% ee. 相似文献
48.
Gil MC Lee MH Seo JI Choi YL Kim MK Jung KC Park SH Kim TJ 《Experimental & molecular medicine》2002,34(6):411-418
CD99 plays a critical role in the diapedesis of monocytes, T cell differentiation, and the transport of MHC molecules. Engagement of CD99 by agonistic monoclonal antibodies has been reported to trigger multifactorial events including T cell activation as well as cell-cell adhesion during hematopoietic cell differentiation. In this study, to identify the functional domains participating in the cellular events, we mapped the epitopes of CD99, which are recognized by two agonistic CD99 monoclonal antibodies, DN16 and YG32. Using recombinant fusion proteins of GST with whole or parts of CD99, we found that both antibodies interact with CD99 molecules independently of sugar moieties. DN16 mAb detected a linear epitope located in the amino terminal region of CD99 while YG32 mAb bound another linear epitope in the center of the extracellular domain. To confirm that the identified epitopes of CD99 are actually recognized by the two mAbs, we showed the presence of physical interaction between the mAbs and the fusion proteins or synthetic peptides containing the corresponding epitopes using surface plasmon resonance analyses. The dissociation constants of DN16 and YG32 mAbs for the antigen were calculated as 1.27 x 10(-7) and 7.08 x 10(-9) M, respectively. These studies will help understand the functional domains and the subsequent signaling mechanism of CD99. 相似文献
49.
50.