Influence of chloride anions on the electrodeposition and electroactivity of the polymer matrix in polypyrrole,poly(<Emphasis Type="Italic">N</Emphasis>-methylpyrrole) and polypyrrole derivatives functionalized by titanocene centers,in dry non-aqueous solutions

We report electrochemical studies on the influence of a small concentration of chloride ions on the electroactivity of the polymer matrix of polypyrrole (PPy), poly(N-methylpyrrole) [p(N-MePy)] and a poly(titanocene-propyl-pyrrole) derivative, p(Tc3Py) [Tc(CH₂)₃NC₄H₄; Tc=CpCpTiCl₂; Cp=C₅H₅; Cp=C₅H₄] in acetonitrile (AN), tetrahydrofuran (THF) and N,N-dimethylformamide (DMF). The polymer films were obtained on Pt disc electrodes from AN solutions of the monomers containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF₆) as the supporting electrolyte and then transferred to the corresponding monomer-free solution. Studies in Cl^–-containing solutions have shown that the p(Tc3Py) matrix is very sensitive to the presence of Cl^– ions in all the above solvents, namely that it was subjected to electrochemical degradation at potentials above 0.1 V vs. a Ag/0.01 M Ag⁺ in AN reference electrode. Degradation of the p(Tc3Py) matrix was also observed in chloride-free DMF+TBAPF₆ solutions. Addition of chloride ions to the AN solution containing pyrrole, N-methylpyrrole or Tc3Py inhibits the deposition of the polymer films. On the other hand, we have found that PPy and p(N-MePy) matrices after their deposition in chloride-free AN solutions show much more stable redox responses in contact with chloride and/or DMF solutions. Possible mechanisms of these effects are discussed.Abbreviations AN acetonitrile - Cp cyclopentadienyl - DMF N,N-dimethylformamide - N-MePy N-methylpyrrole - p(N-MePy) poly(N-methylpyrrole) - PPy polypyrrole - p(Tc3Py) poly[Tc(CH₂)₃NC₄H₄] - Py pyrrole - Tc titanocene=bis(cyclopentadienyl)titanium dichloride, Cp₂TiCl₂, or its radical CpCpTiCl₂ (Cp=C₅H₄) - Tc3Py titanocene-propyl-pyrrole, Tc(CH₂)₃NC₄H₄ - THF tetrahydrofuran Contribution to the 3rd Baltic Conference on Electrochemistry, Gdansk-Sobieszewo, Poland, 23–26 April 2003Dedicated to the memory of Harry B. Mark, Jr. (28 February 1934–3 March 2003)     

A note on pseudocompactifications

There exists a countable spaceV _ω such that:

1. V _ω has a single non-isolated point,
2. V _ω has no pseudocompactificationX witht(X)=ω.

     

Rossby solitary vortices,on giant planets and in the laboratory

This is a review of laboratory experiments with a layer of shallow water having a free surface and rotating together with a vessel of parabolic form. Such a (rather original) setup has allowed one to create Rossby solitary vortex for the first time. The latter is an anticyclonic Rossby vortex not subjected to dispersive spread owing to its compensation by the nonlinearity of KdV type. By its structural, collisional, and other properties, including clear-cut cyclonic-anticyclonic asymmetry, it may be considered as a physical prototype of the large-scale long-lived anticyclonic Rossby vortices like the Great Red Spot of Jupiter or the Great Dark Spot of Neptune (this remarkable vortex was discovered by the spacecraft Voyager-2 during its farewell to the Solar System) and other vortices dominating in the atmospheres of giant planets and created by the unstable zonal flows. It has been shown that the vortex under study is a long-lived entity provided it satisfies "antitwisting condition," i.e., it has rather large amplitude (at which it rotates more quickly than it propagates and thereby carries the trapped fluid). In this case, it is not subjected to the "twisting" deformation and may be ascribed by the generalized Charney-Obukhov equation for Rossby vortices on shallow water with a free surface. The results of creating the vortex under consideration by the different methods have been compared with the results obtained by other authors in the experiments on shear-flow generation of Rossby vortices.     

Some remarks on coherent structures out of chaos in planetary atmospheres and oceans

In the context of planetary atmospheres and oceans, it is natural to define "coherent structures" as "long-lived," or "solitary," Rossby vortices. These can be described by the generalized Charney-Obukhov equation (in fluid dynamics) or the analogous generalized Hasegawa-Mima equation (in plasma physics). These two equations contain KdV-type nonlinearities which (together with the compensating dispersive spreading) determine the formation of the coherent structures and explain the clear-cut cyclonic/anticyclonic asymmetry observed experimentally in long-lived planetary Rossby vortices. Examples are given of natural vortices which are (and which are not) coherent structures.     

