Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins, and Trifluoromethylthiolate to Generate Trifluoromethyl Thioethers

Photoinduced, copper-catalyzed coupling reactions are emerging as a powerful method for generating Csp^3–Y (Y = C or heteroatom) bonds from alkyl electrophiles and nucleophiles. Corresponding three-component couplings of alkyl electrophiles, olefins, and nucleophiles have the potential to generate an additional Csp3–Y bond and to efficiently add functional groups to both carbons of an olefin, which serves as a readily available linchpin. In this report, we establish that a variety of electrophiles and a trifluoromethylthiolate nucleophile can add across an array of olefins (including styrenes and electron-poor olefins) in the presence of CuI/binap and blue-LED irradiation, thereby generating trifluoromethyl thioethers in good yield. The process tolerates a wide range of functional groups, and an initial survey of other nucleophiles (i.e., bromide, cyanide, and azide) suggests that this three-component coupling strategy is versatile. Mechanistic studies are consistent with a photoexcited Cu(I)/binap/SCF_3 complex serving as a reductant to generate an alkyl radical from the electrophile, which likely reacts in turn with the olefin and a Cu(II)/SCF_3 complex to afford the coupling product

Two Optimal Strategies for Active Learning of Causal Models from Interventional Data

From observational data alone, a causal DAG is only identifiable up to Markov equivalence. Interventional data generally improves identifiability; however, the gain of an intervention strongly depends on the intervention target, that is, the intervened variables. We present active learning (that is, optimal experimental design) strategies calculating optimal interventions for two different learning goals. The first one is a greedy approach using single-vertex interventions that maximizes the number of edges that can be oriented after each intervention. The second one yields in polynomial time a minimum set of targets of arbitrary size that guarantees full identifiability. This second approach proves a conjecture of Eberhardt (2008) indicating the number of unbounded intervention targets which is sufficient and in the worst case necessary for full identifiability. In a simulation study, we compare our two active learning approaches to random interventions and an existing approach, and analyze the influence of estimation errors on the overall performance of active learning

VO: Vaccine Ontology

Vaccine research, as well as the development, testing, clinical trials, and commercial uses of vaccines involve complex processes with various biological data that include gene and protein expression, analysis of molecular and cellular interactions, study of tissue and whole body responses, and extensive epidemiological modeling. Although many data resources are available to meet different aspects of vaccine needs, it remains a challenge how we are to standardize vaccine annotation, integrate data about varied vaccine types and resources, and support advanced vaccine data analysis and inference. To address these problems, the community-based Vaccine Ontology (VO, "http://www.violinet.org/vaccineontology":http://www.violinet.org/vaccineontology) has been developed through collaboration with vaccine researchers and many national and international centers and programs, including the National Center for Biomedical Ontology (NCBO), the Infectious Disease Ontology (IDO) Initiative, and the Ontology for Biomedical Investigations (OBI). VO utilizes the Basic Formal Ontology (BFO) as the top ontology and the Relation Ontology (RO) for definition of term relationships. VO is represented in the Web Ontology Language (OWL) and edited using the Protégé-OWL. Currently VO contains more than 2000 terms and relationships. VO emphasizes on classification of vaccines and vaccine components, vaccine quality and phenotypes, and host immune response to vaccines. These reflect different aspects of vaccine composition and biology and can thus be used to model individual vaccines. More than 200 licensed vaccines and many vaccine candidates in research or clinical trials have been modeled in VO. VO is being used for vaccine literature mining through collaboration with the National Center for Integrative Biomedical Informatics (NCIBI). Multiple VO applications will be presented.
&#xa

Dimension and bases for geometrically continuous splines on surfaces of arbitrary topology

