609 resultados para Epr
Resumo:
Bitumoid contents in metalliferous sediments from axial parts of the East Pacific Rise (EPR) have been studied. Maximal concentrations of bitumoid matter and aromatic hydrocarbons have been found in the axial zones of the EPR as a result of hydrothermal processes and accumulation of endogenous matter in the sediments. Distribution of bitumoids and hydrocarbons coincides with deposition of ore minerals that indicates similarity of their sources.
Resumo:
The copepod Calanus glacialis plays a key role in the lipid-based energy flux in Arctic shelf seas. By utilizing both ice algae and phytoplankton, this species is able to extend its growth season considerably in these seasonally ice-covered seas. This study investigated the impacts of the variability in timing and extent of the ice algal bloom on the reproduction and population success of C. glacialis. The vertical distribution, reproduction, amount of storage lipids, stable isotopes, fatty acid and fatty alcohol composition of C. glacialis were assessed during the Circumpolar Flaw Lead System Study. Data were collected in the Amundsen Gulf, south-eastern Beaufort Sea, from January to July 2008 with the core-sampling from March to April. The reduction in sea ice thickness and coverage observed in the Amundsen Gulf in 2007 and 2008 affected the life strategy and reproduction of C. glacialis. Developmental stages CIII and CIV dominated the overwintering population, which resulted in the presence of very few CV and females during spring 2008. Spawning began at the peak of the ice algal bloom that preceded the precocious May ice break-up. Although the main recruitment may have occurred later in the season, low abundance of females combined with a potential mismatch between egg production/development to the first feeding stage and phytoplankton bloom resulted in low recruitment of C. glacialis in the early summer of 2008.
Resumo:
Isolated kerogens from four sites in the Middle Valley hydrothermal region of the Juan de Fuca Ridge (Ocean Drilling Project (ODP) Leg 139) were analysed by electron paramagnetic resonance (EPR) spectroscopy. Measurements of peak width, spin density and power saturation for site 857 kerogens, which increased regularly in maturity downhole, show correlation with vitrinite reflectance values from 0.61 to 2.5%, indicating the start of the oil window at depths from 200 to 400 m. Spin density increases to 1.56 * 10**17 spins per gram and peak width decreases to 3.45 G (gauss) with increasing depth. The tendency to power saturate also decreases with increasing maturity and increasing vitrinite reflectance within the oil window. These trends are consistent with a model in which exchange processes are occurring and cause changes in the EPR behavior of samples from this site. Sediments from other Middle Valley sites, 855, 856 and 858 contain large quantities of pyrite with Mn2+ impurities which interact with the carbon radical to distort the EPR measurements.
Resumo:
Basalts from the base of a small seamount on ~1.5-m.y.-old crust west of the East Pacific Rise (EPR) at 9°N are intermediate in chemical and isotopic composition between light-rare-earth-element-depleted tholeiite (normal midocean ridge basalt (MORB)) and alkali basalt. Like oceanic alkali basalt, these rocks contain significantly more Ba, K, P, Sr, Ti, U, and Zr than normal MORB. Since the absolute abundances of these elements are still well below alkali basalt levels, the label transitional is adopted for these basalts. A series of fractionated MORB also occurs in this area, northwest of the Siqueiros Fracture Zone - Transform Fault. The normal tholeiites are either olivine-plagioclase or plagioclase-clinopyroxene phyric, while the transitional basalts are spinel-olivine phyric. Fractional crystallization quantitatively accounts for the chemical variability of the tholeiitic series but not for the transitional basalts. The tholeiitic series probably evolved in a crustal magma chamber ~4 km below the crest of the East Pacific Rise. 143Nd/144Nd and other chemical data suggest that the large-ion-lithophile-enriched transitional basalts may represent a hybrid of normal MORB and Siqueiros area alkali basalt. Incompatible element plots of K, P, and U indicate possible derivation of the transitional basalts by magma mixing. Magma mixing of unfractionated normal MORB and Siqueiros alkali basalt has been quantified. Derivation of the transitional basalts from a 1:1 mixture is supported by all available chemical data, including Cr, Cu, Nd, Ni, Sm, Sr, U, and V. This magma mixing apparently occurred at ?<~30 km depth within a few tens of kilometers from the EPR axis. These Siqueiros area EPR transitional basalts are compared with Mid-Atlantic Ridge (MAR) transitional basalts from the Iceland and Azores areas. The Siqueiros area basalts reflect a profound chemical and isotopic heterogeneity in the upper mantle, similar to that found along the MAR. Unlike the MAR, the EPR shows no evidence of plumelike bulges and associated large-scale outpourings of nonnormal MORB resulting from these mantle heterogeneities. Siqueiros alkali basalt and MORB, as well as transitional basalt and MORB, were recovered from single dredge hauls. Such close spatial and temporal proximity of the inferred mantle sources places severe constraints on geometric and physicochemical upper mantle models.
