An asymmetric homodinuclear complex containing the mu-x-oxobis(mu-x-carboxylato)diruthenium(III) core: X-ray structure of [Ru20(o2ec6H4-p-OMe)3(en) (PPh3)2] (C104)" 3CHC13

Asymmetric tri-bridged diruthenium(III) complexes, [Ru2O(O(2)CR)(3)(en) (PPh(3))(2)](ClO4) (R = C6H4-p-X: X = OMe (1a), Me (1b); en=1,2-diaminoethane), were prepared and structurally characterized. Complex 1a 3CHCl(3), crystallizes in the triclinic space group P (1) over bar with a = 14.029(5), b = 14.205(5), c = 20.610(6) Angstrom, alpha= 107.26(3), beta = 101.84(3), gamma= 97.57(3)degrees, V= 3756(2) Angstrom(3) and Z = 2. The complex has an {Ru-2(mu-O)(mu-O(2)CR)(2)(2+)} core and exhibits [O4PRu(mu-O)RuPO2N2](+) coordination environments for the metal centers. The novel structural feature is the asymmetric arrangement of ligands at the terminal sites of the core which shows an Ru... Ru separation of 3.226(3) Angstrom and an Ru-O-Ru angle of 119.2(5)degrees. An intense visible band observed near 570 nm is assigned to a charge transfer transition involving the d pi-Ru(III) and p pi-mu-O Orbitals. Cyclic voltammetry of the complexes displays a reversible Ru-2(III,III) reversible arrow Ru-2(III,IV) couple near 0.8 V (versus SCE) in MeCN-0.1 M TBAP.

Micropillar compression studies on a bulk metallic glass in different structural states

Uniaxial compression experiments on 0.3, 1 and 3 mu m diameter micropillars of a Zr-based bulk metallic glass in as-cast, shot-peened and structurally relaxed conditions were conducted. Shear band formation and stable propagation is observed to be the plastic deformation mode in all cases, with no detectable difference in yield strength according to either size or condition. The limitations of uniaxial compression tests in assessing the influence of various material conditions on plasticity, when it is inhomogeneous in nature, are illustrated.

Structure of the disodium salt of glucose 1-phosphate hydrate, 2Na+.C6H11O9P2-.3.5H2O

Mr= 367.2, monoclinic, C2, a = 8.429 (1),b= 10.184(2), c= 16.570(2)A, /~= 99.18 (1) °, U= 1404.2 A 3, z = 4, D m = 1.73, D x = 1.74 Mg m -3,Cu K~, 2 = 1.5418 A, g = 2.99 mm -1, F(000) = 764,T= 300K, final R for 1524 observed reflections is0.069. The endocyclic C-O bonds in the glucose ring are nearly equal with C(5)-O(5)= 1.445 (10) and C(1)-O(5)= 1.424(10). The pyranose sugar ring adopts a 4C 1 chair conformation. The conformation about the exocyclic C(5)-C(6) bond is gauche-gauche, in contrast to gauche-trans observed in the structure of the dipotassium salt of glucose 1-phosphate. The phosphate ester bond, P-O(1), is 1.641 (6)A, slightly longer than the 'high-energy' P-,.O bond in the monopotassium salt of phosphoenolpyruvate [1.612 (6)A]. Two sodium ions are six coordinated while the third has only five neighbours.

Origin of anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films

Anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films are established as being due to photochemical modification of the surfaces, by photoemission studies. Mass measurements indicate that the giant thickness reduction on irradiation is predominantly due to the loss of material as a result of photogenerated volatile high vapor pressure oxide fractions on the surface. This extrinsic contribution contradicts the models of the phenomenon proposed so far, which are based purely on intrinsic structural transformations.

Purification and partial characterization of microsomal cytochrome b555 from the higher plant Catharanthus-Roseus

Microsomal b-type hemoprotein designated, cytochrome b555 of C-Roseus seedlings was solubilized using detergents and purified by a combination of ion exchange chromatography and gel filtration to a specific content of 18.5 nmol per mg of protein. The purified cytochrome b555 was homogeneous and estimated to have an apparent molecular weight of 16500 on SDS-PAGE. The absorption spectrum of the reduced form has major peaks at 424, 525 and 555 nm. The α-band of the reduced form is asymmetric with a pronounced shoulder at 559 nm. The spectrum of the pyridine ferrohemochrome shows absorption peaks at 557, 524 and 418 nm indicating that the cytochrome has protoheme prosthetic group. The purified cytochrome is autoxidizable and does not combine with carbon monoxide, azide or cyanide. It is reducible by NADH in the presence of NADH-cytochrome b555 reductase partially purified from C-Roseus microsomes.

