This thesis reports the results of investigations carried out into the composition of the saturate and aromatic unresolved complex mixtures (UCMs) in crude oils. It is divided into two sections. Section A reports on studies of the saturate UCM and Section B reports on studies of the aromatic UCM. UCMs are mixtures of very large numbers of compounds of low individual abundances, hence structural information on individual components is difficult or impossible to obtain using conventional GC or GC-MS techniques. The investigations reported in this thesis used a combination of GC-MS techniques (Section A) and oxidations of UCMs followed by GC-MS characterisation of the oxidation products (Section B) to develop a more detailed picture of the structures of components of the saturate and aromatic UCMs. UCMs are present in all crude oils, and may account for the vast majority of the material present in heavily weathered or biodegraded oils. An understanding of the types of compounds present may have a bearing on the refining processes an oil is subjected to, as well as assessing its potential environmental and toxicological effects.Single branched C(subscript)18 isomers were prepared to establish the chromatographic behaviour and mass spectral fragmentation patterns of open chain compounds with ethyl-, propyl-, butyl- and pentyl- substituents. All open chain structural isomers with a single n-alkyl branch larger than methyl in the range C(subscript)10 to C(subscript)20 were identified at each carbon number in a series of crude oils of varying ages, source types and depositional environments. Also, C(subscript)21 to C(subscript)25 structural isomers containing an ethyl branch were identified in all of these samples. This represents a total of 163 compounds. These monoalkylalkanes comprise approximately 3 % of the alkanes in these oils, with the n-alkanes (35-60 %) and ++ / methylalkanes (10 %) being the most abundant compound classes present. Isoprenoids, alkylcyclohexanes and other branched and/or cyclic alkanes make up the remainder of the material.Rock samples from a sedimentary sequence of Late Cretaceous age were analysed for ethylalkanes using GC-MS techniques. In the less mature samples, 3- and 5-ethylalkanes were in higher abundance relative to the other isomers at odd carbon numbers from C(subscript)17 to C(subscript)23. In the more mature samples, this odd preference was no longer apparent. Several other low maturity sediment samples were analysed and found to have a similar ethylalkane distribution to the shallow sample from the sedimentary sequence. A mature crude oil which was also analysed exhibited a distribution similar to the deeper sample from the sedimentary sequence. Tetralin pyrolysis of a low maturity lignite sample yielded only the 3- and 5-substituted ethylalkanes, providing supporting evidence that the initial odd preference is the result of defunctionalisation of specific natural product precursors containing a 3- or 5-ethylalkyl structural moiety. With increasing maturity this preference is diluted by input of ethylalkanes without preference. A mechanism involving acid-catalysed rearrangement of n-alkenes to form monoalkylalkanes is proposed to account for the loss of preference in ethylalkane relative abundances.Investigations into the composition of aromatic unresolved complex mixtures were conducted by oxidising the total aromatic fraction of a moderately biodegraded crude oil (biodegradation level 4) using potassium permanganate. This reagent cleaves the alkyl substituents attached to aromatic rings between the alpha and beta carbons and oxidises the alpha carbon to a carboxylate group. A biodegraded crude oil was chosen because the majority of the resolved components have been removed by biodegradation, ++ / leaving a complex mixture of compounds almost completely unresolved by gas chromatography. The oxidation product was separated into dichloromethane-soluble monocarboxylic acids (both aliphatic and aromatic) and water-soluble polycarboxylic acids (aromatic only). GC-MS analysis of these oxidation products gave the proportions of monosubstituted:disubstituted:trisubstituted:tetrasubstituted monoaromatic rings as 29:59:12:0.1, of which from one to three substituents were carboxylic acid groups with the remainder of the substituents being unoxidised methyl groups. Of the disubstituted monoaromatic oxidation products, 53 % were dicarboxylic acids with the most sterically hindered 1,2-substitution pattern. This observation was interpreted as evidence for the presence of significant amounts of naphthenoaromatic systems such as tetralins and indanes in the crude oil aromatic fraction. Analysis of the permanganate oxidation products also enabled a quantitative measure of the proportion of methyl substituents to be made. It was found that methyl groups accounted for a significant proportion of the alkyl substituents attached to aromatic systems. Of the disubstituted monoaromatic oxidation products, 59 % had a methyl group as one of the