Synthesis and structure of a novel terminal imido complex of titanium

The reaction of eta(5)-Cp*TiCl3 and (LiNHBu)-Bu-t in hexanes yields a novel [eta(5)-Cp*Ti(=(NBu)-Bu-t)((NHBu)-Bu-t)(2)]Li . (NH2Bu)-Bu-t complex with a terminal tert-butylimido moiety. The synthesis and X-ray structural characterization are described. (C) 1999 Elsevier Science S.A. All rights reserved.

Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

Digital Deadbeat Control Tuning for dc-dc Converters Using Error Correlation

This letter proposes a simple tuning algorithm for digital deadbeat control based on error correlation. By injecting a square-wave reference input and calculating the correlation of the control error, a gain correction for deadbeat control is obtained. The proposed solution is simple, it requires a short tuning time, and it is suitable for different DC-DC converter topologies. Simulation and experimental results on synchronous buck converters confirm the properties of the proposed tuning algorithm.

Nitrates-melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

Layered LiNi0.8Co0.2O2 crystallizing in R (3) over barm space group is synthesized by decomposing the constituent metal-nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals <2% Li-Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge-discharge cycles reflect a first-discharge capacity of 184 mAh g(-1) which is stabilized at 170 mAh g(-1) over 50 cycles.

Influence of ethanol/water mixture on the undrained shear strength of pure clays

The mechanical properties of clays are highly dependent not only on the stress/strain ratio to which the material is subjected but also on the chemistry of the pore fluids which in turn affects the intergranular or the effective stresses. Atterberg limits and vane shear tests were performed with different pore fluids in order to observe how the fine-grained material mechanically responded. The diffuse double layer theory has been used to interpret the data of vane shear tests in order to explain the variation of geotechnical responses with the different clays. Van der Waals forces and double layer forces were obtained and capillary forces calculated. The results show that while for kaolinite and illite the chemistry of the pore fluids has no influence on the water content and hence on the mechanical behaviour of the material, Na-smectite shows a strong correlation between the dielectric constant of the pore fluids and an increase in undrained shear strength. The data obtained extends an understanding of the influence of the dielectric constant (epsilon) of the pore fluids on the geotechnical properties of fine-grained materials.

Mesoporous MnO2 synthesized by hydrothermal route for electrochemical supercapacitor studies

Poorly crystalline mesoporous MnO2, which is suitable for supercapacitor studies, is synthesized from neutral KMnO4 aqueous solution by hydrothermal route. But it requires a high temperature (180 A degrees C) and also a long reaction time (24 h). Addition of a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123), which is generally used as a soft template for the synthesis of nano-structured porous materials, reduces the hydrothermal temperature to 140 A degrees C and also reaction time to 2 h. When the reaction time is increased, the product morphology changes from nanoparticles to nanorods with a concomitant decrease in BET surface area. Also, the product tends to attain crystallinity. The electrochemical capacitance properties of MnO2 synthesized under varied hydrothermal conditions are studied in 0.1 M Na2SO4 electrolyte. A specific capacitance of 193 F g(-1) is obtained for the mesoporous MnO2 sample consisting of nanoparticle and nanorod mixed morphology synthesized in 6 h using P123 at 140 A degrees C.

Metabolites of PPI-2458, a selective, irreversible inhibitor of methionine aminopeptidase-2: structure determination and In vivo activity

The natural product fumagillin exhibits potent antiproliferative and antiangiogenic properties. The semisynthetic analog PPI-2458, (3R,4S,5S,6R)-5-methoxy-4-(2R,3R)-2-methyl-3-(3-methylbut-2-enyl) oxiran-2-yl]-1-oxaspiro2.5]octan-6-yl] N-(2R)-1-amino-3-methyl-1-oxobutan-2-yl]carbamate, demonstrates rapid inactivation of its molecular target, methionine aminopeptidase-2 (MetAP2), and good efficacy in several rodent models of cancer and inflammation with oral dosing despite low apparent oral bioavailability. To probe the basis of its in vivo efficacy, the metabolism of PPI-2458 was studied in detail. Reaction phenotyping identified CYP3A4/5 as the major source of metabolism in humans. Six metabolites were isolated from liver microsomes and characterized by mass spectrometry and nuclear resonance spectroscopy, and their structures were confirmed by chemical synthesis. The synthetic metabolites showed correlated inhibition of MetAP2 enzymatic activity and vascular endothelial cell growth. In an ex vivo experiment, MetAP2 inhibition in white blood cells, thymus, and lymph nodes in rats after single dosing with PPI-2458 and the isolated metabolites was found to correlate with the in vitro activity of the individual species. In a phase 1 clinical study, PPI-2458 was administered to patients with non-Hodgkin lymphoma. At 15 mg administered orally every other day, MetAP2 in whole blood was 80% inactivated for up to 48 hours, although the exposure of the parent compound was only similar to 10% that of the summed cytochrome P450 metabolites. Taken together, the data confirm the participation of active metabolites in the in vivo efficacy of PPI-2458. The structures define a metabolic pathway for PPI-2458 that is distinct from that of TNP-470 ((3R, 4S, 5S, 6R)-5-methoxy-4-(2R, 3R)-2-methyl-3-(3-methylbut-2-enyl)oxiran-2-yl]-1-oxaspiro2.5]octan-6 -yl] N-(2-chloroacetyl)carbamate). The high level of MetAP2 inhibition achieved in vivo supports the value of fumagillin-derived therapeutics for angiogenic diseases.

