New guanosine derivatives: facile O6-phosphorylation,thiophosphinylation sulfonylation and silylation of guanosine derivatives by 4-dimethylaminopyridine catalized reaction

Appropriately protected guanosine derivatives were successfully converted to the corresponding O⁶-substituted guanosine derivatives by treatment with dialkyl- or diaryl-phosphoryl halides, dialkyl- or diaryl-phosphinothioyl halides, arenesulfonyl chlorides, and trialkylsilyl chlorides.     

Molecular Engineering of Quinone-Based Nickel Complexes and Polymers for All-Organic Li-Ion Batteries

All-organic Li-ion batteries appear to be a sustainable and safer alternative to the currently-used Li-ion batteries but their application is still limited due to the lack of organic compounds with high redox potentials toward Li⁺/Li⁰. Herein, we report a computational design of nickel complexes and coordination polymers that have redox potentials spanning the full voltage range: from the highest, 4.7 V, to the lowest, 0.4 V. The complexes and polymers are modeled by binding low- and high-oxidized Ni ions (i.e., Ni(II) and Ni(IV)) to redox-active para-benzoquinone molecules substituted with carboxyl- and cyano-groups. It is found that both the nickel ions and the quinone-derived ligands are redox-active upon lithiation. The type of Ni coordination also has a bearing on the redox potentials. By combining the complex of Ni(IV) with 2-carboxylato-5-cyano-1,4-benzoquinones as a cathode and Ni(II)-2,5-dicarboxylato-3,6-dicyano-1,4-benzoquinone coordination polymer as an anode, all-organic Li-ion batteries could be assembled, operating at an average voltage exceeding 3.0 V and delivering a capacity of more than 300 mAh/g.     

Dual-Metal Electrolytes for Hybrid-Ion Batteries: Synergism or Antagonism?

The construction of hybrid metal-ion batteries faces a plethora of challenges. A critical one is to unveil the solvation/desolvation processes at the molecular level in electrolytes that ensure efficient transfer of several types of charge carriers. This study reports first results on simulations of mixed-ion electrolytes. All combinations of homo- and hetero-binuclear complexes of Li⁺, Na⁺ and Mg²⁺, solvated with varying number of ethylene carbonate (EC) molecules are modeled in non-polar and polar environment by means of first principles calculations and compared to the mononuclear analogues in terms of stability, spatial organization, charge distribution and solvation/desolvation behavior. The used PF₆⁻ counterion is shown to have minor impact on the geometry of the complexes. The desolvation energy penalty of binuclear complexes can be lowered by the fluoride ions, emerging upon the PF₆⁻ decay. These model investigations could be extended to rationalize the solvation structure and ionic mobility in dual-ion electrolytes.     

In Vitro Antineoplastic and Antiviral Activity and In Vivo Toxicity of Geum urbanum L. Extracts

This study evaluated the in vitro antineoplastic and antiviral potential and in vivo toxicity of twelve extracts with different polarity obtained from the herbaceous perennial plant Geum urbanum L. (Rosaceae). In vitro cytotoxicity was determined by ISO 10993-5/2009 on bladder cancer, (T-24 and BC-3C), liver carcinoma (HEP-G2) and normal embryonic kidney (HEK-293) cell lines. The antineoplastic activity was elucidated through assays of cell clonogenicity, apoptosis induction, nuclear factor kappa B p65 (NFκB p65) activation and total glutathione levels. Neutral red uptake study was applied for antiviral activity. The most promising G. urbanum extract was analyzed by UHPLC–HRMS. The acute in vivo toxicity analysis was carried out following OEDC 423. The ethyl acetate extract of aerial parts (EtOAc-AP) exhibited the strongest antineoplastic activity on bladder cancer cell lines (IC₅₀ = 21.33–25.28 µg/mL) by inducing apoptosis and inhibiting NFκB p65 and cell clonogenicity. EtOAc and n-butanol extracts showed moderate antiviral activity against human adenovirus type 5 and human simplex virus type I. Seventy four secondary metabolites (gallic and ellagic acid derivatives, phenolic acids, flavonoids, etc.) were identified in EtOAc-AP by UHPLC–HRMS. This extract induced no signs of acute toxicity in liver and kidney specimens of H-albino mice in doses up to 210 mg/kg. In conclusion, our study contributes substantially to the detailed pharmacological characterization of G. urbanum, thus helping the development of health-promoting phytopreparations.     

