Beiträge zur quantitativen Dünnschichtchromatographie. V

Zusammenfassung Eine dünnschichtchromatographische Trennung des Wismuts von einem Überschuß an Metallen der Schwefelwasserstoffgruppe wurde beschrieben. Als Laufmittel dient ein Gemisch von tert.-Butanol, Salzsäure und Wasser. Nach Absaugen der Sorptionsschicht wird das Wismut mit MDCM spektralphotometrisch bestimmt. Standardabweichung und Varianz des Verfahrens werden angegeben.

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Summary A thin layer Chromatographic separation of the bismuth from an excess of metal ions of the hydrogen sulfide group is described. A mixture of tert. butanol, hydrochloric acid and water serves as mobile phase. After sucking off the sorption layer, the bismuth is determined spectrophotometrically with MDCM. The standard deviation and the variance of the procedure is given.

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Résumé On décrit une séparation par Chromatographie en couche mince du bismuth de métaux en excès du groupe de l'hydrogène sulfuré. On utilise comme éluant un mélange de butanol tert., d'acide chlorhydrique et d'eau. Après aspiration de la couche de sorption, on dose par spectrophotométrie le bismuth par le MDCM. On communique l'écart-type et le coefficient de variation du procédé.

     

ON THE LUMINESCENCE OF L-TRYPTOPHANE AND l-TYROSINE IN AQUEOUS SOLUTION AT 77dK INDUCED BY X-RAYS AND U.V.-LIGHT

Abstract— The lumincscence arising from L-tryptophane and L-tyrosine in aqueous solutions at 77K during irradiation with u.v.-light and with X-rays has been studied. The spectra obtained with the two types of radiation were largely similar, differing only in that the yields of phosphorescence relative to fluorescence were considerably enhanced in the case of X-irradiation. The decay times observed for the exponentially decaying phosphorescence, being 6.6 sec and 2.7 sec for tryptophane and tyrosine respectively, were the same for both kinds of irradiation. The G-value of the X-ray induced luminescence was about 10 for both tryptophane and tyrosine. Thus, about 30 per cent of the total energy absorbed from X-rays in these compounds was re-emitted as light.
It was concluded that the X-ray induced fluorescence and phosphorescence originate from the same levels as does the luminescence caused by u.v.-light, i.e. the lowest excited singlet and the lowest triplet level of the aromatic structure of these compounds. In the case of X-irradiation the enhanced ratios between the yields of phosphorescence and fluorescence indicated that some process other than excitation directly from the ground state contributed considerably to the luminescence yields. Assuming this process to be a recombination between the ionized molecule and its electron, it was calculated that the contribution to the luminescence yield from excitations directly from the ground state relative to that from ionizations, was negligible for both compounds.     

Untersuchungen an oxidischen Katalysatoren. XXIX. Spektroskopische und katalytische Untersuchungen an Ni2+-, Co2+-, Cr3+- und Cu2+-ausgetauschten Mordeniten

Studies on Oxide Catalysts. XXIX. Spectroscopic and Catalytic Investigations on Ni²⁺-, Co²⁺-, Cr³⁺-, and Cu²⁺-exchanged Mordenites NiNaM, CoNaM, CrNaM und CuNaM (M = Mordenite) have been characterized by UV-VIS, EPR and i.r. spectroscopy and the results were compared with the catalytic activity and the activity-time-dependence in the cracking of n-octane and with the shape selectivity in the cracking of a n-octane and isooctane mixture. Water molecules acting as ligands of the exchanged cations are able to dissociate yielding Brönsted acidity. Brönsted sites may be regarded as catalytic active centers in the cracking reaction. Unreduced transition metal cations facilitate the “coking” of the mordenite. The unreduced chromium and cobalt cations for which a position within the main channel is expected, affect the diffusion of the branched paraffin molecule thus increasing shape selectivity.     

