Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

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.     

Five Novel Taccalonolides from the Roots of the Vietnamese Plant Tacca paxiana

Chemical investigation of the roots of the Vietnamese plant Tacca paxiana resulted in the isolation of five new steroidal compounds, taccalonolide R ( 6 ), S ( 7 ), T ( 8 ), U ( 9 ), and V ( 10 ). Their structures were established on the basis of NMR and mass‐spectral data. In addition, the five known taccalonolides A ( 1 ), B ( 2 ), E ( 3 ), K ( 4 ), and N ( 5 ) were also isolated and identified.     

Soft X-ray resonant magnetic scattering studies on Fe/CoO exchange bias system

We have used soft X-ray resonant magnetic scattering (XRMS) to search for the presence of an effective ferromagnetic moment belonging to the antiferromagnetic (AF) layer which is in close contact with a ferromagnetic (F) layer. Taking advantage of the element specificity of the XRMS technique, we have measured hysteresis loops of both Fe and CoO layers of a CoO(40 Å)/Fe (150 Å) exchange bias bilayer. From these measurements we have concluded that the proximity of the F layer induces a magnetic moment in the AF layer. The F moment of the AF layer has two components: one is frozen and does not follow the applied magnetic field and the other one follows in phase the ferromagnetic magnetization of the F layer. The temperature dependence of the F components belonging to the AF layer is shown and discussed.     

Randomization helps to perform independent tasks reliably

This paper is about algorithms that schedule tasks to be performed in a distributed failure‐prone environment, when processors communicate by message‐passing, and when tasks are independent and of unit length. The processors work under synchrony and may fail by crashing. Failure patterns are imposed by adversaries. Linearly‐bounded adversaries may fail up to a constant fraction of the processors. Weakly‐adaptive adversaries have to select, prior to the start of an execution, a subset of processors to be failure‐prone, and then may fail only the selected processors, at arbitrary steps, in the course of the execution. Strongly adaptive adversaries have a total number of failures as the only restriction on failure patterns. The measures of complexity are work, measured as the available processor steps, and communication, measured as the number of point‐to‐point messages. A randomized algorithm is developed, that attains both ??(n log*n) expected work and ??(n log*n) expected communication, against weakly‐adaptive linearly‐bounded adversaries, in the case when the numbers of tasks and processors are both equal to n. This is in contrast with performance of algorithms against strongly‐adaptive linearly‐bounded adversaries, which has to be Ω(n log n/log log n) in terms of work. © 2003 Wiley Periodicals, Inc. Random Struct. Alg., 2004     

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On exactness and isoperimetric profiles of discrete groups

We introduce a quasi-isometry invariant related to Property A and explore its connections to various other invariants of finitely generated groups. This allows to establish a direct relation between asymptotic dimension on one hand and isoperimetry and random walks on the other. We apply these results to reprove sharp estimates on isoperimetric profiles of some groups and to answer some questions in dimension theory.