A convenient synthesis of deuterium labeled tertiary aliphatic nitro ketones and nitriles - starting materials for preparation of deuterated cyclic nitrones, isomeric hydroxylamines, and corresponding C-nitroso compounds

Tertiary aliphatic β- and γ-nitro nitriles and ketones deuterated in (several) selected positions had been synthesized. The deuterated nitro compounds served as a starting material for the corresponding deuterium labeled nitrones or hydroxylamines (reducing with aluminum amalgam). Further oxidation of the last two groups of compounds with sodium periodate or m-CPBA afforded the relevant deuterated tertiary C-nitroso compounds.     

2-Substituted nitrones and isomeric hydroxylamines - obtained via aluminium amalgam reduction of nitro nitriles and ketones—a new access to convenient intermediates for nitroso carbonyl compounds preparation

Substituted five-membered cyclic nitrones (pyrroline N-oxides) have been obtained in good to high yields from tertiary γ-nitro ketones and nitriles employing aluminium amalgam as a reducing agent in moist diethyl ether or THF. Attempts to obtain cyclic amino nitrones from α- or β-nitro nitriles failed and only the corresponding hydroxylamines have been isolated. Both nitrones and hydroxylamines have been used for synthesis of tertiary C-nitroso nitriles or ketones.     

An organocatalytic approach to 2-hydroxyalkyl- and 2-aminoalkyl furanes

The first enantioselective methodology for the synthesis of electron-poor 2-hydroxyalkyl- and 2-aminoalkyl furanes is demonstrated in this study. It utilizes a highly stereoselective organocatalytic one-pot reaction cascade: epoxidation or aziridination of α,β-unsaturated aldehydes followed by Feist-Be?nary reaction of various 1,3-dicarbonyl compounds to give the target furanes. This efficient multibond forming reaction cascade benefits from low catalyst loadings and readily available starting materials. Furthermore, the possibility to interrupt the reaction sequence at the stage of the corresponding optically active 2-hydroxyalkyl- and 2-aminoalkyl 2,3-dihydrofuranes with three stereogenic centers is also presented. Finally, models which account for the formation of the optically active 2,3-dihydrofuranes are proposed.     

Model studies of the optical rotation,and theoretical determination of its sign for β‐pinene and trans‐pinane

We have carried out extensive studies on the basis set dependence of the calculated specific optical rotation (OR) in molecules at the level of the time–dependent Hartree–Fock and density functional approximations. To reach the limits of the basis set saturation, we have devised an artificial model, the asymmetrically deformed (chiral) methane (CM) molecule. This small system permits to use basis sets which are prohibitively large for real chiral molecules and yet shows all the important features of the basis set dependence of the OR values. The convergence of the OR has been studied with n‐aug‐cc‐pVXZ basis sets of Dunning up to the 6–ζ. In a parallel series of calculations, we have used the recently developed large polarized (LPolX) basis sets. The relatively small LPolX sets have been shown to be competitive to very large n‐aug‐cc‐pVXZ basis sets. The conclusions reached in calculations of OR in CM concerning the usefulness of LPolX basis sets have been further tested on (S)‐methyloxirane and (S)‐fluoro‐oxirane. The smallest set of the LPolX family (LPol–ds) has been found to yield OR values of similar quality as those obtained with much larger Dunning's aug‐cc‐pVQZ basis set. These results have encouraged us to carry out the OR calculations with LPol–ds basis sets for systems as large as β‐pinene and trans‐pinane. In both cases, our calculations have lead to the correct sign of the OR value in these molecules. This makes the relatively small LPol–ds basis sets likely to be useful in OR calculations for large molecules. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Fundamental Problems in the Unification of Physics

