Synthesis and evaluation of novel ligands for quantum dot stabilisation and polymerisation studies

This thesis describes the design and synthesis of a variety of functionalised phosphine oxides and sulfides, based on the structure of trioctylphosphine oxide, synthesised for the purpose of surface modification of quantum dots. The ability of the ligands to modify the surface chemistry via displacement of the original hexadecylamine capping layer of quantum dots was evaluated. Finally the surface modified quantum dots were investigated for enhancement in their inherent properties and improved compatibility with the various applications for which they were initially designed. Upon the commencement of research involving quantum dots it became apparent that more information on their behaviour and interaction with the environment was required. The limits of the inherent stability of hexadecylamine capped quantum dots were investigated by exposure to a number of different environments. The effect upon the stability of the quantum dots was monitored by changes in the photoluminescence ability of their cores. Subtle differences between different batches of quantum dots were observed and the necessity to account for these in future applications noted. Lastly the displacement of the original hexadecylamine coating with the "designer" functionalised ligands was evaluated to produce a set of conditions that would result in the best possible surface modification. A general procedure was elucidated however it was discovered that each displacement still required slight adjustment by consideration of the other factors such as the difference in ligand structure and the individuality of the various batches of quantum dots. This thesis also describes a procedure for the addition of a protective layer to the surface of quantum dots by cross-linking the functionalised ligands bound to the surface via an acyclic diene metathesis polymerisation. A detailed description of the problems encountered in the analysis of these materials combined with the use of novel techniques such as diffusion ordered spectroscopy is provided as a means to overcome the limitations encountered. Finally a demonstration of the superior stability, upon exposure to a range of aggressive environments of these protected materials compared with those before cross-linking provided physical proof of the cross-linking process and the advantages of the cross-linking modification. Finally this thesis includes the presentation of initial work into the production of luminescent nanocrystal encoded resin beads for the specific use in solid phase combinatorial chemistry. Demonstration of the successful covalent incorporation of quantum dots into the polymeric matrices of non-functionalised and functionalised resin beads is described. Finally by preliminary work to address and overcome the possible limitations that may be encountered in the production and general employment of these materials in combinatorial techniques is given.

Functional neuroimaging and behavioural studies on global form processing in the human visual system

Magnetoencephalography (MEG), functional magnetic resonance imaging (fMRI) and behavioural experiments were used to investigate the neural processes underlying global form perception in human vision. Behavioural studies using Glass patterns examined sensitivity for detecting radial, rotational and horizontal structure. Neuroimaging experiments using either Glass patterns or arrays of Gabor patches determined the spatio-temporal neural responseto global form. MEG data were analysed using synthetic aperture magnetometry (SAM) to spatially map event-related cortical oscillatory power changes: the temporal sequencing of activity within a discrete cortical area was determined using a Morlet wavelet transform. A case study was conducted to determine the effects of strbismic amblyopia on global form processing: all other observers were normally-sighted. The main findings from normally-sighted observers were: 1) sensitivity to horizontal structure was less than for radial or rotational structure; 2) the neural response to global structure was a reduction in cortical oscillatory power (10-30 Hz) within a network of extrastriate areas, including V4 and V3a; 3) the extend of reduced cortical power was least for horizontal patters; 4) V1 was not identified as a region of peak activity with either MEG or fMRI. The main findings with the strabismic amblyope were: 1) sensitivity for detection of radial, rotational, and horizontal structure was reduced when viewed with the amblyopic- relative to the fellow- eye; 2) cortical power changes within V4 to the presentation of rotational Glass patterns were less when viewed with the amblyopic- compared with the fellow- eye. The main conclusions are: 1) a network of extrastriate cortical areas are involved in the analysis of global form, with the most prominent change in neural activity being a reduction in oscillatory power within the 10-30 Hz band; 2) in strabismic amblyopia, the neuronal assembly associated with form perception in extrastriate cortex may be dysfunctional, the nature of this dysfunction may be a change in the normal temporal pattern of neuronal discharges; 3) MEG, fMRI and behavioural measures support the notion that different neural processes underlie the perception of horizontal as opposed to radial or rotational structure.

