Optical properties of new organic conductors based on the BEDT-TSeF molecule (the κ-(BETS)4Hg2.84Br8 superconductor and κ-(BETS)4Hg3Cl8 Metal) in the range 300–15 K

Polarized reflectance and optical conductivity spectra of single crystals of two new isostructural organic conductors based on the BEDT-TSeF molecule, namely, the κ-(BETS)₄Hg_2.84Br₈ superconductor (T _c =2 K) and the κ-(BETS)₄Hg₃Cl₈ metal, which undergoes a smooth transition to the dielectric state near 35 K, have been obtained in the spectral region 700–6500 cm⁻¹ at temperatures of 300–15 K. At 300 K, the spectra of both compounds are nearly identical and differ from the Drude spectrum characteristic of metals. The nature of the observed difference is discussed, and the spectra are described in terms of a cluster approach with inclusion of electron-electron correlations in the Hubbard approximation combined with the Drude model. The parameters of the theory were determined, including the electron transfer integrals between molecules in a cluster. The spectra in the conducting plane of the crystals were found to be essentially anisotropic, which should be assigned to specific features of in-plane interaction between molecules. The spectra of the superconductor and the metal become increasingly different as the temperature is lowered. The spectra of the metal obtained for T<150 K exhibit splitting of the broad electronic maximum in the mid-IR region into two bands, which is accompanied by a splitting of a vibronic feature deriving from electron interaction with intramolecular BETS vibrations of ν₃(A _g ) symmetry. No such splitting is observed in the superconductor spectra with decreasing temperature. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 11, 2004, pp. 1921–1929. Original Russian Text Copyright ? 2004 by Vlasova, Drichko, Petrov, Semkin, Zhilyaeva, Lyubovskaya, Olejniczak, A. Kobayashi, H. Kobayashi.     

Characterization of protein-ligand interactions by high-resolution solid-state NMR spectroscopy

A novel approach for detection of ligand binding to a protein in solid samples is described. Hydrated precipitates of the anti-apoptotic protein Bcl-xL show well-resolved (13)C-(13)C 2D solid-state NMR spectra that allow site-specific assignment of resonances for many residues in uniformly (13)C-enriched samples. Binding of a small peptide or drug-like organic molecule leads to changes in the chemical shift of resonances from multiple residues in the protein that can be monitored to characterize binding. Differential chemical shifts can be used to distinguish between direct protein-ligand contacts and small conformational changes of the protein induced by ligand binding. The agreement with prior solution-state NMR results indicates that the binding pocket in solid and liquid samples is similar for this protein. Advantages of different labeling schemes involving selective (13)C enrichment of methyl groups of Ala, Val, Leu, and Ile (Cdelta1) for characterizing protein-ligand interactions are also discussed. It is demonstrated that high-resolution solid-state NMR spectroscopy on uniformly or extensively (13)C-enriched samples has the potential to screen proteins of moderate size ( approximately 20 kDa) for ligand binding as hydrated solids. The results presented here suggest the possibility of using solid-state NMR to study ligand binding in proteins not amenable to solution NMR.     

Complexing equilibria and redox potentials of the Ag(II)/Ag(I) system in the presence of 2,2′:6′,2″-terpyridine in water

Summary The conditional protonation constants (=0.1) for 2,2:6,2-terpyridine, logK ₁=4.93, logK ₂=3.69, were determined by thepH-metric method. The compositions of complexes of Ag²⁺ and Ag⁺ ions with 2,2:6,2-terpyridine (tp) were studied and equilibria of the complex formation process were described. The values of conditional complex formation constants are as follows: for Ag(tp) ₂ ⁺ :log₀₁=5.79, log₀₂=9.68, for Ag(tp) ₂ ²⁺ :log₀₂=25.31, while the conditional constant of the Ag(tp)NO₃ precipitate formation is:K _SO=2.45·10⁴. Using coulometric and chronovoltamperometric measurements, the redox systems being formed in the complex solutions of Ag(II) and Ag(I) were determined and described including their formal potentials.

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Komplexibildungsgleichgewichte und Redoxpotentiale des Systems Ag(II)/Ag(I) in Gegenwart von 2,2:6,2-Terpyridin in Wasser

Zusammenfassung Mit Hilfe derpH-metrischen Methode wurden die konditionalen Protonationskonstanten (=0.1) von 2,2:6,2-Terpyridin bestimmt: logK ₁=4.93, logK ₂=3.69. Es wurde auch die Zusammensetzung der Komplexe von Ag(II) und Ag(I) mit 2,2:6,2-Terpyridin(tp) bestimmt sowie die Gleichgewichte der komplexbildung beschrieben. Die Werte der Konditionalkomplexbildungskonstanten sind: für Ag(tp) ₂ ⁺ :log₀₁=5.79, log₀₂=9.68, für Ag(tp) ₂ ²⁺ :log₀₂=25.31 und für das Löslichkeitsprodukt Ag(tp)NO₃:K _SO ^–1 =4.08·10^–5. Die in Komplexlösungen von Ag(II) und Ag(I) vorliegenden Redoxsysteme wurden mittels cyclischer Voltametrie und Coulometrie untersucht und die Formalpotentialwerte dieser Systeme in Wasser bestimmt.

