967 resultados para MANGANESE DIMER


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The crystal structure of [Mn(thiamine)Cl2(H2O)]2[thiamine]2Cl4.2H2O has been determined by X-ray diffraction methods. The compound contains a cyclic dimer of a complex cation with two thiamine ligands bridged by two Mn(II) ions across a crystallographic center of symmetry. Each Mn(II) is coordinated by two chloride atoms, a water molecule, a N(1') atom of the pyrimidine from a thiamine and an O(53) atom of the hydroxyethyl side chain from another thiamine. There are two free-base thiamine molecules related by a center of symmetry in the unit cell, which form a base-pair through the hydrogen bonds. Both the independent thiamine molecules in the asymmetric unit assume the common F conformation with phi-T = 10.0(9) and 3.6(10) and phi-P = 85.6(7) and 79.6(7), respectively. The compound provides a possible model for a metal-bridged enzyme-coenzyme complex in thiamine catalysis. Crystallographic data: triclinic, space group P1BAR, a = 12.441(4), b = 13.572(4), c = 11.267(3) angstrom, alpha = 103.15(2), beta 89.03(3), gamma = 115.64(2)-degrees, Z = 1, D(calc) = 1.524 g cm-3, and R = 0.050 for 3019 observed reflections with I > 3-sigma(I).

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The approach for constructing the qualitative band structure of a polymer from corresponding dimer has been extended to the system possessing two-fold screw axis or. glide plane. The classification of energy levels of the dimer in the present case depends on pseudo-symmetry/antisymmetry instead of psendo-in-phase/out-of-phase property of the orbitals. Several typical conductive polymers are then discussed follow this approach. Among them are cis-polyacetylene, polyparaphenylene with a twist ang...

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Manganese superoxide dismutase (MnSOD) plays an important role in crustacean immune defense reaction by eliminating oxidative stress. Knowledge on MnSOD at molecular level allows us to understand its regulatory mechanism in crustacean immune system. A novel mitochondrial manganese superoxide dismutase (mMnSOD) was cloned from hepatopancreas of Chinese shrimp Fenneropenaeus chinensis by 3' and 5' rapid amplification of cDNA ends (RACE) PCR. The full-length cDNA consists of 1185 bp with a 660 bp open reading frame, encoding 220 amino acids. The deduced amino acid sequence contains a putative signal peptide of 20 amino acids. Sequence comparison showed that the mMnSOD of F. chinensis shares 88% and 82% identity with that of giant freshwater prawn Macrobrachium rosenbergii and blue crab Callinectes sapidus, respectively. mMnSOD transcripts were detected in hepatopancreas, hemocytes, lymphoid organ, intestine, ovary, muscle and gill by Northern blotting. RT-PCR analysis indicated that mMnSOD showed different expression profiles in shrimp hemocytes and hepatopancreas after artificial infection with while spot syndrome virus (WSSV). In addition, a fusion protein containing mMnSOD was produced in vitro. LC-ESI-MS analysis showed that two peptide fragments (-GDVNTVISLAPALK- and -NVRPDYVNAIWK-) of the recombinant protein were identical to the corresponding sequence of M. rosenbergii mMnSOD, and the enzyme activity of the refolded recombinant protein was also measured. (c) 2006 Elsevier Ltd. All rights reserved.

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Manganese abnormity has been observed in the Holocene sediments of the mud area of Bohai Sea. On the basis of grain size, chemical composition, heavy mineral content and accelerator mass spectrometry (AMS) C-14 dating of foraminifer, relationships between manganese abnormity and sedimentation rates, material source, hydrodynamic conditions are probed. Manganese abnormity occurred during the Middle Holocene when sea level and sedimentation rates were higher than those at present. Sedimentary hiatus was not observed when material sources and hydrodynamic conditions were quite similar. Compared with the former period, the latter period showed a decrease in reduction environment and an inclination toward oxidation environment with high manganese content, whereas provenance and hydrodynamic conditions showed only a slight change. From the above observations, it can be concluded that correlation among manganese abnormity, material source, and hydrodynamic conditions is not obvious. Redox environment seems to be the key factor for manganese enrichment, which is mainly related to marine authigenic process.

