Atom transfer radical polymerisation - towards the synthesis of a fully-functional photorefractive polymer

Atom transfer radical polymerisation (ATRP) of styrene in xylene solution initiated with 1-phenylethyl bromide and mediated by CuBr/N-propyl-2- pyridinemethanimine catalyst complex was studied. The polymerisation was ill-controlled, yielding polymers with broad molecular weight distributions and values of number average molecular weight considerably higher than the theoretical values calculated from 100% initiator efficiency. The degree of control afforded over the polymerisation was enhanced by use of a more soluble catalyst complex, CuBr/N-octyl-2-pyridinemethanimine. Furthermore, the use of a more polar solvent, diglyme, generated a homogeneous catalyst complex that facilitated the production of polymers having narrow molecular weight distributions (1.10 < PDi < 1.20). The kinetics of the atom transfer radical polymerisation of methyl methacrylate at 90°C in diglyme solution initiated with ethyl-2-bromoisobutyrate and mediated by CuBr/N-octyl-2-pyridinemethanimine was studied and the orders of the reaction were established. The effect on the rate of polymerisation of the ratio of CuBr:N-octyl-2-pyridinemethanimine was also determined. The temperature dependencies of the rate of polymerisation of methyl methacrylate in diglyme solution and xylene solution were studied, and were found to be non-linear and dependent upon the polarity of the solvent. The use of highly polar aprotic solvents, such as N,N-dimethylformamide and dimethylsulphoxide, was found to be detrimental to the degree of control afforded over the polymerisation of methyl methacrylate. This was circumvented by use of a 5-fold excess, over that conventionally used, of catalyst complex. The atom transfer radical polymerisation of (4-nitrophenyl)-[3-[N-[2- (methacryloyloxy)ethyl]carbazolyl]]diazene in dimethyl sulphoxide solution was studied. Although homopolymerisation yielded only oligomers, copolymerisation of this monomer with methyl methacrylate was found to be readily achievable. Keywords: ATRP, Styrene; Methyl methacrylate; Polar solvents; Fully-functional photorefractive polymer. 2

The structural permeability of concrete at cryogenic temperatures

The thesis describes a programme of research designed to identify concretes for application at cryogenic temperature, in particular for storage of Liquefield Natural Gas which is maintained at a temperature of -165oC. The programme was undertaken in two stages. Stage 1 involved screening tests on seventeen concrete mixes to investigate the effects of strength grade (and water/cement ratio), air entrainment, aggregate type and cement type. Four mixes were selected on the basis of low temperature strength, residual strength after thermal cycling and permeability at ambient temperature. In Stage 2 the selected mixes were subjected to a comprehensive range of tests to measure those properties which determine the leak tightness of a concrete tank at temperatures down to -165oC. These included gas permeability; tensile strength, strain capacity, thermal expansion coefficient and elastic modulus, which in combination provide a measure of resistance to cracking; and bond to reinforcement, which is one of the determining factors regarding crack size and spacing. The results demonstrated that the properties of concrete were generally enhanced at cryogenic temperature, with reduced permeability, reduced crack proneness and, by virtue of increased bond to reinforcement, better control of cracking should it occur. Of the concretes tested, a lightweight mix containing sintered PFA aggregate exhibited the best performance at ambient and cryogenic temperature, having appreciably lower permeability and higher crack resistance than normal weight concretes of the same strength grade. The lightweight mix was most sensitive to thermal cycling, but there was limited evidence that this behaviour would not be significant if the concrete was prestressed. Relationships between various properties have been identified, the most significant being the reduction in gas permeability with increasing strain capacity. The structural implications of the changing properties of the concrete have also been considered.

