Non-selective chemical sensors in analytical chemistry: from “electronic nose” to “electronic tongue”

Development, recent historical background and analytical applications of promising sensor instruments based on sensor arrays with data processing by pattern recognition methods have been described. Attention is paid to the “electronic tongue” based on an array of original non-specific (non-selective) potentiometric chemical sensors. Application results for integral qualitative analysis of beverages and for quantitative analysis of biological liquids and solutions, containing heavy metals are reported. Discriminating abilities and precision obtained allow to consider “electronic tongue” as a perspective analytical tool.     

Determination of the integral toxicity of water in terms of biotesting with a multisensor system sensitive to individual toxicants

Possibility of applying a multisensor potentiometric system of the type of the “electronic tongue” as a method for evaluating the toxicity of a water medium is considered. The multisensor system is preliminarily calibrated against samples with a known toxicity, determined by the biotesting method with the use of living organisms. It is shown that the thus obtained system is suitable for evaluating the quality of water samples in terms of the response of various test objects without direct use of living organisms.     

Hybrid E‐Tongue for the Evaluation of Sweetness and Bitterness of Soft Drinks Fortified with Epigallocatechin Gallate

A home‐made hybrid electronic tongue was set up, validated and applied to discriminate soft drinks fortified with plant extracts of green tea. The e‐tongue consists of a flow injection system equipped with two electrochemical and one optical sensors. Different formulations of soft drinks composed of glucose and epigallocatechin gallate were then discriminated by principal component analysis. Furthermore, two partial least squares regression models were developed to estimate the “sweetness” (r² of 0.992) and “bitterness” (r² of 0.993) of the model solutions and commercial soft drinks, before and after their fortification with epigallocatechin gallate.     

Electronic correlation studies. III. Self-correlated field method. Application to 2S ground state and 2P excited state of three-electron atomic systems

The self-correlated field method is based on the insertion in the group product wave function of pair functions built upon a set of correlated “local” functions and of “nonlocal” functions. This work is an application to three-electron systems. The effects of the outer electron on the inner pair are studied. The total electronic energy and some intermediary results such as pair energies, Coulomb and exchange “correlated” integrals, are given. The results are always better than those given by conventional SCF computations and reach the same level of accuracy as those given by more laborious methods used in correlation studies.     

Chemical sensors and their systems

The review presents a short record of the evolution of chemical sensors (ion selective electrodes) and multisensor systems of an electronic tongue type, based on the organization principles similar to those of biological sensors. The main types of chemical sensors and multisensor electronic tongue combinations elaborated today are considered along with sensitive materials used in them. Recent advances in chemical sensors, for example, lower detection limits and so-called true selectivity are scrutinized. Also, some widespread analytical applications of electron tongues, including those for the identification and classification of liquid media, for the quantification of various components in there, for the control of industrial processes, as well as the type and intensity evaluation of the taste of food and medications are discussed.     

Miniaturized electronic tongue with an integrated reference microelectrode for the recognition of milk samples

This work presents the application of a new construction of an electronic tongue for the classification of milk originating from various producers. Integrated array of microelectrodes was fabricated from epoxy-glass laminate. PVC membranes with various additives were used as chemosensitive layers. The developed device is capable of recognition of milk samples with high correctness. Moreover, the application of miniaturized reference electrode, integrated on the same substrate, also provided satisfactory results, which can be helpful in future constructions of hand-held electronic tongue systems.     

“intelligent” polymers in medicine and biotechnology

One can define “intelligent” polymers as those polymers which respond with large property changes to small physical or chemical stimuli. These polymers may be in various forms, such as in solution, on surfaces, or as solids. One may also combine “intelligent” aqueous polymer systems with biomolecules, to yield a large family of polymers which respond “intelligently” to physical, chemical or biological stimuli. This article overviews such interesting and versatile polymer systems.     

Deactivation of Excited States

Nature abhors an electronically excited state and strives to convert this energy to other forms. This article is concerned with the various pathways involved in the degradation of electronic excitation to ordinary “thermal” forms, but will primarily discuss the quenching of excited states by other molecules. The authors include as examples only those phototransformations and interactions encountered in solution.     

Can we outperform the DIIS approach for electronic structure calculations?

This article regroups various results on self-consistent field algorithms for computing electronic structures of molecular systems. The first part deals with the convergence properties of the “conventional” Roothaan algorithm and of the level-shifting algorithm. In the second part, a new class of algorithms is introduced, for which convergence is guaranteed by mathematical arguments. Computational performance on various test problems is reported; advantages of this new approach are demonstrated. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 82–90, 2000     

Heterocyclic Systems Having Eight π-Electrons. Synthesis,Properties, and Significance

The terms “aromatic” and “antiaromatic” have attracted widespread interest in recent years. After all the discussion about the meaning of words, one fact remains: the energy content of planar systems displaying cyclic electron delocalization depends upon the number of, and the orbital interactions between, the participating electrons. The concept underlying this progress report is that the electronic destabilization of systems having eight π-electrons should be especially pronounced in the case of six-membered rings for steric and electronic reasons. Such systems are found primarily in anionic, but also in neutral, heterocycles containing hetero ring members which possess electron pairs capable of delocalizing into the π-system. The production and reactivity of such systems are investigated and their biological significance discussed.     

