Synthesis, structure and magnetism of the oxalato-bridged chromium(III) complex [NBu4n](4)[Cr-2(ox)(5)]center dot 2CHCl(3)

The binuclear complex [NBu4n](4)[Cr-2(ox)(5)]. 2CHCl(3) has been prepared by an ion-exchange procedure employing Dowex 50WX2 cation-exchange resin in the n-butylammonium form and potassium tris(oxalato)chromate(III). The dimeric complex was characterised by a crystal structure determination: monoclinic, space group C2/c, a = 29.241(7), b = 15.192(2), c = 22.026(5) Angstrom, beta = 94.07(1)degrees, Z = 4. The magnetic susceptibility (300-4.2 K) indicated that the chromium(III) sites were antiferromagnetically coupled (J = -3.1 cm(-1)).

Nickel complexes with tris(2-aminoethyl)amine (tren): [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2)center dot 6H(2)O (ox = oxalate), {[Ni-2(tren)(3)][ClO4](4)center dot H2O}(n), and [Ni-2(tren)(2)(aepd)][ClO4](4)center dot 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidi

Reaction of K-3[Cr(ox)(3)] (ox = oxalate) with nickel(II) and tris(2-aminoethyl)amine (tren) in aqueous solution resulted in isolation of the bimetallic assembly [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O. The polymeric complex {[Ni-2(tren)(3)][ClO4](4). H2O}(n) has been prepared by reaction of nickel(II) perchlorate and tren in aqueous solution. From the same reaction mixture the complex [Ni-2(tren)(2)(aepd)][ClO4](4). 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine), in which a bridging tren ligand contains a carbon-carbon bond between two arms forming a substituted pyrrolidine, has been isolated. The complexes have been characterized by X-ray crystallography. The magnetic susceptibility (300-4.2 K) and magnetization data (2, 4 K, H = 0-5 T) for {[Ni-2(tren)(3)][ClO4](4). H2O}(n) (300 K , 4.23 mu(B)) exhibit evidence of weak antiferromagnetic coupling and zero field splitting (2J = -1.8 cm(-1); \ D\ = 2 cm(-1)) at low temperature. For [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O the susceptibility data at 300 K are indicative of uncoupled nickel(II) and chromium(III) sites with zero-field splitting and intramolecular antiferromagnetic coupling predicted at low temperature.

Temperature dependence of the crystal structure and g-values of [(HC(Ph2PO)(3))(2)Cu] (ClO4)(2)center dot 2H(2)O: Influence of dynamic Jahn-Teller coupling and lattice strain interactions

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.

Structural evolution in a hydrothermal reaction between Nb2O5 and NaOH solution: From Nb2O5 grains to microporous Na2Nb2O6 center dot(2)/3H2O fibers and NaNbO3 cubes

Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO7 decahedra and NbO6 octahedra in the reactant Nb2O5, yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb2O5 powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na2Nb2O6 center dot(2)/3H2O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO3 Cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb2O5. This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO6 octahedra, and then the microporous fibers crystallize and grow by assembling NbO6 octahedra or clusters of NbO6 octahedra and NaO6 units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.

Formation and growth mechanism of tungsten oxide microtubules

Tungsten oxide microtubules, arrayed in a radial flower-like structure, were synthesized by simply using W powders reacting with Ni(NO3)(2) center dot 6H(2)O at a elevated temperature. The formed microtubules, with lengths more than 100 pin and outer diameters of 1-5 mu m, have irregular open ends, showing clear grooves along the growth direction on the tubule surface. A novel aggregation mechanism based on chemical-vapor-deposit process was proposed to describe the growth process of the synthesized tubules, and the possible mechanism for the arrangement of the radial flower-like morphology was discussed.

Vascular smooth muscle relaxation mediated by nitric oxide donors: a comparison with acetylcholine, nitric oxide and nitroxyl ion

