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51.
Quantitation of sunitinib,an oral multitarget tyrosine kinase inhibitor,and its metabolite in urine samples by nonaqueous capillary electrophoresis time of flight mass spectrometry
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Juana Rodríguez Gregorio Castañeda Lorena Muñoz Jose C. Villa 《Electrophoresis》2015,36(14):1580-1587
A rapid, sensitive, and specific method was developed and validated using a nonaqueous‐capillary electrophoresis method with TOF‐MS for determination of sunitinib and N‐desethyl sunitinib in human urine. In order to avoid ionic suppression a urine samples dilution with methanol 1:10 previous step was used. This was the only treatment step to urine samples before the injection. Despite this dilution of the urine, the detection limit was as low as 0.07 mg/L for sunitinib and 0.15 mg/L for N‐desethyl sunitinib. Separation of compounds was achieved with a mixture of 5 mM ammonium formate in methanol. The calibration curves were linear over the range of 0.5–50.0 mg/L for the two analyzed compounds. The within‐run and between‐run precisions were within 5%, while the accuracy ranged from 96.0 to 100.4%. This method can be used in routine clinical practice to monitor sunitinib and N‐desethyl sunitinib drugs in the urine of cancer patients treated with once daily administration. 相似文献
52.
Synthesis and Biological Evaluation of Several Dephosphonated Analogues of CMP‐Neu5Ac as Inhibitors of GM3‐Synthase
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Dr. Paola Rota Dr. Federica Cirillo Dr. Marco Piccoli Dr. Antonio Gregorio Prof. Guido Tettamanti Prof. Pietro Allevi Prof. Luigi Anastasia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14614-14629
Previous studies demonstrated that reducing the GM3 content in myoblasts increased the cell resistance to hypoxic stress, suggesting that a pharmacological inhibition of the GM3 synthesis could be instrumental for the development of new treatments for ischemic diseases. Herein, the synthesis of several dephosphonated CMP‐Neu5Ac congeners and their anti ‐ GM3‐synthase activity is reported. Biological activity testes revealed that some inhibitors almost completely blocked the GM3‐synthase activity in vitro and reduced the GM3 content in living embryonic kidney 293A cells, eventually activating the epidermal growth factor receptor (EGFR) signaling cascade. 相似文献
53.
Mello R Martínez-Ferrer J Alcalde-Aragonés A Varea T Acerete R González-Núñez ME Asensio G 《The Journal of organic chemistry》2011,76(24):10129-10139
The oxygenation of n-butyl and n-butoxy chains bonded to silica with methyl(trifluoromethyl)dioxirane (1) revealed the ability of the silica matrix to release electron density toward the reacting C(2)-H σ-bond through the Si-C(1) and Si-O(1) σ-bonds connecting the alkyl chain to the surface (silicon β-effect). The silica surface impedes neither the alkyl chain adopting the conformation required for the silicon β-effect nor dioxirane 1 approaching the reactive C(2) methylene group. Reaction regioselectivity is insensitive to changes in the solvation of the reacting system, the location of organic ligands on the silica surface, and the H-bonding character of the silica surface. Reaction rates are faster for those organic ligands either within the silica pores or bonded to hydrophilic silica surfaces, which evidence the enhanced molecular dynamics of confined dioxirane 1 and the impact of surface phenomena on the reaction kinetics. The oxygenation of n-butyl and n-butoxy chains carrying trimethylsilyl, trimethoxysilyl, and tert-butyl groups with dioxirane 1 under homogeneous conditions confirms the electronic effects of the silyl substituents and the consequences of steric hindrance on the reaction rate and regioselectivity. Orthosilicic acid esters react preferentially at the methylene group adjacent to the oxygen atom in clear contrast with the reactivity of the carboxylic or sulfonic acid alkyl esters, which efficiently protect this position toward oxidation with 1. 相似文献
54.
García G Timón V Hernández-Laguna A Navarro A Fernández-Gómez M 《Physical chemistry chemical physics : PCCP》2011,13(21):10091-10099
Density Functional Theory has been used to study the structural, electronic and charge-transport properties of two regio-regular head-to-tail polythiophene derivatives, i.e. poly(3-hexyl-thiophene), P3HT, and poly(3-oxyhexyl-thiophene), P3OHT. The effect of substituents on the electronic structure was analyzed by means of bandwidth, bandgap, effective mass, total and partial densities of states and crystal orbital overlap populations. Electronic couplings were estimated from band diagrams as the splitting of the valence band. The neutral and cationic states of isolated oligomers were optimized using the supercell approximation. The hole-transfer rates and mobilities were evaluated according to Marcus's theory. Results provide a compelling illustration of the effect of side chains on the crystal packing, electronic structure and charge-transport properties. Thus, the hole mobility calculated for the alkyl derivative was 0.15 cm(2) V(-1) s(-1) (experimental mobility is 0.10 cm(2) V(-1) s(-1)), while the alkoxy derivative has a theoretical mobility of 0.49 cm(2) V(-1) s(-1). The obtained results hopefully could motivate experimentalists to try out P3OHT for an improved charge carrier mobility. 相似文献
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56.
The synthesis of -cinnamylethers by oxidation of allylbenzene is described. The reaction cannot be explained by formation of an allylic mercurial. A new type of mechanism in the oxidation of alkenes by mercury(II) salts is proposed. 相似文献
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59.
The characterization of the dynamic performances of a manipulator is important both to compare different manipulators and to improve the dynamic performances of a manipulator during the design stage. In a previous paper the concepts of swiftness and of dynamic isotropy were used to characterize some dynamic performances of 3-dof manipulators. This paper analyzes the usefulness of these concepts for three-dof planar manipulators and shows that the concept of swiftness is still significant, whereas the concept of dynamic isotropy has no practical interest. Moreover, it introduces three new dynamic properties that are useful in the design of a 3-dof planar manipulator. Finally, it proposes some indices that measure both the swiftness and the three new dynamic properties and shows how to use them, both for evaluating the dynamic performances of a given 3-dof planar manipulator and for improving the dynamic performances during its design. 相似文献
60.