Zwitterionic titanoxanes {Cp[η-C5H4B(C6F5)3]Ti}2O and {(η-PrC5H4)[η-1,3-PrC5H3B(C6F5)3]Ti}2O as catalysts for cationic ring-opening polymerization

Zwitterionic titanoxanes {Cp[η⁵-C₅H₄B(C₆F₅)₃]Ti}₂O (I) and {(η⁵-ⁱPrC₅H₄)[η⁵-1,3-ⁱPrC₅H₃B(C₆F₅)₃]Ti}₂O (II), which contain two positively charged Ti(IV) centres in the molecule, are able to catalyse the ring-opening polymerization of -caprolactone (-CL) in toluene solution and in bulk. The process proceeds with a noticeable rate even at room temperature and accelerates strongly on raising the temperature to 60 °C. The best results have been obtained on carrying out the reaction in bulk. Under these conditions, the use of I as a catalyst (-CL:I = 1000:1) gives at 60 °C close to quantitative yield of poly--CL with the molecular mass of 197 000. An increase in the -CL:I ratio to 6000:1 increases the molecular mass of poly--CL to 530 000. Tetrahydrofuran (THF) is also polymerized under the action of I albeit with a lesser rate. However, the molecular mass of the resulting poly-THF can reach rather big values under optimal conditions (up to 217 000 at 20 °C and the THF:I ratio of 770:1). A rise in the reaction temperature from 20 to 60 °C results here to a decrease in the efficiency of the process. Titanoxane II is close to I in its catalytic activity in the -CL polymerization but it is much less active in the polymerization of THF. Propylene oxide (PO), in contrast to -CL and THF, gives with I only liquid oligomers in wide temperature and PO:I molar ratio ranges (−30 to +20 °C, PO:I = 500–2000:1). γ-Butyrolactone and 1-methyl-2-pyrrolidone are not polymerized under the action of I at room temperature. The reactions found are the first examples of catalysis of the cationic ring-opening polymerization by zwitterionic metallocenes of the group IVB metals.     

The fluorescent oxidation products of dihydroxyphenylalanine and its esters

Dihydroxyphenylalanine (DOPA), its methyl ester (DOPAM) and the N-acetylated derivative of the ester (DOPAMNA) are found to undergo rapid oxidation in air-saturated alkaline solution. Some of the products of oxidation exhibit fluorescent emission in the 300-500 nm spectral range and their excitation-emission spectra have been determined in acidic and alkaline aqueous solutions. The spectral distributions and positions of the maxima depend on the pH of the solution. Excitation-emission maxima associated with the protonated phenolic form of the compounds occur at shorter wavelengths than those of the conjugate base. At some pH values the phenolic forms of these molecules are excited and undergo rapid deprotonation in the excited state; as a consequence, emission is observed from the phenolate anion. The fluorescence excitation-emission spectrum of an authentic sample of 3,4-dihydroxycinnamic (caffeic) acid has also been determined and features of the fluorescence spectra of the principal oxidation products are consistent with the presence of 3,4-hydroxycinnamoyl compounds in solutions of oxidized DOPAM and DOPAMNA.     

THE SOLUTION PHOTODIMERIZATION OF URIDINE

Abstract— Quenching of the degradative photobleaching of FMN in anaerobic aqueous solution, and of the flavin-sensitized photo-oxidation of EDTA, alcohols, glycols, and glycerol, has been examined using flash techniques. The quenching can be produced by addition of KI, by successive flashes, and by increasing the flavin concentration (self-quenching). It is concluded that the lowest triplet is the photoreactive species in all systems, that the successive flash effect is due to triplet quenching by a reaction product, and that the concentration quenching may be due to either triplet-triplet annihilation or to reaction between a ground-state flavin and a flavin triplet.     

[(C6H5)3P]2Ni(Me3Si?CC?SiMe3). Darstellung,Eigenschaften und Struktur des ersten stabilen Nickel(0)-Komplexes von Bis-trimethylsilylacetylen

[(C₆H₅)₃P]₂Ni(Me₃Si? C?C? SiMe₃). Preparation, Properties, and Structure of the First Stable Nickel(0) Complex with Bis(trimethylsilyl)acetylene The title compound is the first example of a nickel(0) complex with bis(trimethylsilyl)acetylene and obtained from (ph₃P)₂Ni(C₂H₄) and bis(trimethylsilyl)acetylene in tetrahydrofuran. The complex is characterized by some reactions, the i.r. spectrum and by a structural analysis with the aid of X-ray diffraction data. (ph₃P)₂Ni(Me₃Si? C?C? SiMe₃) crystallizes monoclinic in the space group C2/c with four formula units per unit cell (2468 observed, independent reflexions, R = 0.038). The cell dimensions are a = 20.927, b = 13.812, c = 14.238 Å, α = γ = 90°, β = 91.02°. The molecules are monomer in crystalls. The molecule is planar with ligands arranged trigonally about the central atome but distorted to the tetrahedral complex.     

