Classification of generic 3-dimensional Lagrangian singularities with (Z2) l -symmetries

The paper provides the complete list of local models forZ ₂ ^l -invariant generic germs of Lagrangian submanifolds of dimension ≦3. Classification is done directly for genrating functions of Lagrangian submanifolds and contains both elementary singularities and non-elementary ones with continuous moduli. The results demonstrate, in particular, that in contrast to the non-equivariant case the classification of equivariant Lagrangian singularities is not subordinated to the classification of symmetric functions up to the right equivariant equivalences.     

Chiral hydroperoxides as oxygen source in the catalytic stereoselective epoxidation of allylic alcohols by sandwich-type polyoxometalates: control of enantioselectivity through a metal-coordinated template

The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM(2)(ZnW(9)O(34))(2)](q)(-) [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)(2)(ZnW(9)O(34))(2)](12-), is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)(2)(ZnW(9)O(34))(2)](12)(-) and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template.     

Lewis Acid-Promoted Reduction of Bis(triorganotin) Oxides to Hexaorganoditins

Hexalkylditin is prepared by a Lewis acid-promoted (MgCl₂) reductive reaction of bis(trialkyltin) oxide using magnesium metal as reducing agent. Hexabutyl- and hexaphenylditin are synthesized with 95% and 80% yield separately and a radical mechanism is proposed for the reaction condition. Unsymmetric ditin, Bu₃Sn-SnPh₃, was first synthesized by this reductive method.     

Analytical possibilities of square-wave amperometry

The application of improved electronic equipment for square-wave amperometry (SWA) is described. This equipment has better resolution between waiting and sampling times and a simple, low-noise logic part. Titrations with electrogenerated bromine, iodine, iron(II) and silver ions were investigated as examples to compare SWA with d.c. amperometry (DCA). The sensitivity of SWA in titrations of < 10^?5 moll^?1 concentrations with iodine or silver(I) is more than 100 times greater than that of DCA. For measurements of higher concentations, DCA is preferred because of its better linear response. The change in current near the end-point of titrations with silver ions is sharper with SWA than with DCA.     

The accurate determination of cobalt: Gravimetric methods and in particular the phosphate method

Some gravimetric methods for determining cobalt have been examined in order to assess their value for the accurate determination of the metal. The electrolytic method was found to give high results (about 1.4%), and the anthranilate method slightly high results (0.2 – 0.3%). A modification of the phosphate method has been developed in which a former drawback, the solubility of CoNH₄PO₄·H₂O, has been overcome using a rapid spectrophotometric determination of residual cobalt. The final procedure developed has been found to give accurate results ( ±0.1 – 0.2%) and its use is recommended where this degree of accuracy is required.     

PHOTOCHEMISTRY and PHOTOBIOLOGY WITHOUT LIGHT

Abstract— This review covers the literature since 1980 on chemically and enzymatically generated electronically excited species. The emphasis lies on triplet states of carbonyl products that are derived from dioxetanes and dioxetanones as precursors or from suitable enzymatic oxygenations. Singlet oxygen, an important excited state species in biological processes, is not explicitly treated. The utilization of triplet excited carbonyl products to promote photochemical and photobiological transformations by energy transfer are of primordial interest and not the photomechanistic behavior, photophysical properties and inherent photochemical reactions of such excited state species. Thus, the coverage concentrates on photodamage of DNA and RNA, the photochemistry of flavins, vitamin D, tryptophan, arachidonic acid, chlorophyll, lipid peroxidation, urocanase activation, excitation of chlorophlasts, and the aerobic oxidation of Schiff bases derived from amino acids and proteins. The potential perspectives of employing authentic dioxetanes and enzymatically generated dioxetane intermediates as effective photon equivalents in photochemotherapy, phototoxicity, photoaffinity labeling and photogenotoxicity are pointed out, in the hope of stimulating more intensive activity in this emerging and novel bioorganic and photobiological field.     

Intramolecular silyl migration in the singlet oxygenation of 2-methyl-5-trimethylsilylfuran

Tetraphenylporphyrin-sensitized photooxygenation of 2-methyl-5-trimethylsilylfuran ($\text{4}$) affords quantitatively trimethylsilyl 2-oxo-4-pentenoate ($\text{5}$), presumably via intramolecular Baeyer-Villiger rearrangement of the intermediary dioxirane ($\text{3a}$).     

The second order optical potential for theπd system at the threshold

The second order optical potential for thed system is derived in the framework of the Watson formalism and applied to the calculation of the 1s-state energy shift of the atom and thed scattering lengtha _d . The results are in good agreement with those of the Faddeev type calculations.The authors wish to thank V. B. Belyaev, R. Mach, M. G. Sapozhnikov and R. A. Eramzhyan for stimulating discussions and helpful advice.