Doping und Dopinganalytik: Wirkstoffe und Methoden

Since 1997, alterations regarding the anti‐doping rules of sport federations have led to the prohibition of new classes of substances such as plasma volume expanders, anti‐estrogens, aromatase inhibitors and artificial oxygen carriers (e.g. perfluorocarbons, cross‐linked hemoglobins) besides the classical doping agents including stimulants, narcotics, anabolic agents, diuretics and peptide hormones. The determination of doping substances, which has been based mainly on GC‐MS procedures, is more and more performed employing LC‐MS and LC‐MS/MS instruments. For instance, the classes of betablockers, diuretics, corticosteroids and newly proteins such as the cross‐linked hemoglobin 'Hemopure' are effectively detected utilizing LC‐MS(/MS) systems. The urinary identification of erythropoietin (EPO)‐doping is accomplished by means of an assay composed by isoelectric focusing with subsequent visualisation of characteristic EPO bands with monoclonal EPO antibodies (double blotting).     

Ionen-Cyclotron-Resonanz- und Fourier-Transform-Ionen-Cyclotron-Resonanz-Spektroskopie: Technologie und Anwendung

Zusammenfassung Die Technologie von Ionen-Cyclotron-Resonanz- und Fourier-Transform-Ionen-Cyclotron-Resonanz-Spektrometern wird beschrieben. Die Methode kann zur Untersuchung von Ionen/Molekül-Reaktionen in der Gasphase, von thermodynamischen Größen (Gasphasen-Acidität und -Basizität, Protonen- und Elektronen-Affinitäten) und zur Aufklärung von Reaktionsmechanismen und Ionenstrukturen verwendet werden.Ich danke Herrn Prof. Dr. E. Fahr, Institut für Organische Chemie, Universität Mainz, sehr herzlich für anregende Diskussionen und die kritische Durchsicht dieser Arbeit und Frau L. B. Uloth für die Anfertigung der Zeichnungen.     

Neue Metallatrane von Übergangselementen: Chloro- und Cyclopentadienyltitatran und Chloro- und Acetatozirconatran

New Metallatranes of Transition Elements: Chloro- and Cyclopentadienyltitatrane and Chloro- and Acetatozirconatrane Synthesis and characterization of chloro- and cyclopentadienyltitatrane, [ClTi(OCH₂CH₂)₃N]₂ and [CpTi(OCH₂CH₂)₃N], and of chloro- and acetatozirconatrane, [ClZr(OCH₂CH₂)₃N]_n and [CH₃CO₂Zr(OCH₂CH₂)₃N]₂, as well are described as new types of metallatranes of transition elements.     

Chlor-, Brom- und Iodtrisilane: Synthesen und Si-Kernresonanzspektren

Halogenated trisilanes X_nSi₃H_8−n with X = Cl, Br, I and n = 2–7 as well as the tetrasilanes H₂XSiSiX₂SiX₂SiX₂H have been prepared by dearylation of appropriate aryltrisilanes and aryltetrasilanes (aryl = phenyl, p-tolyl) with either liquid or gaseous hydrogen halides. The compounds have been characterized with elemental analysis as well as ²⁹Si NMR spectroscopy.     

Sila-Riechstoffe und Riechstoff-Isostere VII: Reaktionen und Derivate der Benzyldialkylphosphinimide

Zusammenfassung Derivatives of benzyldialkylphosphinimides C₆H₅CH₂-PRR=NH (C) with =NCH₃, =NSiMe ₃, =O, =S, –CS ₂ and –NH₂]NCS instead of =NH groups (compare Scheme 1) were prepared and characterized. They neither show the H/D exchange of CH₂ benzyl protons with CDCl₃ nor the thermal formation of stilbene on heating like the parent compounds C, but they give in the case of =NCH₃ and =NSiMe ₃ analogously aHorner-Wittig reaction with aldehydes. CS₂ reacts with C under NH/S-exchange. The quality of smell ofPhCH₂-PRR =NCH₃ (none, later fishy) is quite different from that of isostericPhCH₂-SiRR –OCH₃ (flowery-honeylike/minty) and the smell of C (metallic/chlorinated hydrocarbon-like) from that ofGrimm hydride isostersPhCH₂–PRR=O (weak; flowery-waxy). The theory ofAmoore (size and shape of molecules control their smell qualities) must be called in question.

---

Sila-perfumes and isosteric perfumes, VII: Reactions and derivatives of benzyldialkylphosphinimides

     

Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen: IV. Chrom-schwefel- und chrom-selen-bindungen: Knüpfung,umwandlungsreaktionen und alkylidenaddition

New dinuclear chromium—sulfur complexes containing one or two sulfur atoms are formed upon reaction of the ionic complex K[(η⁵-C₅Me₅)Cr(CO)₃] (Me = CH₃; 1) with trithiazyl trichloride at temperatures below ambient. The μ(η¹ :η²)-disulfur complex 2a of composition (η⁵-C₅Me₅)₂Cr₂(CO)₅S₂ undergoes concomitant CO-elimination and desulfurization on heating or in the presence of triphenylphosphine; the CrSCr-complex (η⁵-C₅Me₅)₂Cr₂(CO)₄S (2c) is formed in these cases. When diazomethane is treated with 2a, a novel μ,η²-thio- formaldehyde complex (2d) results, again following CO- and S-extrusion. While the triple-bonded CrSCr-skeleton present in 2c does not allow alkylidene additions, such reactions, which proceed cleanly, are observed with the corresponding μ⁵-seleno derivative (η⁵-C₅H₅)₂Cr₂(CO)₄Se (4) synthesized from Na[(η⁵-C₅H₅)Cr(CO)₃] and sodium selenite in the presence of hydrochloric acid.     

Optisch aktive Lycopin-epoxide und Lycopin-glycole: Synthesen und chiroptische Eigenschaften

Optically Active Lycopene Epoxides and Lycopene Glycols: Synthesis and Chiroptical Properties We present extensive spectral and chiroptical data on the pure and crystalline lycopene diepoxides 1–3 and glycols 4–9 . A first synthetic approach to 1–9 with (+)-malic acid as starting material afforded 30 as a complex mixture of isomers (Scheme 1). Pure stereoisomers 1–9 were obtained using the enantiomerically pure epoxygeraniol 31 as starting material (Scheme 2). Differentiation of the (5Z)-from the (all-E)-isomers by ¹H-NMR and UV/VIS alone is very difficult.     

Pentafluorethylschwefeltrifluorid: Synthese und Reaktionen

Pentafluorethyl Sulfurtrifluoride: Synthesis and Reactions By oxidation of (C₂F₅S?)₂ ( 1 ) with AgF₂ at 0°C a mixture of C₂F₅SF₃ ( 2 ) and C₂F₅SF₅ ( 3 ) besides C₂F₅S(O)F ( 4 ) is formed. With elemental fluorine only 3 is isolated, an intermediate in this reaction is (C₂F₅SF₄?)₂ ( 5 ). At ?40 to ?30°C the mixture of 2, 3 and 4 was reacted with TASF and AsF₅, to give TAS⁺ C₂F₅SF₄^? ( 6 ), TAS⁺ C₂F₅S(O)F₂^? ( 7 ) and C₂F₅SF₂⁺AsF₆^? ( 8 ), respectively. While 6 and 7 decompose rapidly in solution even at low temperatures, of thermally stable 8 the solid state structure was determined by x-ray diffraction.