The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure

"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.     

Etorphine‐Related Ferrocenyl‐Substituted Morphinan Alkaloids

The two diastereoisomeric ferrocenyl‐substituted orvinols 2 and 3 were prepared. The modified alkaloids are still able to interact with opioid receptors (see Table). The ferrocene moiety allows highly selective and sensitive electrochemical detection. The X‐ray crystal structure of the major isomer 2 was determined. The combination of a metallocene and a morphinan alkaloid holds promise for useful antitumor activity.     

Antisymmetry and analytic structure in the spectrum of a uniform Fréchet algebra

Let M be a C-smooth submanifold of a domain GCⁿ. Denote by 0(M) the algebra of germs of holomorphic functions on M, that is, each f0(M) is holomorphic in some neighbourhood of M, the neighbourhood dependent of f. Now define A(M) as the closure of 0(M) with respect to the topology of compact convergence on M.If M coincides with A(M), the spectrum of A(M), we give a necessary and sufficient condition for A(M) such that M is a complex manifold.     

Ebene Äquiforme Zwangläufe im Grossen II

Im ersten Teil dieser Arbeit¹ wurden die orientierten Flächeninhalte der Punktbahnen ebener äquiformer Zwangläufe studiert und einige Anwendungen der erzielten Resultate angeführt. Der vorliegende zweite Teil beschäftigt sich - unter Beibehaltung der Bezeichnungen, der Numerierung der Abschnitte, Sätze usw. - einerseits mit Geradenhüllbahnen, andererseits mit globalen Eigenschaften spezieller äquiformer Zwangläufe, und zwar mit der äquiformen Bewegung der Krümmungsstrecken einer ebenen Kurve, mit äquiformen Konchoiden-bewegungen und mit der äquiformen Bewegung der Durchmesser eines beschränkten konvexen Bereichs. Beim Studium der durch formale Integration gewonnenen, vorzeichenbehafteten “Längen” der Geradenhüllbahnen wurden zur Interpretation des Vorzeichens orientierte Geraden des Gangsystems betrachtet. Dieser anscheinend notwendige Übergang zu Speeren wurde bislang bei der Formulierung von Holditch-Sätzen über Längen von Geradenhüllbahnen (vgl.[11],[39]) nicht beachtet. Wie schon im ersten Teil gestatten die Ergebnisse eine Anwendung in der globalen euklidischen n-Lagentheorie sowie auf nichtgeschlossene euklidische Zwangläufe.     

DAMAGE TO URACIL- AND ADENINE-CONTAINING BASES, NUCLEOSIDES, NUCLEOTIDES AND POLYNUCLEOTIDES: QUANTUM YIELDS ON IRRADIATION AT 193 AND 254 NM

Abstract Photoreactions, such as base release and decomposition of the base moiety, induced by either 20 ns laser pulses at 193 nm or continuous 254 nm irradiation, were studied for a series of uracil and adenine derivatives in neutral aqueous solution. The quantum yield of chromophore loss (φ) depends significantly on the nature of the nucleic acid constituent and the saturating gas (Ar, N₂O or O₂). In the case of polynucleotides the destruction of nucleotides was measured by high-performance liquid chromatography after hydrolysis; the quantum yields (φ) are comparable to those of chromophore loss or larger. The φ_cl and aφ_dn of 0.04–0.1 for poly(U) and poly(dU), obtained for both wavelengths of irradiation, are due to processes originating from the lowest excited singlet state, i.e. formation of photohydrates and photodimers, and a second part from photoionization using λ_irr= 193 nm. Irradiation at 193 nm effectively splits pyrimidine dimers and thus reverts them into monomers. The quantum yield for release of undamaged bases (φ_br) from nucleosides, nucleotides and polynucleotides upon irradiation at 254 nm is typically φ_br= (0.1–1) × 10^?4 Breakage of the N-glycosidic bond is significantly more efficient for λ_irr=193 nm, e.g. φ_br= 1.1 × 10^?3, 0.8 × 10^?3, 4.3 × 10^?3 and 0.5 × 10^?3 for poly(A), poly(dA), poly(U) and poly(dU) in Ar-saturated solution, respectively. Enhanced φ values for λ_irr= 193 nm, essentially for adenine and its derivatives, are caused by photo-processes that are initiated by photoionization.     

Mixed Azines of Naloxone with Dihydromorphinone Derivatives

The mixed azines 4 and 5 were prepared by reaction of naloxazone ( 2 ) with either oxymorphone ( 6 ) or 14-O-methyloxymorphone ( 7 ) and tested in vitro using opioid receptor binding assays and in vivo using the AcOH-writhing test in mice. Compound 4 was found to be a partial agonist, while compound 5 was a potent opioid agonist with higher potency than morphine.     

