743 resultados para BENT METALLOCENES
Resumo:
What kind of science is appropriate for understanding the Facebook? How does Google find what you're looking for... ...and exactly how do they make money doing so? What structural properties might we expect any social network to have? How does your position in an economic network (dis)advantage you? How are individual and collective behavior related in complex networks? What might we mean by the economics of spam? What do game theory and the Paris subway have to do with Internet routing? What's going on in the pictures to the left and right? Networked Life looks at how our world is connected -- socially, economically, strategically and technologically -- and why it matters. The answers to the questions above are related. They have been the subject of a fascinating intersection of disciplines including computer science, physics, psychology, mathematics, economics and finance. Researchers from these areas all strive to quantify and explain the growing complexity and connectivity of the world around us, and they have begun to develop a rich new science along the way. Networked Life will explore recent scientific efforts to explain social, economic and technological structures -- and the way these structures interact -- on many different scales, from the behavior of individuals or small groups to that of complex networks such as the Internet and the global economy. This course covers computer science topics and other material that is mathematical, but all material will be presented in a way that is accessible to an educated audience with or without a strong technical background. The course is open to all majors and all levels, and is taught accordingly. There will be ample opportunities for those of a quantitative bent to dig deeper into the topics we examine. The majority of the course is grounded in scientific and mathematical findings of the past two decades or less.
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El Glioblastoma multiforme (GBM), es el tumor cerebral más frecuente, con pronóstico grave y baja sensibilidad al tratamiento inicial. El propósito de este estudio fue evaluar si la Difusión en RM (IDRM), es un biomarcador temprano de respuesta tumoral, útil para tomar decisiones tempranas de tratamiento y para obtener información pronostica. Metodología La búsqueda se realizo en las bases de datos EMBASE, CENTRAL, MEDLINE; las bibliografías también fueron revisadas. Los artículos seleccionados fueron estudios observacionales (casos y controles, cohortes, corte transversal), no se encontró ningún ensayo clínico; todos los participante tenían diagnostico histopatológico de GBM, sometidos a resección quirúrgica y/o radio-quimioterapia y seguimiento de respuesta al tratamiento con IDRM por al menos 6 meses. Los datos extraídos de forma independiente fueron tipo de estudio, participantes, intervenciones, seguimiento, desenlaces (sobrevida, progresión/estabilización de la enfermedad, muerte) Resultados Quince estudios cumplieron los criterios de inclusión. Entre las técnicas empleadas de IDRM para evaluar respuesta radiológica al tratamiento, fueron histogramas del coeficiente aparente de difusion ADC (compararon valores inferiores a la media y el percentil 10 de ADC, con los valores superiores); encontrando en términos generales que un ADC bajo es un fuerte predictor de sobrevida y/o progresión del tumor. (Esto fue significativo en 5 estudios); mapas funcionales de difusion (FDM) (midieron el porcentaje de cambio de ADC basal vs pos tratamiento) que mostro ser un fuerte predictor de sobrevida en pacientes con progresión tumoral. DISCUSION Desafortunadamente la calidad de los estudios fue intermedia-baja lo que hace que la aplicabilidad de los estudios sea limitada.
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El archipiélago de San Andrés y Providencia tiene lazos históricos con el Caribe Inglés tan sólidos como el resto del país con América latina. El haber sido una colonia Británica lo acerca al gran Caribe, lo que facilita el acercamiento de esta región con Colombia, en términos similares a los que se dan en la dinámica con los Estados hispanos de la zona, convirtiéndose en la puerta de entrada hacia un área que ofrece oportunidades de mercado y cooperación de gran importancia para el país.
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Este ensayo discute dos aspectos relacionados con la naturaleza de la guerra contemporánea: el tipo de guerra que se está luchando y el rol de lo militar en dicha guerra. Si el terrorismo es interpretado como una aproximación táctica de las organizaciones que subvierten el orden público internacional, entonces el concepto de asimetría no proporciona nuevos elementos al desarrollo del pensamiento estratégico moderno. La naturaleza de una guerra revolucionaria resulta una noción más poderosa, pero no permite generalizaciones para la construcción de un modelo de conflicto global. A falta de un mejor concepto, el terrorismo aparece en una era posmilitar donde las fuerzas armadas desempeñan un rol esencial para los gobiernos democráticos a través de la política exterior.-----This essay discusses two questions related to contemporary warfare: The kind of war being fought and the role of the military in such a war. If terrorism is taken to be a tactical approach undertaken by organizations bent on subverting the international public order, then the concept of asymmetry adds little to the development of modern strategic thought. Revolutionary warfare is a more potent notion, but does not allow for generalizations given current pattern of global conflict. For lack of a better concept, terrorism appears in a post-military era where the armed forces play an enabling role for democratic governments through international policing.
