Contractile and vasorelaxant effects of hydrogen sulfide and its biosynthesis in the human internal mammary artery

This study aimed to test these hypotheses: cystathionine gamma-lyase (CSE) is expressed in a human artery, it generates hydrogen sulfide (H2S), and H2S relaxes a human artery. H2S is produced endogenously in rat arteries from cysteine by CSE. Endogenously produced H2S dilates rat resistance arteries. Although CSE is expressed in rat arteries, its presence in human blood vessels has not been described. In this study, we showed that both CSE mRNA, determined by reverse transcription-polymerase chain reaction, and CSE protein, determined by Western blotting, apparently occur in the human internal mammary artery (internal thoracic artery). Artery homogenates converted cysteine to H2S, and the H2S production was inhibited by DL-propargylglycine, an inhibitor of CSE. We also showed that H2S relaxes phenylephrine-precontracted human internal mammary artery at higher concentrations but produces contraction at low concentrations. The latter contractions are stronger in acetylcholine-prerelaxed arteries, suggesting inhibition of nitric oxide action. The relaxation is partially blocked by glibenclamide, an inhibitor of K-ATP channels. The present results indicate that CSE protein is expressed in human arteries, that human arteries synthesize H2S, and that higher concentrations of H2S relax human arteries, in part by opening K-ATP channels. Low concentrations of H2S contract the human internal mammary artery, possibly by reacting with nitric oxide to form an inactive nitrosothiol. The possibility that CSE, and the H2S it generates, together play a physiological role in regulating the diameter of arteries in humans, as has been demonstrated in rats, should be considered.

Collective decoherence of cold atoms coupled to a Bose-Einstein condensate

We examine the time evolution of cold atoms (impurities) interacting with an environment consisting of a degenerate bosonic quantum gas. The impurity atoms differ from the environment atoms, being of a different species. This allows one to superimpose two independent trapping potentials, each being effective only on one atomic kind, while transparent to the other. When the environment is homogeneous and the impurities are confined in a potential consisting of a set of double wells, the system can be described in terms of an effective spin-boson model, where the occupation of the left or right well of each site represents the two (pseudo)-spin states. The irreversible dynamics of such system is here studied exactly, i.e. not in terms of a Markovian master equation. The dynamics of one and two impurities is remarkably different in respect of the standard decoherence of the spin-boson system. In particular, we show: (i) the appearance of coherence oscillations, (ii) the presence of super and subdecoherent states that differ from the standard ones of the spin-boson model, and (iii) the persistence of coherence in the system at long times. We show that this behaviour is due to the fact that the pseudospins have an internal spatial structure. We argue that collective decoherence also prompts information about the correlation length of the environment. In a one-dimensional (1D) configuration, one can change even more strongly the qualitative behaviour of the dephasing just by tuning the interaction of the bath.

Assembly of a coordination cage with four aromatic channel receptors on the outside

Silver salts and triphosphine ligands with biphenyl substituents assemble to give coordination cages with four external aromatic channel receptors in a pseudo-tetrahedral arrangement.

A TMA De-Arraying Method for High Throughput Biomarker Discovery in Tissue Research

Background: Tissue MicroArrays (TMAs) represent a potential high-throughput platform for the analysis and discovery of tissue biomarkers. As TMA slides are produced manually and subject to processing and sectioning artefacts, the layout of TMA cores on the final slide and subsequent digital scan (TMA digital slide) is often disturbed making it difficult to associate cores with their original position in the planned TMA map. Additionally, the individual cores can be greatly altered and contain numerous irregularities such as missing cores, grid rotation and stretching. These factors demand the development of a robust method for de-arraying TMAs which identifies each TMA core, and assigns them to their appropriate coordinates on the constructed TMA slide.

Methodology: This study presents a robust TMA de-arraying method consisting of three functional phases: TMA core segmentation, gridding and mapping. The segmentation of TMA cores uses a set of morphological operations to identify each TMA core. Gridding then utilises a Delaunay Triangulation based method to find the row and column indices of each TMA core. Finally, mapping correlates each TMA core from a high resolution TMA whole slide image with its name within a TMAMap.

Conclusion: This study describes a genuine robust TMA de-arraying algorithm for the rapid identification of TMA cores from digital slides. The result of this de-arraying algorithm allows the easy partition of each TMA core for further processing. Based on a test group of 19 TMA slides (3129 cores), 99.84% of cores were segmented successfully, 99.81% of cores were gridded correctly and 99.96% of cores were mapped with their correct names via TMAMaps. The gridding of TMA cores were also extensively tested using a set of 113 pseudo slide (13,536 cores) with a variety of irregular grid layouts including missing cores, rotation and stretching. 100% of the cores were gridded correctly.

