Oestron-dimethylphosphins?ureester, ein Beispiel einer neuen Derivatklasse zum empfindlichen, gas-chromatographischen Nachweis von Steroiden

Zusammenfassung Die Darstellung eines neuartigen, zum gas-chromatographischen Nachweis geeigneten Phosphorderivats von Oestron wird beschrieben. Der Oestron-dimethylphosphinsäureester läßt sich sehr empfindlich mit dem Alkaliflammenionisationsdetektor (AFID) nachweisen. Die Umsetzung von Dimethylaminodimethylphosphin mit Oestron ist unter den angegebenen Bedingungen quantitativ und sehr gut reproduzierbar. Bezugskurven mit Oestronkonzentrationen von 2–50 g Oestron im Ansatz hatten bei Nachweis mit dem FID einen Korrelationskoeffizienten von 0,999, bei Nachweis mit dem AFID von 0,998. 200 pg des Derivats konnten noch gut gemessen werden. Die Reaktionsbedingungen werden diskutiert. Auf die erfolgreiche Derivatisierung anderer Steroidhormone wird abschließend hingewiesen.

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Estrone-dimethylphosphinic ester, a new type of derivatives for the sensitive, gas chromatographic determination of steroids

The synthesis of estrone-dimethyl phosphinic ester, with good gas chromatographic properties is described. This ester is very sensitively detectable with the alkali detector. The reaction of dimethyl-amino-dimethylphosphine with estrone is quantitative and reproducible. Calibration curves with concentrations of estrone varying from 2 to 50 g per sample detected by a FID yielded a correlation coefficient of 0.999, detected by an AFID one of 0.998. The smallest amount which could be measured was 200 pg. The reaction conditions are discussed. The possibility of the derivatisation of other steroid hormones is shown.

     

Hydrogenative Depolymerization of End-of-Life Poly-(Bisphenol A Carbonate) Catalyzed by a Ruthenium-MACHO-Complex

The valorization of waste to valuable chemicals can contribute to a more resource-efficient and circular chemistry. In this regard, the selective degradation of end-of-life polymers/plastics to produce useful chemical building blocks can be a promising target. We have investigated the hydrogenative depolymerization of end-of-life poly(bisphenol A carbonate). Applying catalytic amounts of the commercial available Ruthenium-MACHO-BH complex the end-of-life polycarbonate was converted to bisphenol A and methanol. Importantly, bisphenol A can be reprocessed for the manufacture of new poly-(bisphenol A carbonate) and methanol can be utilized as energy storage material.     

2.2 Organische industrielle produkte

Ohne Zusammenfassung

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A rapid immunological method for determining the activity of creatine-phosphokinase-MB in the serum of patients with myocardial infarction

     

Spin correlations in nonperturbative electron–positron pair creation by petawatt laser pulses colliding with a TeV proton beam

The influence of the electron spin degree of freedom on nonperturbative electron–positron pair production by high-energy proton impact on an intense laser field of circular polarization is analyzed. Predictions from the Dirac and Klein–Gordon theories are compared and a spin-resolved calculation is performed. We show that the various spin configurations possess very different production probabilities and discuss the transfer of helicity in this highly nonlinear process. Our predictions could be tested by combining the few-TeV proton beam at CERN-LHC with an intense laser pulse from a table-top petawatt laser source.     

Detection of non-typical porphyrin isomers in human urines by ion-pair reversed-phase high-performance liquid chromatography

An improved ion-pair reversed-phase high-performance liquid chromatographic system has been developed for the separation of uroporphyrin isomers I, II and III, whereas the isomers III and IV could not be resolved. Application of this method to the analysis of urines from porphyric patients indicated the presence of small amounts of the non-typical uroporphyrin isomer II. The questionable presence of the isomer IV was confirmed by acid-catalyzed decarboxylation to the corresponding coproporphyrin isomers, which were completely separated by a modified ion-pair method at elevated column temperatures. These procedures enabled the detection of small fractions of the atypical isomers II (1-3%) and IV (8-15%) besides the normal isomers I and III in urines of patients suffering from attacks of acute intermittent porphyria. Because such urines contain large amounts of porphobilinogen, the nonenzymatic self-condensation of porphobilinogen to uroporphyrinogens was studied under mild reaction conditions. In these experiments quite similar isomeric compositions were observed as compared to those in urines of patients with acute intermittent porphyria. Thus the non-typical uroporphyrin isomers II and IV present in human urines originate from a simple non-enzymatic condensation of porphobilinogen.     

Spektralphotometrische Bestimmung von Val5-Angiotensin II Asp1-β-amid durch Azokupplung mit p-Chlorbenzoldiazoniumchlorid

Through the azocoupling of Val⁵-angiotensin II-Asp¹-β-amide (Hypertensin-CIBA) with p-halogene substituted benzenediazonium salts the possibility is shown for quantitative determination of polypeptides containing tyrosine and/or histidine. 1 to 2 nanomoles of the coupling-product could be measured photometrically. The detection limit can be lowered, if the polypeptide is coupled with a radioactive labelled diazonium salt. The preferable reaction conditions for diazotising and coupling are reported. The reaction-product showed an uniform behaviour in the used paper-chromatographic system. Probably it is a monoazo compound. Under the chosen conditions the tyrosyl group is very likely the reacting part of the hypertensin molecule.