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101.
102.
Dr. Jana Hudecová Dr. Josef Kapitán Prof. Martin Dračínský Pavel Michal Dr. Václav Profant Prof. Petr Bouř 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202045
The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis2 complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis2 is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems. 相似文献
103.
Emmanouil Veroutis Steffen Merz Rüdiger-A. Eichel Josef Granwehr 《Chemphyschem》2022,23(1):e202100602
Choline-based electrolytes have been proposed as environmentally friendly and low-cost alternatives for secondary zinc air batteries. Choline acetate [Ch]+[OAc]− in protic (D2O) and aprotic (DMSO-d6) solvents has been studied by means of concentration-dependent 1H NMR, viscosity, and density measurements. The viscosities have been calculated on the basis of the Jones-Dole equation and showed that the dominant contribution originates from short-range ion-solvent interactions. Site-specific association affinities were assigned from NMR chemical shift titrations. In DMSO-d6, the hydroxyl group of choline was found to have the smallest dissociation constant followed by the methyl group of acetate. The corresponding Gibbs energies at low concentration were found to be in agreement with a solvent-separated ion pair (2SIP) configuration, whereas at concentrations above 300 mM, a solvent-shared ion pair (SIP) configuration was assigned. For [Ch]+[OAc]− in D2O, association effects were found to be weaker, attributed to the high dielectric constant of the solvent. On time scales on the order of 100 ms, NMR linewidth perturbations indicated a change in the local rotational dynamics of the ions, attributed to short-range cation-solvent interactions and not to solvent viscosity. At 184 mM, 40 % of the cations in DMSO-d6 and 10 % in D2O were found to exhibit short-range interactions, as indicated by the linewidth perturbations. It was found that at about 300 mM, the ions in DMSO-d6 exhibit a transition from free to collective translational dynamics on time scales on the order of 400 ms. In DMSO-d6, both ions were found to be almost equally solvated, whereas in D2O solvation of acetate was stronger, as indicated by the obtained effective hydrodynamic radii. For [Ch]+[OAc]− in DMSO-d6, the results suggest a solvent-shared ion association with weak H-bonding interactions for concentrations between 0.3–1 M. Overall, the extent of ion association in solvents such as DMSO is not expected to significantly limit charge transport and hinder the performance of choline-based electrolytes. 相似文献
104.
105.
Josef Bartos Marta Klimov 《Journal of polymer science. Part A, Polymer chemistry》1996,34(9):1741-1746
For a series of five amorphous polymers with a broad range of Tg values the kinetics of macroradical decay was measured by ESR technique and evaluated by the second-order kinetic model. It was found that the temperature Ttr of the transition between two regions of different reactivity in free radical decay reaction agrees quite well with the temperature parameter T0 of the Vogel-Fulcher-Tamman-Hesse (VFTH) equation for α-segmental dynamics. This parameter represents the onset of α-segmental mobility in glassy state below Tg. A nontraditional way of the estimation of T0 values for α-segmental dynamics through study of the macroradical decay in glassy state of amorphous polymers has been suggested. © 1996 John Wiley & Sons, Inc. 相似文献
106.
King BT Körbe S Schreiber PJ Clayton J Nemcova A Havlas Z Vyakaranam K Fete MG Zharov I Ceremuga J Michl J 《Journal of the American Chemical Society》2007,129(43):12960-12980
The 15 symmetrically methylated derivatives of the CB11H12(-) anion (1a) have been synthesized and found to vary greatly in ease of oxidation. Cyclic voltammetry in liquid SO2 yielded fully reversible oxidation potentials for five of those that have no adjacent unsubstituted vertices in positions 7-12; three others showed some indication of reversibility. The anions 1a-16a and the Jahn-Teller distorted neutral radicals 1r-16r have been characterized by ab initio and density functional theory calculations. In the state average CASSCF(13,12)/6-31+G* approximation, the ground state potential energy surface of 1r contains five symmetry-related pairs of minima. The computational results account for the reversible redox potentials very well when the solvent is included explicitly (RI-DFT(BP)/TZVP, COSMO). For display and for a semiquantitative understanding of methyl substituent effects in terms of perturbation theory, the molecular orbitals of 1a have been expressed in the symmetry-adapted cluster basis. The results serve as an underpinning for a set of additive empirical increments for redox potential prediction. Relative to the usual hydrogen standard, a single methyl group facilitates oxidation by approximately 50, 70, 70, and 10 mV in positions 1, 2, 7, and 12, respectively. This electron donor effect on the redox potential is due to a contribution, whereas those of (inductive and direct field) type are negligible. 相似文献
107.
108.
For symmetry-constrained boranes B10H, B12H, and their valence isoelectronic analogues containing a single hetero atom, completely optimized geometries were obtained using Hartree–Fock SCF calculations with the 3-21G and 6-31G* basis sets. For the anionic and dianionic species, the geometry optimization was also carried out using the 6-31 + G* basis set. Harmonic vibrational frequencies were obtained at HF/3-21G level. The results compare well with experiment where available. 相似文献
109.
Ravi Madhukar Mawale Mayuri Vilas Ausekar Lubomír Prokeš Virginie Nazabal Emeline Baudet Tomáš Halenkovič Marek Bouška Milan Alberti Petr Němec Josef Havel 《Journal of the American Society for Mass Spectrometry》2017,28(12):2569-2579
Laser desorption ionization using time-of-flight mass spectrometer afforded with quadrupole ion trap was used to study As2Ch3 (Ch = S, Se, and Te) bulk chalcogenide materials. The main goal of the study is the identification of species present in the plasma originating from the interaction of laser pulses with solid state material. The generated clusters in both positive and negative ion mode are identified as 10 unary (S p +/– and As m +/– ) and 34 binary (As m S p +/– ) species for As2S3 glass, 2 unary (Se q +/– ) and 26 binary (As m Se q +/– ) species for As2Se3 glass, 7 unary (Te r +/– ) and 23 binary (As m Te r +/– ) species for As2Te3 material. The fragmentation of chalcogenide materials was diminished using some polymers and in this way 45 new, higher mass clusters have been detected. This novel approach opens a new possibility for laser desorption ionization mass spectrometry analysis of chalcogenides as well as other materials. 相似文献
110.