Graph Games on Ordinals

We consider an extension of Church\'s synthesis problem to ordinals by adding limit transitions to graph games. We consider game arenas where these limit transitions are defined using the sets of cofinal states. In a previous paper, we have shown that such games of ordinal length are determined and that the winner problem is PSPACE-complete, for a subclass of arenas where the length of plays is always smaller than \\omega^\\omega. However, \nthe proof uses a rather involved reduction to classical Muller games, and the resulting strategies need infinite memory. \n \nWe adapt the LAR reduction to prove the determinacy in the general case, and to generate strategies with finite memory, using a reduction to games where the limit transitions are defined by priorities. We provide an algorithm for computing the winning regions of both players in these games, with a complexity similar to parity games. Its analysis yields three results: determinacy without hypothesis on the length of the plays, existence of \nmemoryless strategies, and membership of the winner problem in NP and co-NP

Minimizing Tree Automata for Unranked Trees

International audienceAutomata for unranked trees form a foundation for XML schemas, querying and pattern languages. We study the problem of efficiently minimizing such automata. We start with the unranked tree automata (UTAs) that are standard in database theory, assuming bottom-up determinism and that horizontal recursion is represented by deterministic finite automata. We show that minimal UTAs in that class are not unique and that minimization is NP-hard. We then study more recent automata classes that do allow for polynomial time minimization. Among those, we show that bottom-up deterministic stepwise tree automata yield the most succinct representations

Scope and Mechanistic Study of the Coupling Reaction of α,β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4– (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C–H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as follows: rate = k[1]1[propene]0[cinnamate]−1. A negligible deuterium kinetic isotope effect (kH/kD = 1.1 ± 0.1) was measured from both (E)-C6H5CH═C(CH3)CONHCH3 and (E)-C6H5CD═C(CH3)CONHCH3 with styrene. In contrast, a significant normal isotope effect (kH/kD = 1.7 ± 0.1) was observed from the reaction of (E)-C6H5CH═C(CH3)CONHCH3 with styrene and styrene-d8. A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C6H5CH═CHCO2Et with propene (13C(recovered)/13C(virgin) at Cβ = 1.019(6)), while a negligible carbon isotope effect (13C(recovered)/13C(virgin) at Cβ = 0.999(4)) was obtained from the reaction of (E)-C6H5CH═C(CH3)CONHCH3 with styrene. Hammett plots from the correlation of para-substituted p-X-C6H4CH═CHCO2Et (X = OCH3, CH3, H, F, Cl, CO2Me, CF3) with propene and from the treatment of (E)-C6H5CH═CHCO2Et with a series of para-substituted styrenes p-Y-C6H4CH═CH2 (Y = OCH3, CH3, H, F, Cl, CF3) gave the positive slopes for both cases (ρ = +1.1 ± 0.1 and +1.5 ± 0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, ΔH⧧ = 20 ± 2 kcal mol–1 and ΔS⧧ = −42 ± 5 eu. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies

Two-pronged attack: dual inhibition of Plasmodium falciparum M1 and M17 metalloaminopeptidases by a novel series of hydroxamic acid-based inhibitors

Plasmodium parasites, the causative agents of malaria, have developed resistance to most of our current antimalarial therapies, including artemisinin combination therapies which are widely described as our last line of defense. Antimalarial agents with a novel mode of action are urgently required. Two Plasmodium falciparum aminopeptidases, PfA-M1 and PfA-M17, play crucial roles in the erythrocytic stage of infection and have been validated as potential antimalarial targets. Using compound-bound crystal structures of both enzymes, we have used a structure-guided approach to develop a novel series of inhibitors capable of potent inhibition of both PfA-M1 and PfA-M17 activity and parasite growth in culture. Herein we describe the design, synthesis, and evaluation of a series of hydroxamic acid-based inhibitors and demonstrate the compounds to be exciting new leads for the development of novel antimalarial therapeutics

High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film

[EN] Metal oxide nanoparticles supported on graphene exhibit high catalytic activity for oxidation, reduction and coupling reactions. Here we show that pyrolysis at 900 C under inert atmosphere of copper(II) nitrate embedded in chitosan films affords 1.1.1 facet-oriented copper nanoplatelets supported on few-layered graphene. Oriented (1.1.1) copper nanoplatelets on graphene undergo spontaneous oxidation to render oriented (2.0.0) copper(I) oxide nanoplatelets on few-layered graphene. These films containing oriented copper(I) oxide exhibit as catalyst turnover numbers that can be three orders of magnitude higher for the Ullmann-type coupling, dehydrogenative coupling of dimethylphenylsilane with n-butanol and C–N cross-coupling than those of analogous unoriented graphene-supported copper(I) oxide nanoplatelets.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315) and Generalitat Valenciana (Prometeo 2013-019) is gratefully acknowledged. Partial financial support from European Union (Being Energy project) is also acknowledged. J.F.B. and I. E.-A. thank the Technical University of Valencia and the Spanish Ministry of Science for PhD scholarships, respectively. The authors are grateful to Mrs. Amparo Forneli for her assistance in the sample preparation and to Dr. Agouram Said from SCSIE, University of Valencia for the sample preparation and HRTEM characterization of samples. AD thanks University Grants Commission, New Delhi, for the award of Assistant Professorship under its Faculty Recharge Programme. AD also thanks Department of Science and Technology, India, for the financial support through Fast Track project (SB/FT/CS-166/2013) and the Generalidad Valenciana for financial aid supporting his stay at Valencia through the Prometeo programme. VP thanks UEFISCDI for financial support through PN-II-ID-PCE-2011-3-0060 project (275/2011).Primo Arnau, AM.; Esteve Adell, I.; Blandez Barradas, JF.; Amarajothi, D.; Alvaro Rodríguez, MM.; Candu, N.; Coman, SM.... (2015). High catalytic activity of oriented 2.0.0 copper(I) oxide grown on graphene film. Nature Communications. 6. https://doi.org/10.1038/ncomms9561S85616Huang, J. et al. Nanocomposites of size-controlled gold nanoparticles and graphene oxide: formation and applications in SERS and catalysis. Nanoscale 2, 2733–2738 (2010).Li, X., Wang, X., Song, S., Liu, D. & Zhang, H. 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