Acoustic Field Effect on Electrochemiluminescence of Organic Molecules in Solutions

Electrochemical reactions in solutions causing the production of electrochemiluminescence (ECL) have been studied already for more than ten years^1–4. In the main the ECL mechanism is established, the main regularities of this interesting phenomenon are determined. The attention is paid to the ECL in connection with the fact that its radiation gives a vast information about the electrochemical reactions in solutions. Moreover on this basis an effective and convenient transformators of the electrical signals into light can be carried out (the quantum efficiency is 20% for some solutions⁵). As a rule the ECL experiments are made under conditions controlled by an ordinary or convective diffusion. In this paper the results of investigations of the ECL upon condition of great external disturbances of solution whic occure due to the applicatin of the ultrasonic fields to the cell are given. To our Knowledge suvh investigations have not been undertaken earlier.     

Two Interfering Effects in Optogalvanic Detector Hollow Cathode Discharge

Two effects in optogalvanic detector—hollow cathode discharge are reported. They appear at light irradiation of the detector and interfere with its properties. First effect, connected with Penning process in Ar-Cd plasma, is used for identification of negative plasma resistance. The other effect is a light induced potential on the cathode.     

Homogenization and concentrated capacity for the heat equation with non-linear variational data in reticular almost disconnected structures and applications to visual transduction

Out of a right, circular cylinder of height H and cross-section a disc of radius R+ one removes a stack of nH/ parallel, equi-spaced cylinders C_j,j=1,2,...,n, each of radius R and height . Here , are fixed positive numbers and is a positive parameter to be allowed to go to zero. The union of the C_j almost fills in the sense that any two contiguous cylinders C_j are at a mutual distance of the order of and that the outer shell, i.e., the gap S=-_o has thickness of the order of (_o is obtained from by formally setting =0). The cylinder from which the C_j are removed, is an almost disconnected structure, it is denoted by , and it arises in the mathematical theory of phototransduction.For each >0 we consider the heat equation in the almost disconnected structure , for the unknown function u, with variational boundary data on the faces of the removed cylinders C_j. The limit of this family of problems as 0 is computed by concentrating heat capacity and diffusivity on the outer shell, and by homogenizing the u within the limiting cylinder _o.It is shown that the limiting problem consists of an interior diffusion in _o and a boundary diffusion on the lateral boundary S of _o. The interior diffusion is governed by the 2-dimensional heat equation in _o, for an interior limiting function u. The boundary diffusion is governed by the Laplace–Beltrami heat equation on S, for a boundary limiting function u_S. Moreover the exterior flux of the interior limit u provides the source term for the boundary diffusion on S. Finally the interior limit u, computed on S in the sense of the traces, coincides with the boundary limit u_S. As a consequence of the geometry of , local arguments do not suffice to prove convergence in _o, and also we have to take into account the behavior of the solution in S. A key, novel idea consists in extending equi-bounded and equi-Hölder continuous functions in -dependent domains, into equi-bounded and equi-Hölder continuous functions in the whole ^N, by means of the Kirzbraun–Pucci extension technique.The biological origin of this problem is traced, and its application to signal transduction in the retina rod cells of vertebrates is discussed. Mathematics Subject Classification (2000) 35B27, 35K50, 92C37     

‘Purposive’ Molecular Design for Multifunctional Artificial Receptors

This account describes recent examples of multifunctional artificial receptors, which demonstrates our approach to purposive molecular design. The paper is divided into two parts. The first deals with novel crowned spirobenzopyrans as dual-mode signal transducers. The new crowned spirobenzopyrans complement previous crowned spirobenzopyrans from the viewpoint of molecular devices, and a detailed comparison between them is given. The second part is concerned with polypyridine-macrocyclic structures as ribofuranoside receptors. The design of the ribofuranoside receptors was based on the multipoint hydrogen bond complementarity between the receptors and methyl -(d)-ribofuranoside. The binding affinity of the receptors was very high, so that even native ribose was extracted by them into nonpolar solvents.     

An evaluation of orthogonal signal correction methods for the characterisation of arabica and robusta coffee varieties by NIRS

Two orthogonal signal correction methods (OSC and DOSC) were applied on a set of 83 roasted coffee NIR spectra from varied origins and varieties in order to remove information unrelated to a specific chemical response (caffeine), which was selected due to its high discriminant ability to differentiate between arabica and robusta coffee varieties. These corrected NIR spectra, as well as raw NIR spectra and three chemical quantities (caffeine, chlorogenic acids and total acidity), were used to develop separate classification models accordingly using the potential functions method as a class-modelling technique in order to evaluate their respective capacities to discriminate between coffee varieties and the influence of these pre-processing methods on the classification of the coffee samples into their corresponding variety class. The transformation of roasted coffee NIR spectra by means of an orthogonal signal correction method, taking into account in this correction a chemical response closely related to the sample origin, prompted a notable improvement in the specificity of the constructed classification models.     

