Electron spin dynamics in photoexcited diamagnetic and paramagnetic corroles

Three corroles, which differ by their cavity's core, namely, diamagnetic free-base tris(pentafluorophenyl)corrole and its gallium(III) complex and the paramagnetic oxo-chromium(V) complex, were studied by steady-state and time-resolved electron paramagnetic resonance (EPR) spectroscopy. The magnetic and orientational parameters of the corroles, oriented in a nematic liquid crystal, were determined and interpreted in terms of their structure, geometry, and excited states spin dynamics. It was shown that both diamagnetic corroles, photoexcited to their triplet states, exhibit similar EPR line shapes, which is characterized by a negative zero-field splitting parameter, D, whose origin is due to molecular "stretching". Photoexcited Cr(V)O-corrole exhibits polarized ground-state EPR spectrum in emission mode. This polarization stems from the sequence of photophysical and photochemical reactions, involving the formation of the trip-quartet/trip-doublet composite states and their selective quenching via a charge transfer state.     

On the interactions of free radicals with gold nanoparticles

Electron paramagnetic resonance (EPR) spectroscopy was used to study the interactions between stable free radicals and gold nanoparticles. The nitroxyl free radicals used were TEMPO, TEMPAMINE, and TEMPONE. Two sizes of Au particles, 15 and 2.5 nm in diameter, were synthesized to investigate the interactions with the metallic particles. We find that the EPR signal is reduced upon adsorption of the radicals onto the 15 nm Au particle surface. Despite the strong adsorption of TEMPAMINE on the particles, the signal intensity recovers upon the introduction of a high concentration of ethanolamine to the solution. The signal reduction was proportional to the concentration of Au particles, and the signal totally disappeared at high concentrations of Au particles. Possible explanations of the signal reduction are discussed in this Article. We propose that the reduction in signal intensity arises from exchange interactions between the unpaired electrons of the adsorbed radicals and conduction-band electrons of the metallic particles. In addition, in the presence of oxygen, the adsorbed TEMPAMINE radicals are catalytically oxidized to the carbonyl derivative, TEMPONE. A mechanism for this unexpected catalytic reaction is proposed.     

Microsolvation of a partially bonded complex by non-polar and weakly polar microsolvents: a microwave and ab initio study of HCN–SO3–Ar and HCN–SO3–CO – ARTICLE WITHDRAWN

WITHDRAWN TO APPEAR IN SPECIAL ISSUE IN 2007     

A computer‐supplemented revision course

The authors have developed a computer‐supplemented course suitable for use as a revision aid in obstetrics and gynaecology. It can be used on an interactive basis using time‐sharing facilities. Additional notes are printed out for each question. It provides individualized instruction but is also suitable for small group discussion.     

Filling factor of a paramagnetic sample in a rectangular cavity: theory and application

A computational method is presented for calculating the filling factor of an electron paramagnetic resonance (EPR) tube in a rectangular TE102 cavity. The algorithm employs the conventional finite element method. In addition to the filling factor, the algorithm allows to calculate the quality factor and the reflection coefficient of the loaded cavity. This method allows calculating very accurately the EPR signal intensities from which the spin concentration of paramagnetic samples can be determined. A comparison between the predicted EPR signal intensities to several experimental results was found to be satisfactory. The method also allows optimizing the EPR tube dimensions and its glass quality to improve measurement sensitivity.     

Transitivity and Dense Periodicity for Graph Maps

In 1984, Blokh proved [A. M. Blockh, On transitive mappings of one-dimensional branched manifolds, Differential-Difference Equations and Problems of Mathematical physics (Russian), Akad. Nauk Ukrain. SSR Inst. Mat., Kiev, 131, pp. 3–9, 1984] that any topologically transitive continuous map from a graph into itself which has periodic points has a dense set of periodic points and has positive topological entropy (in this proof a crucial role is played by the specification property, which implies these two statements). Also, he characterized the topologically transitive continuous graph maps without periodic points. Unfortunately, this clever paper is only available in Russian (except for a translation to English of the statements of the theorems without proofs—see [A. M. Blockh, The connection between entropy and transitivity for one-dimensional mappings, Uspekhi Mat. Nauk, 42(5(257)) (1987), pp. 209–210]).     

Discrete Dichotomies and Asymptotic Behavior for Abstract Retarded Functional Difference Equations in Phase Space

We study the problem of asymptotic behavior between weighted bounded solutions of a system of homogeneous linear functional difference equations and its perturbation under non-classical dichotomic properties and also we obtain some results about approximation. We apply our results to Volterra difference systems with infinite delay.     

Photoexcited state properties of H2-porphyrin/C60-based rotaxanes as studied by time-resolved electron paramagnetic resonance spectroscopy

Light-driven intramolecular electron transfer (ET) and energy transfer (EnT) processes in two rotaxanes, the first containing two free base porphyrins and C(60) fullerene moieties incorporated around a Cu(I)bisphenanthroline core ((H(2)P)(2)-Cu(I)(phen)(2)-C(60)) and a second lacking the fullerene moiety ((H(2)P)(2)-Cu(I)(phen)(2)), were studied by X-band (9.5 GHz) time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The experiments were performed in frozen toluene and ethanol and different phases of the nematic liquid crystal (E-7). It is demonstrated that the ET and EnT processes in the (H(2)P)(2)-Cu(I)(phen)(2)-C(60) rotaxane in different media result in the formation of the same charge-separated state, namely (H(2)P)(2)(?+)-Cu(I)(phen)(2)(?-)-C(60), while photoexcitation of the (H(2)P)(2)-Cu(I)(phen)(2) rotaxane does not induce noticeable transfer processes in these matrices. The results are discussed in terms of the high conformational mobility of the rotaxanes, which enables changes in the molecular topography and resultant modification of the rates and routes of photoinduced processes occurring in these systems. The parameters of the transfer processes are compared with those obtained in our previous study of (ZnP)(2)-Cu(I)(phen)(2)-C(60) and (ZnP)(2)-Cu(I)(phen)(2) rotaxanes under the same experimental conditions.