Polymeric membrane ion-selective and cross-sensitive electrode-based electronic tongue for qualitative analysis of beverages

An electronic tongue based on the sensor array of polymeric membrane ion-selective electrodes combined with pattern recognition tools was applied to qualitative analysis of various brands of orange juice, tonic, and milk. The capability of this device to reliably discriminate between different brands of those products was presented. The tests of the system were performed using products of the same brand, but with different manufacture dates (and thus comparable by the term of taste). The fusion of two types of sensors-classical selective ones and partially selective in one versatile array, and working out the sensor array's response by means of principal component analysis and back propagation neural network methods allowed the discrimination between different brands of various beverages with very high accuracy (90-100%). The real performance of the electronic tongue was evaluated applying testing samples from another manufacture lot, than the samples used in the learning set.     

Metal Insertion into C−C Bonds in Solution

What kind of ligated metal center is necessary for insertion into the “hidden” C−C bond? How can one tune the metal center for C−C bond activation by variation of the steric and electronic properties of ligands? What are the possible mechanisms of C−C bond activation in various reaction systems? A systematic look at the available data on C−C bond activation in solution provides some answers to these questions.     

Synthesis and Bonding in Carbene Complexes of an Unsymmetrical Dilithio Methandiide: A Combined Experimental and Theoretical Study

Herein, we report the preparation of a new unsymmetrical, bis(thiophosphinoyl)‐substituted dilithio methandiide and its application for the synthesis of zirconium‐ and palladium‐carbene complexes. These complexes were found to exhibit remarkably shielded ¹³C NMR shifts, which are much more highfield‐shifted than those of “normal” carbene complexes. DFT calculations were performed to determine the origin of these observations and to distinguish the electronic structure of these and related carbene complexes compared with the classical Fischer and Schrock‐type complexes. Various methods show that these systems are best described as highly polarized Schrock‐type complexes, in which the metal–carbon bond possesses more electrostatic contributions than in the prototype Schrock systems, or even as “masked” methandiides. As such, geminal dianions represent a kind of “extreme” Schrock‐type ligands favoring the ionic resonance structure M⁺? CR₂^? as often used in textbooks to explain the nucleophilic nature of Schrock complexes.     

Electronic tongues and their analytical application

Electronic tongues for liquid analysis, based on the organizational principles of biological sensory systems, developed rapidly during the last decade. A brief historical overview of the research and development in the field of electronic tongue systems is presented. Current achievements of scientific groups working in this field are outlined and critically reviewed. The performance of electronic tongues in quantitative analysis and in classification of multicomponent media is considered. The exciting possibility of establishing a correlation between the output from an electronic tongue and human sensory assessment of food flavour, thereby enabling quantification of taste and flavour, is described. Application areas of electronic tongue systems including foodstuffs, clinical, industrial, and environmental analysis are discussed in depth. Prospective research and development in the field of electronic tongues is discussed.     

Characterization of groundwater humic and fulvic acids of different origin by GPC with UV/Vis and fluorescence detection

Gel permeation chromatography (GPC) was applied for recognizing the origin of groundwater humic and fulvic acids. GPC was performed with Fraktogel TSK HW-50 in 0.1 M NaCl, pH 8.5 (0.05 M phosphate buffer), 1 mM EDTA, with 10% by volume methanol added. Humic substances from groundwaters and sediments of four different aquifer systems in Germany were isolated, purified and characterized. Both UV/Vis and fluorescence detection were applied. UV/Vis detection was found to be more powerful in identifying differences between the various humic and fulvic acids. The four aquifer systems investigated (“Gorleben”, “Fuhrberg”, “Franconian Albvorland” and “Munich”) differed from one another with respect to hydrological and geochemical conditions. The results showed that the GPC-elution behavior reflects the geochemical environment and origin (source material and generation process) of aquatic humic and fulvic acids.     

Structure of phosphorus clusters by simulated annealing

The combination of density functional (DF) theory with molecular dynamics (MD) allows one to simulate dynamical processes in solids, clusters and molecules without requiring a parameterization of the forces in the system. The method can also be used with the strategy of “simulated annealing” to determine structural isomers. We demonstrate the capabilities of the scheme in the case of the structure of neutral and charged phosphorus clusters, and discuss relationship between these structures and those of bulk systems (crystalline and amorphous). The results show clearly the tendency of phosphorus structures to have threefold coordination as well as “tubular” structures similar to that found in Hittorf's phosphorus (H-P). We discuss the interplay between electronic and geometric structure.     

Statistical representation of atomic systems structure. II. classification of the representation; entropy dependence of the total energy for isoelectronic series

The energies of the ground states of the mononuclear atomic systems, until now determined merely by approximate methods, turn out to exhibit some almost exact interdependencies. A simple statistical functional of the electronic structure (the “γ representation”) turns out to be decisive for the system energy. In this paper that interdependence is further traced for the N-electron systems in isoelectronic series (with constant N and varying Z). The resulting “combinatorial formula” reproduces the experimental data with the errors at least ten times smaller than those of the conventional Hartree–Fock approximation. The reason why there is such an exact formula for the ground-state energy remains to be clarified. The limiting behavior of our energy formula for large Z exhibits consistency with the Thomas–Fermi and the Z^?1perturbation expansion models.     

Sensor arrays for liquid sensing--electronic tongue systems

Electronic tongue systems are multisensor devices dedicated to automatic analysis of complicated composition samples and to the recognition of their characteristic properties. Recently, the number of publications covering this topic has significantly increased. Many possible architectures of such devices were proposed: potentiometric, voltammetric, as well as approaches embracing mass- and optical-sensors. For the analysis of sensor array data, various pattern recognition systems were proposed. All of these topics are summarized in this review. Moreover, additional problems are considered: miniaturization of electronic tongues and hybrid systems for liquid sensing.