Drag reduction by a forward facing aerospike for a large angle blunt cone in high enthalpy flows

Drag reduction studies are conducted using a flat disc tipped aerospike for a 120-degree apex angle blunt cone model in high enthalpy flows. Accelerometer based force balance is used for the drag force measurement in the newly established free piston driven shock tunnel, HST3. Drag reduction upto about 58 percent has been achieved for Mach 8 flow of 5 MJ/kg specific enthalpy at zero degree angle of attack.

Detection,amplification and sequence homology of sodC in clinical isolates of Salmonella sp

Background & objectives: Periplasmic copper and zinc superoxide dismutase (Cu,Zn-SOD or SodC) is an important component of the antioxidant shield which protects bacteria from the phagocytic oxidative burst. Cu,Zn-SODs protect Gram-negative bacteria against oxygen damage which have also been shown to contribute to the pathogenicity of these bacterial species. We report the presence of SodC in drug resistant Salmonella sp. isolated from patients suffering from enteric fever. Further sodC was amplified, cloned into Escherichia coli and the nucleotide sequence and amino acid sequence homology were compared with the standard strain Salmonella Typhimurium 14028. Methods: Salmonella enterica serovar Typhi (S. Typhi) and Salmonellaenterica serovar Paratyphi (S. Paratyphi) were isolated and identified from blood samples of the patients. The isolates were screened for the presence of Cu, Zn-SOD by PAGE using KCN as inhibitor of Cu,Zn-SOD. The gene (sodC) was amplified by PCR, cloned and sequenced. The nucleotide and amino acid sequences of sodC were compared using CLUSTAL X.Results: SodC was detected in 35 per cent of the Salmonella isolates. Amplification of the genomic DNA of S. Typhi and S. Paratyphi with sodC specific primers resulted in 519 and 515 bp amplicons respectively. Single mutational difference at position 489 was observed between thesodC of S. Typhi and S. Paratyphi while they differed at 6 positions with the sodC of S. Typhimurium 14028. The SodC amino acid sequences of the two isolates were homologous but 3 amino acid difference was observed with that of standard strain S. Typhimurium 14028.Interpretation & conclusions: The presence of SodC in pathogenic bacteria could be a novel candidate as phylogenetic marker.

Generalization of Dynkin's Identity and Some Applications

Let X(t) be a right continuous temporally homogeneous Markov pro- cess, Tt the corresponding semigroup and A the weak infinitesimal genera- tor. Let g(t) be absolutely continuous and r a stopping time satisfying E.( S f I g(t) I dt) < oo and E.( f " I g'(t) I dt) < oo Then for f e 9iJ(A) with f(X(t)) right continuous the identity Exg(r)f(X(z)) - g(O)f(x) = E( 5 " g'(s)f(X(s)) ds) + E.( 5 " g(s)Af(X(s)) ds) is a simple generalization of Dynkin's identity (g(t) 1). With further restrictions on f and r the following identity is obtained as a corollary: Ex(f(X(z))) = f(x) + k! Ex~rkAkf(X(z))) + n-1E + (n ) )!.E,(so un-1Anf(X(u)) du). These identities are applied to processes with stationary independent increments to obtain a number of new and known results relating the moments of stopping times to the moments of the stopped processes.

Sensitive high-resolution ion microprobe U-Pb dating of prograde and retrograde ultrahigh-temperature metamorphism as exemplified by Sri Lankan granulites

