The ring opening polymerization of ring strained cyclic ethers

The kinetics and mechanisms of the ring-opening polymerization of oxetane were studied using cationic and coordinated anionic catalysts. The cationic initiators used were BF30Et2!/ethanol, BF30Et2!/ethanediol and BF30Et2/propantriol. Kinetic determinations with the BF30Et2/diol system indicated that a 1: 1 BF3:0H ratio gave the maximum rate of polymerization and this ratio was employed to detenmne the overall rates of polymerization. An overall second-order dependence was obtained when the system involved ethanediol or propantriol as co-catalyst and a 3/2-order dependence with ethanol, in each case the monomer gave a first-order relationship. This suggested that two mechanisms accounted for the cationic polymerization. These mechanisms were investigated and further evidence for these was obtained from the study of the complex formation of BF30Et2 and the co-catalysts by 1H NMR. Molecular weight studies (using size-exclusion chromatography) indicated that the hydroxyl ion acted as a chain transfer reagent when the [OH] > [BF3]. A linear relationship was observed when the number average molecular weight was plotted against [oxetane] at constant [BF3:0H], and similarly a linear dependency was observed on the BF3:0H 1:1 adduct at constant oxetane concentration. Copolymerization of oxetane and THF was carried out using BF30Et2/ethanol system. The reactivity ratios were calculated as rOXT = 1.2 ± 0.30 and rTHF = 0.14 ± 0.03. These copolymers were random copolymers with no evidence of oligomer formation. The coordinated anionic catalyst, porphinato-aluminium chloride [(TPP)AICl], was used to produce a living polymerization of oxetane. An overall third-order kinetics was obtained, with a second-order with respect to the [(TPP)AICl] and a first-order with respect to the [oxetane] and a mechanism was postulated using these results. The stereochemistry of [(TPP)AlCl] catalyst was investigated using cyclohexene and cyclopentene oxide monomers, using extensive 1H NMR, 2-D COSY and decoupling NMR techniques it was concluded that [(TPP)AlCl] gave rise to stereoregular polymers.

Flexible high speed machinery

The thesis describes an investigation into methods for the design of flexible high-speed product processing machinery, consisting of independent electromechanically actuated machine functions which operate under software coordination and control. An analysis is made of the elements of traditionally designed cam-actuated, mechanically coupled machinery, so that the operational functions and principal performance limitations of the separate machine elements may be identified. These are then used to define the requirements for independent actuators machinery, with a discussion of how this type of design approach is more suited to modern manufacturing trends. A distributed machine controller topology is developed which is a hybrid of hierarchical and pipeline control. An analysis is made, with the aid of dynamic simulation modelling, which confirms the suitability of the controller for flexible machinery control. The simulations include complex models of multiple independent actuators systems, which enable product flow and failure analyses to be performed. An analysis is made of high performance brushless d.c. servomotors and their suitability for actuating machine motions is assessed. Procedures are developed for the selection of brushless servomotors for intermittent machine motions. An experimental rig is described which has enabled the actuation and control methods developed to be implemented. With reference to this, an evaluation is made of the suitability of the machine design method and a discussion is given of the developments which are necessary for operational independent actuators machinery to be attained.

The relationship between measurement method and corneal structure on apparent intraocular pressure in glaucoma and ocular hypertension

