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Query: UNIPROT:P06889 (Mol)
 630,302 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

EPR, Optical and IR spectral studies on a naturally occurring mineral melanterite are carried out at room temperature. EPR studies indicate the presence of Cu(II) ion in tetragonally distorted octahedral site and hyperfine lines could not be resolved due to higher concentration of the paramagnetic impurity in the mineral. Optical absorption spectrum is a characteristic of Fe(II) and Cu(II) ions. Crystal field parameters are evaluated. IR spectrum confirms the presence of water and sulphate ions.
Spectrochim Acta A Mol Biomol Spectrosc 2001 May
PMID:Spectral investigations on melanterite mineral from France. 1141 70

Analytical expressions for the spin polarized EPR lineshapes of weakly coupled radical pairs (RPs) are derived as functions of the angles between the anisotropic g-tensors of the radicals and the vector describing the dipolar coupling. It is shown that with a singlet precursor the EPR signal of the RP can be written as a linear function of the dipolar coupling. Under these conditions, the calculated powder spectrum can be expressed as a linear combination of four powder spectra, which are independent of the geometry of the RP. To reproduce the experimental spectra the optimal set of coefficients can be found by least-squares fitting. The advantage of this approach is that the four powder spectra must only be calculated once. This treatment shows very clearly the restrictions placed on the information obtainable from such spectra. Most importantly, a unique set of angles can only be obtained if the absolute amplitude of the spectrum is known. In general, the calculated spectrum is related to the experimental spectrum by an unknown, arbitrary scaling factor. In this case, sets of angles consistent with the data are obtained. Possible strategies for obtaining unique geometric information are discussed and demonstrated with the experimental data for the state P+*(865)Q-*(A) in Zn-substituted bacterial reaction centres.
Spectrochim Acta A Mol Biomol Spectrosc 2001 Jul
PMID:A new approach to determining the geometry of weakly coupled radical pairs from their electron spin polarization patterns. 1147 22

A series of novel complexes with 5-sulphadiazineazo-3-phenyl-2-thioxo-4-thiazolidinone (H2L1) and 5-sulphamethazineazo-3-phenyl-2-thioxo-4-thiazolidinone (H2L2) and various anions were prepared. Their structures and properties were characterized by elemental analyses, IR, UV-vis, EPR spectroscopy and magnetic measurements. The visible and EPR spectral studies indicated that the Cu(II) complexes have distorted octahedral. From the electron paramagnetic resonance and spectral data, the orbital reduction factors k(parallel) and k(perpendicular) were calculated. In all cases k(perpendicular) > k(parallel) indicates a 2B1g ground state. The crystal field parameters for Co(II) and Ni(II) complexes were calculated. The electronic absorption and a g(parallel)/A(parallel) values are indicative for the beginning of tetragonal distortion. The complexes, however, have lower symmetries and the amount of distortion in terms of DT/Dp, applying NSH 'Hamiltonian Theory' has been evaluated which indicate that the complexes are moderately distorted.
Spectrochim Acta A Mol Biomol Spectrosc 2001 Aug
PMID:Spectral studies on metal-ligand bonding of novel rhodanine azodye sulphadrugs. 1150 26

Human erythrocyte spectrin dimers associate at the N-terminal region of alpha spectrin (alpha N) and the C-terminal region of beta-spectrin (beta C) to form tetramers. We have prepared model peptides to study the tetramerization region. Based on phasing information obtained from enzyme digests, we prepared spectrin fragments consisting of the first 156 amino-acid residues and the first 368 amino-acid residues of alpha-spectrin (Sp alpha 1-156 and Sp alpha 1-368, respectively), and found that both peptides associate with a beta-spectrin model peptide, with an affinity similar to that found in alpha beta dimer tetramerization. Spin label EPR studies show that the region consisting of residues 21-46 in alpha-spectrin is helical even in the absence of its beta-partner. Multi-dimensional nuclear magnetic resonance studies of samples with and without a spin label attached to residue 154 show that Sp alpha 1-156 consists of four helices, with the first helix unassociated with the remaining three helices, which bundle to form a triple helical coiled coil bundle. A comparison of the structures of erythrocyte spectrin with other published structures of Drosophila and chicken brain spectrin is discussed. Circular dichroism studies show that the lone helix in Sp alpha-156 associates with helices in the beta peptide to form a coiled coil bundle. Based on NMR and CD results, we suggest that the helices in Sp alpha 1-156 exhibit a looser (frayed) conformation, and that the helices convert to a tighter conformation upon association with its beta-partner. This suggestion does not rule out possible conversion of a non-structured conformation to a structured conformation in various parts of the molecule upon association. Spectrin mutations at residues 28 and 45 of alpha-spectrin have been found in patients with hereditary elliptocytosis. NMR studies were also carried out on Sp alpha 1-156R28S, Sp alpha 1-156R45S and Sp alpha 1-156R45T. A comparison of the structures of Sp alpha 1-156 and Sp alpha 1-156R28S, Sp alpha 1-156R45S and Sp alpha 1-156R45T is discussed.
Cell Mol Biol Lett 2001
PMID:Studies of the erythrocyte spectrin tetramerization region. 1159 35

