Conformational search and spectroscopic analysis of bis-β-d-glucopyranosyl azacrown derivative

1,10-N,N′-bis-(β-d-ureidoglucopyranosyl)-4,7,13-trioxa-1,10-diazacyclopentadecane is a new, recently synthesized compound, which exhibits complexation ability towards drugs. In the present study various theoretical methods, including molecular mechanics, computer simulations, semiempirical and DFT calculations, are applied to find the lowest energy conformers of this molecule in vacuo and in aqueous solution. For the most stable structures the vibrational frequencies as well as the C and H chemical shifts were computed. Along with the theoretical investigation the IR in the KBr discs and the NMR spectra in water and in pyridine were experimentally recorded. It is shown that in the lowest energy structures the two glucosyl units are placed on the same side of the diazacrown ring with their mutual orientations favoring formation of hydrogen bonds. The “open” structure, in which no such hydrogen bonds can be formed, is found to have much higher energy. The computed and measured IR spectra and NMR chemical shifts are compared and discussed in detail. The most stable structures are analyzed with respect to the possible mechanism of complexation of drugs.     

Quantum Dynamics of Oxyhydrogen Complex-Forming Reactions for the HO2 and HO3 Systems

Complex-forming reactions widely exist in gas-phase chemical reactions.Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered.The complex-forming reactions usually have small or no barrier in the entrance channel, which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions.Theoretically, quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier.However, it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels.This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems, HO₂ and HO₃, which are significant in combustion, atmospheric, and interstellar chemistry.We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.     

Dissipaton Equation of Motion Theory versus Fokker-Planck Quantum Master Equation

The quest of exact and nonperturbative methods on quantum dissipation with nonlinear coupling environments remains in general a great challenge. In this review we present a comprehensive account on two approaches to the entangled system-and-environment dynamics, in the presence of linear-plus-quadratic coupling bath. One is the dissipaton-equation-ofmotion (DEOM) theory that has been extended recently to treat the nonlinear coupling environment. Another is the extended Fokker-Planck quantum master equation (FP-QME) approach that will be constructed in this work, based on its DEOM correspondence. We closely compare these two approaches, with the focus on the underlying quasi-particle picture, physical implications, and implementations.     

Average Arrival Time: an Alternative Approach for Studying Fluorescent Behavior of Single Quantum Dots?

Due to photoluminescence intermittency of single colloidal quantum dots (QDs), the traditional exponential fluorescence lifetime analysis is not perfect to characterize QDs' fluorescent emission behavior. In this work we used the time-tagged time-resolved (TTTR) mode to record the fluorescent photons from single QDs. We showed that this method is compatible with the traditional lifetime analysis. In addition, by constructing the trajectory over time and the distribution of average arrival time (AAT) of the fluorescent photons, more details about the emission behavior of QDs were revealed.     

Photochemical preparation of tricyclic hydroxyketones by transanular cyclization of bridged 4-benzoylcyclohexanones

Summary The bridged 4-benzoyl-cyclohexanones3a–f were synthesized by ,-annelation of cyclic ketones. Irradiation of3a–f revealed a strong dependence of the photochemical behaviour on the ring size and the introduction of a nitrogen atom. Ketones which are able to form 1,6-biradicals (3b,c,e) undergo unselective photolytic decomposition, whereas3a,d,f afforded tricyclic hydroxyketones. The diastereoselectivity of ring closure is remarkably improved by introduction of a protected nitrogen atom (3d,f) in comparison to the carbocyclic diketone3a. Moreover, the N protective group of 4-azatricyclo-4.3.1.0^3,8]decan-7-one (7) could be removed affording the free hydroxy amino ketone8 in good yields. An explanation of the diastereoselective cyclization of3a and of the surprisingly low quantum yield of3d was found by conformational analysis of the corresponding triplet biradicals.

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Photochemische Darstellung tricyclischer Ketone durch transanulare Cyclisierung verbrückter 4-Benzoylcyclohexanone

Zusammenfassung Die verbrückten 4-Benzoyl-cyclohexanone3a–f wurden durch ,-Anellierung cyclischer Ketone synthetisiert. Das photochemische Verhalten von3a–f hängt in starkem Maße von der Ringgröße und von der Einführung eines Stickstoffatoms ab. Ketone, die in der Lage sind, 1,6-Biradikale zu bilden (3b,c,e), unterliegen einer unselektiven photolytischen Zersetzung, während3a,d,f tricyclische Hydroxyketone liefern. Die Diastereoselektivität des Ringschlusses wird durch Einführung eines Stickstoffatoms (3d,f) im Vergleich zum carbocyclischen Analogon3a deutlich gesteigert. Weiterhin gelang es, die N-Schutzgruppe im 4-Azatricyclo-[4.3.1.0^3,8]decan-7-on (7) unter Bildung des freien Hydroxyaminoketons8 in guten Ausbeuten zu entfernen. Eine Erklärung für die diastereoselektive Cyclisierung von3a und für die überraschend geringe Quantenausbeute von3d wurde durch Konformationsanalyse der entsprechenden Triplett-Biradikale gefunden.

     

Probability measures in -algebras in Hilbert spaces with conjugation

Let be a real -algebra of -real bounded operators containing no central summand of type in a complex Hilbert space with conjugation . Denote by the quantum logic of all -orthogonal projections in the von Neumann algebra . Let be a probability measure. It is shown that contains a finite central summand and there exists a normal finite trace on such that , .

     

Dirichlet Forms and Dirichlet Operators for Gibbs Measures of Quantum Unbounded Spin Systems: Essential Self-Adjointness and Log-Sobolev Inequality

For each [0, 1] we consider the Dirichlet form and the associated Dirichlet operator for the Gibbs measure of quantum unbounded spin systems interacting via superstable and regular potential. The Gibbs measure is related to the Gibbs state of the system via a (functional) Euclidean integral procedure. The configuration space for the spin systems is given by We formulate Dirichlet forms in the framework of rigged Hilbert spaces which are related to the space . Under appropriate conditions on the potential, we show that the Dirichlet operator is essentially self-adjoint on the domain of smooth cylinder functions. We give sufficient conditions on the potential so that the corresponding Gibbs measure is uniformly log-concave (ULC). This property gives the spectral gap of the Dirichlet operator at the lower end of the spectrum. Furthermore, we prove that under the conditions of (ULC), the unique Gibbs measure satisfies the log-Sobolev inequality (LS). We use an approximate argument used in the study of the same subjects for loop spaces, which in turn is a modification of the method originally developed by S. Albeverio, Yu. G. Kondratiev, and M. Röckner.     

也谈量子力学的基础

本文通过在不同边界条件下动量算符的厄密性和自伴性的区分,给出了对量子力学的一维无限深方势阱中基态粒子的动量分布问题的严格分析,论证了量子力学基本假设的严谨性和自洽性.     

A family of quantum projective spaces and related -hypergeometric orthogonal polynomials

A one-parameter family of two-sided coideals in is defined and the corresponding algebras of infinitesimally right invariant functions on the quantum unitary group are studied. The Plancherel decomposition of these algebras with respect to the natural transitive -action is shown to be the same as in the case of a complex projective space. By computing the radial part of a suitable Casimir operator, we identify the zonal spherical functions (i.e. infinitesimally bi-invariant matrix coefficients of finite-dimensional irreducible representations) as Askey-Wilson polynomials containing two continuous and one discrete parameter. In certain limit cases, the zonal spherical functions are expressed as big and little -Jacobi polynomials depending on one discrete parameter.