A comparison of different methods to determine diffusion length in dye-sensitized solar cells

A new steady state method for determination of the electron diffusion length in dye-sensitized solar cells (DSCs) is described and illustrated with data obtained using cells containing three different types of electrolyte. The method is based on using near-IR absorbance methods to establish pairs of illumination intensity for which the total number of trapped electrons is the same at open circuit (where all electrons are lost by interfacial electron transfer) as at short circuit (where the majority of electrons are collected at the contact). Electron diffusion length values obtained by this method are compared with values derived by intensity modulated methods and by impedance measurements under illumination. The results indicate that the values of electron diffusion length derived from the steady state measurements are consistently lower than the values obtained by the non steady-state methods. For all three electrolytes used in the study, the electron diffusion length was sufficiently high to guarantee electron collection efficiencies greater than 90%. Measurement of the trap distributions by near-IR absorption confirmed earlier observations of much higher electron trap densities for electrolytes containing Li+ ions. It is suggested that the electron trap distributions may not be intrinsic properties of the TiO2 nanoparticles, but may be associated with electron-ion interactions.

Mobile data technologies and SME adoption and diffusion : an empirical study on barriers and facilitators

The technological environment in which Australian SMEs operate can be best described as dynamic and vital. The rate of technological change provides the SME owner/manager a complex and challenging operational context. Wireless applications are being developed that provide mobile devices with Internet content and e-business services. In Australia the adoption of e-commerce by large organisations has been relatively high, however the same cannot be said for SMEs where adoption has been slower than other developed countries. In contrast however mobile telephone adoption and diffusion is relatively high by SMEs. This exploratory study identifies attitudes, perceptions and issues for mobile data technologies by regional SME owner/managers across a range of industry sectors. The major issues include the sector the firm belongs to, the current adoption status of the firm, the level of mistrust of the IT industry, the cost of the technologies and the applications and attributes of the technologies.

Confusion with diffusion? Unravelling is diffusion and innovation literature with a focus on SMEs

The aim of this paper is to contribute to the understanding of various models used in research for the adoption and diffusion of information technology in small and medium-sized enterprises (SMEs). Starting with Rogers' diffusion theory and behavioural models, technology adoption models used in IS research are discussed. Empirical research has shown that the reasons why firms choose to adopt or not adopt technology is dependent on a number of factors. These factors can be categorised as owner/manager characteristics, firm characteristics and other characteristics. The existing models explaining IS diffusion and adoption by SMEs overlap and complement each other. This paper reviews the existing literature and proposes a comprehensive model which includes the whole array of variables from earlier models.

Mobile data technologies and small business adoption and diffusion : an empirical study of barriers and facilitators

The technological environment in which contemporary small- and medium-sized enterprises (SMEs) operate can only be described as dynamic. The exponential rate of technological change, characterised by perceived increases in the benefits associated with various technologies, shortening product life cycles and changing standards, provides for the SME a complex and challenging operational context. The primary aim of this research was to identify the needs of SMEs in regional areas for mobile data technologies (MDT). In this study a distinction was drawn between those respondents who were full-adopters of technology, those who were partial-adopters, and those who were non-adopters and these three segments articulated different needs and requirements for MDT. Overall, the needs of regional SMEs for MDT can be conceptualised into three areas where the technology will assist business practices; communication, e-commerce and security

Who needs it? An exploratory investigation into the reaction of small and medium enterprises to mobile data technologies

The technological environment in which contemporary small and medium-sized enterprises (SMEs) operate can only be described as dynamic. The seemingly exponential nature of technological change, characterised by perceived increases in the benefits associated with various technologies, shortening product life cycles and changing standards, provides for the small and medium-sized enterprise a complex and challenging operational context. The development of infrastructures capable of supporting the Wireless Application Protocol (WAP)and associated 'wireless' applications represents the latest generation of technological innovation with potential appeal to SMEs and end-users alike. The primary aim of this research was to understand the mobile data technology needs of SMEs in a regional setting. The research was especially concerned with perceived needs across three market segments; non-adopters of new technology, partial-adopters of new technology and full-adopters of new technology. Working with an industry partner, focus groups were conducted with each of these segments with the discussions focused on the use of the latest WP products and services. Some of the results are presented in this paper.

Emotional and behavioural reaction to intrusive thoughts

A self-report measure of the emotional and behavioural reactions to intrusive thoughts was developed. The paper presents data that confirm the stability, reliability and validity of the new 7-item measure. Emotional and behavioural reactions to intrusions emerged as separate factors on the Emotional and Behavioural Reactions to Intrusions Questionnaire (EBRIQ), a finding confirmed by an independent stress study. Test retest reliability over 30-70 days was good. Expected relationships with other constructs were significant. Stronger negative responses to intrusions were associated with lower mindfulness scores and higher ratings of experiential avoidance, thought suppression and intensity and frequency of craving. The EBRIQ will help explore differences in reactions to intrusive thoughts in clinical and non clinical populations, and across different emotional and behavioural states. It will also be useful in assessing the effects of therapeutic approaches such as mindfulness.

