Rapid and efficient synthesis of optically active pyrazoles under solvent-free conditions

2-Formyl glycals undergo rapid condensation with arylhydrazines under solvent-free conditions to give the corresponding optically pure 4-substituted pyrazoles in good yields with high selectivity. The stereochemistry of the products was assigned by various NMR experiments.     

Tautomeric Equilibrium in Polyfluoroalkylated 5,6,7,8-Tetrahydrofurans by IR Spectroscopy

The tautomeric equilibrium in substituted 5,6,7,8-tetrahydroquinazolines was studied by IR spectroscopy. The effect of various substitutents in the pyrimidine ring and the solvent on the state of the tautomeric equilibrium was evaluated.     

Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Nonreciprocity of losses and shift of the zero point in a laser gyroscope

Results of calculations of intensities, losses, and frequencies of counterpropagating waves in a ring resonator containing a weakly nonlinear active medium and an aperture are given. It is shown that inequalities of frequencies and intensities of generation of counterpropagating waves occur in such a resonator. The behavior of these inequalities is determined by the nonreciprocity of frequency-dependent losses of the counterpropagating waves.     

A new approach to obtain the non-Condon factors in closed form for two one-dimensional harmonic oscillators

A simple algebraic approach to calculate general Franck-Condon overlaps is extended to evaluate non-Condon factors for two one-dimensional harmonic oscillators. The method is based on the use of eigenstates of the harmonic oscillator annihilation operator which allows to obtain in terms of a multi-dimensional Hermite polynomial the overlap of harmonic oscillator functions associated with different Born-Oppenheimer potentials. The presented approach is self-contained, only basic concepts of quantum mechanics associated with the harmonic oscillator system are needed. The obtained expression for the Franck-Condon overlaps is similar to the Ansbacher’s formula and equivalent to the one calculated by Malkin and Man’ko. However our final expression has the advantages that only real numbers are involved and it is straightforward to get the limit case of equal frequencies. Concerning the non-Condon factors two approaches leading to different formulas are considered, both of which reduce to triple sums of products of three Hermite polynomials.     

Nonextensive Statistical Mechanics Application to Vibrational Dynamics of Protein Folding

The vibrational dynamics of protein folding is analyzed in the framework of Tsallis statistics. We employ exact expressions for classical harmonic oscillators by considering the unnormalized constraints. As q→1, we show that these approximations agree with the result of Gaussian network model.