Ultrahigh-temperature (UHT) granulites of the central Highland Complex, Sri Lanka, underwent some of the highest known peak temperatures of crustal metamorphism. Zircon and monazite U-Pb systems in granulites near Kandy, the highest grade region (similar to 1050 degrees C; 0.9 GPa), preserve both a record of the timing of prograde and retrograde phases of UHT metamorphism and evidence for the ages of older protolith components. Zircon grains from a quartz-saturated granulite containing relics of the peak UHT assemblage have remnant detrital cores with dates of ca. 2.5-0.83 Ga. Date clusters of ca. 1.7 and 1.04-0.83 Ga record episodes of zircon growth in the source region of the protolith sediment. Two generations of overgrowths with contrasting Th/U record metamorphic zircon growth at 569 +/- 5 and 551 +/- 7 Ma, probably in the absence and presence of monazite, respectively. The age of coexisting metamorphic monazite (547 +/- 7 Ma) is indistinguishable from that of the younger, low-Th/U zircon overgrowths. Zircon from a quartz-undersaturated monazite-absent UHT granulite with a mainly retrograde assemblage is mostly metamorphic (551 +/- 5 Ma). The ca. 570 Ma zircon overgrowths in the quartz-saturated granulite probably record partial melting just before or at the metamorphic peak. The ca. 550 Ma zircon in both rocks, and the ca. 550 Ma monazite in the quartz-saturated sample, record post-peak isothermal decompression. A possible model for this pressure-temperature-time evolution is ultrahot collisional orogeny during the assembly of Gondwana, locally superheated by basaltic underplating, followed by fast extensional exhumation.

NUcache: A Multicore Cache Organization Based on Next-Use Distance

In this work, we propose a new organization for the last level shared cache of a rnulticore system. Our design is based on the observation that the Next-Use distance, measured in terms of intervening misses between the eviction of a line and its next use, for lines brought in by a given delinquent PC falls within a predictable range of values. We exploit this correlation to improve the performance of shared caches in multi-core architectures by proposing the NUcache organization.

Effect of blocking oestrogen synthesis with a new generation aromatase inhibitor CGS 16949A on follicular maturation induced by pregnant mare serum gonadotrophin in the immature rat

While the endocrine role of oestrogen is well established, its function in follicular maturation as an autocrine or paracrine regulator is less well understood. This study was designed to delineate the requirement of oestrogen for follicular development in immature rats. Exogenous gonadotrophin (25 IU pregnant mare serum gonadotrophin (PMSG) per rat) was administered to 21- to 23-day old female rats to induce follicular growth and development. In the experimental animals, synthesis of oestrogen was blocked by implanting an Alzet pump containing the aromatase inhibitor (AI) CGS 16949A (fadrozole hydrochloride; 50 mu g/rat per day). The treatment resulted in blockade of the PMSG induced increase in both serum and intrafollicular oestrogen (>95%), thus leading to an inhibition in uterine weight increment. Compared with the controls, ovarian weight increased markedly in both the PMSG (295%)- and PMSG+AI (216%)-primed animals. There was no significant difference in either the proliferative capabilities of the ovarian granulosa cells or their responsiveness to human chorionic gonadotrophin (hCG; 200 pg/ml) and ovine FSH (20 ng/ml) between the PMSG- and PMSG+AI-treated groups. Histological examination of the ovary, however, indicated a decrease in the number of healthy antral follicles in the Al-treated group compared with the PMSG-primed animals but both the groups showed a percentage increase over the controls (PMSG, 225; PMSG+AI, 158). The responsiveness of the animals to an ovulatory dose of hCG was drastically reduced (>80% inhibition of ovulation) in the oestrogen-deprived animals; this could be overriden by exogenous administration of oestrogen. In conclusion, although blocking oestrogen synthesis in the PMSG-primed rat does not seem to alter the functional properties of the isolated granulosa cells in vitro there appears to be an effect on the number of follicles which complete maturation and are able to ovulate in vivo.

Dry sliding wear of Al alloy 2024-Al203 particle metal matrix composites

In the present investigation, Al 2024-15vol.%Al2O3 particulate (average size, 18 mu m) composites were fabricated using the liquid metallurgy route. The wear and friction characteristics of Al alloy 2024 and Al 2024-15vol.%Al2O3p, composite in the as-extruded and peak-aged conditions were studied using a pin-on-disc machine (with a steel disc as the counterface material). The worn surfaces, subsurfaces and the debris were analysed in a scanning electron microscope.The performance of the composite in the as-extruded condition is slightly inferior to that of the unreinforced alloy. However, in the T6 condition, although the wear rates of two materials are initially comparable, the unreinforced alloy seizes while the composite does not within the tested range employed. In the as-extruded condition, the presence of Al2O3 particles is not particularly beneficial as they fracture and result in extensive localized cracking and removal of material from the surface. In the peak-aged condition, however, while the unreinforced alloy exhibits severe plastic deformation and undergoes seizure, there is no significant change in the mechanism in the case of the composite. Except in the case of the peak-aged unreinforced alloy, worn surfaces of all other materials show the presence of an iron-rich layer.

