Tunneling and delocalization in hydrogen bonded systems: a study in position and momentum space

Novel experimental and computational studies have uncovered the proton momentum distribution in hydrogen bonded systems. In this work, we utilize recently developed open path integral Car-Parrinello molecular dynamics methodology in order to study the momentum distribution in phases of high pressure ice. Some of these phases exhibit symmetric hydrogen bonds and quantum tunneling. We find that the symmetric hydrogen bonded phase possesses a narrowed momentum distribution as compared with a covalently bonded phase, in agreement with recent experimental findings. The signatures of tunneling that we observe are a narrowed distribution in the low-to-intermediate momentum region, with a tail that extends to match the result of the covalently bonded state. The transition to tunneling behavior shows similarity to features observed in recent experiments performed on confined water. We corroborate our ice simulations with a study of a particle in a model one-dimensional double well potential that mimics some of the effects observed in bulk simulations. The temperature dependence of the momentum distribution in the one-dimensional model allows for the differentiation between ground state and mixed state tunneling effects.Comment: 14 pages, 13 figure

Efficient multiple time scale molecular dynamics: using colored noise thermostats to stabilize resonances

Multiple time scale molecular dynamics enhances computational efficiency by updating slow motions less frequently than fast motions. However, in practice the largest outer time step possible is limited not by the physical forces but by resonances between the fast and slow modes. In this paper we show that this problem can be alleviated by using a simple colored noise thermostatting scheme which selectively targets the high frequency modes in the system. For two sample problems, flexible water and solvated alanine dipeptide, we demonstrate that this allows the use of large outer time steps while still obtaining accurate sampling and minimizing the perturbation of the dynamics. Furthermore, this approach is shown to be comparable to constraining fast motions, thus providing an alternative to molecular dynamics with constraints.Comment: accepted for publication by the Journal of Chemical Physic

El líder étnico, liderar y liderazgo. Los Yahatti, Lepin, Juan Manuel Cachul y Juan Catriel: hombres políticos en la frontera bonaerense

Desde que se asume que los encuentros entre hispanocriollos e indígenas no fueron sólo bélicos, que hubo convivencias cotidianas, intercambios y contactos armónicos, se abre la posibilidad de pensar y analizar este contacto –violento o armónico– como el contexto relacional que exteriorizó y demandó líderes o interlocutores en cada sociedad. La región de la actual provincia de Buenos Aires conocida como “frontera bonaerense”, durante mediados del siglo XVIII y la primera mitad del XIX, será el marco espacio-temporal que permitirá situar el análisis de cuatro hombres políticos: los Yahatti, Lepin, Juan Manuel Cachul y Juan Catriel. Este análisis busca aportar elementos nominadores y significativos sobre el liderazgo étnico. En consecuencia, buscamos territorializar e historizar el liderazgo étnico de estos hombres, para poder determinar si es factible hablar de transformaciones en el liderazgo y cambios de los líderes en la relación con sus seguidores a partir del acuerdo de paces establecido con las autoridades estatales. Es decir, buscamos establecer fisonomías que nos permitan construir una enunciación descriptiva y analítica sobre dichos líderes y sus estrategias de construcción y sostenimiento de autoridad.Since it is assumed that contact between Hispanic-Creole and indigenous people was not only violent, and that it included daily life coexistence, exchanges and harmonic contact, it is possible to think and analyze these aspects as the relational context that exteriorized and required new leaders or mediators from each society. The region of present Buenos Aires province known as “frontera bonaerense”, from mid-eighteenth century to the first half of the nineteenth century, will be the space-time frame to analyze four political men: the Yahatti, Lepin, Juan Manuel Cachul and Juan Catriel. This research tries to support nominative and significant elements about ethnic leadership. Therefore, we look forward to territorialize and historicize the ethnic leadership of these men in order to determinate to which extent is viable to speak about its transformations towards their followers by means of treating peace with state authorities. Taking everything into account, we try to set characters which allow us to build a descriptive and analytical enunciation about those leaders and their authority strategies

Análise de endemismo de táxons neotropicais de Pentatomidae (Hemiptera: Heteroptera)

