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51.
Fujiwara Y Dixon JA Rodriguez RA Baxter RD Dixon DD Collins MR Blackmond DG Baran PS 《Journal of the American Chemical Society》2012,134(3):1494-1497
Molecular scaffolds containing alkylfluorine substituents are desired in many areas of chemical research from materials to pharmaceuticals. Herein, we report the invention of a new reagent (Zn(SO(2)CF(2)H)(2), DFMS) for the innate difluoromethylation of organic substrates via a radical process. This mild, operationally simple, chemoselective, and scalable difluoromethylation method is compatible with a range of nitrogen-containing heteroarene substrates of varying complexity as well as select classes of conjugated π-systems and thiols. Regiochemical comparisons suggest that the CF(2)H radical generated from the new reagent possesses nucleophilic character. 相似文献
52.
Jonathan T. Smith Janice Ward James A. Guthrie Maria B. Sheridan Sheila Boyes Daniel Wilson Judy I. Wyatt Darren Treanor Philip J. Robinson 《Magnetic resonance imaging》2012
Objective
Chemotherapy commonly causes liver injury through sinusoidal obstructive syndrome and steatosis. Chemotherapy-induced liver injury may make it more difficult to detect metastases secondary to reduced contrast between the injured liver and metastases. The aim of this study was to determine the sensitivity of superparamagnetic iron oxide (SPIO) contrast-enhanced imaging in patients who have undergone chemotherapy prior to liver surgery.Methods
Local ethics committee approval was obtained. Thirty-one patients with hepatic metastases completing preoperative chemotherapy were prospectively recruited. Images were reviewed independently by two blinded observers who identified and localized lesions with a four-point confidence scale. The alternative free-response receiver operator characteristic method was used to analyze the results.Results
The sensitivity in detecting colorectal metastases following chemotherapy was 78% and 76%, respectively, for observers 1 and 2 (95% confidence interval: 71%–85% and 68%–82%). The areas under the alternative free-response receiver operator curves were 0.73 and 0.80 for observers 1 and 2, respectively.Conclusion
Compared to previously published work on chemotherapy-naïve patients, it is clear that the sensitivity of SPIO-enhanced magnetic resonance imaging (MRI) in detecting colorectal metastases following chemotherapy is reduced. It is therefore critical that all imaging — pre-, during and postchemotherapy — is reviewed when reporting liver MRI prior to surgery. 相似文献53.
Uchida M Morris DS Kang S Jolley CC Lucon J Liepold LO LaFrance B Prevelige PE Douglas T 《Langmuir : the ACS journal of surfaces and colloids》2012,28(4):1998-2006
Protein cage nanoparticles (PCNs) are attractive platforms for developing functional nanomaterials using biomimetic approaches for functionalization and cargo encapsulation. Many strategies have been employed to direct the loading of molecular cargos inside a wide range of PCN architectures. Here we demonstrate the exploitation of a metal-ligand coordination bond with respect to the direct packing of guest molecules on the interior interface of a virus-like PCN derived from Salmonella typhimurium bacteriophage P22. The incorporation of these guest species was assessed using mass spectrometry, multiangle laser light scattering, and analytical ultracentrifugation. In addition to small-molecule encapsulation, this approach was also effective for the directed synthesis of a large macromolecular coordination polymer packed inside of the P22 capsid and initiated on the interior surface. A wide range of metals and ligands with different thermodynamic affinities and kinetic stabilities are potentially available for this approach, highlighting the potential for metal-ligand coordination chemistry to direct the site-specific incorporation of cargo molecules for a variety of applications. 相似文献
54.
The utility of the Suzuki cross-coupling to synthesize biaryl compounds is expanded herein to include reactions of resin-supported chloropyrimidines with boronic acids. In particular, an efficient method is described for the synthesis of a library of biaryl compounds from solid-supported chloropyrimidines. The Suzuki reaction was performed in an inert atmosphere using Pd(2)(dba)(3)/P(t-Bu)(3) as catalyst, spray-dried KF as base, and THF as solvent. The reaction was allowed to proceed overnight at 50 degrees C. Upon cleavage with acid, a library of 4-(substituted amino)-6-arylpyrimidines was obtained in moderate yield and high purity. 相似文献
55.
The article presents a study for the evolution of growth interface in crystal growth by Liquid Phase Diffusion (LPD). Specific LPD experiments were designed to grow compositionally graded, germanium‐rich SixGe1‐x single crystals of 25 mm in diameter with various thicknesses. Measured interface shapes show the evolution of the growth interface. Silicon compositions were measured by the Energy Dispersive X‐ray analysis (EDX) in the growth and radial directions. The study shows the feasibility of extracting the desired seeds of uniform composition from LPD grown crystals, for subsequent use in other epitaxial growth processes. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim 相似文献
56.
Model calculations on anion carrier ligands related to trifluoroacetophenone were carried out using the semiempirical AM 1 method in order to investigate the factors involved in such anion-ligand complexation. The reaction of halogen derivatives of acetophenone with various nucleophiles such as water, carbonic acid, and bicarbonate anion was studied. By this means, the effect of various structural changes, such as variation of the ring substituents and variation of the degree and type of halogen atom substitution, could be determined. It is shown that in terms of relative stability, fluorine derivatives are preferable to chlorine derivatives for the binding of water and carbonic acid. Monosubstitution of a methoxy group in the ortho position of the trifluoroacetophenone ring also brought about stability in the case of the hydration reaction. An electron-withdrawing ester group in the para position on the trifluoroacetophenone ring brings about stabilization also. 相似文献
57.
Spencer introduced a chip firing game on a line, which was generalized by Björner, Lovasz and Shor to graphs. This paper characterizes those configurations which may be repeated in a game, and analyzes the game forn-cycles.This research was funded by NSERC operating grants. 相似文献
58.
The syntheses of azabicyclo[3.1.0]hexane transition state (TS) analogs are described. Cyclopropanation of N-Boc-3-pyrroline with ethyl diazoacetate afforded a 1.6:1 exo/endo ratio of the resulting ester. Reduction of the endo-isomer with LiAlH4 yielded the alcohol which was phosphorylated, or iodinated to provide access to aglycon containing TS analogs. 相似文献
59.
Allylic alcohols have been found to react with Fe2(CO)9 in ether to afford after addition of HBF4/acetic anhydride, the corresponding (η3-allyl)Fe(CO)4+BF4?- species (I) in moderate to good yields. The geometry of the starting alcohol is retained in the product complex; thus E-crotyl and -cinnamyl alcohols led to anti-substituted complexes, whereas the corresponding Z-alcohols produced syn-complexes. 相似文献
60.
Lemos Paulo Vitor França Barbosa Leandro Santos Ramos Ingrid Graça Coelho Rodrigo Estevam Druzian Janice Izabel 《Journal of Thermal Analysis and Calorimetry》2018,131(3):2555-2567
Journal of Thermal Analysis and Calorimetry - The thermal features of potato, banana, corn and cassava starches were correlated with structural properties. These starches were characterized by SEM,... 相似文献