Major depression with ischemic heart disease: Effects of paroxetine and nortriptyline on measures of nonlinearity and chaos of heart rate

Depression is associated with increased cardiovascular mortality in patients with preexisting cardiac illness. A decrease in cardiac vagal function as suggested by a decrease in heart rate variability (HRV) or heart period variability has been linked to sudden death in patients with cardiac disease as well as in normal controls. Recent studies have shown decreased vagal function in cardiac patients with depression as well as in depressed patients without cardiac illness. In this study, we compared 20 h awake and sleep heart period nonlinear measures using quantification of nonlinearity and chaos in two groups of patients with major depression and ischemic heart disease (mean age 59-60 years) before and after 6 weeks of treatment with paroxetine or nortriptyline. Patients received paroxetine, 20-30 mg/day or nortriptyline targeted to 190-570 nmol/l for 6 weeks. For HRV analysis, 24 patients were included in the paroxetine treatment study and 20 patients in the nortriptyline study who had at least 20,000 s of awake data. The ages of these groups were 60.4 +/- 10.5 years for paroxetine and 60.8 +/- 13.4 years for nortriptyline. There was a significant decrease in the largest Lyapunov exponent (LLE) after treatment with nortriptyline but not paroxetine. There were also significant decreases in nonlinearity scores on S-netPR and S-netGS after nortriptyline, which may be due to a decrease in cardiac vagal modulation of HRV. S-netGS and awake LLE were the most significant variables that contributed to the discrimination of postparoxetine and postnortriptyline groups even with the inclusion of time and frequency domain measures. These findings suggest that nortriptyline decreases the measures of chaos probably through its stronger vagolytic effects on cardiac autonomic function compared with paroxetine, which is in agreement with previous clinical and preclinical reports. Nortriptyline was also associated with a significant decrease in nonlinearity scores, which may be due to anticholinergic and/or sympatholytic effects. As depression is associated with a strong risk factor for cardiovascular mortality, one should be careful about using any drug that adversely affects cardiac vagal function. Copyright (C) 2002 S. Karger AG, Basel.

Manipulation of the Hydration Levels in Minerals of Sodium Cadmium Bisulfate toward the Design of Functional Materials

Several variants of hydrated sodium cadmium bisulfate, Na(2)Cd(2)(SO(4))(3) center dot 3H(2)O, Na(2)Cd(SO(4))(2) center dot 2H(2)O, and Na(2)Cd(SO(4))(2) center dot 4H(2)O have been synthesized, and their thermal properties followed by phase transitions have been invesigated. The formation of these phases depends on the stochiometry and the time taken for crystallization from water. Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O, which crystallizes in the trigonal system, space group P3c, is grown from the aqueous solution in about four weeks. The krohnkite type mineral Na(2)Cd(SO(4))(2) center dot 2H(2)O and the mineral astrakhanite, also known as blodite, Na(2)Cd (SO(4))(2)center dot 4H(2)O, crystallize concomittantly in about 24 weeks. Both these minerals belong to the monoclinic system(space group P2(1)/c). Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O loses water completely when heated to 250 degrees C and transforms to a dehydrated phase (cubic system, space group I (4) over bar 3d) whose structure has been established using ab initio powder diffration techniques. Na(2)Cd(SO(4))(2)center dot 2H(2)O transforms to alpha-Na(2)Cd(SO(4))(2) (space group C2/c) on heating to 150 degrees C which is a known high ionic conductor and remains intact over prolonged periods of exposure to moisture (over six months). However, when alpha-Na(2)Cd(SO(4))(2) is heated to 570 degrees C followed by sudden quenching in liquid nitrogen beta-Na(2)Cd(SO(4))(2) (P2(1)/c) is formed. beta-Na(2)Cd(SO(4))(2) takes up water from the atmosphere and gets converted completely to the krohnkite type mineral in about four weeks. Further, beta-Na(2)Cd(SO(4))(2) has a conductivity behavior comparable to the a-form up to 280 degrees C, the temperature required for the transformation of the beta- to alpha-form. These experiments demonstrate the possibility of utilizing the abundantly available mineral sources as precursors to design materials with special properties.