Purpose: To analyse the relationship between measured intraocular pressure (IOP) and central corneal thickness (CCT), corneal hysteresis (CH) and corneal resistance factor (CRF) in ocular hypertension (OHT), primary open-angle (POAG) and normal tension glaucoma (NTG) eyes using multiple tonometry devices. Methods: Right eyes of patients diagnosed with OHT (n=47), normal tension glaucoma (n=17) and POAG (n=50) were assessed, IOP was measured in random order with four devices: Goldmann applanation tonometry (GAT); Pascal(R) dynamic contour tonometer (DCT); Reichert(R) ocular response analyser (ORA); and Tono-Pen(R) XL. CCT was then measured using a hand-held ultrasonic pachymeter. CH and CRF were derived from the air pressure to corneal reflectance relationship of the ORA data. Results: Compared to the GAT, the Tonopen and ORA Goldmann equivalent (IOPg) and corneal compensated (IOPcc) measured higher IOP readings (F=19.351, p<0.001), particularly in NTG (F=12.604, p<0.001). DCT was closest to Goldmann IOP and had the lowest variance. CCT was significantly different (F=8.305, p<0.001) between the 3 conditions as was CH (F=6.854, p=0.002) and CRF (F=19.653, p<0.001). IOPcc measures were not affected by CCT. The DCT was generally not affected by corneal biomechanical factors. Conclusion: This study suggests that as the true pressure of the eye cannot be determined non-invasively, measurements from any tonometer should be interpreted with care, particularly when alterations in the corneal tissue are suspected.

Factors affecting corneoscleral topography

PURPOSE: To evaluate factors affecting corneoscleral profile (CSP) using Anterior Segment Optical Coherence Tomography (AS-OCT) in combination with conventional videokeratoscopy. METHODS: OCT data were collected from 204 subjects of mean age 34.9 years (SD: ±15.2 yrs, range 18 to 65) using the Zeiss Visante AS-OCT and Medmont M300 corneal topographer. Measurements of corneal diameter (CD), corneal sagittal height (CS), iris diameter (ID), corneoscleral junction angle (CSJ) and scleral radius (SR) were extracted from multiple OCT images. Horizontal visible iris diameter (HVID) and vertical palpebral aperture (PA) were measured using a slit lamp graticule. Subject body height was also measured. Associations were then sought between CSP variables and age, height, ethnicity, sex and refractive error data collected. Results: Significant correlations were found between age and ocular topography variables of HVID, PA, CSJ, SR and ID (P<0.0001), while height correlated with HVID, CD and ID, and power vector terms only with vertical plane keratometry, CD and CS. Significant differences were noted between ethnicities with respect to CD (P=0.0046), horizontal and vertical CS (P=0.0068 and P=0.0095), and also horizontal ID (P=0.0010), while the same variables, with the exception of vertical CS, also varied with sex; horizontal CD (P=0.0018), horizontal CS (P=0.0018) and ID (P=0.0012). Age accounted for up to 36% of the variance in CSP variables. Conclusion: Age is the main factor influencing corneoscleral topography; consequently, this should be taken into consideration in contact lens design, in the optimization of surgical procedures involving the cornea and sclera and in IOL selection.

Individual spirit at work and its outcomes:an empirical examination in corporate Thailand

The purpose of the present study was to conduct empirical research in corporate Thailand in order to (1) investigate the relationships between individual spirit at work and three employee work attitudinal variables (organisational identification, job satisfaction and psychological well-being) and three organisational outcomes (in-role performance, organisational citizenship behaviours (OCB), and turnover intentions) (2) further examine causal relations among these organisational behaviour variables with a longitudinal design (3) examine three employee work attitudes as mediator variables between individual spirit at work and three organisational outcomes and (4) explore the potential antecedents of organisational conditions that foster employee experienced individual spirit at work. The 715 completed questionnaires were received from the first wave of data collection during July 2008 and the second wave was conducted again within the same organisations and 501 completed questionnaires were received during April 2009. Data were obtained through 52 organisations which were from three types of organisations within Thailand: public organisations (N=237,185), for-profit organisations (N=244,155), and not-for-profit organisations (N=234,161). Confirmatory factor analysis of all measures used in the study and hypothesized model were tested with structural equation modeling techniques. Results were strongly supportive. In addition, although the model was invariant across rater of performance and OCB, there were differences across self report and supervisor rating. Additionally, the antecedents of organisational conditions that fostered employees experienced individual spirit at work and the implications of these findings for practice and research are discussed.

