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991.
992.
Srnec M Chalupský J Fojta M Zendlová L Havran L Hocek M Kývala M Rulísek L 《Journal of the American Chemical Society》2008,130(33):10947-10954
Reduction potentials of several M(2+/3+) (M = Ru, Os) octahedral complexes, namely, [M(H2O)6](2+/3+), [MCl6](4-/3-), [M(NH3)6](2+/3+), [M(en)3](2+/3+) [M(bipy)3](2+/3+), and [M(CN)6](4-/3-), were calculated using the CASSCF/CASPT2/CASSI and MRCI methods including spin-orbit coupling (SOC) by means of first-order quasi-degenerate perturbation theory. It was shown that the effect of SOC accounts for a systematic shift of approximately -70 mV in the reduction potentials of the studied ruthenium (II/III) complexes and an approximately -300 mV shift for the osmium(II/III) complexes. SOC splits the sixfold-degenerate (2)T(2g) ground electronic state (in ideal octahedral symmetry) of the M(3+) ions into the E((5/2)g) Kramers doublet and G((3/2)g) quartet, which were calculated to split by 1354-1573 cm(-1) in the Ru(3+) complexes and 4155-5061 cm(-1) in the Os(3+) complexes. It was demonstrated that this splitting represents the main contribution to the stabilization of the M(3+) ground state with respect to the closed-shell (1)A(1g) ground state in M(2+) systems. Moreover, it was shown that the accuracy of the calculated reduction potentials depends on the calculated solvation energies of both the oxidized and reduced forms. For smaller ligands, it involves explicit inclusion of the second solvation sphere into the calculations, whereas implicit solvation models yield results of sufficient accuracy for complexes with larger ligands. In such cases (e.g., [M(bipy)3](2+/3+) and its derivatives), very good agreement between the calculated (SOC-corrected) values of the reduction potentials and the available experimental values was obtained. These results led us to the conclusion that especially for Os(2+/3+) complexes, inclusion of SOC is necessary to avoid systematic errors of approximately 300 mV in the calculated reduction potentials. 相似文献
993.
Filippov S Hrubý M Konák C Macková H Spírková M Stepánek P 《Langmuir : the ACS journal of surfaces and colloids》2008,24(17):9295-9301
In this work we report a new type of pH-responsive micelle-like nanoparticle. Reversible nanoscale structures are formed in solutions of a pH-sensitive hydrophobic polyelectrolyte, poly( N-methacryloyl- l-valine) or poly( N-methacryloyl- l-phenylalanine), and nonionic surfactant (Brij 98) in the presence of hydrochloric acid. The influence of composition and pH on particles size and shape was investigated by a variety of methods. An entity's size and polydispersity could be varied in a broad range making them a perspective candidate as a drug carrier. Unlike the case of typical micelles, our results indicate the presence of cavities in the formed particles. A hypothetical model of a nanoparticle and mechanism of formation are proposed. 相似文献
994.
Milko P Roithová J Schröder D Lemaire J Schwarz H Holthausen MC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(14):4318-4327
The "bare" complex [Cu(PhOH)(PhO)](+) with a phenol (PhOH) and a phenoxy (PhO) ligand bound to copper is studied both experimentally and computationally. The binding energies and structure of this complex are probed by mass spectrometry, infrared multi-photon dissociation, and DFT calculations. Further, the monoligated complexes [Cu(PhO)](+) and [Cu(PhOH)](+) are investigated for comparison. DFT calculations on the [Cu(PhOH)(PhO)](+) complex predict that a phenolate anion interacts with copper(II) preferentially through the oxygen atom, and the bonding is associated with electron transfer to the metal center resulting in location of the unpaired electron at the aromatic moiety. Neutral phenol, on the other hand, interacts with copper preferentially through the aromatic ring. The same arrangements are also found in the monoligated complexes [Cu(PhO)](+) and [Cu(PhOH)](+). The calculations further indicate that the bond strength between the copper atom and the oxygen atom of the phenoxy radical is weakened by the presence of neutral phenol from 2.6 eV in bare [Cu(PhO)](+) to 2.1 eV in [Cu(PhOH)(PhO)](+). 相似文献
995.
The performance of the contactless conductivity (C4D) and diode array photometric (DAD) detectors has been compared for CE separations of creatinine, arginine and 3‐methylhistidine in acetic acid background electrolytes. The contactless conductivity detector response has also been modeled. It has been found that the two detectors provide similar responses and can readily be used for dual CE detection. Changes in the acetic acid concentration affect the C4D noise less than the DAD noise, but their effect on the C4D response to the analytes is greater than with DAD. In general, C4D provides better detection results at higher acetic acid concentrations, while DAD is more sensitive and reliable at very low ones. Capillaries with greater internal diameters are preferable for both detectors, provided that the separation efficiency is not adversely affected. Acetic acid is a suitable background electrolyte for CE separations of small, basic organic molecules. 相似文献
996.
