Porous Nanoshells Research Articles

Determination of Pore Sizes and Relative Porosity in Porous Nanoshell Architectures Using Dextran Retention with Single Monomer Resolution and Proton Permeation

Unilamellar phospholipid vesicles prepared using the polymerizable lipid bis-sorbylphosphatidylcholine (bis-SorbPC) yield three-dimensional nanoarchitectures that are highly permeable to small molecules. The resulting porous phospholipid nanoshells (PPNs) are potentially useful for a range of biomedical applications including nanosensors and nanodelivery vehicles for cellular assays and manipulations. The uniformity and size distribution of the pores, key properties for sensor design and utilization, have not previously been reported. Fluorophore-assisted carbohydrate electrophoresis (FACE) was utilized to assess the nominal molecular weight cutoff limit (NMCL) of the PPN via analysis of retained dextran with single monomer resolution. The NMCL of PPNs prepared from pure bis-SorbPC was equivalent to a 1800 Da linear dextran, corresponding to a maximum pore diameter of 2.6 nm. Further investigation of PPNs prepared using binary mixtures of bis-SorbPC and dioleoylphosphatidylcholine (DOPC) revealed a similar NMCL when the bis-SorbPC content exceeded 30 mol %, whereas different size-dependent permeation was observed below this composition. Below 30 mol % bis-SorbPC, dextran retention provided insufficient mass resolution (162 Da) to observe porosity on the experimental time scale; however, proton permeability showed a marked enhancement for bis-SorbPC ≥ 10 mol %. Combined, these data suggest that the NMCL for native pores in bis-SorbPC PPNs results from an inherent property within the lipid assembly that can be partially disrupted by dilution of bis-SorbPC below a critical value for domain formation. Additionally, the analytical method described herein should prove useful for the challenging task of elucidating porosity in a range of three-dimensional nanomaterials.

Controlled synthesis of porous Ag/Au bimetallic hollow nanoshells with tunable plasmonic and catalytic properties

This paper describes a simple and facile method for the synthesis of Ag/Au bimetallic hollow and porous nanoshells (HPNSs) with controllable porosity, using polycrystalline Ag nanoparticles as starting templates. The optical and catalytic properties of the HPNSs can be easily tuned by using hydrogen peroxide as a mild etchant to controllably dissolve Ag atoms from the precursor Ag/Au bimetallic hollow nanoshells (NSs). The surface plasmon bands of the HPNSs can be easily tuned from the visible to the near infrared (NIR) region. As a model reaction to evaluate the catalytic activity of the HPNSs, we chose the reduction of p-nitrophenol by NaBH4 to afford p-aminophenol. The porous NSs exhibit higher catalytic activity than non-porous NSs even though the latter have higher Au/Ag ratios than the former. Although the composition (Au/Ag ratio) may have some effect, the morphology (porosity) of the HPNSs plays the most important role in the catalysis. The as-synthesized plasmonic HPNSs, due to their facile aqueous-phase preparation, tunable optical properties (in the visible and NIR windows), and unique porous hollow structures, have promising potential applications in various fields ranging from biosensing, nanomedicine (drug/gene delivery, cancer theranostics, etc.), to catalysis and solar cells.

Alloying and Dealloying Processes Involved in the Preparation of Metal Nanoshells through a Galvanic Replacement Reaction

The galvanic replacement reaction between Ag nanoparticles and an aqueous HAuCl4 solution has recently been demonstrated as a simple and convenient route to metal nanostructures with hollow interiors and highly crystalline walls (see, for example, Sun, Y.; Mayers, B. T.; Xia, Y. Nano Lett. 2002, 2, 481. Sun, Y.; Xia, Y. Science, 2002, 298, 2176). However, the details of morphological, compositional, structural, and spectral changes involved in the entire process of this template-engaged reaction is yet to be elucidated. The experimental results described in this letter indicate that the templating process proceeded through two distinctive steps: (i) formation of pinhole-free nanoshells with homogeneous, uniform walls of Au/Ag alloys via a combination of the replacement reaction and alloying; and (ii) formation of porous nanoshells (nanocages) through a dealloying process, in which Ag was selectively dissolved from the walls made of Au/Ag alloys. As alloying and dealloying proceeded, the surface plasmon resonance peaks of resultant metal nanostructures could be continuously tuned from ∼425 to ∼1030 nm.