Benzolactams. 4. Reaction of 3',4'- or 4',5'-dialkoxy-substituted 1-(2'-Bromobenzyl)-2-ethoxycarbonyl-1,2,3,4-tetrahydroisoquinolines with alkyllithium. 1,2 and 1,4 additions of alkyllithium to benzolactams

Treatment of 1-(2'-bromo-3',4'-dialkoxybenzyl)-1,2,3, 4-tetrahydroisoquinoline carbamates, 1a,c, with excess alkyllithium gave 8-oxoberbines, 2a,c, which were successively attacked in situ with another molecule of alkyllithium to give 1,2 and/or 1,4 addition products. A primary alkyllithium, such as MeLi or BuLi, gave a 1,2 addition product, 8-methyleneberbine 9a or 8-butylideneberbine 3a. t-BuLi preferred 1,4 addition, followed by elimination of the alkoxy group, to give 9-tert-butyl-8-oxoberbine 6a or 7c. s-BuLi gave a mixture of 1,2 and 1,4 addition products, 1-[2'-(2' '-methylbutyryl)benzyl]-1,2,3,4-tetrahydroisoquinoline 4a and 9-s-butyl-8-oxoberbine 5a. Similar treatments of carbamate 1b having no alkoxy group at its 3' position gave 1,2 addition products, 8-butylideneberbine 3b, 1-[2'-(2' '-methylbutyryl)benzyl]-1,2,3, 4-tetrahydroisoquinoline 4b, and 1-(2'-pivaloylbenzyl)-1,2,3, 4-tetrahydroisoquinoline 6b, in all cases. Reactions of 1a with s-BuMgCl and isoPrMgCl also gave the 1,4 adduct, 5a, and its 9-isoPr analogue, 12a. Treatment of 9a with excess NaBH(4) in AcOH gave (+/-)-coralydine (10b).     

Coordination Complexes of Some Group(IV) Halides with Monodentate Schiff Bases

Coordination compounds resulting from the interaction of N-(phenyl)benzalaldimine and its derivatives containing a methyl group in different positions of the aniline ring and group(IV) halides, MX₄ (where M = Si or Sn and X = Cl or Br), have been prepared and characterized by elemental analyses and electronic, infrared and Raman spectra.     

Infrared spectroscopic study of the structure of the tetrabutyl S-dithiopyrophosphate complex of silver

The structure of the complex Ag·TBDTPP (tetrabutyl S-dithiopyrophosphate) formed in HNO₃ medium was studied by IR and NMR methods. The complex is involved in the isomerization of TBDTPP in the presence of Ag⁺ and NO ₃ ⁻ ions. In the IR spectra, we observe the disappearance of P−O−P band and the occurrence of new absorption bands associated with P−S−P and P=O bonds. The silver ion is coordinated to the thiophosphoryl group of the isomer molecule. The influence of HNO₃ concentration on complex formation is discussed.     

The stability of silver iodide sols in the presence of polyacrylic acids of various molecular weights

Summary The effect of a series of polyacrylic acids, ranging in molecular weight from 1.67×10⁴ to 2.36×10⁶, on the stability of positively charged silver iodide particles has been examined. Flocculation of the sol occurred at a well defined concentration of polyacrylic acid,c _f , and a further increase in concentration of the polyelectrolyte caused restabilization of the sol. Over the range examinedc _f appeared to be related to the viscosity average molecular weight of the acid,M _v , by an equation of the form,c _f =a ·M _v ^{– b} wherea andb are constants.     

Action of photoreactivating light on pyrimidine heteroadduct in bacteria

Abstract— In stationary-phase Escherichia coli B/r, photoreactivation (PR) at 313 nm of ultraviolet (u.v.) killing is inefficient compared with PR at 405 nm, and can be explained solely by photoenzymatic reversal of pyrimidine dimers. In Staphylococcus epidermidis, PR shows a maximum at 313 nm, suggesting that this organism shows the Type III PR proposed by Jagger et al.[5] for Streptomyces strains. Reversal of pyrimidine dimers is not sufficient to explain this PR. The mechanism of Type III PR remains unknown. With both S. epidermidis and E. coli B/r, the amount of uracil–thymine heteroadduct in DNA hydrolysates decreases if the cells are given a post-u.v. treatment at 313 nm, but no decrease is observed if the post-u.v. treatment is at 405 nm. The biological significance of this adduct and of its removal is not clear. It may play a role in Type III PR.     

Direkte fluorimetrische Bestimmung von 3,4-Benzpyren im w?\rigen Medium

Zusammenfassung Es wurde eine direkte Bestimmung des 3,4-Benzpyrens in wä\riger Lösung beschrieben, die auf der Löslichkeitserhöhung beruht, die das in Wasser schwer lösliche 3,4-Benzpyren durch Coffein erfährt. Es können so noch 4 ng/ml bei der angegebenen Standardisierung bestimmt werden. Bei der Direktbestimmung des 3,4-Benzpyrens im System Coffein-Wasser ist ein p_H >6,0 einzuhalten, da bei höheren Wasserstoffionenkonzentrationen die Fluorescenzintensität stark abnimmt.

