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81.
Shannon E. Cooney Alex A. Fertig Madeleine R. Buisch William W. Brennessel Ellen M. Matson 《Chemical science》2022,13(43):12726
Hydrogen-atom (H-atom) transfer at the surface of heterogeneous metal oxides has received significant attention owing to its relevance in energy conversion and storage processes. Here, we present the synthesis and characterization of an organofunctionalized polyoxovanadate cluster, (calix)V6O5(OH2)(OMe)8 (calix = 4-tert-butylcalix[4]arene). Through a series of equilibrium studies, we establish the BDFE(O–H)avg of the aquo ligand as 62.4 ± 0.2 kcal mol−1, indicating substantial bond weaking of water upon coordination to the cluster surface. Subsequent kinetic isotope effect studies and Eyring analysis indicate the mechanism by which the hydrogenation of organic substrates occurs proceeds through a concerted proton–electron transfer from the aquo ligand. Atomistic resolution of surface reactivity presents a novel route of hydrogenation reactivity from metal oxide surfaces through H-atom transfer from surface-bound water molecules.Coordination-induced bond weakening facilitates H-atom transfer from polyoxovanadate surface. 相似文献
82.
83.
Margaret S. Cheney und Ellen Swallow Richards 《Fresenius' Journal of Analytical Chemistry》1878,17(1):214-216
Ohne Zusammenfassung 相似文献
84.
Mann AK Steinmiller EM Skrabalak SE 《Dalton transactions (Cambridge, England : 2003)》2012,41(26):7939-7945
Polycrystalline microspheres and single-crystalline microplates of Bi(2)WO(6) have been synthesized by ultrasonic spray pyrolysis. Herein, these materials are evaluated as photocatalysts for the visible light mediated degradation of rhodamine B, a model pollutant, and the results compared to those obtained with Bi(2)WO(6) prepared by traditional methods. The microplates, which displayed the best crystallinity and highest surface area, were anticipated to facilitate the greatest rate of dye photodegradation. However, the polycrystalline microspheres outperformed both the Bi(2)WO(6) microplates and traditional samples. To understand the origin of this result, the local and macroscale structures of the Bi(2)WO(6) samples were comprehensively characterized by spectroscopy techniques (diffuse reflectance, fluorescence, Raman, and X-ray photoelectron spectroscopy) as well as electron microscopy and diffraction. This analysis found that the enhanced performance of the Bi(2)WO(6) microspheres results from the expression of a hydrophilic surface, a low concentration of point defects, and a moderate surface area. This finding highlights the significant role synthesis plays in imparting structure and functionality to solid materials. 相似文献
85.
NEW PHTHALOCYANINE PHOTOSENSITIZERS FOR PHOTODYNAMIC THERAPY 总被引:2,自引:1,他引:2
Nancy L. Oleinick Antonio R. Antunez Marian E. Clay Boris D. Rihter Malcolm E. Kenney 《Photochemistry and photobiology》1993,57(2):242-247
Six new aluminum and silicon phthalocyanines have been synthesized and their photocytotoxicity toward V79 cells has been studied. The compounds that have been prepared are: AIPcOSi(CH3)2(CH2),N(CH3)2, I; AIPcOSi(CH3)2(CH2)3N(CH3)3+I?, II; CH3SiPcOSi(CH3)2(CH2)3N(CH3)2, III; HOSiPcOSi(CH3)2(CH2)3N(CH3)2, IV; HOSiPcOSi(CH3)2(CH2)3)3(CH3)3+I?, V; and SiPc[OSi(CH3)2(CH2)3N(CH3)3+I?]2, VI. Relative growth delay values for compounds I-VI and relative cytotoxicity values for compounds I, II, IV, V and VI have been determined. Compounds I and II have been shown to be comparable in photocytotoxicity to what is presumed to be AIPcOH.xH2O, and compound IV has been shown to have greater activity. The classes of compounds to which these six compounds belong appear to have potential for photodynamic therapy. 相似文献
86.