The paper describes recent advances towards the construction of functional mimics of the oxygen evolving complex in photosystem II (PSII) that are coupled to photoinduced charge separation. Some key principles of PSII and artificial systems for light-induced charge accumulation are discussed. Systems are described where biomimetic electron donors--manganese complexes and tyrosine--have been linked to a Ru(II)-polypyridine photosensitiser. Oxidation of the donors by intramolecular electron transfer from the photo-oxidised Ru(III) complex has been studied using optical flash photolysis and EPR experiments. A step-wise electron transfer Mn(III,III)-->tyrosine Ru(III) has been demonstrated, in analogy to the reaction on the donor side of PSII. Electron transfer from the tyrosine to Ru(III) was coupled to tyrosine deprotonation. This resulted in a large reorganisation energy and thus a slow reaction rate, unless the tyrosine was hydrogen bonded or already deprotonated. A comparison with analogous reactions in PSII is made. Finally, light-induced oxidation of a manganese dimer linked to a Ru(II)-photosensitiser has been observed. Preliminary results suggest the possibility of photo-oxidising manganese dimers in several steps, which is an important advancement towards water oxidation.
Spectrochim Acta A Mol Biomol Spectrosc 2001 Sep 14
PMID:A biomimetic approach to artificial photosynthesis: Ru(II)-polypyridine photo-sensitisers linked to tyrosine and manganese electron donors. 1160 36

The inner-sphere reorganization energy of the electron self-exchange of the couple cyclooctatetraene/cyclooctatetraene radical anion has been investigated by quantum mechanical calculations. The more stable Jahn Teller distorted B2g conformation of the radical anion has been used in this study. Two different theories have been applied in this first part. The harmonic approximation in the classical Marcus scheme has been modified by using projected force constants, which are obtained from the complete force constant matrix and the geometry changes of the molecule during the ET (introduced by Mikkelsen). A different approach (introduced by Nelsen) combines the different energies of the neutral and radical anion with and without relaxation corresponding to the vertical ionization potential and the vertical electron affinity. The electronic energies of the neutral molecule and the radical anion differ dramatically applying three different levels of quantum mechanical calculations (UAM1, UB3LYP, PMP2 with three different basis sets with and without diffuse functions). Nevertheless the Nelsen method gives almost consistent results for the inner-sphere reorganization energies: 120.1 kJ/mol for semiempirical UAM1 method, 159.3 kJ/mol, 156.4 kJ/mol and 158.3 kJ/mol for density functional UB3LYP/6-31G*, UB3LYP/6-31++G* and UB3LYP/AUG-cc-pVDZ calculations and 192.5 kJ/mol for ab-initio PMP2/6-31G* investigations, respectively. These values are in agreement with earlier experimental work supposing the total reorganization energy to be larger than 38 kcal/mol assuming an electron self-exchange rate of 10(4) M(-1) s(-1). The simple harmonic approximation of Marcus relation has not yet been applied for a molecule like cyclooctatetraene with large torsional geometry changes. Using the projected force constants after scaling, considerably different results for the inner-sphere reorganization energy have been calculated: 738.1 kJ/mol for the UB3LYP/6-31G*, 743.3 kJ/mol for UB3LYP/6-31++G* and 759.1 kJ/mol for UB3LYP/AUG-cc-pVDZ level of theory. Comparison with our concentration dependent EPR experiments are controversial to the earlier experimental results, but the latter supports the assumption that the electron self-exchange occurs in a time scale so that the molecules cannot complete their vibrational motions. Therefore the projected Marcus relation is not valid for cyclooctatetraene/cyclooctatetraene radical anion including a large torsional change during the electron transfer.
Spectrochim Acta A Mol Biomol Spectrosc 2001 Sep 01
PMID:Quantum mechanical investigation of the inner-sphere reorganization energy of cyclooctatetraene/cyclooctatetraene radical anion. Part I. 1166 76

