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11.
Nicholas Douglas Charles J. Neef Robert A. Rogers Jake A. Stanley Jacob Armitage Ben Martin Todd W. Hudnall William J. Brittain 《Journal of Physical Organic Chemistry》2013,26(8):688-695
The synthesis and reactivity of a tetrahydrochromeno[2,3‐b]indoles are reported. Evidence for reversible ring‐opening is based on H/D exchange and trapping experiments. These compounds readily undergo reaction with tetra‐n‐butylammonium cyanide. The cyanide reaction is 10–100× faster when the solution is irradiated with 350 nm light. Reaction with trimethylsilyl cyanide occurs only with UV irradiation demonstrating photoreactivity. The rate of tetrahydrochromeno[2,3‐b]indole ring‐opening is greater for (i) Me substitution at the hemiaminal carbon (compared to Ph), and (ii) substitution of fluorine at the 9‐position of the indole. Under acidic conditions, the ring‐opened indolium ion is observed. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
12.
Interfacial energy is a fundamental physiochemical property of any multi-phase system. Among the most direct approaches for determining solid–liquid interfacial energy is a technique based on measuring the shape of grain boundary grooves in specimens subjected to a linear temperature gradient. This technique was adapted to crystallizing colloids in a gravitational field. Such colloids exhibit a freezing–melting phase transition and are important not only as self-assembling precursors to photonic crystals, but also as physical models of atomic and molecular systems. The grain boundary groove technique was tested using suspensions of sterically stabilized poly(methyl methacrylate) spheres, which have been shown to closely approximate the hard sphere potential. Whereas isotropic models did not fit grain boundary groove data well, the capillary vector model, which is suitable for both isotropic and anisotropic surface energies, produced γ110?=?0.58?±?0.05 k B T/σ2. This value of interfacial energy is in agreement with many of the published values for hard spheres, supporting the validity of our grain boundary groove technique adaptations to colloidal systems in a gravitational field. Finally, kinks observed in groove profiles suggest a minimum anisotropy parameter of ε?=?0.029 for hard spheres. 相似文献
13.
J. R. Norris L. C. G. Rogers David Williams 《Probability Theory and Related Fields》1987,74(2):271-287
Summary A natural model for a self-avoiding Brownian motion inR
d, when specialised and simplified tod=1, becomes the stochastic differential equation
, where {L(t, x):t0,xR} is the local time process ofX. ThoughX is not Markovian, an analogue of the Ray-Knight theorem holds for {L(,x):xR}, which allows one to prove in many cases of interest that
exists almost surely, and to identify the limit. 相似文献
14.
Brown coal from two areas in New Zealand was treated with acids (HF and HCl) to remove the clays. Iron was then introduced into the “cleaned” coal by ion exchange. Mössbauer spectra of the untreated coal, the low temperature ash of the coal, “cleaned” coal and ion-exchanged coal were analysed. From these spectra we conclude that a pair of lines with QS~1 mm s?1 and IS~0.45 mm s?1 is probably due to organically bonded iron. 相似文献
15.
We have detected large deviations of the MJ = 0, J = 2 ← 1 Stark effect transition in the linear molecule HCN?HF from predictions of second-, and even fourth-, order perturbation theory. In order to account satisfactorily for the observed effect it has been necessary to set up and diagonalize the appropriate energy matrix. Smaller deviations in the case of MJ = 1, J = 2 ← 1 have likewise been treated. The values of the electric dipole moment for HCN?HF calculated from these transitions, which show large and small deviations from second-order theory, and from one (MJ = 3, J = 4 ← 3) which shows effectively zero deviation, are now consistent and are as follows:
μ/D | |||
2 ← 1 | 0 | 5.627 | |
1 | 5.601 | ||
4 ← 3 | 3 | 5.608 | |
Mean | 5.612 |