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A novel manganese superoxide dismutase (MnSOD) was cloned from bay scallop Argopecten irradians by 3' and 5' rapid amplification of cDNA ends (RACE) PCR. The full-length cDNA of MnSOD was of 1207 bp with a 678 bp open reading frame encoding 226 amino acids. The deduced amino acid sequence contained a putative signal peptide of 26 amino acids. Sequence comparison showed that the MnSOD of A. irradians shared high identity with MnSOD in invertebrates and vertebrates, such as MnSOD from abalone Haliotis discus discus (ABG88843) and frog Xenopus laevis (AAQ63483). Furthermore, the 3D structure of bay scallop MnSOD was predicted by SWISS-MODEL Protein Modelling Server and compared with those of other MnSODs. The overall structure of bay scallop MnSOD was similar to those of zebrafish Danio rerio, fruit fly Drosophila melanogaster, Chinese shrimp Fenneropenaeus chinensis, human Homo sapiens, and had the highest similarity to scallop Mizuhopecten yessoensis and abalone H. discus discus. A quantitative real-time PCR (qRT-PCR) assay was developed to detect the mRNA expression of MnSOD in different tissues and the temporal expression in haemocytes following challenge with the bacterium Vibrio anguillarum. A higher-level of mRNA expression of MnSOD was detected in gill and mantle. The expression of MnSOD reached the highest level at 3 h post-injection with V. anguillarum and then slightly recovered from 6 to 48 h. The results indicated that bay scallop MnSOD was a constitutive and inducible protein and thus could play an important role in the immune responses against V anguillarum infection. (c) 2008 Elsevier Ltd. All rights reserved.

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Manganese-modified mesoporous MCM-41 molecular sieves were synthesized at the absence of alkaline metal ions under mild alkaline condition using cetylpyridinium bromide surfactant as a template, and characterized with X-ray diffraction, N-2 adsorption, transmission electron microscopy, electron spin resonance (ESR), and nuclear magnetic resonance (NMR) spectroscopies. The synthesized MnMCM-41 has a high pore volume of 1.30 cm(3) g(-1) with a corresponding surface area of 1510 m(2) g(-1). The ESR and Si-29 MAS NMR spectra revealed the presence of framework manganese ions in either the as-synthesized or calcined forms. (C) 2002 Elsevier Science B.V. All rights reserved.

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The polymer-supported bimetallic catalyst PVP-PdCl2-MnCl2 (PVP=poly(N-vinyl-2-pyrrolidone)) exhibits high activity and selectivity for the oxidative carbonylation of amines with carbon monoxide and oxygen to carbamate esters under atmospheric pressure in the presence of a base (NaOAc). This catalyst is prepared by the addition of MnCl2 to the alcoholic solution of PVP-PdCl2 in situ. A remarkable bimetallic synergic effect and the role of PVP in PVP-PdCl2-MXn (MXn=the second transition metal component such as NiCl2, CoCl2, MnCl2 and FeCl3) gives rise to an obvious increase in the conversion and selectivity for the reaction. Among the second metal components tested, Mn-Pd exerts the strongest synergic effect. (C) 1999 Elsevier Science B.V. All rights reserved.

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Total oxidation of chlorinated aromatics on supported manganese oxide catalysts was investigated. The catalysts have been prepared by wet impregnation method and characterized by XRD and TPR. Among the catalysts with the supports of TiO(2), Al(2)O(3) and SiO(2), titania supported catalyst (MnO(x)/TiO(2)) gives the highest catalytic activity. MnO(x)/TiO(2) (Mn loading, 1.9 wt.%) shows the total oxidation of chlorobenzene at about 400 degreesC. The activity can be stable for over 82 h except for the first few hours. At lower Mn loadings for MnO(x)/TiO(2), only one reduction peak appears at about 400 degreesC due to the highly dispersed manganese oxide. With the increase of Mn loading, another reduction peak emerges at about 500 degreesC, which is close to the reduction peak of bulk Mn(2)O(3) at 520 degreesC. TPR of the used catalyst is totally different from that of the fresh one indicating that the chemical state of the active species is changed during the chlorobenzene oxidation. The characterization studies of MnO(x)/TiO(2) showed that the highly dispersed MnO(x) is the precursor of the active phase, which can be converted into the active phase, mainly oxychlorinated manganese (MnO(y)Cl(z)), under working conditions of chlorobenzene oxidation. (C) 2001 Elsevier Science B.V. All rights reserved.

