Time controlled photo-oxidation of polyolefins by polymer bound additives

A variety of iron compounds containing vinyl or thiol functional groups (used as photoactivators) have been synthesised and some of these were successfully bound to both polyethylene and polypropylene backbones during processing in the presence of peroxide and interlinking agent. Concentrates (masterbatches) of the photoactivators in PP and PE were prepared and the pro-oxidant effect of the diluted masterbatches in absence and presence of an antioxidant was evaluated. An antioxidant photoactivator (FeDNC ) was found to sensitise the photoactivity of pro-oxidants (Metone A / Metone M) whereas an antioxidant (ZnDNC) was found to stabilise the polymer (PP and PE) containing both of these combinations. It was observed that the lower concentration of FeDNC sensitises the stability of the polymer containing very small concentration of NiDNC whereas higher concentration of FeDNC stabilises the polymer (LDPE) containing same amount of NiDNC compared to FeDNC alone. The photostability of unstabilised PP containing FeAc could be varied by varying the concentration of ZnDEC. Both the induction period and the UV - life time of the polymer increased by increasing concentration of ZnDEC. It is suggested that ligand exchange reaction may take place between FeAc and ZnDNC. A polymer bound UV stabiliser (HAEB) and a thermal stabiliser (DBBA) were used with a non extractable photoactivator (FeAc) in PP. Small concentrations of the stabilisers (HAEB and DBBA) in combination with the photoactivator (FeAc) sensitise the polymer. The antioxidant present in commercial polymer (LDPE and PP) was found to be of a hindered phenol type, which was found to antagonise with ZnDNC when used in combination with the photoactivators.

The effects of varying forms and degrees of government intervention upon the effective competitiveness of UK small businesses

This doctoral thesis responds to the need for greater understanding of small businesses and their inherent unique problem-types. Integral to the investigation is the theme that for governments to effectively influence small business, a sound understanding of the factors they are seeking to influence is essential. Moreover, the study, in its recognition of the many shortcomings in management research and, in particular that the research methods and approaches adopted often fail to give adequate understanding of issues under study, attempts to develop an innovative and creative research approach. The aim thus being to produce, not only advances in small business management knowledge from the standpoints of government policy makers and `lq recipient small business, but also insights into future potential research method for the continued development of that knowledge. The origins of the methodology lay in the non-acceptance of traditional philosophical positions in epistemology and ontology, with a philosophical standpoint of internal realism underpinning the research. Internal realism presents the basis for the potential co-existence of qualitative and quantitative research strategy and underlines the crucial contributory role of research method in provision of ultimate factual status of the assertions of research findings. The concept of epistemological bootstrapping is thus used to develop a `lq partial research framework to foothold case study research, thereby avoiding limitations of objectivism and brute inductivism. The major insights and issues highlighted by the `lq bootstrap, guide the researcher around the participant case studies. A novel attempt at contextualist (linked multi-level and processual) analysis was attempted in the major in-depth case study, with two further cases playing a support role and contributing to a balanced emphasis of empirical research within the context of time constraints inherent within part-time research.

Enhancing the humidity response time of polymer optical fiber Bragg grating by using laser micromachining

The humidity sensors constructed from polymer optical fiber Bragg gratings (POFBG) respond to the water content change in the fiber induced by varying environmental condition. The water content change is a diffusion process. Therefore the response time of the POFBG sensor strongly depends on the geometry and size of the fiber. In this work we investigate the use of laser micromachining of D-shaped and slotted structures to improve the response time of polymer fiber grating based humidity sensors. A significant improvement in the response time has been achieved in laser micromachined D-shaped POFBG humidity sensors. The slotted geometry allows water rapid access to the core region but this does not of itself improve response time due to the slow expansion of the bulk of the cladding. We show that by straining the slotted sensor, the expansion component can be removed resulting in the response time being determined only by the more rapid, water induced change in core refractive index. In this way the response time is reduced by a factor of 2.5.

