The study of biological analytes in their native environment is a major challenge for biochemistry and molecular biology. Luminesce spectroscopy is well suited for this task due to its non-invasiveness, high spatial and temporal resolution, and high signal to noise ratio. This thesis describes the development and applications of Ln-based luminescent probes for detecting small molecules and enzymes. Specifically the probes presented are based on coumarin sensitizers coupled to a DO3A chelated LnIII center. The 1st generation of these probes employ 7-OH coumarins, caged at the 7-O position (Chapter 2). By use of p-pinacolatoboron benzyl or p-methoxybenzyl cages, this design allowed the construction of ratiometric EuIII-based probes capable of detecting the reactive oxygen species H2O2, NO and ONOO−. The second and third part of the thesis describes a further improvement of the design (Chapters 3 and 4). By employing caged coumarin precursors EuIII and TbIII-based probes were developed for a variety of different analytes (F−, Pd0, H2O2, β-galactosidase, β-glucosidase, α-mannosidase and phosphatase). Most of these probes displayed excellent turn-on responses when treated with their respective analytes. Furthermore they could be used for detecting multiple analytes simultaneously (Chapter 4). By use of one Eu-based and another Tb-based probe, the simultaneous detection of two analytes was possible. This could further be extended to simultaneous three analyte detection by the additional employment of an organic coumarin-based probe. The last part of the thesis (Chapter 5) describes protocols for the rapid and efficient access to triazole-linked lanthanide-antenna complexes by use of the copper-catalyzed azide-alkyne cycloaddition reaction. For robust substrates, microwave heating at 100 °C enabled rapid (15-60 min) access to various lanthanide complexes, which could be isolated via simple precipitation. Using these conditions pure bi- and tri-homometallic lanthanide complexes could be prepared. A second protocol, for substrates carrying sensitive functionalities was also developed. The application of catalytic amounts of CuOAc, BimPy2 ligand, and a large excess of NaAsc afforded a variety of lanthanide complexes, among them caged responsive probes, in moderate to good yields.
| Identifer | oai:union.ndltd.org:UPSALLA1/oai:DiVA.org:uu-236760 |
| Date | January 2014 |
| Creators | Pershagen, Elias |
| Publisher | Uppsala universitet, Fysikalisk-organisk kemi |
| Source Sets | DiVA Archive at Upsalla University |
| Language | English |
| Detected Language | English |
| Type | Doctoral thesis, comprehensive summary, info:eu-repo/semantics/doctoralThesis, text |
| Format | application/pdf |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, 1651-6214 ; 1208 |
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