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El texto analiza el impacto de la corrupción policial presentada por los medios de comunicación desde 1993 hasta el 2012 en la estructura interna de la Policía Nacional de Colombia. En el primer capítulo se plantea un estado del arte del concepto de corrupción policial, asimismo, se incluyen las teorías bajo las cuales se ha entendido el fenómeno a nivel mundial buscando generar soluciones plausibles a un flagelo en el que se ven inmiscuidos una gran cantidad de cuerpos policiales en el mundo. En el segundo apartado, se evalúa de manera cuantitativa cómo los casos de corrupción han modificado la estructura de la Policía Nacional, pero a su vez, cómo éstas modificaciones han sido evanescentes. En el tercer capítulo, se escudriña el impacto y los cambios estructurales desde la perspectiva de los miembros del cuerpo policial, recurriendo a la recolección de datos de manera cualitativa por medio de entrevistas y encuestas. En el cuarto momento se analiza la incidencia de los directores de la policía en la lucha contra la corrupción policial y como se establece una relación entre los subalternos y los mandos medios al momento de realizar este tipo de actividades. Finalmente se plasman las conclusiones a las que se llegó posterior a la realización del trabajo investigativo.
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Kavita busca algo especial. Su padre quiere hacer una rica sopa de bananas verdes, pìcante y brillante como el Caribe para obsequiar a la madre que ha traído un hermanito a casa. Kavita busca y rebusca las bananas verdes como manzanas y duras como patatas, como le dice su padre, pero no son fáciles de encontrar.
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Here we discuss two consecutive MERLIN observations of the X-ray binary LS I +61° 303 . The first observation shows a double-sided jet extending up to about 200 AU on both sides of a central source. The jet shows a bent S-shaped structure similar to the one displayed by the well-known precessing jet of SS 433 . The precession suggested in the first MERLIN image becomes evident in the second one, showing a one-sided bent jet significantly rotated with respect to the jet of the day before. We conclude that the derived precession of the relativistic (beta=0.6) jet explains puzzling previous VLBI results. Moreover, the fact that the precession is fast could be the explanation of the never understood short term (days) variability of the associated gamma-ray source 2CG 135+01 / 3EG J0241+6103
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Analytical potential energy functions are reported for HOX (X=F, Cl, Br, I). The surface for HOF predicts two metastable minima as well as the equilibrium configuration. These correspond to HFO (bent) and OHF (linear). Ab initio calculations performed for the HOF surface confirm these predictions. Comparisons are drawn between the two sets of results, and a vibrational analysis is undertaken for the hydrogen bonded OHF species. For HOCl, one further minimum is predicted, corresponding to HClO (bent), the parameters for which compare favourably with those reported from ab initio studies. In contrast, only the equilibrium configurations are predicted to be stable for HOBr and HOI.
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The microwave spectra of 2-aminopyridine-NH2, -ND2, and of both of the two possible -NHD molecules have been observed and assigned in the 0+ vibrational state of the amino group inversion vibration; the assignment for three of the molecules in the 0− state is also made. From intensity measurements the 0+-0− splitting is estimated to be 135 ± 25 cm−1 for the -NH2 molecule and 95 ± 30 cm−1 for the -ND2 molecule. The rotational constants are interpreted in terms of a structure in which the amino group is bent about 32° out of the molecular plane, the c coordinates of the two amino H atoms being 0.21 and 0.28 Å. Stark effect measurements give a dipole moment of about 0.9 D which is almost entirely in the b axis, and which changes quite significantly between the 0+ and 0− states.
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The lowest-wavenumber vibration of HCNO and DCNO, ν5, is known to involve a largeamplitude low-frequency anharmonic bending of the CH bond against the CNO frame. In this paper the anomalous vibrational dependence of the observed rotational constants B(v5, l5), and of the observed l-doubling interactions, is interpreted according to a simple effective vibration-rotation Hamiltonian in which the appropriate vibrational operators are averaged in an anharmonic potential surface over the normal coordinates (Q5x, Q5y). All of the data on both isotopes are interpreted according to a single potential surface having a minimum energy at a slightly bent configuration of the HCN angle ( 170°) with a maximum at the linear configuration about 2 cm−1 higher. The other coefficients in the Hamiltonian are also interpreted in terms of the structure and the harmonic and anharmonic force fields; the substitution structure at the “hypothetical linear configuration” determined in this way gives a CH bond length of 1.060 Å, in contrast to the value 1.027 Å determined from the ground-state rotational constants. We also discuss the difficulties in rationalizing our effective Hamiltonian in terms of more fundamental theory, as well as the success and limitations of its use in practice.
