Vertically aligning carbon nanotubes (VACNTs) onto 2D porous materials is advantageous for many conceivable
electronic applications but also for investigating the unique water transport properties of CNTs and the molecular
separation of molecules during fluid transport through their inner shell. Here we report a wet chemical technique to
produce vertically-aligned single walled CNT arrays on porous silicon (pSi). The nanotubes were first acid treated to
produce carboxylic acid functionalities on the single-walled CNT. The carboxy-functional nanotubes were then
covalently immobilised on a pSi surface that had been either ozone treated or silanated with aminopropyl triethoxysilane
(APTES). The VACNT surfaces were analysed with atomic force microscopy (AFM), confocal Raman spectral imaging
and Fourier transform infrared (FTIR) spectroscopy. Dense arrays of VACNTs were observed with the obtained CNT
orientation and surface coverage depending upon attachment method and attachment reaction time.
The preparation of bilayer lipid membranes (BLMs) on solid surfaces is important for many studies probing various
important biological phenomena including the cell barrier properties, ion-channels, biosensing, drug discovery and
protein/ligand interactions. In this work we present new membrane platforms based on suspended BLMs on nanoporous
anodic aluminium oxide (AAO) membranes. AAO membranes were prepared by electrochemical anodisation of
aluminium foil in 0.3 M oxalic acid using a custom-built etching cell and applying voltage of 40 V, at 1oC. AAO
membranes with controlled diameter of pores from 30 - 40 nm (top of membrane) and 60 -70 nm (bottom of membrane)
were fabricated. Pore dimensions have been confirmed by scanning electron microscopy (SEM) and atomic force
microscopy (AFM). AAO membranes were chemically functionalised with 3-aminopropyltriethoxysilane (APTES).
Confirmation of the APTES attachment to the AAO membrane was achieved by means of infrared spectroscopy, X-ray
photoelectron spectroscopy and contact angle measurements. The Fourier transform infrared (FTIR) spectra of
functionalised membranes show several peaks from 2800 to 3000 cm-1 which were assigned to symmetric and
antisymmetric CH2 bands. XPS data of the membrane showed a distinct increase in C1s (285 eV), N1s (402 eV) and
Si2p (102 eV) peaks after silanisation. The water contact angle of the functionalised membrane was 80o as compared to
20o for the untreated membrane. The formation of BLMs comprising dioleoyl-phosphatidylserine (DOPS) on APTESmodified
AAO membranes was carried using the vesicle spreading technique. AFM imaging and force spectroscopy was
used to characterise the structural and nanomechanical properties of the suspended membrane. This technique also
confirmed the stability of bilayers on the nanoporous alumina support for several days. Fabricated suspended BLMs on
nanoporous AAO hold promise for the construction of biomimetic membrane architectures with embedded
transmembrane proteins.
Atomic layer deposition (ALD) of SiO2 onto nanoporous alumina (PA) membranes was investigated with the aim of
adjusting the pore size and transport properties. PA membranes from commercial sources with a range of pore diameters
(20 nm, 100 nm and 200 nm) were used and modified by atomic layer deposition using tris(tert-butoxy)silanol and water
as the precursor couple. By adjusting the number of deposition cycles, the thickness of the conformal silica coating was
controlled, reducing the effective pore diameter, and subsequently changing the transport properties of the PA
membrane. Silica coated PA membranes with desired pore diameters from <5 nm to 100 nm were fabricated. In addition
to the pore size, the transport properties and selectivity of fabricated silica coated PA membranes were controlled by
chemical functionalisation using a silane with hydrophobic properties. Structural and chemical properties of modified
membranes were studied by dynamic secondary ion mass spectrometry (DSIMS) and scanning electron microscopy
(SEM). Spectrophotometric methods were used to evaluate the transport properties and selectivity of silica coated
membranes by permeation studies of hydrophobic and hydrophilic organic molecules. The resultant silica/PA
membranes with specific surface chemistry and controlled pore size are applicable for molecular separation, cell culture,
bioreactors, biosensing and drug delivery.
Here, we report on a novel method of incorporating carbon nanotubes into a polymer matrix by using
carbon nanotubes as a chain transfer agent (CTA) in Reversible Addition-Fragmentation chain Transfer
(RAFT) polymerisations. The dithioester RAFT agents were covalently linked to multi-walled carbon
nanotubes (MWCNTs) via a method, which involved the reaction of acyl halide MWCNTs with a
magnesium chloride dithiopropanoate salt. Polystyrene (PSt) was subsequently grafted from the
MWCNT surface via the core-first technique, which implies an outward growth of polymer chains
from the core, using the R-group approach. The structure and morphology of the hybrid nanomaterials
were investigated using FTIR, NMR, thrmogravimetric analysis (TGA) and atomic force microscopy
(AFM) techniques. The results showed that the MWCNT chain transfer agent could be successfully
used to mediate the growth of polystyrene polymer from the MWCNT surface via the living radical
polymerisation approach.
Silane encapsulated magnetic iron oxide nanoparticles were synthesized through a sequential approach. The
nanoparticles were synthesised via a coprecipitation method to form Fe3O4 particles with an average particle size of 8.3 ±
2.3nm. Iron oxide nanoparticles were then coated with 3-glycidoxypropyltrimethoxysilane (GPTMS) to form core-shell
type particles. Coating was performed using a base catalysed sol-gel process involving the direct condensation of
GPTMS onto the particle surface. Elemental composition and crystal structure of the uncoated nanoparticles were
determined by XRD. The coated particles were characterised with infra-red spectroscopy and energy dispersive x-ray
spectroscopy (EDX) to confirm the presence of silane on the particles. TEM analysis and Scherrer broadening analysis of
XRD were used to determine particle size and morphology of both coated and uncoated particles.
