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551.
552.
G. W. A. Milne J. Zupan S. R. Heller J. A. Miller 《Magnetic resonance in chemistry : MRC》1979,12(5):289-296
A link between a substructure searching system and a 13C NMR data base has been established and permits the retrieval and examination of the chemical shifts associated with specific substructures. The means by which these searches are accomplished is described and the results from the searches are presented and discussed. The system is interactive, and can be used to locate in the data base the chemical shifts of carbon atoms in precisely defined environments. Alternatively, it may be used to learn the range of the chemical shifts possessed by particular types of carbon atoms, such as N-methyl or O-methyl carbons. 相似文献
553.
Barbara Heller 《Journal of multivariate analysis》1983,13(3):473-487
Characterizations of the binomial, negative binomial, gamma, Poisson, and normal distributions are obtained by the property of zero regression of certain polynomial statistics of arbitrary degree, on the mean. In each case, the equations which express zero regression are derived from the recurrence relations of a set of special functions. The differential recurrence relations of these special functions are used in the proofs of the characterization theorems. 相似文献
554.
555.
Motivated by neutron scattering experiments, we investigate the decay of the fidelity with which a wave packet is reconstructed by a perfect time-reversal operation performed after a phase-space displacement. In the semiclassical limit, we show that the decay rate is generically given by the Lyapunov exponent of the classical dynamics. For small displacements, we additionally show that, following a short-time Lyapunov decay, the decay freezes well above the ergodic value because of quantum effects. Our analytical results are corroborated by numerical simulations. 相似文献
556.
Substitution of oxygen with a weak hydrogen bond acceptor such as fluorine provides a single-atom modification that can have grave effects on the chemical and medicinal properties of nucleoside analogues. To that end, we present a simple and high-yielding method for the novel synthesis of 5'-deoxy-5'-fluoroguanosine and 5'-deoxy-5'-fluoroinosine utilizing an intramolecular electron-withdrawing approach. The properties of the resulting modified nucleosides, as well as the halogenated intermediates, are notable for their similarity to nucleoside analogues used in the treatment of cancer, as well as enzyme inhibitors designed to target parasitic protozoa. 相似文献
557.
Heller DN 《Rapid communications in mass spectrometry : RCM》2007,21(5):644-652
A number of techniques have been suggested to date for assessing matrix effects on quantitative atmospheric pressure ionization mass spectrometry (API-LC/MS) methods. A newly designed experiment has the aim of efficiently simulating the quantitative behavior of an LC/MS method as a function of the amount of co-injected matrix extract. Two sets of mixtures were prepared in different formats to study matrix effects as a function of analyte or matrix amount. Chromatographic conditions were varied as well, to alter the separation between analyte and co-extractants, and thereby provide different matrix effect conditions for testing the same mixtures. Graphical presentation of the results was used to gain insight into the matrix effect phenomenon. The results suggest that ruggedness for API-LC/MS methods may be defined as the absence of significant variation in results as a function of the amount of co-injected matrix. That is, a non-rugged API-LC/MS method may give consistent results only if a fixed amount of matrix is co-injected on a specific instrument. The results also point to the existence of a specific matrix concentration for the onset of matrix effects, below which these effects are not significant. These issues are important to the US FDA Center for Veterinary Medicine, which has regulatory authority for methods used to monitor for drug residues in food tissues from animals. The ruggedness testing technique suggested here may be an important factor in determining that a method is ready for multi-laboratory testing on multiple instruments. 相似文献
558.
Cycloaddition reactions compose one of the most important classes of reactions when it comes to the simultaneous formation of several bonds in one reaction step. The de novo construction of carbocyclic aromatic systems from acetylenes was also found as an excellent possibility for the assembly of heteroaromatic systems. The transition metal-catalysed [2 + 2 + 2] cycloaddition reaction constitutes a fascinating tool for the synthesis of pyridines from nitriles and the most recent developments demonstrate the ability to control the substitution pattern as well as the possibility of introducing chirality by the use of achiral substrates and a chiral catalyst under mild conditions. In this tutorial review we are focusing on the de novo construction of pyridine ring systems by the transition metal-catalysed [2 + 2 + 2] cycloaddition reaction. After surveying the mechanistic features and intermediates of the reaction depending on the different metal complexes used, we depict the preparation of achiral pyridine derivatives. The last section describes the advances in the synthesis of chiral pyridines and biaryls using the cyclotrimerization method. The various possibilities of introducing chirality by catalytic means are presented and illustrated by instructive examples. This review will be of interest for people active in: Organic Chemistry, Organometallic Chemistry, Transition Metal Chemistry, Stereoselective Synthesis, Heterocyclic Chemistry. 相似文献
559.
Shin W Lee JM Nagarale RK Shin SJ Heller A 《Journal of the American Chemical Society》2011,133(8):2374-2377
Electroosmotic pumps are arguably the simplest of all pumps, consisting merely of two flow-through electrodes separated by a porous membrane. Most use platinum electrodes and operate at high voltages, electrolyzing water. Because evolved gas bubbles adhere and block parts of the electrodes and the membrane, steady pumping rates are difficult to sustain. Here we show that when the platinum electrodes are replaced by consumed Ag/Ag(2)O electrodes, the pumps operate well below 1.23 V, the thermodynamic threshold for electrolysis of water at 25 °C, where neither H(2) nor O(2) is produced. The pumping of water is efficient: 13?000 water molecules are pumped per reacted electron and 4.8 mL of water are pumped per joule at a flow rate of 0.13 mL min(-1) V(-1) cm(-2), and a flow rate per unit of power is 290 mL min(-1) W(-1). The water is driven by protons produced in the anode reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-), traveling through the porous membrane, consumed by hydroxide ions generated in the cathode reaction Ag(2)O(s) + 2 H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). A pump of 2 mm thickness and 0.3 cm(2) cross-sectional area produces flow of 5-30 μL min(-1) when operating at 0.2-0.8 V and 0.04-0.2 mA. Its flow rate can be either voltage or current controlled. The flow rate suffices for the delivery of drugs, such as a meal-associated boli of insulin. 相似文献
560.
van Dalen KN Drijkoningen GG Smeulders DM Heller HK Glorieux C Sarens B Verstraeten B 《The Journal of the Acoustical Society of America》2011,130(3):1299-1312
The interface-wave impedance and ellipticity are wave attributes that interrelate the full waveforms as observed in different components. For each of the fluid/elastic-solid interface waves, i.e., the pseudo-Rayleigh (pR) and Stoneley (St) waves, the impedance and ellipticity are found to have different functional dependencies on Young's modulus and Poisson's ratio. By combining the attributes in a cost function, unique and stable estimates of these parameters can be obtained, particularly when using the St wave. In a validation experiment, the impedance of the laser-excited pR wave is successfully extracted from simultaneous measurements of the normal particle displacement and the fluid pressure at a water/aluminum interface. The displacement is measured using a laser Doppler vibrometer (LDV) and the pressure with a needle hydrophone. Any LDV measurement is perturbed by refractive-index changes along the LDV beam once acoustic waves interfere with the beam. Using a model that accounts for these perturbations, an impedance decrease of 28% with respect to the plane wave impedance of the pR wave is predicted for the water/aluminum configuration. Although this deviation is different for the experimentally extracted impedance, there is excellent agreement between the observed and predicted pR waveforms in both the particle displacement and fluid pressure. 相似文献