Two isomeric reaction products: hydrogen-bonded sheets in methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitrobenzoate and hydrogen-bonded chains of edge-fused rings in methyl 3-nitro-4-[(5-phenyl-1H-pyrazol-3-yl)amino] benzoate

In methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitrobenzoate, C17H14N4O4, the molecules are linked into complex sheets by a combination of N-H center dot center dot center dot N, N-H center dot center dot center dot O and C - H center dot center dot center dot O hydrogen bonds. In the isomeric methyl 3-nitro-4-[(5-phenyl- 1H-pyrazol-3-yl)amino] benzoate, molecules exhibit a polarized molecular-electronic structure and are linked into chains of edge-fused rings by a combination of N-H center dot center dot center dot O and C - H center dot center dot center dot O hydrogen bonds.

Three substituted 4-pyrazolylbenzoates: hydrogen-bonded supramolecular structures in one, two and three dimensions

The molecules of ethyl 4-(5-amino-3-methyl-1H-pyrazol-1yl) benzoate, C13H15N3O2, are linked by two independent N-H center dot center dot center dot O hydrogen bonds into a chain of edge-fused and alternating R-4(2)(8) and R-2(2)(20) rings. A combination of N-H center dot center dot center dot N and N-H center dot center dot center dot O hydrogen bonds links the molecules of methyl 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl) benzoate, C15H19N3O2, into sheets of alternating R-2(2)(20) and R-6(6)(32) rings. In 4-(5-amino-3-methyl-1H-pyrazol-1-yl) benzoic acid monohydrate, C11H11N3O2 center dot H2O, the molecular components are linked into a three-dimensional framework structure by a combination of five independent hydrogen bonds, two of O-H center dot center dot center dot N type and one each of O-H center dot center dot center dot O, N-H center dot center dot center dot O and N-H center dot center dot center dot N types

The age of excess : America 1920-1932.

Entre 1920 y 1932 Estados Unidos aumentó en gran medida su nivel de prosperidad y, a continuación, se estrelló en las profundidades de la depresión. América es la tierra de la oportunidad y su sistema democrático ofrece un sueño de libertad a pesar de los problemas raciales, la intolerancia política, la prohibición, los gangsters, la violencia y las diferencias religiosas. Estos años fueron los locos años veinte que terminaron con el Crash de 1929.Incluye fragmentos de fuentes históricas originales, así como, material de aprendizaje activo: ejercicios, preguntas y pruebas.

Basis set superposition error-counterpoise corrected potential energy surfaces : application to hydrogen peroxide ... X (X=F-, Cl-, Br-, Li+, Na+) complexes

Møller-Plesset (MP2) and Becke-3-Lee-Yang-Parr (B3LYP) calculations have been used to compare the geometrical parameters, hydrogen-bonding properties, vibrational frequencies and relative energies for several X- and X+ hydrogen peroxide complexes. The geometries and interaction energies were corrected for the basis set superposition error (BSSE) in all the complexes (1-5), using the full counterpoise method, yielding small BSSE values for the 6-311 + G(3df,2p) basis set used. The interaction energies calculated ranged from medium to strong hydrogen-bonding systems (1-3) and strong electrostatic interactions (4 and 5). The molecular interactions have been characterized using the atoms in molecules theory (AIM), and by the analysis of the vibrational frequencies. The minima on the BSSE-counterpoise corrected potential-energy surface (PES) have been determined as described by S. Simón, M. Duran, and J. J. Dannenberg, and the results were compared with the uncorrected PES

How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?

We describe a simple method to automate the geometric optimization of molecular orbital calculations of supermolecules on potential surfaces that are corrected for basis set superposition error using the counterpoise (CP) method. This method is applied to the H-bonding complexes HF/HCN, HF/H2O, and HCCH/H2O using the 6-31G(d,p) and D95 + + (d,p) basis sets at both the Hartree-Fock and second-order Møller-Plesset levels. We report the interaction energies, geometries, and vibrational frequencies of these complexes on the CP-optimized surfaces; and compare them with similar values calculated using traditional methods, including the (more traditional) single point CP correction. Upon optimization on the CP-corrected surface, the interaction energies become more negative (before vibrational corrections) and the H-bonding stretching vibrations decrease in all cases. The extent of the effects vary from extremely small to quite large depending on the complex and the calculational method. The relative magnitudes of the vibrational corrections cannot be predicted from the H-bond stretching frequencies alone

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack

Destabilizing Mutations Alter the Hydrogen Exchange Mechanism in Ribonuclease A

The effect of strongly destabilizing mutations, I106A and V108G of Ribonuclease A (RNase A), on its structure and stability has been determined by NMR. The solution structures of these variants are essentially equivalent to RNase A. The exchange rates of the most protected amide protons in RNase A (35ºC), the I106A variant (35ºC), and the V108G variant (10ºC) yield stability values of 9.9, 6.0, and 6.8 kcal/mol, respectively, when analyzed assuming an EX2 exchange mechanism. Thus, the destabilization induced by these mutations is propagated throughout the protein. Simulation of RNase A hydrogen exchange indicates that the most protected protons in RNase A and the V108G variant exchange via the EX2 regime, whereas those of I106A exchange through a mixed EX1 1 EX2 process. It is striking that a single point mutation can alter the overall exchange mechanism. Thus, destabilizing mutations joins high temperatures, high pH and the presence of denaturating agents as a factor that induces EX1 exchange in proteins. The calculations also indicate a shift from the EX2 to the EX1 mechanism for less protected groups within the same protein. This should be borne in mind when interpreting exchange data as a measure of local stability in less protected regions

