Zeolite-Y scaffolded donor-acceptor systems for nanoelectronics

Zeolites can act as hosts for supramolecular organization of molecules and complexes. A key objective in supramolecular chemistry is the development of donor acceptor systems capable of controlled photoinduced electron and energy transfer. This thesis focuses on a fundamental study of the capacity of zeolite materials to accommodate dipolar communication between metal complex guest species as well as exploring the effect of zeolite materials on the photophysical properties of guest molecules. Chapter 1 and 2 outline the current state of zeolite host-guest chemistry and the experimental procedures and instrumentation ultilised in this work. Chapter 3 investigates the ability of Y-zeolite to accommodate energy transfer processes between co-doped donors and acceptors. A series of [Ru(bpy)3]2+ (where bpy is 2,2’-bipyridine) doped Zeolite Y materials co-doped with iron polypyridyl complexes [Fe(bpy)3]2+ and [Fe(tpy)2]2+ were prepared via the ‘ship in a bottle’ syntesis. The co-encapsulated [Ru(bpy)3]2+ complex undergoes efficient energy transfer to both iron polypyridyl complexes over distances of between of 32 Å and 27 Å. Chapter 4 examines the influence of zeolite-Y entrapment upon the photophysical properties of the Iridium (III) polypyridyl complexes [Ir(bpy)3]3+ and [Ir(tpy)2]3+. Their preparation and photophysical characterization is described. Dramatic changes in the emission spectra of the complexes were observed due to both the polarity of the zeolite interior as well as distortions caused by tight steric confinement. Chapter 5 quantifies the extent of the excited state distortion of guest molecules entrapped within the pores of zeolite-Y by Huang-Rhys analysis. It was found that the zeolite environment impacts on the excited state geometry of the complexes generally limiting the amount of structural distortion the complex can undergo. In Chapter 6, iridium polypyridyl complexes in a zeolite-Y matrix were codoped with europium bis-bipyridine. The photophysical properties of these materials were studied and indicated that sensitisation of the zeolite included europium acceptor by a co-included iridium polypyridyl energy donor complex occurred. Chapter 7 offers conclusions on this thesis and outlines future work

Embedding a Blended Learning Approach From First Year

As DIT strives to enhance the transition of students into third level education, a number of priority areas were identified as part of the ongoing STEER (Student Transition, Expectations, Engagement, Retention) initiative. Ultimately the onus is on DIT to enable students to become self-directed learners. Blended learning is positioned as a solution to aid in this transition. It has been described as the combination of traditional face-to-face teaching methods with authentic online learning activities (Davies & Fill, 2007, p. 817). However, it is not without risk to assume that first year students have a natural affinity with blended approaches, as Garrison and Vaughan (cited in Moore & Gilmartin, 2010, p.4) opined those who have grown up with interactive technology are not always comfortable with the information transmission approach of large lectures. Students expect a relevant and engaging learning experience . The purpose of our project is to provide a rationale for redesigning a module for blended delivery and how blended learning can be implemented, with specific focus on first year undergraduate modules. It is hope that this report can help address current challenges in the application of blended learning, and also make a definite contribution to the laudable STEER goals. This report will initially consider the background to blended learning and the challenges associated with the approach, before finally exploring the practical implications of introducing blended learning to early stage students in a staged fashion and presenting a practical How to guide for blended learning

Review: the use of real-time fluorescence instrumentation to monitor ambient primary biological aerosol particles (PBAP)

