Jingfang Zhou

Functionalized gold nanoparticles: Synthesis, structure and colloid stability

Gold nanoparticles and their arrays are some of the most studied nanomaterials, with promising applications in many fields such as electronics, optoelectronics, catalysis and biology. In order to protect bare gold nanoparticles from aggregation, to manipulate the optical, electronic and catalytic properties of the gold core, as well as to control interfacial properties, the gold nanoparticles are generally capped by an organic layer. Previous studies [C.D. Bain, G.M. Whitesides, J. Am. Chem. Soc. 110 (1988) 3665-3666] have revealed that many phenomena (e.g., wetting, friction and adhesion), are sensitive to the top few angstroms of a surface. The interfacial properties of a gold surface derivatized with a self-assembled monolayer will thus be dictated by the functionalities present on the outer side of the monolayer. The synthesis, functionalization and surface structure of monolayer-protected gold nanoparticles have been intensively studied in recent times [M.-C. Daniel, D. Astruc, Chem. Rev. 104 (2004) 293-346]. In addition, the aggregation and dispersion of colloidal nanoparticles is one of the key issues related to their potential applications. The forces that govern the colloid stability of nanoparticle dispersions, and how to control them, have yet to be fully investigated. Here special attention has been paid to control of colloid stability using external stimuli. In this feature article, the following five areas are reviewed: synthesis and applications of nanostructured particles; formation and structure of self-assembled monolayer protected gold nanoparticles; colloid stability-DLVO and non-DLVO forces; photochemistry, photochromism and pyrimidine; and manipulation of colloid stability with external stimuli.

Light-Induced Aggregation of Colloidal Gold Nanoparticles Capped by Thymine Derivatives

The colloid stability of thymine-coated gold nanoparticles under light irradiation as a function of particle size, surface charge, and exposure time was investigated in alkaline, aqueous solutions as well as in a 0.5 vol % of DMF in H(2)O mixture. With increasing exposure to light irradiation at 280 nm, more and more particles coagulated. Light-induced aggregation of colloidal gold nanoparticles was attributed to reorientation of thymine terminal groups tethered on gold particle surfaces. A smaller particle size and negatively charged surface reduced the rate of photodimerization or even inhibited the photoreaction. UV-vis and FTIR spectroscopy confirmed the photodimerization of terminal thymine molecules under 280 nm light irradiation. The reaction kinetics of thymine photodimerization appears to be a combination of first-order reactions, each having different rates, reflecting the inhomogeneity and high curvature of the gold nanoparticle surfaces.

Microfluidic Solvent Extraction of Metal Ions from Industrial Grade Leach Solutions: Extraction Performance and Channel Aging

Microfluidic solvent extraction (microSX) of metal ions from industrial grade mineral leach solutions was studied. In conventional bulk-scale SX, partially hydrophobic nanoparticles that are present in the leach solution readily adsorb at the liquid-liquid interface of the dispersed droplets, causing delayed or incomplete phase separation and reduce efficiency. In contrast, microSX employs continuous microscopic streams of aqueous and organic phases (without mixing the phases) and, in this way, bypasses the need for a conventional phase separation stage. This makes the technique promising for handling complex leach solutions. The stability of the two-phase flow is considered in terms of the surface wettability and guiding geometry of the microchannel, which determines the Laplace pressure window that stabilizes the liquid-liquid interface. We show that careful characterization of the microchannel wettability, including contact angle hysteresis, is essential to predict long-term flow stability.

Design of Pyrimidine-Based Photoresponsive Surfaces and Light-Regulated Wettability

Photoresponsive surfaces were prepared by attaching pyrimidine-terminated molecules to flat gold substrates (as thiol self-assembled monolayers) or by dip-coating quartz surfaces. Both types of films underwent photodimerization (two pyrimidine rings react with one another and form a cyclobutane type dimer through the C5=C6 double bond) when irradiated with light of 280 nm wavelength. The reverse reaction was carried out by irradiating the dimerized surface with light of 240 nm wavelength. The photoinduced chemical changes are accompanied by a change in the physical properties of the surface (e.g., wettability and acidity), and are highly dependent on the structure of the photoactive molecules. The surface dimerization reaction follows a pseudo-first order reaction. The rate constant is determined by the structure of the pyrimidine headgroup. In self-assembled monolayers, uracil derivatives dimerize faster than thymine derivatives due to a reduced steric repulsion near the reaction center. In dip-coated films, however, uracil derivatives appear to be less ordered and, correspondingly, the efficiency of the reaction is lower. The reaction rate is also very sensitive to the ordering within the layer, which can be manipulated through the structure of the tail. In SAMs, faster dimerization occurs with molecules containing flexible chains. In dip-coated films, the presence of a polar group at the chain terminus favors dimerization.

Microfluidic Solvent Extraction of Copper for Mineral Processing

Solvent extraction of copper has been explored in a microfluidic chip (μSX). The transfer efficiency and rate of phase separation in μSX were compared to that achieved using conventional methods (bulk dispersion) both with and without fine silica particles present. Using the microfluidic approach, transfer efficiency was comparable to that achieved in conventional extraction. Phase separation is slow or totally arrested in bulk extraction, while instantaneous phase separation was achieved in μSX, even at high particle concentrations.Copyright