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61.
Six 2-(alkylthio)-substituted 4,4-dimethyl-1,3-thiazole-5(4H)-thiones were synthesized according to a new method. The reactions of these compounds with allyl- and benzyllithium reagents, 1,3-dipoles, and dimethyl acetylenedicarboxylate proceeded in a similar manner to 2-alkyl-substituted analogues, while methyllithium reacted in a different way yielding trithio-orthoester derivatives. 相似文献
62.
63.
Helmut Marko Norbert Müller Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》1989,120(2):163-168
Summary The intermolecular complex formation of bilirubin and biliverdin with two proteins (basic pancreatic trypsin inhibitor and lysozyme) were studied by optical and chiroptical methods. Evidence for specific intermolecular interactions of biliverdin with both proteins was found. Bilirubin forms a soluble complex only with lysozyme.
UV-VIS und CD-spektroskopische Untersuchungen intermolekularer Wechselwirkungen von Gallenpigmenten mit kleinen Proteinen
Zusammenfassung Die intermolekulare Komplexbildung von Bilirubin und Biliverdin mit zwei Proteinen (basischer pankreatischer Trypsininhibitor und Lysozym) wurden mittels optischer und chiroptischer Spektroskopie untersucht. Für Biliverdin konnten intermolekulare Wechselwirkungen mit beiden Proteinen nachgewiesen werden. Bilirubin bildet nur mit Lysozym einen löslichen Komplex.相似文献
64.
Klärner FG Lobert M Naatz U Bandmann H Boese R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(20):5036-5047
The novel trimethylene-bridged clips 3 and 4 have been synthesized by using repetitive stereoselective Diels-Alder reactions of the benzo- and naphthobismethylenenorbornenes 8 and 19 as dienes and norbornadiene 9 as bisdienophile, and subsequent dehydrogenation of the primary cyclobisadducts 10 and 20 by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Clips 3 and 4 serve as receptors for a variety of electron-deficient neutral and cationic aromatic substrates, comparable to the molecular tweezers 1 and 2. The thermodynamic parameters of the complex formation, K(a) and DeltaG, were determined by (1)H NMR titration experiments and, in the case of the highly stable complex TCNB 32@4, by the use of isothermal titration microcalorimetry. The finding that clip 4 forms more stable complexes than 3 can be explained by the larger van der Waals contact surfaces of the naphthalene sidewalls in 4 compared to the corresponding benzene systems in 3. In the complexes with 4 as receptor, the plane of each aromatic substrate molecule is calculated to be oriented almost parallel to the naphthalene sidewalls. However, in the complexes of tweezers 2, the substrate is usually oriented parallel to the central naphthalene spacer unit. Due to the more open topology of 4, most complexes were calculated to consist of two or more equilibrating noncovalent conformers. 相似文献
65.
Heinz Falk Karl Grubmayr Martha Marko 《Monatshefte für Chemie / Chemical Monthly》1989,120(8-9):771-779
Summary A violinoid and a 2,3-dihydrobilindione chromophore is attachedvia an appendix anchored at rings A of the pigments by means of reacting them with the polyacryl-N-acryloxysuccinimid copolymer to yield water-soluble chromopolymers. They are characterized by a molecular mass of about 4000 to 6000 and a relation of one chromophoric unit per 6 to 22 monomers. Their absorption spectra and circular dichroism recorded in water and dimethylsulfoxide as solvents are discussed with respect to structural aspects, and in comparison with monomeric chromophore derivatives.
Herrn Prof. Dr. K. Schlögl mit den besten Wünschen zum 65. Geburtstag gewidmet 相似文献
66.
The carrier mediated transport of cations using model compounds of the verdinoid and rubinoid bile pigment structural type as ionophores is studied. Verdinoid bile pigments turn out to be very effective carriers for cations exhibiting a pronounced selectivity for certain transition metal ions like Cr+-+, Fe++, Cu++ and Zn++. The scope of this behaviour of verdinoid bile pigments is compared to [18]-crown-6 and meso-tetraphenylporphin and is discussed with regard to structural, biological, analytical and technical implications. 相似文献
67.
Roland A. Obermüller Christoph Etzlstorfer Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》2002,133(1):89-96
Summary. A hypericin derivative was synthesized in which instead of the methyl groups two benzene rings were condensed to the chromophoric
system in order to extend its conjugation. This derivative showed lowered fluorescence and concomitantly enhanced sensitized
production of active oxygen species as compared to hypericin. However, in contrast to intuition its long wavelength band remained
unshifted in comparison to its parent compound hypericin. Geometry and absorption properties were also investigated by means
of semiempirical calculations.
Received July 27, 2001. Accepted August 9, 2001 相似文献
68.
Bernd?Lackner Yulita?Popova Christoph?Etzlstorfer Andrija A.?Smelcerovic Christian W.?Klampfl Heinz?FalkEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(5):777-793
Summary. The syntheses of the two heterocyclically substituted title hypericin derivatives were achieved starting either from 6-benzothiazolyl-tri-O-methyl-6-demethylemodin or 6-benzoxazolyl-tri-O-methyl-6-demethylemodin. The use of microwave assisted synthesis for the preparation of these anthraquinone synthons and the chemical as well as photochemical properties of the corresponding unique hypericin derivatives, which might constitute new photodynamic therapy agents, are reported. The tautomeric and stereochemical aspects of these hypericin derivatives were investigated by means of semiempirical calculations (AM1). 相似文献
69.
Christoph Kratky Heinz Falk Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1985,116(5):607-623
The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet. 相似文献
70.
Heinz Falk Franz Lehner Marianne Rothböck 《Monatshefte für Chemie / Chemical Monthly》1985,116(11):1359-1361
Donors are added regioselectively to position 10 of 2,3-dihydrobilatrienes-abc in a reversible reaction, which is complicated in case of strongly basic donors due to the easy deprotonation of the partially saturated ring. Compared to the bilatrienes-abc the addition equilibrium is retarded by about two orders of magnitude. 相似文献