Nonlinear inverse synthesis technique for optical links with lumped amplification

The nonlinear inverse synthesis (NIS) method, in which information is encoded directly onto the continuous part of the nonlinear signal spectrum, has been proposed recently as a promising digital signal processing technique for combating fiber nonlinearity impairments. However, because the NIS method is based on the integrability property of the lossless nonlinear Schrödinger equation, the original approach can only be applied directly to optical links with ideal distributed Raman amplification. In this paper, we propose and assess a modified scheme of the NIS method, which can be used effectively in standard optical links with lumped amplifiers, such as, erbium-doped fiber amplifiers (EDFAs). The proposed scheme takes into account the average effect of the fiber loss to obtain an integrable model (lossless path-averaged model) to which the NIS technique is applicable. We found that the error between lossless pathaveraged and lossy models increases linearly with transmission distance and input power (measured in dB). We numerically demonstrate the feasibility of the proposed NIS scheme in a burst mode with orthogonal frequency division multiplexing (OFDM) transmission scheme with advanced modulation formats (e.g., QPSK, 16QAM, and 64QAM), showing a performance improvement up to 3.5 dB; these results are comparable to those achievable with multi-step per span digital backpropagation.

Run-time connector synthesis for autonomic systems of systems

A key objective of autonomic computing is to reduce the cost and expertise required for the management of complex IT systems. As a growing number of these systems are implemented as hierarchies or federations of lower-level systems, techniques that support the development of autonomic systems of systems are required. This article introduces one such technique, which involves the run-time synthesis of autonomic system connectors. These connectors are specified by means of a new type of autonomic computing policy termed a resource definition policy, and enable the dynamic realisation of collections of collaborating autonomic systems, as envisaged by the original vision of autonomic computing. We propose a framework for the formal specification of autonomic computing policies, and use it to define the new policy type and to describe its application to the development of autonomic system of systems. To validate the approach, we present a sample data-centre application that was built using connectors synthesised from resource-definition policies.

Hypercoiling and hydrophobically associating polymers : interfacial synthesis, surface properties and pharmaceutical applications

The objective of the work described was to identify and synthesize a range of biodegradable hypercoiling or hydrophobically associating polymers to mimic natural apoproteins, such as those found in lung surfactant or plasma apolipoproteins. Stirred interfacial polymerization was used to synthesize potentially biodegradable aromatic polyamides (Mw of 12,000-26,000) based on L-Iysine, L-Iysine ethyl ester, L-ornithine and DL-diaminopropionic acid, by reaction with isophthaloyl chloride. A similar technique was used to synthesize aliphatic polyamides based on L-Iysine ethyl ester and either adipoyl chloride or glutaryl chloride resulting in the synthesis of poly(lysine ethyl ester adipamide) [PLETESA] or poly(lysine ethyl ester glutaramide) (Mw of 126,000 and 26,000, respectively). PLETESA was found to be soluble in both polar and non-polar solvents and the hydrophobic/hydrophilic balance could be modified by partial saponification (66-75%) of the ethyl ester side chains. Surface or interfacial tension/pH profiles were used to assess the conformation of both the poly(isophthalamides) and partially saponified PLETESA in aqueous solution. The results demonstrated that a loss of charge from the polymer was accompanied by an initial fall in surface activity, followed by a rise in activity, and ultimately, by polymer precipitation. These observations were explained by a collapse of the polymer chains into non-surface active intramolecular coils, followed by a transition to an amphipathic conformation, and finally to a collapsed hydrophobe. 2-Dimensional NMR analysis of polymer conformation in polar and non-polar solvents revealed intramolecular associations between the hydrophobic groups within partially saponified PLETESA. Unsaponified PLETESA appeared to form a coiled structure in polar solvents where the ethyl ester side chains were contained within the polymer coil. The implications of the secondary structure of PLETESA and potential biomedical applications are discussed.

