Imprinting with sensor development – On the way to synthetic antibodies

Molecular imprinting is an attractive tool for the development of artificial recognition systems. Even non-covalent imprinting provides universal interaction centers for sensoric applications. The coated chemical sensors have high stabilities under harsh conditions in both the gas and liquid phases. With adequate efforts optical and mass-sensitive sensors (quartz crystal microbalance, QCM, surface acoustic wave detector, SAW) are suitable for analysis down to the ppb (nL/L) range. PAHs, isomer VOCs as well as complex oil mixtures are appropriate analytes. Received: 4 November 1998 / Revised: 29 April 1999 / Accepted: 5 May 1999     

Vibrational overtone combination spectroscopy (VOCSY)—a new way of using IR and NIR data

This work explores a novel method for rearranging 1st order (one-way) infra-red (IR) and/or near infra-red (NIR) ordinary spectra into a representation suitable for multi-way modelling and analysis. The method is based on the fact that the fundamental IR absorption and the first, second, and consecutive overtones of NIR absorptions represent identical chemical information. It is therefore possible to rearrange these overtone regions of the vectors comprising an IR and NIR spectrum into a matrix where the fundamental, 1st, 2nd, and consecutive overtones of the spectrum are arranged as either rows or columns in a matrix, resulting in a true three-way tensor of data for several samples. This tensorization facilitates explorative analysis and modelling with multi-way methods, for example parallel factor analysis (PARAFAC), N-way partial least squares (N-PLS), and Tucker models. The vibrational overtone combination spectroscopy (VOCSY) arrangement is shown to benefit from the “order advantage”, producing more robust, stable, and interpretable models than, for example, the traditional PLS modelling method. The proposed method also opens the field of NIR for true peak decomposition—a feature unique to the method because the latent factors acquired using PARAFAC can represent pure spectral components whereas latent factors in principal component analysis (PCA) and PLS usually do not.     

Needs for fundamental atomic reference data and data distribution: fundamental analytical spectroscopy—response to a questionnaire

This paper presents a survey of the needs for fundamental data of analytical spectroscopists with special reference to basic research (plasma diagnostics). Differences in needs between analytical spectroscopists and other atomic spectroscopists are pointed out. Inadequacy of Ar and Fe transition probability data for analytical needs and lack of adequate tabulations of collision cross-sections are noted. Issues concerning access to data are also discussed.     

A new way to synthesize ZnS nanoparticles

ZnS nanoparticles were prepared with normal ZnO and Na2S by solid-liquid chemical reaction under ultrasonic condition andcharacterized by XRD,TEM,SEM,IR and TG-DTG.The results showed that these particles were good crystal cubic zinc blendedwith average size of 50 nm,possess good IR transmittance in the range of 400-4000 cm and good thermal stability.     

Desymmetric ring-opening of meso-epoxides with anilines: a simple way to chiral β-amino alcohols

Chiral β-amino alcohols were afforded by desymmetric ring-opening of meso-epoxides with anilines catalyzed by chiral Yb triflate complex in up to 80.1% ee.     

Inhibition and substrate recognition – a computational approach applied to HIV protease

We have developed a computational approach in which an inhibitor's strength is determined from its interaction energy with a limited set of amino acid residues of the inhibited protein. We applied this method to HIV protease. The method uses a consensus structure built from X-ray crystallographic data. All inhibitors are docked into the consensus structure. Given that not every ligand-protein interaction causes inhibition, we implemented a genetic algorithm to determine the relevant set of residues. The algorithm optimizes the q2 between the sum of interaction energies and the observed inhibition constants. The best possible predictive model resulting has a q2 of 0.63. External validation by examining the predictivity for compounds not used in derivation of the model leads to a prediction accuracy between 0.9 and 1.5 log10 unit. Out of 198 residues in the whole protein, the best internally predictive model defines a subset of 20 residues and the best externally predictive model one of 9 residues. These residues are distributed over the subsites of the enzyme. This approach provides insight in which interactions are important for inhibiting HIV protease and it allows for quantitative prediction of inhibitor strength.     

Asymmetric induction in photocatalysis – Discovering a new side to light-driven chemistry

The state of asymmetric photocatalysis is exceptionally promising, as chemists from different fields and backgrounds have converged to solve a longstanding issue: stereocontrol in photochemistry. As a strategy that relies heavily on the elevated reactivity of radical intermediates, managing to suppress the background racemic reactions in favor of the stereoselective processes is a challenging endeavor many researchers have embarked on. In order to tackle this matter, conceptually diverse activation modes have been developed, obtaining valuable results across mechanistically-distinct types of reactions, all while setting the stage for future breakthroughs in the field.     

Interfacing cytochrome c to electrodes with a DNA – carbon nanotube composite film

Multi-walled carbon nanotube (MWCNT) is successfully immobilized on the surface of platinum electrode by mixing with DNA. The DNA/MWCNT modified electrodes are characterized by electrochemical impedance spectroscopy and cyclic voltammetry. Further research indicates that cytochrome c can strongly adsorbed on the surface of the modified electrode, and forms an approximate monolayer. The immobilized MWCNT can promote the redox of horse heart cytochrome c which gives reversible redox peaks with a formal potential of 81 mV vs SCE.     