Studies of the radiation chemistry and grafting of a fluoropolymer

The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

A hydrogen tethered inhibitor of matrix metalloproteinases

During wound repair, the balance between matrix metalloproteinases (MMPs) and their natural inhibitors (the TIMPs) is crucial for the normal extra cellular matrix turnover. However, the over expression of several MMPs including MMP-1, 2, 3, 8, 9 and MMP-10, combined with abnormally high levels of activation or low expression of TIMPs, may contribute to excessive degradation of connective tissue and formation of chronic ulcers. There are many groups exploring strategies for promoting wound healing involving delivery of growth factors, cells, ECM components and small molecules. Our approach for improving the balance of MMPs is not to add anything more to the wound, but instead to neutralise the over-expressed MMPs using inhibitors tethered to a bandage-like hydrogel. Our in vitro experiments using designed synthetic pseudo peptide inhibitors have been demonstrated to inhibit MMP activity in standard solutions. These inhibitors have also been tethered to polyethylene glycol hydrogels using a facile reaction between the linker unit on the inhibitor and the gel. After tethering the inhibition of MMPs diminishes to some extent and we postulate that this arises due to poor diffusion of the MMPs into the gels. When the tethered inhibitors were tested against chronic wound fluid obtained against patients we observed over 40% inhibition in proteolytic activity suggesting our approach may prove useful in rebalancing MMPs within chronic wounds.

A peptidomimetic inhibitor of matrix metalloproteinases containing a tetherable linker group

Successful wound repair and normal turnover of the extracellular matrix relies on a balance between matrix metalloproteinases (MMPs) and their natural inhibitors (the TIMPs). When over-expression of MMPs and abnormally high levels of activation or low expression of TIMPs are encountered, excessive degradation of connective tissue and the formation of chronic ulcers can occur. One strategy to rebalance MMPs and TIMPs is to use inhibitors. We have designed a synthetic pseudopeptide inhibitor with an amine linker group based on a known high-affinity peptidomimetic MMP inhibitor have demonstrated inhibition of MMP-1, -2, -3 and -9 activity in standard solutions. The inhibitor was also tethered to a polyethylene glycol hydrogel using a facile reaction between the linker unit on the inhibitor and the hydrogel precursors. After tethering, we observed inhibition of the MMPs although there was an increase in the IC50s which was attributed to poor diffusion of the MMPs into the hydrogels, reduced activity of the tethered inhibitor or incomplete incorporation of the inhibitor into the hydrogels. When the tethered inhibitors were tested against chronic wound fluid we observed significant inhibition in proteolytic activity suggesting our approach may prove useful in rebalancing MMPs within chronic wounds.

Nonlinear control of the Reaction Wheel Pendulum

In this paper we introduce the Reaction Wheel Pendulum, a novel mechanical system consisting of a physical pendulum with a rotating bob. This system has several attractive features both from a pedagogical standpoint and from a research standpoint. From a pedagogical standpoint, the dynamics are the simplest among the various pendulum experiments available so that the system can be introduced to students earlier in their education. At the same time, the system is nonlinear and underactuated so that it can be used as a benchmark experiment to study recent advanced methodologies in nonlinear control, such as feedback linearization, passivity methods, backstepping and hybrid control. In this paper we discuss two control approaches for the problems of swingup and balance, namely, feedback linearization and passivity based control. We first show that the system is locally feedback linearizable by a local diffeomorphism in state space and nonlinear feedback. We compare the feedback linearization control with a linear pole-placement control for the problem of balancing the pendulum about the inverted position. For the swingup problem we discuss an energy approach based on collocated partial feedback linearization, and passivity of the resulting zero dynamics. A hybrid/switching control strategy is used to switch between the swingup and the balance control. Experimental results are presented.

