New Monoterpene-Substituted Dihydrochalcones from Piper aduncum

Five New unusual monoterpene-substituted dihydrochalcones, the adunctins A–E (1″S)-1-{2′-hydroxy-4′-methoxy-6′-[4″-methyl-1″-(1?-methylethyl)cyclohex-3″ -en-1″ -yloxy]phenyl}-3-phenylpropan-1-one ( 1 ), (5aR*,8R*,9aR*)-3-phenyl-1-[5′,8′,9′,9′a-tetrahydro-3′-hydroxy-1′-methoxy-8′-(1″-methylethyl)-5′-a-methyldibenzo-[b,d]furan-4′-yl]propan-1-one ( 2 ), (2′R*,4″S*)-1-{6′-hydroxy-4′-methoxy-4″-(1?-methylethyl)spiro[benzo[b]-furan-2′(3′H),1″ -cyclohex-2″ -en]-7′-yl}-3-phenylpropan-1-one ( 3 ), (2′R*,4″R*)-1-{6′-hydroxy-4′-methylethyl-4″-(1?-methylethyl)spiro[benzo[b]furan-2′(3′H),1″-cyclohex-2″-en]-7′-yl}-3-phenypropan-1-one ( 4 ), and (5′aR*,6′S*, 9′R*,9′aS*)-1-[5′a,6′,7′,8′,9′a-hexahydro-3′,6′-methoxy-6′-methyl-9′-(1″-methylethyl)dibenzo[b,d]-furan-4′-yl]-3-phenylpropan-1-one ( 5 ) were isolated from the leaves of Piper aduncum (Piperaceae) by preparative liquid chromatography. In addition, (?)-methyllindaretin ( 6 ), trans-phytol, and α-tocopherol ( = vitamin E) were also isolated and identified. The structures were elucidated by spectroscopic methods, including 1D- and 2D-NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The antibacterial and cytotoxic potentials of the isolates were also investigated.     

Analysis of mouse beta-haptoglobin chain by lectin affinoblotting detection

Two different human mammary carcinoma cell lines were xenotransplanted into nude mice. Serum samples were obtained prior to and after transplantation and investigated by two-dimensional electrophoresis (2-DE). By comparison of these silver-stained patterns additional protein spots were detected resulting either from proteins secreted or shed by the tumor itself or from mouse proteins induced by the tumor or the transplantation procedure. One group of spots detectable in post-transplantation serum as well as in control serum after mock-transplantation but not in pretransplantation serum was microsequenced and identified as mouse beta-haptoglobin. The carbohydrate structures of beta-haptoglobin were characterized by two different immunochemical glycoprotein staining procedures to detect differential terminal glycan modifications.     

Verproside,a New Iridoid Glucoside from Veronica officinalis L. (Scrophulariaceae)

A new iridoid glucoside, verproside (2) , has been isolated from Veronica officinalis L. and its structure has been established to be 6-O-protocatechuoylcatalpol.     

Elucidation of the structures of 3-alkylthio-, 3-benzylthio-, 2-arylthio- and 2-heteroarylthio-N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamines by one- and two-dimensional NMR spectroscopy

Nucleophilic addition of alkyl- and benzylthiols to benzoquinone diimine (1) gave the corresponding 3-alkylthio- or 3-benzylthio-1,4-phenylenediamines (2-5). However, addition of aryl- or heteroarylthiols to 1 formed 2-arylthio- or 2-heteroarylthio-1,4-phenylenediamines (6-14). The structures of 2-14, obtained in 55-91% yields, were confirmed in CDCl3 or DMSO-d6 solution using 1D (NOE difference, coupled 13C NMR spectra, APT and DEPT) and 2D NMR techniques [DQCOSY, NOESY, HETCOR and heteronuclear multiple bond coherence (HMBC)] that resulted in unambiguous proton and carbon NMR resonance assignments. The substituent-induced 13C NMR chemical shift differences were calculated in 2-14 relative to carbon atoms in the model compound N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamine (DMBPPD) (15) (a reduced form of benzoquinone diimine).     

