Mechanistic studies of organotellurium chemistry

The oxidation of bis(p-ethoxyphenyl) ditelluride by hydrogen peroxide has been studied kinetically. The reaction monitored was an oxidation from tellurium(I) to tellurium(II). The reaction stoichiometry ratio was found to depend upon the initial reagent concentrations. The presence of dioxygen was found to retard the rate and attributed to a dioxygen-ditelluride adduct. The rate varies in the following order of different atmospheres N2> Air> > O2. The final product obtained from the oxidation has been characterised by IR, NMR and ESR spectroscopy. A mechanism for the oxidation has been suggested. The reduction of p-EtOPhTeCl3 by the hydrazinium ion has been studied kinetically. The stoichiometric measurements show that four moles p-EtOPhTeCl3 are equivalent to three moles hydrazinium ion. The kinetics were studied under pseudo first order conditions. No ammonia was detected as a nitrogen containing product. The reduction proceeds via a two-electron process which indicates that it is inner-sphere in nature. A mechanism for the reduction is suggested. The solvolysis of p-EtOPhTeCl3 by methanol in benzene/methanol media has been studied. The study shows that the solvolysis is a reversible, acid catalysed reaction. Replacement of the chlorides on tellurium by methanol is agreed to be associative and replacement of the first chloride is rate determining. The rate of solvolysis varies in the order trichloride > tribromide > triiodide. A mechanism for the solvolysis is suggested. The synthesis of some tellurium heterocyclics is reported. The synthesis and characterisation of telluranthrene is reported. The attempted synthesis of telluraxanthene was unsuccessful.

Mirror-image relations in category learning

The discrimination of patterns that are mirror-symmetric counterparts of each other is difficult and requires substantial training. We explored whether mirror-image discrimination during expertise acquisition is based on associative learning strategies or involves a representational shift towards configural pattern descriptions that permit resolution of symmetry relations. Subjects were trained to discriminate between sets of unfamiliar grey-level patterns in two conditions, which either required the separation of mirror images or not. Both groups were subsequently tested in a 4-class category-learning task employing the same set of stimuli. The results show that subjects who had successfully learned to discriminate between mirror-symmetric counterparts were distinctly faster in the categorization task, indicating a transfer of conceptual knowledge between the two tasks. Additional computer simulations suggest that the development of such symmetry concepts involves the construction of configural, protoholistic descriptions, in which positions of pattern parts are encoded relative to a spatial frame of reference.

Individual differences in human-computer interaction

This thesis initially presents an 'assay' of the literature pertaining to individual differences in human-computer interaction. A series of experiments is then reported, designed to investigate the association between a variety of individual characteristics and various computer task and interface factors. Predictor variables included age, computer expertise, and psychometric tests of spatial visualisation, spatial memory, logical reasoning, associative memory, and verbal ability. These were studied in relation to a variety of computer-based tacks, including: (1) word processing and its component elements; (ii) the location of target words within passages of text; (iii) the navigation of networks and menus; (iv) command generation using menus and command line interfaces; (v) the search and selection of icons and text labels; (vi) information retrieval. A measure of self-report workload was also included in several of these experiments. The main experimental findings included: (i) an interaction between spatial ability and the manipulation of semantic but not spatial interface content; (ii) verbal ability being only predictive of certain task components of word processing; (iii) age differences in word processing and information retrieval speed but not accuracy; (iv) evidence of compensatory strategies being employed by older subjects; (v) evidence of performance strategy differences which disadvantaged high spatial subjects in conditions of low spatial information content; (vi) interactive effects of associative memory, expertise and command strategy; (vii) an association between logical reasoning and word processing but not information retrieval; (viii) an interaction between expertise and cognitive demand; and (ix) a stronger association between cognitive ability and novice performance than expert performance.

The application of methods of uncertain reasoning to the biological classification of river water quality

This thesis presents an investigation into the application of methods of uncertain reasoning to the biological classification of river water quality. Existing biological methods for reporting river water quality are critically evaluated, and the adoption of a discrete biological classification scheme advocated. Reasoning methods for managing uncertainty are explained, in which the Bayesian and Dempster-Shafer calculi are cited as primary numerical schemes. Elicitation of qualitative knowledge on benthic invertebrates is described. The specificity of benthic response to changes in water quality leads to the adoption of a sensor model of data interpretation, in which a reference set of taxa provide probabilistic support for the biological classes. The significance of sensor states, including that of absence, is shown. Novel techniques of directly eliciting the required uncertainty measures are presented. Bayesian and Dempster-Shafer calculi were used to combine the evidence provided by the sensors. The performance of these automatic classifiers was compared with the expert's own discrete classification of sampled sites. Variations of sensor data weighting, combination order and belief representation were examined for their effect on classification performance. The behaviour of the calculi under evidential conflict and alternative combination rules was investigated. Small variations in evidential weight and the inclusion of evidence from sensors absent from a sample improved classification performance of Bayesian belief and support for singleton hypotheses. For simple support, inclusion of absent evidence decreased classification rate. The performance of Dempster-Shafer classification using consonant belief functions was comparable to Bayesian and singleton belief. Recommendations are made for further work in biological classification using uncertain reasoning methods, including the combination of multiple-expert opinion, the use of Bayesian networks, and the integration of classification software within a decision support system for water quality assessment.

