Effects of the molecular properties of mixed solvents on the elution of alkyl benzoates in RPLC.

The retention behavior and mechanism of methyl, ethyl, propyl, isopropyl, buthyl and isobuthyl benzoates have been studied at different eluent compositions of aqueous mixtures with water-soluble organic solvents (methanol, ethanol, 1-propanol, 2-propanol, acetonitrile (AN), 1,4-dioxane and tetrahydrofuran (THF)) in RPLC. The retention of the solutes is discussed based on the solvent composition, solvent polarity (ETN value), preferential solvation, hydrogen bonding and solvent clusters of the eluents. The smaller ETN values and the larger preferential solvation of the mixed solvent eluted the solutes faster. The IR spectra of HDO suggested that the solvents, except for methanol and ethanol, break the hydrogen bonding between water molecules, resulting in fast elution of the solutes. Based upon the results, we chose an optimum solvent composition for the separation of benzoates and applied it to the determination of the benzoates in clove.     

Control of peroxyoxalate chemiluminescence by nitrogen-containing ligand quenching: turning off and on by ligand-metal ion host-guest interactions

The control of peroxyoxalate chemiluminescence (PO-CL) by the coordination of nitrogen-containing ligands and metal cations was investigated. Turning the CL off and on was done by PO-CL using 15-monoazacrown-5-tethered anthracene and alkali metal ions. CL quenching and regeneration was also observed in the separated molecular system of 15-monoazacrown-5 and the fluorophores. CL quenching by a number of ligands bearing dipicolylamino groups was evaluated by these PO-CL reactions and found to be closely related to their oxidation potentials, which is dependent on the Weller rate law for electron exchange and this provides strong support for the existence of the CIEEL PO-CL process. When Zn²⁺ or Cu²⁺ are added to the PO-CL system quenched by the ligand, N-[2-(2,2′-dipicolylamino)ethyl]aniline, CL was turned on because the electron donating ability of the ligands was modulated. This was controlled by the coordination of the studied metal ions and, therefore, this system results in CL because of host-guest interactions.     

Efficiency comparison of various friction models of a hydraulic cylinder in the framework of multibody system dynamics

Nonlinear Dynamics - Dynamic simulation of mechanical systems can be performed using a multibody system dynamics approach. The approach allows to account systems of other physical nature, such as...     

Diversity of Ligularia kanaitzensis in sesquiterpenoid composition and neutral DNA sequences

Twenty-six eremophilane-type sesquiterpenoids, including six new compounds, were isolated from the title species. One of the new compounds, kanaitzensol, suggested the presence of an enzyme for the conversion of eremophil-7(11)-en-8-one derivative to furanoeremophilanes. The plant was collected at 15 locations in Yunnan Province of China and found to be diverse with respect to its sesquiterpenoid composition. DNA sequencing also revealed a large intraspecific diversity of the plant.     

Lifetime distribution and estimation problems of consecutive-k-out-of-n:F systems

Explicit formula is given for the lifetime distribution of a consecutive-k-out-of-n:F system. It is given as a linear combination of distributions of order statistics of the lifetimes of n components. We assume that the lifetimes are independent and identically distributed. The results should make it possible to treat the parametric estimation problems based on the observations of the lifetimes of the system. In fact, we take up, as some examples, the cases where the lifetimes of the components follow the exponential, the Weibull, and the Pareto distributions, and obtain feasible estimators by moment method. In particular, it is shown that the moment estimator is quite good for the exponential case in the sense that the asymptotic efficiency is close to one.This research was partially supported by the ISM Cooperative Research Program (94-ISM-CRP-5).     

Estimation of parameters in the discrete distributions of order k

This paper considers estimating parameters in the discrete distributions of order k such as the binomial, the geometric, the Poisson and the logarithmic series distributions of order k. It is discussed how to calculate maximum likelihood estimates of parameters of the distributions based on independent observations. Further, asymptotic properties of estimators by the method of moments are investigated. In some cases, it is found that the values of asymptotic efficiency of the moment estimators are surprisingly close to one.     

Sonochemical immobilization of noble metal nanoparticles on the surface of maghemite: mechanism and morphological control of the products

Aqueous sample solutions containing noble metal ions (HAuCl₄, Na₂PdCl₄, H₂PtCl₆), polyethyleneglycol monostearate, and magnetic maghemite nanoparticles were irradiated with high power ultrasound. Analyses of the products showed that noble metal ions were reduced by the effects of ultrasound, and the formed noble metal nanoparticles were uniformly immobilized on the surface of the maghemite. The present “one pot process” significantly simplifies the immobilization of noble metal nanoparticles on the surface of supports, compared with the conventional impregnation method. The average diameter of immobilized Au was 7–13 nm, and the diameters of Pd and Pt were several nm. The diameters depended upon the concentration of polyethyleneglycol monostearate and the concentration of noble metal ions, but not upon the maghemite concentration, indicating the possibility of the morphological controls of the products by adjusting these preparation conditions. The measurements of the average diameters and the numbers of immobilized Au nanoparticles obtained under various conditions suggest that the nucleation of Au does not occur on the surface of maghemite, but it might occur in the homogeneous bulk solution.     

Tip‐heating‐assisted Raman spectroscopy at elevated temperatures

We demonstrate tip‐heating‐assisted enhanced Raman spectroscopy to investigate the temperature dependence of the carbon nanotube G‐band with nanoscale resolution. The controllable and nanoscale heat generated at the tip apex was used to thermally perturb and characterize a small volume in a carbon nanotube sample that is precisely positioned underneath the tip. The dependence of tip enhancement with temperature was also experimentally examined, which is in good agreement with the enhancement calculated from the electromagnetic model of isolated spheroids. The technique presented may open up opportunities in the study of controlled heat‐assisted biochemical reactions and physical transformations of nanostructures. It can also be used for thermal characterization of various materials requiring site‐selective and controllable nanoscale heat source and could enable the realization of new photothermal devices. Copyright © 2010 John Wiley & Sons, Ltd.     

Joint distributions of numbers of occurrences of a discrete pattern and weak convergence of an empirical process for the pattern

For a {0, 1}-pattern of finite length, an empirical process is introduced in order to describe the number of overlapping occurrences of the pattern at each level t[0,1] in a sequence of the corresponding indicators of i.i.d. [0, 1]-valued observations of length n. A method for obtaining the exact finite-dimensional distributions of the empirical process is given. The weak convergence of the process to a Gaussian process in D[0,1] as n tends to infinity is also established. The limiting process depends on the given pattern. The exact covariance function is compared with the asymptotic covariance function in a numerical example.