PHOTOINDUCED ELECTRON TRANSFER IN A CAROTENOBUCKMINSTERFULLERENE DYAD

A carotenoid-fullerene dyad has been synthesized by condensing a carotenoid amine with an acid group attached to C₆₀ by a cyclopropane-based linkage. The lowest excited singlet state of the fullerene is strongly quenched by electron transfer from the carotenoid moiety to generate the charge-separated species Car⁺-C₆₀^.-. In CS₂ solution Car⁺-C₆₀^.- has a rise time of 0.8 ps and decays by charge recombination in 534 ps. Light absorbed by either chromophore produces a high yield of Car⁺-C₆₀^.-, which implies that internal conversion in the carotenoid is negligible. The lowest triplet level in the dyad is localized on the carotenoid and is populated in low yield from the charge-separated species. The sensitization of singlet oxygen by the fullerene component is effectively curtailed in the dyad.     

Observation of self-amplified spontaneous emission and exponential growth at 530 nm

Experimental evidence for self-amplified spontaneous emission (SASE) at 530 nm is reported. The measurements were made at the low-energy undulator test line facility at the Advanced Photon Source, Argonne National Laboratory. The experimental setup and details of the experimental results are presented, as well as preliminary analysis. This experiment extends to shorter wavelengths the operational knowledge of a linac-based SASE free-electron laser and explicitly shows the predicted exponential growth in intensity of the optical pulse as a function of length along the undulator.     

Effects of Citrus aurantium (bitter orange) fruit extracts and p-synephrine on metabolic fluxes in the rat liver

The fruit extracts of Citrus aurantium (bitter orange) are traditionally used as weight-loss products and as appetite supressants. An important fruit component is p-synephrine, which is structurally similar to the adrenergic agents. Weight-loss and adrenergic actions are always related to metabolic changes and this work was designed to investigate a possible action of the C. aurantium extract on liver metabolism. The isolated perfused rat liver was used to measure catabolic and anabolic pathways, including oxygen uptake and perfusion pressure. The C. aurantium extract and p-synephrine increased glycogenolysis, glycolysis, oxygen uptake and perfusion pressure. These changes were partly sensitive to α- and β-adrenergic antagonists. p-Synephrine (200 μM) produced an increase in glucose output that was only 15% smaller than the increment caused by the extract containing 196 μM p-synephrine. At low concentrations the C. aurantium extract tended to increase gluconeogenesis, but at high concentrations it was inhibitory, opposite to what happened with p-synephrine. The action of the C. aurantium extract on liver metabolism is similar to the well known actions of adrenergic agents and can be partly attributed to its content in p-synephrine. Many of these actions are catabolic and compatible with the weight-loss effects usually attributed to C. aurantium.     

Strong lensing of gravitational waves as seen by LISA

We discuss strong gravitational lensing of gravitational waves from the merging of massive black hole binaries in the context of the LISA mission. Detection of multiple events would provide invaluable information on competing theories of gravity, evolution and formation of structures and, possibly, constraints on H0 and other cosmological parameters. Most of the optical depth for lensing is provided by intervening massive galactic halos, for which wave optics effects are negligible. Probabilities to observe multiple events are sizable for a broad range of formation histories. For the most optimistic models, up to ? 4 multiple events with a signal to noise ratio ? 8 are expected in a 5-year mission. Chances are significant even for conservative models with either light (? 60%) or heavy (? 40%) seeds. Because of lensing amplification, some intrinsically too faint signals are brought over threshold (? 2 per year).     

Acoustic and perceptual evaluation of Mandarin tone productions before and after perceptual training

Training American listeners to perceive Mandarin tones has been shown to be effective, with trainees' identification improving by 21%. Improvement also generalized to new stimuli and new talkers, and was retained when tested six months after training [Y. Wang et al., J. Acoust. Soc. Am. 106, 3649-3658 (1999)]. The present study investigates whether the tone contrasts gained perceptually transferred to production. Before their perception pretest and after their post-test, the trainees were recorded producing a list of Mandarin words. Their productions were first judged by native Mandarin listeners in an identification task. Identification of trainees' post-test tone productions improved by 18% relative to their pretest productions, indicating significant tone production improvement after perceptual training. Acoustic analyses of the pre- and post-training productions further reveal the nature of the improvement, showing that post-training tone contours approximate native norms to a greater degree than pretraining tone contours. Furthermore, pitch height and pitch contour are not mastered in parallel, with the former being more resistant to improvement than the latter. These results are discussed in terms of the relationship between non-native tone perception and production as well as learning at the suprasegmental level.     