Describing and communicating uncertainty within the semantic web

The Semantic Web relies on carefully structured, well defined, data to allow machines to communicate and understand one another. In many domains (e.g. geospatial) the data being described contains some uncertainty, often due to incomplete knowledge; meaningful processing of this data requires these uncertainties to be carefully analysed and integrated into the process chain. Currently, within the SemanticWeb there is no standard mechanism for interoperable description and exchange of uncertain information, which renders the automated processing of such information implausible, particularly where error must be considered and captured as it propagates through a processing sequence. In particular we adopt a Bayesian perspective and focus on the case where the inputs / outputs are naturally treated as random variables. This paper discusses a solution to the problem in the form of the Uncertainty Markup Language (UncertML). UncertML is a conceptual model, realised as an XML schema, that allows uncertainty to be quantified in a variety of ways i.e. realisations, statistics and probability distributions. UncertML is based upon a soft-typed XML schema design that provides a generic framework from which any statistic or distribution may be created. Making extensive use of Geography Markup Language (GML) dictionaries, UncertML provides a collection of definitions for common uncertainty types. Containing both written descriptions and mathematical functions, encoded as MathML, the definitions within these dictionaries provide a robust mechanism for defining any statistic or distribution and can be easily extended. Universal Resource Identifiers (URIs) are used to introduce semantics to the soft-typed elements by linking to these dictionary definitions. The INTAMAP (INTeroperability and Automated MAPping) project provides a use case for UncertML. This paper demonstrates how observation errors can be quantified using UncertML and wrapped within an Observations & Measurements (O&M) Observation. The interpolation service uses the information within these observations to influence the prediction outcome. The output uncertainties may be encoded in a variety of UncertML types, e.g. a series of marginal Gaussian distributions, a set of statistics, such as the first three marginal moments, or a set of realisations from a Monte Carlo treatment. Quantifying and propagating uncertainty in this way allows such interpolation results to be consumed by other services. This could form part of a risk management chain or a decision support system, and ultimately paves the way for complex data processing chains in the Semantic Web.

Can illness perceptions and coping predict psychological distress amongst allergy sufferers?

Objective. The aim of the present study was to measure the extent to which illness perceptions and coping strategies are associated with the levels of psychological distress amongst allergy sufferers. Design and method. One hundred and fifty-six allergy sufferers (all members of Allergy U.K.) completed a postal survey consisting of the Revised Illness Perception Questionnaire (IPQ-R) and the COPE. Psychological distress was measured using the General Health Questionnaire (GHQ-28) and the Perceived Stress Scale (PSS). Results. Multiple regression analyses indicated that illness perceptions explained between 6 and 26% of variance on measures of psychological distress; coping strategies explained between 12 and 25%. A strong illness identity and emotional representations of the allergy were associated with higher levels of psychological distress; as were less adaptive coping strategies such as focusing on and venting of emotions. Strong personal control beliefs were associated with the lower levels of distress, as were adaptive coping strategies such as positive reinterpretation and growth. Coping partially mediated the link between the illness perceptions and the outcome; however, illness identity, emotional representations and personal control retained an independent significant association with psychological distress. Conclusion. The findings support a role for illness perceptions and coping in explaining levels of psychological distress amongst allergy sufferers. This has implications for targeted health interventions aimed at reducing the strength of illness identity and emotional representations and increasing a sense of control and the use of more adaptive coping strategies.

Secure key distribution over a 500 km long link using a Raman ultra-long fiber laser

In traditional communication systems the transmission medium is considered as a given characteristic of the channel, which does not depend on the properties of the transmitter and the receiver. Recent experimental demonstrations of the feasibility of extending the laser cavity over the whole communication link connecting the two parties, forming an ultra-long fiber laser (UFL), have raised groundbreaking possibilities in communication and particularly in secure communications. Here, a 500 km long secure key distribution link based on Raman gain UFL is demonstrated. An error-free distribution of a random key with an average rate of 100 bps between the users is demonstrated and the key is shown to be unrecoverable to an eavesdropper employing either time or frequency domain passive attacks. In traditional communication systems the transmission medium is considered as a given characteristic of the channel, which does not depend on the properties of the transmitter and the receiver. Recent demonstrations of the feasibility of extending the laser cavity over the whole communication link connecting the two parties, forming an ultra-long fiber laser (UFL), have raised groundbreaking possibilities in communication. Here, a 500 km long secure key distribution link based on Raman gain UFL is demonstrated. © 2014 by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Site-restricted web searches for data collection in regional dialectology

