972 resultados para Re(I) complex
Resumo:
Wavenumber-frequency spectral analysis and linear wave theory are combined in a novel method to quantitatively estimate equatorial wave activity in the tropical lower stratosphere. The method requires temperature and velocity observations that are regularly spaced in latitude, longitude and time; it is therefore applied to the ECMWF 15-year re-analysis dataset (ERA-15). Signals consistent with idealized Kelvin and Rossby-gravity waves are found at wavenumbers and frequencies in agreement with previous studies. When averaged over 1981-93, the Kelvin wave explains approximately 1 K-2 of temperature variance on the equator at 100 hPa, while the Rossby-gravity wave explains approximately 1 m(2)s(-2) of meridional wind variance. Some inertio-gravity wave and equatorial Rossby wave signals are also found; however the resolution of ERA-15 is not sufficient for the method to provide an accurate climatology of waves with high meridional structure.
Determinants of fruit and vegetable intake in England: a re-examination based on quantile regression
Resumo:
Objective To examine die sociodemographic determinants of fruit and vegetable (F&V) consumption in England and determine the differential effects of socioeconomic variables at various parts of the intake distribution, with a special focus on severely inadequate intakes Design Quantile regression, expressing F&V intake as a function of sociodemographic variables, is employed. Here, quantile regression flexibly allows variables such as ethnicity to exert effects on F&V intake that. vary depending oil existing levels of intake. Setting The 2003 Health survey of England. Subjects Data were from 11044 adult individuals. Results The influence of particular sociodemographic variables is found to vary significantly across the intake distribution We conclude that women consume more F&V than men, Asians and Hacks mole dian Whites, co-habiting individuals more than single-living ones Increased incomes and education also boost intake However, the key general finding of the present study is that the influence of most variables is relatively weak in the area of greatest concern, i e among those with the most inadequate intakes in any reference group. Conclusions. Our findings emphasise the importance of allowing the effects of socio-economic drivers to vary across the intake distribution The main finding, that variables which exert significant influence on F&V Intake at other parts Of the conditional distribution have a relatively weak influence at the lower tail, is cause for concern. It implies that in any defined group, those consuming the lease F&V are hard to influence using compaigns or policy levers.
Resumo:
This paper analyses acarological evidence from a 130-year-old forensic investigation. It was the first case in forensic acarology, i.e., the first case where mites provided substantial information to estimate the post-mortem interval (PMI). In 1878, the mites found in the mummified body of a newborn baby girl in Paris, France, were studied by acarologist and forensic entomologist Jean Pierre M,gnin. M,gnin estimated around 2.4 million mites in the skull and identified them as Tyroglyphus longior (Gervais), a junior synonym of Tyrophagus longior. He suggested that the arrival of these mites at the corpse would have occurred by phoresy on carrier insects, roughly 5 months before the autopsy. There is no doubt about the identification of the mites, M,gnin was a highly respected acarologist. However, two main factors affecting the biology of Tyrophagus mites were not included in the original analysis. First, M,gnin stated that the mites were phoretic. However, he probably did not have access to information about the natural history of the species, because as a rule Tyrophagus mites are non-phoretic. Considering the omnipresence of Tyrophagus mites in soil, most likely the mites will have arrived almost immediately after death. Second, temperature was not taken into account during the estimations of the mite population growth rate. The new analysis is based on current knowledge of Tyrophagus biology and includes temperature, estimated following a handful of weather reports of the years 1877 and 1878. The new projections indicate that non-phoretic mites may have colonised the body just after death and the colony would have built up over 8 months, contrary to the 5 months proposed by M,gnin. This new lapse of time agrees with the PMI proposed by Brouardel: on 15 January 1878 he postulated the death of the newborn to have occurred some 8 months before the autopsy.
Resumo:
In the present study, a genomic analysis of full VP1 sequence region of 15 clinical re-isolates (14 healthy vaccinees and one bone marrow tumor patient) was conducted, aiming to the identification of mutations and to the assessment of their impact on virus fitness, providing also insights relevant with the natural evolution of Sabin strains. Clinical re-isolates were analyzed by RT-PCR, sequencing and computational analysis. Some re-isolates were characterized by an unusual mutational pattern in which non-synonymous mutations outnumbered the synonymous ones. Furthermore, the majority of amino-acid substitutions were located in the capsid exterior, specifically in N-Ags, near N-Ags and in the north rim of the canyon. Also mutations, which are well-known determinants of attenuation, were identified. The results of this study propose that some re-isolates are characterized by an evolutionary pattern in which non-synonymous mutations with a direct phenotypic impact on viral fitness are fixed in viral genomes, in spite of synonymous ones with no phenotypic impact on viral fitness. Results of the present retrospective characterization of Sabin clinical re-isolates, based on the full VP1 sequence, suggest that vaccine-derived viruses may make their way through narrow breaches and may evolve into transmissible pathogens even in adequately immunized populations. For this reason increased poliovirus laboratory surveillance should be permanent and full VP1 sequence analysis should be conducted even in isolates originating from healthy vaccinees.