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Direct fluorimetric determination of benzo(a)pyrene in aqueous medium

A method for the direct determination of benzo(a)pyrene in aqueous solution is based on the increase of its solubility by coffeine. 4 ng of benzo(a)pyrene/ml can be determined by the procedure described. In this direct determination in the system coffeine-water the p_H has to be adjusted to >6.0, as the fluorescence intensity considerably decreases with higher H⁺ concentrations.

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Eine ausführliche Darstellung findet sich in der Dissertation von G. Becker, Univ. Karlsruhe 1968.

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Die Messungen zu dieser Arbeit -wurden an dem Chemischen Untersuchungsamt für das Saarland, Saarbrücken, mit einem Spektralphotometer der Deutschen Forschungsgemeinschaft ausgeführt. Beiden Institutionen sind wir zu Dank verpflichtet.     

THE EFFECTS OF HOST-CELL REACTIVATION ON ASSAY OF U.V.-IRRADIATED HAEMOPHILUS INFLUENZAE TRANSFORMING DNA

Abstract— The host cell reactivation (HCR) mechanism in Haemophilus influenzae cells is inhibited by sub-microgram concentrations of acriflavine (as is already known to be true for Escherichia coli ). Exposure of these cells to similar concentrations of the drug during bacterial transformation increases the apparent ultraviolet light (u.v.) sensitivity of previously irradiated transforming DNA, indicating a repair of this DNA after uptake by the cells under normal conditions. Repair is inhibited by applying acriflavine at any time up to one hour after competent cells contact the irradiated transforming DNA. The fraction of the u.v. damage repaired by HCR is very different for different genetic markers. Those markers which are most u.v. sensitive when assayed in the absence of acriflavine are most poorly repaired, suggesting that this is the reason for their higher sensitivity. For all markers the fraction of the damage repairable by in vitro photoreactivation is approximately constant, and strongly overlaps the damage repairable by HCR. The degree of HCR achieved can be altered by experimental treatment of the H. influenzae DNA prior to transformation. Thus treatment of irradiated DNA with an enzyme from Micrococcus lysodeikticus –known to attack u.v. damaged, but not undamaged DNA–prevents subsequent intracellular repair of the same u.v. lesions whose repair is inhibited by acriflavine. Similarly, partial replacement of the thymine in transforming DNA by 5-bromouracil (BU) strongly inhibits repair of subsequent u.v. damage. As in bacteriophage, the BU effect is relieved if the u.v. exposure occurs in the presence of cysteamine. It is clear that intracellular repair must be considered in interpreting experiments with u.v.-irradiated transforming DNA.     

Austausch von Chrom(III) mit Chrom(II) und Szilard—Chalmers-Reaktion von Kaliumchromat

Zusammenfassung Durch Versuche mit⁵¹Cr wird gezeigt, daß Cr³⁺ mit Cr²⁺ austauscht, wenn man ein Chrom(III)-Salz in wässeriger Cr²⁺-Lösung auflöst, d. h. die Hydratation zum reaktionsträgen [Cr(H₂O)₆]³⁺ verläuft relativ langsam. Die Bedeutung dieses Austausches für dieSzilard—Chalmers-Reaktion von Chromat wird diskutiert.

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Experiments with⁵¹Cr prove the exchange of Cr³⁺ with Cr²⁺ when a Cr(III)-salt is dissolved in an aqueous solution of Cr²⁺. This indicates that the hydration to the inert [Cr(H₂O)₆]³⁺ is relatively slow. The importance of this exchange for theSzilard—Chalmers reaction of chromate is discussed.

     

Treatment of cutaneous T cell lymphoma with extracorporeal photopheresis induces Fas-ligand expression on treated T cells,but does not suppress the expression of co-stimulatory molecules on monocytes

Following extracorporeal photopheresis (ECP), lymphocytes become apoptotic and upregulate class I MHC antigenic peptides. Conversely, ECP treated monocytes demonstrate activation markers and have an increased avidity for the phagocytosis of apoptotic T cells. Processing of apoptotic T cells by monocytes, following ECP, is thought to induce an immunomodulatory response, which targets untreated, but clonal T cells. Recently we detected apoptotic lymphocytes immediately post ECP. Although enhanced CD95 (Fas) expression has been observed 24 h post ECP, CD95 and Fas-ligand (Fas-L) expression have not been determined at this very early apoptotic stage. Exposure of monocytes to UV has previously suppressed expression of the co-stimulatory molecules required for the presentation of processed antigens to T cells. Our data demonstrate no increase in CD95 or Fas-L expression on T cells tested immediately following ECP. However, the number of T cells expressing Fas-L significantly increased 24 h post ECP (P<0.005). The expression of the co-stimulatory molecules, CD54, CD80 and CD86, remained unaltered on monocytes treated by ECP. Although the mechanism responsible for early induction of lymphocyte apoptosis remains unclear, the later apoptosis involves Fas-L expression. The maintenance of co-stimulatory molecules, on treated monocytes, indicates that they retain the ability to induce an immunomodulatory response.     

Dimethylzinc-mediated addition of alkenylzirconocenes to alpha-keto and alpha-imino esters

[reaction: see text] Hydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivities.