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171.
172.
Michael P. Doyle Doina G. Ene Chad S. Peterson Vince Lynch 《Angewandte Chemie (International ed. in English)》1999,38(5):700-702
The intramolecular addition of a diazo ester group to a triple bond in the presence of chiral dirhodium(II ) carboxamidate catalysts gives macrocyclic lactones with a fused cycloproprene ring [Eq. (a)]. This efficient reaction is characterized by high enantiocontrol (up to 98% ee) and chemoselectivity. 相似文献
173.
Patrick Lynch Herman Krier Nick Glumac 《Proceedings of the Combustion Institute》2009,32(2):1887-1893
A study of the combustion times for aluminum particles in the size range of 3–11 μm with oxygen, carbon dioxide, and water vapor oxidizers at high temperatures (>2400 K), high pressures (4–25 atm), and oxidizer composition (15–70% by volume in inert diluent) in a heterogeneous shock tube has generated a correlation valid in the transition regime. The deviation from diffusion limited behavior and burn times that could otherwise be accurately predicted by the widely accepted Beckstead correlation is seen, for example, in particles below 20 μm, and is evidenced by the lowering of the diameter dependence on the burn time, a dependence on pressure, and a reversal of the relative oxidizer strengths of carbon dioxide and water vapor. The strong dependence on temperature of burn time that is seen in nano-Al is not observed in these micron-sized particles. The burning rates of aluminum in these oxidizers can be added to predict an overall mixture burnout time adequately. This correlation should extend the ability of modelers to predict combustion rates of particles in solid rocket motor environments down to particle diameters of a few microns. 相似文献
174.
Kent A. Nielsen Dr. Eric Levillain Dr. Vincent M. Lynch Dr. Jonathan L. Sessler Prof. Jan O. Jeppesen Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(2):506-516
Four tetrathiafulvalene (TTF)‐annulated porphyrins 1 – 4 were synthesized and characterized. All contain a tetraphenylporphyrin (TPP) core onto which four, two, or one TTF subunits were annulated. Absorption and fluorescence spectroscopic studies together with electrochemical investigations reveal that interactions between the porphyrin system and the annulated TTF units take place in solution. The annulation of one or more TTF units to the porphyrin core has a profound effect on the reduction potentials associated with this latter framework, with positive shifts in the range of 0.105 to 0.355 V and 0.200 to 0.370 V for the first and second reduction potential, respectively, compared to the corresponding processes in the model compound TPP, 18 . The redox potentials for the first oxidation of the TTF units are considerably shifted in 4 (ΔEox1=+0.285 V) and 2 (ΔEox1=?0.140 V), whereas for 1 and 3 these potentials remain within the region expected for a normal TTF unit. Considerable changes in the second oxidation potential associated with the TTF subunits were seen for 2 (ΔEox1=?0.085) and 3 (ΔEox1=?0.175). The emission spectra of 1 – 4 revealed that the porphyrin fluorescence is almost quenched in the neutral state of the TTF‐annulated porphyrins, a finding that is consistent with substantial electron transfer taking place from the TTF subunits to the porphyrin core. Oxidation of the TTF unit(s) (TTF→TTF.+) present in 1 – 4 leads to the emission intensity being restored. 相似文献
175.
Nielsen KA Cho WS Lyskawa J Levillain E Lynch VM Sessler JL Jeppesen JO 《Journal of the American Chemical Society》2006,128(7):2444-2451
The syntheses of monotetrathiafulvalene-calix[4]pyrrole 5 and bistetrathiafulvalene-calix[4]pyrrole 6, prepared from the acid-catalyzed condensation of monopyrrolo[3,4-d]tetrathiafulvalene (MPTTF, 7) with acetone in the presence of tripyrrane 8 and dipyrromethane 9, respectively, are described. Compound 5 and the previously reported tetrathiafulvalene-calix[4]pyrrole 4 both adopt a 1,3-alternative conformation in the solid state, as determined from X-ray crystallographic analysis. The anion binding properties of the tetrathiafulvalene-calix[4]pyrroles 5 and 6, as well as those of the parent meso-octamethylcalix[4]pyrrole (1), were investigated in acetone using (1)H NMR spectroscopic and isothermal titration calorimetry (ITC) techniques and, within the error limits of the methods, were generally found to give concordant results. On the basis of the results of the ITC studies carried out in 1,2-dichloroethane, increasing the number of tetrathiafulvalene units annulated to the calix[4]pyrrole system serves to enhance the anion binding affinities substantially but at the price of lowered selectivity. Cyclic voltammetry (CV) studies, carried out in 1,2-dichloroethane, provided evidence of an anion-dependent electrochemical response with Cl(-) and Br(-) ions. This response was particularly dramatic in the case of the monotetrathiafulvalene-calix[4]pyrrole 5, with a DeltaE(max) of -145 mV being seen after the addition of approximately 1 equiv of Cl(-) ion. 相似文献
176.
