David A. Beattie

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.

Probing buried interfaces with non-linear optical spectroscopy

The importance of buried interfaces in our everyday lives and in current scientific research is highlighted, along with experimental difficulty associated with studying such systems. We present an overview of the application of second harmonic generation and sum-frequency spectroscopy to the study of buried interfaces. Several examples from the current literature are presented, ranging from chemical and biological, to electrical and magnetic interfaces. The importance of this work in the context of ongoing research in these areas is discussed. Finally, we provide a snapshot of the state of the art in non-linear optical spectroscopy by mentioning several new directions that are likely to have a large impact on future research into the physics and chemistry of buried interfaces.

In situ particle film ATR FTIR spectroscopy of carboxymethyl cellulose adsorption on talc: binding mechanism, pH effects, and adsorption kinetics.

Carboxymethyl cellulose (CMC), in solution and adsorbed on the surface of talc, has been studied with ATR FTIR spectroscopy as a function of the solution pH. The solution spectra enable the calculation of the extent of ionization of the polymer (due to protonation and deprotonation of the carboxyl group) at various pH values, yielding a value of 3.50 for the pK(app)(1/2) (pH at which half of all carboxyl groups are ionized) in a simple electrolyte solution and a value of 3.37 for the pK(app)(1/2) in solutions containing magnesium ions (3.33 x 10(-4) M). The spectra of the adsorbed layer reveal that CMC interacts with the talc surface through a chemical complexation mechanism, via the carboxyl groups substituted on the polymer backbone. The binding mechanism is active at all pH values down to pH 2 and up to pH 11. The adsorbed layer spectra reveal that protonation and deprotonation of the polymer are affected by adsorption, with an increase in the pK(app)(1/2) to a value of 4.80. Spectra of the adsorbed polymer were also acquired as a function of the adsorption time. Adsorption kinetic data reveal that the polymer most likely has two different interactions with the talc surface, with a stronger interaction with the talc edge through chemical complexation and a weaker interaction with the talc basal plane presumably through the hydrophobic interaction.

Direct attachment of well-aligned single-walled carbon nanotube architectures to silicon (100) surfaces : a simple approach for device assembly

A new approach for the attachment of vertically-aligned shortened carbon nanotube architectures to a silicon (100) substrate by chemical anchoring directly to the surface has been demonstrated for the first time. The ordered assembly of single-walled carbon nanotubes (SWCNTs) was accomplished by hydroxylating the silicon surface followed by a condensation reaction with carboxylic acid functionalised SWCNTs. This new nanostructure has been characterised by X-ray photoelectron, Raman and Fourier transform infrared (FTIR) spectroscopy as well as scanning electron and atomic force microscopy. The assembly behaviour of SWCNTs onto the silicon surface shows a fast initial step producing isolated functionalised carbon nanotubes or nanotube bundles anchored to the silicon surface followed by a slower step where the adsorbed nanotubes grow into larger aggregates via van der Waals interactions between adsorbed and solvated nanotubes. The electrochemical and optical properties of the SWCNTs directly attached to silicon have also been investigated. These new nanostructures are excellent electrochemical electrodes. They also fluoresce in the wavelength range 650-800 nm. The successful attachment of the SWCNTs directly to silicon provides a simple, new avenue for fabrication and development of silicon-based nanoelectronic, nano-optoelectronic and sensing devices. Compared to existing techniques, this new approach has several advantages including low operating temperature, low cost and the possibility of further modification.

Chemical Defects in the Highly Fluorescent Conjugated Polymer Dots

We present strong evidence for the oxidation of conjugated polymers in the formation of conjugated polymer dots (CPdots) using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Although recent studies show that folding of the polymer chain into a compact 3D structure is involved in the formation of these nanoparticles, the process by which these intrinsically hydrophobic nanoscale particles circumvent aggregation in water is still not well understood. Zeta potential results show that these dots have a negatively charged surface at neutral pH, with a zeta potential and surface charge density of approximately -40 mV and (1.39 - 1.70) × 10(-2) C/m(2), respectively. In addition, quantitative elemental analysis of CPdots indicates that oxygen composes 7-13% of these nanoparticles. The overall results support the presence of chemical defects in forming a hydrophilic surface of CPdots. As a consequence, the charged surface contributes to inhibiting the aggregation of CPdots in water, leading to colloidal stability.

