Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes
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...
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Uppsala universitet, Fysikalisk-organisk kemi
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ndltd-UPSALLA1-oai-DiVA.org-uu-2367602015-02-04T04:44:52ZDevelopment and Multicolor Imaging Applications of Lanthanide-Based Luminescent ProbesengPershagen, EliasUppsala universitet, Fysikalisk-organisk kemi2014Lanthanideluminescent probemulticolorThe 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. Doctoral thesis, comprehensive summaryinfo:eu-repo/semantics/doctoralThesistexthttp://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-236760urn:isbn:978-91-554-9112-3Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, 1651-6214 ; 1208application/pdfinfo:eu-repo/semantics/openAccess |
collection |
NDLTD |
language |
English |
format |
Doctoral Thesis |
sources |
NDLTD |
topic |
Lanthanide luminescent probe multicolor |
spellingShingle |
Lanthanide luminescent probe multicolor Pershagen, Elias Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes |
description |
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. |
author |
Pershagen, Elias |
author_facet |
Pershagen, Elias |
author_sort |
Pershagen, Elias |
title |
Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes |
title_short |
Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes |
title_full |
Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes |
title_fullStr |
Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes |
title_full_unstemmed |
Development and Multicolor Imaging Applications of Lanthanide-Based Luminescent Probes |
title_sort |
development and multicolor imaging applications of lanthanide-based luminescent probes |
publisher |
Uppsala universitet, Fysikalisk-organisk kemi |
publishDate |
2014 |
url |
http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-236760 http://nbn-resolving.de/urn:isbn:978-91-554-9112-3 |
work_keys_str_mv |
AT pershagenelias developmentandmulticolorimagingapplicationsoflanthanidebasedluminescentprobes |
_version_ |
1716730013543301120 |