substituents, while of trisubstituted monoaromatic systems, 41% had one methyl and 37 % had two methyls. Compounds containing a biphenyl carbon skeleton comprised 3 % of the aromatic oxidation products, with isomers containing from one to four substituents of which one was a carboxylic acid group and the remainder were unoxidised methyls. This indicates that biphenyls containing more than one alkyl (>C(subscript)1) substituent were not present. Of the monosubstituted biphenylcarboxylic acids, the ratio of ortho:meta:para substituted isomers was 0:65:35, which correlates well with literature reports of the relative abundances of methylbiphenyl ++ / isomers, and suggests that the overall distribution of all monosubstituted biphenyls has not been significantly affected by biodegradation to level 4.The monoaromatic, diaromatic and triaromatic fractions of the same biodegraded crude oil (level 4) were separately treated with ruthenium tetroxide, which cleaves aromatic rings so that the ring carbon bearing the substituent is oxidised to become the carbonyl carbon of a carboxylic acid. These oxidation products represent the alkyl moieties that were attached to aromatic rings in the initial crude oil aromatic fractions. Identification of these alkyl side chains provides an insight into the nature of the components of the aromatic crude oil UCM. The oxidation products were separated into dichloromethane-soluble monocarboxylic acids, which were subsequently reduced to monodeuterated hydrocarbons for characterisation using gas chromatography-mass spectrometry (GC-MS) techniques, and water-soluble dicarboxylic acids which were analysed as dimethyl esters. n-Alkanes, methylalkanes, alkylalkanes, alkylcyclohexands, methylalkylcyclohexanes, isoprenoids and bicyclic alkanes were identified in the monodeuterated hydrocarbon samples derived from all three aromatic fractions. Most of these compounds had carbon skeletons strikingly similar to those observed in the saturate fractions of unbiodegraded crude oils, with the only differences being the addition of a carbon from the aromatic ring, and the presence of a deuterium atom attached to that carbon. Because the electron-withdrawing nature of carboxylic acid groups prevents further aromatic ring oxidation, numerous aromatic monocarboxylic acids were also identified in the acidic products of the oxidation of the crude oil diaromatic and triaromatic fractions. These included C(subscript)1 to C(subscript)3 alkyl-substituted benzoic acids derived from compounds containing a biphenyl ++ / or phenylnaphthalene structural moiety, as well as omega-phenylalkanoic acids with chain lengths up to C(subscript)11, derived from compounds in which two aromatic systems are connected by an alkyl chain. The main components of the dicarboxylic acid oxidation products of all three aromatic fractions were alpha, omega-dicarboxylic acids and alkylcyclopentane-dicarboxylic acids and alkylcyclohexane-dicarboxylic acids, with phthalic acids also present in the oxidation products of the diaromatic and triaromatic fractions. The observation that 1,5-pentanedicarboxylic acids and 1,6-hexanedicarboxylic acids were the only alpha, omega-dicarboxylic acids in the oxidation products of the crude oil monoaromatic fraction, and were present in high abundance relative to other alpha, omega-dicarboxylic acids in the oxidation products of the diaromatic and triaromatic fractions indicated that substituted indanes and/or tetralins were quantitatively important constituents of the overall crude oil aromatic fraction. This finding is supported by the results of the analysis of the mass spectra of the crude oil aromatic fractions.These studies of aromatic UCMs have provided new insights into the origins of the aromatic components of petroleum. The presence of a pronounced odd-over-even predominance in the C(subscript)25, C(subscript)27, and C(subscript)29 monodeuterated n-alkanes (CPI = 1.07), which corresponds to the odd-over-even predominance observed in the n-alkane components of unbiodegraded crude oils from the same basin, suggests that the n-alkyl side chains and the n-alkanes have a common source. Evidence is presented to support the hypothesis that the n-alkylaromatics are formed in part by geosynthetic processes involving alkylation of aromatic systems by electrophilic species such as carbocations and acylium ions formed from carboxylic acids. This hypothesis is then extended to ++ / explain the formation of other groups of compounds, including aromatic systems with isoprenoidal-, methylalkyl- and monoalkyl-branched side chains. Because isoprenoids, methylalkanes and alkylalkanes are well-known components of petroleum, these results suggest that these alkylaromatic components of petroleum may share a common source with the corresponding alkane components. It is suggested that aromatic unresolved complex mixtures arise due to the very large number of structurally related compounds present, which are formed by geosynthetic processes such as alkylation of aromatic rings.