The formation and impact of hazard control policy:a study of the regulation of white lead paint in Britain

Government regulation of industrial hazards is examined in the context of the economic and technical processes of industrial development. Technical problems and costs of control are considered as factors in both the formation and impact of regulation. This thesis focuses on an historical case-study of the regulation of the hazard to painting workers from the use of lead pigments in paint. A regulatory strategy based on the prohibition of lead paints gained initial acceptance within the British state in 1911, but was subsequently rejected in favour of a strategy that allowed continued use of lead paint subject to hygiene precautions. The development of paint technology and its determinants, including concern about health hazards, are analysed, focusing on the innovation and diffusion into the paint industry of the major white pigments: white lead (PbC03 .PB(OH)2)and its substitutes. The process of regulatory development is examined, and the protracted and polarised regulatory d~bate contrasted to the prevailing 'consensual' methods of workplace regulation. The rejection of prohibition is analysed in terms of the different political and technical resources of those groups in conflict over this policy. This highlights the problems of consensus formation around such a strategy, and demonstrates certain constraints on state regulatory activity, particularly regarding industrial development. Member-states of the International Labour Organisation agreed to introduce partial prohibition of lead paint in 1921. Whether this was implemented is related to the economic importance of lead and non-lead metal and pigment industries to a nation. An analysis is made of the control of lead poisoning. The rate of control is related to the economic and technological trajectory of the regulated industry. Technical and organisational characteristics are considered as well as regulatory factors which range from voluntary compliance and informal pressures to direct legal requirements. The implications of this case-study for the analysis of the development and impacts of regulation are assessed.

Modelling manufacturing planning and control systems:the application of object-oriented principles and discrete-event simulation

Manufacturing planning and control systems are fundamental to the successful operations of a manufacturing organisation. 10 order to improve their business performance, significant investment is made by companies into planning and control systems; however, not all companies realise the benefits sought Many companies continue to suffer from high levels of inventory, shortages, obsolete parts, poor resource utilisation and poor delivery performance. This thesis argues that the fit between the planning and control system and the manufacturing organisation is a crucial element of success. The design of appropriate control systems is, therefore, important. The different approaches to the design of manufacturing planning and control systems are investigated. It is concluded that there is no provision within these design methodologies to properly assess the impact of a proposed design on the manufacturing facility. Consequently, an understanding of how a new (or modified) planning and control system will perform in the context of the complete manufacturing system is unlikely to be gained until after the system has been implemented and is running. There are many modelling techniques available, however discrete-event simulation is unique in its ability to model the complex dynamics inherent in manufacturing systems, of which the planning and control system is an integral component. The existing application of simulation to manufacturing control system issues is limited: although operational issues are addressed, application to the more fundamental design of control systems is rarely, if at all, considered. The lack of a suitable simulation-based modelling tool does not help matters. The requirements of a simulation tool capable of modelling a host of different planning and control systems is presented. It is argued that only through the application of object-oriented principles can these extensive requirements be achieved. This thesis reports on the development of an extensible class library called WBS/Control, which is based on object-oriented principles and discrete-event simulation. The functionality, both current and future, offered by WBS/Control means that different planning and control systems can be modelled: not only the more standard implementations but also hybrid systems and new designs. The flexibility implicit in the development of WBS/Control supports its application to design and operational issues. WBS/Control wholly integrates with an existing manufacturing simulator to provide a more complete modelling environment.

Cost and time control of construction project: inhibiting factors and mitigating measures in practice

Despite the availability of various control techniques and project control software many construction projects still do not achieve their cost and time objectives. Research in this area so far has mainly been devoted to identifying causes of cost and time overruns. There is limited research geared towards studying factors inhibiting the ability of practitioners to effectively control their projects. To fill this gap, a survey was conducted on 250 construction project organizations in the UK, which was followed by face-to-face interviews with experienced practitioners from 15 of these organizations. The common factors that inhibit both time and cost control during construction projects were first identified. Subsequently 90 mitigating measures have been developed for the top five leading inhibiting factors—design changes, risks/uncertainties, inaccurate evaluation of project time/duration, complexities and non-performance of subcontractors were recommended. These mitigating measures were classified as: preventive, predictive, corrective and organizational measures. They can be used as a checklist of good practice and help project managers to improve the effectiveness of control of their projects.