Functional polymers for biomedical application : synthesis and applications

Aromatic and aliphatic diacid chlorides were used to condense naturally occurring diamino acids and their esterified derivatives. It was anticipated the resulting functional polyamides would biodegrade to physiologically acceptable compounds and show pH dependant solubility could be used for biomedical applications ranging from enteric coatings to hydrosoluble drug delivery vehicles capable of targeting areas of low physiological pH. With these applications in mind the polymers were characterised by infra red spectroscopy, gel permeation chromatography and in the case of aqueous soluble polymers by potentiometric titration. Thin films of poly (lysine ethyl ester isophthalamide) plasticised with poly (caprolactone) were cast from DMSO/chloroform solutions and their mechanical properties measured on a Hounsfield Hti tensiometer. Interfacial synthesis was investigated as a synthetic route for the production of linear functional polyamides. High molecular weight polymer was obtained only when esterified diamino acids were condensed with aromatic diacid chlorides. The method was unsuitable for the production of copolymers of free and esterified amino acids with a diacid chloride. A novel miscible mixed solvent single phase reaction was investigated for production of copolymers of esterified and non-esterified amino acids with diacid chlorides. Aliphatic diacid chlorides were unsuitable for condensing diamino acids using this technique because of high rates of hydrolysis. The technique gave high molecular weight homopolymers from esterified diamino acids and aromatic diacid chlorides.

Synthesis and characterisation of hydrogel polymers for medical applications

A fundamental if poorly understood problem that hydrogels display is the tendency of these contact lens materials to dehydrate, causing certain complications of the corneal epithelium. However, recent studies have indicated that the evaporation rate of water from different hydrogel lenses is the same and the severity of conditions such as corneal staining is controlled by the states of water in the material. A study was therefore undertaken which concluded that increased corneal desiccating staining occurred as the proportion of water existing in the bound state decreased. The possibility of using dehydrated hydrogels as packaging materials with desiccating properties has also been investigated. As hydrogels have a high affinity for water they have adequate ability to function as a moisture scavenger in an enclosed atmosphere. It was concluded that this ability is maximised by a high total water content and an increase in the proportion of this water existing in the bound state for the material when it is fully hydrated. N-vinyl pyrrolidone has a low reactivity in vinyl polymerisation reactions which results in polymers with local domains of the same chemical type which can lead to deposition. As contact lenses comprising of this monomer are susceptible to deposition, a monomer with a higher reactivity in vinyl polymerisations is acryloylmorpholine and its incorporation in favour of NVP is encouraged. Unfortunately a large proportion of high EWC hydrogels are mechanically weak and attempts to increase this property by increasing hydrophobicity or cross-linking results in a decrease in EWC. Monomers with the potential to carry a positive charge were incorporated into a high EWC, AMO-HEMA copolymer and the physical properties were investigated. Although EWC increased, mechanical properties decreased only slightly. Therefore simultaneous incorporation of a positively charged monomer and a negatively charged monomer was investigated. The resulting copolymers showed increased water content and increased initial modulus. A technique for measuring the coefficient of friction of contact lenses during lubrication has been developed.

Chemical synthesis of isotopically labelled (M+4) purine nucleosides and their incorporation into DNA oligomers

Development of accurate and sensitive analytical methods to measure the level of biomarkers, such as 8-oxo-guanine or its corresponding nucleoside, 8-oxo-2’-deoxyguanosine, has become imperative in the study of DNA oxidative damage in vivo. Of the most promising techniques, HPLC-MS/MS, has many attractive advantages. Like any method that employs the MS technique, its accuracy depends on the use of multiply, isotopically-labelled internal standards. This project is aimed at making available such internal standards. The first task was to synthesise the multiply, isotopically-labelled bases (M+4) guanine and (M+4) 8-oxo-guanine. Synthetic routes for both (M+4) guanine and (M+4) 8-oxo-guanine were designed and validated using the unlabelled compounds. The reaction conditions were also optimized during the “dry runs”. The amination of the 4-hydroxy-2,6-dichloropyrimidine, appeared to be very sensitive to the purity of the commercial [15]N benzylamine reagent. Having failed, after several attempts, to obtain the pure reagent from commercial suppliers, [15]N benzylamine was successfully synthesised in our laboratory and used in the first synthesis of (M+4) guanine. Although (M+4) bases can be, and indeed have been used as internal standards in the quantitative analysis of oxidative damage, they can not account for the errors that may occur during the early sample preparation stages. Therefore, internal standards in the form of nucleosides and DNA oligomers are more desirable. After evaluating a number of methods, an enzymatic transglycolization technique was adopted for the transfer of the labelled bases to give their corresponding nucleosides. Both (M+4) 2-deoxyguanosine and (M+4) 8-oxo-2’-deoxyguanosine can be purified on micro scale by HPLC. The challenge came from the purification of larger scale (>50 mg) synthesis of nucleosides. A gel filtration method was successfully developed, which resulted in excellent separation of (M+4) 2’-deoxyguanosine from the incubation mixture. The (M+4) 2’-deoxyguanosine was then fully protected in three steps and successfully incorporated, by solid supported synthesis, into a DNA oligomer containing 18 residues. Thus, synthesis of 8-oxo-deoxyguanosine on a bigger scale for its future incorporation into DNA oligomers is now a possibility resulting from this thesis work. We believe that these internal standards can be used to develop procedures that can make the measurement of oxidative DNA damage more accurate and sensitive.