New mono- and dinuclear ruthenium complexes containing the 3,5-bis(2-pyridyl)pyrazole ligand. Synthesis, characterization and applications

Se han sintetizado dos nuevos complejos mononucleares de Ru, con formula [RuCl2(Hbpp)(dmso)2], a partir de la reacción entre [RuCl2(dmso)4] y Hbpp (3,5-bis(2-piridil)pirazola). El hecho que sólo tres de los seis posibles estereoisómeros se obtengan a partir de esta reacción, se ha racionalizado en base a factores estructurales y electrónicos. Estos complejos se han caracterizado de forma estructural, espectroscópica y electroquímica. En acetonitrilo en medio básico, el isómero trans,cis-[RuCl2(Hbpp)(dmso)2] da lugar a procesos de isomerización de enlace de un ligando dmso cuando el Ru(II) se oxida a Ru(III). Las constantes termodinámicas y cinéticas para el proceso se han determinado por voltametria cíclica. La irradiación de trans,cis-[RuCl2(Hbpp)(dmso)2] y cis(out),cis-[RuCl2(Hbpp)(dmso)2] con luz UV o solar da lugar a reacciones de fotosustitución de un ligando dmso por una molécula de acetonitrilo para dar un nuevo compuesto el cual ha sido caracterizado en solución por técnicas espectroscópicas y electroquímicas. Ambos complejos resultan catalizadores útiles en la transferencia de hidrógeno de isopropanol a acetofenona, obteniéndose 1-feniletanol como único producto y un 42.1% de conversión (36.1 ciclos metálicos) a 80ºC con el isómero trans,cis-[RuCl2(Hbpp)(dmso)2], que resulta significativamente más eficaz que el complejo cis(out),cis-[RuCl2(Hbpp)(dmso)2]. La reacción de cis(out),cis-[RuCl2(Hbpp)(dmso)2] con trpy (2,2':6',2"-terpiridina) da lugar a los dos isómeros geométricos del complejo [Ru(Hbpp)(trpy)(Cl)]+, el in y el out. Estos complejos se han aislado y caracterizado por técnicas estructurales, espectroscópicas y electroquímicas. Estos cloro complejos han sido utilizados como precursores para la síntesis de los complejos análogos con ligandos aqua (in,out-[Ru(Hbpp)(trpy)(H2O)]2+) y piridina (in,out-[Ru(Hbpp)(trpy)(py)]2+), los cuales también han sido aislados y caracterizados. Las propiedades ácido-base de los aqua complejos, y del complejo out-py se han estudiado detalladamente por voltametria cíclica y mediante valoraciones espectrofotométricas ácido-base. El tratamiento matemático de los datos así obtenidos nos ha permitido determinar los valores de pKa para los distintos equilibrios de protonación de los complejos en los estados de oxidación II y III. El complejo out-aqua ha demostrado ser un buen catalizador para la oxidación electroquímica del alcohol benzílico, presumiblemente a benzaldehido. La constante de velocidad de segundo orden para el proceso ha sido determinada como 17.1 M-1 s-1, por simulación matemática. El dímero con un puente cloro, [Ru2Cl(bpp)(trpy)2]2+ ha sido preparado por dos rutas sintéticas diferentes. El dímero análogo con un puente acetato se ha obtenido por reacción del cloro dímero con un exceso de acetato sódico. El dímero con dos ligandos aqua [Ru2(bpp)(trpy)2(OH2)2]3+ puede obtenerse por hidrólisis ácida del complejo con un acetato puente o por hidrólisis básica del complejo con un puente cloro. Estos complejos han sido caracterizados por técnicas estructurales, espectroscópicas y electroquímicas. Las soluciones del dímero con dos ligandos aqua en medio ácido resultan inestables a la coordinación de aniones de la solución con el tiempo. Las propiedades ácido-base del dímero con dos aguas coordinadas han sido estudiadas por voltametria cíclica y mediante experimentos de electrólisis a potencial controlado. El pKa para la desprotonación de uno de los ligandos aqua ha sido determinado mediante una valoración espectrofotométrica ácido-base como 6.7. Este valor tan bajo de pKa se atribuye a la formación de la entidad {Ru2O2H3}, favorable termodinámicamente. Los espectros UV-vis para los distintos estados de oxidación del aqua dímero, de RuIIRuII a RuIIIRuIV, han sido obtenidos por oxidación química y electroquímica del complejo. Se han llevado a cabo estudios cinéticos de la oxidación, paso a paso, de RuII,II a RuIV,IV , y se han determinado las constantes de oxidación de segundo orden para los distintos procesos de oxidación. La capacidad del aqua dímero en la oxidación del agua a oxígeno molecular ha sido investigada en solución homogénea utilizando CeIV como oxidante. La evolución de oxígeno se ha demostrado por cromatografia de gases. Se ha obtenido una eficiencia del 73% y 18.6 ciclos catalíticos, cuando 1.83 x 10-6 moles de dímero se han mezclado con un exceso de 100 equivalentes de cerio. El dímero con dos aguas cataliza también la oxidación del agua de forma heterogénea, con el complejo adsorbido sobre una membrana de nafion, aunque la eficiencia es menor. Se ha propuesto un mecanismo intramolecular para la reacción de oxidación del agua. Consiste en la oxidación a 4 electrones del dímero, de RuII,II a RuIV,IV, el cual reacciona con el agua para formar oxígeno y revierte nuevamente al estado de oxidación II,II. Este modelo es consistente con estudios catalíticos de la evolución de oxígeno en función de las concentraciones de cerio y catalizador, llevados a cabo en solución ácida homogénea, que demuestran que la oxidación a 4 electrones del agua se encuentra catalizada por una sola molécula de complejo bajo concentraciones elevadas de cerio. La constante de pseudo-primer-orden para la evolución de oxígeno tiene un valor de 1.4 x 10-2 s-1, que es uno de los valores de constante más elevados obtenidos hasta la fecha. Desafortunadamente, el aqua dímero se desactiva durante el proceso de catálisis dando lugar a una especie naranja, la cual estamos actualmente tratando de caracterizar.