Parallel Class Intersection Matrices of Orthogonal Resolutions

This work was partially supported by the Bulgarian National Science Fund under Contract No MM 1405. Part of the results were announced at the Fifth International Workshop on Optimal Codes and Related Topics (OCRT), White Lagoon, June 2007, Bulgaria

A quantum Jensen-Shannon graph kernel using discrete-time quantum walks

In this paper, we develop a new graph kernel by using the quantum Jensen-Shannon divergence and the discrete-time quantum walk. To this end, we commence by performing a discrete-time quantum walk to compute a density matrix over each graph being compared. For a pair of graphs, we compare the mixed quantum states represented by their density matrices using the quantum Jensen-Shannon divergence. With the density matrices for a pair of graphs to hand, the quantum graph kernel between the pair of graphs is defined by exponentiating the negative quantum Jensen-Shannon divergence between the graph density matrices. We evaluate the performance of our kernel on several standard graph datasets, and demonstrate the effectiveness of the new kernel.

Stochastic calculations for fibre Raman amplifiers with randomly varying birefringence

For the first time for the model of real-world forward-pumped fibre Raman amplifier with the randomly varying birefringence, the stochastic calculations have been done numerically based on the Kloeden-Platen-Schurz algorithm. The results obtained for the averaged gain and gain fluctuations as a function of polarization mode dispersion (PMD) parameter agree quantitatively with the results of previously developed analytical model. Simultaneously, the direct numerical simulations demonstrate an increased stochastisation (maximum in averaged gain variation) within the region of the polarization mode dispersion parameter of 0.1÷0.3 ps/km1/2. The results give an insight into margins of applicability of a generic multi-scale technique widely used to derive coupled Manakov equations and allow generalizing analytic model with accounting for pump depletion, group-delay dispersion and Kerr-nonlinearity that is of great interest for development of the high-transmission-rates optical networks.

The time course of changes in retinal vessel diameter in response to differing durations of flicker light provocation

Purpose: To determine the response of retinal vessels to differing durations of flicker light (FL) sitmulation. Methods: We recorded retinal arterial and venous vessel dilation to 12.5 Hz flicker light provocation (Retinal Vessel Analyzer, Imedos Systems) of varying duration (5, 7, 10 and 20 seconds) in twelve healthy young individuals (age range 26-45 yrs). All participants underwent a full ocular examination including intraocular pressure and blood pressure measurements. Results: Maximum dilation (MD) did not show a significant dependence on flicker duration in arteries whereas maximum constriction (MC) did. However, in veins MD significantly increased with flicker duration. Approximately 80-90% of MD in arteries is reached within 10 seconds of flicker light stimulation. Conclusions: The vast majority of arterial dilatory capacity is reached within 10 seconds of flicker light stimulation even though venous dilation continues strongly. Since the MC of arteries shows a significant dependence on flicker duration measurements at two different durations can provide more information about the retinal vascular system than at a single flicker duration alone.

An inconsistency control system based on incomplete pairwise comparison matrices

Incomplete pairwise comparison matrix was introduced by Harker in 1987 for the case in which the decision maker does not fill in the whole matrix completely due to, e.g., time limitations. However, incomplete matrices occur in a natural way even if the decision maker provides a completely filled in matrix in the end. In each step of the total n(n–1)/2, an incomplete pairwise comparison is given, except for the last one where the matrix turns into complete. Recent results on incomplete matrices make it possible to estimate inconsistency indices CR and CM by the computation of tight lower bounds in each step of the filling in process. Additional information on ordinal inconsistency is also provided. Results can be applied in any decision support system based on pairwise comparison matrices. The decision maker gets an immediate feedback in case of mistypes, possibly causing a high level of inconsistency.

The development of direct ultra-fast PCR for forensic genotyping using short channel microfluidic systems with enhanced sieving matrices

There are situations in which it is very important to quickly and positively identify an individual. Examples include suspects detained in the neighborhood of a bombing or terrorist incident, individuals detained attempting to enter or leave the country, and victims of mass disasters. Systems utilized for these purposes must be fast, portable, and easy to maintain. The goal of this project was to develop an ultra fast, direct PCR method for forensic genotyping of oral swabs. The procedure developed eliminates the need for cellular digestion and extraction of the sample by performing those steps in the PCR tube itself. Then, special high-speed polymerases are added which are capable of amplifying a newly developed 7 loci multiplex in under 16 minutes. Following the amplification, a postage stamp sized microfluidic device equipped with specially designed entangled polymer separation matrix, yields a complete genotype in 80 seconds. The entire process is rapid and reliable, reducing the time from sample to genotype from 1-2 days to under 20 minutes. Operation requires minimal equipment and can be easily performed with a small high-speed thermal-cycler, reagents, and a microfluidic device with a laptop. The system was optimized and validated using a number of test parameters and a small test population. The overall precision was better than 0.17 bp and provided a power of discrimination greater than 1 in 106. The small footprint, and ease of use will permit this system to be an effective tool to quickly screen and identify individuals detained at ports of entry, police stations and remote locations. The system is robust, portable and demonstrates to the forensic community a simple solution to the problem of rapid determination of genetic identity.