Resumo:
Caliciviruses are a major cause of gastroenteritis in humans and cause a wide variety of other diseases in animals. Here, the characterization of protein-protein interactions between the individual proteins of Feline calicivirus (FCV), a model system for other members of the family Caliciviridae, is reported. Using the yeast two-hybrid system combined with a number of other approaches, it is demonstrated that the p32 protein (the picornavirus 2B analogue) of FCV interacts with p39 (2C), p30 (3A) and p76 (3CD). The FCV protease/RNA polymerase (ProPol) p76 was found to form homo-oligomers, as well as to interact with VPg and ORF2, the region encoding the major capsid protein VP1. A weak interaction was also observed between p76 and the minor capsid protein encoded by ORF3 (VP2). ORF2 protein was found to interact with VPg, p76 and VP2. The potential roles of the interactions in calicivirus replication are discussed.
Resumo:
Repair of the mature mammalian myocardium following injury is impaired by the inability of the majority of cardiomyocytes to undergo cell division. We show that overexpression of the cyclin B1-CDC2 (cell division cycle 2 kinase) complex re-initiates cell division in adult cardiomyocytes. Thus strategies targeting the cyclin B1-CDC2 complex might re-initiate cell division in mature cardiomyocytes in vivo and facilitate myocardial regeneration following injury.
Resumo:
Equilibrium study on complex formation of Co(II), Ni(II), Cu(II) and Zn(II), hereafter M(II), with the quadridentate (O-, N, O-, N) donor ligand, N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his, hereafter H2L), in the absence and in the presence of typical (N, N) donor bidentate ligands, 1,10 phenanthroline(phen), 2, 2'-bipyridine(bipy), ethylenediamine(en), hereafter B, in aqueous solution at 25 +/- 1 degrees C was done at a fixed ionic strength, I = 0.1 mol dm(-3) (NaNO3) by combined pH-metric, UV-Vis and EPR measurements provide evidence for the formation of mononuclear and dinuclear binary and mixed ligand complexes of the types: M(L), M(L)(2)(2-), M-2(L)(2+), M-2(H-1L)(+), M(L)(B), (B)M(H-1L)M(B)(+). The imidazole moiety of the ligand is found to act as a bridging bidentate ligand in the dinuclear M-2(L)(2+), M-2(H-1L)(+) and (B)M(H-1L)M(B)(+) complexes, using its N-3 atom and N1-H deprotonated moiety. Stability constants of the complexes provide evidence of discrimination of Cu(II) from the other M(II) ions by this ligand. Solid complexes: [Ni(L)(H2O)(2)] (1), [Cu(L)(H2O)] (2), and [Ni(L)(bipy)] (.) H2O (3) have been isolated and characterized by various physicochemical studies. Single crystal X-ray diffraction of the ternary complex, 3, shows an octahedral [(O-,N,N,O-)(N,N)] geometry with extensive pi-pi stacking of the aromatic rings and H-bonding with imidazole (N1-H), secondary amino N-atom, the lattice H2O molecule, and the carboxylate and phenolate O-atoms. (c) 2006 Elsevier B.V. All rights reserved.
Resumo:
The ligands PhL and MeL are obtained by condensing 2-formylpyridine with benzil dihydrazone and diacetyl dihydrazone, respectively, in 2: 1 molar proportion. With silver( I), PhL yields a double-stranded dinuclear cationic helicate 1 in which the metal is tetrahedral but MeL gives a cationic one-dimensional polymeric complex 2 where silver( I) is distorted square planar and the ligand backbone is nearly planar. In both complexes, metal: ligand ratio is 1: 1. Ab initio calculations on the ligands at the HF/6-31+G* level reveal that while PhL strongly prefers a helical conformation, MeL has a natural inclination to remain in a planar conformation. Density functional theory calculations on model silver( I) complexes show that formation of the linear polymer in the case of MeL is also an important factor in imposing the planar geometry of Ag(I) in 2.
