Hydrogels for dermal applications

This thesis is concerned with the development of hydrogels that adhere to skin and can be used for topical or trans dermal release of active compounds for therapeutic or cosmetic use. The suitability of a range of monomers and initiator systems for the production of skin adhesive hydro gels by photopolymerisation was explored and an approximate order of monomer reactivity in aqueous solution was determined. Most notably, the increased reactivity of N-vinyl pyrrolidone within an aqueous system, as compared to its low rate of polymerisation in organic solvents, was observed. The efficacy of a series of photoinitiator systems for the preparation of sheet hydrogels was investigated. Supplementary redox and thermal initiators were also examined. The most successful initiator system was found to be Irgacure 184, which is commonly used in commercial moving web production systems that employ photopolymerisation. The influence of ionic and non-ionic monomers, crosslinking systems, water and glycerol on the adhesive and dynamic mechanical behaviour of partially hydrated hydrogel systems was examined. The aim was to manipulate hydrogel behaviour to modify topical and transdermal delivery capability and investigated the possibility of using monomer combinations that would influence the release characteristics of gels by modifying their hydrophobic and ionic nature. The copolymerisation of neutral monomers (N-vinyl pyrrolidone, N,N-dimethyl acrylamide and N-acryloyl morpholine) with ionic monomers (2-acrylamido-2-methylpropane sulphonic acid; sodium salt, and the potassium salt of 3-sulphopropyl acrylate) formed the basis of the study. Release from fully and partially hydrated hydrogels was studied, using model compounds and a non-steroidal anti-inflammatory drug, Ibuprofen. Release followed a common 3-stage kinetic profile that includes an initial burst phase, a secondary phase of approximate first order release and a final stage of infinitesimally slow release such that the compound is effectively retained within the hydrogel. Use of partition coefficients, the pKa of the active and a knowledge of charge-based and polar interactions of polymer and drug were complementary in interpreting experimental results. In summary, drug ionisation, hydrogel composition and external release medium characteristics interact to influence release behaviour. The information generated provides the basis for the optimal design of hydrogels for specific dermal release applications and some understanding of the limitations of these systems for controlled release applications.

Novel complex gratings with third-order group-delay variations for tunable pure dispersion slope compensation

We present a novel tunable dispersion compensator that can provide pure slope compensation. The approach uses two specially designed complex fiber Bragg gratings (FBGs) with reversely varied third-order group delay curves to generate the dispersion slope. The slope can be changed by adjusting the relative wavelength positions of the two FBGs. Several design examples of such complex gratings are presented and discussed. Experimentally, we achieve a dispersion slope tuning range of +/-650ps/nm2 with >0.9nm usable bandwidth.

The stability and formulation of topical analgesics

High-performance liquid chromatographic methods are developed for the simultaneous determination of various salicylates, their p-hydroxy isomers and nicotinic acid esters. The method is sensitive enough to detect trace amounts (~µM/L)of the product generated from cross reactivity between the drugs and the vehicle. The developed method also allows analysis of various topical products containing salicylate and nicotinate esters in their formulations. Applying this method, the degradation profiles of salicylates, nicotinates, p-hydroxy benzoate, o-methoxy benzoate and aspirin prodrugs in alkaline media are determined. The profile for alkyl salicylate degradation is found to be first order (A---? B) When the alcoholic radical is similar to that of the ester. In alcohol having a radical different from that of the ester function, the degradation is found to proceed through competitive transesterification and hydrolysis. The intermediates are identified following synthesis and isolation. The rate and extent of transesterification depends on the proportion of alcohol present in the system. Equations are presented to model the time profiles of reactant and product concentration. The reactions are base catalysed and the predominant pathway involves a concerted solvent attack upon the salicylate anion. Competitive hydrolysis of both ester components also follows this mechanism at moderate pH values but rates increase under strongly alkaline conditions as direct hydroxide attack becomes significant. In contrast, transesterification is independent of base concentration once full ionization is accomplished. The competitive hydrolysis is modelled using equations involving the dielectric constant of the medium. A range of other esters are also shown to undergo base-catalysed transesterification. In non-alcoholic solution phenyl salicylate undergoes a concentration-dependent oligomerisation which yields salsalate among the products. Competitive transesterification and hydrolysis also occur in products for topical use which have vehicles based upon alcohol, glycol or glycol polymers. Such reactions may compromise stability assessments, pharmaceutical integrity and delivery profiles.

Extended-range fiber polarimetric strain sensor

We describe a frequency-modulation technique that is applicable to two-beam interferometric systems illuminated by semiconductor diode lasers. The technique permits a determination of the optical path difference between the two arms of the interferometer and is used here to extend the range of a fiber polarimetric strain sensor by determining the order of the particular polarimetric fringe under consideration.

The fracture toughness of a range of cast steels

A range of plain carbon, carbon-manganese and low alloy cast steels were tested in order to determine their various fracture toughness values under elastic and elastic-plastic conditions. The main fracture toughness parameters which are considered are (1) Linear Elastic Fracture Mechanics (LEFM), (2) the J-Contour Integral, and (3) Crack Opening Displacement (COD). Results are obtained from fracture toughness specimens of various dimensions and the relevance of the validity criteria to cast steels is considered in some detail. In addition, the effect of casting position on specimen toughness values was noted. Valid KIC results according to LEFM, were obtained for three of the eight cast steels tested. Although KIC values from LEFM were not obtained from the remaining five steels, critical COD and J-integral values were determined. It is postulated that these values and particularly the critical J values can be used, with confidence for material selection or in defect tolerance calculations using these steels. Toughness values were found to vary with casting position in several of the steels tested and the possible reasons for such variations are discussed in the Thesis.

Performance analysis of DSRC priority mechanism for road safety applications in vehicular networks

Dedicated short range communications (DSRC) has been regarded as one of the most promising technologies to provide robust communications for large scale vehicle networks. It is designed to support both road safety and commercial applications. Road safety applications will require reliable and timely wireless communications. However, as the medium access control (MAC) layer of DSRC is based on the IEEE 802.11 distributed coordination function (DCF), it is well known that the random channel access based MAC cannot provide guaranteed quality of services (QoS). It is very important to understand the quantitative performance of DSRC, in order to make better decisions on its adoption, control, adaptation, and improvement. In this paper, we propose an analytic model to evaluate the DSRC-based inter-vehicle communication. We investigate the impacts of the channel access parameters associated with the different services including arbitration inter-frame space (AIFS) and contention window (CW). Based on the proposed model, we analyze the successful message delivery ratio and channel service delay for broadcast messages. The proposed analytical model can provide a convenient tool to evaluate the inter-vehicle safety applications and analyze the suitability of DSRC for road safety applications.

Impact of third-order fibre dispersion on the evolution of parabolic optical pulses

We develop a perturbation analysis that describes the effect of third-order dispersion on the similariton pulse solution of the nonlinear Schrodinger equation in a fibre gain medium. The theoretical model predicts with sufficient accuracy the pulse structural changes induced, which are observed through direct numerical simulations.

Parabolic optical pulses under the action of the third-order dispersion

Recent developments in nonlinear optics reveal an interesting class of pulses with a parabolic intensity profile in the energy-containing core and a linear frequency chirp that can propagate in a fiber with normal group-velocity dispersion. Parabolic pulses propagate in a stable selfsimilar manner, holding certain relations (scaling) between pulse power, width, and chirp parameter. In the additional presence of linear amplification, they enjoy the remarkable property of representing a common asymptotic state (or attractor) for arbitrary initial conditions. Analytically, self-similar (SS) parabolic pulses can be found as asymptotic, approximate solutions of the nonlinear Schr¨odinger equation (NLSE) with gain in the semi-classical (largeamplitude/small-dispersion) limit. By analogy with the well-known stable dynamics of solitary waves - solitons, these SS parabolic pulses have come to be known as similaritons. In practical fiber systems, inherent third-order dispersion (TOD) in the fiber always introduces a certain degree of asymmetry in the structure of the propagating pulse, eventually leading to pulse break-up. To date, there is no analytic theory of parabolic pulses under the action of TOD. Here, we develop aWKB perturbation analysis that describes the effect of weak TOD on the parabolic pulse solution of the NLSE in a fiber gain medium. The induced perturbation in phase and amplitude can be found to any order. The theoretical model predicts with sufficient accuracy the pulse structural changes induced by TOD, which are observed through direct numerical NLSE simulations.

The throughput order of multicast traffics with physical-layer network coding in random wireless ad hoc networks

This paper attempts to address the effectiveness of physical-layer network coding (PNC) on the throughput improvement for multi-hop multicast in random wireless ad hoc networks (WAHNs). We prove that the per session throughput order with PNC is tightly bounded as T((nvmR (n))-1) if m = O(R-2 (n)), where n is the total number of nodes, R(n) is the communication range, and m is the number of destinations for each multicast session. We also show that per-session throughput order with PNC is tight bounded as T(n-1), when m = O(R-2(n)). The results of this paper imply that PNC cannot improve the throughput order of multicast in random WAHNs, which is different from the intuition that PNC may improve the throughput order as it allows simultaneous signal access and combination.