Zimmermann H Bader V Poupko R Wachtel EJ Luz Z 《Journal of the American Chemical Society》2002,124(51):15286-15301
Nona-alkanoyloxy tribenzocyclononene (CTV-n, where n is the number of carbons in the side chains) were prepared for n = 2 to 14. The homologues of this series appear in two stable isomeric forms, rigid crown and flexible saddle. We report on their isomerization equilibria and dynamics in solution and on their mesomorphic properties in the neat state. The crown-saddle equilibrium and interconversion kinetics of the CTV-8 isomers were studied in dimethyl formamide solutions using high-resolution (1)H NMR in the temperature range from 50 to 130 degrees C. At lower temperatures, the isomerization is too slow to measure. In this range the equilibrium saddle fraction increases from approximately 0.40 to approximately 0.65, whereas the isomerization rate increases from approximately 10(-)(4) to approximately 1 s(-)(1). The saddle isomer undergoes fast pseudorotation at room temperature, but below about -50 degrees C, it becomes slow enough to affect the NMR line width. The rate parameters for this process were estimated from the carbon-13 spectra in methylene chloride solutions to be, k(p)(-100 degrees C) approximately 1.7 x 10(3) s(-)(1) and E(a) approximately 9.6 kJ/mol. The slow crown-saddle isomerization at room temperature (half-life of about one year) allows quantitative separation (by chromatography) of the two isomers and their separate investigation. When the alkanoyloxy side chains are sufficiently long both isomers are mesogenic (n >or= 4 for the saddle and n >or= 5 for the crown), exhibiting hexagonal columnar mesophases. The structure, dynamics, and mesomorphic properties of these mesophase were investigated by X-ray diffraction, optical polarizing microscopy, differential scanning calorimetry, and NMR. The lattice parameters of the crown and saddle mesophases of corresponding homologues are almost identical and increase monotonically with increasing length of the side chains. The clearing temperatures of the saddle isomers are consistently lower than those of the corresponding crowns. Within each series, the clearing temperatures are almost independent of the length of the side chains (156 to 170 degrees C for the crown and 115 to 148 degrees C for the saddle). The thermal and kinetic properties of the neat compounds lead to peculiar phase sequences, as observed in the polarizing microscope and in the DSC thermogram, involving repeated, back and forth, interconversion between the two isomers. Carbon-13 MAS NMR measurements of the crown and saddle mesophases of several homologues were carried out. The spectra of the crown mesophase exhibit dynamic features consistent with planar 3-fold molecular jumps about the column axes. A quantitative analysis for the CTV-8 crown homologue yielded the following Arrhenius parameters, A = 3.1 x 10(22)s(-)(1) and E(a) = 130.1kJ/mol. These unusually high values suggest that the barrier to the jump process is temperature dependent, decreasing with increasing temperature. The rate of this 3-fold jump process is slower for the lower homologues and faster for the higher ones. In contrast, the saddle isomers in the mesophase do not show dynamic effects in their carbon-13 MAS spectra. They do not undergo pseudorotation, and it appears that the molecules remain locked within the columns in a saddle conformation, up to the clearing temperature. However, on (super-)cooling to room temperature and below, selective line broadening is observed in their carbon-13 MAS spectra. This suggests that the saddle conformation is twisted in the mesophase and undergoes fast high-amplitude jumps between the twisted forms. On cooling, these high-amplitude librations freeze out to give an orientationally disordered state. On a very long time scale (of the order of days at 100 degrees C), the saddle mesophase transforms into that of the crown, apparently by sublimation. 相似文献
87.
Summary Measurements have been made of the sea-level size spectrum of cosmic-ray showers at a number of zenith angles and the relationship
between shower size and atmospheric depth has been derived for a number of integral cosmic-ray fluxes. These measurements
extend the available data to ∼ 1400 g·cm−2 and emphasize the discrepancy between measurements made on Mt. Chacaltaya and those made at other observatories.
Riassunto Sono state fatte misurazioni dello spettro delle dimensioni a livello del mare di sciami di raggi cosmici ad un certo numero di angoli zenitali ed è stata dedotta la relazione tra la grandezza dello sciame e la profondità atmosferica per un certo numero di flussi integrali di raggi cosmici. Queste misurazioni estendono i dati disponibili a∼1400 g·cm−2 ed evidenziano la discrepanza tra le misurazioni fatte sul Monte Chalcaltaya e quelle di altri osservatori.
Резюме Проводятся измерения спектра размеров ливней космических лучей на уровне моря при различных зенитных углах и соотношения между размером ливня и толщиной атмосферы для ряда интегральных потоков космических лучей. Эти измерения уточняют имеющиеся данные до толщии∼1400 г·см−2. Отмечается расхождение между измерениями, проведенными на горе Чакалтайа, и измерениями в других обсерваториях.相似文献
88.
Ellen R. Goldman Igor L. Medintz George P. Anderson Brent L. Iverson George Georgiou Hedi Mattoussi 《Analytica chimica acta》2005,534(1):63-67
We report a simple and versatile approach for the conjugation of luminescent CdSe-ZnS core-shell quantum dots (QDs) to proteins through coordination of engineered C-terminal oligohistidine sequences. Several histidine tail containing proteins were self-assembled onto the QD surface using this method. A recombinant antibody specific for the high explosive 2,4,6-trinitrotoluene (TNT) was conjugated to QDs through a carboxy terminal histidine tail and the bioconjugate used to detect TNT by competitive immunoassay. TNT was detected over the range of 10 μg/ml down to 41 ng/ml using the scFv conjugated to QDs. These results open up the possibility to conjugate luminescent QDs to a whole range of proteins to form QD bioconjugates that can be effectively used in bio-oriented applications, such as sensing, imaging, immunoassay and other diagnostics. 相似文献
89.
Gielen E Smisdom N De Clercq B Vandeven M Gijsbers R Debyser Z Rigo JM Hofkens J Engelborghs Y Ameloot M 《Journal of fluorescence》2008,18(5):813-819
Many membrane proteins and lipids are partially confined in substructures ranging from tens of nanometers to micrometers in
size. Evidence for heterogeneities in the membrane of oligodendrocytes, i.e. the myelin-producing cells of the central nervous
system, is almost exclusively based on detergent methods. However, as application of detergents can alter the membrane phase
behaviour, it is important to investigate membrane heterogeneities in living cells. Here, we report on the first investigations
of the diffusion behavior of the myelin-specific protein MOG (myelin oligodendrocyte glycoprotein) in OLN-93 as studied by
the recently developed RICS (raster-scanning image correlation spectroscopy) technique. We implemented RICS on a standard
confocal laser-scanning microscope with one-photon excitation and analog detection. Measurements on FITC-dextran were used
to evaluate the performance of the system and the data analysis procedure.
Ellen Gielen and Nick Smisdom contributed equally to this work. 相似文献
90.