A central goal of this study is to better understand why some mothers become unresolved with respect to experiences of loss whereas others do not. Adults are considered to be unresolved with respect to loss if they display signs of mental disorganization while discussing an attachment-related loss due to death – for example, talking in the present tense about a deceased person as if the person is still alive (Main, Goldwyn, & Hesse, 2002). Studies have accumulated documenting the negative consequences of being unresolved. Researchers have linked unresolved attachment to frightened/frightening maternal behavior (Jacobvitz, Leon, & Hazen, 2006), drug/alcohol abuse (Riggs & Jacobvitz, 2002), and other Axis I and II disorders (Ward, Lee, & Polan, 2006; Fonagy et al., 1996); as well as anxiety, anger, (Busch, Cowan, & Cowan, 2008) and controlling behavior (Creasey, 2002) in romantic relationships. Less is known about the conditions under which a person becomes unresolved. This study will be one of the first to examine the comprehensive effects of several risk factors known to influence a person’s ability to resolve a loss including kinship, cause of death, and suddenness as well as primary attachment pattern. Other factors included in this study are social support and lifestyle changes. Although attachment theory provides a thorough explanation for an individual’s inability to resolve a loss, it is only one of many theoretical explanations of this phenomenon (Rando, 1993). One theory that is conceptually similar to unresolved loss is the theory of complicated grief, the process of painful searching and yearning for a deceased person (Prigerson et al., 1995b). Like those who study unresolved loss, complicated grief researchers are still seeking to understand what factors can predict whether an individual will experience prolonged symptoms of grief (van der Houwen et al., 2010). Also similar to unresolved loss, complicated grief involves irregular patterns of mental processes following a loss; however, complicated grief seems to be a conscious process, whereas unresolved loss has non-conscious components. Hence, this dissertation also examined whether complicated grief was related to unresolved loss and, if so, whether the origins for complicated grief were similar to unresolved loss. / text

A new method for constructing probability tables in the Unresolved Resonance Region (URR) has been developed. This new methodology is an extensive modification of the Single-Level Breit-Wigner (SLBW) resonance-pair sequence method commonly used to generate probability tables in the URR. Using a Monte Carlo process, many resonance-pair sequences are generated by sampling the average resonance parameter data for the unresolved resonance region from the ENDF data file. The resonance parameters are then converted to the Reich-Moore format to take advantage of the more robust R-Matrix Limited (RML) format. For each sampled set of resonance-pair sequences, the temperature-dependent cross sections are calculated on a small grid around the energy of reference using the RML formalism and the Leal-Hwang Doppler broadening methodology. The effective cross sections calculated at the energy of reference are then used to construct probability tables in the unresolved resonance region. The RML cross section reconstruction algorithm has been rigorously tested for a variety of isotopes, including O-16, F-19, Cl-35, Fe-56, Cu-63, and Cu-65. The new URR method also produced normalized cross-section factor probability tables for U-238 that were found to be in agreement with current standards. The modified U-238 probability tables were shown to produce k-eff results in excellent agreement with several standard benchmarks, including the IEU-MET-FAST-007, IEU-MET-FAST-003, and IEU-COMP-FAST-004 benchmarks.