Adaptive rate control of dedicated short range communications based vehicle networks for road safety applications

Dedicated Short Range Communication (DSRC) is a promising technique for vehicle ad-hoc network (VANET) and collaborative road safety applications. As road safety applications require strict quality of services (QoS) from the VANET, it is crucial for DSRC to provide timely and reliable communications to make safety applications successful. In this paper we propose two adaptive message rate control algorithms for low priority safety messages, in order to provide highly available channel for high priority emergency messages while improve channel utilization. In the algorithms each vehicle monitors channel loads and independently controls message rate by a modified additive increase and multiplicative decrease (AIMD) method. Simulation results demonstrated the effectiveness of the proposed rate control algorithms in adapting to dynamic traffic load.

Enhanced slotted aloha protocols for underwater sensor networks with large propagation delay

Recently underwater sensor networks (UWSN) attracted large research interests. Medium access control (MAC) is one of the major challenges faced by UWSN due to the large propagation delay and narrow channel bandwidth of acoustic communications used for UWSN. Widely used slotted aloha (S-Aloha) protocol suffers large performance loss in UWSNs, which can only achieve performance close to pure aloha (P-Aloha). In this paper we theoretically model the performances of S-Aloha and P-Aloha protocols and analyze the adverse impact of propagation delay. According to the observation on the performances of S-Aloha protocol we propose two enhanced S-Aloha protocols in order to minimize the adverse impact of propagation delay on S-Aloha protocol. The first enhancement is a synchronized arrival S-Aloha (SA-Aloha) protocol, in which frames are transmitted at carefully calculated time to align the frame arrival time with the start of time slots. Propagation delay is taken into consideration in the calculation of transmit time. As estimation error on propagation delay may exist and can affect network performance, an improved SA-Aloha (denoted by ISA-Aloha) is proposed, which adjusts the slot size according to the range of delay estimation errors. Simulation results show that both SA-Aloha and ISA-Aloha perform remarkably better than S-Aloha and P-Aloha for UWSN, and ISA-Aloha is more robust even when the propagation delay estimation error is large. © 2011 IEEE.

An alternating method for Cauchy problems for Helmholtz-type operators in non-homogeneous medium

Kozlov & Maz'ya (1989, Algebra Anal., 1, 144–170) proposed an alternating iterative method for solving Cauchy problems for general strongly elliptic and formally self-adjoint systems. However, in many applied problems, operators appear that do not satisfy these requirements, e.g. Helmholtz-type operators. Therefore, in this study, an alternating procedure for solving Cauchy problems for self-adjoint non-coercive elliptic operators of second order is presented. A convergence proof of this procedure is given.

Impact of third-order dispersion on the evolution of parabolic pulses

We present a perturbation analysis that describes the effect of third-order dispersion on the similariton pulse solution of the nonlinear Schrödinger equation in a fibre gain medium. The theoretical model predicts with sufficient accuracy the pulse structural changes induced, which are observed through direct numerical simulations.

Quasi-lossless transmission using second-order Raman amplification and fibre Bragg gratings

A novel distributed amplification scheme for quasi-lossless transmission is presented. The system is studied numerically and shown to be able to strongly reduce signal power variations in comparison with currently employed schemes of similar complexity. As an example, variations of less than 3.1 dB for 100 km distance between pumps and below 0.42 dB for 60 km are obtained when using standard single-mode fibre as the transmission medium with an input signal average power of 0 dBm, and a total pump power of about 1.7 W. © 2004 Optical Society of America.

Corporate cyberstalking:an invitation to build theory

Cyberstalking describes a relatively new form of stalking behaviour where technology is used as the medium of harassment. The term corporate cyberstalking is often used to describe incidents that involve organisations, such as companies and government departments. This paper uses a number of case studies in order to propose a typology of corporate cyberstalking. It is suggested that incidents involving corporate cyberstalking can be divided into two broad groups, depending on whether or not the organisation acts as a stalker or as a victim. Examining the motivations behind corporate cyberstalking allows these groups to be subdidvided further. The motives behind corporate cyberstalking can range from a desire for revenge against an employer to cyberterrorism. The paper also briefly discusses definitions of stalking and cyberstalking, concluding with a revised definition of cyberstalking that is more in keeping with the material discussed.