Cost and time control of construction projects: a survey of contractors and consultants in the UK

Numerous techniques have been developed to control cost and time of construction projects. However, there is limited research on issues surrounding the practical usage of these techniques. To address this, a survey was conducted on the top 150 construction companies and 100 construction consultancies in the UK aimed at identifying common project control practices and factors inhibiting effective project control in practice. It found that despite the vast application of control techniques a high proportion of respondents still experienced cost and time overruns on a significant proportion of their projects. Analysis of the survey results concluded that more effort should be geared at the management of the identified top project control inhibiting factors. This paper has outlined some measures for mitigating these inhibiting factors so that the outcome of project time and cost control can be improved in practice.

Does child weight influence how mothers report their feeding practices?

Objectives. The present study aimed to ascertain whether parental reports of their feeding practices are associated with independent observations of these behaviours, and whether the reliability of maternal report depends upon the child's weight. Methods. A total of 56 mothers and their children ate a lunch to satiety which was videotaped and coded for maternal use of control during feeding. Mothers also completed questionnaires about their feeding practices and children were weighed and measured. Results. Maternal reports of controlling feeding practices were poorly related to independent observations of these behaviours in the laboratory. However, there was a significant interaction between child BMI z score and observed pressure to eat in predicting maternally reported pressure to eat. There was also a significant interaction between child BMI z score and observed maternal restriction with food in predicting maternally reported restriction. When decomposed, these interactions suggested that only mothers of relatively underweight children were accurate at reporting their use of pressure to eat when compared to independent observations. For mothers of relatively overweight children there was a significant negative relationship between observed and reported restriction over food. Conclusions. Overall there was poor correspondence between maternal reports and independent observations of the use of controlling feeding practices. Further research is needed to replicate these findings and to ascertain whether parents who are inaccurate at reporting their use of these feeding practices are unaware that they are using controlling feeding practices or whether they are responding in socially desirable ways to questionnaires assessing their feeding behaviour. © 2011 Informa Healthcare.

Control of spatiotemporal chaos in catalytic CO oxidation by laser-induced pacemakers

Control of spatiotemporal chaos is achieved in the catalytic oxidation of CO on Pt(110) by localized modification of the kinetic properties of the surface chemical reaction. In the experiment, a small temperature heterogeneity is created on the surface by a focused laser beam. This heterogeneity constitutes a pacemaker and starts to emit target waves. These waves slowly entrain the medium and suppress the spatiotemporal chaos that is present in the absence of control. We compare this experimental result with a numerical study of the Krischer-Eiswirth-Ertl model for CO oxidation on Pt(110). We confirm the experimental findings and identify regimes where complete and partial controls are possible.

Milk feeding, solid feeding, and obesity risk:a review of the relationships between early life feeding practices and later adiposity

Childhood obesity is a major health issue with associated ill-health consequences during childhood and into later adolescence and adulthood. Given that eating behaviors are formed during early childhood, it is important to evaluate the relationships between early life feeding practices and later child adiposity. This review describes and evaluates recent literature exploring associations between child weight and the mode of milk feeding, the age of introducing solid foods and caregivers’ solid feeding practices. There are many inconsistencies in the literature linking early life feeding to later obesity risk and discrepancies may be related to inconsistent definitions, or a lack of control for confounding variables. This review summarizes the literature in this area and identifies the need for large scale longitudinal studies to effectively explore how early life feeding experiences may interact with each other and with nutritional provision during later childhood to predict obesity risk.

