“… to make Chemistry more Applicable and Generally Beneficial”—The Transition in Scientific Perspective in Eighteenth Century Chemistry

In 1751, the Swedish chemist Johan Gottschalk Wallerius first differentiated between “pure” and “applied” chemistry, a distinction which was quickly adopted by the other branches of science. Behind this was a new scientific concept of chemistry which emphasized the importance of applying chemistry's accumulated knowledge and its capabilities of providing for the general economic benefit. It also provided chemistry with a new position within the hierarchy of the sciences as well as with a new function in society. The reasons behind and causes of the change in scientific perspective associated with this concept point to the social and institutional conditions under which this field has developed into an independent academic discipline.     

In-gel deglycosylation of sodiumdodecyl sulfate polyacrylamide gel electrophoresis-separated glycoproteins for carbohydrate estimation by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Mass determination by mass spectrometric methods (electrospray ionization mass spectrometry (ESI-MS), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS)) of sodiumdodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE)-separated proteins is a well known procedure and reliable protocols are available. In our efforts to use the established methods to determine the molecular mass of the disulfide bridged, heterodimeric glycoprotein GP3 and to determine the carbohydrate content of each protein subunit we developed an in-gel chemical deglycosylation method. For this purpose we established experimental conditions that allow maximum extraction of the high molecular mass protein subunits and developed a routine method to apply the HF-pyridine deglycosylation protocol to proteins isolated from polyacrylamide gel pieces. The novel protocol and extraction procedure described can be used to analyze O-glycosylated proteins up to 150 kDa after SDS-PAGE separation.     

Preparation and stereoselectivity of 1,3-dipolar cycloaddition ofD-glucose-derived nitrones to N-arylmaleimides

Summary Nitrones2 derived fromD-glucose oxime and benzaldehydes without employing any protection of hydroxyl group were isolated in pure state. The 1,3-dipolar cycloaddition of2 to N-arylmaleimides gave predominantly theanti isoxazolidines3 and was rationalized byZ/E isomerization of N-glycosylnitrones2. The structure and steric configuration of the products have been assigned on the basis of¹H- and¹³C-NMR spectroscopy. AM1 calculations of the nitrones and MM2 calculations of the adducts were performed.

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Darstellung und Stereoselektivität der 1,3-dipolaren Cycloaddition vonD-Glucose-abgeleiteten Nitronen an N-Arylmaleimiden

Zusammenfassung Die Nitrone2 wurden ausD-Glucoseoxim und Benzaldehyden ohne Schutz von Hydroxylgruppen in reinem Zustand erhalten. Die 1,3-dipolare Cycloaddition von2 an N-Arylmaleimiden ergab bevorzugt dieanti-Isoxazolidine3; dies wurde über eineZ/E-Isomerisierung der N-Glycosylnitrone2 rationalisiert. Struktur und Stereochemie wurden auf Basis von¹H- und¹³C-NMR-Spektroskopie ermittelt. Außerdem wurden AM1-Berechnungen an den Nitronen und MM2-Rechnungen an den Addukten ausgeführt.

     

The reaction of phenylarsenazo with chromium(III)

The conditions for the reaction between phenylarsenazo (PAA) (2-[(2-arsonophenyl)azoj-7-(phenylazo)-1, 8-dihydroxynaphthalene-3,6-disulphonic acid) and chromium(III) have been studied. A blue 1:1 complex is formed at pH 2.2 on heating the reactants at 100 degrees for 15 min. It has maximum absorption at 635 nm and is stable for at least 24 hr. The molar absorptivity is 3.3 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed in the chromium concentration range 0-1.4 mug ml . The reaction has been successfully applied to determination of chromium in alloy steel.     

Synthesis of 1,1-dihydroperfluorooxaalkan-1-ols and their interaction with terephthaloyl chloride

A series of 1,1-dihydroperfluorooxaalkan-1-ols and ,,,-tetrahydroperfluorooxaalkanediols has been synthesized. Some tercphthalates were synthesized by the reaction of these alcohols and diols with terephthaloyl chloride.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1573–1576, June, 1996.     

The electronic structure of molecules by a many-body approach

The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C₃H₆ the ordering of the ionization potentials is 2e(), 1e(), 2a₁(), 1a₂(), 1e(). The assignment of the 2a₁ and the 1a₂ ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C₂H₄O the ordering of the ionization potentials is 2b ₁(), 4a ₁, 1a ₂(), 2b ₂,3a ₁, 1b ₁(), 1b ₂, 2a ₁ and for C₂H₅N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory.     

Compehensive two-dimensional gas chromatography (GC×GC) and its applicability to the characterization of complex (petrochemical) mixtures

In general, petrochemical products contain only a limited number of chemical classes of compounds (sample dimensionality). The enormous number of individual components within these classes, however, soon puts limitations upon a single chromatographic technique when it comes to adequate characterization of these products. Comprehensive two-dimensional gas chromatography (GC×GC) clearly opens the possibility of estimating the composition of hydrocarbon mixtures in a far more detailed fashion than hitherto possible. Although the emphasis of papers of GCxGC thus far almost exclusively applies to the unsurpassed peak-capacity, in the oil industry there is a need for characterization, rather than for analyzing all the individual compounds. In principle a GCxGC system can provide an almost perfect match between its intrinsic properties and the dimensionality of oil samples. To establish the applicability of GCxGC towards petrochemical analytical challenges, a commercially aavailable prototype instrument was subjected to an exhaustive characterization of a typical hydrocarbon precess stream and a fast characterization of a light gas oil. Although there are no fundamental limitations towards the quantitative aspects of a GCxGC system, this paper confines itself to qualitative results only. Quantitative aspects of GCxGC will be published in a forthcoming paper.     

Note on the ab initio PUHF treatment of open-shell systems

Ab initio projected-unrestricted Hartree-Fock calculations have been carried out on a number of excited and ionic states of the water molecule. Results have been compared with large-scale CI calculations, with IVO calculations, and with those of Mrozek and Golebiewski obtained by the 2 × 2 rotation method applied to orbitals. It is concluded that the PUHF method may provide the most useful alternative to large-scale CI for calculating properties of open-shell systems. But it will not be generally useful for calculating spectral transition energies.     

Carob pod: A new substrate for citric acid production by Aspergillus niger

The production of citric acid from carob pod extract byA. niger in surface fermentation was investigated. A maximum citric acid concentration (85.5 g/L), citric acid productivity (4.07 g/L/d), specific citric acid production rate (0.18 g/g/d), and specific sugar uptake rate (0.358 g/g/d) was achieved at an initial sugar concentration of 200 g/L, pH of 6.5, and a temperature of 30°C. Other kinetic parameters, namely, citric acid yield, biomass yield, specific biomass production rate, and fermentation efficiency were maximum at pH 6.5, temperature 30°C, and initial sugar concentration 100 g/L. The external addition of methanol into the carob pod extract at a concentration up to 4% (v/v) improved the production of citric acid.     

On the stabilizer subgroup of a fair of matrices

Let (F,G) be a pair of matrices defined over an arbitrary field, Fn × n, Gn × m. Consider the natural action of GL_n x GL_m on this pair given by (F,G) ? (gFg^-1,gGh^-1), where (g,h) ∈ GL_n × GL_m. This action is of interest in system theory as well as the representation theory of quivers. In this paper we study the stabilizer subgroup of this action stab(F,G), i.e.

$\text{{(g,h) ∈ GL}{}_{\mathrm{n}}\text{x GL}{}_{\mathrm{m}}\text{|gFg}{}^{-1}\text{= F,gGh}{}^{-1}\text{= G}}$

.