Component reconstruction in the primary space of spectra and concentrations. Alternating regression and related direct methods

A set of methods that extract the spectral components in a chromatographic run is considered. The methods do not need libraries of previously known spectra or retention times. The methods have been developed for two-dimensional spectra but they can also be used for chromatographic analyses with a single-channel detector. The methods are direct; they do not use principal components as the starting point. Alternating regression (AR) remains in the primary space of spectra and concentrations during the calculations. Random numbers are used as the starting spectra. Regression is used to solve first for the concentrations, then for the spectra. The method uses two kinds of constraints: all spectra and concentrations are forced to be positive; and all concentration profiles are forced to a unimodal shape with a single local maximum. It is assumed that all observations are a linear sum of components. Compact alternating regression (CAR) is a new variant of the basic AR. The idea is to replace multiplication of a large matrix by two multiplications of smaller matrices. This typically speeds up the iterations by a factor of ten. AR and CAR have been successfully used with combined techniques such as gas chromatography—mass spectrometry and liquid chromatography with UV—visible detection. The reliability of the solution is checked by repeatedly injecting noise and performing the analysis several times. This produces estimates of confidence intervals. AR and CAR have recently been extended to handle single-dimensional signals. Examples are single-channel detectors such as the flame ionization detector in gas or liquid chromatography with a fixed-wavelength UV detector. A batch of samples is used as the observation matrix. As a result, one obtains both the concentrations and the elution shapes of individual chromatographic peaks.     

Scalable synthesis of (−)-trans-3-hydroxypipecolic acid via a useful chiral building block

A scalable synthesis of (−)-trans-2-(hydroxymethyl)-1,2,3,6-tetrahydropyridin-3-ol, a versatile chiral building block is described along with its transformation to (−)-trans-3-hydroxypipecolic acid.     

CE and asymmetrical flow‐field flow fractionation studies of polymer interactions with surfaces and solutes reveal conformation changes of polymers

Amphiphilic diblock copolymers consisting of a hydrophobic core containing a polymerized ionic liquid and an outer shell composed of poly(N‐isoprolylacrylamide) were investigated by capillary electrophoresis and asymmetrical flow‐field flow fractionation. The polymerized ionic liquid comprised poly(2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate) with a constant block length (n = 24), while the length of the poly(N‐isoprolylacrylamide) block varied (n = 14; 26; 59; 88). Possible adsorption of the block copolymer on the fused silica capillary, due to alterations in the polymeric conformation upon a change in the temperature (25 and 45 °C), was initially studied. For comparison, the effect of temperature on the copolymer conformation/hydrodynamic size was determined with the aid of asymmetrical flow‐field flow fractionation and light scattering. To get more information about the hydrophilic/hydrophobic properties of the synthesized block copolymers, they were used as a pseudostationary phase in electrokinetic chromatography for the separation of some model compounds, that is, benzoates and steroids. Of particular interest was to find out whether a change in the length or concentration of the poly(N‐isoprolylacrylamide) block would affect the separation of the model compounds. Overall, our results show that capillary electrophoresis and asymmetrical flow‐field flow fractionation are suitable methods for characterizing conformational changes of such diblock copolymers.     

Diagnostic performance of low field MRI in acute knee injuries

The diagnostic performance of low field (0.1 T) magnetic resonance imaging (MRI) was studied prospectively and double-blindly among 33 patients with acute knee injuries. The subsequent arthroscopy was the golden standard. For lesions of the medial meniscus low field MR had a sensitivity of 88% and a specificity of 80%; for lesions of the lateral meniscus the sensitivity was 25% and the specificity 97%. For anterior cruciate ligament tears, low field MRI had a sensitivity of 83% and a specificity of 85%. The specificity for posterior cruciate ligament tears was 97%. The performance of low field MRI equalled that reported earlier for high field MRI, the only exception being the sensitivity for lateral meniscus lesions.     

A compact olfactometer for IMS measurements and testing human perception

Production of easily controllable and measurable odor stimuli is needed when studying human olfaction, olfaction-related physiology and psychological reactions to odors. Controlled odor producing instruments are called olfactometers. For testing and calibrating new olfactometers or sensor arrays, a reliable input signal has to be produced to verify their accurate functionality. A common input signal in various olfactometers has been the use of volatile organic compounds (VOCs) in gaseous form. We present a compact olfactometer able to produce controlled continuous odor stimuli from three individual channels. For measuring the output gas flow, we used a ChemPro 100i (Environics, Finland) device that is based on aspiration ion mobility spectrometry (aIMS). IMS is a robust and sensitive method for measuring VOCs and is used especially in detecting toxic industrial chemicals and chemical warfare agents, but the technology is also suitable for other olfactory-related applications. The olfactometer was used to produce synthetic jasmine scent using three main odor components from jasmine oil and all the components were diluted using propylene glycol. The dilutions were supplied to the system using programmable syringe pumps, which guided the dilutions to individual evaporation units. We conducted experiments to verify the functionality of our olfactometer. Analysis of the ChemPro100i data showed that olfactometer can use different odor components to produce continuous, stable output flows with controlled concentrations.     

New polymer electrolyte membranes for low temperature fuel cells

Partially fluorinated proton exchange materials were synthesised by pre-irradiation grafting of styrene into poly(vinylidene fluoride) films with subsequent sulfonation. The grafted and sulfonated membranes, PVDF-g-PSSA membranes, have been studied with respect to water uptake, ion and water clustering, ion conductivity and water diffusion coefficients. Water associates with the membranes in three different ways: bound non-freezable water, freezable bound water and freezable free water. The proton conductivity of the membrane is strongly dependent on the hydration, it decreases more rapidly than the water self diffusion with decreasing water content. Ion clusters with a Bragg distance of 25 Å form the conducting channels in the membranes.     

Integrable equations for the partition function of the six-vertex model

The partition function of the six-vertex model with the domain-wall boundary condition is considered in the homogeneous and inhomogeneous cases. The determinant representation allows us to show that the partition function is a solution of the Toda equation in the homogeneous case and a solution of the Hirota equation in the inhomogeneous case. Bibliography: 10 titles. Translated fromZapiski Nauchnykh Seminarov POMI, Vol. 245, 1997, pp. 207–215. Translated by N. A. Kitanin.     

Biocatalytic Oxidation Reactions: A Chemist's Perspective

Oxidation chemistry using enzymes is approaching maturity and practical applicability in organic synthesis. Oxidoreductases (enzymes catalysing redox reactions) enable chemists to perform highly selective and efficient transformations ranging from simple alcohol oxidations to stereoselective halogenations of non‐activated C?H bonds. For many of these reactions, no “classical” chemical counterpart is known. Hence oxidoreductases open up shorter synthesis routes based on a more direct access to the target products. The generally very mild reaction conditions may also reduce the environmental impact of biocatalytic reactions compared to classical counterparts. In this Review, we critically summarise the most important recent developments in the field of biocatalytic oxidation chemistry and identify the most pressing bottlenecks as well as promising solutions.