This article presents a new method for data collection in regional dialectology based on site-restricted web searches. The method measures the usage and determines the distribution of lexical variants across a region of interest using common web search engines, such as Google or Bing. The method involves estimating the proportions of the variants of a lexical alternation variable over a series of cities by counting the number of webpages that contain the variants on newspaper websites originating from these cities through site-restricted web searches. The method is evaluated by mapping the 26 variants of 10 lexical variables with known distributions in American English. In almost all cases, the maps based on site-restricted web searches align closely with traditional dialect maps based on data gathered through questionnaires, demonstrating the accuracy of this method for the observation of regional linguistic variation. However, unlike collecting dialect data using traditional methods, which is a relatively slow process, the use of site-restricted web searches allows for dialect data to be collected from across a region as large as the United States in a matter of days.

Secret key exchange in ultra-long lasers by radio-frequency spectrum coding

We propose a new approach to the generation of an alphabet for secret key exchange relying on small variations in the cavity length of an ultra-long fiber laser. This new concept is supported by experimental results showing how the radio-frequency spectrum of the laser can be exploited as a carrier to exchange information. The test bench for our proof of principle is a 50 km-long fiber laser linking two users, Alice and Bob, where each user can randomly add an extra 1 km-long segment of fiber. The choice of laser length is driven by two independent random binary values, which makes such length become itself a random variable. The security of key exchange is ensured whenever the two independent random choices lead to the same laser length and, hence, to the same free spectral range.

The potential for pharmacists to manage children attending emergency departments

AIM: There have been concerns about maintaining appropriate clinical staff levels in Emergency Departments in England.1 The aim of this study was to determine if Emergency Department attendees aged from 0-16 years could be managed by community pharmacists or hospital independent prescriber pharmacists with or without further advanced clinical practice training. METHOD: A prospective, 48 site, cross-sectional, observational study of patients attending Emergency Departments (ED) in England, UK was conducted. Pharmacists at each site collected up to 400 admissions and paediatric patients were included in the data collection. The pharmacist independent prescribers (one for each site) were asked to identify patient attendance at their Emergency Department, record anonymised details of the cases-age, weight, presenting complaint, clinical grouping (e.g. medicine, orthopaedics), and categorise each presentation into one of four possible categories: CP, Community Pharmacist, cases which could be managed by a community pharmacist outside an ED setting; IP-cases that could be managed at ED by a hospital pharmacist with independent prescriber status; IPT, Independent Prescriber Pharmacist with additional training-cases which could be managed at ED by a hospital pharmacist independent prescriber with additional clinical training; and MT, Medical Team only-cases that were unsuitable for the pharmacist to manage. An Impact Index was calculated for the two most frequent clinical groupings using the formula: Impact index=percentage of the total workload of the clinical grouping multiplied by the percentage ability of pharmacists to manage that clinical group. RESULTS: 1623 out of 18,229 (9%) attendees, from 45 of the 48 sites, were children aged from 0 to 16 years of age (median 8 yrs, range 0-16), 749 were female and 874 were male. Of the 1623 admissions, 9% of the cases were judged to be suitable for clinical management by a community pharmacist (CP), 4% suitable for a hospital pharmacist independent prescriber (IP), 32% suitable for a hospital independent pharmacist prescriber with additional training (IPT); and the remaining 55% were only suitable for the Medical Team (MT). The most frequent clinical groups and impact index for the attendees were General Medicine=10.78 and orthopaedics=10.60. CONCLUSION: Paediatric patients attending Emergency Departments were judged by pharmacists to be suitable for management outside a hospital setting in approximately 1 in 11 cases, and by hospital independent prescriber pharmacists in 4 in 10 cases. With further training, it was found that the total proportion of cases that could be managed by a pharmacist was 45%. The greatest impact for pharmacist management occurs in general medicine and orthopaedics.