A modular holistic approach to prosody modelling for Standard Yorùbá speech synthesis

This paper presents a novel prosody model in the context of computer text-to-speech synthesis applications for tone languages. We have demonstrated its applicability using the Standard Yorùbá (SY) language. Our approach is motivated by the theory that abstract and realised forms of various prosody dimensions should be modelled within a modular and unified framework [Coleman, J.S., 1994. Polysyllabic words in the YorkTalk synthesis system. In: Keating, P.A. (Ed.), Phonological Structure and Forms: Papers in Laboratory Phonology III, Cambridge University Press, Cambridge, pp. 293–324]. We have implemented this framework using the Relational Tree (R-Tree) technique. R-Tree is a sophisticated data structure for representing a multi-dimensional waveform in the form of a tree. The underlying assumption of this research is that it is possible to develop a practical prosody model by using appropriate computational tools and techniques which combine acoustic data with an encoding of the phonological and phonetic knowledge provided by experts. To implement the intonation dimension, fuzzy logic based rules were developed using speech data from native speakers of Yorùbá. The Fuzzy Decision Tree (FDT) and the Classification and Regression Tree (CART) techniques were tested in modelling the duration dimension. For practical reasons, we have selected the FDT for implementing the duration dimension of our prosody model. To establish the effectiveness of our prosody model, we have also developed a Stem-ML prosody model for SY. We have performed both quantitative and qualitative evaluations on our implemented prosody models. The results suggest that, although the R-Tree model does not predict the numerical speech prosody data as accurately as the Stem-ML model, it produces synthetic speech prosody with better intelligibility and naturalness. The R-Tree model is particularly suitable for speech prosody modelling for languages with limited language resources and expertise, e.g. African languages. Furthermore, the R-Tree model is easy to implement, interpret and analyse.

Synthesis, characterisation and applications of diamond materials

This thesis presented a detailed research work on diamond materials. Chapter 1 is an overall introduction of the thesis. In the Chapter 2, the literature review on the physical, chemical, optical, mechanical, as well as other properties of diamond materials are summarised. Followed by this chapter, several advanced diamond growth and characterisation techniques used in experimental work are also introduced. Then, the successful installation and applications of chemical vapour deposition system was demonstrated in Chapter 4. Diamond growth on a variety of different substrates has been investigated such as on silicon, diamond-like carbon or silica fibres. In Chapter 5, the single crystalline diamond substrate was used as the substrate to perform femtosecond laser inscription. The results proved the potentially feasibility of this technique, which could be utilised in fabricating future biochemistry microfluidic channels on diamond substrates. In Chapter 6, the hydrogen-terminated nanodiamond powder was studied using impedance spectroscopy. Its intrinsic electrical properties and its thermal stability were presented and analysed in details. As the first PhD student within Nanoscience Research Group at Aston, my initial research work was focused on the installation and testing of the microwave plasma enhanced chemical vapour deposition system (MPECVD), which will be beneficial to all the future researchers in the group. The fundamental of the on MPECVD system will be introduced in details. After optimisation of the growth parameters, the uniform diamond deposition has been achieved with a good surface coverage and uniformity. Furthermore, one of the most significant contributions of this work is the successful pattern inscription on diamond substrates by femtosecond laser system. Previous research of femtosecond laser inscription on diamond was simple lines or dots, with little characterisation techniques were used. In my research work, the femtosecond laser has been successfully used to inscribe patterns on diamond substrate and fully characterisation techniques, e.g. by SEM, Raman, XPS, as well as AFM, have been carried out. After the femtosecond laser inscription, the depth of microfluidic channels on diamond film has been found to be 300~400 nm, with a graphitic layer thickness of 165~190 nm. Another important outcome of this work is the first time to characterise the electrical properties of hydrogenterminated nanodiamond with impedance spectroscopy. Based on the experimental evaluation and mathematic fitting, the resistance of hydrogen-terminated nanodiamond reduced to 0.25 MO, which were four orders of magnitude lower than untreated nanodiamond. Meanwhile, a theoretical equivalent circuit has been proposed to fit the results. Furthermore, the hydrogenterminated nanodiamond samples were annealed at different temperature to study its thermal stability. The XPS and FTIR results indicate that hydrogen-terminated nanodiamond will start to oxidize over 100ºC and the C-H bonds can survive up to 400ºC. This research work reports the fundamental electrical properties of hydrogen-terminated nanodiamond, which can be used in future applications in physical or chemical area.