Structural and kinetic studies on adenylosuccinate lyase from Mycobacterium smegmatis and Mycobacterium tuberculosis provide new insights on the catalytic residues of the enzyme

Adenylosuccinate lyase (ASL), an enzyme involved in purine biosynthesis, has been recognized as a drug target against microbial infections. In the present study, ASL from Mycobacteriumsmegmatis (MsASL) and Mycobacteriumtuberculosis (MtbASL) were cloned, purified and crystallized. The X-ray crystal structure of MsASL was determined at a resolution of 2.16 angstrom. It is the first report of an apo-ASL structure with a partially ordered active site C3 loop. Diffracting crystals of MtbASL could not be obtained and a model for its structure was derived using MsASL as a template. These structures suggest that His149 and either Lys285 or Ser279 of MsASL are the residues most likely to function as the catalytic acid and base, respectively. Most of the active site residues were found to be conserved, with the exception of Ser148 and Gly319 of MsASL. Ser148 is structurally equivalent to a threonine in most other ASLs. Gly319 is replaced by an arginine residue in most ASLs. The two enzymes were catalytically much less active compared to ASLs from other organisms. Arg319Gly substitution and reduced flexibility of the C3 loop might account for the low catalytic activity of mycobacterial ASLs. The low activity is consistent with the slow growth rate of Mycobacteria and their high GC containing genomes, as well as their dependence on other salvage pathways for the supply of purine nucleotides. Structured digital abstract andby()

Secure Transmission in Cooperative Networks with Weak Eavesdroppers

In this letter, we propose a scheme to improve the secrecy rate of cooperative networks using Analog Network Coding (ANC). ANC mixes the signals in the air; the desired signal is then separated out, from the mixed signals, at the legitimate receiver using techniques like self interference subtraction and signal nulling, thereby achieving better secrecy rates. Assuming global channel state information, memoryless adversaries and the decode-and-forward strategy, we seek to maximize the average secrecy rate between the source and the destination, subject to an overall power budget. Then, exploiting the structure of the optimization problem, we compute its optimal solution. Finally, we use numerical evaluations to compare our scheme with the conventional approaches.

Hemoparásitos en bovinos de engorde en las fincas Cañas Gordas y Las Alturas, comarca San Agustín, Acoyapa, Chontales, en los meses de agosto - octubre 2012

Con el objetivo de determinar la prevalencia de hemoparásitos en bovinos de engorde y su efecto sobre la productividad de los animales; se identificó la presencia de ectoparásitos vectores y se analizaron los factores agroecológicos que permiten la presencia de estas parasitosis en Las fincas Cañas Gordas y Las Alturas ubicadas en la comarca San Agustín, municipio de Acoyapa, departamento de Chontales; Cañas Gordas con las coordenadas geográficas latitud norte 11° 52´ 60” y longitud oeste 85°24´0”, con una elevación de 36 msnm y Las Alturas con las coordenadas geográficas latitud norte 11° 58´ 03.41”, longitud oeste 85°21´47.47” y con una elevación de 136 msnm, comprendidas en una zona subtropical de montaña, ambas fincas con una humedad relativa del 76%, precipitación promedio anual de 1 134,1 mm y una temperatura anual promedio 27. 2 °C. Para realizar el estudio se tomó un lote de 150 animales por cada finca en un rango de peso de 280 a 320 kg muestreando el 10% de la población total, tomando 15 animales por finca, para un total de 30 exámenes, efectuando 4 muestreos con intervalos de 21 días entre los meses de agosto, septiembre y octubre. La toma de muestra se realizó mediante venopunción de la yugular, trasladándose estas al laboratorio de Parasitología (FACA – UNA) se procedió a realizar 2 frotis sanguíneos por cada muestra utilizando el método de tinción coloración Giemsa, para la posterior observación de los hemoparásitos. Obteniendo tres especies de hemoparásitos Babesia, Anaplasma y Tripanosoma, Se determinó que en la finca Cañas Gordas la prevalencia de Babesia es de 53%, en Las Alturas es del 73%; en ambas fincas la prevalencia de Anaplasma es de 93%; de Tripanosoma es del 27% únicamente en Cañas Gordas, este último debido a la presencia del lago Cocibolca en las inmediaciones de la finca que permite un ambiente húmedo favorable para una mayor presencia del hospedero intermediario (Tábanus). Las pérdidas económicas anuales ocasionadas por la presencia de hemoparásitos en Las Alturas fué de C$ 139,243.50 en un lote de 150 animales; en Cañas Gordas fué de C$ 234,837.00. Para realizar un control eficaz de los hemoparásitos se debe contar con un plan de control de ectoparásitos, efectuar exámenes complementarios periódicamente para determinar la especie de hemoparásitos y así aplicar un tratamiento específico, además de mantener un plan de vigilancia permanente.