Classification and contextual enhancement of remotely sensed data

The aims of the project were twofold: 1) To investigate classification procedures for remotely sensed digital data, in order to develop modifications to existing algorithms and propose novel classification procedures; and 2) To investigate and develop algorithms for contextual enhancement of classified imagery in order to increase classification accuracy. The following classifiers were examined: box, decision tree, minimum distance, maximum likelihood. In addition to these the following algorithms were developed during the course of the research: deviant distance, look up table and an automated decision tree classifier using expert systems technology. Clustering techniques for unsupervised classification were also investigated. Contextual enhancements investigated were: mode filters, small area replacement and Wharton's CONAN algorithm. Additionally methods for noise and edge based declassification and contextual reclassification, non-probabilitic relaxation and relaxation based on Markov chain theory were developed. The advantages of per-field classifiers and Geographical Information Systems were investigated. The conclusions presented suggest suitable combinations of classifier and contextual enhancement, given user accuracy requirements and time constraints. These were then tested for validity using a different data set. A brief examination of the utility of the recommended contextual algorithms for reducing the effects of data noise was also carried out.

The application of artificial neural networks to the interpretation and classification of freshwater benthic invertebrate communities

This thesis presents a thorough and principled investigation into the application of artificial neural networks to the biological monitoring of freshwater. It contains original ideas on the classification and interpretation of benthic macroinvertebrates, and aims to demonstrate their superiority over the biotic systems currently used in the UK to report river water quality. The conceptual basis of a new biological classification system is described, and a full review and analysis of a number of river data sets is presented. The biological classification is compared to the common biotic systems using data from the Upper Trent catchment. This data contained 292 expertly classified invertebrate samples identified to mixed taxonomic levels. The neural network experimental work concentrates on the classification of the invertebrate samples into biological class, where only a subset of the sample is used to form the classification. Other experimentation is conducted into the identification of novel input samples, the classification of samples from different biotopes and the use of prior information in the neural network models. The biological classification is shown to provide an intuitive interpretation of a graphical representation, generated without reference to the class labels, of the Upper Trent data. The selection of key indicator taxa is considered using three different approaches; one novel, one from information theory and one from classical statistical methods. Good indicators of quality class based on these analyses are found to be in good agreement with those chosen by a domain expert. The change in information associated with different levels of identification and enumeration of taxa is quantified. The feasibility of using neural network classifiers and predictors to develop numeric criteria for the biological assessment of sediment contamination in the Great Lakes is also investigated.

Predictive gene lists for breast cancer prognosis: a topographic visualisation study

Background: The controversy surrounding the non-uniqueness of predictive gene lists (PGL) of small selected subsets of genes from very large potential candidates as available in DNA microarray experiments is now widely acknowledged 1. Many of these studies have focused on constructing discriminative semi-parametric models and as such are also subject to the issue of random correlations of sparse model selection in high dimensional spaces. In this work we outline a different approach based around an unsupervised patient-specific nonlinear topographic projection in predictive gene lists. Methods: We construct nonlinear topographic projection maps based on inter-patient gene-list relative dissimilarities. The Neuroscale, the Stochastic Neighbor Embedding(SNE) and the Locally Linear Embedding(LLE) techniques have been used to construct two-dimensional projective visualisation plots of 70 dimensional PGLs per patient, classifiers are also constructed to identify the prognosis indicator of each patient using the resulting projections from those visualisation techniques and investigate whether a-posteriori two prognosis groups are separable on the evidence of the gene lists. A literature-proposed predictive gene list for breast cancer is benchmarked against a separate gene list using the above methods. Generalisation ability is investigated by using the mapping capability of Neuroscale to visualise the follow-up study, but based on the projections derived from the original dataset. Results: The results indicate that small subsets of patient-specific PGLs have insufficient prognostic dissimilarity to permit a distinction between two prognosis patients. Uncertainty and diversity across multiple gene expressions prevents unambiguous or even confident patient grouping. Comparative projections across different PGLs provide similar results. Conclusion: The random correlation effect to an arbitrary outcome induced by small subset selection from very high dimensional interrelated gene expression profiles leads to an outcome with associated uncertainty. This continuum and uncertainty precludes any attempts at constructing discriminative classifiers. However a patient's gene expression profile could possibly be used in treatment planning, based on knowledge of other patients' responses. We conclude that many of the patients involved in such medical studies are intrinsically unclassifiable on the basis of provided PGL evidence. This additional category of 'unclassifiable' should be accommodated within medical decision support systems if serious errors and unnecessary adjuvant therapy are to be avoided.