Resumo:
The presently available microwave, millimeter wave, and far-infrared data of five isotopic species of isocyanic acid, namely, HNCO, H15NCO, HN13CO, HNC18O, and DNCO, have been used to obtain improved values of the ground-state rotational constants, the five quartic distortion constants, and some higher-order distortion constants in the Ir S reduced Hamiltonian of Watson. The appropriate planarity relation among the quartic centrifugal distortion constants has been imposed in the fitting procedure. The general harmonic force field of isocyanic acid has been determined using all existing data, and assuming a trans bent equilibrium geometry of the molecule with an NCO angle of 170°. Finally an rz structure has been obtained using the Az, Bz, and Cz rotational constants of five isotopic species. The bending of the NCO chain is found to be 8° in the trans configuration.
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Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with NO. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 299-592 K. The second-order rate constants at 10 Torr fitted the Arrhenius equation log(k/cm(3) molecule(-1) s(-1)) = (- 11.66 +/- 0.01) + (6.20 +/- 0.10 kJ mol(-1))IRT In 10 The rate constants showed a variation with pressure of a factor of ca. 2 over the available range, almost independent of temperature. The data could not be fitted by RRKM calculations to a simple third body assisted association reaction alone. However, a mechanistic model with an additional (pressure independent) side channel gave a reasonable fit to the data. Ab initio calculations at the G3 level supported a mechanism in which the initial adduct, bent H2SiNO, can ring close to form cyclo-H2SiNO, which is partially collisionally stabilized. In addition, bent H2SiNO can undergo a low barrier isomerization reaction leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are NH2 + SiO. The rate controlling barrier for this latter pathway is only 16 kJ mol(-1) below the energy of SiH2 + NO. This is consistent with the kinetic findings. A particular outcome of this work is that, despite the pressure dependence and the effects of the secondary barrier (in the side reaction), the initial encounter of SiH2 with NO occurs at the collision rate. Thus, silylene can be as reactive with odd electron molecules as with many even electron species. Some comparisons are drawn with the reactions of CH2 + NO and SiCl2 + NO.
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The three lowest (1(2)A('), 2(2)A('), and 1(2)A(')) potential-energy surfaces of the C2Cl radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio using a large basis set and multireference configuration-interaction techniques. The electronic ground state is confirmed to be bent with a very low barrier to linearity, due to the strong nonadiabatic electronic interactions taking place in this system. The rovibronic energy levels of the (CCCl)-C-12-C-12-Cl-35 isotopomer and the absolute absorption intensities at a temperature of 5 K have been calculated, to an upper limit of 2000 cm(-1), using diabatic potential-energy and dipole moment surfaces and a recently developed variational method. The resulting vibronic states arise from a strong mixture of all the three electronic components and their assignments are intrinsically ambiguous. (c) 2005 American Institute of Physics.
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The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.
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Ligands such as CO, O2, or NO are involved in the biological function of myoglobin. Here we investigate the energetics and dynamics of NO interacting with the Fe(II) heme group in native myoglobin using ab initio and molecular dynamics simulations. At the global minimum of the ab initio potential energy surface (PES), the binding energy of 23.4 kcal/mol and the Fe-NO structure compare well with the experimental results. Interestingly, the PES is found to exhibit two minima: There exists a metastable, linear Fe-O-N minimum in addition to the known, bent Fe-N-O global minimum conformation. Moreover, the T-shaped configuration is found to be a saddle point, in contrast to the corresponding minimum for NO interacting with Fe(III). To use the ab initio results for finite temperature molecular dynamics simulations, an analytical function was fitted to represent the Fe-NO interaction. The simulations show that the secondary minimum is dynamically stable up to 250 K and has a lifetime of several hundred picoseconds at 300 K. The difference in the topology of the heme-NO PES from that assumed previously (one deep, single Fe-NO minimum) suggests that it is important to use the full PES for a quantitative understanding of this system. Why the metastable state has not been observed in the many spectroscopic studies of myoglobin interacting with NO is discussed, and possible approaches to finding it are outlined.