Objective and psychophysical studies of infant visual development

Distortion or deprivation of vision during an early `critical' period of visual development can result in permanent visual impairment which indicates the need to identify and treat visually at-risk individuals early. A significant difficulty in this respect is that conventional, subjective methods of visual acuity determination are ineffective before approximately three years of age. In laboratory studies, infant visual function has been quantified precisely, using objective methods based on visual evoked potentials (VEP), preferential looking (PL) and optokinetic nystagmus (OKN) but clinical assessment of infant vision has presented a particular difficulty. An initial aim of this study was to evaluate the relative clinical merits of the three techniques. Clinical derivatives were devised, the OKN method proved unsuitable but the PL and VEP methods were evaluated in a pilot study. Most infants participating in the study had known ocular and/or neurological abnormalities but a few normals were included for comparison. The study suggested that the PL method was more clinically appropriate for the objective assessment of infant acuity. A study of normal visual development from birth to one year was subsequently conducted. Observations included cycloplegic refraction, ophthalmoscopy and preferential looking visual acuity assessment using horizontally and vertically oriented square wave gratings. The aims of the work were to investigate the efficiency and sensitivity of the technique and to study possible correlates of visual development. The success rate of the PL method varied with age; 87% of newborns and 98% of infants attending follow-up successfully completed at least one acuity test. Below two months monocular acuities were difficult to secure; infants were most testable around six months. The results produced were similar to published data using the acuity card procedure and slightly lower than, but comparable with acuity data derived using extended PL methods. Acuity development was not impaired in infants found to have retinal haemorrhages as newborns. A significant relationship was found between newborn binocular acuity and anisometropia but not with other refractive findings. No strong or consistent correlations between grating acuity and refraction were found for three, six or twelve months olds. Improvements in acuity and decreases in levels of hyperopia over the first week of life were suggestive of recovery from minor birth trauma. The refractive data was analysed separately to investigate the natural history of refraction in normal infants. Most newborns (80%) were hyperopic, significant astigmatism was found in 86% and significant anisometropia in 22%. No significant alteration in spherical equivalent refraction was noted between birth and three months, a significant reduction in hyperopia was evident by six months and this trend continued until one year. Observations on the astigmatic component of the refractive error revealed a rather erratic series of changes which would be worthy of further investigation since a repeat refraction study suggested difficulties in obtaining stable measurements in newborns. Astigmatism tended to decrease between birth and three months, increased significantly from three to six months and decreased significantly from six to twelve months. A constant decrease in the degree of anisometropia was evident throughout the first year. These findings have implications for the correction of infantile refractive error.

Adjusting to institutional realities: the 2006 NGO law and its effects on civil society in Russia

Key findings: The paper investigates the impact that the legislative changes of 2006 had on civil society in Russia. This legislation has change the regulatory environment in which civil society actors such as Third Sector Organisations operate. Using the past development of civil society organisations as well as insights about how the institutional environment influences this article illustrates: - the undemocratic nature and motivation of the law and how it exploits the structural weaknesses of civil society - how Third Sector Organisations rationalise and translate the legislative changes into their organisational realities and how this changed or did not change their behaviour - the shift in state-civil society relations away from liberal co-existence into more hierarchical arrangements were Third Sector Organisations are subordinated to the state. These trends have far reaching implications for civil society. The empirical evidence shows that state now manages civil society to meet its own political ends. It also shows that organisations in the field welcome the more engage and directive nature of the Russian state. Why is this important? What does it mean for business or other users? Are there policy implications? The research is important as it shows how Third Sector Organisations have reacted to the legislative changes. Further it provides a basis for interpretation of the potential future development of civil society. Additional it highlights how the continuous process of democratisation in transition economies sometimes might come unstuck. In particular donor agencies will need to consider these trends when disturbing funding to Third Sector Organisations.

Similarity between class A and class B G-protein-coupled receptors exemplified through calcitonin gene-related peptide receptor modelling and mutagenesis studies

Modelling class B G-protein-coupled receptors (GPCRs) using class A GPCR structural templates is difficult due to lack of homology. The plant GPCR, GCR1, has homology to both class A and class B GPCRs. We have used this to generate a class A-class B alignment, and by incorporating maximum lagged correlation of entropy and hydrophobicity into a consensus score, we have been able to align receptor transmembrane regions. We have applied this analysis to generate active and inactive homology models of the class B calcitonin gene-related peptide (CGRP) receptor, and have supported it with site-directed mutagenesis data using 122 CGRP receptor residues and 144 published mutagenesis results on other class B GPCRs. The variation of sequence variability with structure, the analysis of polarity violations, the alignment of group-conserved residues and the mutagenesis results at 27 key positions were particularly informative in distinguishing between the proposed and plausible alternative alignments. Furthermore, we have been able to associate the key molecular features of the class B GPCR signalling machinery with their class A counterparts for the first time. These include the [K/R]KLH motif in intracellular loop 1, [I/L]xxxL and KxxK at the intracellular end of TM5 and TM6, the NPXXY/VAVLY motif on TM7 and small group-conserved residues in TM1, TM2, TM3 and TM7. The equivalent of the class A DRY motif is proposed to involve Arg(2.39), His(2.43) and Glu(3.46), which makes a polar lock with T(6.37). These alignments and models provide useful tools for understanding class B GPCR function.

