Molecular recognition of 2,4,6-trinitrotoluene by 6-aminohexanethiol and surface-enhanced Raman scattering sensor

2,4,6-trinitrotoluene (TNT) is one of the most commonly used nitro aromatic explosives in landmine, military and mining industry. This article demonstrates rapid and selective identification of TNT by surface-enhanced Raman spectroscopy (SERS) using 6-aminohexanethiol (AHT) as a new recognition molecule. First, Meisenheimer complex formation between AHT and TNT is confirmed by the development of pink colour and appearance of new band around 500 nm in UV-visible spectrum. Solution Raman spectroscopy study also supported the AHT:TNT complex formation by demonstrating changes in the vibrational stretching of AHT molecule between 2800-3000 cm−1. For surface enhanced Raman spectroscopy analysis, a self-assembled monolayer (SAM) of AHT is formed over the gold nanostructure (AuNS) SERS substrate in order to selectively capture TNT onto the surface. Electrochemical desorption and X-ray photoelectron studies are performed over AHT SAM modified surface to examine the presence of free amine groups with appropriate orientation for complex formation. Further, AHT and butanethiol (BT) mixed monolayer system is explored to improve the AHT:TNT complex formation efficiency. Using a 9:1 AHT:BT mixed monolayer, a very low detection limit (LOD) of 100 fM TNT was realized. The new method delivers high selectivity towards TNT over 2,4 DNT and picric acid. Finally, real sample analysis is demonstrated by the extraction and SERS detection of 302 pM of TNT from spiked.

Premonolayer oxidation of nanostructured gold : an important factor influencing electrocatalytic activity

The study of the electrodeposition of polycrystalline gold in aqueous solution is important from the viewpoint that in electrocatalysis applications ill-defined micro- and nanostructured surfaces are often employed. In this work, the morphology of gold was controlled by the electrodeposition potential and the introduction of Pb(CH3COO)2•3H2O into the plating solution to give either smooth or nanostructured gold crystallites or large dendritic structures which have been characterized by scanning electron microscopy (SEM). The latter structures were achieved through a novel in situ galvanic replacement of lead with AuCl4−(aq) during the course of gold electrodeposition. The electrochemical behavior of electrodeposited gold in the double layer region was studied in acidic and alkaline media and related to electrocatalytic performance for the oxidation of hydrogen peroxide and methanol. It was found that electrodeposited gold is a significantly better electrocatalyst than a polished gold electrode; however, performance is highly dependent on the chosen deposition parameters. The fabrication of a deposit with highly active surface states, comparable to those achieved at severely disrupted metal surfaces through thermal and electrochemical methods, does not result in the most effective electrocatalyst. This is due to significant premonolayer oxidation that occurs in the double layer region of the electrodeposited gold. In particular, in alkaline solution, where gold usually shows the most electrocatalytic activity, these active surface states may be overoxidized and inhibit the electrocatalytic reaction. However, the activity and morphology of an electrodeposited film can be tailored whereby electrodeposited gold that exhibits nanostructure within the crystallites on the surface demonstrated enhanced electrocatalytic activity compared to smaller smooth gold crystallites and larger dendritic structures in potential regions well within the double layer region.

An acoustically enhanced gold film Raman sensor on a lithium niobate substrate

The surface enhanced Raman scattering effect has shown immense potential for detecting trace amounts of explosive vapor molecules. To date, efforts to produce a commercially available, reliable SERS sensor have been impeded by an inability to separate the electromagnetic enhancement produced by the metallic nanostructure from other signal enhancing effects. Here, we show a new Raman sensor that uses surface acoustic waves (SAWs) to produce controllable surface structures on gold films deposited on LiNbO3 substrates that modulate the Raman signal of a target compound (thiophenol) adsorbed on the films. We demonstrate that this sensor can dynamically control the Raman signal simply by changing the SAW’s amplitude, allowing the Raman signal enhancement factor to be directly measured with no variation in the concentration of the target compound. The physically adsorbed molecules can be removed from the sensor without physical cleaning or damage, making it possible to reuse it for real-time Raman detection.

An indexing model for stormwater quality in the Gold Coast

In the era of climate change sustainable urban development and in particular provision of sustainable urban infrastructure has become a key concept in dealing with environmental challenges. This paper discusses issues affecting stormwater quality and introduces a new indexing model that is to be used in evaluation of the stormwater quality in urban areas. The model has recently been developed and will be tested in a number of pilot projects in the Gold Coast, one of the fastest growing and environmentally challenged cities of Australia.

Members abroad - Australia - Brisbane and the Gold Coast

Brisbane's sub-tropical climate, vegetation and urban history as a British settlement, endow the region with many characteristics that are familiar in KwaZulu-Natal. Brisbane settlement, firstly as a penal conlony to accommodate the hardiest criminals dispatched from Sydney, was established in 1825 on a wide river, several kilometers upstream from Moreton Bay with the Pacific Ocean beyond. The penal colony was short lived and was soon opened up to free settlement in 1842. The growth of the fledgling town was characterized by brick warehouse and service buildings to the port that was established on its riverbanks, resembling those of the old Point Road area in Durban. Government and administration buildings heralded Brisbane as the captial city of the State of Queensland, annexed from New South Wales in 1859. Morphological studies reveal that Brisbane had reached its first zenith around 1930 as a commerical city of four and five storey buildings. The urban form remained stagnant until the post-1960's building boom and the developments from this period on, consolidated land amalgamations largely ignoring the urban characteristics of the established city. Public space was poorly observed, resulting in a city that had turned its back on the river. It is only in recent times that the currency of good urban design, under the custodial direction of the City Council, has fostered a re-engagemed urban realm that, enabled by the recent building boom, has delivered high quality urban environments

