Publications

Biological applications of colloidal nanocrystals

Due to their interesting properties, research on colloidal nanocrystals has moved in the last few years from fundamental research to first applications in materials science and life sciences. In this review some recent biological applications of colloidal nanocrystals are discussed, without going into biological or chemical details. First, the properties of colloidal nanocrystals and how they can be synthesized are described. Second, the conjugation of nanocrystals with biological molecules is discussed. And third, three different biological applications are introduced: (i) the arrangement of nanocrystal–oligonucleotide conjugates using molecular scaffolds such as single-stranded DNA, (ii) the use of nanocrystal–protein conjugates as fluorescent probes for cellular imaging, and (iii) a motility assay based on the uptake of nanocrystals by living cells.

Multilayer Diffraction Reveals That Colloidal Superlattices Approach the Structural Perfection of Single Crystals

Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called "atomically precise". That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, the constructive interference of X-rays diffracted by the nanocrystals dominates the diffraction pattern, offering a wealth of structural information. By treating nanocrystals as scattering sources forming a self-probing interferometer, we developed a multilayer diffraction method that enabled the accurate determination of the nanocrystal size, interparticle spacing, and their fluctuations for samples of self-assembled CsPbBr₃ and PbS nanomaterials. The multilayer diffraction method requires only a laboratory-grade diffractometer and an open-source fitting algorithm for data analysis. The average nanocrystal displacement of 0.33 to 1.43 Å in the studied superlattices provides a figure of merit for their structural perfection and approaches the atomic displacement parameters found in traditional crystals.

Strain and deformation in ultra-hard nanocomposites nc-TiN/a-BN under hydrostatic pressure

Electronic Spectra of Semiconductor Nanocystals

In recent years, techniques have been developed to prepare highly monodisperse and crystalline particles of many common semiconductors in the nanometer size regime. These particles, Consisting of a hundred to tens of thousands of atoms, exhibit electronic spectra that evolve in interesting ways with size. Recent experiments on electric field modulation of absorption and emission, resonance Raman scattering and photon echoes will be presented, with a view towards presenting a unified picture of the electronic spectra in these materials.

Pyramidal and Chiral Groupings of Gold Nanocrystals Assembled Using DNA Scaffolds

Nanostructures constructed from metal and semiconductor nanocrystals conjugated to and organized by DNA are an emerging class of materials with collective optical properties. We created discrete pyramids of DNA with gold nanocrystals at the tips. By taking small-angle X-ray scattering measurements from solutions of these pyramids, we confirmed that this pyramidal geometry creates structures which are more rigid in solution than linear DNA. We then took advantage of the tetrahedral symmetry to demonstrate construction of chiral nanostructures.

Imaging Degradation of III-V Quantum Dots Using Liquid-Phase TEM

Origin and Scaling of the Permanent Dipole Moment in CdSe Nanorods

Transient electric birefringence measurements were performed on dilute solutions of CdSe nanorods. The results confirm the existence of a permanent dipole along the c-crystallographic axis. Measurements on nanorods with different widths and lengths show that the longitudinal permanent dipole moment scales linearly with volume, suggesting it arise from the noncentrosymmetric crystallographic lattice.

Photoemission investigation of compound semiconductor monodisperse clusters

We have used synchrotron radiation photoemission to probe the valence and core level electronic structure of compound-semiconductor monodisperse clusters (nanocrystals). These clusters exhibited a 10% or less variation relative to the mean diameter and were attached to the metal substrates via alkane chains. Direct evidence of gap broadening due to size variation in CdS clusters was observed. The novel utilization of alkane chain attachment is the key to eliminating the otherwise debilitating problem of sample charging, as occurs with powders. The quality of sample preparation was confirmed by other methods such as transmission electron microscopy, Raman scattering, and x-ray diffraction. This work provides a direct link between photoemission studies of expitaxial ultrathin films of compound semiconductors, the photon-spectroscopy measurements of cluster powders and the existing theories of quantum confinement in reduced dimensionality structures.

Measuring Cell Motility Using Quantum Dot Probes

The ability of cancer cells to migrate and metastasize is known to be directly related to tumor cell motility. Therefore, assaying the level of tumor cell motility is an excellent indicator of metastatic potential. We have developed an efficient and sensitive two-dimensional cell motility assay to image the phagokinetic uptake of colloidal CdSe/ZnS semiconductor nanocrystals (quantum dots [QDs]). As cells move across a thin, homogeneous layer of QDs, they engulf and uptake the nanocrystals and leave behind a fluorescent-free trail. By measuring the ratio of trail area to cell area we have discovered that it is possible to distinguish between noninvasive and invasive cancer cells lines. This technique has, therefore, the potential to be used as a rapid, robust, and quantitative in vitro measure of metastatic potential. Because the technique only relies on fluorescence detection, requires no significant data processing, and is used with live cells, it is both rapid and straightforward.

Threshold for quasicontinuum absorption and reduced luminescence efficiency in CdSe nanocrystals

Luminescence excitation spectra are employed to study the electronic states of CdSe nanocrystals ranging in size from 9 to 26 Å radius at 77 K. These studies show that all samples have, in addition to the discrete manifold of quantum confined electronic excitations, a threshold for continuum absorption. Absorption into this continuum results in substantially reduced luminescence efficiency.