I Vasorelaxant properties of three nitric oxide (NO) donor drugs (glyceryl trinitrate, sodium nitroprusside and spermine NONOate) in mouse aorta (phenylephrine pre-contracted) were compared with those of endothelium-derived NO (generated with acetylcholine), NO free radical (NO; NO gas solution) and nitroxyl ion (NO-; from Angeli's salt). 2 The soluble guanylate cyclase inhibitor, ODQ (1H-(1,2,4-)oxadiazolo(4,3-a)-quinoxalin-1-one; 0.3, 1 and 10 muM), concentration-dependently inhibited responses to all agents. 10 muM ODQ abolished responses to acetylcholine and glyceryl trinitrate, almost abolished responses to sodium nitroprusside but produced parallel shifts (to a higher concentration range; no depression in maxima) in the concentration-response curves for NO gas solution, Angeli's salt and spermine NONOate. 3 The NO scavengers, carboxy-PTIO, (2-(4-carboxyphenyl)-4,4,5,5-tetramethyl-indazoline-1-oxyl-3-oxide; 100 muM) and hydroxocobalamin (100 muM), both inhibited responses to NO gas solution and to the three NO donor drugs, but not Angeli's salt. Hydroxocobalamin, but not carboxy-PTIO, also inhibited responses to acetylcholine. 4 The NO- inhibitor, L-cysteine (3 mm), inhibited responses to Angeli's salt, acetylcholine and the three NO donor drugs, but not NO gas solution. 5 The data suggest that, in mouse aorta, responses to all three NO donors involve (i) activation of soluble guanylate cyclase, but to differing degrees and (ii) generation of both NO and NO-. Glyceryl trinitrate and sodium nitroprusside, which generate NO following tissue bioactivation, have profiles resembling the profile of endothelium-derived NO more than that of exogenous NO. Spermine NONOate, which generates NO spontaneously outside the tissue, was the drug that most closely resembled (but was not identical to) exogenous NO.

Three distinct molecular surfaces in ephrin-A5 are essential for a functional interaction with EphA3

Eph receptor tyrosine kinases (Ephs) function as molecular relays that interact with cell surface-bound ephrin ligands to direct the position of migrating cells. Structural studies revealed that, through two distinct contact surfaces on opposite sites of each protein, Eph and ephrin binding domains assemble into symmetric, circular heterotetramers. However, Eph signal initiation requires the assembly of higher order oligomers, suggesting additional points of contact. By screening a random library of EphA3 binding-compromised ephrin-A5 mutants, we have now determined ephrin-A5 residues that are essential for the assembly of high affinity EphA3 signaling complexes. In addition to the two interfaces predicted from the crystal structure of the homologous EphB2 center dot ephrin-B2 complex, we identified a cluster of 10 residues on the ephrin-A5 E alpha-helix, the E-F loop, the underlying H beta-strand, as well as the nearby B - C loop, which define a distinct third surface required for oligomerization and activation of EphA3 signaling. Together with a corresponding third surface region identified recently outside of the minimal ephrin binding domain of EphA3, our findings provide experimental evidence for the essential contribution of three distinct protein-interaction interfaces to assemble functional EphA3 signaling complexes.

Phase equilibria in the system Fe-Zn-O at intermediate conditions between metallic-iron saturation and air

The phase equilibria in the FeO-Fe2O3-ZnO system have been experimentally investigated at oxygen partial pressures between metallic iron saturation and air using a specially developed quenching technique, followed by electron probe X-ray microanalysis (EPMA) and then wet chemistry for determination of ferrous and ferric iron concentrations. Gas mixtures of H-2, N-2, and CO2 or CO and CO2 controlled the atmosphere in the furnace. The determined metal cation ratios in phases at equilibrium were used for the construction of the 1200 degrees C isothermal section of the Fe-Zn-O system. The univariant equilibria between the gas phase, spinel, wustite, and zincite was found to be close to pO(2) = 1 center dot 10(-8) atm at 1200 degrees C. The ferric and ferrous iron concentrations in zincite and spinel at equilibrium were also determined at temperatures from 1200 degrees C to 1400 degrees C at pO(2) = 1 center dot 10(-6) atm and at 1200 degrees C at pO(2) values ranging from 1 center dot 10(-4) to 1 center dot 10(-8) atm. Implications of the phase equilibria in the Fe-Zn-O system for the formation of the platelike zincite, especially important for the Imperial Smelting Process (ISP), are discussed.

Incidence and risk factors associated with exertional rhabdomyolysis syndrome in National Hunt racehorses in Great Britain

A telephone survey of 51 National Hunt racing yards with 1140 horses in training was made in April and May 2003 to establish the incidence of exertional rhabdomyolysis syndrome during the previous year. A case-control study was used to investigate the risk factors for the syndrome in eight yards selected on the basis that cases had been confirmed by the analysis of serum muscle enzymes. The overall incidence of syndrome was 6 center dot 1 cases per 100 horses per year, and 55 per cent of the yards reported at least one case. The risk factors identified were sex, the average length of the training gallop, and the type of horse (steeplechaser, bumper/unraced or hurdler). There were no significant associations with the horses' temperament, age or Timeform rating.