用环形激波聚焦实现爆轰波直接起爆的数值模拟

利用基元反应模型和有限体积法对环形激波在可燃气体中聚焦实现爆轰波直接起爆进行了数值模拟.研究结果表明,标准状态下的氢气-空气混合气体在马赫数为3.1以上的环形激波聚焦产生的高温高压区作用下会诱发可燃气体的直接起爆形成爆轰波,爆轰波与激波和接触间断相互作用产生了复杂的波系结构;爆轰波爆点位置在对称轴上并不是固定的点,而是随着初始激波马赫数的变化而发生移动;可燃气体初始温度和压力对起爆临界马赫数都有影响,但是初始温度的影响大得多.

焊接接头热影响区表面裂纹疲劳扩展速率

给出了数据处理的方法，通过对试验数据的分析，给出了裂纹扩展速率与ΔK的关系，为油 田的安全生产提供了依据。

Prueba de diferentes insecticidas químicos, botánico y biológico para el control del minador de los citricos en Lima Tahiti bajo condiciones de vivero

El presente trabajo se realizó en la Cooperativa Agropecuaria "Humberto Tapia Barquero" finca CHELOL, ubicada a 1.5 Km. al suroeste de Jinotepe-Carazo. El experimento se estableció en el periodo comprendido de Abril a Julio de 1995, en condiciones de vivero predominando los suelos franco­ arcillosos, profundos, bien drenados, pH: 6.5-6.7. Los 7 tratamientos fueron arreglados en un diseño completamente azarizado (D.C.A), con 20 repeticiones (plantas), para su análisis estadístico se utilizó la prueba de rangos múltiples de Tukey al 5 % de significancia como método de comparación. Se probaron 4 insecticidas químicos (Filitox, Decís, Thiodan y Diazinon), un insecticida biológico (Dipel) y un insecticida botánico (Neern), y un tratamiento sin aplicación (Testigo) evaluados para el control de Phyllocnislis citrella Stainton a nivel de vivero en plantas de lima tabití. Las variables evaluadas fueron: altura de plantas, diámetro de ramas principales, número de brotes nuevos y afectados por plantas, número de hojas dañadas por planta, número de larvas vivas y muertas por planta y número de minas por hojas. El tratamiento que presentó mayor mortalidad en todo el periodo de estudio fue el Filitox=67.32%, mientras que el Testigo=l.49"/o presentó el menor valor de los tratamientos en estudio. Todos los tratamientos a excepción del testigo probaron ser eficaces para el control del minador de la hoja de los cítricos, sin afectar de ninguna manera el normal crecimiento y desarrollo de las plantas de lima tahití.

Caracterización y evaluación preliminar de treinta y tres cultivares de maiz (Zea mays L.) recolectadas en diferentes localidades de Nicaragua

En los terrenos del Programa de Recursos Genéticos Nicaragüenses (REGEN), adscrito a la Universidad Nacional Agraria (UNA), Km 12 ½ carretera Norte, Managua. Se estableció en Postrera de 1994 un experimento, con el objetivo de caracterizar y evaluar preliminarmente 32 cultivares criollos procedentes de diversas localidades de Nicaragua y una variedad comercial como testigo (NB-6). Se utilizó un diseño característico de ensayos preliminares, sin repetición. Para la descripción del germoplasma se usaron 14 descriptores cualitativos y 28 cuantitativos. Los resultados demostraron que en el país existe germoplasma criollo con variabilidad genética significativa para la mayoría de los caracteres de interés agronómico, como es el caso de Olotillo (1676), Olote colorado (2165), Tusa Morada (3077) y Rocamel Mejo (3103); que sobresalieron en caracteres de mazorca (longitud, peso y ancho de mazorca). En función del conjunto de descriptores de grano (longitud, ancho y grosor de grano), los cultivares: Masaya (2504), Maíz Rocamel (3074), Maíz Salco (3076), Blanco (2695) y Olotillo (3117) fueron catalogados como promisorios por presentar grano grande, estos caracteres pueden ser utilizados en programas de mejoramiento y/o aprovechados directamente en la producción de maíz en Nicaragua. Para la evaluación preliminar 12 cultivares superaron en rendimiento los 2 761 kg/ha que el testigo mostró, siendo Maíz Salco (3076) de Nueva Segovia, el cultivar sobresaliente al presentar rendimiento mayor a 4 000 kg/ha. En cuanto a precocidad, los cultivares Olotillo (3117) y Pujagua (2175) ambos originario de León, se catalogaron como material precoz, al obtener el inicio de la floración masculina a los 39 y 42 días después de la siembra respectivamente y 90 días para la cosecha. El cultivar Tusa Morada (3077) de Nueva Segovia, con 59 días después de la siembra para el inicio de floración masculina, obtuvo 121 días para la cosecha catalogado como material tardío, el resto del material evaluado se consideró de ciclo intermedio.