Exploring ant-based algorithms for gene expression data analysis

Objective: Recently, much research has been proposed using nature inspired algorithms to perform complex machine learning tasks. Ant colony optimization (ACO) is one such algorithm based on swarm intelligence and is derived from a model inspired by the collective foraging behavior of ants. Taking advantage of the ACO in traits such as self-organization and robustness, this paper investigates ant-based algorithms for gene expression data clustering and associative classification. Methods and material: An ant-based clustering (Ant-C) and an ant-based association rule mining (Ant-ARM) algorithms are proposed for gene expression data analysis. The proposed algorithms make use of the natural behavior of ants such as cooperation and adaptation to allow for a flexible robust search for a good candidate solution. Results: Ant-C has been tested on the three datasets selected from the Stanford Genomic Resource Database and achieved relatively high accuracy compared to other classical clustering methods. Ant-ARM has been tested on the acute lymphoblastic leukemia (ALL)/acute myeloid leukemia (AML) dataset and generated about 30 classification rules with high accuracy. Conclusions: Ant-C can generate optimal number of clusters without incorporating any other algorithms such as K-means or agglomerative hierarchical clustering. For associative classification, while a few of the well-known algorithms such as Apriori, FP-growth and Magnum Opus are unable to mine any association rules from the ALL/AML dataset within a reasonable period of time, Ant-ARM is able to extract associative classification rules.

Automatically extracting polarity-bearing topics for cross-domain sentiment classification

Joint sentiment-topic (JST) model was previously proposed to detect sentiment and topic simultaneously from text. The only supervision required by JST model learning is domain-independent polarity word priors. In this paper, we modify the JST model by incorporating word polarity priors through modifying the topic-word Dirichlet priors. We study the polarity-bearing topics extracted by JST and show that by augmenting the original feature space with polarity-bearing topics, the in-domain supervised classifiers learned from augmented feature representation achieve the state-of-the-art performance of 95% on the movie review data and an average of 90% on the multi-domain sentiment dataset. Furthermore, using feature augmentation and selection according to the information gain criteria for cross-domain sentiment classification, our proposed approach performs either better or comparably compared to previous approaches. Nevertheless, our approach is much simpler and does not require difficult parameter tuning.

Semantic sentiment analysis of Twitter

Sentiment analysis over Twitter offer organisations a fast and effective way to monitor the publics' feelings towards their brand, business, directors, etc. A wide range of features and methods for training sentiment classifiers for Twitter datasets have been researched in recent years with varying results. In this paper, we introduce a novel approach of adding semantics as additional features into the training set for sentiment analysis. For each extracted entity (e.g. iPhone) from tweets, we add its semantic concept (e.g. Apple product) as an additional feature, and measure the correlation of the representative concept with negative/positive sentiment. We apply this approach to predict sentiment for three different Twitter datasets. Our results show an average increase of F harmonic accuracy score for identifying both negative and positive sentiment of around 6.5% and 4.8% over the baselines of unigrams and part-of-speech features respectively. We also compare against an approach based on sentiment-bearing topic analysis, and find that semantic features produce better Recall and F score when classifying negative sentiment, and better Precision with lower Recall and F score in positive sentiment classification.

Novel speech signal processing algorithms for high-accuracy classification of Parkinson's disease

There has been considerable recent research into the connection between Parkinson's disease (PD) and speech impairment. Recently, a wide range of speech signal processing algorithms (dysphonia measures) aiming to predict PD symptom severity using speech signals have been introduced. In this paper, we test how accurately these novel algorithms can be used to discriminate PD subjects from healthy controls. In total, we compute 132 dysphonia measures from sustained vowels. Then, we select four parsimonious subsets of these dysphonia measures using four feature selection algorithms, and map these feature subsets to a binary classification response using two statistical classifiers: random forests and support vector machines. We use an existing database consisting of 263 samples from 43 subjects, and demonstrate that these new dysphonia measures can outperform state-of-the-art results, reaching almost 99% overall classification accuracy using only ten dysphonia features. We find that some of the recently proposed dysphonia measures complement existing algorithms in maximizing the ability of the classifiers to discriminate healthy controls from PD subjects. We see these results as an important step toward noninvasive diagnostic decision support in PD.

