Nuclear magnetic resonance studies of molecular interactions and structures

This thesis is concerned with the investigation, by nuclear magnetic resonance spectroscopy, of the molecular interactions occurring in mixtures of benzene and cyclohexane to which either chloroform or deutero-chloroform has been added. The effect of the added polar molecule on the liquid structure has been studied using spin-lattice relaxation time, 1H chemical shift, and nuclear Overhauser effect measurements. The main purpose of the work has been to validate a model for molecular interaction involving local ordering of benzene around chloroform. A chemical method for removing dissolved oxygen from samples has been developed to encompass a number of types of sample, including quantitative mixtures, and its supremacy over conventional deoxygenation technique is shown. A set of spectrometer conditions, the use of which produces the minimal variation in peak height in the steady state, is presented. To separate the general diluting effects of deutero-chloroform from its effects due to the production of local order a series of mixtures involving carbon tetrachloride, instead of deutero-chloroform, have been used as non-interacting references. The effect of molecular interaction is shown to be explainable using a solvation model, whilst an approach involving 1:1 complex formation is shown not to account for the observations. It is calculated that each solvation shell, based on deutero-chloroform, contains about twelve molecules of benzene or cyclohexane. The equations produced to account for the T1 variations have been adapted to account for the 1H chemical shift variations in the same system. The shift measurements are shown to substantiate the solvent cage model with a cage capacity of twelve molecules around each chloroform molecule. Nuclear Overhauser effect data have been analysed quantitatively in a manner consistent with the solvation model. The results show that discrete shells only exist when the mole fraction of deutero-chloroform is below about 0.08.

Packet voice/data in local broadcast networks

A local area network that can support both voice and data packets offers economic advantages due to the use of only a single network for both types of traffic, greater flexibility to changing user demands, and it also enables efficient use to be made of the transmission capacity. The latter aspect is very important in local broadcast networks where the capacity is a scarce resource, for example mobile radio. This research has examined two types of local broadcast network, these being the Ethernet-type bus local area network and a mobile radio network with a central base station. With such contention networks, medium access control (MAC) protocols are required to gain access to the channel. MAC protocols must provide efficient scheduling on the channel between the distributed population of stations who want to transmit. No access scheme can exceed the performance of a single server queue, due to the spatial distribution of the stations. Stations cannot in general form a queue without using part of the channel capacity to exchange protocol information. In this research, several medium access protocols have been examined and developed in order to increase the channel throughput compared to existing protocols. However, the established performance measures of average packet time delay and throughput cannot adequately characterise protocol performance for packet voice. Rather, the percentage of bits delivered within a given time bound becomes the relevant performance measure. Performance evaluation of the protocols has been examined using discrete event simulation and in some cases also by mathematical modelling. All the protocols use either implicit or explicit reservation schemes, with their efficiency dependent on the fact that many voice packets are generated periodically within a talkspurt. Two of the protocols are based on the existing 'Reservation Virtual Time CSMA/CD' protocol, which forms a distributed queue through implicit reservations. This protocol has been improved firstly by utilising two channels, a packet transmission channel and a packet contention channel. Packet contention is then performed in parallel with a packet transmission to increase throughput. The second protocol uses variable length packets to reduce the contention time between transmissions on a single channel. A third protocol developed, is based on contention for explicit reservations. Once a station has achieved a reservation, it maintains this effective queue position for the remainder of the talkspurt and transmits after it has sensed the transmission from the preceeding station within the queue. In the mobile radio environment, adaptions to the protocols were necessary in order that their operation was robust to signal fading. This was achieved through centralised control at a base station, unlike the local area network versions where the control was distributed at the stations. The results show an improvement in throughput compared to some previous protocols. Further work includes subjective testing to validate the protocols' effectiveness.

What is second-order vision for? Discriminating illumination versus material changes

The human visual system is sensitive to second-order modulations of the local contrast (CM) or amplitude (AM) of a carrier signal. Second-order cues are detected independently of first-order luminance signals; however, it is not clear why vision should benet from second-order sensitivity. Analysis of the first-and second-order contents of natural images suggests that these cues tend to occur together, but their phase relationship varies. We have shown that in-phase combinations of LM and AM are perceived as a shaded corrugated surface whereas the anti-phase combination can be seen as corrugated when presented alone or as a flat material change when presented in a plaid containing the in-phase cue. We now extend these findings using new stimulus types and a novel haptic matching task. We also introduce a computational model based on initially separate first-and second-order channels that are combined within orientation and subsequently across orientation to produce a shading signal. Contrast gain control allows the LM + AM cue to suppress responses to the LM-AM when presented in a plaid. Thus, the model sees LM -AM as flat in these circumstances. We conclude that second-order vision plays a key role in disambiguating the origin of luminance changes within an image. © ARVO.