Bioaccessibility of trace elements in soils in Northern Ireland

Assessment of elevated concentrations of potentially toxic elements (PTE) in soils and the association with specific soil parent material have been the focus of research for a number of years. Risk-based assessment of potential exposure scenarios to identified elevated PTE concentrations has led to the derivation of site- and contaminant-specific soil guideline values (SGVs), which represent generic assessment criteria (GACs) to identify exceeded levels that may reflect an unacceptable risk to human health. A better understanding of the ‘bioavailable’ or ‘bioaccessible’ contaminant concentrations offers an opportunity to better refine contaminant exposure assessments. Utilizing a comprehensive soil geochemical dataset for Northern Ireland provided by the Tellus Survey (GSNI) in conjunction with supplementary bioaccessibility testing of selected soil samples following the Unified BARGE Method, this paper uses exploratory data analysis and geostatistical analysis to investigate the spatial variability of pseudo-total and bioaccessible concentrations of As, Cd, Co, Cr. Cu, Ni, Pb, U, V and Zn. The paper investigates variations in individual element concentrations as well as cross-element correlations and observed lithological/pedological associations. The analysis of PTE concentrations highlighted exceeded levels of GAC values for V and Cr and exceeded SGV/GAC values for Cd, Cu, Ni, Pb, and Zn. UBM testing showed that for some soil parent materials associated with elevated PTE concentrations e.g. the Antrim Lava Group with high Ni concentrations, the measured oral bioaccessible fraction was relatively low. For other soil parent materials with relatively moderate PTE concentrations, measured oral bioaccessible fraction was relatively high (e.g. the Gala Sandstone Group of the Southern Uplands-Down Longford Terrain). These findings have implications for regional human health risk assessments for specific PTEs.

Retention of toxic chromium from aqueous phase by H3PO4-activated lignin: Effect of salts and desorption studies

In this study, the feasibility of using H₃PO₄-activated lignin for hexavalent chromium adsorption has been investigated. The composite of activated lignin was characterized using FTIR, XRD and SEM with EDAX analysis. It was observed that the pH had a strong effect on the adsorption capacity; adsorption of Cr(VI) was more favorable at acidic pH with maximum uptake at pH 2. The adsorption equilibrium data were best represented by Koble-Corrigan isotherm. The monolayer sorption capacity obtained from the Langmuir model was found to be 77.85 mg/g. Adsorption showed pseudo-second order rate kinetics and the process involving the rate-controlling step is complex as it involves both film and intraparticle diffusion processes. The NaOH desorbing agent was able to release approximately 84% of metal ions. Thermodynamic parameters showed that the sorption process is exothermic and non-spontaneous. The overall Cr(VI) retention on the activated lignin surface perhaps includes both the physical adsorption of Cr(VI) and the consequent reduction of Cr(VI) to Cr(III). (C) 2011 Elsevier B.V. All rights reserved.

Biosorption of toxic chromium from aqueous phase by lignin: mechanism, effect of other metal ions and salts

Surface reaction methodology was implicated in the optimization of hexavalent chromium removal onto lignin with respect to the process parameters. The influence of altering the conditions for removal of chromium(VI), for instance; solution pH, ionic strength, initial concentration, the dose of biosorbent, presence of other metals (Zn and Cu), presence of salts and biosorption-desorption studies, were investigated. It was found that the biosorption capacity of lignin depends on solution pH, with a maximum biosorption capacity for chromium at pH 2. Experimental equilibrium data were fitted to five different isotherm models by non-linear regression method, however, the biosorption equilibrium data were well interpreted by the Freundlich isotherm. The maximum biosorption capacities (q(max)) obtained using Dubinin-Radushkevich and Khan isotherms for Cr(VI) biosorption are 31.6 and 29.1 mg/g. respectively. Biosorption showed pseudo second order rate kinetics at different initial concentrations of Cr(VI). The intraparticle diffusion study indicated that film diffusion may be involved in the current study. The percentage removal of chromium on lignin decreased significantly in the presence of NaHCO3 and K2P2O7 salts. Desorption data revealed that nearly 70% of the Cr(VI) adsorbed on lignin could be desorbed using 0.1 M NaOH. It was evident that the biosorption mechanism involves the attraction of both hexavalent chromium (anionic) and trivalent chromium (cationic) onto the surface of lignin. (C) 2011 Elsevier B.V. All rights reserved.

Electron-impact excitation of CrII: A theoretical calculation of effective collision strengths for optically allowed transitions.