Increased expression of proteasome subunits in skeletal muscle of cancer patients with weight loss

Atrophy of skeletal muscle is common in patients with cancer and results in increased morbidity and mortality. In order to design effective therapy the mechanism by which this occurs needs to be elucidated. Most studies suggest that the ubiquitin-proteasome proteolytic pathway is most important in intracellular proteolysis, although there have been no reports on the activity of this pathway in patients with different extents of weight loss. In this report the expression of the ubiquitin-proteasome pathway in rectus abdominis muscle has been determined in cancer patients with weight loss of 0-34% using a competitive reverse transcriptase polymerase chain reaction to measure expression of mRNA for proteasome subunits C2 and C5, while protein expression has been determined by western blotting. Overall, both C2 and C5 gene expression was increased by about three-fold in skeletal muscle of cachectic cancer patients (average weight loss 14.5 ± 2.5%), compared with that in patients without weight loss, with or without cancer. The level of gene expression was dependent on the amount of weight loss, increasing maximally for both proteasome subunits in patients with weight loss of 12-19%. Further increases in weight loss reduced expression of mRNA for both proteasome subunits, although it was still elevated in comparison with patients with no weight loss. There was no evidence for an increase in expression at weight losses less than 10%. There was a good correlation between expression of proteasome 20Sα subunits, detected by western blotting, and C2 and C5 mRNA, showing that increased gene expression resulted in increased protein synthesis. Expression of the ubiquitin conjugating enzyme, E214k, with weight loss followed a similar pattern to that of proteasome subunits. These results suggest variations in the expression of key components of the ubiquitin-proteasome pathway with weight loss of cancer patients, and suggest that another mechanism of protein degradation must be operative for patients with weight loss less than 10%. © 2004 Elsevier Ltd. All rights reserved.

Probabilistic synchronisation of pinning control

This paper is concerned with synchronization of complex stochastic dynamical networks in the presence of noise and functional uncertainty. A probabilistic control method for adaptive synchronization is presented. All required probabilistic models of the network are assumed to be unknown therefore estimated to be dependent on the connectivity strength, the state and control values. Robustness of the probabilistic controller is proved via the Liapunov method. Furthermore, based on the residual error of the network states we introduce the definition of stochastic pinning controllability. A coupled map lattice with spatiotemporal chaos is taken as an example to illustrate all theoretical developments. The theoretical derivation is complemented by its validation on two representative examples.

Teaching our children when to eat:how parental feeding practices inform the development of emotional eating-a longitudinal experimental design

Background: Emotional eating in children has been related to the consumption of energy-dense foods and obesity, but the development of emotional eating in young children is poorly understood. Objectives: We evaluated whether emotional eating can be induced in 5-7-y-old children in the laboratory and assessed whether parental use of overly controlling feeding practices at 3-5 y of age predicts a greater subsequent tendency for children to eat under conditions of mild stress at ages 5-7 y. Design: Forty-one parent-child dyads were recruited to participate in this longitudinal study, which involved parents and children being observed consuming a standard lunch, completing questionnaire measures of parental feeding practices, participating in a research procedure to induce child emotion (or a control procedure), and observing children's consumption of snack foods. Results: Children at ages 5-7 y who were exposed to a mild emotional stressor consumed significantly more calories from snack foods in the absence of hunger than did children in a control group. Parents who reported the use of more food as a reward and restriction of food for health reasons with their children at ages 3-5 y were more likely to have children who ate more under conditions of negative emotion at ages 5-7 y. Conclusions: Parents who overly control children's food intake may unintentionally teach children to rely on palatable foods to cope with negative emotions. Additional research is needed to evaluate the implications of these findings for children's food intake and weight outside of the laboratory setting. This trial was registered at clinicaltrials.gov as NCT01122290.

Classification of Maximal Optical Orthogonal Codes of Weight 3 and Small Lengths

Dedicated to the memory of the late professor Stefan Dodunekov on the occasion of his 70th anniversary. We classify up to multiplier equivalence maximal (v, 3, 1) optical orthogonal codes (OOCs) with v ≤ 61 and maximal (v, 3, 2, 1) OOCs with v ≤ 99. There is a one-to-one correspondence between maximal (v, 3, 1) OOCs, maximal cyclic binary constant weight codes of weight 3 and minimum dis tance 4, (v, 3; ⌊(v − 1)/6⌋) difference packings, and maximal (v, 3, 1) binary cyclically permutable constant weight codes. Therefore the classification of (v, 3, 1) OOCs holds for them too. Some of the classified (v, 3, 1) OOCs are perfect and they are equivalent to cyclic Steiner triple systems of order v and (v, 3, 1) cyclic difference families.