Differential expression of muscle damage in humans following acute fast and slow velocity eccentric exercise

We sought to determine if the velocity of an acute bout of eccentric contractions influenced the duration and severity of several common indirect markers of muscle damage. Subjects performed 36 maximal fast (FST, n=8: 3.14 rad center dot s(-1)) or slow (SLW, n=7: 0.52 rad center dot s(-1)) velocity isokinetic eccentric contractions with the elbow flexors of the non-dominant arm. Muscle soreness, limb girth, plasma creatine kinase (CK) activity, isometric torque and concentric and eccentric torque at 0.52 and 3.14 rad center dot s(-1) were assessed prior to and for several days following the eccentric bout. Peak plasma CK activity was similar in SLW (4030 +/- 1029 U center dot l(-1)) and FST (5864 +/- 2664 U center dot l(-1)) groups, (p > 0.05). Both groups experienced similar decrement in all strength variables during the 48 hr following the eccentric bout. However, recovery occurred more rapidly in the FST group during eccentric (0.52 and 3.14 rad center dot s(-1)) and concentric (3.14 rad center dot s(-1)) post-testing. The severity of muscle soreness was similar in both groups. However, the FST group experienced peak muscle soreness 48 hr later than the SLW group (24 hr vs. 72 hr). The SLW group experienced a greater increase in upper arm girth than the FST group 20 min, 24 hr and 96 hr following the eccentric exercise bout. The contraction velocity of an acute bout of eccentric exercise differentially influences the magnitude and time course of several indirect markers of muscle damage.

Minimal disease activity for rheumatoid arthritis: A preliminary definition

Agreement on response criteria in rheumatoid arthritis (RA) has allowed better standardization and interpretation of clinical trial reports. With recent advances in therapy, the proportion of patients achieving a satisfactory state of minimal disease activity (MDA) is becoming a more important measure with which to compare different treatment strategies. The threshold for MDA is between high disease activity and remission and, by definition, anyone in remission will also be in MDA. True remission is still rare in RA; in addition, the American College of Rheumatology definition is difficult to apply in the context of trials. Participants at OMERACT 6 in 2002 agreed on a conceptual definition of minimal disease activity (MDA): "that state of disease activity deemed a useful target of treatment by both the patient and the physician, given current treatment possibilities and limitations." To prepare for a preliminary operational definition of MDA for use in clinical trials, we asked rheumatologists to assess 60 patient profiles describing real RA patients seen in routine clinical practice. Based on their responses, several candidate definitions for MDA were designed and discussed at the OMERACT 7 in 2004. Feedback from participants and additional on-site analyses in a cross-sectional database allowed the formulation of 2 preliminary, equivalent definitions of MDA: one based on the Disease Activity Score 28 (DAS28) index, and one based on meeting cutpoints in 5 out the 7 WHO/ILAR core set measures. Researchers applying these definitions first need to choose whether to use the DAS28 or the core set definition, because although each selects a similar proportion in a population, these are not always the same patients. In both MDA definitions, an initial decision node places all patients in MDA who have a tender joint count of 0 and a swollen joint count of 0, and an erythrocyte sedimentation rate (ESR) no greater than 10 mm. If this condition is not met: center dot The DAS28 definition places patients in MDA when DAS28

Relationship between laboratory-measured variables and heart rate during an ultra-endurance triathlon

The aim of the present study was to examine the relationship between the performance heart rate during an ultra-endurance triathlon and the heart rate corresponding to several demarcation points measured during laboratory-based progressive cycle ergometry and treadmill running. Less than one month before an ultra-endurance triathlon, 21 well-trained ultra-endurance triathletes (mean +/- s: age 35 +/- 6 years, height 1.77 +/- 0.05 in, mass 74.0 +/- 6.9 kg, (V) over dot O-2peak = 4.75 +/- 0.42 1 center dot min(-1)) performed progressive exercise tests of cycle ergometry and treadmill running for the determination of peak oxygen uptake ((V) over do O-2peak), heart rate corresponding to the first and second ventilatory thresholds, as well as the heart rate deflection point. Portable telemetry units recorded heart rate at 60 s increments throughout the ultra-endurance triathlon. Heart rate during the cycle and run phases of the ultra-endurance triathlon (148 +/- 9 and 143 +/- 13 beats center dot min(-1) respectively) were significantly (P < 0.05) less than the second ventilatory thresholds (160 +/- 13 and 165 +/- 14 beats center dot min(-1) respectively) and heart rate deflection points (170 +/- 13 and 179 +/- 9 beats center dot min(-1) respectively). However, mean heart rate during the cycle and run phases of the ultra-endurance triathlon were significantly related to (r = 0.76 and 0.66; P < 0.01), and not significantly different from, the first ventilatory thresholds (146 +/- 12 and 148 +/- 15 beats center dot min(-1) respectively). Furthermore, the difference between heart rate during the cycle phase of the ultra-endurance triathlon and heart rate at the first ventilatory threshold was related to marathon run time (r = 0.61; P < 0.01) and overall ultra-endurance triathlon time (r = 0.45; P < 0.05). The results suggest that triathletes perform the cycle and run phases of the ultra-endurance triathlon at an exercise intensity near their first ventilatory threshold

Leukocyte subset responses during exercise under heat stress with carbohydrate or water intake