Separation of alkylaminonaphthylenesulfonyl peptides and amin acids by high-performance liquid chromatography. Methods for measuring melanotropin inhibiting factor breakdown

N,N-Dimethyl diethyl, dipropyl, dibutyl, and N-monoisopropylaminoaphthylenesulfonyl derivatives of melanotropin inhibiting factor (MIF) and its metabolites were prepared, and their chromatographic behavior was investigated with thin-layer chromatography (TLC) and high-performance liquid chromatography (HPLC), using five solvent systems on polyamide layers and ten solvent systems on muBondapak C18 and muBondapak phenyl columns. A mixture of MIF and its metabolites derivatized with Dns chloride was adequately resolved by two-dimensional chromatography on polyamide layer with solvent systems, formic acid-water (3:97) and benzene-acetic acid (9:1). Bns-MIF and its metabolites were separated with muBondapak C18 column with the solvent system acetonitrile-0.01 M sodium sulphate buffer, pH 7 (50:50). They were separated into five groups: Gly and Bns acid; Pro-Leu, Leu-Gly and Leu; Pro; Gly-NH2; and MIF. The alkylaminonaphthylenesulfonyl derivates had strong fluorescence, which permitted their detection at the level of 10(-11) to 10(-9) mol. Dns-MIF and its derivatives had the lowest detectable amounts. HPLC with the aid of the Dns derivation is reliable and fast, and is the preferable method for study of neuropeptide breakdown.     

RECOVERY OF HAEMOPHILUS INFLUENZAE FROM ULTRAVIOLET AND X-RAY DAMAGE

Abstract— Results of experiments on reactivation of ultraviolet (u.v.)-irradiated Haemophilus influenzae and cellular reactivation of u.v.-damaged transforming deoxyribonucleic acid (DNA) and bacteriophage are reported. Liquid-holding recovery (LHR) is small for the u.v.-sensitive mutant BC100 which, relative to the wild type, also has greatly reduced host-cell reactivation (HCR) of u.v.-inactivated phage, and competent cultures show reduced competent cell reactivation (CCR) of u.v.-inactivated transforming DNA. BC100 cells can be transformed with DNA isolated from the wild type strain Rd to a u.v. resistance similar to that of Rd, and irradiation of the DNA reduces the transformation frequency for this marker (uvr). The u.v.-resistant mutant BC200 displays very little LHR under the usual conditions where reactivation occurs after plating. The colony-forming ability (cfa) of irradiated BC200 is greater than that of Rd, but HCR and CCR are the same on this mutant as on the wild type. The major difference between Rd and BC200 is the enhanced u.v. survival of cfa of the latter. It was determined that this difference reflects cell lysis of irradiated Rd and lack of lysis in BC200 cultures. That lysis is closely correlated with damage to the bacterial chromosome is suggested by the finding that the lytic response of Rd (as determined turbidimetrically) can be negated by the liquid-holding procedure, but lysis of BC100 (which lacks comparable DNA-repair ability) can be only partially inhibited by this procedure. LHR occurs when post-plating dark recovery is incomplete, is temperature-sensitive, and occurs unimpeded when post-u.v. protein synthesis is inhibited by chloramphenicol. It is suggested that enzymatically catalyzed reactivation of DNA occurs or is initiated during liquid-holding of u.v.-irradiated H. influenzae Rd and that the necessary enzyme(s) exists prior to appearance of u.v. lesions in the DNA. Results are reported for X-ray inactivation of transforming DNA as assayed on BC100, Rd and BC200 and of the cfa of the three strains.     

Studies on antimony oxides: Part I

Thermogravimetry (TG), differential thermal analysis (DTA) and X-ray diffraction studies of antimony(III) oxide, (Sb₂O₃), in air, nitrogen and argon atmospheres have been made. In air Sb₂O₃ becomes oxidized to Sb₂O₄ above 510°. The oxidation reaction proceeds in two stages as revealed by the TG and DTA curves. The behaviour of Sb₂O₃ is similar in both N₂ and Ar. Sb₂O₃ remains unaffected up to 430°, above which there is a slow, and continuous mass loss up to 550°. Above 550° Sb₂O₃ volatilizes resulting in an enormous weight loss. X-ray studies of the sublimate and the residue indicate the former to be the cubic form of Sb₂O₃ (Senarmontite) while the residue is the orthorhombic (Valentinite) structure. From the DTA curves in air, N₂ and Ar, the transition temperature for the cubic to the orthorhombic modification has been estimated to be around 610°.     