Analysis of linear relationships in block ciphers

This thesis is devoted to the study of linear relationships in symmetric block ciphers. A block cipher is designed so that the ciphertext is produced as a nonlinear function of the plaintext and secret master key. However, linear relationships within the cipher can still exist if the texts and components of the cipher are manipulated in a number of ways, as shown in this thesis. There are four main contributions of this thesis. The first contribution is the extension of the applicability of integral attacks from word-based to bitbased block ciphers. Integral attacks exploit the linear relationship between texts at intermediate stages of encryption. This relationship can be used to recover subkey bits in a key recovery attack. In principle, integral attacks can be applied to bit-based block ciphers. However, specific tools to define the attack on these ciphers are not available. This problem is addressed in this thesis by introducing a refined set of notations to describe the attack. The bit patternbased integral attack is successfully demonstrated on reduced-round variants of the block ciphers Noekeon, Present and Serpent. The second contribution is the discovery of a very small system of equations that describe the LEX-AES stream cipher. LEX-AES is based heavily on the 128-bit-key (16-byte) Advanced Encryption Standard (AES) block cipher. In one instance, the system contains 21 equations and 17 unknown bytes. This is very close to the upper limit for an exhaustive key search, which is 16 bytes. One only needs to acquire 36 bytes of keystream to generate the equations. Therefore, the security of this cipher depends on the difficulty of solving this small system of equations. The third contribution is the proposal of an alternative method to measure diffusion in the linear transformation of Substitution-Permutation-Network (SPN) block ciphers. Currently, the branch number is widely used for this purpose. It is useful for estimating the possible success of differential and linear attacks on a particular SPN cipher. However, the measure does not give information on the number of input bits that are left unchanged by the transformation when producing the output bits. The new measure introduced in this thesis is intended to complement the current branch number technique. The measure is based on fixed points and simple linear relationships between the input and output words of the linear transformation. The measure represents the average fraction of input words to a linear diffusion transformation that are not effectively changed by the transformation. This measure is applied to the block ciphers AES, ARIA, Serpent and Present. It is shown that except for Serpent, the linear transformations used in the block ciphers examined do not behave as expected for a random linear transformation. The fourth contribution is the identification of linear paths in the nonlinear round function of the SMS4 block cipher. The SMS4 block cipher is used as a standard in the Chinese Wireless LAN Wired Authentication and Privacy Infrastructure (WAPI) and hence, the round function should exhibit a high level of nonlinearity. However, the findings in this thesis on the existence of linear relationships show that this is not the case. It is shown that in some exceptional cases, the first four rounds of SMS4 are effectively linear. In these cases, the effective number of rounds for SMS4 is reduced by four, from 32 to 28. The findings raise questions about the security provided by SMS4, and might provide clues on the existence of a flaw in the design of the cipher.

Novel analytical and numerical methods for solving fractional dynamical systems

During the past three decades, the subject of fractional calculus (that is, calculus of integrals and derivatives of arbitrary order) has gained considerable popularity and importance, mainly due to its demonstrated applications in numerous diverse and widespread fields in science and engineering. For example, fractional calculus has been successfully applied to problems in system biology, physics, chemistry and biochemistry, hydrology, medicine, and finance. In many cases these new fractional-order models are more adequate than the previously used integer-order models, because fractional derivatives and integrals enable the description of the memory and hereditary properties inherent in various materials and processes that are governed by anomalous diffusion. Hence, there is a growing need to find the solution behaviour of these fractional differential equations. However, the analytic solutions of most fractional differential equations generally cannot be obtained. As a consequence, approximate and numerical techniques are playing an important role in identifying the solution behaviour of such fractional equations and exploring their applications. The main objective of this thesis is to develop new effective numerical methods and supporting analysis, based on the finite difference and finite element methods, for solving time, space and time-space fractional dynamical systems involving fractional derivatives in one and two spatial dimensions. A series of five published papers and one manuscript in preparation will be presented on the solution of the space fractional diffusion equation, space fractional advectiondispersion equation, time and space fractional diffusion equation, time and space fractional Fokker-Planck equation with a linear or non-linear source term, and fractional cable equation involving two time fractional derivatives, respectively. One important contribution of this thesis is the demonstration of how to choose different approximation techniques for different fractional derivatives. Special attention has been paid to the Riesz space fractional derivative, due to its important application in the field of groundwater flow, system biology and finance. We present three numerical methods to approximate the Riesz space fractional derivative, namely the L1/ L2-approximation method, the standard/shifted Gr¨unwald method, and the matrix transform method (MTM). The first two methods are based on the finite difference method, while the MTM allows discretisation in space using either the finite difference or finite element methods. Furthermore, we prove the equivalence of the Riesz fractional derivative and the fractional Laplacian operator under homogeneous Dirichlet boundary conditions – a result that had not previously been established. This result justifies the aforementioned use of the MTM to approximate the Riesz fractional derivative. After spatial discretisation, the time-space fractional partial differential equation is transformed into a system of fractional-in-time differential equations. We then investigate numerical methods to handle time fractional derivatives, be they Caputo type or Riemann-Liouville type. This leads to new methods utilising either finite difference strategies or the Laplace transform method for advancing the solution in time. The stability and convergence of our proposed numerical methods are also investigated. Numerical experiments are carried out in support of our theoretical analysis. We also emphasise that the numerical methods we develop are applicable for many other types of fractional partial differential equations.