This study deals with the pastoral counselling of people who became ill as a result of unresolved trauma. Some of the important questions raised in this study, included: Why are certain traumatic events physically harmful to people? 0 What is the relationship between unresolved trauma and the development of disease in the human body? Which additional factors play a role in the development of disease? The basis theoretical research clearly showed that a wounded person can be healed and restored by God; even if the wounding took place a long time ago. The traumatized person can bring his/her pain to God, uninhibitedly, with the expectation that God's healing power can heal. Negative thoughts and emotions, which are harmful to a person, must be brought under the truth of the Word, through the guidance of the Holy Spirit; with the intention to correct these thoughts and emotions. The meta-theoretical research has clearly shown a relationship between unresolved trauma and the development of disease in humans. Unresolved emotions can create certain emotions that work in negatively on a person's body. Unresolved trauma can also lead to Post-Traumatic Stress Disorder. For the purpose of the empirical study, four cases, of people who experienced trauma, were selected and studied. These people all struggled with new diseases after their traumatic experiences. The results highlighted the importance of considering the unique personal history of each individual; especially with reference to unresolved traumatic experiences in a person's past. The co-operation between the researcher and the medical profession regarding the results of the case studies should be noted. Chapter 6 clearly points out that the point of departure in pastoral counselling is God, the Holy Trinity. Vital dimensions of the Biblical counselling process are the following: Establishing involvement with counselees. Inspiring in them Biblical hope. 0 A thorough inventory and Biblical interpretation of counselees and their problems. Instructing counselees in an accurate and appropriately Biblical way to inspire in them decisive commitment to Biblical obedience and the implementation of Biblical instructions. / Thesis (M.A. (Pastoral))--North-West University, Potchefstroom Campus, 2006.

This study deals with the pastoral counselling of people who became ill as a result of unresolved trauma. Some of the important questions raised in this study, included: Why are certain traumatic events physically harmful to people? 0 What is the relationship between unresolved trauma and the development of disease in the human body? Which additional factors play a role in the development of disease? The basis theoretical research clearly showed that a wounded person can be healed and restored by God; even if the wounding took place a long time ago. The traumatized person can bring his/her pain to God, uninhibitedly, with the expectation that God's healing power can heal. Negative thoughts and emotions, which are harmful to a person, must be brought under the truth of the Word, through the guidance of the Holy Spirit; with the intention to correct these thoughts and emotions. The meta-theoretical research has clearly shown a relationship between unresolved trauma and the development of disease in humans. Unresolved emotions can create certain emotions that work in negatively on a person's body. Unresolved trauma can also lead to Post-Traumatic Stress Disorder. For the purpose of the empirical study, four cases, of people who experienced trauma, were selected and studied. These people all struggled with new diseases after their traumatic experiences. The results highlighted the importance of considering the unique personal history of each individual; especially with reference to unresolved traumatic experiences in a person's past. The co-operation between the researcher and the medical profession regarding the results of the case studies should be noted. Chapter 6 clearly points out that the point of departure in pastoral counselling is God, the Holy Trinity. Vital dimensions of the Biblical counselling process are the following: Establishing involvement with counselees. Inspiring in them Biblical hope. 0 A thorough inventory and Biblical interpretation of counselees and their problems. Instructing counselees in an accurate and appropriately Biblical way to inspire in them decisive commitment to Biblical obedience and the implementation of Biblical instructions. / Thesis (M.A. (Pastoral))--North-West University, Potchefstroom Campus, 2006.

<p> Detection and estimation of multiple unresolved targets with a monopulse radar is a challenging problem. For ideal single bin processing, it was shown in the literature that at most two unresolved targets can be extracted from the complex matched filter output signal. In this thesis, a new algorithm is developed to jointly detect and track more than two targets from a single detection. This method involves the use of tracking data in the detection process. For this purpose, target states are transformed into the detection parameter space, which involves high nonlinearity. In order to handle this, the sequential Monte Carlo (SMC) method, which has proven to be effective in nonlinear non-Gaussian estimation problems, is used as the basis of the closed loop system for tracking multiple unresolved targets. In addition to the standard SMC steps, the detection parameters corresponding to the predicted particles are evaluated using the nonlinear monopulse radar beam model. This in turn enables the evaluation of the likelihood of the monopulse signal given tracking data. Hypothesis testing is then used to find the correct detection event. The particles are updated and resampled according to the hypothesis that has the highest likelihood (score). A simulated amplitude comparison monopulse radar is used to generate the data and to validate the extraction and tracking of more than two unresolved targets.</p> / Thesis / Master of Applied Science (MASc)