Fenntarthatósági szempontok beépítése a beszállító értékelésébe a DEA/CI összetett indikátorok módszere alkalmazásával (Integrating sustainability criteria in supplier evaluation with application of the method of of DEA/CI complex indicators)

A környezeti hatások rendszerint túlmutatnak egy vállalat határain, éppen ezért az ellátási lánc kontextusban a környezeti szempontok érvényesítése során fontos szerep jut a beszerzési döntéseknek is. Számos olyan példát lehetne említeni, amikor egy adott szempont szerint egy alternatíva környezetileg előnyös, de az ellátási lánc egészét nézve már környezetterhelő. A környezeti hatások ellátási lánc szinten való mérése azonban komoly kihívásokat jelent. Ezzel jelentős kutatásokat és fejlesztéseket inspirált a téma. Az egyik olyan terület, amelyben komoly kutatási eredmények születtek, az a környezeti szempontok beszállítói értékelésbe való beépítése. A kutatások ezen irányához csatlakozva a szerzők tanulmányunkban azt keresik, hogyan lehet meghatározni az egyik legáltalánosabban használt szállítóértékelési módszerben, a súlyozott pontrendszerben egy adott szemponthoz azt a súlyt, amely mellett az adott szempont már döntésbefolyásoló tényezővé válik. Ehhez a DEA (Data Envelopment Analysis) összetett indikátorok (Composite Indicators, CI) módszerét alkalmazzák. A szempontok közös súlyának fontossága megállapításához a lineáris programozás elméletét használják. _____ Management decisions often have an environmental effect not just within the company, but outside as well, this is why supply chain context is highlighted in literature. Measuring environmental issues of supply decisions raise a lot of problems from methodological and practical point of view. This inspires a rapidly growing literature as a lot of studies were published focusing on how to incorporate environmental issues into supplier evaluation. This paper contributes to this stream of research as it develops a method to help weight selection. In the authors’ paper the method of Data Envelope Analysis (DEA) is used to study the extension of traditional supplier selection methods with environmental factors. The selection of the weight system can control the result of the selection process.

A deontic analysis of inter -organizational control requirements

This research focuses on the design and verification of inter-organizational controls. Instead of looking at a documentary procedure, which is the flow of documents and data among the parties, the research examines the underlying deontic purpose of the procedure, the so-called deontic process, and identifies control requirements to secure this purpose. The vision of the research is a formal theory for streamlining bureaucracy in business and government procedures. ^ Underpinning most inter-organizational procedures are deontic relations, which are about rights and obligations of the parties. When all parties trust each other, they are willing to fulfill their obligations and honor the counter parties’ rights; thus controls may not be needed. The challenge is in cases where trust may not be assumed. In these cases, the parties need to rely on explicit controls to reduce their exposure to the risk of opportunism. However, at present there is no analytic approach or technique to determine which controls are needed for a given contracting or governance situation. ^ The research proposes a formal method for deriving inter-organizational control requirements based on static analysis of deontic relations and dynamic analysis of deontic changes. The formal method will take a deontic process model of an inter-organizational transaction and certain domain knowledge as inputs to automatically generate control requirements that a documentary procedure needs to satisfy in order to limit fraud potentials. The deliverables of the research include a formal representation namely Deontic Petri Nets that combine multiple modal logics and Petri nets for modeling deontic processes, a set of control principles that represent an initial formal theory on the relationships between deontic processes and documentary procedures, and a working prototype that uses model checking technique to identify fraud potentials in a deontic process and generate control requirements to limit them. Fourteen scenarios of two well-known international payment procedures—cash in advance and documentary credit—have been used to test the prototype. The results showed that all control requirements stipulated in these procedures could be derived automatically.^