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101.
Synthesis, cytotoxicity and cellular uptake studies of N3 functionalized Re(CO)3 thymidine complexes
Bartholomä MD Vortherms AR Hillier S Joyal J Babich J Doyle RP Zubieta J 《Dalton transactions (Cambridge, England : 2003)》2011,40(23):6216-6225
Nucleoside-derived drugs play an important role in the treatment of cancer. Here, we present the synthesis and characterization of an intriguing series of N3 conjugated Re(CO)(3) thymidine complexes. The complexes were characterized by NMR spectroscopy and mass spectrometry and their cytotoxicity was assessed against A549 cells. A similar dependence on the spacer length and the toxicity has been found for N3 functionalized complexes as recently reported for their C5' counterparts. A remarkable cytotoxic complex 22, carrying a dodecylene spacer at position N3 with a bis-quinoline metal chelate moiety, with an IC(50) value of 3.4 ± 1.6 μM, has been identified. Addition of a 100-fold excess of thymidine did not statistically reduce the observed cytotoxicity of all complexes. Cellular uptake studies of complex 22 have been performed by fluorescent microscopy, showing that compound 22 was clearly internalized into A549 cells. Temperature dependent uptake studies, blocking experiments with thymidine, and endosomal co-localization suggest that uptake of 22 occurs via passive diffusion and endocytosis. 相似文献
102.
West NP Cergol KM Xue M Randall EJ Britton WJ Payne RJ 《Chemical communications (Cambridge, England)》2011,47(18):5166-5168
The first targeted inhibitors of an essential M. tuberculosis cell wall lipase, Rv3802c, are described. Lead compounds exhibited nanomolar inhibition of the enzyme, and encouraging antibacterial activity against M. tuberculosis in vitro, supporting Rv3802c as a novel TB drug target. 相似文献
103.
Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates. 相似文献
104.
Sawyer BC Stuhl BK Yeo M Tscherbul TV Hummon MT Xia Y Kłos J Patterson D Doyle JM Ye J 《Physical chemistry chemical physics : PCCP》2011,13(42):19059-19066
Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule. 相似文献
105.
Britton Chang Anne Greenbaum Eric Machorro 《Numerical Linear Algebra with Applications》2011,18(1):141-154
In this paper, we prove that the piecewise bilinear Petrov‐Galerkin discretization for the mono‐directional neutron transport equation described in (J. Comput. Phys. 1986; 64 :96–111) is convergent and second‐order accurate, provided that the true solution to the problem has continuous partial derivatives of all orders up through three. We do this by giving a bound on the 2‐norm of the inverse of the system matrix that is independent of the mesh size. This shows that the global error is of the same order as the local truncation error. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
106.
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109.
S. Aukkaravittayapun P. J. King K. A. Benedict Yu. I. Latyshev I. G. Gorlova S. Zybtsev A. Campbell R. A. Doyle J. Johnson W. S. Seow 《Physica C: Superconductivity and its Applications》1996,270(3-4)
We describe three mechanisms for the anomalous voltage reversals which are occasionally observed during four contact current-voltage measurements on the high temperature superconductors. Voltage reversals have been frequently observed for whiskers of the bismuth strontium calcium copper oxide (BSSCO) compounds, and we describe measurements made on high quality whiskers of the 2:2:1:2 and 2:2:2:3 phases. A simple model based on extreme anisotropy plus offset contacts can explain the gross features of four contact measurements in the ohmic flux-flow regime, but not the wealth of reversal phenomena found for the IVVI configuration in the lower temperature irreversibility region. 相似文献
110.
A. T. Britton J. L. Sullivan K. J. Smith 《Journal of Polymer Science.Polymer Physics》1980,18(3):537-546
Thermoelasticity studies of poly(vinyl alcohol) networks swollen in aqueous glycol indicate that the effects of specific polymer-diluent interactions diminish at high swelling, much as in the situation of poly(vinyl alcohol) in pure water reported earlier. In 20% glycol, the ratio of the energy component fe of the force to the total force f was found to be ?0.59 at high swelling. Swelling was controlled by the degree of network crosslinking. Evidence that fe/f could be determined under the condition of a null thermal expansion coefficient was not obtained; in fact, the contrary was indicated. 相似文献