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921.
Mahal HS Kapoor S Satpati AK Mukherjee T 《The journal of physical chemistry. B》2005,109(50):24197-24202
A series of metal-ligand complexes were prepared by the reaction of various metal ions, namely, Cu(II), Mn(II), or Fe(II) with phenolic derivatives of [catechol, chlorogenic acid (CGA), n-propyl gallate (nPG), 3-hydroxy anthranilic acid, resveratrol, and rutin] and characterized by UV-vis spectroscopy. The metal/ligand complexing ratio and complexation constants have been determined. The complexes were probed for their reactivity toward various free radicals (e aq-, CO2*-, and O2*-). Pulse radiolysis studies showed that the one-electron reduction of metal/phenol complexes by CO2*- radicals was metal-centered, and this was confirmed by the formation of an initial adduct with CO2*- radicals. Rate constants for the scavenging of superoxide anions with metal complexes ranged between 10(7)-10(9) dm3 mol(-1) s(-1) and those for the reaction of e aq- with the metal complexes were in the range of (1-5) x 10(9) dm3 mol(-1) s(-1), depending on the pH of the solution. Cyclic and differential pulse voltammetric studies showed that the reduction potential of the complexes are found to range between -0.022 to 0.45 V vs normal hydrogen electrode. 相似文献
922.
Protein–DNA interactions induce conformational changes in DNA such as B‐ to A‐form transitions at a local level. Such transitions are associated with a junction free energy cost at the boundary of two different conformations in a DNA molecule. In this study, we performed umbrella sampling simulations to find the free energy values of the B–A transition at the dinucleotide and trinucleotide level of DNA. Using a combination of dinucleotide and trinucleotide free energy costs obtained from simulations, we calculated the B/A junction free energy. Our study shows that the B/A junction free energy is 0.52 kcal mol?1 for the A‐philic GG step and 1.59 kcal mol?1 for the B‐philic AA step. This observation is in agreement with experimentally derived values. After excluding junction effects, we obtained an absolute free energy cost for the B‐ to A‐form conversion for all the dinucleotide steps. These absolute free energies may be used for predicting the propensity of structural transitions in DNA. 相似文献
923.
Surface Enhanced Raman Spectra (SERS) of 2-methylthiophene (2-MT) and 3-methylthiophene (3-MT) in silver colloid are compared with their normal Raman spectra in the bulk and in acetonitrile solution. Experimental results indicate that both the methylthiophene molecules are adsorbed on a metal surface through the sulfur atom. Assuming the image dipole theory to be valid, the observed surface enhancement factor of the C-H stretching mode in 2-MT indicates that the C-H bond of this isomer makes an angle of 51 degrees with the surface normal. The experimental results further suggest that the 3-MT molecule is adsorbed with its ring plane almost vertical to the metal surface; the 2-MT molecule, on the other hand, is tilted more than 45 degrees to the surface normal. The concentration dependence of the relative enhancement factor indicates that a monomolecular layer is formed on the metal surface at a specific concentration of the methylthiophenes in silver sol. No oligomerization of the two methylthiophenes on the silver surface is observed. Copyright 1999 Academic Press. 相似文献
924.
ABSTRACTIn this work, we report the results of DC susceptibility, AC susceptibility and related technique, resistivity, transverse and longitudinal magnetoresistance and heat capacity on polycrystalline magnetic semimetal CeAlGe. This compound undergoes antiferromagnetic type ordering around 5.2 K (T1). Under the application of external magnetic fields, parallel alignment of magnetic moments is favoured above 0.5?T. At low field and temperature, frequency and AC field amplitude response of AC susceptibility indicate the presence of spin–lattice relaxation phenomena. The observation of spin–lattice interaction suggests the presence of the Rashba–Dresselhaus spin–orbit interaction which is associated with inversion and time-reversal symmetry breaking. Additionally, the presence of negative and asymmetric longitudinal magnetoresistance indicates anomalous velocity contribution to the magnetoresistance due to the Rashba–Dresselhaus spin–orbit interaction which is further studied by heat capacity. 相似文献
925.
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928.
The complex ion [FeIII2(μ‐O)(phen)4(H2O)2]4+ ( 1 ) (phen = 1,10‐phenanthroline) and its hydrolytic derivatives [FeIII2(μ‐O)(phen)4(H2O)(OH)]3+ ( 1a ) and [FeIII2(μ‐O)(phen)4‐ (OH)2]2+ ( 2a ) coexist in rapid equilibria in the range pH 4.23–5.35 in the presence of excess phenanthroline (pKa1 = 3.71±0.03, pKa2 = 5.28± 0.07). The solution reacts quantitatively with I− to produce [Fe(phen)3]2+ and I2. Only 1 but none of its hydrolytic derivatives is kinetically active. Both inner and outer sphere pathways operate. The observed rate constants show second‐order dependence on the concentration of iodide, while the dependence on [H+] is complex in nature. Added Cl− inhibits the formation of adduct with I− and thus retards the rate of inner sphere path, leading to a rate saturation at high [Cl−], where only the outer sphere mechanism is active. Kinetic data indicate that simultaneous presence of two I− in the vicinity of diiron core is necessary for the reduction of 1 . © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 737–743, 2005 相似文献
929.
Supriya Mukherjee A. Roy Chowdhury 《International Journal of Theoretical Physics》2003,42(12):2991-2998
A new integrable system describing the process of self-induced transparency with spatial dispersion is analyzed from the viewpoint of inverse scattering transform. The coupled set of Gelfand–Levitan equation is established and solved for one soliton solutions. The explicit structure of the solutions are exhibited graphically. 相似文献
930.
Utilizing one-particle one-hole variations of ATDHF states by invoking commutators obtained from generators of complete set
of coordinates and of momenta, the ATDHF equations were shown in an earlier work to yield the valley condition. In principle,
variations of ATDHF states should also be exploited by using anticommutators involving the said generators. It is demonstrated
here that owing to the canonicity condition relating the generators of coordinates and of momenta, use of anticommutators
gives rise to exactly the same valley condition on the ATDHF path. 相似文献