The purpose of this research was to utilise attachment theory in understanding the experience of bereavement in childhood. Research objectives were addressed by using a mixed method design. Study One explored how experience of bereavement in childhood relates to current attachment style in adulthood. This was a qualitative interview-based study utilising thematic analysis and a quantitative assessment of attachment styles. Twenty-four participants were employed. The established Experience in Close Relationships (ECR) questionnaire was used. The results through the thematic analysis indicated that people with different attachment styles provide different narratives about their childhood bereavement. This study provides evidence that this was so. Study Two was a co-relational study employing 121 participants who experienced loss of caregiver in childhood. Four established questionnaires were used: Inventory of Complicated Grief (ICG; Prigerson et al., 1995), Experience in Close Relationships Questionnaire-Revised (ECR; Fraley, Waller, & Brennan, 2000), Separation Anxiety Symptom Inventory (SASI; Silove, Manicavasagar, O’Connell, Blaszczynski, Wagner, & Henry, 1993) and Parental Bonding Instrument (PBI; Parker, Tupling, & Brown, 1979). The results showed that complicated grief was related to parental care and overprotection, separation anxiety, and adult attachment style. Anxious attachment style fully mediated the effects of parental bonding on complicated grief. Study Three was a quantitative co-relational study to compare two groups of parents (with and without a bereaved child) on child behavioural differences and links between child behavioural problems and parental characteristics. Two hundred and forty participants were employed: 139 parents of children with bereavement experience and 101 without bereavement experience. Five established questionnaires were used: Child Stress Questionnaire (CSQ), Strengths and Difficulties Questionnaire (SDQ), The Parenting Scale (PS), Inventory of Complicated Grief (ICG), and Experience in Close Relationships Questionnaire-Revised (ECR-R). The results showed that child problems were closely associated to parental qualities. It is proposed that this research can make a contribution towards utilising attachment theory in understanding the experience of bereavement in children.

InterRAI is an internationally validated assessment tool used in many different contexts to assist different groups of people and patients to live fuller, safer and more productive lives. In 2008, the New Zealand Ministry of Health, after the completion a trial of the interRAI – Home Care assessment tool in the District Health Board, rolled out implementation of the interRAI – Home Care tool throughout New Zealand’s 21 District Health Boards. The Quality of Life survey itself is currently being assessed and trialled throughout the world as a follow-up to the Home Care assessment. It will enable researchers and assessors to enable for a comprehensive perspective by bringing together the views of both service providers and recipients of care service. The assessments will be completed by the person directly, as a self assessment, or through interview The overall research aim of the study itself is to evaluate the adequacy of the interRAI Quality of Life survey in assessing the Quality of Life issues and needs of the elderly living in their own homes in the community with some sort of publicly funded health care, social or community support such as meals on wheels, personal care, etc., for the purpose of demonstrating the importance of it as a useful tool within New Zealand. The objectives of the research are as follows: • Objective 1 - To review the management and application of quality of life indicators for the elderly. • Objective 2 – To understand the pressures which an ageing population places on public policy. • Objective 3 - To consider how quality of life measures can best be applied alongside interRAI in New Zealand. The research itself focused on the Quality of Life of thirty participants. Each participant was first assessed through an interRAI – HC assessment at their own home by an assessor from the Canterbury District Health Board. Upon completion of the assessment, they were given the option of being contacted by the researcher about participation in the interRAI Quality of Life Survey. Contact by the researcher by telephone ensued, which was then followed up by a face to face information session at the home of the participant. At this time, thirty out of thirty one potential participants decided to sign the informed consent form for participation. As the Quality of Life Survey itself is self reported, each participant was free to read through the survey and answer for themselves questions regarding their thoughts about their own quality of life. Participants responded to forty six statements from nine different domains on the Quality of Life Survey. Overall results showed a majority of responses of ‘Always’, which were positive. Areas of concern which emerged from the data were of possible issues of social isolation and unresolved emotional health. Limitations of the research included factors such as the small sample size of thirty, the geography of the study which was limited to Christchurch, and the fact that there was no follow up visit to the first and only interview. In conclusion, it is apparent that a larger trial throughout the District Health Board is required to overcome the aforementioned limitations of sample size and geography. Also, it is imperative that a follow-up visit is scheduled after the initial visit to allow for intervention into quality of life issues which emerge from the participant’s self-assessment.

