Using ultrafast transient absorption and time-resolved photoluminescence spectroscopies, we studied multiple exciton generation (MEG) in quantum dots (QDs) consisting of either PbSe, PbS, or a PbSxSe1-x alloy for various QD diameters with corresponding bandgaps (E-g) ranging from 0.6 to 1 eV. For each QD sample, we determine the MEG efficiency, eta(MEG), defined in terms of the electronhole pair creation energy (epsilon(eh)) such that eta(MEG) = E-g/epsilon(eh). In previous reports, we found that eta(MEG) is about two times greater in PbSe QDs compared to bulk PbSe, however, little could be said about the QD-size dependence of MEG. In this study, we find for both PbS and PbSxSe1-x alloyed QDs that eta(MEG) decreases lineally with increasing QD diameter within the strong confinement regime. When the QD radius is normalized by a material-dependent characteristic radius, defined as the radius at which the electronhole Coulomb and confinement energies are equivalent, PbSe, PbS, and PbSxSe1-x exhibit similar MEG behaviors. Our results suggest that MEG increases with quantum confinement, and we discuss the interplay between a size-dependent MEG rate versus hot exciton cooling.

We have synthesized alkylselenide reagents to replace the native oleate ligand on PbSe quantum dots (QDs) in order to investigate the effect of surface modification on their stoichiometry, photophysics, and air stability. The alkylselenide reagent removes all of the oleate on the QD surface and results in Se addition; however, complete Se enrichment does not occur, achieving a 53% decrease in the amount of excess Pb for 2 nm diameter QDs and a 23% decrease for 10 nm QDs. Our analysis suggests that the Se ligand preferentially binds to the {111} faces, which are more prevalent in smaller QDs. We find that attachment of the alkylselenide ligand to the QD surface enhances oxidative resistance, likely resulting from a more stable bond between surface Pb atoms and the alkylselenide ligand compared to Pb-oleate. However, binding of the alkylselenide ligand produces a separate nonradiative relaxation route that partially quenches PL, suggesting the formation of a dark hole-trap.

We report the synthesis and characterization of composition-tunable ternary lead chalcogenide alloys PbSe(x)Te(1-x), PbS(x)Te(1-x), and PbS(x)Se(1-x). This work explores the relative reaction rates of chalcogenide precursors to produce alloyed quantum dots (QDs), and we find the highly reactive bis(trimethylsilyl) (TMS(2))-based precursors allow for the homogeneous incorporation of anions. By varying the Pb to oleic acid ratio, we demonstrate size control of similar composition alloys. We find the resulting QDs are Pb-rich but the Pb/anion ratio is size- and composition-dependent in all alloyed QD as well as in PbSe, PbTe, and PbS QDs and is consistent with the reaction rates of the anion precursors. A more reactive anion precursor results in a lower Pb/anion ratio.

Binary superlattices (BSLs) of sterically stabilized, hydrophobic, large (A; 11.5 nm diameter) Fe(2)O(3) and small (B; 6.1 nm diameter) Au nanocrystals were assembled by slow evaporation of colloidal dispersions on tilted substrates. A detailed analysis of the BSL structure was carried out using transmission and scanning electron microscopy (TEM and SEM) and grazing incidence small-angle X-ray scattering (GISAXS). The BSLs were simple hexagonal (sh) AB(2) superlattices (isostructural with the compound AlB(2); space group 191, P6/mmm) of large nanocrystals occupying a simple hexagonal lattice with small nanocrystals in the interstitial spaces. SEM and GISAXS confirmed long-range order of the BSLs and GISAXS revealed that the superlattice is slightly contracted (8-12%) perpendicular to the substrate as a result of solvent drying in the deposition process. When the sh-AB(2) superlattice deposits on a (100) plane, this shrinkage occurs in the [210] direction and changes the lattice symmetry to centered orthorhombic. Additionally, nearly periodic superlattice dislocations consisting of inserted half-planes of gold nanocrystals were observed by SEM in some BSLs.