An indexing model for sustainable urban environmental management : the case of Gold Coast, Australia

Improving urban ecosystems and the quality of life of citizens have become a central issue in the global effort of creating sustainable built environments. As human beings our lives completely depend on the sustainability of the nature and we need to protect and manage natural resources in a more sustainable way in order to sustain our existence. As a result of population growth and rapid urbanisation, increasing demand of productivity depletes and degrades natural resources. However, the increasing activities and rapid development require more resources, and therefore, ecological planning becomes an essential vehicle in preserving scarce natural resources. This paper aims to indentify the interation between urban ecosystems and human activities in the context of urban sustainability and explores the degrading environmental impacts of this interaction and the necessity and benefits of using sustainability indicators as a tool in sustainable urban evnironmental management. Additionally, the paper also introduces an environmental sustainability indexing model (ASSURE) as an innovative approach to evaluate the environmental conditions of built environment.

An indexing model for stormwater quality assessment : stormwater management in the Gold Coast

In the age of climate change and rapid urbanisation, stormwater management and water sensitive urban design have become important issues for urban policy makers. This paper reports the initial findings of a research study that develops an indexing model for assessing stormwater quality in the Gold Coast.

Interactions of phenyldithioesters with gold nanoparticles (AuNPs): Implications for AuNP functionalization and molecular barcoding of AuNP assemblies

The interactions of phenyldithioesters with gold nanoparticles (AuNPs) have been studied by monitoring changes in the surface plasmon resonance (SPR), depolarised light scattering, and surface enhanced Raman spectroscopy (SERS). Changes in the SPR indicated that an AuNP-phenyldithioester charge transfer complex forms in equilibrium with free AuNPs and phenyldithioester. Analysis of the Langmuir binding isotherms indicated that the equilibrium adsorption constant, Kads, was 2.3 ± 0.1 × 106 M−1, which corresponded to a free energy of adsorption of 36 ± 1 kJ mol−1. These values are comparable to those reported for interactions of aryl thiols with gold and are of a similar order of magnitude to moderate hydrogen bonding interactions. This has significant implications in the application of phenyldithioesters for the functionalization of AuNPs. The SERS results indicated that the phenyldithioesters interact with AuNPs through the C═S bond, and the molecules do not disassociate upon adsorption to the AuNPs. The SERS spectra are dominated by the portions of the molecule that dominate the charge transfer complex with the AuNPs. The significance of this in relation to the use of phenyldithioesters for molecular barcoding of nanoparticle assemblies is discussed.

The encapsulation of gold nanoparticles using RAFT, ATRP and miniemulsion polymerisation techniques

The investigation into the encapsulation of gold nanoparticles (AuNPs) by poly(methyl methacrylate) (PMMA) was undertaken. This was performed by three polymerisation techniques including: grafting PMMA synthesised by reversible addition-fragmentation chain transfer (RAFT) polymerisation to AuNPs, grafting PMMA synthesised by atom transfer radical polymerisation (ATRP) from the surface of functionalised AuNPs and by encapsulation of AuNPs within PMMA latexes produced through photo-initiated oil-in-water (o/w) miniemulsion polymerisation. The grafting of RAFT PMMA to AuNPs was performed by the addition of the RAFT functionalised PMMA to citrate stabilised AuNPs. This was conducted with a range of PMMA of varying molecular weight distribution (MWD) as either the dithioester or thiol end-group functionalities. The RAFT PMMA polymers were characterised by gel permeation chromatography (GPC), ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), Fourier transform Raman (FT-Raman) and proton nuclear magnetic resonance (1H NMR) spectroscopies. The attachment of PMMA to AuNPs showed a tendency for AuNPs to associate with the PMMA structures formed, though significant aggregation occurred. Interestingly, thiol functionalised end-group PMMA showed very little aggregation of AuNPs. The spherical polymer-AuNP structures did not vary in size with variations in PMMA MWD. The PMMA-AuNP structures were characterised using scanning electron microscopy (SEM), transition electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and UV-vis spectroscopy. The surface confined ATRP grafting of PMMA from initiator functionalised AuNPs was polymerised in both homogeneous and heterogeneous media. 11,11’- dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane] (DSBr) was used as the surface-confined initiator and was synthesised in a three step procedure from mercaptoundecanol (MUD). All compounds were characterised by 1H NMR, FTIR-ATR and Raman spectroscopies. The grafting in homogeneous media resulted in amorphous PMMA with significant AuNP aggregation. Individually grafted AuNPs were difficult to separate and characterise, though SEM, TEM, EDAX and UV-vis spectroscopy was used. The heterogeneous polymerisation did not produce grafted AuNPs as characterised by SEM and EDAX. The encapsulation of AuNPs within PMMA latexes through the process of photoinitiated miniemulsion polymerisation was successfully achieved. Initially, photoinitiated miniemulsion polymerisation was conducted as a viable low temperature method of miniemulsion initiation. This proved successful producing a stable PMMA with good conversion efficiency and narrow particle size distribution (PSD). This is the first report of such a system. The photo-initiated technique was further optimised and AuNPs were included into the miniemulsion. AuNP encapsulation was very effective, producing reproducible AuNP encapsulated PMMA latexes. Again, this is the first reported case of this. The latexes were characterised by TEM, SEM, GPC, gravimetric analysis and dynamic light scattering (DLS).