     

ON THE CONVERGENCE OF THE PARABOLIC APPROXIMATION OF A CONSERVATION LAW IN SEVERAL SPACE DIMENSIONS

1.IntrodnctionWegiveaproofofthestrongconvergenceinofthesolutionoftheparabolicapproximationtowardstheentropicsolutiontothescalarconservationlawwhereuo(RN),udenotessomeapproximationofuosuchthatandthefluxfsatisfiesTheconvergenceoftheapproximatesolutions...     

Deuteron NMR spectra of ammonium ion isotopomers at low temperatures

Partially deuterated ammonium compounds contain ammonium ion isotopomers with relative abundances given by the binomial distribution of protons and deuterons. All isotopomers with deuterons contribute characteristic deuteron NMR spectra at 5K. Experimental NMR spectra were separated and respective contributions of isotopomers were determined. The derived contributions agree with expected values for a given deuteration in the case of ammonium hexafluorophosphate. In ammonium hexachlorotellurate both NH2D2+ and about 50% of NH3D+ ions are rigid, while the remaining NH3D+ perform limited jumps. NHD3+ and ND4+ ions undergo tunnelling rotation, NH3D+ ions perform either jumps about C2 axis or limited jumps, but some stay rigid in ammonium hexachlorostannate. NH2D2+, NHD 3+ and ND4+ undergo rotational tunnelling. In the case of ammonium perchlorate, the NH3D+ ions perform either jumps about C3 axis or limited jumps whilst some remain rigid. Very low values of activation energies were derived for all spectral components from the temperature dependence of their spectra, up to about 20K, which indicates an incoherent tunnelling nature of the observed dynamic processes. The diverse mobility of NH3D+ ions appears to be the most interesting and new feature.     

STM/STS investigation of carbon nanotube junctions

In this paper we present scanning tunneling microscopy/spectroscopy investigations of multiwall carbon nanotube junctions. We concentrated on bent and narrowing junctions, which my be formed by introducing pentagon–heptagon defects into a hexagonal network of a carbon nanotube. It was expected that the defects introduced to the nanotube could cause changes in the local density of states. The scanning tunneling spectroscopy results were used to search for and identify these defects. We also discuss a hypothesis for a combination of a telescope junction and a pentagon–heptagon induced junction. PACS 68.37.Ef; 73.22.–f; 61.46.Fg; 71.20.Tx     

Room and high-temperature scanning tunnelling microscopy and spectroscopy (HT-STM/STS) investigations of surface nanomodifications created on the TiO2(1 1 0) surface

High-temperature scanning tunnelling microscopy, scanning tunnelling spectroscopy and current imaging tunnelling spectroscopy (HT-STM/STS/CITS) were used to study the topographic and electronic structures changes due to surface modifications of the TiO₂(1 1 0) surface caused by the STM tip. In situ high-temperature STM results showed that the created modifications were stable even at elevated temperatures. The STS/CITS results showed the presence of energy gap below the Fermi level on the untreated regions. The disappearance of energy gap below the Fermi level on the modifications created by the tip was observed. It is assumed that the presence of the tip can change the chemical stoichiometry of the surface from TiO_2−x towards Ti₂O₃.     

Experimental and Theoretical Investigation of Vibrational Spectra of Coordination Polymers Based on TCE‐TTF

The room‐temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7‐tetrakis(2‐cyanoethylthio)‐tetrathiafulvalene (TCE‐TTF) with paramagnetic (Co^II, Mn^II) and diamagnetic (Zn^II, Cd^II) ions, together with BF₄^? or ClO₄^? anions are reported. Infrared and Raman‐active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE‐TTF using density functional theory (DFT) methods. It is confirmed that the TCE‐TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C?C stretching vibrations of TCE‐TTF are analyzed assuming the occurrence of electron–molecular vibration coupling (EMV). The presence of the antisymmetric C?C dimeric mode provides evidence that charge transfer takes place between TCE‐TTF molecules belonging to neighboring polymeric networks.     

Solid-State Dynamics and High-Pressure Studies of a Supramolecular Spiral Gear

The structures and solid-state dynamics of the supramolecular salts of the general formula [(12-crown-4)₂ ⋅ DABCOH₂](X)₂ (where DABCO=1,4-diazabicyclo[2.2.2]octane, X=BF₄, ClO₄) have been investigated as a function of temperature (from 100 to 360 K) and pressure (up to 3.4 GPa), through the combination of variable-temperature and variable-pressure XRD techniques and variable-temperature solid-state NMR spectroscopy. The two salts are isomorphous and crystallize in the enantiomeric space groups P3₂2₁ and P3₁2₁. All building blocks composing the supramolecular complex display dynamic processes at ambient temperature and pressure. It has been demonstrated that the motion of the crown ethers is maintained on lowering the temperature (down to 100 K) or on increasing the pressure (up to 1.5 GPa) thanks to the correlation between neighboring molecules, which mesh and rotate in a concerted manner similar to spiral gears. Above 1.55 GPa, a collapse-type transition to a lower-symmetry ordered structure, not attainable at a temperature of 100 K, takes place, proving, thus, that the pressure acts as the means to couple and decouple the gears. The relationship between temperature and pressure effects on molecular motion in the solid state has also been discussed.