X-ray crystallographic and theoretical studies of an anticonvulsant enaminone:methyl 4-(4'-bromophenyl)amino-6-methyl-2-oxocyclohex-3-en-1-oate

Objective: The aims of this study were to establish the structure of the potent anticonvulsant enaminone methyl 4-(4′-bromophenyl)amino-6-methyl-2- oxocyclohex-3-en-1-oate (E139), and to determine the energetically preferred conformation of the molecule, which is responsible for the biological activity. Materials and Methods: The structure of the molecule was determined by X-ray crystallography. Theoretical ab initio calculations with different basis sets were used to compare the energies of the different enantiomers and to other structurally related compounds. Results: The X-ray crystal structure revealed two independent molecules of E139, both with absolute configuration C11(S), C12(R), and their inverse. Ab initio calculations with the 6-31G, 3-21G and STO-3G basis sets confirmed that the C11(S), C12(R) enantiomer with both substituents equatorial had the lowest energy. Compared to relevant crystal structures, the geometry of the theoretical structures shows a longer C-N and shorter C=O distance with more cyclohexene ring puckering in the isolated molecule. Conclusion: Based on a pharmacophoric model it is suggested that the enaminone system HN-C=C-C=O and the 4-bromophenyl group in E139 are necessary to confer anticonvulsant property that could lead to the design of new and improved anticonvulsant agents. Copyright © 2003 S. Karger AG, Basel.

Tutorial on Computing: Technological Advances, Social Implications, Ethical and Legal Issues

Computing and information technology have made significant advances. The use of computing and technology is a major aspect of our lives, and this use will only continue to increase in our lifetime. Electronic digital computers and high performance communication networks are central to contemporary information technology. The computing applications in a wide range of areas including business, communications, medical research, transportation, entertainments, and education are transforming local and global societies around the globe. The rapid changes in the fields of computing and information technology also make the study of ethics exciting and challenging, as nearly every day, the media report on a new invention, controversy, or court ruling. This tutorial will explore a broad overview on the scientific foundations, technological advances, social implications, and ethical and legal issues related to computing. It will provide the milestones in computing and in networking, social context of computing, professional and ethical responsibilities, philosophical frameworks, and social, ethical, historical, and political implications of computer and information technology. It will outline the impact of the tremendous growth of computer and information technology on people, ethics and law. Political and legal implications will become clear when we analyze how technology has outpaced the legal and political arenas.

Women’s Entrepreneurship: closing the gender gap in access to financial and other services and in social entrepreneurship

This study explores differences between men and women entrepreneurs and social entrepreneurs. It explores the barriers and discriminatory effects that hinder women’s entrepreneurship, including access to finance in the European Union. The study includes four case studies covering the situation in the Czech Republic, Italy, Sweden, and the United Kingdom.

The role of law and ethics in developing business management as a profession

Currently, business management is far from being recognised as a profession. This paper suggests that a professional spirit should be developed which could function as a filter of commercial reasoning. Broadly, management will not be organised within the framework of a well-established profession unless formal knowledge, licensing, professional autonomy and professional codes of conduct are developed sufficiently. In developing business management as a profession, law may play a key role. Where the idea is that business management should be more professsionalised, managers must show that they are willing to adopt ethical values, while arriving at business decisions. The paper argues that ethics cannot survive without legal regulation, which, in turn, will not be supported by law unless lawyers can find alternative solutions to the large mechanisms of the official society, secured by the monopolised coercion of the nation state. From a micro perspective of law and business ethics, communities can be developed with their own conventions, rules and standards that are generated and sanctioned within the boundaries of the communities themselves.

Trichloroethylene fate and transport studies and biodegradation kinetics in the saturated zone

