Eine Mikrobestimmung von Veronal in Blut und Liquor

Zusammenfassung Es wird ein Verfahren beschrieben, mit dem geringste Mengen Veronal in Blut und Liquor bestimmt werden können. Das Untersuchungsmaterial wird mit einer sauren Pufferlösung versetzt, um das Ausfallen des Bluteiweißes zu verhindern, und das Veronal im Perforator mit Äther extrahiert. Der Ätherextrakt wird nach der Trocknung mit Kohle und Magnesiumoxyd gereinigt, filtriert, im Schälchen verdunstet und der Rückstand im Sublimationsapparat der quantitativen Sublimation unterworfen. Die Mikrosublimate werden auf der Mikrowaage gewogen. Der zur Extraktion verwendete Äther muß sorgfältig gereinigt werden. Die Fehlergrenze beträgt 2,5 bis 6,7% bei Blut (verwendet wurde Menschen-, Rinder- und Katzenblut) und 2,5 bis 4,8% bei Liquor, wenn Mengen von 70 bis 300 Veronal Verwendung fanden. Durch dieses Verfahren ist die Möglichkeit gegeben, abgesehen von tierexperimentellen Untersuchungen bei Vergiftungsfällen aus den in Liquor und Blut gefundenen Veronalmengen Schlüsse auf die Höhe der verabreichten Dosis zu ziehen.Im Anschluß daran wird eine Trennung von Veronal und Bernsteinsäure mit Hilfe von Adsorptionsmitteln beschrieben.

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Summary A procedure is described which renders possible the determination of minimal amounts of veronal in blood and liquor cerebrospinalis (spinal fluid). The material under examination is treated with an acid buffer solution to prevent separation of albumen from the blood, and the veronal extracted with ether. The extract, after drying, is purified by treatment with charcoal and magnesia, filtered, the filtrate evaporated, and the residue sublimed quantitatively in a sublimation apparatus, the sublimates obtained being weighed on a micro-balance. It is necessary that only very carefully purified ether be used for the extraction. The limits of error range between 2,5 to 6,7% in the case of blood (blood from cattle, cats, and human beings was investigated) and between 2,5 to 4,8% in the case of liquor cerebrospinalis (spinal fluid); in all cases quantities of veronal ranging from 70 to 300 were involved. The above procedure enables conclusions to be drawn (quite apart from vivisection experiments), from the quantities of veronal found in the liquor and blood as to the magnitude of the original dose of the drug.A separation of veronal from succinic acid with the help of adsorption agents is also given in the paper.

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Résumé On décrit un procédé à l'aide duquel on peut déterminer les plus petites quantités du véronal dans le sang et dans le liquor. On ajoute une solution tampon (Pufferlösung) acide à la matière à essayer, pour éviter la précipitation des protéines du sang et on extrait le véronal au perforateur. L'extrait d'éther est purifié après séchage avec du charbon et d'oxyde de magnésium, filtré, évaporé en petite capsule et sublimé quantitativement dans l'appareil de sublimation. Les micro-sublimés sont pesés sur la microbalance. L'éther, employé pour l'extraction, doit être purifié très exactement. La limite d'erreurs est de 2,5 à 6,7% analysant le sang (on a essayé du sang d'homme, de vache et de chat) et de 2,5 à 4,8% analysant le liquor, quand on avait appliqué de 70 à 300 de véronal. Il est possible de calculer ainsi de la quantité de véronal, trouvée dans le sang ou dans le liquor, la dose administrée chez des intoxications.A cet occasion on décrit encore la séparation du véronal de l'acide succinique à l'aide des moyens d'adsorption.

     

Models for the Active Center of Pterin-Containing Molybdenum Enzymes: Crystal structure of a molybdenum complex with sulfur and pterin ligands

