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971.
D. Brynn Hibbert Allen Stenhouse Cary Murphy Mark Jarrett Roy Osborne John H. Vine Linda Glowacki Charles Russo 《Accreditation and quality assurance》2008,13(9):523-530
Samples of plasma from chosen horses are collected prior to racing for the analysis of total carbon dioxide (TCO2). Five or six (dependent on jurisdiction) tubes of blood are taken as required for a screen, followed (if positive) by confirmation
(two tubes in quadruplicate) and, further confirmation (two tubes in quadruplicate) at a second referee laboratory. The threshold
limit prescribed by the rules of racing is an amount concentration of 36.0 mM, with further action ensuing if the reported
concentration is greater than 37.2 mM. Using QC data and an analysis of the measurement procedure, the combined standard measurement
uncertainty of a measurement result was estimated to be 0.22 mM. This leads to a conclusion that the odds of incorrectly deciding
that a sample at the threshold limit exceeded the action concentration, are 13 000 000:1 against. The combined standard measurement
uncertainty could be reduced to 0.20 mM by combining results from the first and referee laboratories. An allowance for uncertainty
of measurement of 1.0 mM is proposed, which leads to odds of 185 000:1 against concluding a sample is over the threshold limit
when, in fact, it is not. 相似文献
972.
On the basis of quantum chemical calculations C(alpha)-glycyl radical parameters have been developed for the OPLS-AA/L force field. The molecular mechanics hypersurface was fitted to the calculated quantum chemical surface by minimizing their molecular mechanics parameter dependent sum-of-squares deviations. To do this, a computer program in which the molecular mechanics energy derivatives with respect to the parameters were calculated analytically was developed, implementing the general method of Lifson and Warshel (J Chem Phys 1968, 49, 5116) for force field parameter optimization. This program, in principle, can determine the optimal parameter set in one calculation if enough representative value points on the quantum chemical potential energy surface are available and there is no linear dependency between the parameters. Some of the parameters in quantum calculations, including several new torsion types around a bond as well as angle parameters at a new central atom type, are not completely separable. Consequently, some restrictions and/or presumptions were necessary during parameter optimization. The relative OPLS-AA energies reproduced those calculated quantum chemically almost perfectly. 相似文献
973.
Sven Festersen Stjepan B. Hrkac Christian T. Koops Benjamin Runge Thomas Dane Bridget M. Murphy Olaf M. Magnussen 《Journal of synchrotron radiation》2018,25(2):432-438
X‐ray reflectivity studies of the structure of liquid–vapour and liquid–liquid interfaces at modern sources, such as free‐electron lasers, are currently impeded by the lack of dedicated liquid surface diffractometers. It is shown that this obstacle can be overcome by an alternative experimental approach that uses the natural curvature of a liquid drop for variation of the angle of incidence. Two modes of operation are shown: (i) sequential reflectivity measurements by a nanometre beam and (ii) parallel acquisition of large ranges of a reflectivity curve by micrometre beams. The feasibility of the two methods is demonstrated by studies of the Hg/vapour, H2O/vapour and Hg/0.1 M NaF interface. The obtained reflectivity curves match the data obtained by conventional techniques up to 5αc in micro‐beam mode and up to 35αc in nano‐beam mode, allowing observation of the Hg layering peak. 相似文献
974.
975.
The behavior of the fiber stretch in simple shear of soft materials fiber-reinforced with a single family of oriented parallel fibers is examined. The analysis is purely kinematical and the results are valid for both compressible and incompressible materials. It is shown that for a given amount of shear, for all fiber orientation angles in the range \(0 < \theta < \pi /4\), the fiber stretch increases with increasing \(\theta\) whereas in the range \(\pi /4 < \theta < \pi /2\), this is no longer the case and there is a particular fiber orientation for which the fiber stretch is a maximum. For a particular amount of shear corresponding to a special angle of shear (a “magic” angle of \(35.26^{\circ}\)), the fiber-orientation angle at which the fiber stretch is a maximum is its geometric complement namely a magic angle of \(54.74^{\circ}\). The results are also valid for torsion of a circular cylinder reinforced with a single family of helically wound fibers. 相似文献
976.
977.
B. Maffei P. A. R. Ade C. E. Tucker E. Wakui R. J. Wylde J. A. Murphy R. M. Colgan 《International Journal of Infrared and Millimeter Waves》2000,21(12):2023-2033
Novel corrugated horn have been modelled, manufactured and measured which give low-sidelobe patterns required by CMB Anisotropy experiments. These horns have a Back-to-Back structure with mode filtering at their centres. They are corrugated to give axial symmetric low-sidelobe patterns, profiled to reduce their length, and have a Gaussian flare at their entrance apertures to further suppress sidelobes to -40dB. Modelling and experimental results show excellent agreement to well below 50 dB. 相似文献
978.
Pat Wheelan Joseph A. Zirrolli Robert C. Murphy 《Journal of the American Society for Mass Spectrometry》1995,6(1):40-51
Electron ionization (EI) gas chromatography/mass spectrometry (GC/MS) analysis of pentafluorobenzyl ester-trimethyl sllyl ether (PFB-TMS) derivatives of hydroxy-subshtuted fatty acids provides structural information comparable to that obtained in analysis of methyl ester-trimethyl silyl ether (Me-TMS) derivatives. Use of this derivative eliminates the need to prepare two separate derivatives, the PFB-TMS derivative for molecular weight determination by electron capture ionization (negative ions) analysis and the Me-TMS derivative for structural determination by EI GC/MS analysis. The relative abundance of fragment ions observed during EI GC/MS analysis of these derivatized unsaturated fatty acids indicates the location of the —OTMS substituents relative to double bond positions in those cases studied. The most abundant fragment ions are observed when the compound contains an unsaturation two carbon atoms removed from the —OTMS ether carbon (the β-OTMS position). The “saddle effect” observed in the GC/MS analyses of some derivatized monohy— droxy unsaturated fatty acids is suggested to be due to a thermally allowed pericyclic double bond rearrangement and indicates the presence of a conjugated diene one carbon atom removed from the —OTMS ether carbon (the α-OTMS position). The saddle effect is most prominent for fatty acids that contain additional unsaturation separated by a single methylene unit from the conjugated diene moiety. 相似文献
979.
Constance M. Murphy Catherine Fenselau Peter L. Gutierrez 《Journal of the American Society for Mass Spectrometry》1992,3(8):815-822
Product ion spectra of fifteen monoglutathione and diglutathione conjugates have been measured using activation by 6000-eV collisions with helium in the third field-free region of a four-sector tandem mass spectrometer of EBEB configuration. Fragmentation patterns in the cation spectra have been analyzed for decompositions of the glutathione moiety that would permit recognition of an unknown as a glutathione conjugate. Five spectra from an earlier study of high-energy collisional activation on a BEEB four-sector instrument have also been included in this analysis. A suite of appropriate ions was found to occur consistently, including ions of m/z 307 comprising the glutathione tripeptide and the complementary ion [MH — 307]+ or the ion radical [MH — 306]+’. 相似文献
980.
It is proved that the maximum number of collisions among three identical hard spheres in more than one dimension is four. It is conjectured that the maximum number of collisions amongn hard spheres ind dimensions is independent ofd, provideddn-1. 相似文献