Primary biological aerosol particles (PBAP) encompass many particle types that are derived from several biological kingdoms. These aerosol particles can be composed of both whole living units such as pollen, bacteria, and fungi, as well as from mechanically formed particles, such as plant debris. They constitute a significant proportion of the overall atmospheric particle load and have been linked with adverse health issues and climatic effects on the environment. Traditional methods for their analysis have focused on the direct capture of PBAP before subsequent laboratory analysis. These analysis types have generally relied on direct optical microscopy or incubation on agar plates, followed by time-consuming microbiological investigation. In an effort to address some of these deficits, real-time fluorescence monitors have come to prominence in the analysis of PBAP. These instruments offer significant advantages over traditional methods, including the measurement of concentrations, as well as the potential to simultaneously identify individual analyte particles in real-time. Due to the automated nature of these measurements, large data sets can be collected and analyzed with relative ease. This review seeks to highlight and discuss the extensive literature pertaining to the most commonly used commercially available real-time fluorescence monitors (WIBS, UV-APS and BioScout). It discusses the instruments operating principles, their limitations and advantages, and the various environments in which they have been deployed. The review provides a detailed examination of the ambient fluorescent aerosol particle concentration profiles that are obtained by these studies, along with the various strategies adopted by researchers to analyze the substantial data sets the instruments generate. Finally, a brief reflection is presented on the role that future instrumentation may provide in revolutionizing this area of atmospheric research

Review: The Use of Real-Time Fluorescence Instrumentation to Monitor Ambient Primary Biological Aerosol Particles (PBAP)

Primary biological aerosol particles (PBAP) encompass many particle types that are derived from several biological kingdoms. These aerosol particles can be composed of both whole living units such as pollen, bacteria, and fungi, as well as from mechanically formed particles, such as plant debris. They constitute a significant proportion of the overall atmospheric particle load and have been linked with adverse health issues and climatic effects on the environment. Traditional methods for their analysis have focused on the direct capture of PBAP before subsequent laboratory analysis. These analysis types have generally relied on direct optical microscopy or incubation on agar plates, followed by time-consuming microbiological investigation. In an effort to address some of these deficits, real-time fluorescence monitors have come to prominence in the analysis of PBAP. These instruments offer significant advantages over traditional methods, including the measurement of concentrations, as well as the potential to simultaneously identify individual analyte particles in real-time. Due to the automated nature of these measurements, large data sets can be collected and analyzed with relative ease. This review seeks to highlight and discuss the extensive literature pertaining to the most commonly used commercially available real-time fluorescence monitors (WIBS, UV-APS and BioScout). It discusses the instruments operating principles, their limitations and advantages, and the various environments in which they have been deployed. The review provides a detailed examination of the ambient fluorescent aerosol particle concentration profiles that are obtained by these studies, along with the various strategies adopted by researchers to analyze the substantial data sets the instruments generate. Finally, a brief reflection is presented on the role that future instrumentation may provide in revolutionizing this area of atmospheric research. Keywords: PBAP; WIBS; UV-APS; BioScout; fluorescence; real-time; bioaerosols

Airborne Fungal Spore Review, New Advances and Automatisation

Fungal spores make up a significant portion of Primary Biological Aerosol Particles (PBAPs) with large quantities of such particles noted in the air. Fungal particles are of interest because of their potential to affect the health of both plants and humans. They are omnipresent in the atmosphere year-round, with concentrations varying due to meteorological parameters and location. Equally, differences between indoor and outdoor fungal spore concentrations and dispersal play an important role in occupational health. This review attempts to summarise the different spore sampling methods, identify the most important spore types in terms of negative effects on crops and the public, the factors affecting their growth/dispersal, and different methods of predicting fungal spore concentrations currently in use

Intersection types for unbind and rebind

We define a type system with intersection types for an extension of lambda-calculus with unbind and rebind operators. In this calculus, a term with free variables, representing open code, can be packed into an "unbound" term, and passed around as a value. In order to execute inside code, an unbound term should be explicitly rebound at the point where it is used. Unbinding and rebinding are hierarchical, that is, the term can contain arbitrarily nested unbound terms, whose inside code can only be executed after a sequence of rebinds has been applied. Correspondingly, types are decorated with levels, and a term has type decorated with k if it needs k rebinds in order to reduce to a value. With intersection types we model the fact that a term can be used differently in contexts providing different numbers of unbinds. In particular, top-level terms, that is, terms not requiring unbinds to reduce to values, should have a value type, that is, an intersection type where at least one element has level 0. With the proposed intersection type system we get soundness under the call-by-value strategy, an issue which was not resolved by previous type systems.Comment: In Proceedings ITRS 2010, arXiv:1101.410

