Ultrahigh stress and strain in hierarchically structured hollow nanoparticles.

Nanocrystalline materials offer very high strength but are typically limited in their strain to failure, and efforts to improve deformability in these materials are usually found to be at the expense of strength. Using a combination of quantitative in situ compression in a transmission electron microscope and finite-element analysis, we show that the mechanical properties of nanoparticles can be directly measured and interpreted on an individual basis. We find that nanocrystalline CdS synthesized into a spherical shell geometry is capable of withstanding extreme stresses (approaching the ideal shear strength of CdS). This unusual strength enables the spherical shells to exhibit considerable deformation to failure (up to 20% of the sphere's diameter). By taking into account the structural hierarchy intrinsic to novel nanocrystalline materials such as this, we show it is possible to achieve and characterize the ultrahigh stresses and strains that exist within a single nanoparticle during deformation.

Gel electrophoresis of gold-DNA nanoconjugates.

Gold-DNA conjugates were investigated in detail by a comprehensive gel electrophoresis study based on 1200 gels. A controlled number of single-stranded DNA of different length was attached specifically via thiol-Au bonds to phosphine-stabilized colloidal gold nanoparticles. Alternatively, the surface of the gold particles was saturated with single stranded DNA of different length either specifically via thiol-Au bonds or by nonspecific adsorption. From the experimentally determined electrophoretic mobilities, estimates for the effective diameters of the gold-DNA conjugates were derived by applying two different data treatment approaches. The first method is based on making a calibration curve for the relation between effective diameters and mobilities with gold nanoparticles of known diameter. The second method is based on Ferguson analysis which uses gold nanoparticles of known diameter as reference database. Our study shows that effective diameters derived from gel electrophoresis measurements are affected with a high error bar as the determined values strongly depend on the method of evaluation, though relative changes in size upon binding of molecules can be detected with high precision. Furthermore, in this study, the specific attachment of DNA via gold-thiol bonds to Au nanoparticles is compared to nonspecific adsorption of DNA. Also, the maximum number of DNA molecules that can be bound per particle was determined.

Electric-field-assisted assembly of perpendicularly oriented nanorod superlattices.

We observe the assembly of CdS nanorod superlattices by the combination of a DC electric field and solvent evaporation. In each electric-field (1 V/microm) assisted assembly, CdS nanorods (5 nm x 30 nm) suspended initially in toluene were observed to align perpendicular to the substrate. Azimuthal alignment along the nanorod crystal faces and the presence of stacking faults indicate that both 2D and 3D assemblies were formed by a process of controlled super crystal growth.

Linearly polarized emission from colloidal semiconductor quantum rods.

Colloidal quantum rods of cadmium selenide (CdSe) exhibit linearly polarized emission. Empirical pseudopotential calculations predict that slightly elongated CdSe nanocrystals have polarized emission along the long axis, unlike spherical dots, which emit plane-polarized light. Single-molecule luminescence spectroscopy measurements on CdSe quantum rods with an aspect ratio between 1 and 30 confirm a sharp transition from nonpolarized to purely linearly polarized emission at an aspect ratio of 2. Linearly polarized luminescent chromophores are highly desirable in a variety of applications.

Colloidal nanocrystal shape and size control: the case of cobalt.

We show that a relatively simple approach for controlling the colloidal synthesis of anisotropic cadmium selenide semiconductor nanorods can be extended to the size-controlled preparation of magnetic cobalt nanorods as well as spherically shaped nanocrystals. This approach helps define a minimum feature set needed to separately control the sizes and shapes of nanocrystals. The resulting cobalt nanocrystals produce interesting two- and three-dimensional superstructures, including ribbons of nanorods.

Time-gated biological imaging by use of colloidal quantum dots.

The long (but not too long) fluorescence lifetime of CdSe semiconductor quantum dots was exploited to enhance fluorescence biological imaging contrast and sensitivity by time-gated detection. Significant and selective reduction of the autofluorescence contribution to the overall image was achieved, and enhancement of the signal-to-background ratio by more than an order of magnitude was demonstrated.

Ultrahigh-resolution multicolor colocalization of single fluorescent probes.

