1,721,538 research outputs found
Two-photon sensitive protecting groups for biological application
Full text linkCaged compounds are a class of photosensitive reagents used to stimulate cells with spatial control down to a sub-cellular level, and millisecond temporal control. They comprise of biologically important molecule which is modified with a photolabile protecting group. In the absence of light, caged compounds are physiologically silent but irradiation with light induces the release of biologically active species. Illumination under two-photon conditions is particularly advantageous as it enables restriction of the photolysis volume to ~1 fL and it provides deeper penetration into scattering samples. This thesis reports the development of new protecting groups for two-photon uncaging in neuroscience. Mechanistically, the deprotection in these novel groups is designed to operate via an intramolecular photoinduced electron transfer (PeT) between the absorbing unit (electron-donor) and the release module (electron-acceptor). The modular design of these cages ensures separation of absorption and release steps, and allows each process to be tuned and optimized independently. Chapter 1 provides an introduction to the two-photon absorption phenomenon and a historic overview of the uncaging technique. It also discusses recent advances in the development of two-photon sensitive probes used in neuroscience. Chapter 2 describes the exploration of molecular designs for novel protecting groups. A two-photon absorbing dye (electron-donor; fluorene dye) and three different release units (electron-acceptors; nitrobenzyl, pyridinium and phenacyl) were identified as suitable building blocks for the current project. Efficiency of the intramolecular electron transfer between chosen units was evaluated using model dyads which constitute covalently linked electron-donor and acceptor species. Chapter 3 is devoted to the synthesis and photophysical evaluation of nitrobenzyl-based protecting group. Chapter 4 describes the preparation of pyridinium-derived protecting group and demonstrates PeT-mediated release of tryptophan and GABA under one- and two-photon excitation. Hydrolytic instability of pyridinium esters is highlighted. Chapter 5 reports the synthesis, hydrolytic stability and one-photon uncaging efficiency of phenacyl-based derivatives. Chapter 6 discusses properties of developed caged compounds and compares them with other compounds reported in literature. It contains overall conclusions and outlook for the current project. Chapter 7 details the experimental procedures and the characterization of compounds synthesized during this work
Alien Registration- Anderson, Harry W. (Lewiston, Androscoggin County)
Full text linkhttps://digitalmaine.com/alien_docs/22712/thumbnail.jp
Anthracene-fused porphyrins
Full text linkThis thesis describes the synthesis of a novel family of porphyrins fused to anthracenes, together with investigations into their optical and electrochemical properties, as well as exploring their potential for application in dye-sensitised solar cells.Chapter 1 gives an overview of the structure-property relationships of large planar pi- systems for organic electronic applications. Porphyrins are introduced as suitable building blocks for such systems, and approaches for extending the pi-conjugation of these macrocycles are presented.A literature review of porphyrins fused to aromatic units is presented in Chapter 2, with a focus on the influence of structure on the optoelectronic properties of such systems. The chapter concludes with a summary of my previous work on the synthesis of anthracene-fused porphyrins, and the aims of this project are stated.Chapter 3 describes the syntheses of fully and partially fused bis-anthracene porphyrin monomers and dimers. By varying peripheral substituents, it was possible to solve problems of aggregation encountered for these systems. Fusion of anthracene units to a porphyrin core was found to result in systems displaying strong absorption in the near-IR, small HOMO-LUMO gaps, and low oxidation potentials.Chapter 4 explores the synthesis, crystal structure and optoelectronic properties of a porphyrin fused to four anthracenes, revealing this system to exhibit the longest wavelength absorption of any porphyrin monomer. The synthesis of a liquid crystalline tetra-anthracene-fused porphyrin was proposed, and attempts to synthesise the necessary anthracene precursors were undertaken.Chapter 5 describes the molecular design and synthetic pathway to a mono-anthracene fused porphyrin, and its unfused analogue, for use in liquid electrolyte dye-sensitised solar cells. By varying the metal oxide layer or lithium ion concentration of the device, it was possible to achieve incident photon to current conversion efficiency (IPCE) responses at wavelengths beyond 1050 nm.Chapter 6 details the experimental synthetic procedures and characterisation data for all the compounds synthesised during this project
Imaging membrane potential
Full text linkImaging membrane potential is a promising technique in the elucidation of the interactions of large networks of neurons. The membrane potential in a neuron varies as an action potential, the basic electrical signal of neuronal communication, travels along the length of the cell. Voltage sensitive dyes play a key role by providing an optical readout of the electric field generated across a neuron membrane by the action potential. However, none of the dyes reviewed in Chapter 1 generate sufficient signal change with changes in membrane potential; this sensitivity problem limits the ability of the imaging membrane potential technique to allow the high spatial and temporal resolution necessary for neuronal networks to be better understood. This thesis features two avenues of research that are expected to result in the necessary enhancements to voltage sensitive dyes to improve the signal change. The first avenue is based on the effect of an electric field upon the non-linear optical properties of a porphyrin macromolecule. The encouraging field sensitivity of a previous porphyrin monomer voltage sensor inspired an investigation which identified optimisations to enhance the voltage sensitivity (Chapter 2). The design, synthesis and initial characterisation of optimised porphyrin voltage sensors is detailed in Chapter 3. The second avenue is based on the effect of an electric field upon the rate of intermolecular electron transfer. In a suitably designed dye, the competition between electron transfer and fluorescence, following excitation by incoming light, allows the fluorescence intensity to act as an optical indicator of the electron transfer rate. New dyes were rationally designed and synthesised, as this effect had not been applied to voltage sensitive imaging before the research detailed in Chapter 4. The challenging purification of the new amphiphilic dyes synthesised also inspired research into a novel testing method which does not require amphiphilic dyes (Chapter 5)
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Full text link“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Full text linkWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
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