Pattern recognition analyses of brain activation elicited by happy and neutral faces in unipolar and bipolar depression

Objectives: Recently, pattern recognition approaches have been used to classify patterns of brain activity elicited by sensory or cognitive processes. In the clinical context, these approaches have been mainly applied to classify groups of individuals based on structural magnetic resonance imaging (MRI) data. Only a few studies have applied similar methods to functional MRI (fMRI) data. Methods: We used a novel analytic framework to examine the extent to which unipolar and bipolar depressed individuals differed on discrimination between patterns of neural activity for happy and neutral faces. We used data from 18 currently depressed individuals with bipolar I disorder (BD) and 18 currently depressed individuals with recurrent unipolar depression (UD), matched on depression severity, age, and illness duration, and 18 age- and gender ratio-matched healthy comparison subjects (HC). fMRI data were analyzed using a general linear model and Gaussian process classifiers. Results: The accuracy for discriminating between patterns of neural activity for happy versus neutral faces overall was lower in both patient groups relative to HC. The predictive probabilities for intense and mild happy faces were higher in HC than in BD, and for mild happy faces were higher in HC than UD (all p < 0.001). Interestingly, the predictive probability for intense happy faces was significantly higher in UD than BD (p = 0.03). Conclusions: These results indicate that patterns of whole-brain neural activity to intense happy faces were significantly less distinct from those for neutral faces in BD than in either HC or UD. These findings indicate that pattern recognition approaches can be used to identify abnormal brain activity patterns in patient populations and have promising clinical utility as techniques that can help to discriminate between patients with different psychiatric illnesses.

Examination of the predictive value of structural magnetic resonance scans in bipolar disorder:a pattern classification approach

Background - Bipolar disorder (BD) is one of the leading causes of disability worldwide. Patients are further disadvantaged by delays in accurate diagnosis ranging between 5 and 10 years. We applied Gaussian process classifiers (GPCs) to structural magnetic resonance imaging (sMRI) data to evaluate the feasibility of using pattern recognition techniques for the diagnostic classification of patients with BD. Method - GPCs were applied to gray (GM) and white matter (WM) sMRI data derived from two independent samples of patients with BD (cohort 1: n = 26; cohort 2: n = 14). Within each cohort patients were matched on age, sex and IQ to an equal number of healthy controls. Results - The diagnostic accuracy of the GPC for GM was 73% in cohort 1 and 72% in cohort 2; the sensitivity and specificity of the GM classification were respectively 69% and 77% in cohort 1 and 64% and 99% in cohort 2. The diagnostic accuracy of the GPC for WM was 69% in cohort 1 and 78% in cohort 2; the sensitivity and specificity of the WM classification were both 69% in cohort 1 and 71% and 86% respectively in cohort 2. In both samples, GM and WM clusters discriminating between patients and controls were localized within cortical and subcortical structures implicated in BD. Conclusions - Our results demonstrate the predictive value of neuroanatomical data in discriminating patients with BD from healthy individuals. The overlap between discriminative networks and regions implicated in the pathophysiology of BD supports the biological plausibility of the classifiers.

How weak categorizers based upon different principles strengthen performance

Combining the results of classifiers has shown much promise in machine learning generally. However, published work on combining text categorizers suggests that, for this particular application, improvements in performance are hard to attain. Explorative research using a simple voting system is presented and discussed in the light of a probabilistic model that was originally developed for safety critical software. It was found that typical categorization approaches produce predictions which are too similar for combining them to be effective since they tend to fail on the same records. Further experiments using two less orthodox categorizers are also presented which suggest that combining text categorizers can be successful, provided the essential element of ‘difference’ is considered.

Sustainable agricultural production:an investigation in Brazilian semi-arid livestock farms

This paper investigates the environmental sustainability and competitiveness perceptions of small farmers in a region in northern Brazil. The main data collection instruments included a survey questionnaire and an analysis of the region's strategic plan. In total, ninety-nine goat and sheep breeding farmers were surveyed. Data analysis methods included descriptive statistics, cluster analysis, and chi-squared tests. The main results relate to the impact of education, land size, and location on the farmers' perceptions of competitiveness and environmental issues. Farmers with longer periods of education have higher perception scores about business competitiveness and environmental sustainability than those with less formal education. Farmers who are working larger land areas also have higher scores than those with smaller farms. Lastly, location can yield factors that impact on farmers' perceptions. In our study, farmers located in Angicos and Lajes had higher perception scores than Pedro Avelino and Afonso Bezerra, despite the geographical proximity of these municipalities. On the other hand, three other profile variables did not impact on farmers' perceptions, namely: family income, dairy production volume, and associative condition. The authors believe the results and insights can be extended to livestock farming in other developing countries and contribute generally to fostering effective sustainable development policies, mainly in the agribusiness sector. © 2013 Elsevier Ltd. All rights reserved.