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The design of nanoparticles is critical for their efficient use in many applications ranging from biomedicine to sensing and energy. While shape and size are responsible for the properties of the inorganic nanoparticle core, the choice of ligands is of utmost importance for the colloidal stability and function of the nanoparticles. Moreover, the selection of ligands employed in nanoparticle synthesis can determine their final size and shape. Ligands added after nanoparticle synthesis infer both new properties as well as provide enhanced colloidal stability. In this article, we provide a comprehensive review on the role of the ligands with respect to the nanoparticle morphology, stability, and function. We analyze the interaction of nanoparticle surface and ligands with different chemical groups, the types of bonding, the final dispersibility of ligand-coated nanoparticles in complex media, their reactivity, and their performance in biomedicine, photodetectors, photovoltaic devices, light-emitting devices, sensors, memory devices, thermoelectric applications, and catalysis.

The surfactant-mediated shape evolution of titanium dioxide anatase nanocrystals in nonaqueous media was studied. The shape evolves from bullet and diamond structures to rods and branched rods. The modulation of surface energies of the different crystallographic faces through the use of a surface selective surfactant is the key parameter for the shape control.

The structural and magnetic properties of nanocrystalline manganese, cobalt, and nickel spinel ferrites dispersed in a highly porous SiO 2 aerogel matrix were studied. X-ray diffraction and high-resolution transmission electron microscopy indicate that single crystalline ferrite nanoparticles are well dispersed in the amorphous matrix. The cation distribution between the octahedral and tetrahedral sites of the spinel structure was investigated by X-ray absorption spectroscopy. The analysis of both the X-ray absorption near edge structure and the extended X-ray absorption fine structure indicates that the degree of inversion of the spinel structure increases in the series Mn, Co, and Ni spinel, in accordance with the values commonly found in the corresponding bulk spinels. In particular, fitting of the EXAFS data indicates that the degree of inversion in nanosized ferrites is 0.20 for MnFe 2 O 4 , 0.68 for CoFe 2 O 4 , and 1.00 for NiFe 2 O 4 . Magnetic characterization further supports these findings.

PbSe nanocrystals with rock-salt structure are grown on the tips of colloidal CdS and CdSe nanorods. The facets of wurtzite rods provide a substrate with various degrees of reactivity for the growth of PbSe. The presence of dangling Cd bonds may explain subtle differences between nonequivalent facets resulting in the selective nucleation of PbSe only on one of the two tips of each CdS rod. This approach has the potential to facilitate the fabrication of heterostructures with tailored optical and electronic properties.

RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) TITLE RUNNING HEAD. Monodisperse Iron Oxide Nanodisks by Delayed Nucleation 2 ABSTRACT A comprehensive study of iron oxide nanocrystal growth through non-hydrolitic, surfactantmediated thermal reaction of iron pentacarbonyl and an oxidizer has been conducted, which includes size control, anisotropic shape evolution, and crystallographic phase transition of monodisperse iron oxide colloidal nanocrystals. The reaction was monitored by in situ UV-Vis spectroscopy taking advantage of the color change accompanying the iron oxide colloid formation allowing measurement of the induction time for nucleation. Features of the synthesis such as the size control and reproducibility are related to the occurrence of the observed delayed nucleation process. As a separate source of iron and oxygen is adopted, phase control could also be achieved by sequential injections of oxidizer.3

Novel systems based on suspensions of colloidal magnetic nanoparticles have been investigated as perspective superparamagnetic contrast agents (CA) for magnetic resonance imaging (MRI). The nanostructures that we have studied contain surfactant-capped magnetite (Fe3O4) inorganic cores with different controlled sizes, ranging from 5.5 to 12 nm. The as-synthesized nanostructures are passivated by hydrophobic surfactants and thus are fully dispersible in nonpolar media. The magnetic nanocrystals have been transferred into aqueous media by a procedure based on the surface intercalation and coating with an amphiphilic polymer shell. The MRI efficiency in contrasting images, i.e., the NMR relaxivities r1 and r2, have been compared with Endorem and Sinerem, commercial superparamagnetic MRI contrast agents. We found that our nanostructures exhibit r1 and r2 relaxivities comparable to those of commercial CA over the whole frequency range. The MRI efficiency of our samples was related to their microstructural and magnetic properties. The transverse relaxivity r2, leading the contrast in “negative” superparamagnetic agents, was found to improve as the diameter of the inorganic core is increased. The NMR relaxometry profile confirmed the nature of the physical mechanisms inducing the increase of the nuclear relaxation rates at low (magnetic anisotropy) and high (Curie relaxation) fields.

For imaging with different modalities, labels, which provide contrast for all modalities, are required. Colloidal nanoparticles composed out of an inorganic core and a polymer shell offer progress in this direction. Both, the core and the polymer shell, can be synthesized to be fluorescent, magnetic, or radioactive. When different cores are combined with different polymer shells, different types of particles for dual imaging can be obtained, as for example, fluorescent cores with radioactive polymer shells. Properties and perspectives of such nanoparticles for multimodal imaging are discussed.