Purpose: This study investigated leukocyte subset responses to moderate-intensity exercise under heat stress, with water (W) or carbohydrate (CHO) drink ingestion. Methods: In repeated trials, 13 soldiers consumed either a W or CHO drink during 3 h of walking at 4.4 km center dot h(-1) with a 5% gradient (15 min rest per hour) under heat stress (35 C and 55% relative humidity). The soldiers wore combat uniforms and carried water bottles and dummy rifles and ammunition, altogether weighing about 11.5 +/- 1.0 kg. Results: Plasma glucose concentration was significantly higher with CHO than W ingestion during exercise (p < 0.01). There were no significant differences between W and CHO conditions in exercise performance, plasma cortisol concentration, heart rate, or core temperature. CHO ingestion significantly moderated the increases in leukocyte (83% in W, 28% in CHO; p < 0.001), monocyte (60% in W, 34% in CHO; p < 0.05), and granulocyte counts (120% in W, 30% in CHO; p < 0.001), but not in lymphocyte count (41% in W, 25% in CHO). Conclusions: The increases in leukocyte and subset counts during moderate-intensity exercise under heat stress may be comparable to those observed during intense exercise in cool conditions. The response of immune cell counts is blunted by CHO intake during moderate-intensity exercise in the heat, and may not occur through the cortisol pathway.

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes

The effects of pressure and temperature on the energy (E-op) of the metal-to-metal charge transfer (MMCT, Fe-II --> Co-III) transition of the cyano-bridged complexes trans - [(LCoNCFe)-Co-14(CN)(5)](-) and cis-[(LCoNCFe)-Co-14(CN)(5)](-) (where L-14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) were examined. The changes in the redox potentials of the cobalt and iron metal centres with pressure and temperature were also examined and the results interpreted with Marcus Hush theory. The observed redox reaction volumes can mainly be accounted for in terms of localised electrostriction effects. The shifts in E-op due to both pressure and temperature were found to be less than the shifts in the energy difference (E degrees) between the Co-III-Fe-II and Co-II-Fe-III redox isomers. The pressure and temperature dependence of the reorganisational energy, as well as contributions arising from the different spin states of Co-II, are discussed in order to account for this trend. To study the effect of pressure on Co-III electronic absorption bands, a new cyano-bridged complex, trans - [(LCoNCCo)-Co-14(CN)(5)], was prepared and characterised spectroscopically and structurally. X-Ray crystallography revealed this complex to be isostructural with trans -[(LCoNCFe)-Co-14(CN)(5)] center dot 5H(2)O.

The efficacy of a vitamin D-3 metabolite for improving the myofibrillar tenderness of meat from Bos indicus cattle

The influence of a once only administration of a metabolite of vitamin D-3 (HY center dot D-(R)-25-hydroxy vitamin D-3) on myofibrillar meat tenderness in Australian Brahman cattle was studied. Ninety-six Brahman steers of three phenotypes (indo-Brazil, US and US/European) and with two previous hormonal growth promotant (HGP) histories (implanted or not implanted with Compudose((R))) were fed a standard feedlot ration for 70 d. Treatment groups of 24 steers were offered daily 10 g/head HY center dot D-(R) (125 mg 25-hydroxyvitamin D-3) for 6, 4, or 2 d before slaughter. One other group of 24 steers was given the basal diet without HY center dot D-(R). Feed lot performance, blood and muscle samples and carcass quality data were collected at slaughter. Calcium, magnesium, potassium, sodium, iron and Vitamin D-3 metabolites were measured in plasma and longissimus dorsi muscle. Warner-Bratzler (WB) shear force (peak force, initial yield) and other objective meat quality measurements were made on the longissimus dorsi muscle of each steer after ageing for 1, 7 and 14 d post-mortem at 0-2 degrees C. There were no significant effects of HY center dot D-(R) supplements on average daily gain (ADG, 1.28-1.45 kg/d) over the experimental period. HY center dot D-(R) supplements given 6 d prior to slaughter resulted in significantly higher (P < 0.05) initial yield values compared to supplements given 2 d prior to slaughter. Supplementation had no significant effect on meat colour, ultimate pH, sarcomere length, cooking loss, instron compression or peak force. There was a significant treatment (HY center dot D-(R)) by phenotype/HGP interaction for peak force (P = 0.028), in which Indo-Brazil steers without previous HGP treatment responded positively (increased tenderness) to HY center dot D-(R) supplements at 2 d when compared with Indo-Brazil steers previously given HGP. There were no significant effects of treatment on other phenotypes. HY center dot D-(R) supplements did not affect muscle or plasma concentrations of calcium, potassium or sodium, but did significantly decrease plasma magnesium and iron concentrations when given 2 d before slaughter. There were no detectable amounts of 25-hydroxyvitamin D-3 in the blood or muscle of any cattle at slaughter. (c) 2005 Elsevier Ltd. All rights reserved.