Understanding excited-state structure in metal polypyridyl complexes using resonance Raman excitation profiles,time-resolved resonance Raman spectroscopy and density functional theory

This article discusses the use of Raman spectroscopy, in concert with density functional theory, as a strategy for understanding excited-state structure in metal polypyridyl complexes. The first sections of the article discuss how one can use resonance Raman spectra of the ground-state molecule to understand the resonant Franck-Condon excited state. The theories behind these analyses are based on the sum-over-states and time-dependent approaches; a brief introduction to each of these methods is given. The use of density functional theory and its use in the determination of normal modes of vibration and infrared and Raman band intensities are discussed, with reference to a number of recent papers. The application of these methods is illustrated through the analysis of a number of selected examples which exemplify the strategies used to extract data from probing the Franck-Condon region. These data include the displacements of the resonant excited state with respect to the electronic ground state, the reorganisation energies associated with photoexcitation, bond length changes with excitation and other electronic parameters. The use, and limitations, of these methods are discussed. The direct calculation of resonance Raman band intensities is introduced. The direct measurement of excited-state vibrational spectra through time-resolved methods is discussed in the latter section of the article; with particular regard to the use of transient resonance Raman and time-resolved resonance Raman techniques to probe structural changes in metal polypyridyl complexes.     

Hydrodynamic chronocoulometry

The technique which we call hydrodynamic chronocoulometry was developed to fulfill our need to know the diffusion coefficient and concentration of oxygen in aqueous buffer solutions which we use for experiments with polymer-film modified electrodes. The utility of the technique is most apparent in its application to this type of analysis, a dissolved electroactive gas in solution. Standard solutions for these analyses are difficult to prepare and to store. Techniques for the simultaneous determination of diffusion coefficients and concentration exist, but some are difficult to use because the techniques themselves are complex or require changes of electrode or instrumentation. Hydrodynamic chronocoulometry promises to solve these problems through use of a single measurement at a single electrode, with a single analyte solution. The results are simple in form and straightforward analysis is possible.     

Templating hydrogels

Templating processes for creating polymerized hydrogels are reviewed. The use of contact photonic crystals and of non-contact colloidal crystalline arrays as templates are described and applications to chemical sensing and device fabrication are illustrated. Emulsion templating is illustrated in the formation of microporous membranes, and templating on reverse emulsions and double emulsions is described. Templating in solutions of macromolecules and micelles is discussed and then various applications of hydrogel templating on surfactant liquid crystalline mesophases are illustrated, including a nanoscale analogue of colloidal crystalline array templating, except that the bead array in this case is a cubic array of nonionic micelles. The use of particles as templates in making core-shell and hollow microgel beads is described, as is the use of membrane pores as another illustration of confinement templating.     

Scanning electrochemical microscopy: a new way of making electrochemical experiments

A short review is given on scanning electrochemical microscopy (SECM). The historic background of the technique is briefly summarized and the basic principles outlined. The three different directions of its use: chemical microscopic imaging, the measuring of physicochemical constants and coefficients, and use as a micromachining tool are briefly discussed. The general built-up of the SECM apparatus is described. Preparation and use of several different measuring tips are introduced. A few examples are given of the application of SECM measurement in different studies.     

Scanning electrochemical microscopy: a new way of making electrochemical experiments

A short review is given on scanning electrochemical microscopy (SECM). The historic background of the technique is briefly summarized and the basic principles outlined. The three different directions of its use: chemical microscopic imaging, the measuring of physicochemical constants and coefficients, and use as a micromachining tool are briefly discussed. The general built-up of the SECM apparatus is described. Preparation and use of several different measuring tips are introduced. A few examples are given of the application of SECM measurement in different studies.     

Hydrotalcite catalysis for the synthesis of new chiral building blocks

The use of hydrotalcites for the synthesis of two chiral building blocks in a simple way is described as a new and green methodology. The synthesis of these compounds implies a regioselective Baeyer–Villiger reaction in a very selective way with ulterior opening and lactonisation. This methodology should be considered green for the use of hydrogen peroxide as the only oxidant and hydrotalcites as the catalyst, and because no residues are produced apart from water. The procedure is very adequate for using in gram scale, in order to increase the value of the obtained compounds. The conditions are excellent and can be applied for nonstable compounds, as they are very mild. The synthesised compounds are magnific starting materials for the synthesis of biologically active or natural compounds. The use of a cheap, commercial and chiral compound as carvone disposable in both enantiomeric forms adds an extra value to this methodology.     

