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.     

Planar Chromatography of Some 1-Arylpiperazines Behaving as Dopaminergic Ligands

JPC – Journal of Planar Chromatography – Modern TLC - The chromatographic behavior of fourteen 1-arylpiperazine derivatives has been studied by thin-layer chromatography on both silica...     

Experimental identification of physical parameters of fluid-filled pipes using acoustical signal processing

A method is formulated for the identification of an unknown physical parameter of a fluid-filled pipe using the measurement of sound speed in the pipe. The method uses a simple formula which provides the relationship between the sound speed and a few physical parameters of the pipe: thickness, diameter, wall material constants and fluid constants. Once the sound speed in the pipe is measured, the simple formula can be used to extract one of the unknown parameters providing the remaining ones are known.The sound speed in the pipe is measured using a 3-transducer array. In order to demonstrate the potential of the technique the results of several measurements obtained in a water-filled steel pipe are presented.The required accuracy of the measurement of sound speed and of the specification of known parameters is analysed. The accuracy depends on the unknown parameter which is to be identified. For example, if the pipe thickness is the unknown parameter, the other parameters have to be known within a very narrow margin of error. On the contrary, if the fluid properties have to be identified the needed accuracy of known parameters gets much lower.     

Statistical theory for hydrogen bonding fluid system of A a D d type (I): The geometrical phase transition

The influence of hydrogen bonds on the physical and chemical properties of hydrogen bonding fluid system of A _a D _d type is investigated from two viewpoints by the principle of statistical mechanics. In detail, we proposed two new ways that can be used to obtain the equilibrium size distribution of the hydrogen bonding clusters, and derived the analytical expression of a relationship between the hydrogen bonding free energy and hydrogen bonding degree. For the nonlinear hydrogen bonding systems, it is shown that the sol-gel phase transition can take place under proper conditions, which is further proven to be a kind of geometrical phase transition rather than a thermodynamic one. Moreover, several problems associated with the geometrical phase transition and liquid-solid phase transition in nonlinear hydrogen bonding systems are discussed.     

On classification of conformally flat spaces

Classification of conformally flat n-dimensional pseudo-Riemannian spaces via Plebanski's method is discussed. It is based on embedding these spaces into a flat (n + 2)-dimensional space and on finding their minimal isometry groups which are subgroups of the conformal group. In particular, the case n = 4 is given in full detail and compared with incomplete results known in the literature. The found conformally flat spacetimes are identified with the associated solutions of the Einstein equations and with the spacetimes used in various cosmological considerations.     

A simple Markov chain structure for the evolution of credit ratings

We focus on continuous Markov chains as a model to describe the evolution of credit ratings. In this work it is checked whether a simple, tridiagonal type of generator provides a good approximation to a general one. Three different tridiagonal approximations are proposed and their performance is checked against two generators, corresponding to a volatile and a stable period, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Transition metal complexes with Girard reagent-based ligands

The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H₂SalGT]Cl (1), and two complexes [Cu(HSalGT)X₂]·H₂O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH₃)₃ group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption spectra.     

Renormalization group approach to lattice gauge field theories

We study four-dimensional pure gauge field theories by the renormalization group approach. The analysis is restricted to small field approximation. In this region we construct a sequence of localized effective actions by cluster expansions in one step renormalization transformations. We construct also -functions and we define a coupling constant renormalization by a recursive system of renormalization group equations.