Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Surface of Ru/Fe2O3 catalysts used in water-gas shift reaction studied by auger electron spectrometry

Summary Carbon deposits on the surface ofRu/Fe₂O₃ catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to reduce the amount of carbon deposit. .      

Chern and Pontryagin Numbers in Perfect Symmetries of Spheres

The paper presents a procedure for constructing smooth actions of finite perfect groups on spheres with fixed point sets having certain prescribed properties (Theorem A); in particular, having any prescribed configuration of Chern and Pontryagin numbers (Corollary C). The main ingredients used are equivariant thickening and equivariant surgery.     

Super-Brownian motion with reflecting historical paths. II. Convergence of approximations

We prove that the sequence of finite reflecting branching Brownian motion forests defined by Burdzy and Le Gall ([1]) converges in probability to the “super-Brownian motion with reflecting historical paths.” This solves an open problem posed in [1], where only tightness was proved for the sequence of approximations. Several results on path behavior were proved in [1] for all subsequential limits–they obviously hold for the unique limit found in the present paper.Mathematics Subject Classification (2000): Primary 60H15, Secondary 35R60Supported in part by NSF Grant DMS-0071486, Israel Science Foundation Grants 12/98 and 116/01 - 10.0, and the U.S.-Israel Binational Science Foundation (grant No. 2000065).     

Deposition of boron nitride on graphite at 1300 K

A method for the deposition of BN onto graphite and other substrates is described. Boron trichloride (BCl₃) and ammonia (NH₃) diluted with Ar were used as reacting gases. The deposition process was carried out at 1300 K as well as lower temperatures in an open system at pressures of 1 atm. The consequences of the introduction of hydrogen to the system were considered. It was demonstrated that the replacement of argon with hydrogen increases the efficiency of the process as well as the theoretical rate of BN deposition. However, the acceleration of the deposition seems to be unprofitable, because the resulting supersaturation leads to the formation of an amorphous phase. The modification of the experimental conditions were proposed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Boundary G/G Theory and Topological Poisson–Lie Sigma Model

We study a boundary version of the gauged WZW model with a Poisson–Lie group G as the target. The Poisson–Lie structure of G is used to define the Wess–Zumino term of the action on surfaces with boundary. We clarify the relation of the model to the topological Poisson sigma model with the dual Poisson–Lie group G ^* as the target and show that the phase space of the theory on a strip is essentially the Heisenberg double of G introduced by Semenov–Tian–Shansky.     

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

The single crystal X-ray structure of (AsPh₄)[W(bpy)(CN)₆] is described. The structure of octa- and hepta-coordinated intermediates of substitutional photolysis of [Mo(CN)₈]⁴⁻ ion in aqueous media were determined by performing semi-empirical calculations. On the basis of obtained results as well as on empirical data the photolysis scheme has been postulated.     

SU(2) Chern-Simons theory at genus zero

We present a detailed study of the Schrödinger picture space of states in theSU(2) Chern-Simons topological gauge theory in the simplest geometry. The space coincides with that of the solutions of the chiral Ward identities for the WZW model. We prove that its dimension is given by E. Verlinde's formulae.