The first crystal structure of a molybdenum complex 9 with a hydrogenated pterin and a sulfur ligand contributes to the discussion about the active center of molybdenum and tungsten enzymes containing a molybdopterin cofactor. Complex 9 was synthesized through a redox reaction of [Mo^VIO₂ (LN-S₂)] ( 8 ; LN-S₂ = pyridine-2, 6-bis(methanethiolato)) with 5, 6, 7, 8-tetrahydropterin ( 7 ). 2 HCl (H₄Ptr.2 HCl). The complex crystallizes, with a non-coordinating Cl-atom acting as a counterion, in the monoclinic space group C2/c (No. 15) with cell dimensions a = 22.900(5), b = 10.716(2), c = 17.551(4) Å, β = 120.36(3)°, and Z = 8. We interpret 9 as [Mo^IVO(LN-S₂)(H⁺-q-H₂Ptr)]Cl (q = quinonoid; H₂Ptr = dihydropterin), i.e., a Mo^IV monooxo center coordinated by a pyridine-2, 6-bis(methanethiolato) ligand and a protonated dihydropterin. The spectroscopic properties of this new complex are comparable to those of other crystalline molybdenum complexes of hydrogenated pterins without additional S-coordination. The slightly H₂O-soluble complex 9 reacts with the natural enzyme substrate DMSO very slowly, possibly due to the lack of easily dissociable ligands at the metal center.     

Energy-dispersive x-ray laue measurements with anomalous dispersion effects

By using an energy dispersive solid state detector, harmonics were separated in a Lauetype diffraction experiment with a single crystal and white primary radiation (Bremsstrahlung) from a conventional x-ray tube. Intensity changes around the absorption edge of an atom species in the crystal could be verified according to theory.Dedicated to Prof. Dr. H.E. Müser on the occasion of his 60th birthday     

Dynamics of vector spin glasses with random anisotropy

The dynamics of vector spin glasses with additional random anisotropy is investigated in the mean field approximation. We find a cross-over of the upper critical line from a behaviour of Heisenberg spins with a field-temperature dependence , for large fieldsH, to Ising like behaviourT _f –TT ^2/3 , for small fields and fixed anisotropy, in agreement with results of Kotliar and Sompolinsky. Here, andT _f are characteristic spin glass temperatures. In addition, one has a second line with reversed behaviour which presumably represents a cross-over line from weak to strong non-ergodicity. The local transverse susceptibility _T () varies for large fields and 0 along the upper critical line as ^vT , with a critical exponentV _T = 1/2 – 11D/60 J, whereD andJ are the anisotropy and exchange coupling constants, respectively. On the Ising-like part of the upper critical line one has isotropic spin glass parameters,q _L =q _T , and susceptibilities, and a critical exponent, which is similar to that of Ising spins along the de Almeida-Thouless line.Dedicated to B. Mühlschlegel on the occasion of his 60th birthdaySFB Aachen-Jülich-Köln     

σ,π-acetylido complexes via P---C bond cleavage of phosphinoacetylenes: X-ray structure of Fe2(CO)6(CCPh)(PPh2)

Solutions of Co^II salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis).     

Synthesis,Structure, and Optical Properties of Terminally Sulfur‐Functionalized Core‐Substituted Naphthalene‐Bisimide Dyes

The synthesis, characterization, and optical properties of a series of new 2,6‐disubstituted naphthalene‐bisimide dyes as molecular rods comprising terminal AcS groups is reported. The first series of dyes ( 1 – 3 ), comprising phenylhetero (Ph‐X) core substituents, cover a broad range of the VIS spectrum, ranging from yellow ( 2 ) over red ( 3 ) to blue ( 1 ). The second series of dyes contains benzylhetero (Bn‐X) core substituents ( 4 – 7 ). For the same heteroatom connecting the substituent to the naphthalene core, both series were found to display comparable colors. For the second series, the colors were blue ( 4 ), red ( 5 ), and violet ( 6, 7 ). The Ph‐X‐substituted dyes 1 – 3 are nonfluorescent, in contrast to the Bn‐X‐substituted compounds 4 – 7 . This rich variety of optical features that can be adjusted by rather small alterations of the core substituents makes these structurally very comparable molecular rods ideal candidates for optically triggered molecular‐transport investigations. Also, thanks to the terminal AcS groups, these compounds can be placed between nobel‐metal electrodes for optically triggered transport experiments.     

The determination of chlorinated biphenyls,chlorinated dibenzodioxins,and chlorinated dibenzofurans by GC-MS

High resolution gas chromatography, with mass selective detection, has been used for the analysis of PCB on methyl 50 % octyl polysiloxane (SB 50 Octyl), methyl octadecyl polysiloxane, and a smectic polysiloxane (SB Smectic); and for the analysis of polychlorodibenzodioxins and polychlorodibenzofurans with 1 to 8 chlorine substituents on 100 % cyanopropyl siloxane (SP 2331), smectic polysiloxane (SB Smectic), a new polar stationary phase (DB-Dioxin). The analysis has also been performed by column coupling.