Quantum confinement and ultrafast dephasing dynamics in InP nanocrystals

The electronic level structure and dephasing dynamics of InP nanocrystals in the strong quantum-confinement regime are studied by two complementary techniques: nanosecond hole burning and the femtosecond three-pulse photon echo. Hole burning yields the homogeneous electronic level structure while the photon echo allows the extraction of the linewidth of the band-gap transition. The congestion of electronic levels observed close to the band-edge transition in the hole-burning experiments gives rise to a pulse-width-limited initial decay in the photon-echo signal. The level structure is calculated and assigned using a model which includes valence-band mixing. The homogeneous linewidth of the band-edge transition is approximately 5 meV at 20 K and is broadened considerably at higher temperatures. The temperature dependence of the linewidth is consistent with an intrinsic dephasing mechanism of coupling to low-frequency acoustic modes mediated by the deformation potential. Quantum-confinement effects in III-V semiconductor InP are compared to those of the prototypical CdSe II-VI semiconductor nanocrystal system.

Cation Exchange Reactions in Ionic Nanocrystals

Cation exchange has been investigated in a wide range of nanocrystals of varying composition, size, and shape. Complete and fully reversible exchange occurs, and the rates of the reactions are much faster than in bulk cation exchange processes. A critical size has been identified below which the shapes of complex nanocrystals evolve toward the equilibrium shape with lowest energy during the exchange reaction. Above the critical size, the anion sublattice remains intact and the basic shapes of the initial nanocrystals are retained throughout the cation exchange. The size-dependent shape change can also be used to infer features of the microscopic mechanism.

Spiers Memorial Lecture : New tools for observing the growth and assembly of colloidal inorganic nanocrystals

We present two examples of the use of liquid cells to study colloidal inorganic nanocrystals using <italic>in situ</italic> transmission electron microscopy. The first uses a liquid cell to quantify the interaction potential between pairs of colloidal nanocrystals, and the second demonstrates direct imaging of nanocrystal growth and structure in the liquid cell.

End-to-End Alignment of Nanorods in Thin Films

A simple approach to obtain end-to-end assemblies of nanorods over macroscopic distances in thin films is described. Nanorods with aspect ratio of 8-12 can be aligned parallel to the surface in an end-to-end fashion by imposing geometric confinement via block copolymer-based supramolecular assemblies. Successful control over the orientation and location of nanorods requires a balance of particle-particle interactions and entropy associated with geometric confinement from the supramolecular framework, as well as consideration of the kinetics of assembly.

Conformation of Oligonucleotides Attached to Gold Nanocrystals Probed by Gel Electrophoresis

Thiol-modified single stranded oligonucleotides of different lengths (8 to 135 bases) were attached to the surface of 10 nm diameter Au nanocrystals with different DNA/Au ratios (1, 2, ..., saturation). The electrophoretic mobility of these conjugates was determined on 2% agarose gels, and the effective diameter of the DNA/Au conjugates was determined. This diameter depends on the conformation of the oligonucleotides adsorbed on the Au surface. For low surface coverage, nonspecific wrapping of the DNA around the nanoparticles was observed. For high surface coverage, short oligonucleotides were shown to be oriented perpendicular to the surface and fully stretched. For high surface coverage and long oligonucleotides, the inner part close to the Au surface was determined to be fully stretched and pointed perpendicular to the surface, whereas the outer part adopts random coil shape.

Synthesis of Pt₃Y and Other Early–Late Intermetallic Nanoparticles by Way of a Molten Reducing Agent

Early-late intermetallic phases have garnered increased attention recently for their catalytic properties. To achieve the high surface areas needed for industrially relevant applications, these phases must be synthesized as nanoparticles in a scalable fashion. Herein, Pt₃Y-targeted as a prototypical example of an early-late intermetallic-has been synthesized as nanoparticles approximately 5-20 nm in diameter via a solution process and characterized by XRD, TEM, EDS, and XPS. The key development is the use of a molten borohydride (MEt₃BH, M = Na, K) as both the reducing agent and reaction medium. Readily available halide precursors of the two metals are used. Accordingly, no organic ligands are necessary, as the resulting halide salt byproduct prevents sintering, which further permits dispersion of the nanoscale intermetallic onto a support. The versatility of this approach was validated by the synthesis of other intermetallic phases such as Pt₃Sc, Pt₃Lu, Pt₂Na, and Au₂Y.

Structural transformations and metastability in semiconductor nanocrystals

Abstract Abstract Pressure-induced structural phase transitions have been studied in CdSe, CdS, InP and Si semiconductor nanocrystals. Nanocrystals transform via single nucleation of the phase transition with a kinetic barrier that increases in increasing cluster size. The structural transition path causes a shape change in the nanocrystals, which dictates the surface energy and thus the kinetic and thermodynamic stability of the transformed nanocrystal. These finite size effects can be used to tune the metastability of the nanocrystals versus pressure. Enhanced metastability allows structural and optical measurements in a regime inaccessible to the bulk solid, as well as possible recovery of the dense high pressure phase to atmospheric pressure. Key Words: MetastabilityNanocrystalPhase transitionHigh pressureKinetics

ChemInform Abstract: Resonance Raman Scattering and Optical Absorption Studies of CdSe Microclusters at High Pressure.