Resumo:
Metal ion binding properties of the immunosuppressant drug cyclosporin A have been investigated. Complexation studies in acetonitrile solution using H-1 NMR and CD spectroscopy yielded 1:1 metal-peptide binding constants (log(10)K) for potassium(l), < 1, magnesium(II), 4.8 +/- 0.2. and calcium(II), 5.0 +/- 1.0. The interaction of copper(II) with cyclosporin A in methanol was investigated with UV/visible and electron paramagnetic resonance (EPR) spectroscopy. No complexation of copper(II) was observed in neutral solution. In the presence of base, monomeric copper(II) complexes were detected. These results support the possibility that cyclosporin A has ionophoric properties for biologically important essential metal ions. (C) 2003 Elsevier Inc. All rights reserved.
Resumo:
Cytochromes from the SoxAX family have a major role in thiosulfate oxidation via the thiosulfate-oxidizing multi-enzyme system (TOMES). Previously characterized SoxAX proteins from Rhodovulum sulficlophilum and Paracoccus pantotrophus contain three heme c groups, two of which are located on the SoxA subunit. In contrast, the SoxAX protein purified from Starkeya novella was found to contain only two heme groups. Mass spectrometry showed that a disulfide bond replaced the second heme group found in the diheme SoxA subunits. Apparent molecular masses of 27,229 +/- 10.3 Da and 20,258.6 +/- 1 Da were determined for SoxA and SoxX with an overall mass of 49.7 kDa, indicating a heterodimeric structure. Optical redox potentiometry found that the two heme cofactors are reduced at similar potentials (versus NHE) that are as follows: + 133 mV (pH 6.0); + 104 mV (pH 7.0); +49 (pH 7.9) and +10 mV (pH 8.7). EPR spectroscopy revealed that both ferric heme groups are in the low spin state, and the spectra were consistent with one heme having a His/Cys axial ligation and the other having a His/Met axial ligation. The His/Cys ligated heme is present in different conformational states and gives rise to three distinct signals. Amino acid sequencing was used to unambiguously assign the protein to the encoding genes, soxAX, which are part of a complete sox gene cluster found in S. novella. Phylogenetic analysis of soxA- and soxX-related gene sequences indicates a parallel development of SoxA and SoxY, with the diheme and monoheme SoxA sequences located on clearly separated branches of a phylogenetic tree.
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We present an experimental analysis of quadrature entanglement produced from a pair of amplitude squeezed beams. The correlation matrix of the state is characterized within a set of reasonable assumptions, and the strength of the entanglement is gauged using measures of the degree of inseparability and the degree of Einstein-Podolsky-Rosen (EPR) paradox. We introduce controlled decoherence in the form of optical loss to the entangled state, and demonstrate qualitative differences in the response of the degrees of inseparability and EPR paradox to this loss. The entanglement is represented on a photon number diagram that provides an intuitive and physically relevant description of the state. We calculate efficacy contours for several quantum information protocols on this diagram, and use them to predict the effectiveness of our entanglement in those protocols.