Synthesis of hydrazine by the fixation process

A critical review of the literature concerning organic derivatives of hydrazine, the ammonia-chlorine reaction and the electrolytic formation of hydrazine has been carried out. Apparatus was constructed to study the electrolysis of liquid ammonia, the formation of chloramine and the fixation of chloramine with a ketone to form an isohydrazone. In the latter case the reaction was carried out in a 3" diameter stirred tank and also in a 1" diameter, 2' high column reactor where the liquid phase was continuously recirculated. Two methods of analysis of azines and isohydrazones in a ketone solution have been developed. One is a colorimetric technique using p-dimethylaminobenzaldehyde and the other involves the hydrolysis of the organic derivative to hydrazine sulphate. Hydrazine was detected in low concentration in some of the electrolytic experiments carried out but it was concluded that this method did not show sufficient promise to warrant further investigation. The gas phase formation of chloramine and acetone isohydrazone has also been studied but in this system difficulties were encountered with the chlorine jet blocking with ammonium chloride. The formation of isohydrazones in a stirred tank reactor has been investigated in some detail and the effect of several parameters was determined. The yield was found to be extremely sensitive to chlorine concentration and in order to obtain yields of more than 90 per cent, the molar concentration of chlorine in the gas phase had to be of the order of 5 per cent. An optimum temperature in the region of 0°C was also detected. These results disagree with those quoted in previous studies but extensive experimental work has confirmed the information presented in this thesis. It has also been shown that at high yields the chloramine formation reaction took place in the gas phase.

A fuzzy decision tree-based duration model for Standard Yorùbá text-to-speech synthesis

In this paper, we present syllable-based duration modelling in the context of a prosody model for Standard Yorùbá (SY) text-to-speech (TTS) synthesis applications. Our prosody model is conceptualised around a modular holistic framework. This framework is implemented using the Relational Tree (R-Tree) techniques. An important feature of our R-Tree framework is its flexibility in that it facilitates the independent implementation of the different dimensions of prosody, i.e. duration, intonation, and intensity, using different techniques and their subsequent integration. We applied the Fuzzy Decision Tree (FDT) technique to model the duration dimension. In order to evaluate the effectiveness of FDT in duration modelling, we have also developed a Classification And Regression Tree (CART) based duration model using the same speech data. Each of these models was integrated into our R-Tree based prosody model. We performed both quantitative (i.e. Root Mean Square Error (RMSE) and Correlation (Corr)) and qualitative (i.e. intelligibility and naturalness) evaluations on the two duration models. The results show that CART models the training data more accurately than FDT. The FDT model, however, shows a better ability to extrapolate from the training data since it achieved a better accuracy for the test data set. Our qualitative evaluation results show that our FDT model produces synthesised speech that is perceived to be more natural than our CART model. In addition, we also observed that the expressiveness of FDT is much better than that of CART. That is because the representation in FDT is not restricted to a set of piece-wise or discrete constant approximation. We, therefore, conclude that the FDT approach is a practical approach for duration modelling in SY TTS applications. © 2006 Elsevier Ltd. All rights reserved.

Intonation contour realisation for Standard Yorùbá text-to-speech synthesis:a fuzzy computational approach

This paper presents a novel intonation modelling approach and demonstrates its applicability using the Standard Yorùbá language. Our approach is motivated by the theory that abstract and realised forms of intonation and other dimensions of prosody should be modelled within a modular and unified framework. In our model, this framework is implemented using the Relational Tree (R-Tree) technique. The R-Tree is a sophisticated data structure for representing a multi-dimensional waveform in the form of a tree. Our R-Tree for an utterance is generated in two steps. First, the abstract structure of the waveform, called the Skeletal Tree (S-Tree), is generated using tone phonological rules for the target language. Second, the numerical values of the perceptually significant peaks and valleys on the S-Tree are computed using a fuzzy logic based model. The resulting points are then joined by applying interpolation techniques. The actual intonation contour is synthesised by Pitch Synchronous Overlap Technique (PSOLA) using the Praat software. We performed both quantitative and qualitative evaluations of our model. The preliminary results suggest that, although the model does not predict the numerical speech data as accurately as contemporary data-driven approaches, it produces synthetic speech with comparable intelligibility and naturalness. Furthermore, our model is easy to implement, interpret and adapt to other tone languages.