We discuss the following problems, plaguing the present search for the “final theory”: (1) How to find a mathematical structure rich enough to be suitably approximated by the mathematical structures of general relativity and quantum mechanics? (2) How to reconcile nonlocal phenomena of quantum mechanics with time honored causality and reality postulates? (3) Does the collapse of the wave function contain some hints concerning the future quantum gravity theory? (4) It seems that the final theory cannot avoid the problem of dynamics, and consequently the problem of time. What kind of time, if this theory is supposed to be background free? (5) Will the dynamics of the “final theory” be probabilistic? Quantum probability exhibits some essential differences as compared with classical probability; are they but variations of some more general probabilistic measure theory? (6) Do we need a radically new interpretation of quantum mechanics, or rather an entirely new theory of which the present quantum mechanics is an approximation? (7) If the final theory is to be background free, it should provide a mechanism of space-time generation. Should we try to explain not only the generation of space-time, but also the generation of its material content? (8) As far as the existence of the initial singularity is concerned, one usually expects either “yes” or “not” answers from the final theory. However, if the mathematical structure of the future theory is supposed to be truly more general that the mathematical structures of the present general relativity and quantum mechanics, is a “third answer“ possible? Could this third answer be related to the probabilistic character of the final theory? We discuss these questions in the framework of a working model unifying gravity and quanta. The analysis reveals unexpected aspects of these rather wildly discussed issues.     

Laser frequency stabilization by magnetically assisted rotation spectroscopy

We present a method of Doppler-free laser frequency stabilization based on magnetically assisted rotation spectroscopy (MARS) which combines the Doppler-free velocity-selective optical pumping (VSOP) and magnetic rotation spectroscopy. The stabilization is demonstrated for the atomic rubidium transitions at 780 nm. The proposed method is largely independent of stray magnetic fields and does not require any modulation of the laser frequency. Moreover, the discussed method allows one to choose between locking the laser exactly to the line center, or with a magnetically-controlled shift to an arbitrary frequency detuned by up to several natural linewidths. This feature is useful in many situations, e.g. for laser cooling experiments. In addition to presenting the principle of the method, its theoretical background and peculiarities inherent to the repopulation VSOP are discussed.     

Holomorphic mappings preserving Minkowski functionals

We show that the equality _m1(f(x))=_m2(g(x))$m_1\left(f\left(x\right)\right)=m_2\left(g\left(x\right)\right)$ for x$x$ in a neighborhood of a point a$a$ remains valid for all x$x$ provided that f$f$ and g$g$ are open holomorphic maps, f(a)=g(a)=0$f\left(a\right)=g\left(a\right)=0$ and _m1,_m2$m_1,m_2$ are Minkowski functionals of bounded balanced domains. Moreover, a polynomial relation between f$f$ and g$g$ is obtained.     

A Family of Measures of Noncompactness in the Space {L^1_{\text{loc}}(\mathbb{R}_+)} and its Application to Some Nonlinear Volterra Integral Equation

The aim of this paper is to study a new family of measures of noncompactness in the space ${L^1_{\text{loc}}(\mathbb{R}_+)}$ consisting of all real functions locally integrable on ${\mathbb{R}_+}$ , equipped with a suitable topology. As an example of applications of the technique associated with that family of measures of noncompactness, we study the existence of solutions of a nonlinear Volterra integral equation in the space ${L^1_{\text{loc}}(\mathbb{R}_+)}$ . The obtained result generalizes several ones obtained earlier with help of other methods.     

On Hidden Markov Processes with Infinite Excess Entropy

We investigate stationary hidden Markov processes for which mutual information between the past and the future is infinite. It is assumed that the number of observable states is finite and the number of hidden states is countably infinite. Under this assumption, we show that the block mutual information of a hidden Markov process is upper bounded by a power law determined by the tail index of the hidden state distribution. Moreover, we exhibit three examples of processes. The first example, considered previously, is nonergodic and the mutual information between the blocks is bounded by the logarithm of the block length. The second example is also nonergodic but the mutual information between the blocks obeys a power law. The third example obeys the power law and is ergodic.