Resumo:
We present a fully quantum mechanical treatment of the nondegenerate optical parametric oscillator both below and near threshold. This is a nonequilibrium quantum system with a critical point phase transition, that is also known to exhibit strong yet easily observed squeezing and quantum entanglement. Our treatment makes use of the positive P representation and goes beyond the usual linearized theory. We compare our analytical results with numerical simulations and find excellent agreement. We also carry out a detailed comparison of our results with those obtained from stochastic electrodynamics, a theory obtained by truncating the equation of motion for the Wigner function, with a view to locating regions of agreement and disagreement between the two. We calculate commonly used measures of quantum behavior including entanglement, squeezing, and Einstein-Podolsky-Rosen (EPR) correlations as well as higher order tripartite correlations, and show how these are modified as the critical point is approached. These results are compared with those obtained using two degenerate parametric oscillators, and we find that in the near-critical region the nondegenerate oscillator has stronger EPR correlations. In general, the critical fluctuations represent an ultimate limit to the possible entanglement that can be achieved in a nondegenerate parametric oscillator.
Resumo:
Patellamide D (patH(4)) is a cyclic octapeptide isolated from the ascidian Lissoclinum patella. The peptide possesses a 24-azacrown-8 macrocyclic structure containing two oxazoline and two thiazole rings, each separated by an amino acid. The present spectrophotometric, electron paramagnetic resonance (EPR) and mass spectral studies show that patellamide D reacts with CuCl, and triethylamine in acetonitrile to form mononuclear and binuclear copper(II) complexes containing chloride. Molecular modelling and EPR studies suggest that the chloride anion bridges the copper(II) ions in the binuclear complex [Cu-2(patH(2))(mu-Cl)](+). These results contrast with a previous study employing both base and methanol, the latter substituting for chloride in the copper(II) complexes en route to the stable mu-carbonato binuclear copper(II) complex [Cu-2 (patH(2))(mu-CO3)]. Solvent clearly plays an important role in both stabilising these metal ion complexes and influencing their chemical reactivities. (C) 2004 Elsevier Inc. All rights reserved.
Resumo:
Recent experimental measurements of atomic intensity correlations through atom shot noise suggest that atomic quadrature phase correlations may soon be measured with a similar precision. We propose a test of local realism with mesoscopic numbers of massive particles based on such measurements. Using dissociation of a Bose-Einstein condensate of diatomic molecules into bosonic atoms, we demonstrate that strongly entangled atomic beams may be produced which possess Einstein-Podolsky-Rosen (EPR) correlations in field quadratures in direct analogy to the position and momentum correlations originally considered by EPR.
Resumo:
The basis for the neuroprotectant effect of D-mannitol in reducing the sensory neurological disturbances seen in ciguatera poisoning, is unclear. Pacific ciguatoxin-1 (P-CTX-1), at a concentration 10 nM, caused a statistically significant swelling of rat sensory dorsal root ganglia (DRG) neurons that was reversed by hyperosmolar 50 MM D-mannitol. However, using electron paramagnetic resonance (EPR) spectroscopy, it was found that P-CTX-1 failed to generate hydroxyl free radicals at concentrations of toxin that caused profound effects on neuronal excitability. Whole-cell patch-clamp recordings from DRG neurons revealed that both hyper- and iso-osmolar 50 MM D-mannitol prevented the membrane depolarisation and repetitive firing of action potentials induced by P-CTX-1. In addition, both hyper- and iso-osmolar 50 MM D-mannitol prevented the hyperpolarising shift in steady-state inactivation and the rise in leakage current through tetrodotoxin (TTX)-sensitive Na-v channels, as well as the increased rate of recovery from inactivation of TTX-resistant Nav channels induced by P-CTX-1. D-Mannitol also reduced, but did not prevent, the inhibition of peak TTX-sensitive and TTX-resistant I-Na amplitude by P-CTX-1. Additional experiments using hyper- and isoosmolar D-sorbitol, hyperosmolar sucrose and the free radical scavenging agents Trolox (R) and L-ascorbic acid showed that these agents, unlike D-mannitol, failed to prevent the effects of P-CTX-1 on spike electrogenesis and Na-v channel gating. These selective actions of D-mannitol indicate that it does not act purely as an osmotic agent to reduce swelling of nerves, but involves a more complex action dependent on the Nav channel subtype, possibly to alter or reduce toxin association. (c) 2005 Elsevier Ltd. All rights reserved.