A Big Horizontal Solar Telescope of the Main Astronomical Observatory of the Ukrainian National Academy of Sciences in the caucasus

This paper presents the Big Horizonal Solar Telescope of the Main Astronomical Observatory of the Ukrainian National Academy of Sciences installed at the Peak Terskol high-altitude station near Elbrus (the main mirror diameter is 650 mm and the focal length is 17.5 m). The telescope is equipped with a five-camera spectrograph intended for photographic spectral observations of active regions in the solar atmosphere and photoelectric measurements of the solar spectra with high spectral and spatial resolution. The observation procedure is described, and the results of the quality analysis of the recorded spectra and of the early measurements are presented.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 39, No. 10, pp. 1326–1333, October, 1996.The authors wish to express their gratitude to C.I.Gandzha, V.V.Kul'beda, and Yu. M. Gavrilyuk from the Solar Physics Department of the PAO of the Ukrainian NAS and to the Board of Directors of the Observatory and of the High-Altitude Station for help in the development of the instrument.This paper is dedicated to the memory of E. A. Gurtovenko, D.Sc. in Phys. and Math., who initiated the installation of the telescope at Peak Terskol and who was the leader, an executor, and an observer in this project.     

A relationship between the Mahler measure and the discriminant of algebraic numbers

In this note we show that in the well-known Dobrowolski estimate lnM() (ln lnd/ lnd)3,d , where is a nonzero algebraic number of degreed that is not a root of unity andM() is its Mahler measure, the parameterd can be replaced by the quantity=d/() ^1/d, where () is the modulus of the discriminant of. To this end, must satisfy the condition deg ^p=deg for any primep.Translated fromMatematicheskie Zametki, Vol. 59, No. 3, pp. 415–420, March, 1996.     

Synthesis, crystal structure, and nonlinear optical behavior of beta-unsubstituted meso-meso E-vinylene-linked porphyrin dimers

[structure: see text] A vinylene-linked porphyrin dimer, with no substituents at the beta-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the crystal structure of this dimer, the C(2)H(2) bridge is twisted by 45 degrees relative to the plane of the porphyrins. The absorption, emission spectra, and electrochemistry reveal substantial porphyrin-porphyrin pi-conjugation. The triplet excited-state absorption spectrum of this dimer makes it suitable for reverse saturable absorption at 710-900 nm.     

A physico-chemical study of iron-chromium-molybdenum catalysts

In the study of the Fe_1–xCr_xMo_1·5O₆ system by X-ray, IR and Mössbauer methods the formation of solid state substitution solutions has been detected, which possess similar catalytic properties in methanol oxidation.

---

, , Fe_1–xMo_1·5O₆ , .

     

Ultrafast energy-electron transfer cascade in a multichromophoric light-harvesting molecular square

A molecular square with dimensions of about 4 nm, incorporating sixteen pyrene chromophores attached to four ditopic bay-functionalized perylene bisimide chromophores, has been synthesized by coordination to four Pt(II) phosphine corner units and fully characterized via NMR spectroscopy and ESI-FTICR mass spectrometry. Steady-state and time-resolved emission as well as femtosecond transient absorption studies reveal the presence of a highly efficient (>90%) and fast photoinduced energy transfer (k(en) approximately equal to 5.0 x 10(9) s(-1)) from the pyrene to the perylene bisimide chromophores and a very fast and efficient electron transfer (>94%, k(et) approximately equal to 5 x 10(11) up to 43 x 10(11) s(-1)). Spectrotemporal parametrization indicates upper excited-state electron-transfer processes, various energy and electron-transfer pathways, and chromophoric heterogeneity. Temperature-dependent time-resolved emission spectroscopy has shown that the acceptor emission lifetime increases with decreasing temperature from which an electron-transfer barrier is obtained. The extremely fast electron-transfer processes (substantially faster and more efficient than in the free ligand) that are normally only observed in solid materials, together with the closely packed structure of 20 chromophoric units, indicate that we can consider the molecular square as a monodisperse nanoaggregate: a molecularly defined ensemble of chromophores that partly behaves like a solid material.