Shotgun cholanomics of ileal fluid

In this study we have developed a rapid method for the shotgun analysis of bile acids in intestinal fluid. The method is semi-quantitative, and requires little sample preparation. Bile salts might contribute to the pathogenesis of Crohn's disease. In a pilot study we demonstrate the method by analysing the bile acid content of ileal fluid from seven Crohn's disease patients and three healthy controls. The dominant bile acids observed were di and/or trihydroxycholanoates, di- and/or trihydroxycholanoylglycines, di- and/or tri-hydroxycholanoyltaurines, monosulphated dihydroxycholanoates and monosulphated dihydroxycholanoylglycine. The method can be similarly applied to samples derived from other parts of the intestine

Disordered macrophage cytokine secretion underlies impaired acute inflammation and bacterial clearance in Crohn's disease

The cause of Crohn's disease (CD) remains poorly understood. Counterintuitively, these patients possess an impaired acute inflammatory response, which could result in delayed clearance of bacteria penetrating the lining of the bowel and predispose to granuloma formation and chronicity. We tested this hypothesis in human subjects by monitoring responses to killed Escherichia coli injected subcutaneously into the forearm. Accumulation of 111In-labeled neutrophils at these sites and clearance of 32P-labeled bacteria from them were markedly impaired in CD. Locally increased blood flow and bacterial clearance were dependent on the numbers of bacteria injected. Secretion of proinflammatory cytokines by CD macrophages was grossly impaired in response to E. coli or specific Toll-like receptor agonists. Despite normal levels and stability of cytokine messenger RNA, intracellular levels of tumor necrosis factor (TNF) were abnormally low in CD macrophages. Coupled with reduced secretion, these findings indicate accelerated intracellular breakdown. Differential transcription profiles identified disease-specific genes, notably including those encoding proteins involved in vesicle trafficking. Intracellular destruction of TNF was decreased by inhibitors of lysosomal function. Together, our findings suggest that in CD macrophages, an abnormal proportion of cytokines are routed to lysosomes and degraded rather than being released through the normal secretory pathway

C13orf31 (FAMIN) is a central regulator of immunometabolic function.

Single-nucleotide variations in C13orf31 (LACC1) that encode p.C284R and p.I254V in a protein of unknown function (called 'FAMIN' here) are associated with increased risk for systemic juvenile idiopathic arthritis, leprosy and Crohn's disease. Here we set out to identify the biological mechanism affected by these coding variations. FAMIN formed a complex with fatty acid synthase (FASN) on peroxisomes and promoted flux through de novo lipogenesis to concomitantly drive high levels of fatty-acid oxidation (FAO) and glycolysis and, consequently, ATP regeneration. FAMIN-dependent FAO controlled inflammasome activation, mitochondrial and NADPH-oxidase-dependent production of reactive oxygen species (ROS), and the bactericidal activity of macrophages. As p.I254V and p.C284R resulted in diminished function and loss of function, respectively, FAMIN determined resilience to endotoxin shock. Thus, we have identified a central regulator of the metabolic function and bioenergetic state of macrophages that is under evolutionary selection and determines the risk of inflammatory and infectious disease.Supported by the European Research Council under the European Community’s Seventh Framework Programme (FP7/2007-2013)/ERC Grant agreement 260961, the Wellcome Trust (investigator award 106260/Z/14/Z; a PhD fellowship for clinicians; and a Career Re-Entry Fellowship), the Wellcome Trust Sanger Institute, the US National Institutes of Health (5U420D011174 and 5U54HG006348), the Biotechnology and Biological Sciences Research Council, the National Institute for Health Research Cambridge Biomedical Research Centre, the European Crohn’s and Colitis Organisation and the Swedish Medical Research Council and the Olle Engkvist foundation.This is the author accepted manuscript. The final version is available from Nature Publishing Group via http://dx.doi.org/10.1038/ni.353