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91.
The complexes (RN=CH-CH=NR)Co(NO)(CO) with R = isopropyl, 2,6-diisopropylphenyl, or p-tolyl are chemically and electrochemically reducible to radical anions at potentials which strongly depend on R. The DFT calculated structure for the neutral compound with R = iPr agrees with the experiment, and the computed structure of the anion radical reveals changes according to a reduction of the R-DAB ligand. EPR results confirm an (R-DAB)-based singly occupied molecular orbital in [(RNCHCHNR)Co(NO)(CO)](.-), with minor but detectable contributions from NO as supported by IR spectroelectrochemistry and as quantified by DFT spin density calculations. The calculations indicate increasingly stabilized CO, NO, and RNCHCHNR pi* acceptor orbitals, in that order. On the basis of TD-DFT (time-dependent density functional theory) calculations, the lowest-lying excited states are assigned to metal-to-(R-DAB) charge transfer transitions while bands due to the metal-to-nitrosyl charge transfer occur at higher energies but still in the visible region. Resonance Raman studies were used to probe these assignments. 相似文献
92.
Monika Tarnowska Adam Liwo Mark D. Shenderovich Inta Liepiņa Alexander A. Golbraikh Zbigniew Grzonka Anna Tempczyk 《Journal of computer-aided molecular design》1993,7(6):699-719
Summary The effect of the substitution in position 1 on the low-energy conformations of the oxytocin/vasopressin 20-membered ring was investigated by means of molecular mechanics. Three representative substitutions were considered: -mercapto-,-dimethyl)propionic acid (Dmp), (-mercapto-,-cyclopentamethylene)propionic acid (Cpp), both forming strong antagonists, and (,-dimethyl--mercapto)propionic acid (-Dmp), forming analogs of strongly reduced biological activity, with the -mercaptopropionic (Mpa) residue taken as reference. Both ECEPP/2 (rigid valence geometry) and AMBER (flexible valence geometry) force fields were employed in the calculations. Three basic types of backbone conformations were taken into account which are distinguished by the type of -turn at residues 3 and 4: 1/III, II, and I/III, all types containing one or two intra-annular hydrogen bonds. The allowed (ring-closed) disulfide-bridge conformations were searched by an algorithm formulated in terms of scanning the disulfide-bridge torsional angle C-S-S-C. The ECEPP/2 and AMBER energies of the obtained conformations were found to be in reasonable agreement. Two of the low-energy conformers of the [Mpa1]-compound agreed very well with the cyclic part of the two conformers found in the crystal structure of [Mpa1]-oxytocin. An analysis of the effect of -substitution on relative energies showed that the conformations with the N-C-CH2-CH2 (1) and C-CH2-CH2-S (1) angles of the first residue around (–100°, 60°) and (100°, –60°) are not affected; this in most cases implies a left-handed disulfide bridge. In the case of -substitution the allowed values of 1 are close to ± 60°. This requirement, being in contradiction to the one concerning -substitution, could explain the very low biological activity of the -substituted analogs. The conformational preferences of substituted compounds can largely be explained by the analysis of local interactions within the first residue. Based on the selection of the conformations which are low in energy for both the reference and -substituted compounds, two distinct types of possible binding conformations were proposed, the first one being similar to the crystal conformer with a left-handed disulfide bridge, the second one having a right-handed bridge, but a geometry different from that of the crystal conformer with the right-handed bridge. The first type of disulfide-bridge arrangement is equally favorable for both I/III and II types of backbone structure, while the second one is allowed only for the II type of backbone. No conformation of the I/III type has a low enough energy to be considered as a possible binding conformation for all of the active compounds studied in this work. 相似文献
93.
Michael Ptzel Andreas Schulz Jürgen Liebscher Wolfgang Richter Monika Richter 《Journal of heterocyclic chemistry》1992,29(5):1209-1211
Cyclic N-cyanocarbonimidodithioesters 4 or N-aroylcarbonimidothioic acid esters 10 react regioselectively with arylhydrazines and methylhydrazine by a ring chain transformation reaction forming ω-functionalized 3-alkylthio-1,2,4-triazoles 8 and 11 or 5-alkylthio-1,2,4-triazoles 9 . 相似文献
94.
H. Kaupp H. -P. Didra C. Kramer M. Baumann 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,27(4):307-312
Depolarization of excited114Cd 5s5p 3 P 1 atoms induced by collisions with various molecular gases (N2, H2, D2, CO, CO2, CH4, C2H6, C2H4) has been investigated using polarized fluorescence spectroscopy. After pulsed optical excitation of the Cd 53 P 1 level with appropriately polarized light the temporal behaviour of Zeeman quantum beats has been observed showing the influence of collisional destruction of orientation and alignment. By analyzing the signal curves at different molecular gas pressures the corresponding depolarization cross sections for114Cd atoms in the 53 P 1 state have been obtained. With regard to a test of a nuclear spin decoupling model for the collisions the cross sections were compared with previously measured hyperfine structure transfer cross sections of113Cd 5s5p 3 P 1 atoms. 相似文献
95.