A mild and efficient way to prepare ε-caprolactam by using a novel salt related with ionic liquids

The Beckmann rearrangement of several ketoximes has been performed by treatment with tosyl chloride, using ionic liquids as both solvent and catalyst, without the need of any other promoter. High levels of conversion and selectivity were observed in the majority of experiments. Work-up is very simple and the product can be isolated in high yields. When the method was applied to cyclohexanone oxime, the novel salt [TMG][TsO] instead of the ionic liquid was used. This procedure afforded a conversion of 100% to obtain pure ε-caprolactam in a 98% yield. [TMG][TsO] is easy to prepare, cheap, and not corrosive. It can be recovered and reused.     

CuCl-catalyzed radical cyclisation of N-α-perchloroacyl-ketene-N,S-acetals: a new way to prepare disubstituted maleic anhydrides

The copper-catalyzed radical cyclization (RC) of N-α-perchloroacyl cyclic ketene-N,X(X=O, NR, S)-acetals was studied. While the RC of N-acyl ketene-N,O-acetals was unsuccessful, the 5-endo cyclization of the other ketene acetals provided much better results, with the following order of cyclization efficiency: hexa-atomic cyclic ketene-N,NR-acetals<penta-atomic cyclic ketene-N,S-acetals<hexa-atomic cyclic ketene-N,S-acetals. Invariably the catalytic cycle begins with the formation of a carbamoyl methyl radical. This leads to a cascade of reactions, including a radical polar crossover step, which ends with the formation of the maleimide nucleus, or precursors of this. Products from the RC of the hexa-atomic cyclic ketene-N,S-acetals, were efficiently transformed into disubstituted maleic anhydrides.     

The way to AI-controlled synthesis: how far do we need to go?

Chemical synthesis always plays an irreplaceable role in chemical, materials, and pharmacological fields. Meanwhile, artificial intelligence (AI) is causing a rapid technological revolution in many fields by replacing manual chemical synthesis and has exhibited a much more economical and time-efficient manner. However, the rate-determining step of AI-controlled synthesis systems is rarely mentioned, which makes it difficult to apply them in general laboratories. Here, the history of developing AI-aided synthesis has been overviewed and summarized. We propose that the hardware of AI-controlled synthesis systems should be more adaptive to execute reactions with different phase reagents and under different reaction conditions, and the software of AI-controlled synthesis systems should have richer kinds of reaction prediction modules. An updated system will better address more different kinds of syntheses. Our viewpoint could help scientists advance the revolution that combines AI and synthesis to achieve more progress in complicated systems.

It is still a long march for AI-controlled synthesis to enter into general laboratories. Flaws in the architecture of AI-controlled synthesis systems must be overcome.     

Needs for fundamental atomic reference data and data distribution — a collage of discussions

This article reports, in edited form, the discussions following a series of presentations during a Workshop “Needs for Fundamental Atomic Reference Data for Analytical Spectroscopy”. This report forms part of the complete Proceedings of the Workshop, in which the extended and edited texts of the presentations, along with the conclusions, are bundled [Spectrochim. Acta43B, No. 1 (1988)]. In the present “collage”, the discussions are grouped under the following headings: (a) targets of the workshop, (b) distribution of the questionnaire, (c) data compilation, (d) clearinghouse for data — accuracy and critical evaluation of data — confidence in data, (e) spectral simulation — partition functions — COSMIC program —understanding the ICP, (f) work at the National Bureau of Standards (NBS) — information on NBS publications, (g) approaches to and instruments for data compilation — multielement interference corrections, (h) type of database and database manager, (i) atomic fluorescence spectrometry - Rydberg states, and (j) transient discharges.     

Reference materials – a view from a small country

ISO/IEC 17025 has an increased emphasis on traceability and estimation of uncertainty of measurement compared with ISO Guide 25. Demonstration of traceability is a new concept in analytical chemistry and depends on access to relevant reference materials or use of reference methods. Until now most reference materials used in New Zealand have been imported, because they offered international comparability. New Zealand is currently starting to develop the required infrastructure so that it will be able to produce unique reference materials that will contribute to the total international effort in improving the reliability of analytical chemistry. Received: 12 October 2000 / Revised: 18 January 2001 / Accepted: 23 January 2001     

Immunochromatographic techniques – a critical review

Hyphenated techniques have become very popular during the last decade. Nevertheless, the use of biochemical methods, such as immunoassays, in conjunction with instrumental methods, such as chromatography, have not gained widespread acceptance. This review critically discusses many of the implemented and potential options for such coupled systems or components, which might be useful for such systems, including immunoaffinity extraction, immunoaffinity chromatography, immunochemical detectors, immunoblotting, receptor assays, enzyme inhibition assays, displacement assays, flow-injection immunoassays, miniaturized techniques and stationary phases such as restricted access materials or molecularly imprinted polymers. The performance of immunochromatographic systems is discussed regarding their ability to solve highly complex and demanding analytical problems. Received: 7 September 1999 / Revised: 4 November 1999 / Acepted: 8 November 1999     

Imprinting with sensor development – On the way to synthetic antibodies

Molecular imprinting is an attractive tool for the development of artificial recognition systems. Even non-covalent imprinting provides universal interaction centers for sensoric applications. The coated chemical sensors have high stabilities under harsh conditions in both the gas and liquid phases. With adequate efforts optical and mass-sensitive sensors (quartz crystal microbalance, QCM, surface acoustic wave detector, SAW) are suitable for analysis down to the ppb (nL/L) range. PAHs, isomer VOCs as well as complex oil mixtures are appropriate analytes.