86 research outputs found
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Ligand-Thickness Effect Leads to Enhanced Preference for Large Anions in Alkali Metal Extraction by Crown Ethers
Jean-Marie Lehn (Nobel laureate, 1987) suggested ligand thickness to be an important consideration in the design of host molecules for cation recognition. We have recently expanded the role of this simple ligand property by demonstrating a case in which ligand thickness contributes significantly to anion discrimination. It was found that in the extraction of sodium nitrate and perchlorate by a simple crown ether, bis(t-octylbenzo)-14-crown-4 (BOB 14C4), the normal preference for perchlorate is almost completely lost when the complex cation has the open-face sandwich vs. the sandwich structure
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Solvent Extraction of Radionuclides From Aqueous Tank Waste
This task aims toward the development of efficient solvent-extraction processes for the removal of the fission products {sup 99}Tc, {sup 90}Sr, and {sup 137}Cs from alkaline tank wastes. Processes already developed or proposed entail direct treatment of the waste solution with the solvent and subsequent stripping of the extracted contaminants from the solvent into a dilute aqueous solution. Working processes to remove Tc(and SR) separately and Cs separately have been developed; the feasibility of a combined process is under investigation. Since Tc, Sr, and Cs will be vitrified together in the high-level fraction, however, a process that could separate Tc, Sr, and Cs simultaneously, as opposed to sequentially, potentially offers the greatest impact. A figure presents a simplified diagram of a proposed solvent-extraction cycle followed by three possible treatments for the stripping solution. Some degree of recycle of the stripping solution (option a) is expected. Simple evaporation (option c) is possible prior to vitrification; this offers the greatest possible volume reduction with simple operation and no consumption of chemicals, but it is energy intensive. However, if the contaminants are concentrated (option b) by fixed-bed technology, the energy penalty of evaporation can be avoided and vitrification facilitated without any additional secondary waste being produced
Surface Doping Quantum Dots with Chemically Active Native Ligands: Controlling Valence without Ligand Exchange
One remaining challenge in the field of colloidal semiconductor nanocrystal quantum dots is learning to control the degree of functionalization or valence per nanocrystal. Current quantum dot surface modification strategies rely heavily on ligand exchange, which consists of replacing the nanocrystal\u27s native ligands with carboxylate- or amine-terminated thiols, usually added in excess. Removing the nanocrystal\u27s native ligands can cause etching and introduce surface defects, thus affecting the nanocrystal\u27s optical properties. More importantly, ligand exchange methods fail to control the extent of surface modification or number of functional groups introduced per nanocrystal. Here, we report a fundamentally new surface ligand modification or doping approach aimed at controlling the degree of functionalization or valence per nanocrystal while retaining the nanocrystal\u27s original colloidal and photostability. We show that surface-doped quantum dots capped with chemically active native ligands can be prepared directly from a mixture of ligands with similar chain lengths. Specifically, vinyl and azide-terminated carboxylic acid ligands survive the high temperatures needed for nanocrystal synthesis. The ratio between chemically active and inactive-terminated ligands is maintained on the nanocrystal surface, allowing to control the extent of surface modification by straightforward organic reactions. Using a combination of optical and structural characterization tools, including IR and 2D NMR, we show that carboxylates bind in a bidentate chelate fashion, forming a single monolayer of ligands that are perpendicular to the nanocrystal surface. Moreover, we show that mixtures of ligands with similar chain lengths homogeneously distribute themselves on the nanocrystal surface. We expect this new surface doping approach will be widely applicable to other nanocrystal compositions and morphologies, as well as to many specific applications in biology and materials science
Molecular Chemistry to the Fore: New Insights into the Fascinating World of Photoactive Colloidal Semiconductor Nanocrystals
Colloidal semiconductor nanocrystals possess unique properties that are unmatched by other chromophores such as organic dyes or transition-metal complexes. These versatile building blocks have generated much scientific interest and found applications in bioimaging, tracking, lighting, lasing, photovoltaics, photocatalysis, thermoelectrics, and spintronics. Despite these advances, important challenges remain, notably how to produce semiconductor nanostructures with predetermined architecture, how to produce metastable semiconductor nanostructures that are hard to isolate by conventional syntheses, and how to control the degree of surface loading or valence per nanocrystal. Molecular chemists are very familiar with these issues and can use their expertise to help solve these challenges. In this Perspective, we present our group\u27s recent work on bottom-up molecular control of nanoscale composition and morphology, low-temperature photochemical routes to semiconductor heterostructures and metastable phases, solar-to-chemical energy conversion with semiconductor-based photocatalysts, and controlled surface modification of colloidal semiconductors that bypasses ligand exchange
Surface Doping Quantum Dots with Chemically Active Native Ligands: Controlling Valence without Ligand Exchange
Molecular Chemistry to the Fore: New Insights into the Fascinating World of Photoactive Colloidal Semiconductor Nanocrystals
Effect of high pressure and glycerol on the physco-chemical properties of corn tortillas
Frequency Tuning of the CEBAF Upgrade Cavities
Long-term plans for CEBAF at Jefferson Lab calls for achieving 12 GeV in the middle of the next decade and 24 GeV after 2010. In support of these plans, an Upgrade Cryomodule capable of providing more than twice the voltage of the existing ones is under development. One requirement is to operate the superconducting cavities, which are 40% longer than existing ones, at 2.5 times the original design gradient with the same amount of rf power. This puts stringent requirements on the accuracy of the frequency tuner: range of 400 kHz and resolution of 1 Hz. A new tuner design to meet these requirements is under development. This system avoids problem areas of previous designs by holding to the principles of not placing moving parts in the vacuum and/or low temperature space, and of having all drive components readily accessible for maintenance and replacement without cryomodule warm-up
Effect of high pressure and glycerol on the physco-chemical properties of corn tortillas
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