Substituent-dependent reactivity in the photodimerization of N-substituted dibenz[b,f]azepines

The photoprocesses of a series of N-substituted dibenz[b,f]azepines (iminostilbenes) were studied by absorption and emission spectroscopy, by laser flash photolysis, and by preparative irradiation with NMR analysis. In solutions, 2pi+2pi photodimers of N-cyano and N-acyl dibenzazepines are formed via the triplet state upon acetone- or benzophenone-sensitized energy transfer. T-T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N-alkyl dibenzazepines, which do not dimerize. Excited states of npi* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N-acyl and N-cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01-0.1 mol dm(-3)) as well as in the solid state. A selective anti-configuration of the photodimers was found throughout.     

Tantalum Clusters in Oxidic Matrices — Synthesis,Crystal Structure and Magnetic Properties of Eu1.83Ta15O32

The mixed‐valent oxotantalate Eu_1.83Ta₁₅O₃₂ was prepared from a compressed mixture of Ta₂O₅ and the metals in a sealed Ta ampoule at 1400 °C. The crystal structure was determined by means of single crystal X‐ray diffraction: space group R3¯, a = 777.2(6) pm and c = 3523.5(3) pm, Z = 3, 984 symmetrically independent reflections, 83 variables, R_F = 0.027 for I > 2σ (I). The structure is isotypic to Ba₂Nb₁₅O₃₂. The salient feature is a [Ta(+8/3)₆O₁₂ⁱO₆^a] cluster consisting of an octahedral Ta₆ core bonded to 12 edge‐bridging inner and six outer oxygen atoms. The clusters are arranged to slabs which are sandwiched by layers of [Ta(+5)₃O₁₃] triple octahedra. Additional Ta(+5) and Eu(+2) atoms provide the cohesion of these structural units. Twelve‐fold coordinated Eu(+2) atoms are situated on a triply degenerate position 33 pm displaced from the threefold axis of symmetry. A depletion of the Eu(+2) site from 6 to 5.5 atoms per unit cell reduces the number of electrons available for Ta‐Ta bonding from 15 to 14.67 electrons per cluster. Between 125 and 320 K Eu_1.83Ta₁₅O₃₂ is semi‐conducting with a band gap of 0.23 eV. The course of the magnetization is consistently described with the Brillouin function in terms of a M_mol/(N_Aμ_B) versus B/T plot in the temperature range 5 K — 320 K and at magnetic flux densities 0.1 T — 5 T. At moderate flux densities (< 1 T) the magnetic moment agrees fairly well with the expected value of 7.94 μ_B for free Eu (2+) ions with 4f⁷ configuration in ⁸S_7/2 ground state. Below 5 K, anisotropic magnetization measurements at flux densities B < 1 T point to an onset of an antiferromagnetic ordering of Eu spins within the layers and an incipient ferromagnetic ordering perpendicular to the layers.     

Palladium‐Catalyzed 2‐Phenylethenylation of Codeine: 8‐[(1E)‐2‐Phenylethenyl]codeinone Dimethyl Ketal as the Unexpected ‘Masked’ Diene for the Preparation of 19‐Substituted Diels–Alder Adducts of Thebaine

In a search for starting materials for the preparation of 7,8‐fused morphine alkaloid derivatives, 8‐[(1E‐2‐phenylethenyl]codeinone dimethyl ketal ( 4 ) and 8‐[(1E‐2‐phenylethenyl]codeine ( 5 ) were prepared. These dienes were used as substrates in the Diels–Alder reactions. Compound 5 formed the ‘normal’ adduct 12 with N‐phenylmaleimide, while compound 4 behaved in reactions with dienophiles as the ‘masked’ diene 11 , a 8‐[(1E)‐2‐phenylethenyl]‐substituted thebaine, yielding the corresponding 19‐substituted 6,14‐endo‐etheno‐6,7,8,14‐tetrahydrothebaines. Specifically, reaction of 4 with methyl vinyl ketone gave rise to 19‐[(1E)‐phenylethenyl]thevinone ( 14 ) whose structure was elucidated by an X‐ray diffraction analysis. The thebaine derivative 11 was also prepared from 4 .     

FTIR-spectroscopy as a highly sensitive technique to study adsorption and desorption on ionic film and single crystal surfaces

Sample/spectrum relationships are investigated using both a low resolution rapid-scanning NIR monochromator and a Fourier transform instrument capable of high resolution and are evaluated in terms of whether or not the resolution of the instrument is sufficient for measuring the natural bandwidths corresponding to the sample. Based on the sample/spectrum relationship a criterion is developed which must be followed in order to apply either derivative spectroscopy or deconvolution to enhance the resolution of overlapped bands without generating spectral artifacts.