Doping und Dopinganalytik

Doping is banned by national and international sports federations and by the IOC. Doping is the use of a substance belonging to one of the banned groups and te use of a doping method. The groups of doping substances, namely stimulants, narcotics, anabolic agents, diuretics and peptide hormones, are introduced. The main analytical methods are based on gas chromatography and mass spectrometry (MS) and are summarized for stimulants and anabolic steroid hormones. The use of mass spectrometry is unambigously necessary for identification of banned substance. In addition to GC/low resolution MS methods for anabolic agents, more sophisticated methods such as high resolution MS (to increase sensitivity) and carbon isotope raio MS (to distinguish between endogenous production and exogenous application of anabolic hormones) are used in doping control.     

Identity preservation of genetically modified organisms in the food chain: requirements,methods, and costs

The use of the technology of genetic modification (GM) in European agriculture and the food supply chain is currently controversial. Because of strong anti-GM technology sentiments, the use of ingredients derived from plants containing GM have largely been eliminated from foods manufactured for direct human consumption by the food supply chain in much of the European Union (EU). During the past year, the attention of those opposed to the technology has turned to the use of GM ingredients in livestock production systems by incorporation of GM soy and maize in animal feed. A discussion is presented of the key issues relating to this subject, focusing on how supplies of GM or non-GM products are segregated or how their identities are preserved. The discussion is centered on GM maize and soybeans into which agronomic traits, such as herbicide tolerance and/or insect resistance, have been incorporated. These are currently the only crops into which some varieties containing GM have been approved for use in the EU.     

Stable isotope dilution assays in mycotoxin analysis

The principle and applications of stable isotope dilution assays (SIDAs) in mycotoxin analysis are critically reviewed. The general section includes historical aspects of SIDAs, the prerequisites and limitations of the use of stable isotopically labelled internal standards, and possible calibration procedures. In the application section actual SIDAs for the analysis of trichothecenes, zearalenone, fumonisins, patulin, and ochratoxin A are presented. The syntheses and availability of labelled mycotoxins for use as internal standards is reviewed and specific advances in food analysis and toxicology are demonstrated. The review indicates that LC–MS applications, in particular, require the use of stable isotopically labelled standards to compensate for losses during clean-up and for discrimination due to ion suppression. As the commercial availability of these compounds continues to increase, SIDAs can be expected to find expanding use in mycotoxin analysis.     

Liquid chromatographic determination of diltiazem and its metabolites using trans isomers as internal standards, with dynamic modification of the solid phase by addition of an amine to the mobile phase

A selective and sensitive reversed-phase high-performance liquid chromatographic method for simultaneous analysis of diltiazem and its five metabolites known to occur in man is presented. Different C18 columns are compared. The influences of organic co-solvent, pH, ionic strength and the addition of various amines are studied. The use of trans-diltiazem as internal standard is advocated. UV detection at 237 nm is used for plasma analyses. The possibilities of electrochemical detection are also discussed. Before solvent extraction, plasma samples are saturated with sodium chloride and made alkaline. Triethylamine is also added. The use of the method in pharmacokinetic applications is exemplified.     

Discovery Learning Using Chemland Simulation Software

We describe in this paper a set of computer-based simulations for use in general chemistry courses. We detail a discovery-based method of teaching, whereby students are led to discover concepts through guided-inquiry use of the simulation modules. Three methods of using the software are described, as is the development process we have employed. Finally, we describe our evaluation studies of the effects of our methodology and the use of a scientific reasoning instrument. The software is available free for download as part of this article.     

Microextraction of drugs

This review will attempt to provide an overview as well as a theoretical and practical understanding of the use of microextraction technologies for drug analysis. The majority of the published reports to date focus on the use of fibre solid-phase microextraction and so the review is significantly focused on this technology. Other areas of microextraction such as single drop and solvent film microextraction are also described. Where there are insufficient examples in the literature to illustrate important concepts, examples of non-drug analyses are presented. The review is intended for readers new to the field of microextraction or its use in drug extraction, but also provides an overview of the most recent advances in the field which may be of interest to more experienced users. Particular emphasis is placed on the effect various sample matrices have on extraction characteristics.     