Stereoselective total synthesis of 1α,25S,26-trihydroxycholecalciferol

A total synthesis of 1α,25S,26-trihydroxycholecalciferol (2) has been accomplished via an efficient convergent approach. The remote chiral center at C-25 was introduced by a regiospecific and diastereoselective 1,3-dipolar cycloaddition of the C-23 nitrone 27 with methyl methacrylate. Subsequent transformation of the resulting isoxazolidine led to the key synthon 3, which on coupling to the anion 4 and deprotection produced the metabolite 2.     

Streaming maxima in the iodine electroreduction at Hg electrodes in DMSO solutions

A current maximum was observed by d.c. polarography during the electroreduction of iodine at Hg electrodes in DMSO solutions. i?t curves during the drop life were performed to characterize the observed maxima. Changes in the cation of the supporting electrolyte do not. appreciably affect the results. The dependence of the streaming with depolarizer and supporting electrolyte concentration, as well as its independence of flux rate confirmed by linear sweep potential experiments at a hanging mercury electrode, permit us to classify the streaming under study as a positive first kind streaming. Regular current fluctuations at a certain depolarizer concentration and low supporting electrolyte concentration are also reported.     

Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires

Designing molecular platforms for controlling proton and electron movement in artificial photosynthetic systems is crucial to efficient catalysis and solar energy conversion. The transfer of both protons and electrons during a reaction is known as proton-coupled electron transfer (PCET) and is used by nature in myriad ways to provide low overpotential pathways for redox reactions and redox leveling, as well as to generate bioenergetic proton currents. Herein, we describe theoretical and electrochemical studies of a series of bioinspired benzimidazole-phenol (BIP) derivatives and a series of dibenzimidazole-phenol (BI₂P) analogs with each series bearing the same set of terminal proton-accepting (TPA) groups. The set of TPAs spans more than 6 pK_a units. These compounds have been designed to explore the role of the bridging benzimidazole(s) in a one-electron oxidation process coupled to intramolecular proton translocation across either two (the BIP series) or three (the BI₂P series) acid/base sites. These molecular constructs feature an electrochemically active phenol connected to the TPA group through a benzimidazole-based bridge, which together with the phenol and TPA group form a covalent framework supporting a Grotthuss-type hydrogen-bonded network. Infrared spectroelectrochemistry demonstrates that upon oxidation of the phenol, protons translocate across this well-defined hydrogen-bonded network to a TPA group. The experimental data show the benzimidazole bridges are non-innocent participants in the PCET process in that the addition of each benzimidazole unit lowers the redox potential of the phenoxyl radical/phenol couple by 60 mV, regardless of the nature of the TPA group. Using a series of hypothetical thermodynamic steps, density functional theory calculations correctly predicted the dependence of the redox potential of the phenoxyl radical/phenol couple on the nature of the final protonated species and provided insight into the thermodynamic role of dibenzimidazole units in the PCET process. This information is crucial for developing molecular “dry proton wires” with these moieties, which can transfer protons via a Grotthuss-type mechanism over long distances without the intervention of water molecules.

Experimental and theoretical methods characterize the thermodynamics of electrochemically driven proton-coupled electron transfer processes in bioinspired constructs involving multiple proton translocations over Grotthus-type proton wires.     

Influence of Polyfluorinated Side Chains and Soft-Template Method on the Surface Morphologies and Hydrophobic Properties of Electrodeposited Films from Fluorene Bridged Dicarbazole Monomers

A clear case of relationship between the monomer molecular structure and the capability of tuning the morphology of electrodeposited gas bubbles template polymer thin films is shown. To this end, a series of fluorene-bridged dicarbazole derivatives containing either linear or terminally branched polyfluorinated side chains connected to the fluorene subunit were synthesized and their electrochemical properties were investigated. The new compounds underwent electrochemical polymerization over indium tin oxide electrodes to give hydrophobic films with nanostructural and morphological properties strongly dependent on the nature of the side chains. Gas bubbles templated electropolymerization was next achieved by the addition of tiny amounts of water to the monomer solutions, without using surfactants. Within the investigated set of molecules, the nanostructural properties of the soft-templated films obtained from monomers bearing linear side chains could be fine-tuned by adjusting electrochemical parameters, leading to superhydrophobic surfaces.