Self-concordant barriers for hyperbolic means

The geometric mean and the function (det(·)) ^1/m (on the m-by-m positive definite matrices) are examples of “hyperbolic means”: functions of the form p ^1/m , where p is a hyperbolic polynomial of degree m. (A homogeneous polynomial p is “hyperbolic” with respect to a vector d if the polynomial t↦p(x+td) has only real roots for every vector x.) Any hyperbolic mean is positively homogeneous and concave (on a suitable domain): we present a self-concordant barrier for its hypograph, with barrier parameter O(m ²). Our approach is direct, and shows, for example, that the function −mlog(det(·)−1) is an m ²-self-concordant barrier on a natural domain. Such barriers suggest novel interior point approaches to convex programs involving hyperbolic means. Received: December 2, 1999 / Accepted: February 2001?Published online September 3, 2001     

On the invertible objects in tensor categories

The invertible objects in a tensor category form a subcategory the Grothendieck ring of which is the group ring of an abelian group. This abelian fusion ring acts on the objects of the initial category and one can in principle determine all 6j-symbols that contain the lable of an invertible object. Received 1st October 2001 / Received in final form 12 April 2002 Published online 2 October 2002 RID="a" ID="a"e-mail: ganchev@inrne.bas.bg     

Timelike surfaces with zero mean curvature in Minkowski 4-space

On any timelike surface with zero mean curvature in the four-dimensional Minkowski space we introduce special geometric (canonical) parameters and prove that the Gauss curvature and the normal curvature of the surface satisfy a system of two natural partial differential equations. Conversely, any two solutions to this system determine a unique (up to a motion) timelike surface with zero mean curvature so that the given parameters are canonical. We find all timelike surfaces with zero mean curvature in the class of rotational surfaces of Moore type. These examples give rise to a one-parameter family of solutions to the system of natural partial differential equations describing timelike surfaces with zero mean curvature.     

The [CH2CHOH.+, CH3CHO] solvated enol radical cation

The bimolecular reaction of the CH₂CHOH^.+ enol ion (m/z 44) with acetaldehyde gives a strongly dominant product,m/z 45, formed mainly by proton transfer from the ion to the molecule. The abundance of the product coming from a H^. abstraction reaction from the neutral, albeit more exothermic, is negligible. In order to explain this result, the long lived [CH₂CHOH^.+, CH₃CHO] solvated ion was generated by reaction of the CH₂CHOH^.+ enol ion with (CH₃CHO) _n in the cell of a Fourier transform ion cyclotron resonance mass spectrometer. The structure of this solvated ion was clearly established. Labeling indicates that [CH₂CHOH^.+, CH₃CHO], upon low energy collisions, reacts by H^. abstraction more rapidly than by H⁺ transfer to the neutral moiety. This shows that the entropic factors are determinant when the enol ion reacts directly with acetaldehyde.     

Kähler manifolds of quasi-constant holomorphic sectional curvatures

The Kähler manifolds of quasi-constant holomorphic sectional curvatures are introduced as Kähler manifolds with complex distribution of codimension two, whose holomorphic sectional curvature only depends on the corresponding point and the geometric angle, associated with the section. A curvature identity characterizing such manifolds is found. The biconformal group of transformations whose elements transform Kähler metrics into Kähler ones is introduced and biconformal tensor invariants are obtained. This makes it possible to classify the manifolds under consideration locally. The class of locally biconformal flat Kähler metrics is shown to be exactly the class of Kähler metrics whose potential function is only a function of the distance from the origin in ? ⁿ . Finally we show that any rotational even dimensional hypersurface carries locally a natural Kähler structure which is of quasi-constant holomorphic sectional curvatures.