Hyperbranched polymer-gold nanoparticle assemblies : role of polymer architecture in hybrid assembly formation and SERS activity

Plasmonic gold nano-assemblies that self-assemble with the aid of linking molecules or polymers have the potential to yield controlled hierarchies of morphologies and consequently result in materials with tailored optical (e.g. localized surface plasmon resonances (LSPR)) and spectroscopic properties (e.g. surface enhanced Raman scattering (SERS)). Molecular linkers that are structurally well-defined are promising for forming hybrid nano-assemblies which are stable in aqueous solution and are increasingly finding application in nanomedicine. Despite much ongoing research in this field, the precise role of molecular linkers in governing the morphology and properties of the hybrid nano-assemblies remains unclear. Previously we have demonstrated that branched linkers, such as hyperbranched polymers, with specific anchoring end groups can be successfully employed to form assemblies of gold NPs demonstrating near-infrared SPRs and intense SERS scattering. We herein introduce a tailored polymer as a versatile molecular linker, capable of manipulating nano-assembly morphologies and hot-spot density. In addition, this report explores the role of the polymeric linker architecture, specifically the degree of branching of the tailored polymer in determining the formation, morphology and properties of the hybrid nano-assemblies. The degree of branching of the linker polymer, in addition to the concentration and number of anchoring groups, is observed to strongly influence the self-assembly process. The assembly morphology shifts primarily from 1D-like chains to 2D plates and finally to 3D-like globular structures, with increase in degree of branching. Insights have been gained into how the morphology influences the SERS performance of these nano-assemblies with respect to hot-spot density. These findings supplement the understanding of the morphology determining nano-assembly formation and pave the way for the possible application of these nano-assemblies as SERS bio-sensors for medical diagnostics.

Two-photon fluorescence spectroscopy for identification of healthy and malignant biological tissues

Two-photon fluorescence spectroscopy has been performed on rat skeletal muscles to investigate the effect of fixation processes on the micro-environments of the endogenous fluorophors in rat skeletal muscles. The two-photon fluorescence spectra measured for different fixation periods show a differential among those samples that were fixed in water, formalin and methanol, respectively. The results imply that two-photon fluorescence spectroscopy can be a potential technique for identification of healthy and malignant biological tissues.

Vibrational spectroscopy of the sulphate mineral sturmanite from Kuruman manganese deposits, South Africa

The mineral sturmanite is a hydrated calcium iron aluminium manganese sulphate tetrahydroxoborate hydroxide of formula Ca6(Fe, Al, Mn)2(SO4)2(B(OH)4)(OH)12•26H2O. We have studied the mineral sturmanite using a number of techniques, including SEM with EPMA and vibrational spectroscopy. Chemical analysis shows a homogeneous phase, composed by Ca, Fe, Mn, S, Al and Si. B is not determined in this EPMA technique. An intense Raman band at 990 cm−1 is assigned to the SO42− symmetric stretching mode. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1069 cm−1 which may be attributed to a carbonate symmetric stretching mode, indicating the presence of thaumasite. Infrared spectra display two bands at 1080 and 1107 cm−1 assigned to the SO42− antisymmetric stretching modes. The observation of multiple bands in this ν4 spectral region offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3622 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3479 cm−1 to water stretching bands. Infrared spectroscopy shows a set of broad overlapping bands in the OH stretching region. Vibrational spectroscopy enables an assessment of the molecular structure of sturmanite to be made.

A novel identification method for ultra trace detection of biomolecules using functionalised Surface Enhanced Raman Spectroscopy (SERS)

This thesis developed a new method for measuring extremely low amounts of organic and biological molecules, using Surface enhanced Raman Spectroscopy. This method has many potential applications, e.g. medical diagnosis, public health, food provenance, antidoping, forensics and homeland security. The method development used caffeine as the small molecule example, and erythropoietin (EPO) as the large molecule. This method is much more sensitive and specific than currently used methods; rapid, simple and cost effective. The method can be used to detect target molecules in beverages and biological fluids without the usual preparation steps.

A sparse hybrid map for vision-guided mobile robots

This paper introduces a minimalistic approach to produce a visual hybrid map of a mobile robot’s working environment. The proposed system uses omnidirectional images along with odometry information to build an initial dense posegraph map. Then a two level hybrid map is extracted from the dense graph. The hybrid map consists of global and local levels. The global level contains a sparse topological map extracted from the initial graph using a dual clustering approach. The local level contains a spherical view stored at each node of the global level. The spherical views provide both an appearance signature for the nodes, which the robot uses to localize itself in the environment, and heading information when the robot uses the map for visual navigation. In order to show the usefulness of the map, an experiment was conducted where the map was used for multiple visual navigation tasks inside an office workplace.

