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41.
A method for simultaneous determination of lead and thallium by photon activation analysis with radiochemical separation using irradiation with bremsstrahlung produced by a 20 MeV microtron is described. The detection limits for 500-mg samples of 0.9 g·g-1 and 0.15 g·g-1 for lead and thallium, respectively, were achieved that are sufficiently low for the reliable determination of both elements at levels commonly occurring in environmental samples and at elevated levels in biological materials. The accuracy of the procedure developed was proved by analyses of a number of environmental and biological reference materials. Possibilities of detection limit improvements are also discussed. 相似文献
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Lithuanian Mathematical Journal - We study the local regularity of solutions to the Navier–Stokes equations. We show for a suitable weak solution (u, p) on an open space-time domain D that if... 相似文献
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Thomas Boucher CJ Carey Melinda Darby Dyar Sridhar Mahadevan Samuel Clegg Roger Wiens 《Journal of Chemometrics》2015,29(9):484-491
Laser‐induced breakdown spectroscopy (LIBS) is currently being used onboard the Mars Science Laboratory rover Curiosity to predict elemental abundances in dust, rocks, and soils using a partial least squares regression model developed by the ChemCam team. Accuracy of that model is constrained by the number of samples needed in the calibration, which grows exponentially with the dimensionality of the data, a phenomenon known as the curse of dimensionality. LIBS data are very high dimensional, and the number of ground‐truth samples (i.e., standards) recorded with the ChemCam before departing for Mars was small compared with the dimensionality, so strategies to optimize prediction accuracy are needed. In this study, we first use an existing machine learning algorithm, locally linear embedding (LLE), to combat the curse of dimensionality by embedding the data into a low‐dimensional manifold subspace before regressing. LLE constructs its embedding by maintaining local neighborhood distances and discarding large global geodesic distances between samples, in an attempt to preserve the underlying geometric structure of the data. We also introduce a novel supervised version, LLE for regression (LLER), which takes into account the known chemical composition of the training data when embedding. LLER is shown to outperform traditional LLE when predicting most major elements. We show the effectiveness of both algorithms using three different LIBS datasets recorded under Mars‐like conditions. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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Controlling the water exchange kinetics of macrocyclic Gd(3+) chelates, a key parameter in the design of improved magnetic resonance imaging (MRI) contrast media, may be facilitated by selecting the coordination geometry of the chelate. The water exchange kinetics of the mono- capped twisted square antiprism (TSAP) being much closer to optimal than those of the mono capped square antiprism (SAP) render the TSAP isomer more desirable for high relaxivity applications. Two systems have been developed that allow for selection of the TSAP coordination geometry in 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-type Gd(3+) chelates, both based upon the macrocycle nitrobenzyl cyclen. In this paper we report investigations into the stability and formation of these chelates. Particular focus is given to the production of two regioisomeric chelates during the chelation reaction. These regioisomers are distinguished by having the nitrobenzyl substituent either on a corner or on the side of the macrocyclic ring. The origin of these two regioisomers appears to stem from a conformation of the ligand in solution in which it is hypothesized that pendant arms lie both above and below the plane of the macrocycle. The conformational changes that then result during the formation of the intermediate H(2)GdL(+) chelate give rise to differing positions of the nitrobenzyl substituent depending upon from which face of the macrocycle the Ln(3+) approaches the ligand. 相似文献
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Aime S Botta M Garda Z Kucera BE Tircso G Young VG Woods M 《Inorganic chemistry》2011,50(17):7955-7965
The chemistry of polyamino carboxylates and their use as ligands for Ln(3+) ions is of considerable interest from the point of view of the development of new imaging agents. Of particular interest is the chemistry of the macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) and its derivatives. Herein we report that the tetramethylated DOTA derivative, DOTMA, possess several properties that, from an imaging agent development point of view, are more advantageous than those of the parent DOTA. In particular, the Ln(3+) chelates of DOTMA exhibit a marked preference for the monocapped twisted square antiprismatic coordination isomer which imparts more rapid water exchange kinetics on the chelates; τ(M)(298) was determined to be 85 ns for GdDOTMA. Differential analysis of the (17)O R(2ρ) temperature profiles of both GdDOTA and GdDOTMA afforded the τ(M)(298) values for the square (SAP) and twisted square antiprismatic (TSAP) isomers of each chelate that were almost identical: 365 ns (SAP) and 52 ns (TSAP). The origin of this accelerated water exchange in the TSAP isomer appears to be the slightly longer Gd-OH(2) bond distance (2.50 ?) that is observed in the crystal structure of GdDOTMA which crystallizes in the P(2) space group as a TSAP isomer. The Ln(3+) chelates of DOTMA also exhibit high thermodynamic stabilities ranging from log K(ML) = 20.5 for CeDOTMA, 23.5 for EuDOTMA and YbDOTMA comparable to, but a shade lower than, those of DOTA. 相似文献