A novel effective electrophile: β-trifluoroacetylketene diphenyldithioacetal S,S-tetroxide

A synthesis of a novel electrophilic reagent--β-trifluoroacetylketene diphenyldithioacetal S,S-tetroxide 3 is described. The reaction of 3 with various electron-rich aromatics such as 1,3-dimethoxybenzene, 2-methylthiophene, N-methylpyrrole, and 2-methylindole was investigated. In the course of these reactions an unusual migration of a phenylsulfonyl group takes place. An easy and ready for scale-up procedure for the synthesis of previously unknown β-aryl, α-phenylsulphonyl substituted α,β-unsaturated trifluoromethyl ketones is reported.     

Asymmetric bound states of spiral pairs in excitable media

We present a stable regime of asymmetric bound states for spiral pairs in a generic numerical model of a homogeneous excitable medium. In this regime, one spiral tip (slave) rotates around the other (master). Master-slave dynamics occur for both same-chirality and opposite-chirality spiral pairs in a range of parameters and initial conditions. We study the dependency of master-slave characteristics on the medium's excitation threshold and present a phenomenological model that accounts for the qualitative properties of master-slave dynamics.     

Quantum insights from null-strut geometrodynamics

We discuss quantum insights due to the null-strut formalism. These insights deal primarily with two topics: the formalism of a theory of canonical simplicial quantum gravity based on the geometrodynamic duality of null-strut calculus, and the natural implementation of spinors and spin networks in null-strut calculus.     

Electrochemical properties and radical anions of carbocycle‐fluorinated quinoxalines and their substituted derivatives

Electrochemical reduction (ECR) and oxidation (ECO) of 5,6,7,8‐tetrafluoroquinoxaline ( 1 ) and its derivatives bearing various substituents R (7‐H ( 2 ), 7,8‐H₂ (3 ), 6‐CF₃ ( 4 ), 6‐Cl ( 5 ), 5,7‐Cl₂ ( 6 ), 5‐NH₂ ( 7 ), 6‐OCH₃ ( 8 ), 6,7‐(OCH₃)₂ ( 9 ), 6,7,8‐(OCH₃)₃ ( 10 ), 5,6,7,8‐(OCH₃)₄ ( 11 ), 6‐OCH₃,7‐N(CH₃)₂ ( 12 ), 6‐N(CH₃)₂ ( 13 ), 6,7‐(N(CH₃)₂)₂ ( 14 ), 5,6,7‐(N(CH₃)₂)₃ ( 15 ), and 7,8‐cyclo‐(=CF‐CF = CF‐CF=) ( 16 )) in the carbocycle have been studied by cyclic voltammetry in MeCN. For 1 – 4 and 7 – 15 , the first reduction peaks have been found to be 1‐electron and reversible, thus corresponding to the formation of their radical anions (RAs), which are long lived at 295 K except those of 4 – 6 and 15 , 16 . Irreversible hydrodechlorination has been observed for 5 and 6 at the first step of their ECR confirmed by EPR detection of corresponding RAs of 2 and 5,7‐H₂ derivative of 1 ( 17 ) at the next steps. Electrochemically generated RAs of 1 – 3 , 7 – 14 , and 17 have been characterized in MeCN by EPR spectroscopy together with DFT calculations at the (U)B3LYP/6‐31 + G(d) level of theory using PCM to describe the solvent. A noticeable alternation of spin density on the –NCCN– moiety of quinoxaline has been observed for all RAs possessing R‐substitution asymmetry. The comparative electron‐accepting ability of 1 – 15 has been analyzed in terms of their experimental reduction peak potentials and the (U)B3LYP/6‐31 + G(d)‐calculated gas‐phase first adiabatic electron affinities (EAs). The differences in electron transfer solvation energies for 1 – 15 have been evaluated on the basis of ECR peaks' potentials and calculated gas‐phase EAs. The ECO of 1 – 5 and 7 – 14 has been found to be irreversible.     

Reconstructing phase dynamics of oscillator networks

We generalize our recent approach to the reconstruction of phase dynamics of coupled oscillators from data [B. Kralemann et al., Phys. Rev. E 77, 066205 (2008)] to cover the case of small networks of coupled periodic units. Starting from a multivariate time series, we first reconstruct genuine phases and then obtain the coupling functions in terms of these phases. Partial norms of these coupling functions quantify directed coupling between oscillators. We illustrate the method by different network motifs for three coupled oscillators and for random networks of five and nine units. We also discuss nonlinear effects in coupling.     

The Universal Vassiliev Invariant for the Lie Superalgebra

We compute the universal weight system for Vassiliev coming from the Lie superalgebra applying the construction of [13]. This weight system is a function from the space of chord diagrams to the center Z of the universal enveloping algebra of , and we find a combinatorial expression for it in terms of the standard generators of Z. The resulting knot invariants generalize the Alexander-Conway polynomial. Received: 4 July 1996 / Accepted: 21 August 1996     

Dispersion of the nonlinear refractive index in sapphire

The nonlinear refractive index, n2, of sapphire was experimentally measured in the 550-1550-nm wavelength range by use of a picosecond Z-scan technique. It was found that in this spectral region the value of n2 decreases monotonically from approximately 3.3 x 10(-16) to approximately 2.8 x 10(-16) cm2/W. An empirical expression for the wavelength dependence of the nonlinear refractive index in the 270-1550-nm range was obtained.     

Selenium Dihalides Click Chemistry: Highly Efficient Stereoselective Addition to Alkynes and Evaluation of Glutathione Peroxidase-Like Activity of Bis(E-2-halovinyl) Selenides

Highly efficient stereoselective syntheses of novel bis(E-2-chlorovinyl) selenides and bis(E-2-bromovinyl) selenides in quantitative yields by reactions of selenium dichloride and dibromide with alkynes were developed. The reactions proceeded at room temperature as anti-addition giving products exclusively with (E)-stereochemistry. The glutathione peroxidase-like activity of the obtained products was estimated and compounds with high activity were found. The influence of substituents in the products on their glutathione peroxidase-like activity was discussed.     

Local Lyapunov exponents for spatiotemporal chaos

Local Lyapunov exponents are proposed for characterization of perturbations in distributed dynamical systems with chaotic behavior. Their relation to usual and velocity-dependent exponents is discussed. Local Lyapunov exponents are analytically calculated for coupled map lattices using random field approximation. Boundary Lyapunov exponents describing reflection of perturbations at boundaries are also introduced and calculated.     

Electrical turbulence as a result of the critical curvature for propagation in cardiac tissue

In cardiac tissue, the propagation of electrical excitation waves is dependent on the active properties of the cell membrane (ionic channels) and the passive electrical properties of cardiac tissue (passive membrane properties, distribution of gap junctions, and cell shapes). Initiation of cardiac arrhythmias is usually associated with heterogeneities in the active and/or passive properties of cardiac tissue. However, as a result of the effect of wave front geometry (curvature) on propagation of cardiac waves, inexcitable anatomical obstacles, like veins and arteries, may cause the formation of self-sustained vortices and uncontrolled high-frequency excitation in normal homogeneous myocardium. (c) 1998 American Institute of Physics.