An assessment of the industry cluster approach as a tool for local economic development:the case of the new media industry in Birmingham

Industry cluster policies are a current trend in local economic development programmes and represent a major shift from traditional approaches. This trend has been coupled by an increasing interest in new media industry as a significant focus for regional development strategies. In England clusters and new media industry have therefore come to be seen as important tools in promoting local and regional economic development. This study aimed to ascertain the success of these policies. In order to achieve the aims of the study, the Birmingham new media industry was chosen for the study. In addition to an extensive review of the literature, semi-structured interviews were conducted with new media firms and Business Support Agencies (BSAs) offering programmes to promote the development of the new media industry cluster. The key findings of the thesis are that the concerns of new media industry when choosing their location do not conform to the industry cluster theory. Moreover, close proximity in geographical location of the industries does not mean there is collaboration and any costs saved as a result of close proximity to similar firms are at present seen as irrelevant because of the type of products they offer. Building trust between firms is the key in developing the new media industry cluster and the BSAs can act as a broker and provide neutral ground to develop it. The key policy recommendations are that new media industry is continually changing and research must continuously track and analyse cluster dynamics in order to be aware of emerging trends and future developments that can positively and negatively affect the cluster. Policy makers need to keep in mind that there is no uniform tool kit to foster the different sectors in cluster development. It is also important for them to be winning support and trust of new media firms since this is key in the success of the cluster. When cluster programs are introduced they must explain their benefits to industries more effectively in order to encourage them to participate in programmes. The general conclusions of the thesis are that clusters are a potentially important tool in local economic development policy and that the new media industry has a considerable growth potential. The kinds of relationships which cluster theory suggests develop between do not, as yet, appear to exist within the new media cluster. There are however, steps that the BSAs can take to encourage their development. Thus, the BSAs need to ensure that they establish an environment that enables growth of the industry.

The relationships between a developing regional airport and local commerce and industry

This thesis describes an investigation into a Local Authority's desire to use its airport to aid regional economic growth. Short studies on air freight. the impact of an airport on the local economy, incoming tourism. and the factors influencing airlines in their use of airports, show that this desire is valid. but only in so far as the airport enables air services to be provided. A survey of airlines. conducted to remedy some deficiencies in the documented knowledge on airline decision-making criteria. indicates that there is cause for concern about the methods used to develop air services. A comparison with the West German network suggests that Birmingham is underprovided with international scheduled flights, and reinforces the survey conclusion that an airport authority must become actively involved in the development of air services. Participation in the licence applications of two airlines to use Birmingham Airport confirms the need for involvement but without showing the extent of the influence which an airport authority may exert. The conclusion is reached that in order to fulfill its development potential, an airport must be marketed to both the general public and the air transport industry. There is also a need for a national air services plan.

A study of the aerodynamic characteristics of captor hoods in local exhaust ventilation systems

The research objectives were:- 1.To review the literature to establish the factors which have traditionally been regarded as most crucial to the design of effectlve exhaust ventilation systems. 2. To design, construct, install and calibrate a wind tunnel. 3. To develop procedures for air velocity measurement followed by a comprehensive programme of aerodvnamic data collection and data analysis for a variety of conditions. The major research findings were:- a) The literature in the subject is inadequate. There is a particular need for a much greater understanding of the aerodynamics of the suction flow field. b) The discrepancies between the experimentally observed centre-line velocities and those predicted by conventional formulae are unacceptably large. c) There was little agreement between theoretically calculated and observed velocities in the suction zone of captor hoods. d) Improved empirical formulae for the prediction of centre-line velocity applicable to the classical geometrically shaped suction openings and the flanged condition could be (and were) derived. Further analysis of data revealed that: - i) Point velocity is directly proportional to the suction. flow rate and the ratio of the point velocity to the average face velocity is constant. ii) Both shape, and size of the suction opening are significant factors as the coordinates of their points govern the extent of the effect of the suction flow field. iii) The hypothetical ellipsoidal potential function and hyperbolic streamlines were found experimentally to be correct. iv) The effect of guide plates depends on the size, shape and the angle of fitting. The effect was to very approximately double the suction velocity but the exact effect is difficult to predict. v) The axially symmetric openings produce practically symmetric flow fields. Similarity of connection pieces between the suction opening and the main duct in each case is essential in order to induce a similar suction flow field. Additionally a pilot study was made in which an artificial extraneous air flow was created, measured and its interaction with the suction flow field measured and represented graphically.

Trigger release liposome systems:local and remote controlled delivery?

Target-specific delivery has become an integral area of research in order to increase bioavailability and reduce the toxic effects of drugs. As a drug-delivery option, trigger-release liposomes offer sophisticated targeting and greater control-release capabilities. These are broadly divided into two categories; those that utilise the local environment of the target site where there may be an upregulation in certain enzymes or a change in pH and those liposomes that are triggered by an external physical stimulus such as heat, ultrasound or light. These release mechanisms offer a greater degree of control over when and where the drug is released; furthermore, targeting of diseased tissue is enhanced by incorporation of target-specific components such as antibodies. This review aims to show the development of such trigger release liposome systems and the current research in this field.