We analyze the space of geometrically continuous piecewise polynomial functions, or splines, for rectangular and triangular patches with arbitrary topology and general rational transition maps. To define these spaces of G 1 spline functions, we introduce the concept of topological surface with gluing data attached to the edges shared by faces. The framework does not require manifold constructions and is general enough to allow non-orientable surfaces. We describe compatibility conditions on the transition maps so that the space of differentiable functions is ample and show that these conditions are necessary and sufficient to construct ample spline spaces. We determine the dimension of the space of G1 spline functions which are of degree less than or equal to k on triangular pieces and of bi-degree less than or equal to (k, k) on rectangular pieces, for k big enough. A separability property on the edges is involved to obtain the dimension formula. An explicit construction of basis functions attached resspectively to vertices, edges and faces is proposed; examples of bases of G1 splines of small degree for topological surfaces with boundary and without boundary are detailed

Photografted methacrylate-based monolithic columns coated with cellulose tris(3,5-dimethylphenylcarbamate) for chiral separation in CEC

A chiral capillary monolithic column for enantiomer separation in capillary electrochromatography was prepared by coating cellulose tris(3,5-dimethylphenylcarbamate) on porous glycidyl methacrylate-co-ethylene dimethacrylate monolith in capillary format grafted with chains of [2(methacryloyloxy)ethyl] trimethylammonium chloride. The surface modification of the monolith by the photografting of [2(methacryloyloxy)ethyl] trimethylammonium chloride monomer as well as the coating conditions of cellulose tris(3,5-dimethylphenylcarbamate) onto the grafted monolithic scaffold were optimized to obtain a stable and reproducible chiral stationary phase for capillary electrochromatography. The effect of organic modifier (acetonitrile) in aqueous mobile phase for the enantiomer separation by capillary electrochromatography was also investigated. Several pairs of enantiomers including acidic, neutral, and basic analytes were tested and most of them were partially or completely resolved under aqueous mobile phases. The prepared monolithic chiral stationary phases exhibited a good stability, repeatability, and column-to-column reproducibility, with relative standard deviations below 11% in the studied electrochromatographic parameters.Fil: Echevarria, Romina Noel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; ArgentinaFil: Carrasco Correa, Enrique Javier. Universidad de Valencia; EspañaFil: Keunchkarian, Sonia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; ArgentinaFil: Reta, Mario Roberto. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Herrero Martinez, José Manuel. Universidad de Valencia; Españ

Techno-economic model of a second-life energy storage system for utility-scale solar power considering li-ion calendar and cycle aging

While the use of energy storage combined with grid-scale photovoltaic power plants continues to grow, given current lithium-ion battery prices, there remains uncertainty about the profitability of these solar-plus-storage projects. At the same time, the rapid proliferation of electric vehicles is creating a fleet of millions of lithium-ion batteries that will be deemed unsuitable for the transportation industry once they reach 80 percent of their original capacity. The repurposing and deployment of these batteries as stationary energy storage provides an opportunity to reduce the cost of solar-plus-storage systems, if the economics can be proven. We present a techno-economic model of a solar-plus-second-life energy storage project in California, including a data-based model of lithium nickel manganese cobalt oxide battery degradation, to predict its capacity fade over time, and compare it to a project that uses a new lithium-ion battery. By setting certain control policy limits, to minimize cycle aging, we show that a system with SOC limits in a 65 to 15 percent range, extends the project life to over 16 years, assuming a battery reaches its end-of-life at 60 percent of its original capacity. Under these conditions, a second-life project is more economically favorable than a project that uses a new battery and 85 to 20 percent SOC limits, for second-life battery costs that are less than 80 percent of the new battery. The same system reaches break-even and profitability for second-life battery costs that are less than 60 percent of the new battery. Our model shows that using current benchmarked data for the capital and O&M costs of solar-plus-storage systems, and a semi-empirical data-based degradation model, it is possible for EV manufacturers to sell second-life batteries for less than 60 percent of their original price to developers of profitable solar-plus-storage projects.Comment: 19 pages, 6 figure