Self-ordering Electrochemistry: A Simple Approach for Engineering Nanopore and Nanotube Arrays for Emerging Applications*

In this paper, we present recent work from our group focussed on the fabrication of nanopore and nanotube arrays using self-ordered electrochemistry, and their application in several key areas including template synthesis, molecular separation, optical sensing, and drug delivery. We have fabricated nanoporous anodic aluminium oxide (AAO) with controlled pore dimensions (20–200 nm) and shapes, and used them as templates for the preparation of gold nanorod/nanotube arrays and gold nanotube membranes with characteristic properties such as surface enhanced Raman scattering and selective molecular transport. The application of AAO nanopores as a sensing platform for reflective interferometric detection is demonstrated. Finally, a drug release study on fabricated titania nanotubes confirms their potential for implantable drug delivery applications.

Adsorption of modified dextrins on talc: effect of surface coverage and hydration water on hydrophobicity reduction.

The adsorption of three modified dextrins on the basal plane of talc has been studied using in situ tapping mode atomic force microscopy (TMAFM). The images have been used to determine the layer thickness and coverage of the adsorbed polymers. Adsorption isotherms of the polymers on talc particles were also determined using the depletion technique. Values of the adsorbed amount at equilibrium were compared with the volume of adsorbed material as determined using in situ TMAFM, revealing the presence of significant amounts of hydration water in the adsorbed layer structure. This deduction was confirmed by comparing in and ex situ TMAFM images of the adsorbed dextrins. The effect of layer thickness, coverage, and hydration water content on the contact angle of talc particles treated with polymer was investigated using the Washburn method and the equilibrium capillary pressure (ECP) method. Distinct correlations were observed between adsorbed layer properties and the measured contact angles, with the ECP measurements especially highlighting the effect of the adsorbed polymer layer hydration water. The implications for the performance of the modified dextrins in flotation are discussed.

Surface study of the effect of sulphite ions on copper-activated pyrite pre-treated with xanthate

X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry have been used to determine the specific effect of sulphite ions on the surface chemistry of copper-activated pyrite pre-treated with isobutyl xanthate in flotation experiments with nitrogen and air purging at pH 7. The results from these spectroscopic techniques illustrate that sulphite ions affect the surface chemistry of pyrite similarly whether nitrogen or air purged. It was found that sulphite ions interact with adsorbed collector species, as well as with the pyrite surface itself. A reduction in the adsorbed collector concentration and a commensurate increase in surface hydrophilicity explain the low flotation recovery of pyrite in the presence of sulphite. As expected, this effect was more pronounced in the flotation experiments with air purging.

A comparative study of confined organic monolayers by Raman scattering and sum-frequency spectroscopy

Abstract The structure of a Langmuir–Blodgett (LB) monolayer of Zn arachidate at the solid–solid interface has been studied by Raman scattering and sum-frequency (SF) spectroscopy. The monolayer was confined in the contact between a CaF2 prism and a MgF2 lens at an average pressure of 60 MPa. This is the first report of an unenhanced Raman spectrum of an organic monolayer at the solid–solid interface. The Raman and SF spectra both show that the deposited monolayer is conformationally ordered and that the monolayer retains this order when placed between the prism and the lens. The relative intensity of the Raman spectra of the Zn arachidate monolayer at the CaF2/air and CaF2/MgF2 interfaces can be explained in terms of the strength of the interfacial electric fields. The relative intensities of the SF spectra at the two interfaces cannot be interpreted in this manner. Deviations from the expected intensities are discussed in terms of structural changes in the monolayer.

Adsorption of dextrin on hydrophobic minerals.

The adsorption of dextrin on talc, molybdenite, and graphite (three naturally hydrophobic minerals) has been compared. Adsorption isotherms and in situ tapping mode atomic force microscope (TMAFM) imaging have enabled polymer adsorbed amount and morphology of the adsorbed layer (area coverage and polymer domain size) to be determined and also the amount of hydration water in the structure of the adsorbed layer. The effect of the polymer on the mineral contact angles, measured by the captive bubble method on cleaved mineral surfaces, indicates clear correlations between the hydrophobicity reduction of the minerals, the adsorbed amount, and the surface coverage of the adsorbed polymer. Predictions of the flotation recovery of the treated mineral phases have been confirmed by performing batch flotation experiments. The influence of the polymer surface coverage on flotation recovery has highlighted the importance of this key parameter in the predictions of depressant efficiency. The roles of the initial hydrophobicity and the surface structure of the mineral basal plane in determining adsorption parameters and flotation response of the polymer-treated minerals are also discussed.