Synthesis and optical properties of anisotropic metal nanoparticles.

In this paper we overview our recent studies of anisotropic noble metal (e.g. gold and silver) nanoparticles, in which a combination of theory and experiment has been used to elucidate the extinction spectra of the particles, as well as information related to their surface enhanced Raman spectroscopy. We used wet-chemical methods to generate several structurally well-defined nanostructures other than solid spheres, including silver nanodisks and triangular nanoprisms, and gold nanoshells and multipods. When solid spheres are transformed into one of these shapes, the surface plasmon resonances in these particles are strongly affected, typically red-shifting and even splitting into distinctive dipole and quadrupole plasmon modes. In parallel, we have developed computational electrodynamics methods based on the discrete dipole approximation (DDA) method to determine the origins of these intriguing optical features. This has resulted in considerable insight concerning the variation of plasmon wavelength with nanoparticle size, shape and dielectric environment, as well as the use of these particles for optical sensing applications.

Electromagnetic fields around silver nanoparticles and dimers.

We use the discrete dipole approximation to investigate the electromagnetic fields induced by optical excitation of localized surface plasmon resonances of silver nanoparticles, including monomers and dimers, with emphasis on what size, shape, and arrangement leads to the largest local electric field (E-field) enhancement near the particle surfaces. The results are used to determine what conditions are most favorable for producing enhancements large enough to observe single molecule surface enhanced Raman spectroscopy. Most of the calculations refer to triangular prisms, which exhibit distinct dipole and quadrupole resonances that can easily be controlled by varying particle size. In addition, for the dimer calculations we study the influence of dimer separation and orientation, especially for dimers that are separated by a few nanometers. We find that the largest /E/2 values for dimers are about a factor of 10 larger than those for all the monomers examined. For all particles and particle orientations, the plasmon resonances which lead to the largest E-fields are those with the longest wavelength dipolar excitation. The spacing of the particles in the dimer plays a crucial role, and we find that the spacing needed to achieve a given /E/2 is proportional to nanoparticle size for particles below 100 nm in size. Particle shape and curvature are of lesser importance, with a head to tail configuration of two triangles giving enhanced fields comparable to head to head, or rounded head to tail. The largest /E/2 values we have calculated for spacings of 2 nm or more is approximately 10(5).

Magnetically labeled insulin-secreting cells.

Iron oxide nanoparticles have been shown to magnetically label cells in order to visualize them in vivo via MR imaging. This technology has yet to be implemented in insulin secreting cells, thus it is not known whether the presence of these nanoparticles in the cytoplasm of the cells affects insulin secretion. This study investigates the effectiveness and consequence of labeling mouse insulinoma betaTC3 and betaTC-tet cells with monocrystalline iron oxide nanoparticles (MION). Our data show that MION can be internalized in both betaTC3 and betaTC-tet cells following a 24h exposure to 0.02mg/ml MION solution. The metabolic and secretory activities of both MION-labeled cell lines were statistically indistinguishable from sham treatment. Furthermore, cell viability and apoptosis remained constant throughout the cell's exposure to MION. Finally, MR images demonstrated significant contrast between labeled and sham-treated cells. Thus, labeling murine insulinoma cell lines with magnetic iron oxide nanoparticles does not hinder their insulin secretion, while it provides MR imaging contrast.

Magnetic resonance imaging of activated proliferating rhesus macaque T cells labeled with superparamagnetic monocrystalline iron oxide nanoparticles.

Imaging of adoptively transferred cells in vivo by magnetic resonance imaging (MRI) could provide important information on disease-related patterns of lymphocyte homing in nonhuman primate models of AIDS. As a preliminary study to assess the feasibility of visualizing activated rhesus T cells by MRI, anti-CD3/CD28-expanded CD4+ T lymphocytes were labeled in vitro with monocrystalline iron oxide nanoparticles (MION). Intracellular incorporation of MION was determined by transmission electron microscopy (TEM) and inductively coupled plasma mass spectrography (ICP-MS). Pretreatment with colchicine did not affect MION labeling, suggesting that cellular uptake of MION occurred by adsorptive pinocytosis or receptor-mediated endocytosis. TEM analysis revealed that MION were intracellularly compartmentalized exclusively in the cytoplasm and did not cause any measurable physiologic effects on T-cell function, including viability, proliferation, synthesis of select cytokines (interleukin [IL]-2, IL-4, IL-6, IL-10, tumor necrosis factor-alpha, and interferon-gamma), activation antigens (CD25 and CD69), adhesion molecules (alpha4beta7 and CD49d), and susceptibility to in vitro infection with simian immunodeficiency virus mac239. A sensitivity of 0.05% (1 MION-labeled T cell in 2000 unlabeled cells) could be achieved using T2-weighted gradient echo imaging. Furthermore, under these experimental conditions, the MRI signal did not decrease in proliferating MION-labeled CD4+ T cells over a period of 120 hours. These results indicate that intracellular labeling with MION can be a useful technique for noninvasively monitoring trafficking patterns of adoptively transferred leukocyte subsets in real-time by MRI in nonhuman primate models of AIDS.

Controlling anisotropic nanoparticle growth through plasmon excitation.

Inorganic nanoparticles exhibit size-dependent properties that are of interest for applications ranging from biosensing and catalysis to optics and data storage. They are readily available in a wide variety of discrete compositions and sizes. Shape-selective synthesis strategies now also yield shapes other than nanospheres, such as anisotropic metal nanostructures with interesting optical properties. Here we demonstrate that the previously described photoinduced method for converting silver nanospheres into triangular silver nanocrystals--so-called nanoprisms--can be extended to synthesize relatively monodisperse nanoprisms with desired edge lengths in the 30-120 nm range. The particle growth process is controlled using dual-beam illumination of the nanoparticles, and appears to be driven by surface plasmon excitations. We find that, depending on the illumination wavelengths chosen, the plasmon excitations lead either to fusion of nanoprisms in an edge-selective manner or to the growth of the nanoprisms until they reach their light-controlled final size.

Synthesis of silver nanodisks using polystyrene mesospheres as templates.

We report the synthesis of Ag nanodisk using polystyrene mesospheres as templates. TEM measurements show that the average disk thickness is 9.0 +/- 1.0 nm and the diameter is 36 +/- 8 nm. The particles exhibit an intense electronic spectrum that differs markedly from that for spheres (purple vs yellow solutions). We present electromagnetic theory calculations which exhibit a qualitative match with the observed spectrum, enabling us to assign several of the plasmon resonance features.

Preparation of Luminescent Polyelectrolyte/Cu-Doped ZnSe Nanoparticle Multilayer Composite Films.

ZnSe and Cu-doped ZnSe nanoparticle aqueous suspensions were prepared in the presence of mercaptopropionic acid (MPA). Cu-doped ZnSe nanoparticles exhibited a strong blue emission that was strongly dependent upon the Cu dopant level and the chemical surface passivation produced by zinc-mercaptopropionic acid complexes. These Cu-doped ZnSe nanoparticles were further assembled into ultrathin polymer-supported films using electrostatic interactions and the layer-by-layer assembly method. UV-visible spectroscopy and X-ray photoelectron spectroscopy (XPS) provided evidence for the presence and optical activity of Cu-doped ZnSe nanoparticles within the polymer ultrathin films. Moreover, XPS data supported the presence of zinc mercaptopropionic acid complexes on nanoparticle surfaces and the presence of Cu(+) ions with high luminescent activity in the doped nanoparticles. Copyright 2001 Academic Press.