Master and apprentice or difference and complementarity? Local government practioners, doctoral studies and co-produced research

In their search for innovative policy solutions to complex social problematics, local governance practitioners will look to synergising specific policy guidance from government departments with conceptual scientific research outputs. UK academics are also now expected to emphasise the relevance of their research and to increase its utilisation by practitioners. Away from utilitarian pressures, academics from applied discipline, such as Public Administration and Local Government Studies are increasingly drawn to the benefits of co-produced research. Despite the pressure for more co-research there are few opportunities for practitioners and academics to nurture relationships that would support close collaboration. This paper looks at the opportunity for closer collaboration when practitioners undertake research degrees, in order to enhance their cognitive skills and develop greater scientific knowledge of particular policy domains. If this route to closer collaboration is to succeed, it will require academics to think differently about their relationship with practitioner-students.

Induced vertical disparity effects on local and global stereopsis

Purpose: Although significant amounts of vertical misalignment could have a noticeable effect on visual performance, there is no conclusive evidence about the effect of very small amount of vertical disparity on stereopsis and binocular vision. Hence, the aim of this study was to investigate the effects of induced vertical disparity on local and global stereopsis at near. Materials and Methods: Ninety participants wearing best-corrected refraction had local and global stereopsis tested with 0.5 and 1.0 prism diopter (Δ) vertical prism in front of their dominant and non-dominant eye in turn. This was compared to local and global stereopsis in the same subjects without vertical prism. Data were analyzed in SPSS.17 software using the independent samples T and the repeated measures ANOVA tests. Results: Induced vertical disparity decreases local and global stereopsis. This reduction is greater when vertical disparity is induced in front of the non-dominant eye and affects global more than local stereopsis. Repeated measures ANOVA showed differences in the mean stereopsis between the different measured states for local and global values. Local stereopsis thresholds were reduced by 10s of arc or less on average with 1.0Δ of induced vertical prism in front of either eye. However, global stereopsis thresholds were reduced by over 100s of arc by the same 1.0Δ of induced vertical prism. Conclusion: Induced vertical disparity affects global stereopsis thresholds by an order of magnitude (or a factor of 10) more than local stereopsis. Hence, using a test that measures global stereopsis such as the TNO is more sensitive to vertical misalignment than a test such as the Stereofly that measures local stereopsis. © 2014 Informa Healthcare USA, Inc. All rights reserved: reproduction in whole or part not permitted.

Hierarchical control and performance regimes in local government

Purpose – The purpose of this paper is to consider hierarchical control as a mode of governance, and analyses the extent of control exhibited by central government over local government through the best value (BV) and comprehensive performance assessment (CPA) performance regimes. Design/methodology/approach – This paper utilises Ouchi's framework and, specifically, his articulation of bureaucratic or hierarchical control in the move towards achievement of organisational objectives. Hierarchical control may be inferred from the extent of “command and control” by Central Government, use of rewards and sanctions, and alignment to government priorities and discrimination of performance. Findings – CPA represents a more sophisticated performance regime than BV in the governance of local authorities by central government. In comparison to BV, CPA involved less scope for dialogue with local government prior to introduction, closer inspection of and direction of support toward poorer performing authorities, and more alignment to government priorities in the weightings attached to service blocks. Originality/value - The paper focuses upon the hierarchic/bureaucratic mode of governance as articulated by Ouchi and expands on this mode in order to analyse shifts in performance regimes in the public sector.

Disaster risk reduction infrastructure requirements for South-Western Bangladesh:perspectives of local communities

Purpose: Development of effective disaster risk reduction (DRR) strategies for communities at risk of being affected by natural disasters is considered essential, especially in the wake of devastating disaster events reported worldwide. As part of a wider research study investigating community perspectives on existing and potential strategies for enhancing resilience to natural disasters, community perspectives on infrastructure and structural protection requirements were investigated. The paper aims to discuss these issues. Design/methodology/approach: Patuakhali region in South-Western Bangladesh is a region significantly at risk of multiple natural hazards. In order to engage local communities and obtain their perspectives, focus group discussions were held with local community leaders and policy makers of at-risk communities in Patuakhali region, South-Western Bangladesh. Findings: Infrastructure and structural protection requirements highlighted included multi-purpose cyclone shelters, permanent embankments and improved transport infrastructure. Much of the discussions of focus group interviews were focused on cyclone shelters and embankments, suggesting their critical importance in reducing disaster risk and also dependence of coastal communities on those two measures. Originality/value: The research design adopted sought to answer the research questions raised and also to inform local policy makers on community perspectives. Local policy makers involved in DRR initiatives in the region were informed of community perspectives and requirements, thus contributing to community engagement in implementing DRR activities.