Ultra sensitive label free surface enhanced Raman spectroscopy method for the detection of biomolecules

We present a proof of concept for a novel nanosensor for the detection of ultra-trace amounts of bio-active molecules in complex matrices. The nanosensor is comprised of gold nanoparticles with an ultra-thin silica shell and antibody surface attachment, which allows for the immobilization and direct detection of bio-active molecules by surface enhanced Raman spectroscopy (SERS) without requiring a Raman label. The ultra-thin passive layer (~1.3 nm thickness) prevents competing molecules from binding non-selectively to the gold surface without compromising the signal enhancement. The antibodies attached on the surface of the nanoparticles selectively bind to the target molecule with high affinity. The interaction between the nanosensor and the target analyte result in conformational rearrangements of the antibody binding sites, leading to significant changes in the surface enhanced Raman spectra of the nanoparticles when compared to the spectra of the un-reacted nanoparticles. Nanosensors of this design targeting the bio-active compounds erythropoietin and caffeine were able to detect ultra-trace amounts the analyte to the lower quantification limits of 3.5×10−13 M and 1×10−9 M, respectively.

An hybrid approach for efficient multicast stream authentication over unsecured channels

We study the multicast stream authentication problem when an opponent can drop, reorder and inject data packets into the communication channel. In this context, bandwidth limitation and fast authentication are the core concerns. Therefore any authentication scheme is to reduce as much as possible the packet overhead and the time spent at the receiver to check the authenticity of collected elements. Recently, Tartary and Wang developed a provably secure protocol with small packet overhead and a reduced number of signature verifications to be performed at the receiver. In this paper, we propose an hybrid scheme based on Tartary and Wang’s approach and Merkle hash trees. Our construction will exhibit a smaller overhead and a much faster processing at the receiver making it even more suitable for multicast than the earlier approach. As Tartary and Wang’s protocol, our construction is provably secure and allows the total recovery of the data stream despite erasures and injections occurred during transmission.

Core-leaf onion-like carbon/MnO2 hybrid nano-urchins for rechargeable lithium-ion batteries

A hybrid nano-urchin structure consisting of spherical onion-like carbon and MnO2 nanosheets is synthesized by a facile and environmentally-friendly hydrothermal method. Lithium-ion batteries incorporating the hybrid nano-urchin anode exhibit reversible lithium storage with superior specific capacity, enhanced rate capability, stable cycling performance, and nearly 100% Coulombic efficiency. These results demonstrate the effectiveness of designing hybrid nano-architectures with uniform and isotropic structure, high loading of electrochemically-active materials, and good conductivity for the dramatic improvement of lithium storage.

Hybrid graphite film–carbon nanotube platform for enzyme immobilization and protection

A novel platform consisting of a multilayered substrate, activated graphite-like carbon film, and dense forest of long, vertically-aligned multiwall carbon nanotubes grown by the chemical vapor deposition is designed, fabricated, and tested for covalent immobilization of enzymatic biocatalysts with the aim of protecting them from shear forces and microbial attacks present in bioreactors. The covalent bonding ensures enzyme retention in a flow, while the dense nanotube forest may serve as a protection of the enzymes from microbial attack without impeding the flow of reactants and products. This platform was demonstrated for the two reference enzymes, horseradish peroxidase and catalase, which were immobilized without degrading their biological activity. This combination of an activated carbon layer for an efficient immobilization of biocatalysts with a protective layer of inert carbon nanotubes could dramatically improve the efficiency and longevity of enzymatic bio-catalysis employed in a large variety of advanced biotechnological processes.

Low-temperature plasma-assisted growth of optically transparent, highly oriented nanocrystalline AlN

Optically transparent, highly oriented nanocrystalline AlN(002) films have been synthesized using a hybrid plasma enhanced chemical vapor deposition and plasma-assisted radio frequency (rf) magnetron sputtering process in reactive Ar+ N2 and Ar+ N2 + H2 gas mixtures at a low Si(111)/glass substrate temperature of 350 °C. The process conditions, such as the sputtering pressure, rf power, substrate temperature, and N2 concentration were optimized to achieve the desired structural, compositional, and optical characteristics. X-ray diffractometry reveals the formation of highly c -oriented AlN films at a sputtering pressure of 0.8 Pa. Field emission scanning electron microscopy suggests the uniform distribution of AlN grains over large surface areas and also the existence of highly oriented in the (002) direction columnar structures of a typical length ∼100-500 nm with an aspect ratio of ∼7-15. X-ray photoelectron and energy dispersive x-ray spectroscopy suggest that films deposited at a rf power of 400 W feature a chemically pure and near stoichiometric AlN. The bonding states of the AlN films have been confirmed by Raman and Fourier transform infrared spectroscopy showing strong E2 (high) and E1 transverse optical phonon modes. Hydrogenated AlN films feature an excellent optical transmittance of ∼80% in the visible region of the spectrum, promising for advanced optical applications.