Controlled synthesis and processing of a poly(L-lactide-co-ε-caprolactone) copolymer for biomedical use as an absorbable monofilament surgical suture

Poly(L-lactide-co-ε-caprolactone) 75:25% mol, P(LL-co-CL), was synthesized via bulk ring-opening polymerisation (ROP) using a novel tin(II)alkoxide initiator, [Sn(Oct)]2DEG, at 130oC for 48 hrs. The effectiveness of this initiator was compared withthe well-known conventional tin(II) octoateinitiator, Sn(Oct)2. The P(LL-co-CL) copolymersobtained were characterized using a combination of analytical technique including: nuclear magnetic resonance spectroscopy (NMR), differential scanning calorimetry (DSC), thermogravimetry (TG) and gel permeation chromatography (GPC). The P(LL-co-CL) was melt-spun into monofilament fibres of uniform diameter and smooth surface appearance. Modification of the matrix morphology was then built into the as-spun fibresvia a series of controlled off-line annealing and hot-drawing steps. © (2014) Trans Tech Publications, Switzerland.

Synthesis, self-assembly and (absence of) protein interactions of poly(glycerol methacrylate)-silicone macro-amphiphiles

The present study focuses on the synthesis of amphiphilic block copolymers containing poly(glycerol monomethacrylate) (PGMMA), showing the advantages of a protection/deprotection strategy based on silyl groups. PGMMA blocks were synthesized via ATRP started by a double functional poly(dimethyl siloxane) (PDMS) macroinitiator of molecular weight ≈7000 g mol-1. The resulting triblock copolymers were characterized by low polydispersity (generally ≤1.1) and their aggregation concentration in water was essentially dominated by the PDMS block length (critical aggregation concentration substantially invariant for GMMA degree of polymerization ≥30). For GMMA blocks with DP > 50, the self-assembly in water produced 35-50 nm spherical micelles, while shorter hydrophilic chains produced larger aggregates apparently displaying worm-like morphologies. Block copolymers with long GMMA chains (DP ≈ 200) produced particularly stable micellar aggregates, which were then selected for a preliminary assessment of the possibility of adsorption of plasma proteins (albumin and fibrinogen); using diffusion NMR as an analytical technique, no significant adsorption was recorded both on micelles and on soluble PGMMA employed as a control, indicating the possibility of a "stealth" behaviour. This journal is © 2013 The Royal Society of Chemistry.

Nonlinear inverse synthesis for high spectral efficiency transmission in optical fibers

In linear communication channels, spectral components (modes) defined by the Fourier transform of the signal propagate without interactions with each other. In certain nonlinear channels, such as the one modelled by the classical nonlinear Schrödinger equation, there are nonlinear modes (nonlinear signal spectrum) that also propagate without interacting with each other and without corresponding nonlinear cross talk, effectively, in a linear manner. Here, we describe in a constructive way how to introduce such nonlinear modes for a given input signal. We investigate the performance of the nonlinear inverse synthesis (NIS) method, in which the information is encoded directly onto the continuous part of the nonlinear signal spectrum. This transmission technique, combined with the appropriate distributed Raman amplification, can provide an effective eigenvalue division multiplexing with high spectral efficiency, thanks to highly suppressed channel cross talk. The proposed NIS approach can be integrated with any modulation formats. Here, we demonstrate numerically the feasibility of merging the NIS technique in a burst mode with high spectral efficiency methods, such as orthogonal frequency division multiplexing and Nyquist pulse shaping with advanced modulation formats (e.g., QPSK, 16QAM, and 64QAM), showing a performance improvement up to 4.5 dB, which is comparable to results achievable with multi-step per span digital back propagation.

Modified nonlinear inverse synthesis for optical links with distributed Raman amplification

We propose a modification of the nonlinear digital signal processing technique based on the nonlinear inverse synthesis for the systems with distributed Raman amplification. The proposed path-average approach offers 3 dB performance gain, regardless of the signal power profile.