Transition-metal-complexed cyclic [3]- and [4]pseudorotaxanes containing rigid ring-and-filament conjugates: synthesis and solution studies

By using the "gathering-and-threading" effect of copper(I) with rigid ring-and-string conjugates, daisy-chain-type [3]- and [4]pseudorotaxanes could be prepared in high yields. The organic fragment used consisted of a 2,9-diphenyl-1,10-phenanthroline (dpp)-containing ring attached to a coordinating filament capable of threading through the ring of another molecule by coordination to copper(I). The bidentate chelate introduced in the axis was also a 1,10-phenanthroline (phen) derivative with two methyl groups ortho to the nitrogen atoms of the phen unit. The organic component was prepared following a multistep strategy, one of the key steps being the attachment of the ring to the lateral axis. This connection was done by a condensation reaction between an ortho dione located at the back of a ring-incorporated phen and an aromatic aldehyde, which was the end-function of the thread. An oxazole nucleus was obtained after the condensation, which provided a rigid connection between the ring and the axis. In this way, the coordination axes of the ring-incorporated bidentate chelate and of the ligand belonging to the lateral filament were approximately orthogonal to one another. The design was such that the tetrameric complex, a [4]pseudorotaxane, seemed to be the most stable species, owing to the mutual geometrical arrangement of the filament and the ring. Various spectroscopic techniques, such as (1)H NMR spectroscopy, including DOSY, and electrospray ionization mass spectroscopy (ESI-MS), clearly demonstrated that a mixture of cyclic [3]- and [4]pseudorotaxane was obtained; the proportions of both components depended on concentration and temperature. Copper(I) was not the only metal center leading to the formation of cyclic pseudorotaxanes. A similar effect was observed with silver(I) as the templating metal: quantitative formation of threaded species was observed, with a higher proportion of trimer over tetramer than in the copper(I) case. Concentration and temperature effects were investigated for both series of Cu(I) - and Ag(I) -complexed threaded species showing that formation of the trimer was favored upon dilution or heating of the solution.     

Bernstein�CWalsh Type Theorems for Real Analytic Functions in Several Variables

The aim of this paper is to extend the classical maximal convergence theory of Bernstein and Walsh for holomorphic functions in the complex plane to real analytic functions in ℝ ^N . In particular, we investigate the polynomial approximation behavior for functions F:L→ℂ, L={(Re z,Im z):z∈K}, of the structure F=g[`(h)]F=g\overline{h}, where g and h are holomorphic in a neighborhood of a compact set K⊂ℂ <sup>N</sup> . To this end the maximal convergence number ρ(S <sub>c</sub> ,f) for continuous functions f defined on a compact set S <sub>c</sub> ⊂ℂ <sup>N</sup> is connected to a maximal convergence number ρ(S <sub>r</sub> ,F) for continuous functions F defined on a compact set S <sub>r</sub> ⊂ℝ <sup>N</sup> . We prove that ρ(L,F)=min {ρ(K,h)),ρ(K,g)} for functions F=g[`(h)]F=g\overline{h} if K is either a closed Euclidean ball or a closed polydisc. Furthermore, we show that min {ρ(K,h)),ρ(K,g)}≤ρ(L,F) if K is regular in the sense of pluripotential theory and equality does not hold in general. Our results are based on the theory of the pluricomplex Green’s function with pole at infinity and Lundin’s formula for Siciak’s extremal function Φ. A properly chosen transformation of Joukowski type plays an important role.     

