Younan Xia

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

Extending Platinum Catalysts Platinum performs extremely well as a catalyst for the oxygen-reduction reaction that runs under highly acidic conditions in proton-exchange membrane fuel cells, but is expensive. One strategy for reducing costs is to increase the surface area of the platinum. Lim et al. (p. 1302, published online 14 May) describe a simple chemical route, in which Pt ions in solution are reduced onto Pd seed crystals, which creates faceted Pt nanocrystals with a high area owing to their dendritic architecture. On a Pt mass basis, these catalysts are several times more active than conventional Pt catalysts. The catalytic activity of platinum is enhanced through a growth process that creates nanocrystals with high surface area. Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K2PtCl4 with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

Monodispersed Colloidal Spheres: Old Materials with New Applications

This article presents an overview of current research activities that center on monodispersed colloidal spheres whose diameter falls anywhere in the range of 10 nm to 1 μm. It is organized into three parts: The first part briefly discusses several useful methods that have been developed for producing monodispersed colloidal spheres with tightly controlled sizes and well-defined properties (both surface and bulk). The second part surveys some techniques that have been demonstrated for organizing these colloidal spheres into two- and three-dimensionally ordered lattices. The third part highlights a number of unique applications of these crystalline assemblies, such as their uses as photonic bandgap (PBG) crystals; as removable templates to fabricate macroporous materials with highly ordered and three-dimensionally interconnected porous structures; as physical masks in lithographic patterning; and as diffractive elements to fabricate new types of optical sensors. Finally, we conclude with some personal perspectives on the directions towards which future research in this area might be directed.

Soft lithography for micro- and nanoscale patterning.

This protocol provides an introduction to soft lithography—a collection of techniques based on printing, molding and embossing with an elastomeric stamp. Soft lithography provides access to three-dimensional and curved structures, tolerates a wide variety of materials, generates well-defined and controllable surface chemistries, and is generally compatible with biological applications. It is also low in cost, experimentally convenient and has emerged as a technology useful for a number of applications that include cell biology, microfluidics, lab-on-a-chip, microelectromechanical systems and flexible electronics/photonics. As examples, here we focus on three of the commonly used soft lithographic techniques: (i) microcontact printing of alkanethiols and proteins on gold-coated and glass substrates; (ii) replica molding for fabrication of microfluidic devices in poly(dimethyl siloxane), and of nanostructures in polyurethane or epoxy; and (iii) solvent-assisted micromolding of nanostructures in poly(methyl methacrylate).

Gold nanocages covered by smart polymers for controlled release with near-infrared light

Photosensitive caged compounds have enhanced our ability to address the complexity of biological systems by generating effectors with remarkable spatial/temporal resolutions1-3. The caging effect is typically removed by photolysis with ultraviolet light to liberate the bioactive species. Although this technique has been successfully applied to many biological problems, it suffers from a number of intrinsic drawbacks. For example, it requires dedicated efforts to design and synthesize a precursor compound to the effector. The ultraviolet light may cause damage to biological samples and is only suitable for in vitro studies because of its quick attenuation in tissue4. Here we address these issues by developing a platform based on the photothermal effect of gold nanocages. Gold nanocages represent a class of nanostructures with hollow interiors and porous walls5. They can have strong absorption (for the photothermal effect) in the near-infrared (NIR) while maintaining a compact size. When the surface of a gold nanocage is covered with a smart polymer, the pre-loaded effector can be released in a controllable fashion using a NIR laser. This system works well with various effectors without involving sophiscated syntheses, and is well-suited for in vivo studies due to the high transparency of soft tissue in NIR6.

A Comparison Study of the Catalytic Properties of Au-Based Nanocages, Nanoboxes, and Nanoparticles

We have evaluated the catalytic properties of Au-based nanostructures (including nanocages, nanoboxes, and solid nanoparticles) using a model reaction based on the reduction of p-nitrophenol by NaBH(4). From the average reaction rate constants at three different temperatures, we determined the activation energy, the entropy of activation, and the pre-exponential factor for each type of Au nanostructure. The kinetic data indicate that the Au-based nanocages are catalytically more active than both the nanoboxes and nanoparticles probably due to their extremely thin but electrically continuous walls, the high content of Au, and the accessibility of both inner and outer surfaces through the pores in the walls. In addition, a compensation effect was observed in this Au-based catalytic system, which can be primarily interpreted by a model based on kinetic regime switching.