Multi-scale hybrid numerical simulation of the growth of high-aspect-ratio nanostructures

Recently, a variety high-aspect-ratio nanostructures have been grown and profiled for various applications ranging from field emission transistors to gene/drug delivery devices. However, fabricating and processing arrays of these structures and determining how changing certain physical parameters affects the final outcome is quite challenging. We have developed several modules that can be used to simulate the processes of various physical vapour deposition systems from precursor interaction in the gas phase to gas-surface interactions and surface processes. In this paper, multi-scale hybrid numerical simulations are used to study how low-temperature non-equilibrium plasmas can be employed in the processing of high-aspect-ratio structures such that the resulting nanostructures have properties suitable for their eventual device application. We show that whilst using plasma techniques is beneficial in many nanofabrication processes, it is especially useful in making dense arrays of high-aspect-ratio nanostructures.

Application of a hybrid Entropy–McKinsey Matrix method in evaluating sustainable urbanization : a China case study

Although urbanization can promote social and economic development, it can also cause various problems. As the key decision makers of urbanization, local governments should be able to evaluate urbanization performance, summarize experiences, and find problems caused by urbanization. This paper introduces a hybrid Entropy–McKinsey Matrix method for evaluating sustainable urbanization. The McKinsey Matrix is commonly referred to as the GE Matrix. The values of a development index (DI) and coordination index (CI) are calculated by employing the Entropy method and are used as a basis for constructing a GE Matrix. The matrix can assist in assessing sustainable urbanization performance by locating the urbanization state point. A case study of the city of Jinan in China demonstrates the process of using the evaluation method. The case study reveals that the method is an effective tool in helping policy makers understand the performance of urban sustainability and therefore formulate suitable strategies for guiding urbanization toward better sustainability.

A unique battery/supercapacitor direct integration scheme for hybrid electric vehicles

Battery/supercapacitor hybrid energy storage systems have been gaining popularity in electric vehicles due to their excellent power and energy performances. Conventional designs of such systems require interfacing dc-dc converters. These additional dc-dc converters increase power loss, complexity, weight and cost. Therefore, this paper proposes a new direct integration scheme for battery/supercapacitor hybrid energy storage systems using a double ended inverter system. This unique approach eliminates the need for interfacing converters and thus it is free from aforementioned drawbacks. Furthermore, the proposed system offers seven operating modes to improve the effective use of available energy in a typical drive cycle of a hybrid electric vehicle. Simulation results are presented to verify the efficacy of the proposed system and control techniques.

A direct integration scheme for battery-supercapacitor hybrid energy storage systems with the use of grid side inverter

Battery-supercapacitor hybrid energy storage systems are becoming popular in the renewable energy sector due to their improved power and energy performances. These hybrid systems require separate dc-dc converters, or at least one dc-dc converter for the supercapacitor bank, to connect them to the dc-link of the grid interfacing inverter. These additional dc-dc converters increase power losses, complexity and cost. Therefore, possibility of their direct connection is investigated in this paper. The inverter system used in this study is formed by cascading two 3-level inverters, named as the “main inverter” and the “auxiliary inverter”, through a coupling transformer. In the test system the main inverter is connected with the rectified output of a wind generator while the auxiliary inverter is directly attached to a battery and a supercapacitor bank. The major issues with this approach are the dynamic changes in dc-link voltages and inevitable imbalances in the auxiliary inverter voltages, which results in unevenly distributed space vectors. A modified SVM technique is proposed to solve this issue. A PWM based time sharing method is proposed for power sharing between the battery and the supercapacitor. Simulation results are presented to verify the efficacy of the proposed modulation and control techniques.

Hybrid polymer/metal nanoparticles with surface enhanced raman tracking for potential use in nanomedicine

This project was a preliminary step towards the development of novel methods for early stage cancer diagnosis and treatment. Diagnostic imaging agents with high Raman signal enhancement were developed based on tailored assemblies of gold nanoparticles, which demonstrated potential for non-invasive detection from deep under the skin surface. Specifically designed polymers were employed to assemble gold nanoparticles into controlled morphologies including dimers, nanochains, nanoplates, globular and core-satellite nanostructures. Our findings suggest that the Raman enhancement is strongly dependent on assembly morphology and can be tuned to adapt to the requirements of the diagnostic agent.