The development of a high resolution mass spectrometer: A reminiscence

This article is a review of the events leading to the development of the double-focusing tandem mass spectrometer system, which is sometimes called the Johnson-Nier geometry. An essential feature of the geometry is that it eliminates second-order angular aberration, enhancing the sensitivity, without a loss in resolution. Flexibility in the choice of ion source and collector designs is assured because both are outside of regions of electric and magnetic fields. The vacuum housing permits high-temperature baking, ensuring ultrahigh vacuum conditions. Although introduced initially for the purpose of determining precise atomic masses, the design has found its greatest application in studies of structure of heavy molecules, making use of the high resolution to identify fragments. In many cases the composition of a molecule, or fragment, can be deduced from its exact mass by utilizing the known atomic masses of likely constituent atoms.     

Sliding spark spectroscopy

Summary A new analytical radiation source combined with fiber optics linked to a diode array detection device with modified software is described. The direct-reading spectrometer simultaneously covers the wavelength range 185–510 nm with a spectral resolution of <1.5 nm. Intense optical emission is observed when positionally stable high-current surface sparks supplied by a pulse-generator with definite discharge parameters (max. 800 Ampere/pulse) are sliding over compact non-conductive materials such as plastics, glasses, quartz filters or powder pellets. Substrate vaporization, ionization and excitation processes in the surface discharge plasma channel generate emission corresponding to neutral and ionic states. The spectra are essentially composed of lines emitted by the electrode material (e.g. copper, silver), from the substrate under investigation, radiation continuum as well as structured background from the surrounding air atmosphere. Due to the occurrence of emission lines of reactive fillers, inorganic pigments and stabilizers, a rapid multi-element screening method is demonstrated. A rapid identification system (mix-up test) of PVC or fire-retardant thermoplastics within one second has been realized from the atomic emission line intensity originating from the sputtered copper electrode material according to its increased volatility in the presence of chlorine (modified Beilstein test).Puls-Plasma-Technik GmbH, Dortmund     

Fractal porous media III: Transversal Stokes flow through random and Sierpinski carpets

The transversal Stokes flow of a Newtonian fluid through random and Sierpinski carpets is numerically calculated and the transversal permeability derived. In random carpets derived from site percolation, the average macroscopic permeability varies as (- _c)^3/2, close to the critical porosity _c. This exponent is found to be slightly different from the conductivity exponent. Results for Sierpinski carpets are presented up to the fourth generation. The Carman equation is not verified in these two model porous media.     

13C NMR spectra of biologically active compounds

The diastereomeric effects on the¹³C NMR chemical shifts of thirteen epimeric pairs of 16-aryloxy-11-deoxyprostaglandins of the E₁ and F₁ series caused by the change in the configuration of the 15-hydroxy group, which are differential parameters for assigning epimers to the 15- and 15-stereochemical series, have been determined.For Communication (VIII), see [1].Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 123–128, January–February, 1991.     

Bemerkungen zur Synthese von 3-Aminotoluol-5-sulfonsäure und 2-Aminotoluol-3-sulfonsäure

Some comments on the synthesis of 3-aminotoluene-5-sulfonic acid and 2-aminotoluene-3-sulfonic acid. Sulfonation of 3-nitrotoluene ( 5 ) yields predominantly the unsymetrical isomer 5-nitrotoluene-2-sulfonic acid ( 7 ), and lesser amounts of 5-nitrotoluene-3-sulfonic acid ( 6 ), previously reported as the major product. The desired 5-aminotoluene-3-sulfonic acid ( 3 ) was synthesized in preparative amounts from 6-aminotoluene-3-sulfonic acid (4) via the following sequence of reactions: diazotation and Sandmeyer replacement of 6-chlorotoluene-3-sulfonic acid ( 13 ), nitration of the sulfonyl chloride 14 under suitable conditions to give isomer free 6-chloro-5-nitrotoluene-3-sulfonyl chloride ( 15 ), hydrolysis to the sulfonic acid 16 and finally, simultaneous hydrogenolysis and reduction to 3 . The isomeric 7 was unequivocally prepared from 2-amino-5-nitrotoluene ( 9 ) via two routes: (1) diazotation, Sandmeyer thiocyanatation to 5-nitro-2-thiocyanatotoluene ( 10 ), Na₂S reduction to the di(2-methyl-4-nitro-phenyl)-disulfide ( 11 ), treatment with nitric acid and chlorine to give 5-nitrotoluene-2-sulfonyl chloride ( 12 ) and finally alkaline hydrolysis to 7 ; (2) Meerwein's SO₂ treatment of the diazonium salt derived from 9 leads directly to 12 and thence to 7 . 2-Aminotoluene-3-sulfonic acid ( 1 ) was prepared from the key intermediate 3-amino-2-nitrotoluene ( 18 ) via the same two routes used to prepare 7 from 9 . Both reaction sequences provided 2-nitrotoluene-3-sulfonly chloride, the hydrolysis product of which was reduced to 1 . Intermediate 18 was prepared in the following four steps from m-toluic acid ( 19 ): nitration to the 2-nitroderivative ( 20 ), whose acid chloride ( 21 ) was converted to 2-nitro-m-toluamide ( 22 ), and Hoffmann rearrangement to 18 .     

Ab initio studies on polymers. VI. Torsional potential in regular polyethylene chains

Ab initio crystal orbital calculations have been performed on regular polyethylene chains applying basis sets of minimal and double-zeta quality. Relative stabilities of periodic all-trans, all-gauche, and alternating trans–gauche conformers have been evaluated, including extensive geometry optimization. Potential curves for a simultaneous rotation around C? C single bonds from the all-trans to the all-gauche conformation have been computed applying the rigid-rotor approximation, the flexible-rotor approximation, and an additional reoptimization of C? C distances. A rigid-rotor potential curve from the all-trans to the alternating trans-gauche conformation has been computed as well. Results obtained are compared with ab initio calculations on butane and pentane and with semiempirical and empirical force-field studies on polyethylene.     

13C-NMR studies of marine natural products II. Total assignment of the 13C-NMR spectrum of asperdiol

¹³C-nmr spectral assignments for asperdiol are made with the aid of model compounds and T₁ relaxation behavior. Overall isotropic tumbling was inferred from the latter providing a supplemental means of multiplicity determination. Utilization of the T₁ relaxation times as an assignment criterion for select resonances in asperdiol is also described.     

Microchemical characterization of paintings — A case study

Summary The fundamental importance of scientific research for the preservation and restoration of works of art is uncontestable. The methods described in this paper, such as light microscopy, microchemical tests, emission spectroscopy, chromatography, scanning electron analysis, electron microprobe analysis and infrared spectroscopy, are of special significance in this filed. Nevertheless a better understanding of the problems that arise out of new special questions of art history can be obtained only by the right interpretation of the data obtained by scientific methods.

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Mikrochemische Charakterisierung von Gemälden

Zusammenfassung Die grundlegende Bedeutung wissenschaftlicher Forschung für die Erhaltung und Restaurierung von Kunstwerken ist unbestritten. Die hier beschriebenen Methoden (Lichtmikroskopie, mikrochemische Reaktionen, Emissionsspektroskopie, Chromatographie, Rasterelektronen-Analyse und Infrarotspektroskopie) sind hierfür von zunehmender Bedeutung. Sie ermöglichen ein besseres Verständnis neuerer kunsthistorischer Probleme nur durch die richtige Interpretation der Ergebnisse wissenschaftlicher Methoden.