In this paper, we present electron-impact excitation collision strengths and Maxwellian averaged effective collision strengths for the complicated iron-peak ion Cr II. We consider specifically the allowed lines for transitions from the 3d(5) and 3d(4)4s even parity configuration states to the 3d(4)4p odd parity configuration levels. The parallel suite of R-Matrix packages, RMATRX II, which have recently been extended to allow for the inclusion of relativistic effects, were used to compute the collision cross sections. A total of 108 LS pi/280 J pi levels from the basis configurations 3d(5), 3d(4)4s, and 3d(4)4p were included in the wavefunction representation of the target including all doublet, quartet, and sextet terms. Configuration interaction and correlation effects were carefully considered by the inclusion of seven more configurations and a pseudo-corrector (4d) over bar type orbital. The 10 configurations incorporated into the Cr II model thus listed are 3d(5), 3d(4)4s, 3d(4)4p, 3d(3)4s(2), 3d(3)4p(2), 3d(3)4s4p, 3d(4)(4d) over bar, 3d(3)4s (4d) over bar, 3d(3)4p (4d) over bar, and 3d(3)(4d) over bar (2), constituting the largest Cr II target model considered to date in a scattering calculation. The Maxwellian averaged effective collision strengths are computed for a wide range of electron temperatures 2000-100,000 K which are astrophysically significant. Care has been taken to ensure that the partial wave contributions to the collision strengths for these allowed lines have converged with "top-up" from the Burgess-Tully sum rule incorporated. Comparisons are made with the results of Bautista et al. and significant differences are found for some of the optically allowed lines considered.

Carbon Isotopic Fractionation of CFCs during Abiotic and Biotic Degradation

Carbon stable isotope ((13)C) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 °C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (t(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 ± 0.5) × 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to t(1/2) = 17.3 h and k(SA) = -(1.2 ± 0.5) × 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of e(‰) = -5.0 ± 0.3 (CFC-113) and -17.8 ± 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of ?(13)C ~ -13‰ (HCFC-22), ?(13)C ~ -35‰ (CFC-12) and ?(13)C ~ -15‰ (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation.

THE ROLE OF H+ AND H-3+ IONS IN THE DEGRADATION OF INTERSTELLAR-MOLECULES

The results of recent laboratory studies of the reactions of H+ and H-3+ with a number of molecular gases are interpreted from the viewpoint of interstellar chemistry. Many of the reactions of these ions result in the ionization and fragmentation of neutral reactant gases. Pseudo-time-dependent calculations of the chemistry in dense molecular clouds indicate that molecular abundances are reduced by the inclusion of such reactions, but generally by less than a factor of 5.

GAS-PHASE REACTIONS AND RATE COEFFICIENTS FOR USE IN ASTROCHEMISTRY - THE UMIST RATEFILE

We present the rate coefficients of 2880 gas-phase reactions among 313 species involving 12 elements for use in astrochemical models. We describe the motivation behind this work and the caveats which attach to the data in general as well as to specific reactions. We give the permanent electric dipole moments of nearly all the 112 neutral molecules contained in the data set, so that rate coefficients can be calculated at the low temperatures of dark interstellar dust clouds. We have used the data to calculate the pseudo-time-dependent chemical evolution of a dark, dense interstellar cloud and present both early time and steady-state abundances for all 313 species.

bis-cis-dihydrodiols: A new class of metabolites resulting from biphenyl dioxygenase-catalyzed sequential asymmetric cis-dihydroxylation of polycyclic arenes and heteroarenes

The biphenyl dioxygenase-catalyzed asymmetric mono-cis-dihydroxylation of the tetracyclic arenes chrysene 1A, benzo[c]phenanthridine 1B, and benzo[b]naphtho[2,1-d]thiophene 1C, has been observed to occur exclusively at the bay or pseudo-bay region using the bacterium Sphingomonas yanoikuyae B8/36. The mono-cis-dihydrodiol derivatives 2A and 2C, obtained from chrysene 1A by oxidation at the 3,4-bond (2A) and benzo[b]naphtho[2,1-d]thiophene 1C by oxidation at the 1,2-bond (2C), respectively, have been observed to undergo a further dioxygenase-catalyzed asymmetric cis-dihydroxylation at a second bay or pseudo-bay region bond to yield the corresponding bis-cis-dihydrodiols (cis-tetraols) 4A and 4C, the first members of a new class of microbial metabolites in the polycyclic arene series. The enantiopurities and absolute configurations of the new mono-cis-dihydrodiols 2B, 2C, and 3B were determined by H-1 NMR analyses of the corresponding (R)- and (S)-2-(1-methoxyethyl)benzeneboronate (MPBA) ester derivatives. The structure and absolute configurations of the bis-cis-dihydrodiols 4A and 4C were unambiguously determined by spectral analyses, stereochemical correlations, and, for the metabolite 4C, X-ray crystallographic analysis of the bis-acetonide derivative 7C. These results illustrate the marked preference of biphenyl dioxygenase for the cis-di- and tetra-hydroxylations of polycyclic arenes, at the more hindered bay or pseudo-bay regions, by exclusive addition from the same (si:si) face, to yield single enantiomers containing two and four chiral centers.