The gold nanocrystal seed-mediated approach using cetyltrimethylammonium bromide (CTAB) as a stabilizing surfactant is commonly used to make large quantities of monodisperse gold nanorods. This method, however, has been at times difficult to reproduce in different laboratories. We recently showed [Smith, D. K.; Korgel, B. A. Langmuir 2008, 24, 644-649] that a very low concentration impurity in CTAB obtained from some suppliers prevents nanorod growth but were not able to identify the impurity. Here, we report that the impurity is iodide. Inductively coupled plasma mass spectroscopy (ICP-MS) revealed that iodide concentrations vary in CTAB from different suppliers, from less than 2.75 ppm up to 840 ppm. When CTAB with iodide concentrations greater than 50 ppm is used, nanorods do not form and the product consists entirely of spherical nanocrystals. Iodide slows the reduction of Au(III) to Au0. Iodide adsorption on Au {111} surfaces inhibits nanorod growth.

Nanorods have the potential to be employed as bright molecular biomedical labels. However, nanorod samples usually exhibit relatively wide spectral lines. Using CLASS microscopy we found that single gold nanorods have a narrow spectrum.

We report strong two-photon-induced photoluminescence (TPIP) from silica/gold nanoshells (NS). We demonstrate its potential application for imaging the 3D distribution of NS in tumors using a NIR laser scanning multi-photon microscope.

Gold nanorods were used as molecularly targeted contrast agents for two-photon luminescence imaging of cancer cells 160 microns inside a tissue phantom. Nanorod labeled cells exhibit three orders of magnitude brighter signal than unlabeled cells.

We present two-photon luminescence (TPL) imaging of cancer cells through a 10 times 15 times 40 mm 3 miniaturized probe employing a two-axis MEMS scanning mirror and an air-core photonic crystal fiber. The combination of TPL imaging with a small probe represents a potential method of distinguishing cancerous cells in tissue for diagnosis.

Multifunctional colloidal core-shell nanoparticles of magnetic nanocrystals (of iron oxide or FePt) or gold nanorods encapsulated in silica shells doped with the fluorescent dye, Tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate (Rubpy) were synthesized. The as-prepared magnetic nanocrystals are initially hydrophobic and were coated with silica using a microemulsion approach, while the as-prepared gold nanorods are hydrophilic and were coated with silica using a Stöber-type of process. Each approach yielded monodisperse nanoparticles with uniform fluorescent dye-doped silica shells. These colloidal heterostructures have the potential to be used as dual-purpose tags-exhibiting a fluorescent signal that could be combined with either dark-field optical contrast (in the case of the gold nanorods), or enhanced contrast in magnetic resonance images (in the case of magnetic nanocrystal cores). The optical and magnetic properties of the fluorescent silica-coated gold nanorods and magnetic nanocrystals are reported.

Gold nanorods were synthesized by the colloidal seed-mediated, surfactant-assisted approach [Gou et at., Chem. Mater. 2005,17,3668-3672] using CTAB (hexadecylcetyltrimethylammonium bromide) obtained from ten different suppliers. The yield of gold nanorods depended strongly on the CTAB used: with the same recipe, three of the CTABs did not yield nanorods and produced only spherical gold particles, whereas the other CTABs yielded nanorods with nearly 100% yield. These results suggest that an impurity in the CTAB is very important for nanorod formation.

Attempts to realize the important potential of gold nanorods as extremely bright molecular markers have been limited by the broad spectroscopic linewidths usually observed. We identify the origin of this broadening as inhomogeneous broadening due to the extreme sensitivity of the surface plasmon resonance to the nanorod aspect ratio. Using confocal light scattering spectroscopic microscopy, we observed the narrow homogeneously broadened plasmon lines of single gold nanorods and obtained the first quantitative measurements of this homogeneous broadening. We show that homogeneous broadening can be predicted from first principals.

There has been a tremendous research effort in the past few years in colloidal magnetic nanocrystals. New synthetic methods have been developed that enable a wide variety of magnetic materials to be synthesized in nanocrystal form, including ferromagnetic transition metals, intermetallics and metal oxides. These nanocrystals can be obtained with controlled size, shape and composition. Nanocrystal heterostructures, such as core/shell particles and heterodimers can be synthesized. New materials such as doped magnetic semiconductor quantum dots and nanowires have been made. The magnetic properties of these unique nanostructures have been measured and their applications in medicine, information storage and processing and sensing are being developed. This review attempts to provide a summary and a flavor for this exciting research area as it has evolved during the past few years.

