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21.
Brandon L. Frenette Nadine Arsenault Sarah L. Walker Dr. Andreas Decken Prof. Dr. C. Adam Dyker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(33):8528-8536
Optimized synthetic procedures for pyridinium ions featuring iminophosphorano (−N=PR3; R=Ph, Cy) π-donor substituents in the 2- and 4- positions are described. Crystallographic and theoretical studies reveal that the strongly donating substituents severely polarize the π-electrons of the pyridyl ring at the expense of aromaticity. Moreover, the pyridinium ions are readily deprotonated to generate powerful bispyridinylidene (BPY) organic electron donors. Electrochemical studies show exceptionally low redox potentials for the two-electron BPY/BPY2+ couples, ranging from −1.71 V vs the saturated calomel electrode for 3PhPh (with four Ph3P=N− groups) to −1.85 V for 3CyCy (with four Cy3P=N− groups). These new compounds represent the most reducing neutral organic electron donors (OEDs) currently known. Some preliminary reductions involving 3CyCy showed enhanced capability owing to its low redox potential, such as the thermally activated reduction of an aryl chloride, but purification challenges were often encountered. 相似文献
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It has been shown recently that in order for an incoherent optical system to be linear and space invariant, the image of the source at the filter plane must be larger than the filter aperture. We show in this paper that the source image must be larger than the filter by an amount equal to twice the highest spatial frequency of the object, the frequency being measured in the filter plane. 相似文献
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The zeta distribution with regression parameters has been rarely used in statistics because of the difficulty of estimating the parameters by traditional maximum likelihood. We propose an alternative method for estimating the parameters based on an iteratively reweighted least-squares algorithm. The quadratic distance estimator (QDE) obtained is consistent, asymptotically unbiased and normally distributed; the estimate can also serve as the initial value required by an algorithm to maximize the likelihood function. We illustrate the method with a numerical example from the insurance literature; we compare the values of the estimates obtained by the quadratic distance and maximum likelihood methods and their approximate variance–covariance matrix. Finally, we calculate the bias, variance and the asymptotic efficiency of the QDE compared to the maximum likelihood estimator (MLE) for some values of the parameters. 相似文献
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The statistical properties of speckle recorded on photographic film are studied theoretically and experimentally. When saturation and threshold effects are negligible and the gamma is equal to one, the probability distribution function of spatially integrated film transmittance has the form of a double exponential. Experimental results confirm that under those conditions, the density fluctuations caused by the speckle are independent of the signal. 相似文献
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In order to study the effect of substitution of Fe3+ by Al3+ and Cr3+ in Li0.5Fe2.5O4 on its structural and magnetic properties, the spinel system Li0.5Al x Cr x Fe2.5?2x O4 (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and 57Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al3+ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5). 相似文献
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A phase reconstruction method based on the two-dimensional sampling theorem is applied to the case when only the modulus of the Fourier transform and the support of the object are known. The convengence of the algorithm is analysed for different intermediate sampling grids and for different initial values. 相似文献
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Fournier-Bidoz S Arsenault AC Manners I Ozin GA 《Chemical communications (Cambridge, England)》2005,(4):441-443
Self-powered completely synthetic nanorotors have been prepared from barcoded gold-nickel nanorods having the gold end anchored to the surface of a silicon wafer; constant velocity circular movements are observed when hydrogen peroxide fuel is catalytically decomposed to oxygen at the unattached nickel end of the nanorod. 相似文献