Functional polymers,XL. Syntheses of mono- and di(4-methoxy)benzotriazolesubstituted 2,4-dihydroxyaceto(or benzo)phenones

Eight benzotriazoles and (4-methoxy)benzotriazoles, mono- or di-substituted derivatives of 2,4-dihydroxyaceto(or benzo)phenone were synthesized by azo coupling of (4-methoxy)2-nitrobenzenediazonium chloride with 2,4-dihydroxyaceto(or benzo)phenone followed by reductive cyclization. Pure mono-substituted compounds were very difficult to prepare. Careful selection of thepH for the azo coupling and selection of the proper reagents for the reductive cyclization were essential. All compounds were characterized by their ultraviolet, infrared¹H and¹³C NMR spectra and their elemental analysis. These compounds have both the 2(2-hydroxyphenyl)2H-benzotriazole unit and a 2-hydroxyaceto(or benzo)phenone unit in the same molecule and are effective and useful ultraviolet absorbers.Dedicated to Prof. Dr.K. Komarek, Vienna, on the occasion of his 60^th birthday with best wishes.     

Unusually efficient quenching of the fluoroscence of an energy transfer-based optical sensor for oxygen

A two-fluorophore system consisting of pyrene as donor and perylene as energy acceptor undergoes efficient energy transfer when pyrene is electronically excited. The excitation wavelength was that of pyrene and fluorescence was monitored at the emission wavelength of perylene. The fluorescence of pyrene is strongly quenched by oxygen, but that of perylene is not. The two-fluorophore system, in contrast, is very strongly quenched, with a 4-fold increase in the Stern-Volmer quenching constant as compared to the quenching of pyrene, as a result of the effect of oxygen on the formation of the donor-acceptor exciplex, and quenching by oxygen. The results are used to design a fluorescence-based optical oxygen sensor which offers a sensitivity greatly exceeding that of existing oxygen probes.     

Vertical proton affinities of CH2O and CH2OH+ in their ground singlet,excited triplet and ionized doublet states

Vertical proton affinities were calculated with closed and open shell direct SCF-MO methods for the ground, excited triplet and ionized doublet states of CH₂O and CH₂OH⁺.The computed gas phase basicity of CH₂O follows the order: CH₂O(¹ A ₁) > CH₂O*(³ A ₁ or ³ A ₂) > CH₂O⁺(² B ₂ or ² B ₁).     

Emission,Emissionslebensdauer und Absorption von [Cr urea6]X3-Einkristallen

Emission and absorption polarization spectra as well as emission lifetimes between room temperature and 5 °K have been measured of [Cr urea₆]X₃ single crystals, where X stands for ClO ₄ ^– , J^–, NO ₃ ^– , Br^–, Cl^–, F^–, and X₃ for JSO ₄ ^3– . The strong temperature dependence of the fluorescence/phosphorescence-ratios, and of the emission lifetimes is discussed. The differences between the spectra as well as the emission lifetimes of the various salts can be attributed to an anion dependent trigonal perturbation.

Die Autoren danken dem Verband der Chemischen Industrie für finanzielle Unterstützung dieser Arbeit.     

The Stevens rearrangement of methylenedimethyloxonium ylide: A quantum chemical study

The conversion of methylenedimethyloxonium ylide to ethyl methyl ether was investigated by the semiempirical MNDO method. An activation energy of 51 kJ/mol suggests that this rearrangement is a possible elementary reaction in the well-known MTG process.

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Zur Krümmungsverwandtschaft Von Zwangläufen in Affinen CK — Ebenen I

We study a map of osculating elements of an affine Cayley- Klein (CK-) plane into the Lie algebraA ₄(²) of the aequiform transformationsA ₄(²) of the given plane. If we use the real projective spaceP ₃() overA ₄(²) each osculating element defines a straight line inP ₃(). In the first part of this paper this map is studied in detail. In the second part we study second order properties of one- parameter motions and their corresponding properties in the Lie algebraA ₄(²). This is done by considering the analogen to the formula of EULERSAVARY in the image spaceP ³() overA ₄(²).