Reczek JJ Villazor KR Lynch V Swager TM Iverson BL 《Journal of the American Chemical Society》2006,128(24):7995-8002
Derivatives of relatively electron rich 1,5-dialkoxynaphthalene (Dan) donors and relatively electron deficient 1,4,5,8-naphthalenetetracarboxylic diimide (Ndi) acceptors have been exploited in the folding and self-assembly of a variety of complex molecular systems in solution. Here, we report the use of Dan and Ndi derivatives to direct assembly of extended columns with alternating face-centered stacked structure in the solid state. A variety of 1:1 Dan:Ndi mixtures produced mesophases that were found to be stable over temperature ranges extending up to 110 degrees C. Analysis of these mesophases indicates mixtures with soft/plastic crystal phases and a few mixtures with the thermodynamic properties of true liquid crystals, all composed of alternating donor-acceptor columns within. Importantly, a correspondence was found between the clearing and crystallization points of the mesophase mixtures and the melting/clearing points of the component Ndi and Dan units, respectively. This correspondence enables the predictable tuning of mesophase phase transition temperatures. The study of sterically hindered derivatives led to a set of mixtures in which a dramatic and sudden color change (deep red to yellow) was observed upon crystallization of the mesophase due to a phase separation of the component donor and acceptor units. 相似文献
177.
Vesicle dispersions are useful for many applications from medicinal to consumer products. However, using these dispersions requires some knowledge of and control over their colloidal properties. Measuring interparticle interactions between vesicles should allow framing the problem in terms of Smoluchowski kinetic models and consequently anticipating time-dependent aggregation and coalescence for the dispersions. However, this can be a difficult task for many complex mixtures. A primary goal of this paper is to show that it is possible to measure interparticle potential between small vesicles by measuring the concentration-dependent collective motion using dynamic light scattering. These measurements allow determination of the second virial coefficient for the dispersion, providing a convenient platform for summing all contributions to the interaction potential over all vesicle conformations, thus making the analysis of complex mixtures more tractable. As a verification of the approach, a comparison is made to dispersions in which the stability is governed solely by electrostatics, using existing techniques to anticipate instabilities. A second goal of this paper is to build a simple potential model in which the Smoluchowski model can be used to quantitatively anticipate the aggregation behavior of the small vesicle dispersion. Together, these observations constitute a convenient approach to anticipating the behavior of vesicle (and other) dispersions in complex mixtures. 相似文献
178.
Isomeric p- and o-phenylenediamine-containing macrocyclic hosts (Wurster's thiacrown ethers L1 and L2, respectively) were prepared and studied as Hg(II) ionophores. The distinct electrochemical properties of the two hosts allowed for the formation of a coordination compound with the ortho-Wurster's thiacrown ether but not the para isomer. In the latter case, the Hg(II) ion served as an oxidant in an electron-transfer reaction with the host. Solutions of the Hg(II) complex of L2 were studied by 13C NMR spectroscopy and cyclic voltammetry and revealed a strong interaction between the redox-active phenylenediamine subunit and the bound metal cation. An X-ray analysis confirmed the participation of the three macrocyclic S atoms and both phenylenediamine N atoms in the stabilization of the complex. 相似文献
179.
Daniel E. Lynch Ravinder Hayer Samantha Beddows Joy Howdle C. Douglas Thake 《Journal of heterocyclic chemistry》2006,43(1):191-197
180.
Effect of stimulus level and place of stimulation on temporal pitch perception by cochlear implant users 总被引:1,自引:0,他引:1
Three experiments studied the effect of pulse rate on temporal pitch perception by cochlear implant users. Experiment 1 measured rate discrimination for pulse trains presented in bipolar mode to either an apical, middle, or basal electrode and for standard rates of 100 and 200 pps. In each block of trials the signals could have a level of -0.35, 0, or +0.35 dB re the standard, and performance for each signal level was recorded separately. Signal level affected performance for just over half of the combinations of subject, electrode, and standard rate studied. Performance was usually, but not always, better at the higher signal level. Experiment 2 showed that, for a given subject and condition, the direction of the effect was similar in monopolar and bipolar mode. Experiment 3 employed a pitch comparison procedure without feedback, and showed that the signal levels in experiment 1 that produced the best performance for a given subject and condition also led to the signal having a higher pitch. It is concluded that small level differences can have a robust and substantial effect on pitch judgments and argue that these effects are not entirely due to response biases or to co-variation of place-of-excitation with level. 相似文献