Trouillas P Marsal P Svobodová A Vostálová J Gazák R Hrbác J Sedmera P Kren V Lazzaroni R Duroux JL Walterová D 《The journal of physical chemistry. A》2008,112(5):1054-1063
Flavonolignans from silymarin, the standardized plant extract obtained from thistle, exhibit various antioxidant activities, which correlate with the other biological and therapeutic properties of that extract. To highlight the mode of action of flavonolignans as free radical scavengers and antioxidants, 10 flavonolignans, selectively methylated at different positions, were tested in vitro for their capacity to scavenge radicals (DPPH and superoxide) and to inhibit the lipid peroxidation induced on microsome membranes. The results are rationalized on the basis of (i) the oxidation potentials experimentally obtained by cyclic voltammetry and (ii) the theoretical redox properties obtained by quantum-chemical calculations (using a polarizable continuum model (PCM)-density functional theory (DFT) approach) of the ionization potentials and the O-H bond dissociation enthalpies (BDEs) of each OH group of the 10 compounds. We clearly establish the importance of the 3-OH and 20-OH groups as H donors, in the presence of the 2,3 double bond and the catechol moiety in the E-ring, respectively. For silybin derivatives (i.e., in the absence of the 2,3 double bond), secondary mechanisms (i.e., electron transfer (ET) mechanism and adduct formation with radicals) could become more important (or predominant) as the active sites for H atom transfer (HAT) mechanism are much less effective (high BDEs). 相似文献
997.
Civis S Babánková D Cihelka J Sazama P Juha L 《The journal of physical chemistry. A》2008,112(31):7162-7169
Large-scale plasma was created in gas mixtures containing carbon monoxide by high-power laser-induced dielectric breakdown (LIDB). The composition of the mixtures used corresponded to a cometary and/or meteoritic impact into the Earth's early atmosphere. A multiple-centimeter-sized fireball was created by focusing a single 85 J, 450 ps near-infrared laser pulse into the center of a 15 L gas cell. The excited reaction intermediates that formed in various stages of the LIDB plasma chemical evolution were investigated by optical emission spectroscopy (OES) with temporal resolution. Special attention was paid to any OES signs of molecular ions. However, carbon monoxide cations were registered only if their production was enhanced by Penning ionization, i.e., excess He was added to the CO. The chemical consequences of laser-produced plasma generation in a CO-N 2-H 2O mixture were investigated using high resolution Fourier-transform infrared absorption spectroscopy (FTIR) and gas chromatography (GC). Several simple inorganic and organic compounds were identified in the reaction mixture exposed to ten laser sparks. H 2 (18)O was used to avoid possible contamination. The large laser spark triggered more complex reactivity originating in carbon monoxide than expected, when taking into account the strong triple bond of carbon monoxide causing typically inefficient dissociation of this molecule in electrical discharges. 相似文献
998.
The optical activity in porphyrins can easily be induced by a chiral environment, but it is difficult to determine the underlying mechanisms purely on an experimental basis. Therefore, in this study, magnitudes of the perturbational, dipolar, and direct covalent contributions to the electronic circular dichroism (CD) are evaluated with the aid of quantum chemical computations. Electronic properties of model porphyrin chromophores are analyzed. Time-dependent density functional theory (TD DFT), particularly with the hybrid B3LYP functional, appeared suitable for estimation of the electronic excitation energies and spectral intensities. The transition dipole coupling (TDC) between chirally stacked porphyrins was determined as the most important mechanism contributing to their optical activity. This is in agreement with previous experimental observations, where chiral matrices often induce the stacking and large CD signals. About a 10 times smaller signal could be achieved by a chiral orientation of the phenyl or similar residues covalently attached to the porphyrin core. Also, this prediction is in agreement with known experiments. Perturbation models realized by a chirally arranged porphyrin and a point charge, or by a porphyrin and the methane molecule, provided the smallest CD signals. The electrically neutral methane induced similar CD magnitudes as those of the charge, but spectral shapes were different. For a complex of porphyrin and the alanine cation, a significant influence of the solvent on the resultant CD spectral shape was observed, while for the charge and methane perturbations, a negligible solvent effect was found. Detailed dependence of the induced optical activity on variations of geometrical parameters is discussed. The simulations of the induced porphyrin activity can thus bring important information about the structure and intermolecular interactions in chiral complexes. 相似文献
999.
N-K electron energy-loss near-edge structures for TiN/VN layers: an ab initio and experimental study
Lazar P Redinger J Strobl J Podloucky R Rashkova B Dehm G Kothleitner G Sturm S Kutschej K Mitterer C Scheu C 《Analytical and bioanalytical chemistry》2008,390(6):1447-1453
We study N-K-edge electron energy-loss near-edge structures for well-defined TiN/VN bilayers grown on a MgO(100) substrate
by both calculations and experiments. The structural relaxations and the electronic structure of TiN/VN multilayers are calculated
using the Vienna Ab Initio Simulation Package computer code, which uses density functional theory to describe the electronic
interaction. The effects of the core hole created in the excitation process are included in the calculations. For VN, off-stoichiometric
effects due to nitrogen vacancies are modelled. The partial density of states (PDOS) for the N-K edge of atoms in the vicinity
of the TiN/MgO interface revealed that two new peaks appear between 7 and 9 eV instead of a broad shoulder typical for the
bulk. For the VN/TiN interface, the PDOS is modified only slightly, owing to similar bonding on both sides of the interface,
and is thus very similar to the respective bulk spectra. An experimental spectrum taken at the VN/TiN interface is, however,
well described by an average of the simulated spectra for VN and TiN bulk (interface). Such a finding is characteristic of
an intermixed interface.
相似文献
1000.