Reduction of 1,4-dichlorobut-2-yne by titanocene to a 1,2,3-butatriene. Formation of a 1-titanacyclopent-3-yne and a 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene

The 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene (bis-titanocene-mu-(Z)-1,2,3-butatriene complex)3 is formed starting from [Cp2Ti(eta2-Me3SiC2SiMe3)] by in situ generated titanocene and 1,4-dichlorobut-2-yne via the 1-titanacyclobut-3-yne (2).     

Chemische synthese von nonadesoxyribonucleotiden mit den abgewandelten basen uracil, 5-bromuracil und 5-methylcytosin nach dem triester-verfahren

In order to investigate the interaction of Eco RII restriction and modification enzymes with synthetic DNA fragments three nonadeoxyribonucleotides containing the modified bases uracil, 5-bromouracil and 5-methylcytosine were synthesized according to the phosphate tri-ester approach using TPS/l-methylimidazole as the condensation agent. The patterns of these modified DNA fragments obtained by Maxam/Gilbert sequence technique are presented.     

Risikominimierung bei der Portfolioplanung unter besonderer Berücksichtigung singulärer Kovarianzmatrizen

Zusammenfassung Bisher waren die Untersuchungen über Erwartungswert-Streuungs-effiziente Wertpapiermischungen auf den Fall nichtsingulärer Kovarianzmatrizen beschränkt. Der Fall singulärer Kovarianzmatrizen war bisher nicht konstruktiv behandelt worden. Es wird in dem vorstehenden Papier in einem allgemeinen Ansatz, der auch den Fall singulärer Kovarianzmatrizen zuläßt, die allgemeine Gültigkeit des Separationstheorems und des Zwei-Fonds-Theorems nachgewiesen.

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Summary Previous studies of mean-variance-efficient portfolios got constructive results in the case of non-singular covariance matrices only, singular covariance matrices were not treated in a constructional way. The present paper proves the Separation Theorem and the Two-Fonds-Theorem within a general framework including the case of singular covariance matrices.

     

Rapid transacylations of activated ester substrates bound to the primary side β-cyclodextrin-cyclen conjugate and its M2+ complexes

The ability of cyclodextrins to effect rapid transacylations of bound substrates has been well studied. One important difference between cyclodextrin and enzyme-mediated transacylation is the pH required. Because the pK _a of a cyclodextrin secondary-side hydroxyl group is about 12, transacylations are accelerated in the presence of cyclodextrin under basic conditions (pH > 10.5). In 1988, our group reported the synthesis of cyclodextrin with attached cyclen-Co(III) complexes; significant acceleration in the reaction withp-nitrophenyl acetate was observed only with the primary side derivative. Of course, metalloenzymes utilize M²⁺ and not M³⁺ catalytic centers; in addition, large rate accelerations in the transacylations of both activated and unactivated substrates have been observed previously in systems utilizing M²⁺ ions (e.g., Zn, Cu, Ni) as well as M³⁺ ions (e.g. Co, Ir, Cr). In this paper, we describe the ability of CD-cyclen-M²⁺ conjugates to transacylate activated esters, amides, and phosphates. In addition, the ability of the apoenzyme mimic to effect transacylations was examined.     

Influence of solvents on the insertion of methacrolein into zirconacyclopropenes

The reaction of Cp₂Zr(L)(η²-Me₃SiC₂) (L = THF, py) with equimolar amounts of H₂C = CMe-CHO at room temperature depends strongly on the ligands L and the solvents that are used. With L = THF, in the THF solution the insertion product

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1 was isolated, whereas by conducting the reaction in n-hexane solution an alkyne substitution with 1,4-coordination of the methacrolein takes place and the binuclear complex [

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2 was obtained. In conttrast, with L = py (a stronger ligand) only a 1:1 ratio of 1 and 2 was observed in both THF and in n-hexane. At 50°C complex 1 was converted into 2 and the alkyne was eliminated quantitatively.

Complexes 1 and 2 were characterized by IR and NMR spectroscopical measurements and 1 by an additional X-ray structure determination.