Leaf gas exchange characteristics of three neotropical mangrove species in response to varying hydroperiod

We determined how different hydroperiods affected leaf gas exchange characteristics of greenhouse-grown seedlings (2002) and saplings (2003) of the mangrove species Avicennia germinans (L.) Stearn., Laguncularia racemosa (L.) Gaertn. f., and Rhizophora mangle L. Hydroperiod treatments included no flooding (unflooded), intermittent flooding (intermittent), and permanent flooding (flooded). Plants in the intermittent treatment were measured under both flooded and drained states and compared separately. In the greenhouse study, plants of all species maintained different leaf areas in the contrasting hydroperiods during both years. Assimilation-light response curves indicated that the different hydroperiods had little effect on leaf gas exchange characteristics in either seedlings or saplings. However, short-term intermittent flooding for between 6 and 22 days caused a 20% reduction in maximum leaf-level carbon assimilation rate, a 51% lower light requirement to attain 50% of maximum assimilation, and a 38% higher demand from dark respiration. Although interspecific differences were evident for nearly all measured parameters in both years, there was little consistency in ranking of the interspecific responses. Species by hydroperiod interactions were significant only for sapling leaf area. In a field study, R. mangle saplings along the Shark River in the Everglades National Park either demonstrated no significant effect or slight enhancement of carbon assimilation and water-use efficiency while flooded. We obtained little evidence that contrasting hydroperiods affect leaf gas exchange characteristics of mangrove seedlings or saplings over long time intervals; however, intermittent flooding may cause short-term depressions in leaf gas exchange. The resilience of mangrove systems to flooding, as demonstrated in the permanently flooded treatments, will likely promote photosynthetic and morphological adjustment to slight hydroperiod shifts in many settings.

Macroinvertebrate abundance in montane tropical streams of varying land-use, Ecuador

Despite the importance of tropical montane cloud forest streams, studies investigating aquatic communities in these regions are rare and knowledge on the driving factors of community structure is missing. The objectives of this study therefore were to understand how land-use influences habitat structure and macroinvertebrate communities in cloud forest streams of southern Ecuador. We evaluated these relationships in headwater streams with variable land cover, using multivariate statistics to identify relationships between key habitat variables and assemblage structure, and to resolve differences in composition among sites. Results show that shading intensity, substrate type and pH were the environmental parameters most closely related to variation in community composition observed among sites. In addition, macroinvertebrate density and partly diversity was lower in forested sites, possibly because the pH in forested streams lowered to almost 5 during spates. Standard bioindicator metrics were unable to detect the changes in assemblage structure between disturbed and forested streams. In general, our results indicate that tropical montane headwater streams are complex and heterogeneous ecosystems with low invertebrate densities. We also found that some amount of disturbance, i.e. patchy deforestation, can lead at least initially to an increase in macroinvertebrate taxa richness of these streams.

How did varying levels of intensity of the 2005 Pakistan earthquake differentially affect women’s fertility decisions and children’s health outcomes?

This paper uses a difference in difference model to investigate the impact of a large scale and high mortality 2005 earthquake in Pakistan on women’s fertility decisions and children’s health outcomes. Using a nationally representative, cross sectional DHS data from 2006 and geographical data from USGS, this paper investigates how variation in earthquake intensity levels can differentially impact total fertility for women and the likelihood of children suffering from diseases such as diarrhea, Acute Respiratory Infections (ARI) and fever. The post-earthquake results demonstrate a statistically significant increase in total fertility for areas closer to the epicenter of the earthquake, within a 100km radius of the rupture surface and at higher altitudes. Similarly, for children who were in-utero at the time of the earthquake, the probability of having early symptoms of ARI or fever was much smaller in lower earthquake intensity zones compared to the highest intensity zone.