Observation of bi-polarons in blends of conjugated copolymers and fullerene derivatives

From a fundamental and application point of view it is of importance to understand how charge carrier generation and transport in a conjugated polymer (CP):fullerene blend are affected by the blend morphology. In this work light-induced electron spin resonance (LESR) spectra and transient ESR response signals are recorded on non-annealed and annealed blend layers consisting of alkyl substituted thieno[3,2-b]thiophene copolymers (pATBT) and the soluble fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) at temperatures ranging from 10 to 180 K. Annealing of the blend sample leads to a reduction of the steady state concentration of light-induced PCBM anions within the blend at low temperatures (T = 10 K) and continuous illumination. This is explained on the basis of the reducing interfacial area of the blend composite on annealing, and the high activation energy for electron diffusion in PCBM blends leading to trapped electrons near the interface with the CP. As a consequence, these trapped electrons block consecutive electron transfer from an exciton on a CP to the PCBM domain, resulting in a relatively low concentration charge carriers in the annealed blend. Analysis of the transient ESR data allows us to conclude that in annealed samples diamagnetic bi-polaronic states on the CPs are generated at low temperature. The formation of these states is related to the generation and interaction of multiple positive polarons in the large crystalline polymer domains present in the annealed sample.     

An effective force field for molecular dynamics simulations of dimethyl sulfone

A rigid five-site united atom model for dimethyl sulfone (DMSO₂) compatible with the GROMOS force field is parametrized and tested. The parameters were optimized with respect to experimental quantities such as liquid density, heat of vaporization, shear viscosity and excess free energy. Good agreement with pure component properties is achieved except for the static dielectric permittivity which is calculated too low. Together with the SPC model for water the new DMSO₂ model was used to study aqueous mixtures at low concentrations and compared to aqueous mixtures of DMSO. It is concluded that interaction parameters for sulfoxide oxygen are not directly transferable to sulfonyl oxygen.     

Noncommutative spin-1/2 representations

In this letter we apply the methods of our previous paper, hep-th/0108045, to noncommutative fermions. We show that the fermions form a spin-1/2 representation of the Lorentz algebra. The covariant splitting of the conformal transformations into a field-dependent part and a -part implies the Seiberg-Witten differential equations for the fermions. Received: 5 December 2001 / Published online: 22 May 2002     

Studies on photoinduced effects in pulse-electrodeposited Ag/Hg-1212/CdSe hetero-nanostructures

Metal/superconductor/semiconductor (Ag/Hg-1212/CdSe) hetero-nanostructures have been fabricated using pulse-electrodeposition technique and are characterized by X-ray diffraction (XRD), full-width at half-maximum (FWHM) and scanning electron microscopy (SEM) studies. The junction capacitance of Ag/Hg-1212, Hg-1212/CdSe and Ag/Hg-1212/CdSe heterojunctions is measured in dark and under laser irradiation at room temperature. The nature of the junction formed and built-in-junction potentials were determined. The increase in carrier concentration across the junction due to photo-irradiation has been observed.     

Effect of laser irradiation of C-V characteristics of electrodeposited Ag/Tl-2223/CdSe hetero-nanostructures

One of the innovative technological directions for the high-temperature superconductors has been persued by fabricating the heteroepitaxial multilayer structures such as superconductor-semiconductor heterostructures. In the present investigation, metal/superconductor/semiconductor (Ag/Tl-2223/CdSe) hetero-nanostructures have successfully been fabricated using dc electrodeposition technique and were characterized by X-ray diffraction (XRD), full-width at half-maximum (FWHM) and scanning electron microscopy (SEM) studies. The measurement of junction capacitance as a function of biasing voltage was used for the estimation of junction built-in-potential (V _D) and to study the charge distribution in a heterojunction. The Mott-Schottky plots were measured for each junction in dark and under the photo-irradiation. The effect of laser irradiation on C-V characteristics of hetero-nanostructure has been studied.     

Analysis of Coulomb displacement energies and its relation to the proton halo structure of nuclei

We investigate the Coulomb displacement energies of the nuclear systems¹⁶ O core plus several nucleons. This analysis is performed in order to search for peculiarities of the nucleus²⁰Mg which was experimentally found to be a candidate for the occurrence of a proton halo. The structure of²⁰ Mg is discussed on the basis of this analysis. Some evidence is presented that proton correlations play an important role in the structure of this nucleus.