Cu(II) complexes with heterocyclic substituted thiosemicarbazones: the case of 5-formyluracil. Synthesis,characterization, x-ray structures,DNA interaction studies,and biological activity

Two new 5-formyluracil thiosemicarbazone (H(3)ut) derivatives, Me-H(3)ut (1) and Me(2)-H(3)ut (2), were synthesized by reacting thiosemicarbazides, mono- and dimethylated on the aminic nitrogen, with 5-formyluracil and were subsequently characterized. These ligands, treated with copper chloride and nitrate, afforded three complexes: [Cu(Me-H(3)ut)Cl(2)].H(2)O (3), [Cu(Me(2)-H(3)ut)Cl(2)].H(2)O (4), and [Cu(Me-H(3)ut)(NO(3))(OH(2))(2)]NO(3) (5). The crystal structures of these complexes have been determined by single-crystal X-ray diffraction. In 3 and 4, a similar pentacoordination is present; the copper atom is surrounded by the ligand SNO donor atoms and by two chloride ions. The structure of 5 consists of [Cu(Me-H(3)ut)(NO(3))(OH(2))(2)](+) cations and nitrate anions. The copper coordination (4 + 2) involves the SNO ligand atoms and a water oxygen in the basal plane; the apical positions are occupied by a second water oxygen and by an oxygen of a monodentate nitrate group. Two biochemical techniques, namely DNA titration in the UV-vis region and thermal denaturation, have been employed to probe the details of DNA binding of these compounds. Analysis of the results suggests that our compounds are able to interact with DNA by electrostatic and groove binding but not by intercalation. The compounds have been also tested in vitro on human leukemic cell line U937, but they are not able to inhibit significantly cell proliferation.     

Reversible addition–fragmentation chain transfer polymerization of alkyl‐2‐cyanoacrylates: An assessment of livingness

Alkyl 2‐cyanoacrylates (CAs) are primarily used as instant adhesives, including those sold under the Loctite brand. The adhesive action can be inhibited with acid stabilizers allowing radical polymerization to be employed. The following article details the first attempted controlled/living radical polymerization of alkyl CAs: Reversible addition fragmentation chain transfer (RAFT) polymerization mediated by a poly(methyl methacrylate) dithiobenzoate macroRAFT agent for three different CA monomers (ethyl 2‐cyanoacrylate, n‐butyl 2‐cyanoacrylate, and 2‐phenylethyl cyanoacrylate) allowed the preparation of the first block copolymers of this challenging but commercially important monomer class. Nevertheless, GPC with UV detection indicated significant loss of the RAFT end‐group for all three CAs limiting control/living character. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1397–1408     

Weighted a priori estimates for solution of (−Δ)<Superscript><Emphasis Type="Italic">m</Emphasis></Superscript><Emphasis Type="Italic">u</Emphasis> = <Emphasis Type="Italic">f</Emphasis> with homogeneous dirichlet conditions

Let u be a weak solution of (-△)mu = f with Dirichlet boundary conditions in a smooth bounded domain Ω  Rn. Then, the main goal of this paper is to prove the following a priori estimate:‖u‖ Wω2 m,p(Ω) ≤ C ‖f‖ Lωp (Ω),where ω is a weight in the Muckenhoupt class Ap.     

Aλδ-calculus with an algorithmicδ

In this paper we propose a system, based on-calculus, where the restriction of Church's to normal forms is dropped, while the monotony properties are weakened. The main feature of such a system is that the Church-Rosser property is maintained and all provable equalities between closed terms are semidecidable within it.     

Crystal and molecular structure of nitrosyl(1,10-phenanthroline)-bis(triphenylphosphine)iridium(I) Dihexafluorophosphate, [Ir(NO)(phen)(PPh3)2][PF6]2

Summary The structure of [Ir(NO)(phen)(PPh₃)₂][PF₆]₂ has been determined from x-ray diffractometer data. The compound crystallizes in space groupPnam with four molecules in a unit cell witha = 19.924(12),b = 14.793(9) andc = 16.348(9) A. Full-matrix least-squares refinement has led to a final R value of 0.061 for the 4796 observed reflections. The structure consists of well-separated ions, and the geometry around the metal is trigonal bipyramidal with nitrosyl and bidentate 1,10-phenanthroline (in spite of the very narrow bite angle of 75.8°) ligands occupying the equatorial positions and the triphenylphosphine ligands the axial positions. The cation has an imposed crystallographicm symmetry. Important bond lengths are as follows: Ir-P, 2.391(3): Ir-N (nitrosyl) 1.700(12): Ir-N (1,10-phenanthroline) 2.103(12) and 2.142(11): N-O, 1.201(18)A. The nitrosyl ligand is linear [Ir-N-O = 179.9(9)°] so that this complex can be formulated as an NO⁺ complex of iridium(I).     

A characterization of projective-planar signed graphs

A signed graph has a plus or minus sign on each edge. A simple cycle is positive or negative depending on whether it contains an even or odd number of negative edges, respectively. We consider embeddings of a signed graph in the projective plane for which a simple cycle is essential if and only if it is negative. We characterize those signed graphs that have such a projective-planar embedding. Our characterization is in terms of a related signed graph formed by considering the theta subgraphs in the given graph.     

Formality of Donaldson submanifolds

We introduce the concept of s–formal minimal model as an extension of formality. We prove that any orientable compact manifold M, of dimension 2n or (2n−1), is formal if and only if M is (n−1)–formal. The formality and the hard Lefschetz property are studied for the Donaldson submanifolds of symplectic manifolds constructed in [13]. This study permits us to show an example of a Donaldson symplectic submanifold of dimension eight which is formal simply connected and does not satisfy the hard Lefschetz theorem. An erratum to this article is available at .     

The complex Busemann-Petty problem for arbitrary measures

The complex Busemann-Petty problem asks whether origin symmetric convex bodies in with smaller central hyperplane sections necessarily have smaller volume. The answer is affirmative if and negative if . In this article we show that the answer remains the same if the volume is replaced by an “almost” arbitrary measure. This result is the complex analogue of Zvavitch’s generalization to arbitrary measures of the original real Busemann-Petty problem. Received: 6 May 2008     

Vertical and nonvertical participation by sulfur,selenium, and tellurium

The mechanism of stabilization of positive charge on carbon by sulfur, selenium, or tellurium at the beta-position has been investigated kinetically, by measurement of rate enhancements, and structurally, by variation of the bond strength to the leaving group. Stabilization can occur either nonvertically with formation of a bridged intermediate or vertically through hyperconjugation within an open carbocation. We observed large rate enhancements (10(5) for S, 10(6) for Se) in 97% aqueous trifluoroethanol with trifluoroacetate as the leaving group. These enhancements are consistent with either mechanism. Product structures also are consistent with either mechanism. Nine crystal structures revealed that the bond to the leaving group (C-O) is lengthened by the presence of S or Se at the beta-position, in proportion to the basicity of the leaving group. This lengthening is not accompanied by angle distortions expected for the bridging mechanism. The crystallographic data support vertical (hyperconjugative) character along the reaction coordinate, more so for selenium than sulfur.