Stabilisation of dehydrated nanoemulsions using sugar - protein matrices

There are numerous review papers discussing liquid nanoemulsions and how they compare to other emulsion systems. Little research is available on dried nanoemulsions. The objectives of this research were to (i) study the effect of varying the continuous phase of nanoemulsions with different carbohydrate/protein ratios on subsequent emulsion stability, and (ii) compare the physicochemical properties, lactose crystallisation properties, microstructure, and lipid oxidation of spray dried nanoemulsions compared to spray dried conventional emulsions having different water and sugar contents. Nanoemulsions containing sunflower oil (10% w/w), β-casein (2.5–10% w/w) and lactose or trehalose (10–17.5%) were produced following optimisation of the continuous phase by maximising and minimising viscosity and glass transition temperature (Tg’) using mixture design software. Increasing levels of β-casein from caused a significant increase in viscosity, particle size, and nanoemulsion stability, while resulting in a decrease in Tg’. Powders were made from spray drying emulsions/nanoemulsions consisting of lactose or a 70:30 mixture of lactose:sucrose (23.9%), sodium caseinate (5.1%) and sunflower oil (11.5%) in water. Nanoemulsions, produced by microfluidisation (100 MPa), had higher stability and lower viscosity than control emulsions (homogenization at 17 MPa) with lower solvent extractable free fat in the resulting powder. Partial replacement of lactose with sucrose decreased Tg and delayed Tcr. DVS and PLM showed that in powdered nanoemulsions, lactose crystallises faster than in powdered conventional emulsions. Microstructure of both powders (CLSM and cryo-SEM) showed different FGS in powders and different structure post lactose crystallisation. Powdered nanoemulsions had lower pentanal and hexanal (indicators of lipid oxidation) after 24 months storage due to their lower free fat and porosity, measured using a validated GC HS-SPME method, This research has shown the effect of altering the continuous phase of nanoemulsions on microstructure of spray dried nanoemulsions, which affects physical properties, sugar crystallisation, and lipid oxidation.

Gaussian Process Kernels for Cross-Spectrum Analysis in Electrophysiological Time Series

Multi-output Gaussian processes provide a convenient framework for multi-task problems. An illustrative and motivating example of a multi-task problem is multi-region electrophysiological time-series data, where experimentalists are interested in both power and phase coherence between channels. Recently, the spectral mixture (SM) kernel was proposed to model the spectral density of a single task in a Gaussian process framework. This work develops a novel covariance kernel for multiple outputs, called the cross-spectral mixture (CSM) kernel. This new, flexible kernel represents both the power and phase relationship between multiple observation channels. The expressive capabilities of the CSM kernel are demonstrated through implementation of 1) a Bayesian hidden Markov model, where the emission distribution is a multi-output Gaussian process with a CSM covariance kernel, and 2) a Gaussian process factor analysis model, where factor scores represent the utilization of cross-spectral neural circuits. Results are presented for measured multi-region electrophysiological data.

Analyse simultanée des hormones stéroïdiennes et leurs formes chimiques dans les matrices d'eau et d'urine par SPE-LC-MS/MS en ligne.

Dans les dernières années, les perturbateurs endocriniens ont été observés dans les rivières qui reçoivent des entrées importantes d’eaux usées. Parmi les perturbateurs endocriniens, les hormones stéroïdiennes naturelles et synthétiques sont des composés dont le potentiel d'imiter ou d'interférer avec les fonctions hormonales normales (développement, croissance et reproduction), est reconnu même au niveau ultra-traces (ng L-1). Bien que les hormones conjuguées soient moins actives que les hormones libres, elles peuvent être clivées et redevenir libres une fois exposées aux processus microbiens avant ou pendant le traitement des eaux usées. En raison de la nécessité d'identifier et de quantifier ces composés dans l'eau, une nouvelle méthode, entièrement automatisée, a été développée pour la détermination simultanée des deux formes de plusieurs hormones stéroïdiennes (conjuguées et libres) dans les matrices d'eau et dans l’urine des femmes. La méthode est basée sur l'extraction en phase solide couplée en ligne à la chromatographie liquide et la spectrométrie de masse en tandem (SPE-LC-MS/MS). Plusieurs paramètres ont été évalués dans le but d'optimiser l'efficacité de la méthode, tels que le type et le débit de la phase mobile, des différentes colonnes de SPE et de chromatographie, ainsi que différentes sources et modes d'ionisation des échantillons pour la MS. La méthode démontre une bonne linéarité (R2 > 0.993), ainsi qu'une précision avec un coefficient de variance inférieure à 10%. Les limites de quantification varient d’un minimum de 3 à 15 ng L-1 pour un volume d'injection entre 1 mL et 5 mL et le recouvrement des composés varie de 72 % à 117 %.