CYP72A enzymes catalyse 13-hydrolyzation of gibberellins

Bioactive gibberellins (GAs, diterpenes) are essential hormones in land plants, controlling many aspects of plant growth and developments. In flowering plants, 13-OH (low bioactivity; such as GA1) and 13-H GAs (high bioactivity; such as GA4) frequently coexist. However, the bona fide GA 13-hydroxylase and its physiological functions in Arabidopsis remain unknown. Here, we report that novel cytochrome P450 genes (CYP72A9 and its homologs) encode active GA 13- hydroxylases in Brassicaceae plants. CYP72A9-overexpressing plants exhibited semi-dwarfism, which was caused by significant reduction in GA4 levels. Biochemical assays revealed that recombinant CYP72A9 protein catalyzed the conversion from 13-H GAs to the corresponding 13-OH GAs. CYP72A9 was expressed predominantly in developing seeds in Arabidopsis. Freshly harvested seeds of cyp72a9 mutants germinated more quickly than wild-type, while long-term storage and stratification-treated seeds did not. The evolutionary origin of GA 13- oxidases from the CYP72A subfamily also was investigated and discussed here

High-Precision Extraction of Emerging Concepts from Scientific Literature

Identification of new concepts in scientific literature can help power faceted search, scientific trend analysis, knowledge-base construction, and more, but current methods are lacking. Manual identification cannot keep up with the torrent of new publications, while the precision of existing automatic techniques is too low for many applications. We present an unsupervised concept extraction method for scientific literature that achieves much higher precision than previous work. Our approach relies on a simple but novel intuition: each scientific concept is likely to be introduced or popularized by a single paper that is disproportionately cited by subsequent papers mentioning the concept. From a corpus of computer science papers on arXiv, we find that our method achieves a Precision@1000 of 99%, compared to 86% for prior work, and a substantially better precision-yield trade-off across the top 15,000 extractions. To stimulate research in this area, we release our code and data (https://github.com/allenai/ForeCite).Comment: Accepted to SIGIR 202

Interaction of anticancer reduced Schiff base coumarin derivatives with human serum albumin investigated by fluorescence quenching and molecular modeling

The specific binding of five reduced Schiff base derived 7-amino-coumarin compounds with antitumor activity to human serum albumin, the principal binding protein of blood, was studied by fluorescence spectroscopy. Their conditional binding constants were computed and the reversible binding at the Sudlow’s site I was found to be strong (KD ~ 0.03-2.09 M). Based on the data albumin can provide a depot for the compounds and is responsible for their biodistribution and transport processes. The experimental data is complemented by protein– ligand docking calculations for two representatives which support the observations. The proton dissociation constants of the compounds were also determined by UV-Vis spectrophotometric and fluorometric titrations to obtain the actual charges and distribution of the species in the various protonation states at physiological pH

Wall Orientation and Shear Stress in the Lattice Boltzmann Model

The wall shear stress is a quantity of profound importance for clinical diagnosis of artery diseases. The lattice Boltzmann is an easily parallelizable numerical method of solving the flow problems, but it suffers from errors of the velocity field near the boundaries which leads to errors in the wall shear stress and normal vectors computed from the velocity. In this work we present a simple formula to calculate the wall shear stress in the lattice Boltzmann model and propose to compute wall normals, which are necessary to compute the wall shear stress, by taking the weighted mean over boundary facets lying in a vicinity of a wall element. We carry out several tests and observe an increase of accuracy of computed normal vectors over other methods in two and three dimensions. Using the scheme we compute the wall shear stress in an inclined and bent channel fluid flow and show a minor influence of the normal on the numerical error, implying that that the main error arises due to a corrupted velocity field near the staircase boundary. Finally, we calculate the wall shear stress in the human abdominal aorta in steady conditions using our method and compare the results with a standard finite volume solver and experimental data available in the literature. Applications of our ideas in a simplified protocol for data preprocessing in medical applications are discussed.Comment: 9 pages, 11 figure