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The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from the temperature dependence of (17)O NMR relaxation rates. The rate constants at 298 K were obtained as 4.12 x 10(6) s(-1), 5.73 x 10(6) s(-1), and 2.74 x 10(7) s(-1), respectively. On the basis of the determined entropies of activation, an interchange-dissociative mechanism (I(d)) was proposed for the cationic complexes (DeltaS(double dagger) = approximately 0 J mol(-1) K(-1)) whereas a limiting dissociative mechanism (D) was proposed for Mn(III)TSPP(3-) complex (DeltaS(double dagger) = +79 J mol(-1) K(-1)). The obtained water exchange rate of Mn(III)TSPP(3-) corresponded well to the previously assumed value used by Koenig et al. (S. H. Koenig, R. D. Brown and M. Spiller, Magn. Reson. Med., 1987, 4, 52-260) to simulate the (1)H NMRD curves, therefore the measured value supports the theory developed for explaining the anomalous relaxivity of Mn(III)TSPP(3-) complex. A magnitude of the obtained water-exchange rate constants further confirms the suggested inner sphere electron transfer mechanism for the reactions of the two positively charged Mn(iii) porphyrins with the various biologically important oxygen and nitrogen reactive species. Due to the high biological and clinical relevance of the reactions that occur at the metal site of the studied Mn(iii) porphyrins, the determination of water exchange rates advanced our insight into their efficacy and mechanism of action, and in turn should impact their further development for both diagnostic (imaging) and therapeutic purposes.

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The difference in electrostatics and reduction potentials between manganese ortho-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP) and manganese meta-tetrakis(N-ethylpyridinium-3-yl)porphyrin (MnTE-3-PyP) is a challenging topic, particularly because of the high likelihood for their clinical development. Hence, a detailed study of the protolytic and electrochemical speciation of Mn(II-IV)TE-2-PyP and Mn(II-IV)TE-3-PyP in a broad pH range has been performed using the combined spectrophotometric and potentiometric methods. The results reveal that in aqueous solutions within the pH range ∼2-13 the following species exist: (H(2)O)Mn(II)TE-m-PyP(4+), (HO)Mn(II)TE-m-PyP(3+), (H(2)O)(2)Mn(III)TE-m-PyP(5+), (HO)(H(2)O)Mn(III)TE-m-PyP(4+), (O)(H(2)O)Mn(III)TE-m-PyP(3+), (O)(H(2)O)Mn(IV)TE-m-PyP(4+) and (O)(HO)Mn(IV)TE-m-PyP(3+) (m = 2, 3). All the protolytic equilibrium constants that include the accessible species as well as the thermodynamic parameters for each particular protolytic equilibrium have been determined. The corresponding formal reduction potentials related to the reduction of the above species and the thermodynamic parameters describing the accessible reduction couples were calculated as well.

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The equilibrium structure of the hydrogen bonded complex H2O HF has been calculated ab initio using the CCSD(T) method with basis sets up to sextuple- quality with diffuse functions and taking into account the basis set superposition error correction. The calculations carried out confirm the importance of diffuse functions and of counterpoise correction to obtain an accurate geometry. The most important point is that the basis set convergence is extremely slow and, for this reason an accurate ab initio structure requires a very large basis set. Nevertheless, the ab initio structure is significantly different from the experimental r0 and rm structures. Analysis of the basis set convergence and of the approximations used for the determination of the experimental structures indicates that the ab initio structure is expected to be more reliable.

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Absolute line intensities in the v6 and v8 interacting bands of trans-HCOOH, observed near 1105.4 and 1033.5 cm -1, respectively, and the dissociation constant of the formic acid dimer (HCOOH)2 have been measured using Fourier transform spectroscopy at a resolution of 0.002 cm-1. Eleven spectra of formic acid, at 296.0(5) K and pressures ranging from 14.28(25) to 314.0(24) Pa, have been recorded between 600 and 1900 cm-1 with an absorption path length of 19.7(2) cm. 437 integrated absorption coefficients have been measured for 72 lines in the v6 band. Analysis of the pressure dependence yielded the dissociation constant of the formic acid dimer, k p=361(45) Pa, and the absolute intensity of the 72 lines of HCOOH. The accuracy of these results was carefully estimated. The absolute intensities of four lines of the weak v8 band were also measured. Using an appropriate theory, the integrated intensity of the v6 and v 8 bands was determined to be 3.47 × 1017 and 4.68 × 10-19 cm-1/(molecule cm-1) respectively, at 296 K. Both the dissociation constant and integrated intensities were compared to earlier measurements. © 2007 American Institute of Physics.

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