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The pentanucleotide ATTTC repeats occur in hundreds of genes important for various cellular processes, while their insertion and expansion in noncoding regions are associated with neurodegeneration, particularly with subtypes of spinocerebellar ataxia and familial adult myoclonic epilepsy. We describe a new striking domain-swapped DNA\u2013DNA interaction triggered by the addition of divalent cations, including Mg2+ and Ca2+. The results of NMR characterization of d(ATTTC)3 in solution show that the oligonucleotide folds into a novel 3D architecture with two central C:C+ base pairs sandwiched between a couple of T:T base pairs. This structural element, referred to here as the TCCTzip, is characterized by intercalative hydrogen-bonding, while the nucleobase moieties are poorly stacked. The 5\u2032- and 3\u2032-ends of TCCTzip motif are connected by stem-loop segments characterized by A:T base pairs and stacking interactions. Insights embodied in the non-canonical DNA structure are expected to advance our understanding of why only certain pyrimidine-rich DNA repeats appear to be pathogenic, while others can occur in the human genome without any harmful consequences.<\/jats:p>","DOI":"10.1093\/nar\/gkae052","type":"journal-article","created":{"date-parts":[[2024,2,1]],"date-time":"2024-02-01T03:47:55Z","timestamp":1706759275000},"page":"1591-1601","source":"Crossref","is-referenced-by-count":7,"title":["Dimeric structures of DNA ATTTC repeats promoted by divalent cations"],"prefix":"10.1093","volume":"52","author":[{"given":"Marko","family":"Trajkovski","sequence":"first","affiliation":[{"name":"Slovenian NMR Centre, National Institute of Chemistry , 1000\u00a0 Ljubljana , Slovenia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Annalisa","family":"Pastore","sequence":"additional","affiliation":[{"name":"King's College London, the Maurice Wohl Clinical Neuroscience Institute , London , UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1570-8602","authenticated-orcid":false,"given":"Janez","family":"Plavec","sequence":"additional","affiliation":[{"name":"Slovenian NMR Centre, National Institute of Chemistry , 1000\u00a0 Ljubljana , Slovenia"},{"name":"Faculty of Chemistry and Chemical Technology, University of Ljubljana , 1000\u00a0 Ljubljana , Slovenia"},{"name":"EN-FIST, Center of Excellence , 1000\u00a0 Ljubljana , Slovenia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"286","published-online":{"date-parts":[[2024,1,31]]},"reference":[{"key":"2024022807100926800_B1","doi-asserted-by":"crossref","first-page":"737","DOI":"10.1038\/171737a0","article-title":"Molecular structure of nucleic acids","volume":"171","author":"Watson","year":"1953","journal-title":"Nature"},{"key":"2024022807100926800_B2","doi-asserted-by":"crossref","first-page":"1416","DOI":"10.1002\/anie.201106423","article-title":"A-T base pairs are more stable than G-C base pairs in a hydrated ionic liquid","volume":"51","author":"Tateishi-Karimata","year":"2012","journal-title":"Angew. 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