High-resolution field desorption mass spectrometry: Part VII. Explosives and Explosive Mixtures4

Standard explosives and technical mixtures of explosives have been investigated by field desorption mass spectrometry. The compounds investigated gave intense molecular ions or protonated molecules and structurally significant fragmentation. For comparison, the corresponding electron impact and chemical ionization mass spectrometry data are reported. Emission-controlled field desorption, photographic detection, and accurate mass measurements enabled the components of the technical mixtures to be identified. An example of the determination of an additive in a technical product by field desorption mass spectrometry and stable isotope dilution is given. The use of these techniques for quality control of explosives and for forensic investigations appears to be promising.     

The vitamin D3 pathway in human skin and its role for regulation of biological processes

The skin is the only tissue yet known in which the complete ultraviolet-B (UV-B)-induced pathway from 7-dehydrocholesterol to hormonally active calcitriol (1alpha,25-dihydroxyvitamin D(3)) occurs under physiological conditions. Epidermal synthesis of calcitriol could be of fundamental relevance because calcitriol regulates important cellular functions in keratinocytes and immunocompetent cells. Because of their antiproliferative and prodifferentiating effects, calcitriol and other vitamin D analogs are highly efficient in the treatment of psoriasis vulgaris. The known antipsoriatic effect of UV-B light could, at least in part, be mediated via UV-B-induced synthesis of calcitriol. In addition, mounting evidence indicates that cutaneous vitamin D(3) synthesis is of high importance for the prevention of a broad variety of diseases, including various malignancies. New but controversially discussed sun-protection guidelines were established for the prevention of internal cancers. A better understanding of the metabolism of vitamin D in the skin opens new perspectives for therapeutic applications of vitamin D analogs.     

Die Ramanspektren der Jod(III)-nitrate CF3J(NO3)2, C6H5J(NO3)2 und J(NO3)3

Raman Spectra of the Iodine (III) Nitrates CF₃I(NO₃)₂, C₆H₅I(NO₃)₂, and I(NO₃)₃ The Raman spectra of the title compounds are recorded and discussed.     

Template-Reaktion von Bis(acetylacetonato)-dioxo-molybdän(VI) mit Benzoylhydrazin

Template Reaction of Bis(acetylacetonato)-dioxo-molybdenum(VI) with Benzoylhydrazone By reaction of bis(acetylacetonato)-dioxo-molybdenum(VI) with benzoylhydrazine benzoylhydrazido(2?)-acetylacetonebenzoylhydrazonato(2?)-oxo-molybdenum(VI) was formed beside another species. The compound was characterized by mass spectrometry and X-ray structural analysis. Crystallographic data see ?Inhaltsübersicht”?.     

Der erste Magnetoplumbit mit Lanthanoidionen: Nd2FeFeAl9O38

First Magnetoplumbite Structure Including Rare Earth Ions: Nd₂Fe Fe Al₉O₃₈ The hitherto unknown compound Nd₂Fe₁₅Al₉O₃₈ with magnetoplumbite structure was prepared. The symmetry of the isolated red-brown single crystals was determined by X-ray single crystal work (space group D? P6₃//mmc; a = 568.7; c = 2 223 pm; Z = 2) and the distribution of Fe and Al to the metal positions was identified.     

Chemie von α-Aminonitrilen 22. Mitteilung Regioselektive Synthese und Kristallstruktur von Uroporphyrinogen-(Typ I)-octanitril

Chemistry of α-Aminonitriles. Regioselective Synthesis and Crystal Structure of Uroporphyrinogen (Type I) Octanitrile A regioselective synthesis of uroporphyrinogen-octanitrile (type I) based on the strategy of multiple use of (dimethylmethylidene)ammonium iodide for stepwise regioselective functionalization of the pyrrole nucleus is described. This uroporphyrinogen derivative is remarkably stable and beautifully crystallizes in space group P1 with one molecule per unit cell. The crystal structure of the compound shows interesting conformational characteristics which are interpreted to be caused by subtle stereoelectronic effects. The English Footnotes to Schemes 1-3 and Figs. 1-12 provide an extension of this summary.     

Cationic ruthenium allenylidene complexes as catalysts for ring closing olefin metathesis

A series of well accessible cationic ruthenium allenylidene complexes of the general type [(eta6-arene)(R3P)RuCl(=C=CR'2)]+ X- is described which constitute a new class of pre-catalysts for ring closing olefin metathesis reactions (RCM) and provide an unprecedented example for the involvement of metal allenylidenes in catalysis. They effect the cyclization of various functionalized dienes and enynes with good to excellent yields and show a great tolerance towards an array of functional groups. Systematic variations of their basic structural motif have provided insights into the essential parameters responsible for catalytic activity which can be enhanced further by addition of Lewis or Bronsted acids, by irradiation with UV light, or by the adequate choice of the "non-coordinating" counterion X-. The latter turned out to play a particularly important role in determining the rate and selectivity of the reaction. A similarly pronounced influence is exerted by remote substituents on the allenylidene residue which indicates that this ligand (or a ligand derived thereof) may remain attached to the metal throughout the catalytic process. X-ray crystal structures of the catalytically active allenylidene complexes 3b.PF6 and 15.OTf as well as of the chelate complex 10 required for the preparation of the latter catalyst are reported.     