The explosive abilities of porous silicon (pSi) provide an alternative to existing carbon
based explosives, in addition to the possibilities of explosions on a nanoscale. Here,
an investigation into these explosive properties is conducted, by introducing an
oxidiser onto freshly etched pSi with varying pore sizes. Explosions are triggered via
the application of an electric spark. Light output and spectral data are collected to
characterize the exxplosion. The energy output is observed via Differential Scanning
Calorimetry (DSC), and surface images collected using SEM and AFM.
Carbon possesses a number of properties that make it ideal for use in sensor and electrical applications. Using radio frequency plasma with various precursor gases it is possible to prepare carbon surfaces for further molecular attachment or functionalisation. Research in our laboratory has involved studies of plasma fluorination, hydrogenation and methanation of highly ordered pyrolytic graphite (HOPG) (as it serves as a highly ordered, single crystal, model substrate for other more complex forms of carbon), glassy carbon in the form of pyrolysed photoresist films (PPF) and single-walled carbon nanotubes (SWCNTs). Treated surfaces have been characterised using a variety of investigatory surface techniques. In this article we report on results obtained using X-ray Photoelectron Spectroscopy (XPS) for probing the chemical nature of the surface and hence the extent of treatment; Time of Flight Secondary-Ion Mass Spectrometry (ToFSIMS) has been utilised to examine the molecular surface structure and in particular, determine the extent of surface hydrogenation; Scanning Tunnelling Microscopy (STM) measurements provide information on the morphology of treated surfaces, in particular the damage and change in surface structures caused by various plasma treatments. We show in this work that the morphology, mechanisms and extent of modification of the plasma-modified surface obtained is strongly influenced by various experimental conditions. For instance, etching and/or nucleation and growth features are observed, with the type of features and their distribution strongly dependent on the precursor gas that is used to support the plasma. Other important parameters are operating pressure, RF power and exposure time.
In this paper a new approach for directly organizing single-walled carbon nanotubes (SWCNTs) onto a silicon (100) surface by the surface condensation reaction with hydroxyl terminated silicon is presented. X-ray photoelectron spectra, Raman spectroscopy and atomic force microscopy show that the shortened SWCNTs have been organized successfully on silicon. The optical properties of SWCNT array exhibit strong fluorescence in the visible wavelength range from 650-800 nm. The fluorescence can be attributed to the coupling effects between attached SWCNTs and silicon substrate.
Nanosphere lithography, which allows for the fabrication of patterned metal surfaces, is a simple, effective and unconventional technique that exploits a self-assembly process. Using this technique, polystyrene nanospheres with diameters of 500nm, and 100nm were assembled onto a 'muscovite' mica substrate in a hexagonally close packed monolayer array, to provide a physical mask for material deposition. Thermal evaporation was subsequently used to deposit gold through the nanosphere mask layer, to generate a periodic array of gold nanostructures. Upon changing the mask to a multi-layered array of nanospheres, slightly more complex nanostructures were achieved. However due to thermal evaporation being a high temperature process the nanostructures obtained deviated from their predicted quasi triangular shape due to a slight annealing of the polystyrene mask.
A scanning tunneling microscopy (STM) study of [3 x 3] MnII supramolecular grids on Au(111) substrates is presented. Two-dimensional ordering via self-assembly is observed at various coverages. Submolecular resolution is attained with solvent deposition of low concentration samples upon freshly exposed substrates. A comparison of submolecular contrast in STM images is conducted and the importance of suitable image processing techniques is demonstrated in resolving the layer structure of obtained high coverage data.
This paper investigates the ability to modify the surface of silicon wafers for selective cell adhesion and the efficacy of solid phase transfections on the modified surface. Silicon surfaces are first modified by plasma polymerization of allylamine (ALAPP) and subsequent grafting of a protein-resistant layer of poly(ethylene oxide) (PEO) on the plasma polymer surface. Spatially controlled excimer ablation was then used to pattern the graft-copolymer surface for selective cell adhesion. X-ray photoelectron spectroscopy and contact angle measurements confirmed the creation of 2D patterns with different surface chemistry. Cell culture experiments with HEK 293 cells showed that cell attachment is limited to the ablated areas. Furthermore, cells could be transformed with plasmid DNA containing the gene for green fluorescent protein. Therefore, the biochip platform described in this paper, has the potential to be developed into a high-density array for analyzing gene products produced from a matrix of living cells.
This paper presents the use of scanning tunnelling microscopy (STM) and digital image processing for accurate atomic-scale imaging of molecules. The project has involved the development of image enhancement techniques and a calibration procedure for STMs. Graphite imaging has been successfully used as a reliable method for instrument calibration. This calibration is required due to the undesirable effects that are characteristic of STMs, which result in improper scaling and skewing of images. Image enhancement techniques have been created to reduce the noise effects due to thermal drift and tip hysteresis. These techniques were developed for graphite images, but have also been successfully applied to imaging of molecular adsorbates. Low tunnelling currents are used in STM experiments since any experiment uses a tunneling mechanism. This implies low signal-to-noise ratios, resulting in the need for reliable noise removal techniques. These techniques are a necessary step towards the extended use of STM in imaging molecular adsorbates.
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