Synthesis and Photophysical Properties of a Sc3N@C80‐Corrole Electron Donor–Acceptor Conjugate

Embedding endohdedral metallofullerenes (EMFs) into electron donor–acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3‐dipolar cycloaddition reaction of a corrole‐based precursor with Sc₃N@C₈₀ to regioselectively form a [5,6]‐adduct ( 1 ). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]‐bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1 . In the electronically excited state, which is probed in photophysical assays with 1 , a fast electron‐transfer yields the radical ion pair state consisting of the one‐electron‐reduced Sc₃N@C₈₀ and of the one‐electron‐oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.     

Observation of the neutron radiative decay

The aim of this work is the experimental observation of and research into a rare neutron mode, the radiative beta decay, where a new particle, the radiative gamma quantum, is formed along with the expected decay products: a beta electron, a recoil proton, and an antineutrino. The discovery of this rare neutron decay mode was conducted through identification of triple-coincidence events: simultaneous registration of a beta electron, a proton, and a radiative gamma quantum. The ordinary neutron decay was registered by double coincidences of a beta electron and a recoil proton. The statistics collected allow one to deduce the branching ratio (BR) BR = (3.2 ± 1.6) × 10⁻³ (90% C.L.) in the gamma energy region greater than 35 keV. This value of BR is consistent with standard electroweak theory. The text was submitted by the authors in English. An erratum to this article is available at .     

LIDAR mapping of ozone-episode dynamics in Paris and intercomparison with spot analyzers Supplementary material available at http://link.springer.de/journals/apb

Continuous mapping of an ozone episode in Paris in June 1999 has been performed using a differential absorption lidar system. The 2D ozone concentration vertical maps recorded over 33 h at the Champ de Mars are compiled in a video clip that gives access to local photochemical dynamics with unprecedented precision. The lidar data are compared over the whole period with point monitors located at 0-, 50-, and 300-m altitudes on the Eiffel Tower. Very good agreement is found when spatial resolution, acquisition time, and required concentration accuracy are optimized. Sensitivity to these parameters for successful intercomparison in urban areas is discussed. Received: 11 February 2002 / Published online: 14 March 2002     

Effect of nanotube functionalization on the properties of single‐walled carbon nanotube/polyurethane composites

A commercially available aliphatic thermoplastic polyurethane formulated with a methylene bis(cyclohexyl) diisocyanate hard segment and a poly(tetramethylene oxide) soft segment and chain‐extended with 1,4‐butanediol was dissolved in dimethylformamide and mixed with dispersed single‐walled carbon nanotubes. The properties of composites made with unfunctionalized nanotubes were compared with the properties of composites made with nanotubes functionalized to contain hydroxyl groups. Functionalization almost eliminated the conductivity of the tubes according to the conductivity of the composites above the percolation threshold. In most cases, functionalized and unfunctionalized tubes yielded composites with statistically identical mechanical properties. However, composites made with functionalized tubes did have a slightly higher modulus in the rubbery plateau region at higher nanotube fractions. Small‐angle X‐ray scattering patterns indicated that the dispersion reached a plateau in the unfunctionalized composites that was consistent with the plateau in the rubbery plateau region. The room‐temperature modulus and tensile strength increase was proportionally higher than almost all increases seen previously in thermoplastic polyurethanes; however, the increase was still an order of magnitude below what has been reported for the best nanotube–polymer systems. Nanotube addition increased the hard‐segment glass transition temperature slightly, whereas the soft‐segment glass transition was so diffuse that no conclusions could be drawn. Unfunctionalized tubes suppressed the crystallization of the hard segment; whereas functionalized tubes had no effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 490–501, 2007     

Long-Range proton-proton coupling constants. I. Propanic coupling involving a methyl group 4JMeH

An equation is formulated on the basis of theoretical INDO/FPT calculations which describes the angular dependence of the propanic long-range coupling constant ⁴J_MeH in substituted HCCCH₃ fragments. This equation is a truncated Fourier series in the torsion angle ?, HCCMe, which takes into account the dependence of the Fourier coefficients on the bond angle θ, CCMe. The substituent effects are assumed to be additive. Some parameters in the equation may be obtained from the ⁴J_MeH couplings in propane and neopentane derivatives. The calculated effect upon ⁴J_MeH of changes in the bond angle θ is significant and it seems to be in part the cause of some effects which have been attributed to conformational dependence.     

Investigation of turbomixers in continuous flow analysis

This paper describes an investigation of turbomixers as replacements for mixing coils in FIA. The turbomixer is a device that will efficiently mix three streams simultaneously. Although the traditional FIA gradient is not produced, the data shows that the reproducibility of a turbomixer continuous flow system is comparable to a standard FIA system.     

MO-LCAO Calculations of Polymethines

Idealized polymethines are defined as conjugated chain molecules with complete bond equilization and charge alternation. A constant π-bond order along the chain with N atoms has been derived for three types of polymethines which differ by the nature of the heteroatomic end groups. Corresponding to the number of π-electrons they are termined (N + 1)π-, Nπ- or (N ? 1)π-polymethines. This classification embraces closed shell as well as open shell systems. The relations for the energy eigenvalues, coefficients and derived quantities have been obtained in closed form. The results for the different classes of polymethines are strongly related. Their molecular properties should be similar.