Aims: This paper extends previous studies in modeling time varying linear polarization due to axisymmetric magnetic fields in rotating stars. We use the Hanle effect to predict variations in net line polarization, and use geometric arguments to generalize these results to linear polarization due to other mechanisms. Methods: Building on the work of Lopez Ariste et al., we use simple analytic models of rotating stars that are symmetric except for an axisymmetric magnetic field to predict the polarization lightcurve due to the Hanle effect. We highlight the effects for the variable line polarization as a function of viewing inclination and field axis obliquity. Finally, we use geometric arguments to generalize our results to linear polarization from the weak transverse Zeeman effect. Results: We derive analytic expressions to demonstrate that the variable polarization lightcurve for an oblique magnetic rotator is symmetric. This holds for any axisymmetric field distribution and arbitrary viewing inclination to the rotation axis. Conclusions: For the situation under consideration, the amplitude of the polarization variation is set by the Hanle effect, but the shape of the variation in polarization with phase depends largely on geometrical projection effects. Our work generalizes the applicability of results described in Lopez Ariste et al., inasmuch as the assumptions of a spherical star and an axisymmetric field are true, and provides a strategy for separating the effects of perspective from the Hanle effect itself for interpreting polarimetric lightcurves.

Safety, tolerability and efficacy of itraconazole and amphotericin B (AMB) were compared for empirical antifungal treatment of febrile neutropenic cancer patients. Patients and Methods: In an open, randomised study, 162 patients with at least 72 h of antimicrobial treatment received either intravenous followed by oral itraconazole suspension or intravenous AMB for a maximum of 28 days. Permanent discontinuation of study medication due to any adverse event was the primary safety parameter. Efficacy parameters included response and success rate for both treatment groups. Results: Significantly fewer itraconazole patients discontinued treatment due to any adverse event (22.2 vs. 56.8% AMB; p < 0.0001). The main reason for discontinuation was a rise in serum creatinine (1.2% itraconazole vs. 23.5% AMB). Renal toxicity was significantly higher and more drug-related adverse events occurred in the AMB group. Intention-to-treat (ITT) analysis showed favourable efficacy for itraconazole: response and success rate were both significantly higher than for AMB (61.7 vs. 42% and 70.4 vs. 49.3%, both p < 0.0001). Treatment failure was markedly reduced in itraconazole patients (25.9 vs. 43.2%), largely due to the better tolerability. Conclusions: Itraconazole was tolerated significantly better than conventional AMB and also showed advantages regarding efficacy. This study confirms the role of itraconazole as a useful and safe agent in empirical antifungal therapy of febrile neutropenic cancer patients. / Hintergrund: Es wurden die Sicherheit, Verträglichkeit und Wirksamkeit von Itraconazol und Amphotericin B (AMB) in der antimykotischen Therapie der persistierend febrilen Neutropenie verglichen. Patienten und Methoden: In einer offenen, randomisierten Studie erhielten 162 Patienten mit mindestens 72-stündiger antibiotischer Therapie entweder Itraconazol (erst intravenös, dann oral) oder AMB (intravenös) für maximal 28 Tage. Primärer Sicherheitsparameter war die dauerhafte Unterbrechung der Studienmedikation aufgrund von Nebenwirkungen. Die Wirksamkeitsparameter umfassten die Ansprech- und Erfolgsrate für beide Behandlungsgruppen. Ergebnisse: Signifikant weniger Itraconazol-Patienten brachen die Behandlung wegen Nebenwirkungen ab (22,2 vs. 56,8% AMB; p < 0,0001). Hauptursache für Studienabbrüche war der Anstieg des Serum-Kreatinin-Spiegels (1,2% Itraconazol vs. 23,5% AMB). Nephrotoxische und weitere Nebenwirkungen traten im AMB-Studienarm signifikant häufiger auf. Intention-to-Treat (ITT)-Analysen zeigten eine bessere Wirksamkeit von Itraconazol: Ansprech- und Erfolgsrate waren signifikant höher als unter AMB (61,7 vs. 42% und 70,4 vs. 49,3%, beide p < 0,0001). Behandlungsversagen trat bei Itraconazol-Patienten merklich weniger auf (25,9 vs. 43,2%). Schlussfolgerungen: Die Verträglichkeit von Itraconazol war signifikant höher als beim herkömmlichen AMB. Itraconazol zeigte ebenfalls Vorteile in der Wirksamkeit. Diese Studie bestätigt die Rolle von Itraconazol als sinnvolles und sicheres Medikament in der empirischen antimykotischen Therapie von fiebrigen neutropenischen Tumorpatienten. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.