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21.
[reaction: see text] From a common precursor, two unusual dehydrobenzoannulene topologies have been synthesized utilizing either Pd-catalyzed or Cu-mediated oxidative homocoupling as the ring-closure step. 相似文献
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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
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When social groups compete for members, the resulting dynamics may be understandable with mathematical models. We demonstrate that a simple ordinary differential equation (ODE) model is a good fit for religious shift by comparing it to a new international data set tracking religious nonaffiliation. We then generalize the model to include the possibility of nontrivial social interaction networks and examine the limiting case of a continuous system. Analytical and numerical predictions of this generalized system, which is robust to polarizing perturbations, match those of the original ODE model and justify its agreement with real-world data. The resulting predictions highlight possible causes of social shift and suggest future lines of research in both physics and sociology. 相似文献
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A Visible‐Light‐Mediated Radical Smiles Rearrangement and its Application to the Synthesis of a Difluoro‐Substituted Spirocyclic ORL‐1 Antagonist
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Dr. James J. Douglas Haley Albright Martin J. Sevrin Dr. Kevin P. Cole Prof. Corey R. J. Stephenson 《Angewandte Chemie (International ed. in English)》2015,54(49):14898-14902
A visible‐light‐mediated radical Smiles rearrangement has been developed to address the challenging synthesis of the gem‐difluoro group present in an opioid receptor‐like 1 (ORL‐1) antagonist that is currently in development for the treatment of depression and/or obesity. This method enables the direct and efficient introduction of the difluoroethanol motif into a range of aryl and heteroaryl systems, representing a new disconnection for the synthesis of this versatile moiety. When applied to the target compound, the photochemical step could be conducted on 15 g scale using industrially relevant [Ru(bpy)3Cl2] catalyst loadings of 0.01 mol %. This transformation is part of an overall five‐step route to the antagonist that compares favorably to the current synthetic sequence and demonstrates, in this specific case, a clear strategic benefit of photocatalysis. 相似文献
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Chris L. Vonnegut Airlia M. Shonkwiler Muhammad M. Khalifa Dr. Lev N. Zakharov Prof. Darren W. Johnson Prof. Michael M. Haley 《Angewandte Chemie (International ed. in English)》2015,54(45):13318-13322
Treatment of 2‐ethynylanilines with P(OPh)3 gives either 2,2‐diphenoxy‐2‐λ5‐phosphaquinolines or 2‐phenoxy‐2‐λ5‐phosphaquinolin‐2‐ones under transition‐metal‐free conditions. This reaction offers access to an underexplored heterocycle, which opens up the study of the fundamental nature of the N?PV double bond and its potential for delocalization within a cyclic π‐electron system. This heterocycle can serve as a carbostyril mimic, with application as a bioisostere for pharmaceuticals based on the 2‐quinolinone scaffold. It also holds promise as a new fluorophore, since initial screening reveals quantum yields upwards of 40 %, Stokes shifts of 50–150 nm, and emission wavelengths of 380–540 nm. The phosphaquinolin‐2‐ones possess one of the strongest solution‐state dimerization constants for a D–A system (130 M ?1) owing to the close proximity of a strong acceptor (P?O) and a strong donor (phosphonamidate N? H), which suggests that they might hold promise as new hydrogen‐bonding hosts for optoelectronic sensing. 相似文献