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61.
Direct Catalytic Enantio‐ and Diastereoselective Ketone Aldol Reactions of Isocyanoacetates 下载免费PDF全文
Dr. Raquel de la Campa Dr. Irene Ortín Prof. Dr. Darren J. Dixon 《Angewandte Chemie (International ed. in English)》2015,54(16):4895-4898
A catalytic asymmetric aldol addition/cyclization reaction of unactivated ketones with isocyanoacetate pronucleophiles has been developed. A quinine‐derived aminophosphine precatalyst and silver oxide were found to be an effective binary catalyst system and promoted the reaction to afford chiral oxazolines possessing a fully substituted stereocenter with good diastereoselectivities and excellent enantioselectivities. 相似文献
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Milton J. KiefelPradeep Chopra Paul D. MadgeAlex Szyczew Robin J. ThomsonI. Darren Grice Mark von Itzstein 《Tetrahedron letters》2011,52(1):98-100
Sialic acids are 9-carbon acidic sugars involved in a number of important biological processes and human diseases. As part of our ongoing interest in the development of novel sialic acids as biological probes, we have developed an efficient and simple synthesis of C-9 oxidised sialic acid derivatives. The key oxidative step involves the use of TEMPO under carefully controlled aqueous pH conditions. 相似文献
64.
Speelman AL Muñoz-Losa A Hinkle KL VanBeek DB Mennucci B Krueger BP 《The journal of physical chemistry. A》2011,115(16):3997-4008
We provide a critical examination of two different methods for generating a donor-acceptor electronic coupling trajectory from a molecular dynamics (MD) trajectory and three methods for sampling that coupling trajectory, allowing the modeling of experimental observables directly from the MD simulation. In the first coupling method we perform a single quantum-mechanical (QM) calculation to characterize the excited state behavior, specifically the transition dipole moment, of the fluorescent probe, which is then mapped onto the configuration space sampled by MD. We then utilize these transition dipoles within the ideal dipole approximation (IDA) to determine the electronic coupling between the probes that mediates the transfer of energy. In the second method we perform a QM calculation on each snapshot and use the complete transition densities to calculate the electronic coupling without need for the IDA. The resulting coupling trajectories are then sampled using three methods ranging from an independent sampling of each trajectory point (the independent snapshot method) to a Markov chain treatment that accounts for the dynamics of the coupling in determining effective rates. The results show that the IDA significantly overestimates the energy transfer rate (by a factor of 2.6) during the portions of the trajectory in which the probes are close to each other. Comparison of the sampling methods shows that the Markov chain approach yields more realistic observables at both high and low FRET efficiencies. Differences between the three sampling methods are discussed in terms of the different mechanisms for averaging over structural dynamics in the system. Convergence of the Markov chain method is carefully examined. Together, the methods for estimating coupling and for sampling the coupling provide a mechanism for directly connecting the structural dynamics modeled by MD with fluorescence observables determined through FRET experiments. 相似文献
65.
Fu Y Habtemariam A Basri AM Braddick D Clarkson GJ Sadler PJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10553-10562
We report the synthesis and characterisation of 32 half sandwich phenylazopyridine Os(II) arene complexes [Os(η(6)-arene)(phenylazopyridine)X](+) in which X is chloride or iodide, the arene is p-cymene or biphenyl and the pyridine and phenyl rings contain a variety of substituents (F, Cl, Br, I, CF(3), OH or NO(2)). Ten X-ray crystal structures have been determined. Cytotoxicity towards A2780 human ovarian cancer cells ranges from high potency at nanomolar concentrations to inactivity. In general the introduction of an electron-withdrawing group (e.g. F, Cl, Br or I) at specific positions on the pyridine ring significantly increases cytotoxic activity and aqueous solubility. Changing the arene from p-cymene to biphenyl and the monodentate ligand X from chloride to iodide also increases the activity significantly. Activation by hydrolysis and DNA binding appears not to be the major mechanism of action since both the highly active complex [Os(η(6)-bip)(2-F-azpy)I]PF(6) (9) and the moderately active complex [Os(η(6)-bip)(3-Cl-azpy)I]PF(6) (23) are very stable and inert towards aquation. Studies of octanol-water partition coefficients (log P) and subcellular distributions of osmium in A2780 human ovarian cancer cells suggested that cell uptake and targeting to cellular organelles play important roles in determining activity. Although complex 9 induced the production of reactive oxygen species (ROS) in A2780 cells, the ROS level did not appear to play a role in the mechanism of anticancer activity. This class of organometallic osmium complexes has new and unusual features worthy of further exploration for the design of novel anticancer drugs. 相似文献
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Oscar Salas-Solano Kunnel Babu SungAe Suhr Park Xinfeng Zhang Li Zhang Zoran Sosic Boris Boumajny Ming Zeng Kuang-Chuan Cheng Angelia Reed-Bogan Stacey Cummins-Bitz David A. Michels Monica Parker Paulina Bonasia Mingfang Hong Steven Cook Margaret Ruesch David Lamb Dora Bolyan Steffen Kiessig Darren Allender Brian Nunnally 《Chromatographia》2011,73(11-12):1137-1144
Interlaboratory comparisons are essential to bringing emerging technologies into biopharmaceutical industry practice and regulatory acceptance. As a result, an international team including 12 laboratories from 10 independent biopharmaceutical companies in the United States and Switzerland was formed to evaluate the precision and robustness of capillary isoelectric focusing (CIEF) to assess the charge heterogeneity of monoclonal antibodies. The different laboratories determined the apparent pI and the relative distribution of the charge isoforms of a representative monoclonal antibody (rMAb) sample using the same CIEF method. Statistical evaluation of the data was performed to determine within and between-laboratory consistencies and outlying information. The apparent pI data generated for each charge variant peak showed very good precision between laboratories with percentage of RSD values of ??0.5%. Similarly, the percentage of RSD for the rMAb charge variants percent peak area values are ??4.4% across different laboratories with different analysts using different lots of ampholytes and multiple instruments. Taken together, these results validate the appropriate use of CIEF in the biopharmaceutical industry in support of regulatory submissions. 相似文献
67.
An efficient, easy to perform, one-pot reaction cascade for the synthesis of 2,5-disubstituted pyrroles from p-toluenesulfonyl protected imines and 4-nitrobut-1-yne under a combination of base and gold(III) catalysis is reported. 相似文献
68.
Three new [2]rotaxanes with aromatic nitrogen donors appended to the crown ether wheel have been synthesized and used as ligands to coordinate Cd(II) ions. One of these yields a new type of 2-periodic, metal organic rotaxane framework in which the wheel rather than the axle is used to link the metal nodes. 相似文献
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70.
Hierarchical ZnO/Cu "corn-like" materials with high photodegradation and antibacterial capability under visible light 总被引:1,自引:0,他引:1
A novel hierarchical ZnO/Cu "corn-like" material was successfully synthesized via facile low temperature hydrothermal and photo-deposition methods. This novel hierarchical material was well characterized by FESEM, XRD, EDS, UV-Vis. This novel material displayed high photodegradation and antibacterial capability under the irradiation of visible light. This is owing to its unique properties, including maximized light utilization rate via red-shifting the light absorption spectrum, enhanced specific surface area for mass transfer and reaction sites, and retarded recombination of photogenerated electrons and holes. Moreover, this novel hierarchical ZnO/Cu "corn-like" material demonstrated easy recovery from treated water for reuse. All these excellent properties indicate that this novel hierarchical ZnO/Cu "corn-like" material has a bright future in water purification applications. 相似文献