信号处理方法在电分析化学中的应用

评述了数字信号处理方法在电分析化学中进展，着重介绍了这些方法的基本原理及其在电分析化学中的应用．     

Modelling the temporal intensity distribution of laser ablation inductively coupled plasma mass spectrometry in single shot mode

A transport model is proposed that describes the temporal intensity distribution observed in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in single-shot mode using quantitative signal equations. Calculations aim on the deduction of the dispersion function describing the time-dependent part of the signal equation.

The dispersion function depends on transport time in the centre of the transport tube, as related to carrier gas flow rate and tube volume and on the relation between carrier gas flow rate and ablation chamber volume. The equations describing the signal shape standardize signals from different systems and allow quantitative optimization of the ablation chamber, the transport tube and the detector.

Application of the model to ICP-MS shows that only a part of the area filled by the transported vaporization product and thus only a part of the transported vaporization product can be observed at the detector. The model is able to quantify both fractions.

As was calculated, the observed fraction of analyte is always higher than the observed fraction of the sample containing cross section and depends on the chosen transport parameters characterising the dispersion function. Thus, the determination of the signal integrals in the usual way can lead to systematic errors if the parameters influencing the dispersion function are variable.

Therefore, a different method of analysis based on signal equations is proposed and demonstrated. By this method of data treatment, all important system parameters influencing the dispersion function could be calculated and matched with theoretical ones. Furthermore, a complete integral of the transient signal including its statistical variation can be generated from a limited number of measurement points. For example, this can be applied to signals detected incompletely because of detector saturation and enables the use of high-abundance elements as internal standards.

Furthermore, the method can be used to monitor system performance, to identify the flow regime inside the ablation chamber, to take into account the sample volume for quantitative analysis and finally, to detect anomalous signal distributions that would lead to systematic errors. The prospects and limitations of the model are discussed for LA-ICP-MS in single shot mode.     

6/7Li NMR study of the Li1-zNi1+zO2 phases

A series of Li1-zNi1+zO2 materials have been synthesised by the coprecipitation route. An X-ray diffraction study was carried out on these materials using the Rietveld method to determine the departure from the ideal stoichiometry z, which ranges from 0 to 0.138. The actual Li/Ni ratio was also checked by chemical analyses using inductively coupled plasma (ICP) for each sample. The stoichiometric sample (z approximately 0) was obtained using a 15% Li excess. (6/7)Li NMR results from LiNiO2 (z approximately 0) show that the asymmetric shape of the NMR signal is due to anisotropy. Calculations give evidence that the paramagnetic dipolar interaction from the electron spins carried by Ni is anisotropic but does not completely explain the experimental anisotropy. (6)Li MAS NMR (magic angle spinning NMR) experiments and temperature standardisation NMR measurements unambiguously assign the isotropic position at +726 ppm. The static-echo NMR spectra of the non-stoichiometric Li1-zNi1+zO2 phases also exhibit an asymmetric shape whose width increases with the departure from the ideal stoichiometry z. (6/7)Li static and MAS NMR show that the 2zNi(2+) ions thus formed modify the dipolar interaction within the materials and also affect the Fermi contact interaction, since a distribution of Li environments is observed using (6)Li NMR for non-stoichiometric samples.     

Orthogonal signal correction applied to the classification of wine and molasses vinegar samples by near-infrared spectroscopy. Feasibility study for the detection and quantification of adulterated vinegar samples

The most common fraudulent practice in the vinegar industry is the addition of alcohol of different origins to the base wine used to produce wine vinegar with the objective of reducing manufacturing costs. The mixture is then sold commercially as genuine wine vinegar, thus constituting a fraud to consumers and an unfair practice with respect to the rest of the vinegar sector. A method based on near-infrared spectroscopy has been developed to discriminate between white wine vinegar and alcohol or molasses vinegar. Orthogonal signal correction (OSC) was applied to a set of 96 vinegar NIR spectra from both original and artificial blends made in the laboratory, to remove information unrelated to a specific response. The specific response used to correct the spectra was the extent of adulteration of the vinegar samples. Both raw and corrected NIR spectra were used to develop separate classification models using the potential functions method as a class-modeling technique. The previous models were compared to evaluate the suitability of near-infrared spectroscopy as a rapid method for discrimination between vinegar origin. The transformation of vinegar NIR spectra by means of an orthogonal signal-correction method resulted in notable improvement of the specificity of the constructed classification models. The same orthogonal correction approach was also used to perform a calibration model able to detect and quantify the amount of exogenous alcohol added to the commercial product. This regression model can be used to quantify the extent of adulteration of new vinegar samples.