A sovereign wealth fund to lift Germany's curse of excess savings. CEPS Policy Brief No. 280, 28 August 2012

As an alternative to the present system of intermediation of the German savings surplus, this paper suggests that the risk-adjusted rate of return could be improved by creating a sovereign wealth fund for Germany (designated DESWF), which could invest excess German savings globally. Such a DESWF would offer German savers a secure vehicle paying a guaranteed positive minimum real interest rate, with a top-up when real investment returns allowed. The vehicle would invest the funds in a portfolio that is highly diversified by geography and asset classes. Positive real returns can be expected in the long run based on positive real global growth. Since, in this case, a significant amount of funds would flow outside the euro area, the euro would depreciate, which would help crisis countries presently struggling to revive growth through exports and to close their external deficits so as to recoup their international credit-worthiness. Target imbalances would gradually disappear and German claims abroad would move from nominal claims on the ECB to diversified real and nominal claims on various private and public foreign entities in a variety of asset classes.

Predicting origins of passerines migrating through Canadian migration monitoring stations using stable-hydrogen isotope analyses of feathers: a new tool for bird conservation

The Canadian Migration Monitoring Network (CMMN) consists of standardized observation and migration count stations located largely along Canada’s southern border. A major purpose of CMMN is to detect population trends of migratory passerines that breed primarily in the boreal forest and are otherwise poorly monitored by the North American Breeding Bird Survey (BBS). A primary limitation of this approach to monitoring is that it is currently not clear which geographic regions of the boreal forest are represented by the trends generated for each bird species at each station or group of stations. Such information on “catchment areas” for CMMN will greatly enhance their value in contributing to understanding causes of population trends, as well as facilitating joint trend analysis for stations with similar catchments. It is now well established that naturally occurring concentrations of deuterium in feathers grown in North America can provide information on their approximate geographic origins, especially latitude. We used stable hydrogen isotope analyses of feathers (δ²Hf) from 15 species intercepted at 22 CMMN stations to assign approximate origins to populations moving through stations or groups of stations. We further constrained the potential catchment areas using prior information on potential longitudinal origins based upon bird migration trajectories predicted from band recovery data and known breeding distributions. We detected several cases of differences in catchment area of species passing through sites, and between seasons within species. We discuss the importance of our findings, and future directions for using this approach to assist conservation of migratory birds at continental scales.

Hydrogen-bonded interpolymer complexes. Formation, structure and applications

Noncovalent interactions play key roles in many natural processes leading to the self-assembly of molecules with the formation of supramolecular structures. One of the most important forces responsible for self-assembly is hydrogen bonding, which also plays an important role in the self-assembly of synthetic polymers in aqueous solutions. Proton-accepting polymers can associate with proton-donating polymers via hydrogen bonding in aqueous solutions and form polymer-polymer or interpolymer complexes. There has been an increased interest among researchers in hydrogen-bonded interpolymer complexes since the first pioneering papers were published in the early 1960s. Several hundred research papers have been published on various aspects of complex formation reactions in solutions and interfaces, properties of interpolymer complexes and their potential applications. This book focuses on the latest developments in the area of interpolymer complexation via hydrogen bonding. It represents a collection of original and review articles written by recognized experts from Germany, Greece, Kazakhstan, Poland, Romania, Russia, UK, Ukraine, and the USA. It highlights many important applications of interpolymer complexes, including the stabilization of colloidal systems, pharmaceuticals, and nanomaterials.