Ab Initio Study on the Isomerization and Dehydrogenation of Methylnitrene

The ab initio calculations were performed at the RHF/4-31G level with the reaction pathways of the iso-merization and dehydrogenation of methylnitrene by the intrinsic reaction coordinate method. The results show that the transformation from methylnitrene to methylenimine would be very easy. This accountes for the experimental fact that one couldn' t find the methylnitrene, but only obtained the methylenimine in the pyrolysis of methyl azide. The mode-selective study reveals the reaction coordinates (IRC) of isomerization and dehydrogenation of methylnitrene are associated with the molecular deformation mode of 1191 cm-1 and the methyl group unsymmetrical stretch mode, respectively. The coupling between normal coordinates is favourable to select the reaction channel of isomerization.     

ToF-SIMS analysis of a fluorocarbon-grafted PET with a gold cluster ion source

Cluster ions have been recognized as a superb primary species in time of flight secondary ion mass spectroscopy (ToF-SIMS) compared with monatomic primary ions, as they significantly enhance the secondary ion yields from bulk samples. Self-assembled monolayers provide an important system for studying the fundamental mechanism involved in the yield enhancement.We used a gold cluster ion source to analyze a new type of self-assembled monolayer: a fluorocarbon-grafted polyethylene terephthalate. In addition to the structure details, which helped to understand the grafting mechanism, ToF-SIMS analysis revealed that fluorocarbon secondary ion yield enhancements by cluster ions were due to the enhanced sputter efficiency. A larger information depth may also be expected from the enhancement. Both mathematical definitions of damage cross-section and disappearance cross-section were revisited under a new context. Another cross-section parameter, sputter cross-section, was introduced to differentiate the beam induced sputter process from damage process.     

An inverse radiative transfer problem of simultaneously estimating profiles of temperature and radiative parameters from boundary intensity and temperature measurements

A parallel-plane space filled with absorbing, emitting, isotropically scattering, gray medium is studied in this paper. The boundary intensity and boundary temperature profiles are calculated for the inverse analysis. For the simultaneous estimation of temperature, absorption and scattering coefficient profiles in the medium, the sum of residuals of boundary intensity and temperature after being weighted by a balance factor is minimized through using a Newton-type iteration algorithm and the least-squares method. To avoid over-updating for the parameters, the relative updating magnitude during the iteration process is constrained not to be >0.5. It is shown that the boundary intensity measurement alone is not enough to estimate simultaneously the temperature (source) and the radiative properties (both absorption and scattering coefficients) when the measurement data contain sensitive random errors. The boundary temperature measurement can serve as a necessary supplementation to the boundary intensity to make this kind of inverse radiative transfer problem resolvable. It was shown that a compensation relationship between absorption and scattering coefficients makes it difficult to fix them accurately. Parabolic profiles for the three parameters are used to validate the estimation method. When the optical thickness approaches 4.0, the results for the radiative properties are not acceptable, although the result for temperature profile is reasonable. This means the method needs further improvements.     

On the distribution of the number of customers in the symmetric M/G/1 queue

We consider an M/G/1 queue with symmetric service discipline. The class of symmetric service disciplines contains, in particular, the preemptive last-come-first-served discipline and the processor-sharing discipline. It has been conjectured in Kella et al. [1] that the marginal distribution of the queue length at any time is identical for all symmetric disciplines if the queue starts empty. In this paper we show that this conjecture is true if service requirements have an Erlang distribution. We also show by a counterexample, involving the hyperexponential distribution, that the conjecture is generally not true. AMS Subject Classifications Primary—60K25; Secondary—90B22     

Large-scale effects on meso-scale modeling for scalar transport

The transport of scalar quantities passively advected by velocity fields with a component at small scale ℓ can be modeled at scales larger than ℓ by means of an effective drift and an effective diffusivity, which can be determined by means of multiple-scale techniques. We show that the presence of a weak flow at large scales Lℓ induces interesting effects on the scalar transport at the meso-scales (i.e. at scales intermediate between ℓ and L). In particular, it gives rise to non-isotropic and non-homogeneous corrections to the meso-scale drift and diffusivity. We discuss an approximation that allows us to retain the second-order effects caused by the large-scale flow. This provides a rather accurate meso-scale modeling for both asymptotic and pre-asymptotic scalar transport properties. Numerical simulations in model flows are used to illustrate the importance of such large-scale effects.     

New methodologies in trace analysis of volatile organic compounds

Two methods for sampling and concentration of volatile organic compounds are reported. In the first method, traps coated with a very thick film (ca. 100 μm) of cross-linked silicone stationary phase are employed. Such thick films can be prepared with a modified dynamic coating procedure, which is briefly described. The low phase ratio traps can be utilized for enrichment of volatiles from gaseous as well as aqueous matrices. The second technique is based on chromatographic evaporation of a solvent in a capillary tube, where the process is sustained by a repeated sample injection and a cyclic flow reversal. In this way, large solvent volumes can be handled by a small volume system. Under optimal conditions, when using a solvent barrier, quantitative recovery is possible even for compounds of comparatively high volatility. Another important application of the technique is extraction of trace components from gases such as headspace samples, polluted air, etc.     

子系统为S≥3的非线性大系统在近平衡区内的稳定性

本文采用文[1,2]中提出的平衡结构法研究子系统s≥3的非线性大系统在近平衡区内的稳定性;得到了判别这类大系统稳定性的两个一般性准则.     

Cinnamic acid amides and lignanamides from Aptenia cordifolia

Examination of the hydroalcoholic extract of the leaves of Aptenia cordifolia has afforded three cinnamic acid amides and two lignanamides. Structures were established on the basis of spectroscopic data, including 2D-NMR analyses.     

“Optimization of aircraft maintenance/support infrastructure using genetic algorithms—level of repair analysis”

Level of repair analysis (LORA) is an approach used during the design stage of complex equipment for analysis of the cost effectiveness of competing maintenance strategies. LORA is carried as a part of the life cycle cost and cost of ownership analysis and plays a significant role in minimizing the life cycle cost and cost of ownership of the capital equipment. Since many purchasing decisions of complex equipment are based on cost of ownership, it has become essential to carry out LORA to compete in the market. In this paper, we develop a mathematical model for LORA and propose a solution methodology based on genetic algorithms. The concept is illustrated using a hypothetical aircraft engine.