Ilya Gourevich

Ultrathin Gold Nanoframes through Surfactant-Free Templating of Faceted Pentagonal Silver Nanoparticles

Ultrathin gold nanoframes (up to 1.6 nm) were prepared via templating upon well-defined faceted silver morphologies. Starting with silver decahedra, small quantities of gold (1-10 mol% relative to the amount of silver) were selectively deposited on the nanoparticle edges under optimized reducing conditions. Silver dissolution in hydrogen peroxide yielded well-defined gold frames that retained their structural integrity in the ultrathin nanowire regime below 2 nm. The frame formation protocol was also successfully applied to other silver nanoparticle shapes featuring pentagonal twinning and (111) facets (e.g., pentagonal faceted rods and icosahedra). The demonstrated approach can be applied in the controlled preparation of ultrathin metal nanowires complementary to lithography and in the production of ultrafine noble-metal nanostructures for catalytic applications.

A design strategy for the hierarchical fabrication of colloidal hybrid mesostructures

Advances in nanotechnology depend upon expanding the ability to create new and complex materials with well-defined multidimensional mesoscale structures. The creation of hybrid hierarchical structures by combining colloidal organic and inorganic building blocks remains a challenge due to the difficulty in preparing organic structural units of precise size and shape. Here we describe a design strategy to generate controlled hierarchical organic-inorganic hybrid architectures by multistep bottom-up self-assembly. Starting with a suspension of large inorganic nanoparticles, we anchor uniform block copolymer crystallites onto the nanoparticle surface. These colloidally stable multi-component particles can initiate the living growth of uniform cylindrical micelles from their surface, leading to three-dimensional architectures. Structures of greater complexity can be obtained by extending the micelles via addition of a second core-crystalline block copolymer. This controlled growth of polymer micelles from the surface of inorganic particles opens the door to the construction of previously inaccessible colloidal organic-inorganic hybrid structures.

Microgels for the Encapsulation and Stimulus-Responsive Release of Molecules with Distinct Polarities

A microfluidic strategy for the encapsulation and stimulus-responsive release of molecules with distinct polarities from the interior of microgels is reported. The approach relies on (i) the generation of a primary O/W emulsion by the ultrasonication method, (ii) MF emulsification of the primary emulsion, and (iii) photopolymerization of the monomer present in the aqueous phase of the droplets, thereby transforming them into microgels. Non-polar molecules are dissolved in oil droplets embedded in the microgels. Polar molecules are physically associated with the hydrogel network. Upon heating, the microgels contract and release polar and non-polar cargo molecules. The approach paves the way for stimuli-responsive vehicles for multiple drug delivery.

Hybrid porous material produced by polymerization-induced phase separation

Herein we demonstrate a new, straightforward method for the synthesis of macroporous hybrid polymers coated with gold nanorods, which are strongly and uniformly attached to the surface of pores.

Polymer nanostructured material for the recording of biometric features

This communication describes the design, synthesis and application of a polymer multiphase nanostructured material as a recording medium. The material was produced from polymer multilayer particles containing three fluorescent dyes with largely non-overlapping absorption and emission spectra. Recording was conducted by selective photobleaching of the dyes localized in the different phases of the film. We demonstrate two distinct approaches to the recording of biometric features in the polymer material. In the first strategy, we encrypted in the polymer films full colour photographs with different shades of grey. In the second approach, we recorded three spatially overlapping biometric features in the same location of the material with no spectral overlap between them. Each feature was accessed by irradiating the material at a specific well-defined wavelength. The reported material can be used as a medium for the recording of biometric features of holders of identification documents.

A Study of Polymerization-Induced Phase Separation as a Route to Produce Porous Polymer–Metal Materials

We report the results of the experimental study of the preparation of hybrid porous polymer material carrying gold nanorods (NRs) on the surface of pores. The material was prepared by utilizing two effects occurring concurrently: the photoinitiated polymerization-induced phase separation in the polymer-solvent mixture and the migration of the NRs to the interface between the polymer and the porogen solvent. We show that the enrichment of the interface with the NRs is enhanced at high polymerization rate leading to the rapid phase separation. By contrast, more rapid increase in viscosity achieved at high polymerization rate does not have a significant effect on the segregation of NRs to the surface of pores.

Extinction analysis of dielectric multilayer microspheres

This letter reports optical properties of spherical dielectric particles with alternating layers of high and low refractive indices. The authors “predesigned” and synthesized polymer microspheres with alternating polystyrene and poly(trifluoroethyl methacrylate) layers of various thicknesses. Extinction of the microspheres was examined in a broad spectral range. A multipole expansion of electromagnetic field was applied for calculating the extinction efficiency of the particles. Excellent agreement was obtained between experimental and theoretical extinction curves.This letter reports optical properties of spherical dielectric particles with alternating layers of high and low refractive indices. The authors “predesigned” and synthesized polymer microspheres with alternating polystyrene and poly(trifluoroethyl methacrylate) layers of various thicknesses. Extinction of the microspheres was examined in a broad spectral range. A multipole expansion of electromagnetic field was applied for calculating the extinction efficiency of the particles. Excellent agreement was obtained between experimental and theoretical extinction curves.

Synthesis and sensing properties of D5h pentagonal silver star nanoparticles

In this work, we use silver decahedral nanoparticle (AgDeNP) seeds to synthesize pentagonal silver stars (AgStDeNPs) and study the sensing properties of these nanoparticles. The regrowth process of AgStDeNPs is kinetically-controlled, so the purity of the seed NPs is critical to avoid secondary deposition in the highly non-equilibrium reduction. To control the regrowth process, surface blocking with sodium polyacrylate (PANa) was implemented. PANa moderates rough silver nanostructures typically obtained by reduction with ascorbic acid. To modulate polymer binding to the surface and thus to tune surface blocking, pH served as a key synthetic parameter. Under optimal regrowth conditions, new sliver was deposited on the highest energy sites of the decahedra - the vertices of the rims - to yield pentagonal stars. The universality of this regrowth process was established with several different seed particles. The sharpness and size of the stellated tips are tunable by the amount of added silver. Gold deposition onto AgStDeNPs enables the preparation of diverse structures with enhanced stability. Ease of transformation, e.g. rounding, of star branches opens a promising venue for enhanced SPR sensing. Also, AgStDeNPs enable femtomolar detection of 5,5-dithiobis(2-nitrobenzoic acid) in SERS.

Chiral plasmonic activity of cholesteric films formed by gold nanorods and cellulose nanocrystals

Chiral plasmonic films have been prepared by incorporating gold nanorods (NRs) in a macroscopic cholesteric film formed by self-assembled cellulose nanocrystals (CNCs). Composite NR-CNC films revealed strong and tunable plasmonic chiroptical activity, dependent on the photonic properties of the CNC host and plasmonic properties of the NRs1.