Zur Bestimmung von β-Aminocrotonsäureester nach Migration in Lebensmittel

β-Aminocrotonic esters are of great importance as stabilizers for the production of clearly transparent food packaging of PVC. For the purpose of studying the migration into foods a thin-layer Chromatographic and a polarographic method were elaborated. The TLC method consists of the visual comparison of the intensity of the spots after treatment with Fast Blue B salt. The polarographic determination is carried out after nitrosation of the stabilizer. By the TLC method 10^?7 g of ester per spot are still detectable; the concentration which is still determinable by cathode-ray polarography is 5×10^?7 g of ester and by conventional d.c. polarography 5×10^?6g of ester per ml of final solution. After extraction with acetonitrile traces of the stabilizer which are migrated into edible oil are still determinable down to 2 ppm by the methods described.     

Reduction of 2,3,4-substituted quinolines with sodium borohydride

1,2-Dihydroquinolines were obtained by the reduction of 3-substituted 2-methyl-4-phenylquinolines with sodium borohydride in aliphatic carboxylic acids; N-alkyl derivatives are also formed. The corresponding 1,4-dihydroquinoline was obtained in the reaction of 2-methyl-3-nitroquinolinium perchlorate with sodium borohydride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1680–1686, December, 1991.     

A hydrodynamic voltammetric study of the ferricyanide/ferrocyanide system with convective electrodes of platinum,gold, glassy carbon,carbon film,and boron carbide

Hydrodynamic voltammetry employing empirically determined mass transport coefficients is used to determine heterogeneous rate constants and transport coefficients for the ferricyanide/ferrocyanide system in 0.1 M phosphate buffer and other supporting electrolytes with turbulent tubular and rotated disk electrodes of platinum, gold, glassy carbon, carbon film, and boron carbide. Different kinetic parameters are obtained at the various electrode materials. For the platinum, gold, and boron carbide electrodes, the magnitudes of the rate parameters depend on scan direction. The nature of this hysteresis varies with the electrode material and is explained in terms of adsorbed oxide and ionic layers or other phenomena not described by simple double layer theory.     

Partial purification of active delta and epsilon subunits of the membrane ATPase from escherichia coli.

We have partially purified active delta and epsilon subunits of the E. coli membrane-bound Mg2+-ATPase (ECF1). Treating purified ECF1 with 50% pyridine precipitates the major subunits (alpha, beta, and gamma) of the enzyme, but the two minor subunits (delta and epsilon), which are present in relatively small amounts, remain in solution. The delta and epsilon subunits were then resolved from one another by anion exchange chromatography. The partially purified epsilon strongly inhibits the hydrolytic activity of ECF1. The epsilon fraction inhibits both the highly purified five-subunit ATPase and the enzyme deficient in the delta subunit. The latter result indicates that the delta subunit is not required for inhibition by epsilon. By contrast, two-subunit enzyme, consisting chiefly of the alpha and beta subunits, was insensitive to the ATPase inhibitor, suggesting that the gamma subunit may be required for inhibition by epsilon. The partially purified delta subunit restored the capacity of ATPase deficient in delta to recombine with ATPase-depleted membranes and to reconstitute ATP-dependent transhydrogenase. Previously we reported (Biochem, Biophys. Res. Commun. 62:764 [1975]) that a fraction containing both the delta and epsilon subunits of ECF1 restored the capacity of ATPase missing delta to recombine with depleted membranes and to function as a coupling factor in oxidative phosphorylation and for the energized transhydrogenase. These reconstitution experiments using isolated subunits provide rather substantial evidence that the delta subunit is essential for attaching the ATPase to the membrane and that the epsilon subunit has a regulatory function as an inhibitor of the ATPase activity of ECF1.