Resumo:
The linking of orthopalladated ferrocenylene units by parabanato(2-) ligands results in enantiospecific assembly of a hexanuclear complex in which (i) the steric bulk of the ferrocenylene moiety, (ii) the folded configuration dictated by the imidato(2-) bridging ligand, and (iii) the strong preference for a trans arrangement of the carbonyl oxygen and ferrocenyl carbon atoms, combine to ensure that only ferrocenylene-palladium units with the same chirality can be located at adjacent positions in the assembled complex. The resulting tris-parabanato(2-)-bridged, hexapalladium complex is thus homochiral (R,R,R,R,R,R or S,S,S,S,S,S), as demonstrated by H-1 NMR spectroscopy and by X-ray analysis of a racemic crystal which shows the complex to possess a tapering, twisted, trigonal-prismatic skeleton of palladium atoms with threefold crystallographic symmetry. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Resumo:
Hexadecanuclear copper mixed-valence complex 2 containing 10 Cu-II, centers and 6 Cu-I centers was isolated with N,O donor ligands. From the X-ray crystal structure, 2 was found to contain a centrosymmetric dimeric cation - each monomeric unit composed of eight copper centers. It displays a very broad and weak intervalence charge-transfer band around 1100 nm at room temperature in the solid state. Variable-temperature magnetic susceptibility measurements indicate an S = 1/2 ground state for half of 2, explicitly, each Cu-8 moiety has a g value around 2.26. Complex 2 was examined by NMR spectroscopy at room temperature in solution and by EPR at low temperature; the data indicates that the valence is delocalized in 2 at room temperature but localized at low temperature. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Resumo:
X-ray crystallography shows that [Ag2L2(H2O)(2)](BF4)(2) where L is a 1:1 condensate of 1,2-diphenylethane-1,2-dione and 2-(2-aminoethyl pyridine), contains an Ag(I)-Ag(I) bond of length 2.979(2) angstrom and an angular, intraligand interaction of the keto O with the pi cloud of the pyridine moiety (O-pyridine centroid = 3.12 angstrom). Model MP2/6-311++G(d,p) calculations indicate that the observed lone pair-pi type interaction is stabilising and not merely a tolerated short contact. (C) 2008 Elsevier B.V. All rights reserved.
Resumo:
Using the I : 2 condensate of benzil dihydrazone and 2-acetylpyridine as the ligand L, two complexes of zinc, [ZnL(CH3COO)]PF6 (1) and [ZnL(H2O)CIO4]CIO4 H2O (2), are synthesised from Zn(CH3COO)(2).2H(2)O and Zn(CIO4)(2).6H(2)O, respectively. From X-ray crystallography, both the complexes are found to be single helical with the metal in distorted octahedral N4O2 environment. In 1, the two oxygen atoms come from the bidentate acetate while 2 is a monoaqua complex with a perchlorate anion bound to the metal in monodentate fashion. The perchlorate in 2 is not at all weakly bound [Zn-O(perchlorate) 2.256(4) A]. Still in acetonitrile solution, the coordinated perchlorate ion dissociates upon deprotonation [reaction (i)].
Resumo:
Two polymeric azido bridged complexes [Ni2L2(N-3)(3)](n)(ClO4). (1) and [Cu(bpdS)(2)(N-3)],(ClO4),(H2O)(2.5n) (2) [L = Schiff base, obtained from the condensation of pyridine-2-aldehyde with N,N,2,2-tetramethyl-1,3-propanediamine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1, C26H42ClN15Ni2O4, crystallizes in a triclinic system, space group P1 with a 8.089(13), b = 9.392(14), c = 12.267(18) angstrom, a = 107.28(l), b 95.95(1), gamma = 96.92(1)degrees and Z = 2; complex 2, C20H21ClCuN7O6.5S4, crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) angstrom and Z = 4. The crystal structure of I consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging mu-(1,3-N-3) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting,of magnetic data was carried out applying the Borris-Almenar formula for such types of alternating one-dimensional S = 1 systems, based on the Hamiltonian H = -J Sigma(S2iS2i-1 + aS(2i)S(2i+1)). The best-fit parameters obtained are J = -106.7 +/- 2 cm(-1); a = 0.82 +/- 0.02; g = 2.21 +/- 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu-II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo-one-dimensional system, with all copper((II)) atoms linked by [mu(1,3-azido) bridging ligands at axial positions (long Cu...N-3 distances) since the coupling through long bpds is almost nil. The best-fit parameters obtained with this model are J = -1.21 +/- 0.2 cm(-1), g 2.14 +/- 0.02. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).