Optimized Gaussian basis sets for use with relativistic effective (core) potentials: K,Ca, Ga—Kr

Correlation-consistent valence basis sets were developed for the third-row main block elements (K, Ca, Ga—Kr) for use with relativistic effective core potentials. These basis sets are somewhat larger than double-zeta in size, with polarization functions, and are balanced for use in both Hartree–Fock and correlation calculations. Spin–orbit splittings for atoms and molecules are calculated and compared to experiment. These calculations use the approximate spin–orbit operator from the relativistic effective core potentials. The use of these results in the calculation of accurate thermochemical data is discussed. © 1997 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Is the estimation of measurement uncertainty a viable alternative to validation?

Two examples of the use of measurement uncertainty in a development environment are presented and compared to the use of validation. It is concluded that measurement uncertainty is a good alternative to validation for chemical processes in the development stage. Some advantages of measurement uncertainty are described. The major advantages are that the estimations of measurement uncertainty are very efficient, and can be performed before analysis of the samples. The results of measurement uncertainty influence the type of analysis employed in the development process, and the measurement design can be adjusted to the need of the process.     

The Use of Dual Cyclodextrin Chiral Selector Systems in the Enantioseparation of Pharmaceuticals by Capillary Electrophoresis: An Overview

Cyclodextrin (CD) derivatives are the most efficient and frequently used chiral selectors (CSs) in capillary electrophoresis (CE). There are situations when the use of a single CD as CS is not enough to obtain efficient chiral discrimination of the enantiomers; in these cases, sometimes this problem can be resolved using a dual CD system. The use of dual CD systems can often dramatically enhance enantioseparation selectivity and can be applied for the separation of many analytes of pharmaceutical interest for which enantioseparation by CE with another CS systems can be problematic. Usually in a dual CD system an anionic CD is used together with a neutral one, but there are situations when the use of a cationic CD with a neutral one or the use of two neutral CDs or even two ionized CDs can be an efficient solution. In the current review we present general aspects of the use of dual CD systems in the analysis of pharmaceutical substances. Several examples of applications of the use of dual CD systems in the analysis of pharmaceuticals are selected and discussed. Theoretical aspects regarding the separation of enantiomers through simultaneous interaction with the two CSs are also explained. Finally, advantages, disadvantages, potential and new direction in this chiral analysis field are highlighted.     

Status and future prospects for use of the graphite furnace for elemental trace analysis of liquids and solids

Summary An overview of the versatility and use of the graphite furnace for elemental trace analysis of liquids and solids using spectrochemical detection is presented. The analytical performance of conventional graphite furnace atomic absorption spectrometry is compared to other popular state of the art spectrochemical techniques with respect to detection power, precision, sample compatibility and throughput. Some applications of the graphite furnace to practical problem solving in trace analysis are highlighted, including its use with atomic absorption, coherent forward scattering, laser excited atomic fluorescence, laser enhanced ionization and coupled methodologies. Prospects for future use and evaluation are given.     

Stimulated emission at the sum-frequency generation of a bichromatic field interacting with a three-level atom

The Maximum-Entropy formalism is used to obtain approximations to the spherically averaged charge and momentum densities. The only information required is the first few radial expectation values. Analytical and numerical approximations to the central values of the densities are calculated. Moreover, the unused or unknown radial expectation values are estimated by means of the moments of these Maximum-Entropy densities. As illustration, the accuracy of these approximations are numerically studied in a Hartree-Fock framework. This method is complementary to the one which makes use of the Stieltjes-Chebyshev inequalities and leads to the least biased approximate densities compatible with the information we use.     

Bioactive peptides from libraries

New ligands for a variety of biological targets can be selected from biological or synthetic combinatorial peptide libraries. The use of different libraries to select novel peptides with potential therapeutic applications is reviewed. The possible combination of molecular diversity provided by combinatorial libraries and a rational approach derived from computational modeling is also considered. Advantages and disadvantages of different approaches are compared. Possible strategies to bypass loss of peptide bioactivity in the transition from ligand selection to in vivo use are discussed.     

Sorbent trapping of volatile organic compounds from air

The use of sorbents in trapping volatile organic compounds in air for subsequent analysis is reviewed. Sorbents are classified in accordance with the mechanism used to recover the trapped compounds, either solvent or thermal desorption. The use of sorbents is contrasted with other sampling procedures, such as collecting whole air samples using canisters. New developments such as solid-phase microextraction are described. In particular, emphasis is placed on a holistic approach to sampling and analysis, and communication is encouraged between those who take samples in the field, and those who perform the analysis.     

On the possibility of using rubbers in Arctic conditions

This article is devoted to the specific features of the development of compositions and the use of frost-resistant rubbers. The main operating characteristics frost-resistant rubber and the specificity of their use in the Arctic climate are presented.