Resumo:
We show that two evanescently coupled χ((2)) parametric down-converters inside a Fabry-Perot cavity provide a tunable source of quadrature squeezed light, Einstein-Podolsky-Rosen (EPR) correlations and quantum entanglement. Analyzing the operation in the below threshold regime, we show how these properties can be controlled by adjusting the coupling strengths and the cavity detunings. As this can be implemented with integrated optics, it provides a possible route to rugged and stable EPR sources.
Resumo:
Significant new insights into the interactions of the potent insulin-enhancing compound bis(maltolato)oxovanadium(IV) (BMOV) with the serum proteins, apo-transferrin and albumin, are presented. Identical reaction products are observed by electron paramagnetic resonance (EPR) with either BMOV or vanadyl sulfate (VOSO4) in solutions of human serum apo-transferrin. Further detailed study rules out the presence of a ternary ligand-vanadyl-transferrin complex proposed previously. By contrast, differences in reaction products are observed for the interactions of BMOV and VOSO4 with human serum albumin (HSA), wherein adduct formation between albumin and BMOV is detected. In BMOV-albumin solutions, vanadyl ions are bound in a unique manner not observed in comparable solutions Of VOSO4 and albumin. Presentation of chelated vanadyl ions precludes binding at the numerous nonspecific sites and produces a unique EPR spectrum which is assigned to a BMOV-HSA adduct. The adduct species cannot be produced, however, from a solution Of VOSO4 and HSA titrated with maltol. Addition of maltol to a VOSO4-HSA solution instead results in formation of a different end product which has been assigned as a ternary complex, VO(ma)(HSA). Furthermore, analysis of solution equilibria using a model system of BMOV with 1-methylimidazole (formation constant log K = 4.5(1), by difference electronic absorption spectroscopy) lends support to an adduct binding mode (VO(ma)(2)-HSA) proposed herein for BMOV and HSA. This detailed report of an in vitro reactivity difference between VOSO4 and BMOV may have bearing on the form of active vanadium metabolites delivered to target tissues. Albumin binding of vanadium chelates is seen to have a potentially dramatic effect on pharmacokinetics, transport, and efficacy of these antidiabetic chelates.
Resumo:
The temperature dependence of the X-ray crystal structure and powder EPR spectrum of [(HC(Ph2PO)(3))(2)CU]-(ClO4)(2)center dot 2H(2)O is reported, and the structure at room temperature confirms that reported previously. Below similar to 100 K, the data imply a geometry with near elongated tetragonal symmetry for the [(HC(Ph2PO)(3))(2)Cu](2+) complex, but on warming the two higher Cu-O bond lengths and g-values progressively converge, and by 340 K the bond lengths correspond to a compressed tetragonal geometry. The data may be interpreted satisfactorily assuming an equilibrium among the energy levels of a Cu-O-6 polyhedron subjected to Jahn-Teller vibronic coupling and a lattice strain. However, agreement with the experiment is obtained only if the orthorhombic component of the lattice strain decreases to a negligible value as the temperature approaches 340 K.
Resumo:
We show that two evanescently coupled chi((2)) parametric oscillators provide a tunable bright source of quadrature squeezed light, Einstein-Podolsky-Rosen correlations and quantum entanglement. Analysing the system in the above threshold regime, we demonstrate that these properties can be controlled by adjusting the coupling strengths and the cavity detunings. As this can be implemented with integrated optics, it provides a possible route to rugged and stable EPR sources. (C) 2005 Elsevier B.V. All rights reserved.