| Clever, Guido H. (2006): Synthesis and characterization of a metal-salen base pair for the assembly of programmed metal arrays inside the DNA double helix: Synthese und Charakterisierung eines Metall-Salen Basenpaars für den Aufbau von programmierten Metallanordnungen im Inneren von DNA-Doppelhelices. Dissertation, LMU München: Faculty of Chemistry and Pharmacy |
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PDF
Clever_Guido_H.pdf 6Mb |
Abstract
Base pairing in natural oligonucleotides relies on hydrogen bonding and pi-stacking. Applying coordinative interactions between ligand-like nucleobases and metal cations is a new way of assembling artificial oligonucleotide duplexes. The incorporation of numerous metal-base pairs into oligonucleotides may lead to interesting compounds for nano-technological applications. In this thesis, the synthesis of the salen-metal base pair is described, which comprises preparation of a suitable protected salicylic aldehyde precursor and an organo-cuprate mediated C-glycosidation as the key step. An x-ray structure of the monomeric copper-salen base pair shows a very good geometrical match with natural Watson-Crick base pairs. Up to 10 consecutive salicylic aldehyde-nucleobases could be incorporated into DNA oligonucleotides by means of phosphoramidite chemistry. The synthesized double strands with one ligand show typical B-DNA CD-spectra and distinct melting characteristics. Addition of excess ethylenediamine and 1 eq of Mn2+ or Cu2+ increase the melting temp. by 28 °C and 42 °C, respectively. The complexation of these and other metals was examined by UV-, CD- and EPR-spectroscopy and high res. ESI mass spectrometry. It was possible to stack 10 manganese atoms inside the double helix and to prepare sequence specifically arrays of up to 5 copper ions plus 5 mercury ions inside one duplex.
| Item Type: | Thesis (Dissertation, LMU Munich) | |
|---|---|---|
| Keywords: | DNA, DNA-structures, metal-base pair, nanotechnology, salen | |
| Subjects: | 600 Natural sciences and mathematics 600 Natural sciences and mathematics > 540 Chemistry and allied sciences | |
| Faculties: | Faculty of Chemistry and Pharmacy | |
| Language: | English | |
| Date Accepted: | 19. December 2006 | |
| 1. Referee: | Carell, Thomas | |
| Persistent Identifier (URN): | urn:nbn:de:bvb:19-65667 | |
| MD5 Checksum of the PDF-file: | a2e8f0f1b31dc3cfc6dc1fde86799ed9 | |
| Signature of the printed copy: | 0001/UMC 15994 | |
| ID Code: | 6566 | |
| Deposited On: | 06. Mar 2007 | (UTC) |
| Last Modified: | 16. Oct 2012 08:05 | (UTC) |