Chromium (VI) compounds are widely recognized as human carcinogens. Extensive studies in vitro and in model systems indicate that the reactive intermediate, Cr (V), generated by cellular reduction of Cr (VI), is likely the candidate for the ultimate carcinogenic form of chromium compounds. Here we review our current understanding of the in vivo reduction of Cr (VI) and its related free radical generation. Our results demonstrate that Cr (V) is indeed generated from the reduction of Cr (VI) in vivo, and that Cr (V) thus formed can mediate the generation of free radicals. Cr (V) and its related free radicals are very likely to be involved in the mechanism of Cr (VI)-induced toxicity and carcinogenesis. These studies also illustrate that in vivo EPR spectroscopy and magnetic resonance imaging can be very useful and powerful tools for studying paramagnetic metal ions in chemical and biochemical reactions occurring in intact animals.
Mol Cell Biochem 2001 Jun
PMID:In vivo reduction of chromium (VI) and its related free radical generation. 1167 10

The treatment of erythrocyte membranes with peroxynitrite (ONOO-), a cytotoxic species formed in vivo by the almost completely diffusion controlled reaction of nitric oxide (NO*) and the superoxide anion (O2*-), led to the loss of the EPR signal of the nitroxide radical 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO). The decrease in the TEMPO EPR signal was peroxynitrite concentration dependent in the studied peroxynitrite concentration range (100-1000 microM). The absence of such a phenomenon in the control membranes (not treated with peroxynitrite) and in a buffer treated with peroxynitrite indicates that the effect must be caused by nitroxide radicals reacting with the products of peroxynitrite reactions with membrane components. To find out which membrane components are responsible for the decrease in EPR signal, this effect was studied in simple model systems (protein and lipid suspensions). The same phenomenon was observed in both lipid and protein systems treated with peroxynitrite, but in protein solutions the effect was greater and occurred for lower peroxynitrite concentrations. A clear effect of the loss of the EPR signal was observed for both erythrocyte membranes and bovine serum albumin (BSA) solution for a peroxynitrite concentration of 100 microM, while in the case of linolenic acid suspension, a significant difference between control and peroxynitrite-treated samples was achieved for a peroxynitrite concentration of 1000 microM. A comparison of the results obtained for the lipid and protein systems suggests that the reaction of nitroxide radicals with protein derived species plays the main role in the observed decrease in the TEMPO EPR signal in peroxynitrite treated erythrocyte membranes.
Cell Mol Biol Lett 2001
PMID:Decrease in 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) EPR signal in peroxynitrite-treated erythrocyte membranes. 1175 39

The reaction products of metal(II) salts with 5-sulphamethoxazoleazo-3-phenyl-2-thioxo-4-thiazolidinone (H2L) have been characterized by elemental analyses, magnetic susceptibility, electronic, infrared and electron paramagnetic resonance spectral measurements. The spectral data suggest a square pyramidal structure for Cu(II) and Co(II) complexes and an octahedral for Ni(II) complexes. Various EPR parameters have been calculated. From the electron paramagnetic resonance and spectral data, the orbital reduction factors were calculated. In all case kperpendicular > kparallel which indicates a 2B1g ground state. These five coordinated complex of Cu(II) react further with pyridine forming six coordinate base adduct. The different modes of chelation of the ligand and stereochemistry around the metal ion are discussed.
Spectrochim Acta A Mol Biomol Spectrosc 2002 Jan 15
PMID:Coordination modes of novel rhodanine azodye complexes. 1180 38

EPR spectra of single crystals of Mn(II)-doped sarcosine cadmium chloride and sarcosine cadmium bromide are studied in Q-band and in X-band at room temperature. Two magnetically inequivalent sites are observed in both the lattices in a distorted octahedral environment. The spin-Hamiltonian parameters are extracted and are found to have a rhombic symmetry. The angular variation of the zero-field transitions is simulated for one of the sites with an asymmetric zero-field tensor D = 480 x 10(-4) cm(-1), E = -115 x 10(-4) cm(-1) and a = 10 x 10(-4) cm(-1) for Mn(II) in sarcosine cadmium chloride and with D = 460 x 10(-4) cm(-1) E = -98 x 10(-4) cm(-1) and a = 10 x 10(-4) cm(-1) for Mn(II) in sarcosine cadmium bromide. The observed large value of zero-field tensor is due to the steric effects of the crystal packing caused by the ligands. Matumura's plot predicts an average covalency of 8.8 and 7.7% for the manganese-ligand bond in SCC and SCB lattices respectively.
Spectrochim Acta A Mol Biomol Spectrosc 2002 Feb
PMID:Single crystal EPR studies on Mn(II)-doped sarcosine cadmium chloride and sarcosine cadmium bromide: study of zero-field splitting tensor in iso-structural complexes. 1190 36


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