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81.
In this rejoinder to a critique by Raggio and Primas of our paper, On Completely Positive Maps in Generalized Quantum Dynamics, we acknowledge that, contrary to our original assertion, the Bloch equations are indeed completely positive. We then explain briefly why this modification of our analysis does not alter its main conclusions.  相似文献   
82.
Aristoserratine, a New Indole Alkaloid from Aristotelia serrata W.R.B. OLIVER and from A. peduncularis (LABILL .) HOOK . F. The new indole alkaloid aristoserratine (2) has been isolated from Aristotelia. Its structure and absolute configuration were elucidated on the basis of spectroscopic data.  相似文献   
83.
The revised structure 1 is put forward for peduncularine, the main alkaloid of Aristotelia peduncularis (Labill.) HOOK. F. (Elaeocarpaceae), on the basis of its spectroscopic properties and those of its degradation products, the Hofmann base 3 and the hydrogenation product 4 . Structure 1 represents the relative configuration of the alkaloid. Peduncularine belongs to the class of indole alkaloids with a monoterpene unit as the aliphatic portion. To our knowledge it constitutes the first example in which an isopropyl group has become detached from the terpene unit and occurs as a substituent on nitrogen.  相似文献   
84.
A method combining thermal fragmentation and mass spectrometry for the determination of the position of double bonds in an unsaturated ester is presented. The thermal fragmentation of methyl esters of deuterated long chain carboxylic acids yields a homologous series of olefins plus a homologous series of unsaturated esters. The positions of the deuterium atoms in the original ester are revealed by the deuterium content of its fragments as determined by mass spectrometry. Therefore, the positions of double bonds of a polyunsaturated acid can be determined by pyrolysis after saturation by deuterium. The structures of the unsaturated fragments are ascertained by mass spectrometric method, and the formation of the ion [M – 32] in the mass spectrometric fragmentation of unsaturated methyl esters is studied by means of deuterium labeling.  相似文献   
85.
86.
Using laser-induced fluorescence of ozone (to measure the rate of disappearance of O32) and NO2 titration (to determine O atom concentrations), we have determined bimolecular rate constants for the deactivation by O(3P atoms) of ozone in excited stretching and bending modes. These experiments do not distinguish between deactivation by (a) the exchange of vibrational and translational energy or (b) the chemical reaction O3 + O → 2O2. If the non-reactive pathway (a) is assumed to dominate, then O(3P) is 150 times more effective than O2 in deactivating O23. If chemical reaction (b) is dominant, the bimolecular rate constant for O23 + O(3P) is larger by a factor of 150–1500 than that for ground-state ozone.  相似文献   
87.
The efficiency of the photochemical ring-opening of chromenes (or benzopyrans) depends on the vibronic transition selected by the chosen excitation wavelength. In the present work, ab initio CASPT2//CASSCF calculations are used to determine the excited-state ring-opening reaction coordinate for 2H-chromene (C) and 2,2-diethyl-2H-chromene (DEC) and provide an explanation for such an unusual mode-dependent behavior. It is shown that excited-state relaxation and decay occur via a multimodal and barrierless (or nearly barrierless) reaction coordinate. In particular, the relaxation out of the Franck-Condon involves a combination of in-plane skeletal stretching and out-of-plane modes, while the second part of the reaction coordinate is dominated exclusively by a different out-of-plane mode. Population of this last mode is shown to be preparatory with respect to both C-O bond breaking and decay via an S(1)/S(0) conical intersection. The observed mode-dependent ring-opening efficiency is explained by showing that the vibrational mode corresponding to the most efficient vibronic transition has the largest projection onto the out-of-plane mode of the reaction coordinate. To support the computationally derived mechanism, we provide experimental evidence that the photochemical ring-opening reaction of 2,2-dimethyl-7,8-benzo(2H)chromene, that similarly to DEC exhibits a mode-dependent photoreaction, has a low ( approximately 1 kcal mol(-1)) activation energy barrier.  相似文献   
88.
Abstract— The 11-cis and all-trans isomers of a series of poly(ethylene glycol)-oligopeptide - Schiff bases as models for rhodopsin were synthesized and studied. Absorption data for certain of the PEG-peptide Schiff bases demonstrated that no intramolecular hydrogen-bonding (or protonation) occurs between the Schiff base and an acidic amino acid residue, as was previously thought. Photoisomerization of the 11-cis protonated and unprotonated Schiff bases were examined using both steady state and laser flash techniques. Also with 355 nm excitation (and additionally 532 nm in one case), an approximate 40% increase in quantum yield of isomerization (φ) occurred for all protonated PEG-peptide Schiff bases compared to the H+-n-butylamine counterparts (in methanol). In one case, a > 100% increase in φ was found in dichloromethane. These data show that PEG-oligopeptide Schiff bases are still further improved models for rhodopsin compared to their n-butylamine analogs.  相似文献   
89.
We present an analysis of minimum bias events from proton-proton collisions at \(\sqrt s = 7GeV\) in the CERN ISR. We remove the effects of both the leading protons and compare theB=0 mesonic residue of the events to the hadronic events of similar energy produced ine + e ? collisions. This comparison is presented in terms of the standard jet-type analyses involving quantities such as sphericity and aplanarity. We find significant differences between these data and the data frome + e ? annihilations. The data of this experiment are consistent with the predictions of a longitudinal phase space model.  相似文献   
90.
Inclusive production of ?0,f, andg 0 mesons and ofK s 0 ,K *0 (892), ? andK *0(1430)mesons has been measured at <y>~2.6 and <p T >~1.1 GeV/c in proton-proton interactions at \(\sqrt s = 52.5\) GeV. The negative particle from the two-body decays of these resonances were identified by a threshold Cerenkov counter and used for triggering. Starting from the measured differential cross section, total inclusive cross sections for the vector and tensor mesons were determined using various parametrizations for they andp T dependence of the differential cross section. The experimental results are discussed in the framework of production models based on the parton picture. The strangeness suppresion factor λ=(0.30±0.10) due toSU(3) symmetry breaking of the quark sea is derived.  相似文献   
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