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dc.contributor.advisorGunnlaugsson, Thorfinnu
dc.contributor.authorARAMBALLI JAYANTH, SAVYASACHI
dc.date.accessioned2018-02-05T19:01:10Z
dc.date.available2018-02-05T19:01:10Z
dc.date.issued2018en
dc.date.submitted2018
dc.identifier.citationARAMBALLI JAYANTH, SAVYASACHI, Luminescent self-assembled supramolecular polymers and microspheres based on Benzene-1,3,5- tricarboxamide (BTA) derivatives, Trinity College Dublin.School of Chemistry.CHEMISTRY, 2018en
dc.identifier.otherYen
dc.identifier.urihttp://hdl.handle.net/2262/82323
dc.descriptionAPPROVEDen
dc.description.abstractThis thesis, entitled ‘Luminescent Self-assembled Supramolecular Polymers and Microspheres Based on Benzene-1,3,5-tricarboxamide (BTA) Derivatives’ describes the syntheses and characterisation of a new range of tripodal molecules containing terpyridine binding motif and their various supramolecular self-assembly formation. The thesis is divided into five chapters. Chapter 1, the introduction, provides an overview of functional supramolecular materials and the various potential mechanisms for their formation, through diverse supramolecular interactions. The relevant literature and recent advances in the self-assembly of tripodal systems in the formation of supramolecular polymers will be reviewed, with a particular focus on soft materials and systems exhibiting gelation. Recent examples of supramolecular gels from low-molecular weight gelators (LMWGs), as well as higher-ordered aggregates, and their various applications are also discussed. Additionally, this chapter provides an overview of the lanthanide metal ions; detailing the advantages of their interesting photophysical properties etc. The remainder of the chapter covers a short review of the most relevant examples of supramolecular materials contributed by the Gunnlaugsson group in recent times. Chapter 2 describes the design and synthesis of a family of tripodal ligands based on the benzene-1,3,5-tricarboxamide (BTA) core bearing chiral centres, incorporated using a range of amino acids and the terpyridine functionality at the periphery. The europium Eu(III)- directed self-assembly of a pair of enantiomers in solution at two different ligand concentrations are studied through spectroscopic titrations using techniques such as UV-visible absorption, fluorescence and phosphorescence spectroscopy. The titration data was then analysed using non-linear regression fitting (using SPECFIT®) to determine the speciation and relative stability (global stability constants, logβ) for the formation of various self-assembled supramolecular structures at different concentration. The formation of 1:1, 2:1 and 3:1 (M:L) species formed at lower concentration (CL = 5 ✕ 10-6 M) and 1:1 and 3:2 (M:L) species formed at higher concentration (CL = 1 ✕ 10-6 M) was observed. Chapter 3 then focuses on the self-assembly properties of the synthesised BTA molecules described in Chapter 2 for the formation of gels and higher-ordered aggregates (such as microspheres). The analysis of the gels using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and rheology measurements are presented. The properties of the microspheres using various microscopic techniques such as SEM, TEM, Helium Ion Beam microscope (HIB), and focussed-ion beam (FIB) microscopy are discussed. Furthermore, the mechanism of the formation of the microspheres and formation of interesting morphologies formed upon addition of Ln(III) (Ln = Eu(III) and Tb(III)) salts to the solution of microspheres are presented. The chapter concludes with the investigation of the mechanical strength using atomic force microscopy (AFM) and thermal stability of the microsphere formations, in addition to the self-sorting behaviour of these tripodal compounds. Chapter 4 describes the investigations of the microspheres using laser-scanning confocal microscopy (LSCM). The static imaging of the fluorescent microspheres and the real-time imaging of the formation of microspheres in solution are described. Ln(III) containing luminescent microspheres formed upon addition of Ln(III) salts (Ln = Eu and Tb) to the preformed organic microspheres are discussed. These luminescent microparticles are also investigated for their CPL emission. Finally, Chapter 5 gives the experimental details and procedures for the work carried out in the preceding chapters. Following this, literature references and supplementary data and spectra are provided in the appendices.en
dc.language.isoenen
dc.publisherTrinity College Dublin. School of Chemistry. Discipline of Chemistryen
dc.rightsYen
dc.subjectSelf-Assembly, Lanthanide Luminescence, Soft materials, Supramolecular gels, Microspheres, Electron Microscopy and Confocal Microscopy.en
dc.titleLuminescent self-assembled supramolecular polymers and microspheres based on Benzene-1,3,5- tricarboxamide (BTA) derivativesen
dc.typeThesisen
dc.type.supercollectionthesis_dissertationsen
dc.type.supercollectionrefereed_publicationsen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnameDoctor of Philosophy (Ph.D.)en
dc.identifier.peoplefinderurlhttp://people.tcd.ie/ajsaen
dc.identifier.rssinternalid182536en
dc.rights.ecaccessrightsopenAccess
dc.contributor.sponsorTrinity College Dublin (TCD)en
dc.contributor.sponsorScience Foundation Ireland (SFI)en
dc.contributor.sponsorTrinity Biomedical Science Institute (TBSI)en


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