X-ray crystal structures of [XF(6)][Sb(2)F(11)] (X = Cl, Br, I); (35,37)Cl, (79,81)Br, and (127)I NMR studies and electronic structure calculations of the XF(6)(+) cations

The single-crystal X-ray structures of [XF(6)][Sb(2)F(11)] (X = Cl, Br, I) have been determined and represent the first detailed crystallographic study of salts containing the XF(6)(+) cations. The three salts are isomorphous and crystallize in the monoclinic space group P2(1)/n with Z = 4: [ClF(6)][Sb(2)F(11)], a = 11.824(2) A, b = 8.434(2) A, c = 12.088(2) A, beta = 97.783(6) degrees , V = 1194.3(4) A(3), R(1) = 0.0488 at -130 degrees C; [BrF(6)][Sb(2)F(11)], a = 11.931(2) A, b = 8.492(2) A, c = 12.103(2) A, beta = 97.558(4) degrees , V = 1215.5(4) A(3), R(1) = 0.0707 at -130 degrees C; [IF(6)][Sb(2)F(11)], a = 11.844(1) A, b = 8.617(1) A, c = 11.979(2) A, beta = 98.915(2) degrees , V = 1207.8(3) A(3), R(1) = 0.0219 at -173 degrees C. The crystal structure of [IF(6)][Sb(2)F(11)] was also determined at -100 degrees C and was found to crystallize in the monoclinic space group P2(1)/m with Z = 4, a = 11.885(1) A, b = 8.626(1) A, c = 12.000(1) A, beta = 98.44(1), V = 1216.9(2) A(3), R(1) = 0.0635. The XF(6)(+) cations have octahedral geometries with average Cl-F, Br-F, and I-F bond lengths of 1.550(4), 1.666(11) and 1.779(6) [-173 degrees C]/1.774(8) [-100 degrees C] A, respectively. The chemical shifts of the central quadrupolar nuclei, (35,37)Cl, (79,81)Br, and (127)I, were determined for [ClF(6)][AsF(6)] (814 ppm), [BrF(6)][AsF(6)] (2080 ppm), and [IF(6)][Sb(3)F(16)] (3381 ppm) in anhydrous HF solution at 27 degrees C, and spin-inversion-recovery experiments were used to determine the T(1)-relaxation times of (35)Cl (1.32(3) s), (37)Cl (2.58(6) s), (79)Br (24.6(4) ms), (81)Br (35.4(5) ms), and (127)I (6.53(1) ms). Trends among the central halogen chemical shifts and T(1)-relaxation times of XF(6)(+), XO(4)(-), and X(-) are discussed. The isotropic (1)J-coupling constants and reduced coupling constants for the XF(6)(+) cations and isoelectronic hexafluoro species of rows 3-6 are empirically assessed in terms of the relative contributions of the Fermi-contact, spin-dipolar, and spin-orbit mechanisms. Electronic structure calculations using Hartree-Fock, MP2, and local density functional methods were used to determine the energy-minimized gas-phase geometries, atomic charges, and Mayer bond orders of the XF(6)(+) cations. The calculated vibrational frequencies are in accord with the previously published assignments and experimental vibrational frequencies of the XF(6)(+) cations. Bonding trends within the XF(6)(+) cation series have been discussed in terms of natural bond orbital (NBO) analyses, the ligand close-packed (LCP) model, and the electron localization function (ELF).     

Investigation of potential-sensitive fluorescent dyes for application in nitrate sensitive polymer membranes

The applicability of various potential-sensitive dyes (PSD) for optical sensing of anions is reported. Specifically, nitrate-responsive polymer membranes have been developed which are composed of a plasticized polymer, an anion exchange catalyst, and a fluorescent dye. On exposure to nitrate, the fluorescence intensity of such membranes increases, while the wavelengths of the excitation and emission maxima remain virtually unchanged. The membranes typically are 2–4 μm thick and exhibit highest sensitivity to nitrate in the 2 to 200 mgl^–1 range. Signal changes on exposure to 100 mmol/l nitrate can be as high as +300%. The detection limit is 0.2 mgl^–1. The cationic PSD octadecyl acridine organe was tested in combination with a tin-organic and an indium-organic anion carrier rather than with tridodecylmethylammonium chloride, but both carriers were found to display no improved selectivity. Received: 2 December 1995 / Revised: 28 March 1996 / Accepted: 5 April 1996