Permeable reactive barriers (PRB) are constructed from soil solid amendments to support the growth of bacteria that are capable of degrading organic contaminants. The objective of this study was to identify low-cost soil solid amendments that could retard the movement of trichloroethylene (TCE) while serving as long-lived carbon sources to foster its biodegradation in shallow groundwater through the use of a PRB. The natural amendments high in organic carbon content such as eucalyptus mulch, compost, wetland peat, organic humus were compared based on their geophysical characteristics, such as pHw, porosity and total organic carbon (TOC), and as well as TCE sorption potentials. The pHw values were within neutral range except for pine bark mulch and wetland peat. All other geophysical characteristics of the amendments showed suitability for use in a PRB. While the Freundlich model showed better fit for compost and pine bark mulch, the linear sorption model was adequate for eucalyptus mulch, wetland peat and Everglades muck within the concentration range studied (0.2-0.8 mg/L TCE). According to these results, two composts and eucalyptus mulch were selected for laboratory column experiments to evaluate their effectiveness at creating and maintaining conditions suitable for TCE anaerobic dechlorination. The columns were monitored for pH, ORP, TCE degradation, longevity of nutrients and soluble TOC to support TCE dechlorination. Native bacteria in the columns had the ability to convert TCE to DCEs; however, the inoculation with the TCE-degrading culture greatly increased the rate of biodegradation. This caused a significant increase in by-product concentration, mostly in the form of DCEs and VC followed by a slow degradation to ethylene. Of the tested amendments eucalyptus mulch was the most effective at supporting the TCE dechlorination. The experimental results of TCE sequential dechlorination took place in eucalyptus mulch and commercial compost from Savannah River Site columns were then simulated using the Hydrus-1D model. The simulations showed good fit with the experimental data. The results suggested that sorption and degradation were the dominant fate and transport mechanisms for TCE and DCEs in the column, supporting the use of these amendments in a permeable reactive barrier to remediate the TCE.

Otras mitologías (Other Mythologies) and Catch and Release , Book Presentation by Author Reina María Rodríguez

This flyer promotes the event "Otras mitologías (Other Mythologies) and Catch and Release : Book Presentation by Author Reina María Rodríguez" cosponsored by the School of International and Public Affairs and the Department of Modern Languages and Florida International University. The event was held and Books & Books in Coral Gables.

An Institutional, Socio-economic, and Legal Analysis of Fisheries Co-management and Regulation in the Gulf of Nicoya, Costa Rica

Marine Areas for Responsible Artisanal Fishing (AMPR) have emerged as a new model for co-managing small-scale fisheries in Costa Rica, one that involves collaboration between fishers, government agencies and NGOs. This thesis aims to examine the context for collective action and co-management by small-scale fishers; evaluate the design, implementation, and enforcement of AMPRs; and conduct a linguistic analysis of fisheries legislation. The present work relies on the analysis of several types of qualitative data, including interviews with 23 key informants, rapid rural assessments, and legal documents. Findings demonstrate the strong influence of economic factors for sustaining collective action, as well as the importance of certain types of external organizations for community development and co-management. Additionally, significant enforcement gaps and institutional deficiencies were identified in the work of regulating agencies. Legal analysis suggests that mechanisms for government accountability are unavailable and that legal discourse reflects some of the most salient problems in management.

Risk and benefits in lifestyle sports: parkour, law and social value

This paper examines the interrelationship between law and lifestyle sports, viewed through the lens of parkour. We argue that the literature relating to legal approaches to lifestyle sport is currently underdeveloped and so seek to partially fill this lacuna. Hitherto, we argue, the law has been viewed as a largely negative presence, seen particularly in terms of the ways in which counter-cultural activities are policed and regulated, and where such activities are viewed as transgressive or undesirable. We argue that this is a somewhat unsophisticated take on how the law can operate, with law constructed as an outcome of constraints to behaviour (where the law authorises or prohibits), distinct from the legal contexts, environments and spaces in which these relationships occur. We argue that the distinctive settings in which lifestyle sports are practiced needs a more fine-grained analysis as they are settings which bear, and bring to life, laws and regulations that shape how space is to be experienced. We examine specifically the interrelationship between risk and benefit and how the law recognises issues of social utility or value, particularly within the context of lifestyle sport. We seek to move from user-centred constructions of law as an imposition, to a more nuanced position that looks at parkour at the intersections of law, space and lifestyle sport, in order to reveal how law can be used to support and extend claims to space.

Floristic And Ethnobotanical Studies Of Medicinal Plants Of The City Of El -Jadida (MOROCCO)

Abstract: BRIGUICHE. H, ZIDANE. L. Floristic And Ethnobotanical Studies Of Medicinal Plants Of The City Of El -Jadida (MOROCCO). In the framework of the ethnobotanical studies on medicinal plants undertaken by the Laboratory of Biodiversity and Natural Resources of the Faculty of Sciences of Kenitra (Morocco), we are interested in the area of El Jadida which presents a rather important floristic richness thanks to changes in its ecological conditions By using 204 questionnaire, the ethnobotanical surveys were conducted in the field during the years 2012-2013. The location of the different sampling sites was determined by the stratified sampling method. The analysis of the results obtained from the questionnaires and forms using statistical processing allowed us to identify 70 plant species distributed in 69 genera and 37 families. These results also show that most of these species are mainly used in the care of the digestive system and respiratory system. The seed is the most used part in local traditional medicines and the decoction is the most frequent mode with a rate of 31%. The species Origanum compactum is the most used by the population of the city of El Jadida 47 quotes.