Facile synthesis of Ag nanocubes and Au nanocages

This protocol describes a method for the synthesis of Ag nanocubes and their subsequent conversion into Au nanocages via the galvanic replacement reaction. The Ag nanocubes are prepared by a rapid (reaction time < 15 min), sulfide-mediated polyol method in which Ag(I) is reduced to Ag(0) by ethylene glycol in the presence of poly(vinyl pyrrolidone) (PVP) and a trace amount of Na2S. When the concentration of Ag atoms reaches supersaturation, they agglomerate to form seeds that then grow into Ag nanostructures. The presence of both PVP and Na2S facilitate the formation of nanocubes. With this method, Ag nanocubes can be prepared and isolated for use within approximately 3 h. The Ag nanocubes can then serve as sacrificial templates for the preparation of Au nanocages, with a method for their preparation also described herein. The procedure for Au nanocage preparation and isolation requires approximately 5 h.

Gold Nanocages: From Synthesis to Theranostic Applications

Gold nanostructures have garnered considerable attention in recent years for their potential to facilitate both the diagnosis and treatment of cancer through their advantageous chemical and physical properties. The key feature of Au nanostructures for enabling this diverse array of biomedical applications is their attractive optical properties, specifically the scattering and absorption of light at resonant wavelengths due to the excitation of plasmon oscillations. This phenomenon is commonly known as localized surface plasmon resonance (LSPR) and is the source of the ruby red color of conventional Au colloids. The resonant wavelength depends on the size, shape, and geometry of the nanostructures, providing a set of knobs to manipulate the optical properties as needed. For in vivo applications, especially when optical excitation or transduction is involved, the LSPR peaks of the Au nanostructures have to be tuned to the transparent window of soft tissues in the near-infrared (NIR) region (from 700 to 900 nm) to maximize the penetration depth. Gold nanocages represent one class of nanostructures with tunable LSPR peaks in the NIR region. These versatile nanostructures, characterized by hollow interiors and ultrathin, porous walls, can be prepared in relatively large quantities using a remarkably simple procedure based on the galvanic replacement between Ag nanocubes and aqueous chloroauric acid. The LSPR peaks of Au nanocages can be readily and precisely tuned to any wavelength in the NIR region by controlling their size, wall thickness, or both. Other significant features of Au nanocages that make them particularly intriguing materials for biomedical applications include their compact sizes, large absorption cross sections (almost five orders of magnitude greater than those of conventional organic dyes), and their bio-inertness, as well as a robust and straightforward procedure for surface modification based on Au-thiolate chemistry. In this Account, we present some of the most recent advances in the use of Au nanocages for a broad range of theranostic applications. First, we describe their use as tracers for tracking by multiphoton luminescence. Gold nanocages can also serve as contrast agents for photoacoustic (PA) and mutimodal (PA/fluorescence) imaging. In addition, these nanostructures can be used as photothermal agents for the selective destruction of cancerous or diseased tissue. Finally, Au nanocages can serve as drug delivery vehicles for controlled and localized release in response to external stimuli such as NIR radiation or high-intensity focused ultrasound (HIFU).

Understanding the Role of Surface Charges in Cellular Adsorption versus Internalization by Selectively Removing Gold Nanoparticles on the Cell Surface with a I2/KI Etchant

This Letter presents a new method for differentiating the Au nanospheres attached to the cell surface from those being internalized into the cells. We introduced an etching solution based on I2 and KI that can selectively dissolve the Au nanospheres on the cell surface within a short period of time. The advantage of this etchant is its low toxicity to the cells because it is capable of etching away a relatively large amount of Au nanospheres at a low molar concentration. By combining with quantitative elemental analysis, we found that the deposition of Au nanospheres on the surface of cancer cells was highly dependent on the sign of surface charges on the Au nanospheres. In addition, by fitting the uptake data with a kinetic model, we were able to derive the overall and internalization rate constants for Au nanospheres and both of them were found to be governed by the surface charges on Au nanospheres.

Dimers of silver nanospheres: facile synthesis and their use as hot spots for surface-enhanced Raman scattering.

This paper describes a simple, one-pot method that generates dimers of silver nanospheres in one step without any additional assembly steps. The dimers are consisted of single-crystal silver nanospheres approximately 30 nm in diameter and separated by a gap of 1.8 nm wide. The key to the success of this method lies in the control of colloidal stability and oxidative etching by optimizing the amount of chloride added to a polyol synthesis. The dimers provide a well-defined system for studying the hot spot phenomenon (hot spot: the gap region of a pair of strongly coupled silver or gold nanoparticles), an extremely important but poorly understood subject in surface-enhanced Raman scattering (SERS). Because of the relatively small size of the silver nanospheres, only those molecules trapped in the hot spot region are expected to contribute to the detected SERS signals. By correlating SERS measurements with SEM imaging, we found that the SERS enhancement factor within the hot spot region of such a dimer was on the order of 2 x 10(7).