Mercuric triflate catalyzed hydroxylative carbocyclization of 1,6-enynes

[reaction: see text] Hg(OTf)(2) exhibits remarkable catalytic activity for the hydroxylative cyclization of 1,6-enynes. The present procedure should involve a sequence of mercuration of a terminal alkyne, carbocyclization, hydration, and protodemercuration that regenerates the catalyst.     

On Transfer Operators for Continued Fractions with Restricted Digits

For any non-empty subset I of the natural numbers, let _I denotethose numbers in the unit interval whose continued fractiondigits all lie in I. Define the corresponding transfer operator for , where Re (rß) = _I is the abscissa of convergence of the series . When acting on a certain Hilbert space H_I, rß, weshow that the operator L_I, rß is conjugate to an integraloperator K_I, rß. If furthermore rß is real,then K_I, rß is selfadjoint, so that L_I, rß: H_I, rß H_I, rß has purely real spectrum.It is proved that L_I, rß also has purely real spectrumwhen acting on various Hilbert or Banach spaces of holomorphicfunctions, on the nuclear space C [0, 1], and on the Fréchetspace C [0, 1]. The analytic properties of the map rß L_I, rßare investigated. For certain alphabets I of an arithmetic nature(for example, I = primes, I = squares, I an arithmetic progression,I the set of sums of two squares it is shown that rß L_I, rß admits an analytic continuation beyond thehalf-plane Re rß > _I. 2000 Mathematics SubjectClassification 37D35, 37D20, 30B70.     

Influence of rhodium additive on hydrogen electrosorption in palladium-rich Pd�CRh alloys

Hydrogen electrosorption into Pd-rich (>80?at.% Pd in the bulk) Pd?CRh alloys has been studied in acidic solutions (0.5?M H₂SO₄) using cyclic voltammetry and chronoamperometry. The influence of temperature (in the range between 283 and 328?K), electrode potential and alloy bulk composition on hydrogen electrosorption properties of Pd?CRh alloys is presented. It has been found that the additive of Rh to Pd?CRh alloys increases the maximum hydrogen solubility (for Rh bulk content below 10?at.%), decreases the potential of absorbed hydrogen oxidation peak and decreases the potential of the ???????? phase transition. Increasing temperature decreases the potential of absorbed hydrogen oxidation peak, the maximum hydrogen solubility, and the potential of the ???????? phase transition. The amounts of electrosorbed hydrogen for ??- and ??-phase boundaries, i.e., ??_max and ??_min, have been determined from the integration of the initial parts of current?Ctime responses in hydrogen absorption and desorption processes. The H/M ratio corresponding to ??_max increases with increasing Rh content, while for ??_min a maximum of H/M ratio is observed for the alloys containing ca. 95% Rh.     

Nuclear structure effects in the isotope shift with halo nuclei

Corrections to atomic energy levels due to nuclear structure effects are discussed. These are the finite nuclear size combined with relativistic and recoil corrections, and the nuclear polarizability. Good understanding of these effects is necessary for interpretation of high-precision measurements of the isotope shifts with neutron-rich nuclei ^6,8He, ¹¹Li and ¹¹Be. The summary of the results of the accurate atomic structure calculations is presented also.     

Relatively finite measure-preserving extensions and lifting multipliers by Rokhlin cocycles

We show that under some natural ergodicity assumptions, extensions given by Rokhlin cocycles lift the multiplier property if the associated locally compact group extension has only countably many L^∞-eigenvalues. We make use of some analogs of basic results from the theory of finite-rank modules associated to an extension of measure-preserving systems in the setting of a non-singular base.     

The equilibrium states for semigroups of rational maps

We consider the dynamics of skew product maps associated with finitely generated semigroups of rational maps on the Riemann sphere. We show that under some conditions on the dynamics and the potential function ψ, there exists a unique equilibrium state for ψ and a unique exp(P(ψ) − ψ)-conformal measure, where P(ψ) denotes the topological pressure of ψ. The research of M. Urbański was supported in part by the NSF Grant DMS 0400481. H. Sumi thanks University of North Texas for kind hospitality, during his stay there.     

Crystal structure of a novel synthetic inhibitor of HIV-1 protease

The crystal structure of a novel non-peptidic HIV-1 protease inhibitor derived by simple solid-state dimerization of 4-aryl-1,4-dihydropyridines, reveals a strained central cage and the conformation of its phenyl, benzyl, and hydroxymethylene substituents. The polycyclic cage includes two nearly flat cyclobutane rings and four fused piperidine rings in boat conformations. The cage geometry reveals two unexpected features, namely marked distortions of the valence angles in every second piperidine and a shortening of one of the cyclobutane bonds. The molecule displays exact centrosymmetry, but the central cage and the hydroxymethylene substituents also approximate the C₂-symmetry of the target enzyme. The two independent hydroxyl groups are involved in intermolecular hydrogen bonding, one as a donor, the other as an acceptor. The disposition of the hydroxyl groups in the molecular framework is compatible with the dual role of the inhibitor in the active-site cavity of HIV-1 protease, whereby one OH group is hydrogen-bonded to the catalytic aspartates, whereas another one provides an interface to the locked flaps of the enzyme.     

Analysis of terpenes in white wines using SPE-SPME-GC/MS approach

Terpenes contribute to some white wines aroma, especially these produced from Muscat grapes and others aromatic ones of high terpene contents (Gewürtztramminer, Traminer, Huxel, Sylvaner). Terpenes are present in wine in free and bound (in a form of glycosides) forms. Analyses of bound terpenes are usually performed using solid phase extraction after hydrolysis of glycosides. A new method for determination of terpenes from wine, focused on determination of terpenes released after acidic hydrolysis, based on solid phase extraction (SPE) followed by solid phase microextraction (SPME) was developed. Non-polar (free) and polar (bound terpenes) fractions were separated on 500 mg C18 cartridges. Bound terpenes were sampled using SPME immediately after acidic hydrolysis in non-equilibrium conditions. Application of combined SPE-SPME approach allowed quantification of selected terpenes in lower concentrations than in SPE approach and added a selectivity to the method, which enabled detection of compounds non-detectable in SPE extracts. Results obtained by SPE and SPE-SPME approach were correlated for free terpenes and those released after acid hydrolysis 20 white wines obtained from different grape varieties (R² = 0.923). Although developed for wine terpenes analysis, SPE followed by SPME approach has a great potential in analysis of other bound wine flavor compounds, especially those potent odorants present in trace amounts.     

EPR evidence of antiferromagnetic ordering in single‐layer graphene

We report electron paramagnetic resonance (EPR) evidence of the antiferromagnetic ordering in pristine single‐layer graphene. Temperature dependences of the parameters of EPR spectra obtained for vacuum‐processed samples were studied within the temperature range of 4.2–300 K. Our experiment has confirmed recent theoretical predictions that in single‐layer graphene the carrier‐mediated exchange interaction leads to antiferromagnetic coupling. We note some quantitative discrepancies between the theory and experimental findings and discuss their origins. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)