A method is described for determining 10-5–10-4M fluoride in a variety of solutions potentiometrically with a fluoridc-specific electrode, by a standard addition method. Any change of ionic strength or the nature of the solution that might alter activity coefficients or junction potentials is minimized. The relationship between potential and fluoride concentration thus follows the Nernst equation, and the unknown concentration can be calculated. Experimental data are given for solutions of sodium choride, sodium nitrate, acidified sodium silicate and sodium hydroxide, lithium chloride, and phosphoric acid. Metal ions (e.g., Al3+, UO22+, Fe3+, Th4+) that interfere by forming complexes with fluoride can be precomplexed with phosphoric acid. The relative error is estimated at 10%, and the relative standard deviation is less than 5% over the concentration range 10-5–10-4M fluoride. 相似文献
96.
The reaction of the hydrazide of pyridine‐4‐acetic acid with isothiocyanate gave thiosemicarbazide derivatives respectively. Further cyclization with 2% NaOH led to the formation of 4‐substituted 3‐(pyridin‐4‐ylmethyl)‐1,2,4‐triazoline‐5‐thione and 3‐(pyridin‐4‐ylmethyl)‐1,2,4‐triazoline‐5‐thione. The structures of all new products were confirmed by analytical and spectroscopic methods. 相似文献
97.
Dr. Valentin Radtke Niklas Gebel Denis Priester Andreas Ermantraut Monika Bäuerle Dr. Daniel Himmel Regina Stroh Prof. Thorsten Koslowski Prof. Ivo Leito Prof. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(40):e202200509
Utilizing the “ideal” ionic liquid salt bridge to measure Gibbs energies of transfer of silver ions between the solvents water, acetonitrile, propylene carbonate and dimethylformamide results in a consistent data set with a precision of 0.6 kJ mol−1 over 87 measurements in 10 half-cells. This forms the basis for a coherent experimental thermodynamic framework of ion solvation chemistry. In addition, we define the solvent independent - and the values that account for the electronating potential of any redox system similar to the value of a medium that accounts for its protonating potential. This scale is thermodynamically well-defined enabling a straightforward comparison of the redox potentials (reducities) of all media with respect to the aqueous redox potential scale, hence unifying all conventional solvents′ redox potential scales. Thus, using the Gibbs energy of transfer of the silver ion published herein, one can convert and unify all hitherto published redox potentials measured, for example, against ferrocene, to the scale. 相似文献
98.
J. Maier C. S. Kischkel M. Baumann 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,21(2):145-151
Using laser induced fluorescence spectroscopy the hyperfine structure of the even parity levels 4f 146s6d 3 D 1, 4f 14 6s8s 3 S 1 and 4f 13 5d6s6p (7/2, 5/2)J=1,2,3 as well as of the odd parity level 4f 14 6s6p 3 P 2 in neutral ytterbium has been investigated. The isotope shift of the transitions 4f 146s6p 3 P 0 → 4f 14 6s6p 3 D 1 and 4f 14 6s6p 3 P 2 → 4f 14 6s8s 3 S 1, 4f 13 5d6s6p (7/2, 5/2)J=1,2,3 could be measured with high accuracy. The results for the 4f 14 6s6p 3 D 1 level show a considerable influence of second order effects of the hyperfine interaction. The isotope shifts of the 4f 14 6s8s 3 S 1 and 4f 13 5d6s6p (7/2, 5/2)J=1 levels indicate a possible configuration mixing for these levels. 相似文献
99.
100.
P. E. Sulewski E. Bucher N. Stücheli C. S. Oglesby K. Friemelt M. Vögt J. R. Baumann Ch. Kloc 《Applied Physics A: Materials Science & Processing》1992,54(1):79-83
Recently, an anomalously large redshift of the absorption edge with electric field was claimed for -GaSe1–x
S
x
layered crystals. We have studied Bridgman grown -GaSe crystals as well as vapor transport grown -GaS, and 2H-WSe2. While we have observed a shift in the absorption edge for -GaSe similar to that reported in previous work, our results demonstrate that the redshift arises from Joule heating, and is thus temperature induced, rather than intrinsic. For -GaS, much larger resistivities virtually eliminate Joule heating, and our measurements of the electric field induced absorption edge shift yield an estimated upper limit of approximately 0.04 meV · cm/kV for a field of 2.4×103 kV/cm, in good agreement with the theoretical value expected for the Franz-Keldysh effect.Also at University of Konstanz 相似文献