MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

Indexación: Web of Science; Scopus; Scielo.The catalytic activity of systems of type [RuH(CO)(N-N)(PR3)(2)](+) was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO)(3)(PPh3)(2) and RuH3(CO)(PPh3)(2), which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene. Palabras clavehttp://ref.scielo.org/db4yc

Metodologia de investigacion en entomologia de frijol

The general objectives of CIAT's bean entomology program are mentioned. The 1st priority has been given to var. resistance as an ideal pest control method. At CIAT's headquarters (Palmira, Colombia), studies are conducted on Empoasca kraemeri, mites, and storage insects; var. resistance to Apion godmani and Epinotia aporema is being studied at other institutions. The steps of genetic improvement of beans for resistance to E. kraemeri are described: selection of sources of resistance, hybridization of selected materials, and selection of resistant progenies. (CIAT)Se mencionan los objetivos generales del programa de entomologia de frijol del CIAT. La mayor prioridad se ha dado a la resistencia var. como metodo ideal de control de plagas. En la sede principal del CIAT (Palmira, Colombia) se adelantan estudios con Empoasca kraemeri, acaros e insectos del frijol almacenado; en otras instituciones se esta estudiando la resistencia var. a Apion godmani y a Epinotia aporema. Se describen las etapas de mejoramiento genetico del frijol por resistencia a E. kraemeri: escogencia de fuentes de resistencia, hibridacion de los materiales seleccionados y seleccion de progenies resistentes. (CIAT

Functional Cellular Anti-Tumor Mechanisms are Augmented by Genetic Proteoglycan Targeting.

While recent research points to the importance of glycans in cancer immunity, knowledge on functional mechanisms is lacking. In lung carcinoma among other tumors, anti-tumor immunity is suppressed; and while some recent therapies boost T-cell mediated immunity by targeting immune-checkpoint pathways, robust responses are uncommon. Augmenting tumor antigen-specific immune responses by endogenous dendritic cells (DCs) is appealing from a specificity standpoint, but challenging. Here, we show that restricting a heparan sulfate (HS) loss-of-function mutation in the HS sulfating enzyme Ndst1 to predominantly conventional DCs (Ndst1f/f CD11cCre+ mutation) results in marked inhibition of Lewis lung carcinoma growth along with increased tumor-associated CD8+ T cells. In mice deficient in a major DC HS proteoglycan (syndecan-4), splenic CD8+ T cells showed increased anti-tumor cytotoxic responses relative to controls. Studies examining Ndst1f/f CD11cCre + mutants revealed that mutation was associated with an increase in anti-tumor cytolysis using either splenic CD8+ T cells or tumor-infiltrating (TIL) CD8+ T cells purified ex-vivo, and tested in pooled effector-to-target cytolytic assays against tumor cells from respective animals. On glycan compositional analysis, HS purified from Ndst1f/f CD11cCre + mutant DCs had reduced overall sulfation, including reduced sulfation of a tri-sulfated disaccharide species that was intriguingly abundant on wildtype DC HS. Interestingly, antigen presentation in the context of major histocompatibility complex class-I (MHC-I) was enhanced in mutant DCs, with more striking effects in the setting of HS under-sulfation, pointing to a likely regulatory role by sulfated glycans at the antigen/MHC-I - T-cell interface; and possibly future opportunities to improve antigen-specific T cell responses by immunologic targeting of HS proteoglycans in cancer

A FLAMINGOS Deep Near Infrared Imaging Survey of the Rosette Complex I: Identification and Distribution of the Embedded Population

We present the results of a deep near-infrared imaging survey of the Rosette Complex. We studied the distribution of young embedded sources using a variation of the Nearest Neighbor Method applied to a carefully selected sample of near-infrared excess (NIRX) stars which trace the latest episode of star formation in the complex. Our analysis confirmed the existence of seven clusters previously detected in the molecular cloud, and identified four more clusters across the complex. We determined that 60% of the young stars in the complex and 86% of the stars within the molecular cloud are contained in clusters, implying that the majority of stars in the Rosette formed in embedded clusters. We compare the sizes, infrared excess fractions and average extinction towards individual clusters to investigate their early evolution and expansion. We found that the average infrared excess fraction of clusters increases as a function of distance from NGC 2244, implying a temporal sequence of star formation across the complex. This sequence appears to be primordial, possibly resulting from the formation and evolution of the molecular cloud and not from the interaction with the HII region.Comment: Accepted by Astrophysical Journa

Optimizing the Model of the Viking-400 UAS

This project intends to update and redesign imperfections in the scanned 3D CAD model of the Viking 400 aircraft. This aircraft, similar to the Sierra-B UAS, will carry payloads of scientific instruments for research purposes. The goals of this project are to modify the current scanned model such that it better represents the physical qualities of the aircraft, as well as creating the features that are missing from the model. As the model was imported from a different software, many of the critical surfaces did not accurately reflect the actual aircraft. Those parts of the model were redesigned entirely so that they can be edited for future use, as well as correctly representing the aircraft as it is now. Additionally, parts of the aircraft that did not appear in the scanned model were designed and added to the new model. In order to prioritize ease of use for future missions, the model has been reorganized in a logical fashion that enables modification of specific parts of the aircraft. The organization of this model imitates the drawing tree of the Sierra-B, with the intention of maintaining a functional system of redesign, analysis, and implementation. Ultimately, this project will be a catalyst for making Viking 400 into a functional aircraft and increasing scientific research in airborne vehicles

A computer aided approach for river styles-inspired characterization of large basins: The Magdalena river (Colombia)

This paper addresses the geomorphic characterization and classification of large rivers in a framework of scarce information. This is inspired by the River Styles Framework with some modifications that make the process more straightforward and accessible to practitioners and more applicable to large basins, while reducing the subjective, expert-based inputs, as the process is now more systematic. To this aim, it utilizes innovative criteria and some computer-aided procedures and tools based on GIS, Excel and Python. This approach sheds light on the character and the behavior of rivers, which is key to informing planning, management and restoration. The application to the Magdalena River (Colombia) illustrates the characterization and classification process and the type of results, which ultimately highlight the great geomorphic diversity of that river. The process is applicable to many other rivers worldwide