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191.
Triangles and tetrahedra: metal directed self-assembly of metallo-supramolecular structures incorporating bis-beta-diketonato ligands 总被引:1,自引:0,他引:1
Clegg JK Lindoy LF Moubaraki B Murray KS McMurtrie JC 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2417-2423
The interaction of six aryl-linked bis-beta-diketones, including a new naphthylene linked species, with copper(II), iron(III) and, in one instance gallium(III), has been investigated with the aim of obtaining metallo-supramolecular assemblies exhibiting different geometries. New examples of two assembly types incorporating the above bis-beta-diketones (L) were generated. The first type is represented by a range of molecular triangles of formula [Cu(3)(L-H(2))(3)](solvent)(n) while the second is given by a corresponding selection of less-common neutral molecular tetrahedra of formula [Fe(4)(L-H(2))(6)](solvent)(n) as well as [Ga(4)(L-H(2))(6)].8.5THF.0.5H(2)O; an example of each type has been characterised by X-ray crystallography. A magnetochemical investigation of [Fe(4)(-H(2))(6)].6THF is reported. The susceptibility is Curie like and consistent with very weak coupling occurring between the iron(III) d(5)(high spin) centres. The X-ray structures of two trinuclear copper(II) as well as a tetranuclear iron(III) and a tetranuclear gallium(III) assembly confirm their discrete triangular and tetrahedral geometries, respectively. The structure of the gallium(III) species is closely related to that of the corresponding iron(III) species. The tetrahedral structures provide rare examples of such assemblies encapsulating guest solvent molecules--in each case tetrahydrofuran is incorporated in the central cavity. 相似文献
192.
We consider a nonlocal analogue of the Fisher-KPP equation
and its discrete counterpart , , and show that travelling wave solutions of these equations that are bounded between and are unique up to translation. Our proof requires finding exact a priori asymptotics of a travelling wave. This we accomplish with the help of Ikehara's Theorem (which is a Tauberian theorem for Laplace transforms).
0 ~{\rm on}~(0,1),\end{displaymath}">
and its discrete counterpart , , and show that travelling wave solutions of these equations that are bounded between and are unique up to translation. Our proof requires finding exact a priori asymptotics of a travelling wave. This we accomplish with the help of Ikehara's Theorem (which is a Tauberian theorem for Laplace transforms).
193.
Molality as a unit of measure for expressing 1H MRS brain metabolite concentrations in vivo 总被引:1,自引:0,他引:1
Knight-Scott J Haley AP Rossmiller SR Farace E Mai VM Christopher JM Manning CA Simnad VI Siragy HM 《Magnetic resonance imaging》2003,21(7):787-797
Absolute concentrations of cerebral metabolite in in vivo 1H magnetic resonance spectroscopy studies (1H-MRS) are widely reported in molar units as moles per liter of tissue, or in molal units as moles per kilogram of tissue. Such measurements require external referencing or assumptions as to local water content. To reduce the scan time, avoid assumptions that may be invalid under specific pathologies, and provide a universally accessible referencing procedure, we suggest that metabolite concentrations from 1H-MRS measurements in vivo be reported in molal units as moles per kilogram of tissue water. Using internal water referencing, a two-compartment water model, a simulated brain spectrum for peak identification, and a spectroscopic bi-exponential spin-spin relaxation segmentation technique, we measured the absolute concentrations for the four common 1H brain metabolites: choline (Cho), myo-inositol (mIno), phosphocreatine + creatine (Cr), and N-acetyl-aspartate (NAA), in the hippocampal region (n = 26) and along the Sylvian fissure (n = 61) of 35 healthy adults. A stimulated echo localization method (20 ms echo time, 10 ms mixing time, 4 s repetition time) yielded metabolite concentrations, uncorrected for metabolite relaxation or contributions from macromolecule resonances, that were expectantly higher than with molar literature values. Along the Sylvian fissure the average concentrations (coefficient of variation (CV)) in mmoles/kg of tissue water were 17.6 (12%) for NAA, 14.2 (9%) for Cr, 3.6 (13%) for Cho, and 13.2 (15%) for mIno. Respective values for the hippocampal region were 15.7 (20%), 14.7 (16%), 4.6 (19%), and 17.7 (26%). The concentrations of the two regions were significantly different (p = 0.001) for NAA, mIno, and Cho, a trend in agreement with previous studies. All gray matter Sylvian fissure CV values, except for NAA, were also in agreement with previous 1H-MRS gray matter studies. The reduced precision of the NAA concentration was attributed to overlapping signal contributions from glutamate and glutamine (Glx), suggesting that a detailed Glx model is critical for accurate quantitation of the NAA 2.02 ppm resonance. The reduced precision of the measurements in the hippocampal region was attributed to poor spectral resolution. 相似文献
194.
