Giant PbSe/CdSe/CdSe Quantum Dots: Crystal-Structure-Defined Ultrastable Near-Infrared Photoluminescence from Single Nanocrystals.

Toward a truly photostable PbSe quantum dot (QD), we apply the thick-shell or "giant" QD structural motif to this notoriously environmentally sensitive nanocrystal system. Namely, using a sequential application of two shell-growth techniques-partial-cation exchange and successive ionic layer adsorption and reaction (SILAR)-we are able to overcoat the PbSe QDs with sufficiently thick CdSe shells to impart new single-QD-level photostability, as evidenced by suppression of both photobleaching and blinking behavior. We further reveal that the crystal structure of the CdSe shell (cubic zinc-blende or hexagonal wurtzite) plays a key role in determining the photoluminescence properties of these giant QDs, with only cubic nanocrystals sufficiently bright and stable to be observed as single emitters. Moreover, we demonstrate that crystal structure and particle shape (cubic, spherical, or tetrapodal) and, thereby, emission properties can be synthetically tuned by either withholding or including the coordinating ligand, trioctylphosphine, in the SILAR component of the shell-growth process.

Rates of electron self-exchange reactions between oxo-centered ruthenium clusters are determined by orbital overlap.

We report rate constants for electron self-exchange of trinuclear ruthenium clusters of the type [Ru(3)O(OAc)(6)(CO)(L)(2)](0/-), where L is 4-cyanopyridine, pyridine, or 4-(dimethylamino)pyridine. Rate constants were determined by (1)H NMR line-broadening experiments in CD(3)CN, CD(2)Cl(2), and THF-d(8), and range from 6.5 x 10(6) to 2.5 x 10(8) s(-1) M(-1). Faster self-exchange is observed with more electron-withdrawing substituents on the ancillary pyridine ligands. This effect is attributed to increased orbital overlap between the donor and acceptor as more electron density is drawn onto the pyridine ring. This view is supported by measured NMR contact shifts of the pyridyl protons which reflect increased electron spin density with increasing pyridine ligand electron-withdrawing ability. Normal solvent dependence is also observed, where higher outer-sphere reorganization energies lead to slower exchange.

Matching Solid-State to Solution-Phase Photoluminescence for Near-Unity Down-Conversion Efficiency Using Giant Quantum Dots.

Efficient, stable, and narrowband red-emitting fluorophores are needed as down-conversion materials for next-generation solid-state lighting that is both efficient and of high color quality. Semiconductor quantum dots (QDs) are nearly ideal color-shifting phosphors, but solution-phase efficiencies have not traditionally extended to the solid-state, with losses from both intrinsic and environmental effects. Here, we assess the impacts of temperature and flux on QD phosphor performance. By controlling QD core/shell structure, we realize near-unity down-conversion efficiency and enhanced operational stability. Furthermore, we show that a simple modification of the phosphor-coated light-emitting diode device-incorporation of a thin spacer layer-can afford reduced thermal or photon-flux quenching at high driving currents (>200 mA).

Plasmonic giant quantum dots: hybrid nanostructures for truly simultaneous optical imaging, photothermal effect and thermometry.

Hybrid semiconductor-metal nanoscale constructs are of both fundamental and practical interest. Semiconductor nanocrystals are active emitters of photons when stimulated optically, while the interaction of light with nanosized metal objects results in scattering and ohmic damping due to absorption. In a combined structure, the properties of both components can be realized together. At the same time, metal-semiconductor coupling may intervene to modify absorption and/or emission processes taking place in the semiconductor, resulting in a range of effects from photoluminescence quenching to enhancement. We show here that photostable 'giant' quantum dots when placed at the center of an ultrathin gold shell retain their key optical property of bright and blinking-free photoluminescence, while the metal shell imparts efficient photothermal transduction. The latter is despite the highly compact total particle size (40-60 nm "inorganic" diameter and <100 nm hydrodynamic diameter) and the very thin nature of the optically transparent Au shell. Importantly, the sensitivity of the quantum dot emission to local temperature provides a novel internal thermometer for recording temperature during infrared irradiation-induced photothermal heating.

An instrument for sorting of magnetic microparticles in a magnetic field gradient.

BACKGROUND: The goal of our bioassay technique is to demonstrate high throughput, highly parallel, and high sensitivity quantitative molecular analysis that will expand current biomedical research capabilities. To this end, we have built and characterized a magnetophoresis instrument using a flow chamber in a magnetic field gradient to sort magnetic microparticles by their magnetic moment for eventual use as biological labels. METHODS: The flow chamber consists of a sample inlet, differential sheath streams, and eight outlets for collecting the microparticles after they have traversed the chamber. Magnetic microparticles are injected into the flow chamber that is positioned in a linear magnetic field gradient. The trajectory for each microparticle is determined by its total magnetic moment and size. The resulting populations of monodispersed magnetic microparticles in the different outlet bins are sorted by their magnetic moment; with the highest magnetic moments being deflected the furthest. RESULTS: We have characterized the system for sorting both superparamagnetic and ferromagnetic microparticles with approximate diameters of 8 microm and 4.0-4.9 microm, respectively. To characterize the instrument, we used microparticles with a known size distribution and varied the transit time through the chamber. This is equivalent to varying the magnetic moment, while allowing us to hold the particle properties constant from run-to-run. We demonstrated the ability to reproducibly change the distribution of the particles in the collection bins by varying transit time in good agreement with theory. We identified hydrodynamic instabilities responsible for causing dispersion in the flow. Improvements to the flow chamber hydrodynamics such as reducing the aspect ratio between the sample inlet and the chamber depth and stabilizing the sheath flow resulted in narrow sorting distributions. We measured a sorting reproducibility (percentage of particles returning to their original bin upon resorting individual populations) of 84-89%. CONCLUSIONS: We have developed a simple magnetophoresis system for reproducibly sorting magnetic microparticles. This technique will permit the use of microparticles with a wide range of magnetic moments to create a wide range of magnetic labels. Careful consideration of system design and operational parameters enables reliable and reproducible sorting of microparticles with varying size and magnetic content.