The definition of areas of endemism is central to studies of historical biogeography, and their interrelationships are fundamental questions. Consistent hypotheses for the evolution of Pentatomidae in the Neotropical region depend on the accuracy of the units employed in the analyses, which in the case of studies of historical biogeography, may be areas of endemism. In this study, the distribution patterns of 222 species, belonging to 14 Pentatomidae (Hemiptera) genera, predominantly neotropical, were studied with the Analysis of Endemicity (NDM) to identify possible areas of endemism and to correlate them to previously delimited areas. The search by areas of endemism was carried out using grid-cell units of 2.5° and 5° latitude-longitude. The analysis based on groupings of grid-cells of 2.5° of latitude-longitude allowed the identification of 51 areas of endemism, the consensus of these areas resulted in four clusters of grid-cells. The second analysis, with grid-cells units of 5° latitude-longitude, resulted in 109 areas of endemism. The flexible consensus employed resulted in 17 areas of endemism. The analyses were sensitive to the identification of areas of endemism in different scales in the Atlantic Forest. The Amazonian region was identified as a single area in the area of consensus, and its southeastern portion shares elements with the Chacoan and Paraná subregions. The distribution data of the taxa studied, with different units of analysis, did not allow the identification of individual areas of endemism for the Cerrado and Caatinga. The areas of endemism identified here should be seen as primary biogeographic hypotheses.A definição de áreas de endemismo é central aos estudos de Biogeografia Histórica e suas inter-relações são questões fundamentais. Hipóteses consistentes sobre a evolução de Pentatomidae (Hemiptera) na Região Neotropical dependem da acuidade das unidades empregadas nas análises, que no caso de estudos de biogeografia histórica, podem ser áreas endêmicas. Neste trabalho foram estudados os padrões de distribuição de 222 espécies, pertencentes a 14 gêneros de Pentatomidae, com ocorrência predominantemente neotropical, com base em uma Análise de Endemicidade (NDM) a fim de inferir possíveis áreas endêmicas e relacioná-las a áreas previamente delimitadas. A busca por áreas endêmicas foi realizada com quadrículas de 2,5° e 5° latitude-longitude. A análise com base em agrupamentos de 2,5° latitude-longitude permitiu identificar 51 áreas de endemismo, sendo que o consenso destas áreas resultou em quatro agrupamentos de quadrículas. A segunda análise, com quadrículas de 5° latitude-longitude, resultou em 109 áreas de endemismo. O consenso flexível empregado resultou em 17 áreas de endemismo. As análises foram sensíveis à identificação de áreas de endemismo na Mata Atlântica em diferentes escalas. A região Amazônica foi identificada como uma área única no consenso, sendo que a porção sudeste compartilha elementos com as sub-regiões do Chaco e Paraná. Os dados de distribuição dos táxons estudados, com diferentes unidades de análises, não permitiram a identificação de áreas endêmicas para o Cerrado e a Caatinga. As áreas de endemismo aqui identificadas devem ser tratadas como hipóteses biogeográficas primárias.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Universidade Federal do Rio Grande do Sul Laboratório de Entomologia Sistemática Departamento de ZoologiaUniversidade Federal do Paraná Departamento de Zoologia Programa de Pós-Graduação em EntomologiaUniversidade Federal de São Paulo (UNIFESP) Departamento de Ciências BiológicasUNIFESP, Depto. de Ciências BiológicasSciEL

A Functional Genomics Approach to Tanshinone Biosynthesis Provides Stereochemical Insights

Tanshinones are abietane-type norditerpenoid quinone natural products that are the bioactive components of the Chinese medicinal herb Salvia miltiorrhiza Bunge. The initial results from a functional genomics-based investigation of tanshinone biosynthesis, specifically the functional identification of the relevant diterpene synthases from S. miltiorrhiza, are reported. The cyclohexa-1,4-diene arrangement of the distal ring poises the resulting miltiradiene for the ensuing aromatization and hydroxylation to ferruginol suggested for tanshinone biosynthesis

integration of an organic rankine cycle and a photovoltaic unit for micro scale chp applications in the residential sector

Abstract The purpose of this work is to analyse the performance of a novel system for combined heat and power (CHP) generation in small-scale applications. The system is based on an Organic Rankine Cycle (ORC) fed with biomass and a photovoltaic (PV) unit. The ORC and PV sub-systems operate in parallel to produce the required electrical energy. A preliminary investigation is performed to define the proper size of the photovoltaic unit. Afterwards, the analysis is focused on the hybrid system and a comparison between the two configurations is carried out. This work demonstrates the potential for integrating biomass and solar energy resources: during daylight, solar radiation is significant and the ORC system can be switched off or operated at partial load. Furthermore, the adoption of biomass makes it possible to overcome the intermittency of solar resource, increase the self-consumed electrical energy, and produce thermal energy, thereby saving natural gas for heating purposes

time dilation effect in an active observer and virtual environment requires apparent motion no dilation for retinal or world motion alone

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Increasing diterpene yield with a modular metabolic engineering system in E. coli: comparison of MEV and MEP isoprenoid precursor pathway engineering

Engineering biosynthetic pathways in heterologous microbial host organisms offers an elegant approach to pathway elucidation via the incorporation of putative biosynthetic enzymes and characterization of resulting novel metabolites. Our previous work in Escherichia coli demonstrated the feasibility of a facile modular approach to engineering the production of labdane-related diterpene (20 carbon) natural products. However, yield was limited (<0.1 mg/L), presumably due to reliance on endogenous production of the isoprenoid precursors dimethylallyl diphosphate and isopentenyl diphosphate. Here, we report incorporation of either a heterologous mevalonate pathway (MEV) or enhancement of the endogenous methyl erythritol phosphate pathway (MEP) with our modular metabolic engineering system. With MEP pathway enhancement, it was found that pyruvate supplementation of rich media and simultaneous overexpression of three genes (idi, dxs, and dxr) resulted in the greatest increase in diterpene yield, indicating distributed metabolic control within this pathway. Incorporation of a heterologous MEV pathway in bioreactor grown cultures resulted in significantly higher yields than MEP pathway enhancement. We have established suitable growth conditions for diterpene production levels ranging from 10 to >100 mg/L of E. coli culture. These amounts are sufficient for nuclear magnetic resonance analyses, enabling characterization of enzymatic products and hence, pathway elucidation. Furthermore, these results represent an up to >1,000-fold improvement in diterpene production from our facile, modular platform, with MEP pathway enhancement offering a cost effective alternative with reasonable yield. Finally, we reiterate here that this modular approach is expandable and should be easily adaptable to the production of any terpenoid natural product