We demonstrate the use of gold nanorods as molecularly targeted contrast agents for two-photon luminescence (TPL) imaging of cancerous cells 150 mu m deep inside a tissue phantom. We synthesized gold nanorods of 50 nm x 15 nm size with a longitudinal surface plasmon resonance of 760 nm. Gold nanorods were conjugated to antibodies against epidermal growth factor receptor (EGFR) and labeled to A431 human epithelial skin cancer cells in a collagen matrix tissue phantom. Using a 1.4 NA oil immersion objective lens, we found that excitation power needed for similar emission intensity in TPL imaging of labeled cells was up to 64 times less than that needed for two-photon autofluorescence (TPAF) imaging of unlabeled cells, which would correspond to a more than 4,000 times increase in emission intensity under equal excitation energy. However, the aberrations due to refractive index mismatch of the immersion oil and the sample limit imaging depth to 75 mu m. Using a 0.95 NA water immersion objective lens, we observe robust two-photon emission signal from gold nanorods in the tissue phantoms from at depths of up to 150 mu m. Furthermore, the increase in excitation energy required to maintain a constant emission signal intensity as imaging depth was increased was the same in both labeled and unlabeled phantom, suggesting that at the concentrations used, the addition of gold nanorods did not appreciably increase the bulk scattering coefficient of the sample. The remarkable TPL brightness of gold nanorods in comparison to TPAF signal makes them an attractive contrast agent for early detection of cutaneous melanoma.

Evaluation of: Gao J, Liang G, Zhang B et al.: FePt@CoS2Yolk-shell nanocrystals as a potent agent to kill HeLa cells. J. Am. Chem. Soc. 129(5), 1428–1433 (2007) [1]. Here, a recent paper describing the synthesis and cytotoxicity of Pt-containing yolk-shell nanocrystals is evaluated. The authors synthesized FePt nanocrystals and encapsulated them in CoS2 shells. Cervical cancer cells (HeLa) were then exposed to these nanoparticles and examined for cell viability. The nanocrystals exhibited cytotoxicity at Pt concentrations lower than that of the well-established organoplatinum chemotherapy drug, cisplatin. The nanocrystal synthesis, the potential of these nanocrystals for chemotherapy and the implications of this study on the future development of a new class of 'nanochemotherapeutics' are discussed.

We demonstrate the use of gold nanorods as bright contrast agents for two-photon luminescence (TPL) imaging of cancer cells in a three-dimensional tissue phantom down to 75 mum deep. The TPL intensity from gold-nanorod-labeled cancer cells is 3 orders of magnitude brighter than the two-photon autofluorescence (TPAF) emission intensity from unlabeled cancer cells at 760 nm excitation light. Their strong signal, resistance to photobleaching, chemical stability, ease of synthesis, simplicity of conjugation chemistry, and biocompatibility make gold nanorods an attractive contrast agent for two-photon imaging of epithelial cancer.

We demonstrate the use of gold nanorods as molecularly targeted contrast agents for two-photon luminescence (TPL) imaging of cancerous cells 150 mu m deep inside a tissue phantom. We synthesized gold nanorods of 50 nm x 15 run size with a longitudinal surface plasmon resonance of 760 rum. Gold nanorods were conjugated to antibodies against epidermal growth factor receptor (EGFR) and labeled to A431 human epithelial skin cancer cells in a collagen matrix tissue phantom. Using a 1.4 NA oil immersion objective lens, we found that excitation power needed for similar emission intensity in TPL imaging of labeled cells was up to 64 times less than that needed for two-photon autofluorescence (TPAF) imaging of unlabeled cells, which would correspond to a more than 4,000 times increase in emission intensity under equal excitation energy. However, the aberrations due to refractive index mismatch of the immersion oil and the sample limit imaging depth to 75 pun. Using a 0.95 NA water immersion objective lens, we observe robust two-photon emission signal from gold nanorods in. the tissue phantoms from at depths of up to 150 pun. Furthermore, the increase in excitation energy required to maintain a constant emission signal intensity as imaging depth was increased was the same in both labeled and unlabeled phantom, suggesting that at the concentrations used, the addition of gold nanorods did not appreciably increase the bulk scattering coefficient of the sample. The remarkable TPL brightness of gold nanorods in comparison to TPAF signal makes them an attractive contrast agent for early detection of cutaneous melanoma.