An optical ruler based on ultrahigh-resolution colocalization of single fluorescent probes is described in this paper. It relies on the use of two unique families of fluorophores, namely energy-transfer fluorescent beads (TransFluoSpheres) and semiconductor nanocrystal quantum dots, that can be excited by a single laser wavelength but emit at different wavelengths. A multicolor sample-scanning confocal microscope was constructed that allows one to image each fluorescent light emitter, free of chromatic aberrations, by scanning the sample with nanometer scale steps with a piezo-scanner. The resulting spots are accurately localized by fitting them to the known shape of the excitation point-spread function of the microscope. We present results of two-dimensional colocalization of TransFluoSpheres (40 nm in diameter) and of nanocrystals (3-10 nm in diameter) and demonstrate distance-measurement accuracy of better than 10 nm using conventional far-field optics. This ruler bridges the gap between fluorescence resonance energy transfer, near- and far-field imaging, spanning a range of a few nanometers to tens of micrometers.

Biomineralization. Naturally aligned nanocrystals.

The aggregation of nanocrystals has long been believed to result in disordered solids. In his Perspective, Alivisatos discusses recent evidence that nanocrystals may also form oriented assemblies. He highlights the work by Banfield et al. in this issue, who show that such alignment can also occur in natural systems. The results may be of importance not only for geochemistry but also for the synthesis of advanced artificial materials.

Semiconductor nanocrystals as fluorescent biological labels.

Semiconductor nanocrystals were prepared for use as fluorescent probes in biological staining and diagnostics. Compared with conventional fluorophores, the nanocrystals have a narrow, tunable, symmetric emission spectrum and are photochemically stable. The advantages of the broad, continuous excitation spectrum were demonstrated in a dual-emission, single-excitation labeling experiment on mouse fibroblasts. These nanocrystal probes are thus complementary and in some cases may be superior to existing fluorophores.

Organization of 'nanocrystal molecules' using DNA.

Patterning matter on the nanometre scale is an important objective of current materials chemistry and physics. It is driven by both the need to further miniaturize electronic components and the fact that at the nanometre scale, materials properties are strongly size-dependent and thus can be tuned sensitively. In nanoscale crystals, quantum size effects and the large number of surface atoms influence the, chemical, electronic, magnetic and optical behaviour. 'Top-down' (for example, lithographic) methods for nanoscale manipulation reach only to the upper end of the nanometre regime; but whereas 'bottom-up' wet chemical techniques allow for the preparation of mono-disperse, defect-free crystallites just 1-10 nm in size, ways to control the structure of nanocrystal assemblies are scarce. Here we describe a strategy for the synthesis of 'nanocrystal molecules', in which discrete numbers of gold nanocrystals are organized into spatially defined structures based on Watson-Crick base-pairing interactions. We attach single-stranded DNA oligonucleotides of defined length and sequence to individual nanocrystals, and these assemble into dimers and trimers on addition of a complementary single-stranded DNA template. We anticipate that this approach should allow the construction of more complex two- and three-dimensional assemblies.

High-pressure structural transformations in semiconductor nanocrystals.

Pressure-induced structural transformations in semiconductor nanocrystals are examined. High-pressure Raman spectroscopy, EXAFS, X-ray diffraction, and optical absorption are discussed as methods for studying these transformations in CdSe, CdS, and Si nanocrystals. In these nanocrystal systems, each technique shows an elevation in solid-solid structural transformation pressure as crystallite size decreases. By analogy with melting in nanocrystals, this elevation in transformation pressure is explained in terms of an increase in surface energy in the newly formed high-pressure phase crystallites. The increase in surface energy is in turn the result of transition path-induced changes in the shape of the nanocrystals. These changes convert spherical nanocrystals with low-index, low-energy surfaces into oblate or prolate crystallites with higher-index, higher-energy surfaces. The elevation in structural transformation pressure in nanocrystals is thus a kinetic rather than a thermodynamic phenomenon.

Size Dependence of a First Order Solid-Solid Phase Transition: The Wurtzite to Rock Salt Transformation in CdSe Nanocrystals.

Measurements of the size dependence of a solid-solid phase transition are presented. High-pressure x-ray diffraction and optical absorption are used to study the wurtzite to rock salt structural transformation in CdSe nanocrystals. These experiments show that both the thermodynamics and kinetics of this transformation are altered in finite size, as compared to bulk CdSe. An explanation of these results in the context of transformations in bulk systems is presented. Insight into the kinetics of transformations in both bulk and nanocrystal systems can be gained.

Melting in semiconductor nanocrystals.

New physics occurs in semiconductors when one or more dimensions of the crystal are reduced to a size comparable to bulk electron delocalization lengths (tens to hundreds of angstroms). The properties of "quantum dots" or semiconductor nanocrystals are now being studied, as techniques to fabricate the crystallites are developed. Temperature-dependent electron diffraction studies on nanocrystals of CdS show a large depression in the melting temperature with decreasing size, as a larger fraction of the total number of atoms is on the surface. Thermal stability may play a role in determining the uses of semiconductor nanocrystals.