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排序方式: 共有199条查询结果,搜索用时 15 毫秒
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Dendritic molecular capsules for hydrophobic compounds 总被引:1,自引:0,他引:1
Morgan MT Carnahan MA Immoos CE Ribeiro AA Finkelstein S Lee SJ Grinstaff MW 《Journal of the American Chemical Society》2003,125(50):15485-15489
Reichardt's dye, a highly solvatochromic dye, was encapsulated within poly (glycerol succinic acid) ([Gn]-PGLSA-OH) dendrimers to investigate the interior environment of these dendritic macromolecules. The absorption maximum for the encapsulated Reichardt's dye in water was indicative of a relatively high dielectric constant present within the dye/dendrimer complex. (1)H NMR of the encapsulated complex showed the presence of aromatic protons from Reichardt's dye along with the aliphatic protons of the dendrimer. Additionally, there were substantial changes in T(1) and T(2) times of the encapsulated dye when compared with the free dye, and (1)H NOESY spectra for the complex showed a significant number of intermolecular NOE cross-peaks. These data reveal the close through-space proximity of the dye to the dendrimer and the restricted motion of the encapsulated dye. To demonstrate the potential use of these macromolecules as drug delivery vehicles, the poorly water-soluble anticancer drug 10-hydroxycamptothecin (10HCPT) was encapsulated within a carboxylated PGLSA dendrimer ([G4]-PGLSA-COONa). Cytotoxicity assays with human breast cancer cells showed a significant reduction of cell viability, demonstrating that 10HCPT retains activity upon encapsulation. 相似文献
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Powell BJ Baruah T Bernstein N Brake K McKenzie RH Meredith P Pederson MR 《The Journal of chemical physics》2004,120(18):8608-8615
We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, Delta(HL). We show that Delta(HL) is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in Delta(HL) to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins. 相似文献
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Michael H. Gold Hidetoshi Kutsuki Meredith A. Morgan 《Photochemistry and photobiology》1983,38(6):647-651
Oxidation of specifically radiolabeled 14C-lignins by UV/H202. Fenton's reagent, photosesitizing riboflavin. UV- and γ-irradiation was examined. In the presence of UV/H2O2, a hydroxyl radical (·OH) generating system. 14C-methoxy. 2-[14C-sidechain] and 14C-ring labeled lignin were rapidly and extensively degraded as measured by gel filtration of the reaction products on Sephadex LH-20. This suggested that exposure to OH leads to rapid, nonspecific lignin degradation. Rapid degradation of 14C-methoxy, 2-[14C-sidechain] and 14C-ring labeled lignin also occurred in the presence of the ·OH generating system, Fenton's reagent, confirming the primary role of ·OH in these reactions. Photosensitizing riboflavin, also capable of effecting transformation of organic compounds via Type I hydrogen radical abstractions, caused extensive oxidative degradation of 14C-methoxy labeled lignin and significant degradation of 2-(14C-sidechain] and 14C-ring labeled lignin. In addition, UV- and γ-irradiation caused slower but extensive degradation of the polymers, probably via radical type mechanisms. All of these results indicate that ·OH as well as organic radical generating systems are effective agents for the purpose of degrading this heterogeneous, optically inactive and random biopolymer. 相似文献
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Vogel R Meredith P Harvey MD Rubinsztein-Dunlop H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(1-2):245-249
A comparison has been made between the spectroscopic properties of the laser dye rhodamine 6G (R6G) in mesostructured titanium dioxide (TiO(2)) and in ethanol. Steady-state excitation and emission techniques have been used to probe the dye-matrix interactions. We show that the TiO(2)-nanocomposite studied is a good host for R6G, as it allows high dye concentrations, while keeping dye molecules isolated, and preventing aggregation. Our findings have important implications in the context of solid state dye-lasers and microphotonic device applications. 相似文献
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Santiago MB Vélez MM Borrero S Díaz A Casillas CA Hofmann C Guadalupe AR Colón JL 《Electroanalysis》2006,18(6):559-572
We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)2bpy]2+) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)2bpy]2+ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)2bpy]2+. The UV‐vis spectrophotometric results indicate that the [Ru(phend)2bpy]2+ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)2bpy]2+ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented. 相似文献
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Quantal (E,tau) plots are constructed from the eigenvalues of the quantum system. We demonstrate that these representations display the periodic orbits of the classical system, including bifurcations and the transition from stable to unstable. (c) 1995 American Institute of Physics. 相似文献
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We show that the two-photon resonances in the third-order susceptibility can be exploited to yield two-photon spectra of molecular gases at moderately high spectral resolution. This form of spectroscopy does not depend on the occurrence of processes (such as fluorescence of photoionization) leading to indirect methods of two-photon absorption. The method is direct and leads in principle to values for a two-photon cross section. Comparisons of two-photon and coherent anti-Stokes Raman resonances leads to ratios of Raman and two-proton cross sections independent of the laser powers and spatial characteristics. The technique is documented with rotationally resolved spectra of SO2 and NO. A value for |αxxαyy| of 1.5 × 10?52 cm6 was measured for the O12 (6) component of the (A)2Σ ← (X)2 Π transition of nitric oxide. 相似文献