Misra SK Andronenko SI Rinaldi G Chand P Earle KA Freed JH 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,160(2):131-138
Multifrequency electron paramagnetic resonance studies on the Mn(2+) impurity ion in a mixed single crystal NH(4)Cl(0.9)I(0.1) were carried out at 9.62 (X-band) in the range 120-295 K, at 35.87 (Q-band) at 77 and 295 K, and at 249.9 GHz (far-infrared band) at 253 K. The high-field EPR spectra at 249.9 GHz are well into the high-field limit leading to a considerable simplification of the spectra and their interpretation. Three magnetically inequivalent, but physically equivalent, Mn(2+) ions with their respective magnetic Z-axes oriented along the crystallographic [100], [010], [001] axes were observed. Simultaneous fitting of EPR line positions observed at X-, Q-, and far infra-red bands was performed using a least-squares procedure and matrix diagonalization to estimate accurately the Mn(2+) spin-Hamiltonian parameters. The temperature variation of the linewidth and peak-to-peak intensities of the EPR lines indicate the presence of lambda-transitions in the mixed NH(4)Cl(0.9)I(0.1) crystal at 242 and 228 K consistent with those observed in the pure NH(4)Cl and NH(4)I crystals, respectively. A superposition-model analysis of the spin-Hamiltonian parameters reveals that the local environment of the Mn(2+) ion is considerably reorganized to produce axially symmetric crystal fields about the respective Z-axes of the three magnetically inequivalent ions as a consequence of the vacancy created due to charge-compensation when the divalent Mn(2+) ion substitutes for a monovalent NH(4)(+) ion in the NH(4)Cl(0.9)I(0.1) crystal. This reorganization is almost the same as that observed in NH(4)Cl and NH(4)I single crystals, although the latter two are characterized by different, simple cubic and face-centered cubic, structures. 相似文献
195.
Wagner S Nevzorov AA Freed JH Bryant RG 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,160(2):257-165
The 19F nuclear spin-lattice relaxation rate constants were measured as a function of magnetic field strength for 1,12-diaminododecane labeled at one end with a nitroxide radical and at the other with a trifluoromethyl group. The magnetic relaxation dispersion profile (MRD) reports the spectral density function appropriate to the end-to-end correlation function for the doubly labeled molecule. After extrapolation to zero concentration to eliminate the intermolecular relaxation contribution to relaxation, the resulting intramolecular MRD profile was compared with several model approaches. The rotational model for the spectral density functions as included in the Solomon-Bloembergen-Morgan equations does not describe the data well. The earlier model of Freed for nuclear spin relaxation induced by a freely diffusing paramagnetic co-solute is not rigorous for this case because the paramagnet is tethered to the observed nuclear spin and only a restricted space in the immediate vicinity of the nuclear spin is accessible for pseudo-translational diffusion of one end of the molecule with respect to the other. A generalization of the Torrey model for magnetic relaxation by translational diffusion developed by Nevzorov and Freed, which includes the effect of restrictions imposed by the finite length of the chain, describes the experiment within experimental errors. A simple modification of the Hwang-Freed model that does not specifically include the dynamical effects of the finite tether also provides a good approximation to the data when the tether chain is sufficiently long. 相似文献
196.
Jack E. Baldwin Alexander V.W. MaywegGareth J. Pritchard Robert M. Adlington 《Tetrahedron letters》2003,44(24):4543-4545
An expedient ten-step synthesis of a substituted tropolone is described. The synthesis involves a 3-oxidopyrylium [5+2] cycloaddition reaction with acrylonitrile as the key step, affording a highly functionalized [3.2.1]-bicycle 10 as a single regioisomer. The nitrile substituent of the reduced cycloadduct 12 permits efficient ether-bridge cleavage and tropolone 15 is obtained after a final bis-oxidation procedure. The pyranulose acetate cycloaddition precursor was derived from 3-methyl-2-furoate. 相似文献
197.
This article examines how web-based interorganizational information systems(ios)can efficiently support coordination mechanisms between outsourcer and third party logistics (3PL). First, we review the literature on coordination mechanisms andios. Second, we report on the methodology used for gathering information on outsourcers and 3PLs. Third, armed with limited but quality data, we identified two fundamental dimensions: 3PL involvement andios impacts on logistics outsourcing decisions. By combining the two dimensions, we propose a conceptual framework that highlights four main categories ofios that we characterize as neutralios, supply chainios, strategicios and dynamicios. After characterizing and analyzing each category, we discuss how these web basedios support outsourcers and 3PL along the supply chain. Finally, the article discusses the framework’s relevancy and its limits. 相似文献
198.
Singh J Kronenthal DR Schwinden M Godfrey JD Fox R Vawter EJ Zhang B Kissick TP Patel B Mneimne O Humora M Papaioannou CG Szymanski W Wong MK Chen CK Heikes JE DiMarco JD Qiu J Deshpande RP Gougoutas JZ Mueller RH 《Organic letters》2003,5(17):3155-3158
[reaction: see text] An efficient asymmetric synthesis of the vasopeptidase inhibitor BMS-189921 was accomplished. Two short enantioselective syntheses of the common key intermediate (S)-alpha-aminoazepinone 6b were developed. Olefin 3 was converted to 6b via asymmetric hydrogenation. Alternatively, enyne 12 was converted to racemic alpha-aminoazepinone 15b, which was transformed to 6b by a practical dynamic resolution. 相似文献
199.
[reaction: see text] The biomimetic synthesis of the bisesquiterpenoids biatractylolide 1 and biepiasterolide 2 is reported. 相似文献
200.
[reaction: see text] The biomimetic synthesis of the racemic dimer panepophenanthrin was achieved in good yield employing a tandem reaction sequence. 相似文献