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

Ceftriaxone preserves glutamate transporters and prevents intermittent hypoxia-induced vulnerability to brain excitotoxic injury.

Hypoxia alters cellular metabolism and although the effects of sustained hypoxia (SH) have been extensively studied, less is known about chronic intermittent hypoxia (IH), commonly associated with cardiovascular morbidity and stroke. We hypothesize that impaired glutamate homeostasis after chronic IH may underlie vulnerability to stroke-induced excitotoxicity. P16 organotypic hippocampal slices, cultured for 7 days were exposed for 7 days to IH (alternating 2 min 5% O2-15 min 21% O2), SH (5% O2) or RA (21% O2), then 3 glutamate challenges. The first and last exposures were intended as a metabolic stimulus (200 µM glutamate, 15 min); the second emulated excitotoxicity (10 mM glutamate, 10 min). GFAP, MAP2, and EAAT1, EAAT2 glutamate transporters expression were assessed after exposure to each hypoxic protocol. Additionally, cell viability was determined at baseline and after each glutamate challenge, in presence or absence of ceftriaxone that increases glutamate transporter expression. GFAP and MAP2 decreased after 7 days IH and SH. Long-term IH but not SH decreased EAAT1 and EAAT2. Excitotoxic glutamate challenge decreased cell viability and the following 200 µM exposure further increased cell death, particularly in IH-exposed slices. Ceftriaxone prevented glutamate transporter decrease and improved cell viability after IH and excitotoxicity. We conclude that IH is more detrimental to cell survival and glutamate homeostasis than SH. These findings suggest that impaired regulation of extracellular glutamate levels is implicated in the increased brain susceptibility to excitotoxic insult after long-term IH

IH significantly decreases glutamate transporters, MAP2 and GFAP immunoreactivity.

<p>EAAT1, EAAT2, GFAP and MAP2 immunoreactivity in slices exposed to 7 days RA, SH or IH. EAAT1 and EAAT2 expression was unchanged by SH while significantly reduced in IH. MAP2 and GFAP expression decreased in both SH and IH.</p

Intermittent hypoxia decreases cell viability and impairs glutamate response.

<p>Propidium iodide staining (A) and quantification of PI positive cells presented as mean <u>+</u> SD (B) of slices exposed to 7 days RA, SH or IH at baseline (BL), after 200 µM glutamate, and 10 mM glutamate, followed by a second 200 µM glutamate challenge. n = 12–18. *: At all concentrations RA^- < SH^- & IH^- (p<.001). ⁺ At 10mM: SH^- < IH^- (p<.05). ^# At 10 mM & 200 µM#2: BL < SH^- & IH^- (p<.05 and p<.001 respectively).</p

Design and Synthesis of the Next Generation of Crown Ethers for Waste Separations: An Inter-Laboratory Comprehensive Proposal. 1998 Annual Progress Report

'The purpose of this task is to undertake the design, synthesis, and characterization of the next generation of crown ethers for metal-ion separations applicable to USDOE''s environmental needs. Target problems include: Li{sup +} ions leaching from burial sites at the Oak Ridge Y-12 Plant; fission products 90 Sr and {sup 137}Cs contaminating high-level tank wastes at Hanford, INEEL, and Savannah River; and radium in wastes at the Niagara Falls Storage Site. Unfortunately, the technologies needed to address these problems either do not exist or exhibit substantial deficiencies. Separation techniques such as solvent extraction and ion exchange promise to play a strong role, especially as enhanced with highly selective crown ethers and calixarenes. This project is midway through year 2 of a 3-year effort. Below is given a summary of progress in the approximate period September, 1997, to May, 1998, for each of the four co-investigators at Pacific Northwest National Laboratory (PNNL), Argonne National Laboratory (ANL), Oak Ridge National Laboratory (ORNL), and the University of Tennessee (UTK). The overall approach entails utilization of theory and molecular modeling (PNNL), organic synthesis of novel crown compounds (ORNL), solvent extraction studies (ORNL and ANL), and studies of polymer-immobilized crown ethers (UTK).