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41.
Andappan MM Nilsson P von Schenck H Larhed M 《The Journal of organic chemistry》2004,69(16):5212-5218
Arylations of electron-rich heteroatom-substituted olefins were performed with arylboronic acids. This appears to constitute the first example of palladium(II)-catalyzed internal Heck arylations. The novel protocol exploits oxygen gas for environmentally benign reoxidation and a stable 1,10-phenanthroline bidentate ligand to promote the palladium(II) regeneration and to control the regioselectivity. Internal arylation is strongly favored with electron-rich arylboronic acids. DFT calculations support a charge-driven selectivity rationale, where phenyls substituted with electron-donating groups prefer the electron-poor alpha-carbon of the olefin. Experiments, verified by calculations, confirm the cationic nature of the catalytic route. This Heck methodology provides a facile and mild access to functionalized enamides. Controlled microwave heating and increased oxygen pressure were used to further reduce the reaction time to 1 h. 相似文献
42.
Herein we report a rapid, palladium-catalyzed terminal diarylation of the chelating olefin N,N-dimethyl(2-ethenyloxy)ethanamine under noninert conditions utilizing controlled microwave heating as a convenient energy source. Among the aryl bromides examined, both electron-rich and electron-poor substrates were demonstrated to furnish useful yields after only 10-120 min of directed microwave heating at 160-200 degrees C. The good terminal regioselectivity suggests that the precatalyst (Herrmann's palladacycle) serves as a source of weakly coordinated palladium(0) in the investigated high-temperature Heck process. 相似文献
43.
Orrling K Nilsson P Gullberg M Larhed M 《Chemical communications (Cambridge, England)》2004,(7):790-791
This communication describes the development of a controlled microwave methodology for rapid milliliter-scale PCR. 相似文献
44.
We describe a phase retrieval approach for intensity point-spread functions of high-numerical-aperture optical systems such as light microscopes. The method calculates a generalized pupil function defined on a spherical shell, using measured images at several defocus levels. The resultant pupil functionsreproduce measured point-source images significantly better than does an ideal imaging model. Availability of pupil function information will facilitate new approaches to aberration correction in such systems. 相似文献
45.
Optimal detection of a striplike crack residing in an isotropic elastic solid with coarse microstructure by means of ultrasonic nondestructive evaluation (NDE) is considered. A physics-based approach to derive an optimal detector, which achieves the theoretical limitations constrained by the underlying physics, is presented. State-of-the-art physical models of crack echoes and of stochastic backscattering from the material structure in elastic solids are introduced and unified with the theory of optimal detection to yield a practically useful nonlinear filter bank implementation of the optimal detector. Monte Carlo simulations of the detection performance for the special case of a striplike crack with uncertain angular orientation are presented in the form of receiver operating characteristics (ROCs). These new results represent the physical limitations for detecting a crack under the stated conditions and serve as performance bounds to which other detectors should be compared. A physics-based generalized likelihood ratio (GLR) detector, which relies on the same nonlinear filter bank as the optimal detector, is also presented for the special case of a striplike crack. A comparison between the optimal and the GLR detectors shows that the GLR detector only slightly reduces the performance. 相似文献
46.
Wan H Holmén AG Wang Y Lindberg W Englund M Någård MB Thompson RA 《Rapid communications in mass spectrometry : RCM》2003,17(23):2639-2648
A high-throughput pKa screening method based on pressure-assisted capillary electrophoresis (CE) and mass spectrometry (MS) is presented. Effects of buffer type and ionic strength on sensitivity and pKa values were investigated. Influence of dimethyl sulfoxide (DMSO) concentration present in the sample on effective mobility measurement was examined. A series of ten volatile buffers, covering a pH range from 2.5 to 10.5 with the same ionic strength, was employed. The application of volatile background electrolytes resulted in significant signal increase as compared with commonly used non-volatile phosphate buffers. In general, the CE/MS system provided a ten-fold higher sensitivity than conventional UV detection. The newly developed CE/MS method offers high-throughput capacity by pooling a number of compounds into a single sample. Simultaneous measurement of more than 50 compounds was readily achieved in less than 150 min. The measured pKa values are consistent with the published data obtained from the CE/UV method and are also in good agreement with data generated by other methods. Other advantages of using CE/MS for pKa screening are illustrated with typical examples, including poorly soluble compounds and non-UV-absorbing compounds. 相似文献
47.
Torbjørn Helvik Kristian Lindgren Mats G. Nordahl 《Communications in Mathematical Physics》2007,272(1):53-74
We introduce a local version of the Shannon entropy in order to describe information transport in spatially extended dynamical
systems, and to explore to what extent information can be viewed as a local quantity. Using an appropriately defined information
current, this quantity is shown to obey a local conservation law in the case of one-dimensional reversible cellular automata
with arbitrary initial measures. The result is also shown to apply to one-dimensional surjective cellular automata in the
case of shift-invariant measures. Bounds on the information flow are also shown. 相似文献
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