A Robust Co-Localisation Measurement Utilising Z-Stack Image Intensity Similarities for Biological Studies

Background: Co-localisation is a widely used measurement in immunohistochemical analysis to determine if fluorescently labelled biological entities, such as cells, proteins or molecules share a same location. However the measurement of co-localisation is challenging due to the complex nature of such fluorescent images, especially when multiple focal planes are captured. The current state-of-art co-localisation measurements of 3-dimensional (3D) image stacks are biased by noise and cross-overs from non-consecutive planes.

Method: In this study, we have developed Co-localisation Intensity Coefficients (CICs) and Co-localisation Binary Coefficients (CBCs), which uses rich z-stack data from neighbouring focal planes to identify similarities between image intensities of two and potentially more fluorescently-labelled biological entities. This was developed using z-stack images from murine organotypic slice cultures from central nervous system tissue, and two sets of pseudo-data. A large amount of non-specific cross-over situations are excluded using this method. This proposed method is also proven to be robust in recognising co-localisations even when images are polluted with a range of noises.

Results: The proposed CBCs and CICs produce robust co-localisation measurements which are easy to interpret, resilient to noise and capable of removing a large amount of false positivity, such as non-specific cross-overs. Performance of this method of measurement is significantly more accurate than existing measurements, as determined statistically using pseudo datasets of known values. This method provides an important and reliable tool for fluorescent 3D neurobiological studies, and will benefit other biological studies which measure fluorescence co-localisation in 3D.

The initial mode of action of copper on the cardiac physiology of the blue mussel, Mytilus edulis

Previous studies have shown that low levels of copper (down to 0.8 muM) induce bradycardia in the blue mussel (Mytilus edulis) and that this is not caused by prolonged Valve closure. The aim of this study was to determine the precise mechanism responsible. To establish if copper was directly affecting heart cell physiology, recordings of contractions from isolated ventricular strips were made using an isometric force transducer, in response to copper concentrations (as CuCl2) ranging between 1 muM and 1 mM. Inhibition of mechanical activity only occurred at 1 mM copper, suggesting that the copper-induced bradycardia observed in whole animals cannot be attributed to direct cardiotoxicity. Effects of copper on the cardiac nerves were subsequently examined. Following removal of visceral ganglia (from where the cardiac nerves originate), exposure to 12.5 muM copper had no effect on the heart rate of whole animals. The effect of copper on the heart rate of mussels could not be abolished by depletion of the monoamine content of the animal using reserpine. However, pre-treatment of the animals with alpha -bungarotoxin considerably reduced the sensitivity of the heart to copper. These results indicated that the influence of copper on the heart of M. edulis might be mediated by a change in the activity of cholinergic nerves to heart. In the final experiments, mussels were injected with either benzoquinonium or D-tubocurarine, prior to copper exposure, in an attempt to selectively block the inhibitory or excitatory cholinoreceptors of the heart. Only benzoquinonium decreased the susceptibility of the heart to copper, suggesting that copper affects the cardiac activity of blue mussels by stimulating inhibitory cholinergic nerves to the heart. (C) 2001 Elsevier Science B.V. All rights reserved.

Dependence of the kinetics of liquid-phase photocatalyzed reactions on oxygen concentration and light intensity

The initial kinetics of the oxidation of 4-chlorophenol, 4-CP, photocatalyzed by titania films and aqueous dispersions were studied as a function of oxygen partial pressure, P-O2, and incident light intensity, I. The reaction conditions were such that the kinetics were independent of [4-CP] but strongly dependent on PO2-a situation that allowed investigation of the less-often studied kinetics of oxygen reduction. The observed kinetics fit a pseudo-steady-state model in which the oxygen is Langmuir-adsorbed on the titania photocatalyst particles before being reduced by photogenerated electrons. The maximum rate of photocatalysis depends directly on I-beta, where, beta = 1 for films and 0.7 for dispersions of titania, indicating that the kinetics are dominated by the surface reactions of the photogenerated electrons and holes for the films and by direct recombination for the powder dispersions. Using the pseudo-first-order model, for both titania films and dispersions, the apparent Langmuir adsorption constant, K-LH, derived from a Langmuir-Hinshelwood analysis of the kinetics, appears to be largely independent of incident light intensity, unlike KLH for 4-CP Consequently, similar values are obtained for the Langmuir adsorption constant, K-ads, extracted from a pseudosteady-state analysis of the kinetics for oxygen on TiO2 dispersions and films in aqueous solution (i.e., ca. 0.0265 +/- 0.005 kPa(-1)), and for both films and dispersions, oxygen appears to be weakly adsorbed on TiO2 compared with 4-CP, at a rate that would take many minutes to reach equilibrium. The value of Kads for oxygen on titania particles dispersed in solution is ca. 4.7 times lower than that reported for the dark Langmuir adsorption isotherm; possible causes for this difference are discussed. (c) 2006 Elsevier Inc. All rights reserved.