Enzymatic functionalization of carbon-hydrogen bonds

The development of new catalytic methods to functionalize carbon–hydrogen (C–H) bonds continues to progress at a rapid pace due to the significant economic and environmental benefits of these transformations over traditional synthetic methods. In nature, enzymes catalyze regio- and stereoselective C–H bond functionalization using transformations ranging from hydroxylation to hydroalkylation under ambient reaction conditions. The efficiency of these enzymes relative to analogous chemical processes has led to their increased use as biocatalysts in preparative and industrial applications. Furthermore, unlike small molecule catalysts, enzymes can be systematically optimized via directed evolution for a particular application and can be expressed in vivo to augment the biosynthetic capability of living organisms. While a variety of technical challenges must still be overcome for practical application of many enzymes for C–H bond functionalization, continued research on natural enzymes and on novel artificial metalloenzymes will lead to improved synthetic processes for efficient synthesis of complex molecules. In this critical review, we discuss the most prevalent mechanistic strategies used by enzymes to functionalize non-acidic C–H bonds, the application and evolution of these enzymes for chemical synthesis, and a number of potential biosynthetic capabilities uniquely enabled by these powerful catalysts (110 references)

Heavy Pair Production Currents with General Quantum Numbers in Dimensionally Regularized NRQCD

We discuss the form and construction of general color singlet heavy particle-antiparticle pair production currents for arbitrary quantum numbers, and issues related to evanescent spin operators and scheme-dependences in nonrelativistic QCD (NRQCD) in n=3-2epsilon dimensions. The anomalous dimensions of the leading interpolating currents for heavy quark and colored scalar pairs in arbitrary (2S+1)L_J angular-spin states are determined at next-to-leading order in the nonrelativistic power counting.Comment: 39 pages, 2 tables, 10 figures; typos corrected, published versio

Phase Space Matching and Finite Lifetime Effects for Top-Pair Production Close to Threshold

The top-pair $t\bar t$ production cross section close to threshold in $e^+e^-$ collisions is strongly affected by the small lifetime of the top quark. Since the cross section is defined through final states containing the top decay products, a consistent definition of the cross section depends on prescriptions how these final states are accounted for the cross section. Experimentally, these prescriptions are implemented for example through cuts on kinematic quantities such as the reconstructed top quark invariant masses. As long as these cuts do not reject final states that can arise from the decay of a top and an anti-top quark with a small off-shellness compatible with the nonrelativistic power-counting, they can be implemented through imaginary phase space matching conditions in NRQCD. The prescription-dependent cross section can then be determined from the optical theorem using the $e^+e^-$ forward scattering amplitude. We compute the phase space matching conditions associated to cuts on the top and anti-top invariant masses at next-to-next-to-leading logarithmic (NNLL) order and partially at next-to-next-to-next-to-leading logarithmic (N${}^3$LL) order in the nonrelativistic expansion and, together with finite lifetime and electroweak effects known from previous work, analyze their numerical impact on the $t\bar t$ cross section. We show that the phase space matching contributions are essential to make reliable NRQCD predictions, particularly for energies below the peak region, where the cross section is small. We find that irreducible background contributions associated to final states that do not come from top decays are strongly suppressed and can be neglected for the theoretical predictions.Comment: 62 pages, 21 figure

Characterization of a rare analphoid supernumerary marker chromosome in mosaic

Abstract publicado em: Chromosome Research. 2015;23(Suppl 1):67-8. doi:10.1007/s10577-015-9476-6Analphoid supernumerary marker chromosomes (SMCs) are a rare subclass of SMCs C-band-negative and devoid of alpha-satellite DNA. These marker chromosomes cannot be identified unambiguously by conventional banding techniques alone being necessary to apply molecular cytogenetic methods in favour of a detailed characterization. In this work we report an analphoid SMC involving the terminal long arm of chromosome 7, in 9 years-old boy with several dysmorphic features and severe development delay. Cytogenetic analysis revealed a mosaic karyotype with the presence of an extra SMC, de novo, in 20 % of lymphocytes and 73 % of fibroblast cells. FISH analysis with alpha-satellite probes for all chromosomes, whole chromosome painting probe for chromosome 7, and D7S427 and TelVysion 7q probes, allowed establishing the origin of the SMC as an analphoidmarker resulting of an invdup rearrangement of 7q36-qter region. Affimetrix CytoScan HD microarray analysis, redefined the SMC to arr[hg19] 7q35(143696249-159119707)×2~3, which correspond to a gain of 15.42 Mb and encloses 67 OMIM genes, 16 of which are associated to disease. This result, combined with detailed clinical description, will provide an important means for better genotype-phenotype correlation and a more suitable genetic counselling to the patient and his parents, despite the additional difficulty resulting from being a mosaic (expression varies in different tissues). Analphoid SMCs derived from chromosome 7 are very rare, with only three cases reported so far. With this case we hope contribute to a better understanding of this type of chromosome rearrangements which are difficult for genetic counselling

Search for Higgs Bosons in SUSY Cascade Decays and Neutralino Dark Matter

The Minimal Supersymmetric Extension of the Standard Model (MSSM) is a well motivated theoretical framework, which contains an extended Higgs sector, including a light Higgs with Standard Model-like properties in most of the parameter space. Due to the large QCD background, searches for such a Higgs, decaying into a pair of bottom quarks, is very challenging at the LHC. It has been long realized that the situation may be ameliorated by searching for Higgs bosons in supersymmetric decay chains. Moreover, it has been recently suggested that the bobber decay channel may be observed in standard production channels by selecting boosted Higgs bosons, which may be easily identified from the QCD background. Such boosted Higgs bosons are frequent in the MSSM, since they are produced from decays of heavy colored supersymmetric particles. Previous works have emphasized the possibility of observing boosted Higgs bosons in the light higgsino region. In this work, we study the same question in the regions of parameter space consistent with a neutralino dark matter relic density, analyzing its dependence on the non-standard Higgs boson, slepton and squark masses, as well as on the condition of gaugino mass unification. In general, we conclude that, provided sleptons are heavier than the second lightest neutralinos, the presence of boosted Higgs is a common MSSM feature, implying excellent prospects for observation of the light MSSM Higgs boson in the near future.Comment: 30 pages, 9 figures. v2: New Xenon 100 results implemented, version to appear in PR

You are What you Eat (and Drink): Identifying Cultural Boundaries by Analyzing Food & Drink Habits in Foursquare

Food and drink are two of the most basic needs of human beings. However, as society evolved, food and drink became also a strong cultural aspect, being able to describe strong differences among people. Traditional methods used to analyze cross-cultural differences are mainly based on surveys and, for this reason, they are very difficult to represent a significant statistical sample at a global scale. In this paper, we propose a new methodology to identify cultural boundaries and similarities across populations at different scales based on the analysis of Foursquare check-ins. This approach might be useful not only for economic purposes, but also to support existing and novel marketing and social applications. Our methodology consists of the following steps. First, we map food and drink related check-ins extracted from Foursquare into users' cultural preferences. Second, we identify particular individual preferences, such as the taste for a certain type of food or drink, e.g., pizza or sake, as well as temporal habits, such as the time and day of the week when an individual goes to a restaurant or a bar. Third, we show how to analyze this information to assess the cultural distance between two countries, cities or even areas of a city. Fourth, we apply a simple clustering technique, using this cultural distance measure, to draw cultural boundaries across countries, cities and regions.Comment: 10 pages, 10 figures, 1 table. Proceedings of 8th AAAI Intl. Conf. on Weblogs and Social Media (ICWSM 2014