Gas chromatographic determination of estrone,estradiol and estriol in non-pregnancy plasma

Summary A gas Chromatographic method for the determination of estrone, estradiol and estriol in plasma of normal females is described. Purification is done by means of TLC of the free compounds and the acetates and quantitation is achieved by electron capture-gas chromatography of the estrogen heptafluorobutyrates. Experiments on the validation of the method are described along with some examples of its application.

---

Zusammenfassung Eine gaschromatographische Methode zur Bestimmung von Östron, Östradiol und Östriol im normalen weiblichen Plasma wurde beschrieben. Die Reinigung erfolgte durch Dünnschichtchromatographie der freien Verbindungen und ihrer Acetate. Die quantitative Bestimmung wurde gaschromatographisch mit Hilfe eines Elektroneneinfangdetektors an Hand der Östrogenheptafluorobutyrate bewerkstelligt. Versuche zur Bewertung dieser Methode sowie Beispiele für ihre Anwendung wurden beschrieben.

---

---

Supported by USPHS Grants AM 09908 and RCDA 5 K 3-AM-31, 321 (S. K.) and a grant from the Ford Foundation.     

Acetals of lactams and acid amides. 35. Synthesis of condensed two- and three-ring pyridine systems on the basis of enamino amides

The synthesis of 2,3,5,6-tetrahydropyrrolo[3,2-c]pyrid-6-one was accomplished by rearrangement of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1, 2-c]pyrimidine. Pyrrolo[3,2-c]pyrimidine, 1,6-naphthyridine, and pyrimido[4,3-b]-azepine derivatives were synthesized on the basis of enamino dinitriles. The hydrolysis of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1,2-c]-pyrimidine in 50% CH₃COOH leads to a pyrrolo[1,2-c]pyrido[4,3-d]pyrimidine derivative. A similar dipyrido[4,3-d-1,2-c]pyrimidine derivative was obtained from 1-cyano-9-dimethylaminomethylene-2,5,6,7,8,9-hexahydropyrido[1,2-c]pyrimidine under these conditions, and 3,4-dioxo-3,4,7,8,9,10-hexahydropyrido[1,2-c]pyrano[4,3-d]-pyrimidine was synthesized bytreatment with a 1 N solution of HCl.See [1] for Communication 34.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 518–522, April, 1982.     

Two types of kinetics of membrane potential of water plant leaves illuminated by ultraviolet light

The effects of ultraviolet-B (UV-B) radiation on plasma membrane of water plant (Elodea canadensis, Vallisneria spiralis) cells were investigated by using microelectrode methods. A fast and reversible depolarization of membrane potential occurs initially during exposure of leaf cells to UV on a white light background, after which a slow phase of depolarization sets in. On action series, UV is pulsed for 15 s, with dark interval of 3 min, no monotonous response of systems on the UV excitation is observed. The action spectrum of the fast UV response lies in the interval of 300-330 nm and that of the slow phase-in the interval of 280-300 nm. The input impedance of membranes remains unchanged during the period of exposure. It is concluded that the H(+)-extruding complex of plant cell plasma membranes really consists of two types of interrelated electronic H(+)-pumps: an H(+)-pump of redox-active nature and the H(+)-pump of the H(+)-ATPase enzyme complex. Clearly, during the exposure of leaf cells to UV light, initially, the H(+)-pump of redox-active nature and then H(+)-ATPase are inhibited. It is proposed that the initial chromophore of UV-B light on plasma membrane can be one of the components of H(+)-pump of redox-active nature. It is probably the molecular of quinone.     

Electron-donor-acceptor complexing reagents in the analysis of pesticides. VI

Summary Pesticides may be detected following thin-layer chromatography by spraying the chromatogram with a reagent which forms a-complex with the pesticide. The effect of various pesticide structures and substituents in choosing a suitable-complexing reagent is discussed, as well as the effect of these factors in influencing the colour of the complex formed. Quantitative analyses may be performedin situ on the thin-layer chromatogram and positive identification of the-complexed compounds may be made by mass spectrometry. The procedure should be applicable for formulation analysis or studies of pesticide decomposition.

---

Zusammenfassung Zum Nachweis von Pestiziden besprüht man deren Dünnschichtchromatogramme (DC) mit einem zur Bildung eines-Komplexes geeigneten Reagens. Die Bedeutung verschiedener Pestizidstrukturen und -Substituenten bei der Wahl eines solchen Reagens wurde erörtert; ebenso der Einfluß der genannten Faktoren auf die Farbe des Komplexes. Quantitative Bestimmungen lassen sich unmittelbar auf dem DC, Nachweise der einzelnen komplexierten Verbindungen mit Hilfe der Massenspektrometrie durchführen. Das Verfahren eignet sich zur Strukturanalyse sowie zur Untersuchung von Pestizidabbauproblemen.

---

---

Issued as NRCC No. 13120.     

Mittlere ringe-XIII Die intramolekulare acylierung der ω-(1-naphthyl)-fettsäuren

The intramolecular Friedel-Crafts cyclisation of ω-arylalkanoic acids, which is in the benzene series a valuable synthetic route to bicyclic ketones with medium-sized and large rings, has been investigated with ω-(1-naphthyl)alkanoyl chlorides. The lower members, including naphthyl-caproic acid, close the ring at position 2 to form IV. The higher homologous acids show a preference for annellation at 7, making available a new type of heteronuclear naphthalene cyclic ketones (VII). During cyclisation of ω-(1-naphthyl) decanoic acid, the 1,4 ring closure competes with the 1,7 type.

Steric hindrance of resonance as a consequence of “medium ring torsion” was studied in different classes of naphthocyclenones.     

Preparative method of obtaining L- and D-2-hydroxy-3-methylbutyric acids

Summary A preparative method was developed for obtaining L-and D-2-hydroxy-3-methylbutyric acids by the separation of racemic 2-hydroxy-3-methylbutyric acid with the aid of D-and L-threo-2-amino-1-p-nitrophenyl-1,3-propanediols.