Dielectric and13C NMR studies of the carbon monoxide clathrate hydrate

The structure I clathrate hydrate of carbon monoxide has been studied using dielectric measurements and¹³C NMR spectroscopy. Broad, weak dielectric absorption curves with maxima at 2.2–3.8 K yieldE _a = 0.14 kJ mol^–1 for the average Arrhenius activation energy associated with the reorientation of the low polarity guest. Except for H₂S this represents the fastest reorienting polar guest known among the clathrate hydrates. The low temperature dielectric absorption curves can best be fitted with a Cole-Davidson asymmetric distribution of relaxation times and activation energies (with = 0.06 at 4 × 10⁶ Hz), which at 10⁷ Hz has been resolved into a double symmetric distribution of discrete relaxation times for CO in the small and large cages. The cross-polarization magic angle spinning¹³C NMR spectra indicate identical chemical shifts for CO in the small and large cages, in contrast to other hydrates. The static spectra show that the CO molecules undergo anisotropic reorientation in the large cages and that there is still considerable mobility at 77 K. One possible model for the anisotropic motion has the CO rapidly moving among sites over each of the 14 faces of the cage with the CO axis orientated towards the cage centre. The cage occupancy ratio at 220 K, _s/ _L = 1.11, indicates slightly greater preference of CO for the small cage.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Influence of quaternary onium salts,crown ethers and cryptands on olefin epoxidations promoted by HOCl/ClO− in the Presence of Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride

Reaction rates of alkene epoxidations, promoted by aqueous NaOCl and catalyzed by Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride1 (P) in the presence of a lipophilic axial ligand (L) (e.g.N-hexylimidazole) and carried out under H₂O/CH₂Cl₂ two phase conditions at 0°C, are strongly enhanced by lowering the pH of the aqueous phase from 12.7 to 9.5. Under these conditions, a further relevant increase in the reaction rates can be achieved by adding phase-transfer catalysts (PT), e.g. quaternary ammonium salt 3, lipophilic crown ether4 or cryptand5, provided that the amount of L is very small (L/P=1 for very reactive alkenes, e.g. cyclooctene, and 10 for poorly reactive ones, e.g. 1-dodecene). In the case of cyclooctene epoxidation, the use of 0.006–0.03 mol. equiv. of PT completes the reaction in 1–10 min., the initial rates being up to 600 turnovers/min. with (2.2.2,C₁₀) cryptand. In the absence of the axial ligand, the quaternary ammonium salt3 and cryptand5 show an inhibitory effect. Such an effect is due to the formation of the poorly reactive Mn(P)CI species, by Cl– extraction to the organic phase. However, dibenzo crown ether 4 does not show this effect. In the presence of 4, and with L/P =1, the 1-dodecene epoxidation reaches 94% in 1 min. The unique behavior of crown ethers can be explained by their ineffectiveness in extracting alkali chlorides, providing a very low concentration of Cl– in the organic phase and thus avoiding the Mn(III)-porphyrin deactivation.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

A characterization of brownian motion in a lipschitz domain by its killing distributions

Let (Y _t, Q^x) be a strong Markov process in a bounded Lipschitz domainD with continuous paths up to its lifetime , and let (X _t, P^x) be a Brownian motion inD. IfY _– exists in D andQ ^x(Y_– C)=P^x(X_– C) for all Borel subsetsC of D and allx, thenY is a time change ofX.     

Probability theory and polymer physics

This study applies the theory of stochastic processes to the equilibrium statistical physics of polymers in solution. The topics treated include random copolymers and randomly branching polymers, with self-consistent mean field effects. A new and more natural way of dealing with Boltzmann weighting is discussed, which makes it possible from the beginning of a calculation to consider only the physical polymer conformations. We also show that in general the random copolymer problem can be reduced to the ordinary polymer problem, and treat the self-consistent field problem for a general branching polymer.     

Six‐coordinate Co2+ with imidazole,NH3, and H2O ligands: Approaching spin crossover

Octahedral, six‐coordinate Co²⁺ can exist in two spin states: S = 3/2 and S = 1/2. The difference in energy between high spin (S = 3/2) and low spin (S = 1/2) is dependent on both the ligand mix and coordination stereochemistry. B3LYP calculations on combinations of neutral imidazole, NH₃, and H₂O ligands show that low‐spin isomers are stabilized by axial H₂O ligands and in structures that also include trans pairs of equatorial NH₃ and protonated imidazole ligands, spin crossover structures are predicted from spin state energy differences. Occupied Co d orbitals from the DFT calculations provide a means of estimating effective ligand strength for homoleptic and mixed ligand combinations. These calculations suggest that in a labile biological system, a spin crossover environment can be created. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Influence of a water vapor admixture in the carrier gas on capacity coefficients of polar organic compounds

The influence of a water vapor admixture in helium, nitrogen, and carbon dioxide on capacity coefficients of C₃−C₅ alcohols and pyridine during chromatography process in capillary columns with polar (PEG-20M) and nonpolar (SE-30) stationary phases was studied. The introduction of a water admixture into the carrier gas, increases the capacity coefficient of polar organic compounds on the capillary column with PEG-20M and has almost no effect on this value in the case of SE-30. The change in retention of polar organic compounds on the capillary column with the PEG-20M polar phase occurs due to a change in the properties of the stationary phase when it adsorbs water from the mobile phase. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2258–2261, November, 1998.     

Random walk in an inhomogeneous medium with local impurities

In spite of Sinai's result that the decay of the velocity autocorrelation function for a random walk on ^d (d=2) can drastically change if local impurities are present, it is shown that local impurities can not abolish weak convergence to the Brownian motion if d2.     

目标基视频编码中的运动目标提取与跟踪新算法

自动、快速的视频目标提取与跟踪是目标基视频编码中的一项关键技术.本文提出一种运动目标提取与跟踪新算法.首先,根据多帧运动信息和高阶统计检测方法得到二值运动掩模图像,然后提出一种改进分水岭算法对运动区域及其周围部分进行分割.将二者所得结果进行投影运算,得到最终运动目标.最后提出一种运动目标跟踪新算法,能对目标进行有效的跟踪.实验结果说明了本文算法的有效性.     

Brownian diode: Molecular motor based on a semi-permeable Brownian particle with internal potential drop

A model of an autonomous isothermal Brownian motor with an internal propulsion mechanism is considered. The motor is a Brownian particle which is semi-transparent for molecules of surrounding ideal gas. Molecular passage through the particle is controlled by a potential similar to that in the transition rate theory, i.e. characterized by two stationary states with a finite energy difference separated by a potential barrier. The internal potential drop maintains the diode-like asymmetry of molecular fluxes through the particle, which results in the particle?s stationary drift.