Parabolic Potential Surfaces Localize Charge Carriers in Nonblinking Long-Lifetime "Giant" Colloidal Quantum Dots.

Materials for studying biological interactions and for alternative energy applications are continuously under development. Semiconductor quantum dots are a major part of this landscape due to their tunable optoelectronic properties. Size-dependent quantum confinement effects have been utilized to create materials with tunable bandgaps and Auger recombination rates. Other mechanisms of electronic structural control are under investigation as not all of a material's characteristics are affected by quantum confinement. Demonstrated here is a new structure-property concept that imparts the ability to spatially localize electrons or holes within a core/shell heterostructure by tuning the charge carrier's kinetic energy on a parabolic potential energy surface. This charge carrier separation results in extended radiative lifetimes and in continuous emission at the single-nanoparticle level. These properties enable new applications for optics, facilitate novel approaches such as time-gated single-particle imaging, and create inroads for the development of other new advanced materials.

Sorting Nanoparticles by Valency with DNA Barcoding.

Self-assembly of DNA-labeled nanoparticles is an effective strategy to fabricate new nanocomposite materials and nanoscale devices from the bottom-up. To tailor the properties of the resulting material or device, one requires access to a wide range of nanoparticle sizes and shapes, as well as control over the number (valency) of DNA molecules on the nanoparticle surface. Currently, nanoparticles with a defined DNA valency can only be obtained in a narrow range of sizes, and in small quantities, limiting the properties of the resulting composite structures and their applications. Here, we leverage the digital information encoded in the number and sequence of short DNA barcodes to generate preparatory amounts of nanoparticles bearing a specific number of DNA molecules, irrespective of the identity of the nanocomponent. We show that this DNA valency sorting chromatography, which is driven by the selective affinity of Watson-Crick base pairs, is applicable to arbitrary DNA sequences and a broad range of nanoparticle sizes, shapes, and material compositions. To further demonstrate this fact, we use valency-sorted large gold nanospheres directly in self-assembly schemes to create, in one synthesis step, large amounts of several previously inaccessible molecule-like dimer and trimer nanostructures with unique optical properties. We anticipate that the expanded scope of DNA valency-defined nanoparticle reagents, and the increased scale at which they can be produced, will open new avenues for the molecularly precise manipulation of nanoscale matter.

Reproducibly Measuring Plasmon-Enhanced Fluorescence in Bulk Solution Across a 20-Fold Range of Optical Densities.

It is well-known that plasmonic nanoparticles can modify the spectroscopic properties of nearby optical probes, for example, enhanced emission of a fluorescent dye. Yet, the detection and quantification of this effect in bulk solution remain challenging even while size- and shape-controlled nanoparticles have become readily available. We investigated this problem and identified two main difficulties which we were able to overcome through systematic studies. For the detection of fluorescence emanating from optically dense nanoparticle solutions, we describe an analytical model that provides guidelines for experimentalists to maximize the fluorescence intensity by optimizing the concentration, light paths, and excitation-detection volume of the sample. For the quantification of enhancement, which critically hinges upon the comparison to an accurate reference sample, we exploit the tools of DNA nanotechnology to remove the fluorophore from plasmonic coupling on-demand, forming an in situ reference. Using a model system of fluorophore Cy3 and 80 nm gold nanoparticles, we show that these strategies enable the quantitative measurement of plasmonic enhancement across a 20-fold range of optical densities. We anticipate that the presented experimental framework will allow for routine, quantitative measurements for the research and development of plasmon-enhanced phenomena.

Mechanodelivery of nanoparticles to the cytoplasm of living cells.

Nanotechnology has opened up the opportunity to probe, sense, and manipulate the chemical environment of biological systems with an unprecedented level of spatiotemporal control. A major obstacle to the full realization of these novel technologies is the lack of a general, robust, and simple method for the delivery of arbitrary nanostructures to the cytoplasm of intact live cells. Here, we identify a new delivery modality, based on mechanical disruption of the plasma membrane, which efficiently mediates the delivery of nanoparticles to the cytoplasm of mammalian cells. We use two distinct execution modes, two adherent cell lines, and three sizes of semiconducting nanocrystals, or quantum dots, to demonstrate its applicability and effectiveness. As the underlying mechanism is purely physical, we anticipate that such "mechanodelivery" can be generalized to other modes of execution as well as to the cytoplasmic introduction of a structurally diverse array of functional nanomaterials.