We demonstrate a single-step synthetic method for highly luminescent (i.e., quantum yield up to 80%) and stable quantum dots (QDs) by using the reactivity difference between Cd and Zn precursors and that between Se and S precursors. A wide range of emission wavelengths (500-610 nm) with a narrow fwhm (<35 nm) is obtained by changing the ratios of the precursors. Under the reaction conditions selected, Cd-and Se (with a bit of S)-based cores are formed first and Zn-and S-based shells are formed successively; therefore, the QDs have a core/shell structure with composition gradients, which relieve the lattice mismatch between core and shells. The QDs are characterized using the combined techniques of HR-TEM, UV-vis, PL spectroscopy, and ICP-AES. The QDs also have energy gradients depending on their compositions in a radial direction, which energetically confine carriers (electrons and holes) to the cores. This leads to the stability of QDs during their surface passivation from oleic acid to mercaptopropionic acid and ensures their processibility for further purposes such as optoelectronic and biological applications.
Mechanisms of tungstate sorption on the mineral boehmite (γ-AlOOH) were studied using batch uptake experiments and X-ray absorption spectroscopy. Batch uptake experiments over the pH range 4-8 and [W]=50-2000 μM show typical oxyanion behavior, and isotherm experiments reveal continued uptake with increasing tungstate concentration without any clear uptake maximum. Desorption experiments showed that sorption is irreversible at pH 4 and partly reversible at pH 8. Tungsten L1- and L3-edge XANES spectroscopy indicates that all sorbed tungstates are octahedrally coordinated, even though the dominant solution species at pH 8 is a tetrahedral monotungstate. Tungsten L3-edge EXAFS analysis shows that sorbed tungstate occurs as polymeric form(s), as indicated by the presence of corner- and edge-sharing of distorted tungstate octahedra. The occurrence of polymeric tungstate on the surface at pH 8 indicates that sorption is accompanied by polymerization and a coordination change from tetrahedral (in solution) to distorted octahedral (on the surface). The strong tendency for tungstate polymerization on boehmite can explain the continued uptake without an apparent maximum in sorption, and the limited desorption behavior. Our results provide the basis for a predictive model of tungstate uptake by boehmite, which can be important for understanding tungstate mobility, toxicity, and bioavailability.
Eubacterium limosum (ATCC 8486), a strict anaerobe from the human intestinal tract that is capable of O-demethylation of several compounds, was tested for the ability to metabolize three methoxylated isoflavonoids, biochanin A, formononetin, and glycitein. Highperformance liquid chromatography elution profiles of metabolites produced from biochanin A, formononetin, and glycitein showed peaks that had identical retention times to authentic genistein, daidzein, and 6,7,4P-trihydroxyisoflavone, respectively. The metabolites were identified, using an on line liquid chromatography-electrospray mass spectrometer. E. limosum produced 61.4 WM of genistein and 13.2 WM of daidzein from 100 WM of biochanin A and formononetin, after 26 days incubation. O-demethylase activity is cell-associated and was not detected in the extracellular fraction of bacterial culture. This is the first study in which conversion of biochanin A, and formononetin to more potent phytoestrogens by a bacterium has been shown. ß
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