{"id":1906,"date":"2020-03-09T18:09:28","date_gmt":"2020-03-09T18:09:28","guid":{"rendered":"http:\/\/grupodeespectroscopia.es\/MW\/?p=1906"},"modified":"2020-03-09T18:13:09","modified_gmt":"2020-03-09T18:13:09","slug":"our-paper-observation-of-the-unbiased-conformers-of-putative-dna-scaffold-ribosugars-accepted-in-acs-central-science","status":"publish","type":"post","link":"https:\/\/grupodeespectroscopia.es\/MW\/our-paper-observation-of-the-unbiased-conformers-of-putative-dna-scaffold-ribosugars-accepted-in-acs-central-science\/","title":{"rendered":"Our paper “Observation of the Unbiased Conformers of Putative DNA-Scaffold Ribosugars” accepted in ACS Central Science"},"content":{"rendered":"

The constitution, configuration, and flexibility of the core sugars of DNA molecules alter their function in diverse roles. Conformational itineraries of the ribofuranosides (f<\/i>s) have long been known to finely determine rates of processing, yet we also know that, strikingly, semifunctional DNAs containing pyranosides (p<\/i>s) or other configurations can be created, suggesting sufficient but uncompletely understood plasticity. The multiple conformers involved in such processes are necessarily influenced by context and environment: solvent, hosts, ligands. Notably, however, to date the\u00a0un<\/i>biased, \u201cnaked\u201d conformers have not been experimentally determined. Here, the inherent conformational biases of DNA scaffold deoxyribosides in unsolvated and solvated forms have now been defined using gas-phase microwave and solution-phase NMR spectroscopies coupled with computational analyses and exploitation of critical differences between natural-abundance \"\"<\/a>isotopologues. Serial determination of precise, individual spectra for conformers of these 25 isotopologues in alpha (\u03b1-d<\/span>) and beta (\u03b2-d<\/span>); pyrano (p<\/i>) and furano (f<\/i>) methyl 2-deoxy-d<\/span>-ribosides gave not only unprecedented atomic-level resolution structures of associated conformers but also their quantitative populations. Together these experiments revealed that typical\u00a02<\/sup>E and\u00a03<\/sup>E conformations of the sugar found in complex DNA structures are not inherently populated. Moreover, while both OH-5\u2032 and OH-3\u2032 are constrained by intramolecular hydrogen bonding in the unnatural \u03b1f<\/i>\u00a0scaffold, OH-3\u2032 is \u201cborn free\u201d in the \u201cnaked\u201d lowest lying energy conformer of natural \u03b2f<\/i>. Consequently, upon solvation, unnatural \u03b1f<\/i> is strikingly less perturbable (retaining\u00a02<\/sup>T1<\/sub>\u00a0conformation\u00a0in vacuo<\/i>\u00a0and water) than natural \u03b2f<\/i>. Unnatural \u03b1p<\/i>\u00a0and \u03b2p<\/i> ribosides also display low conformational perturbability. These first experimental data on inherent, unbiased conformers therefore suggest that it is the background of conformational flexibility of \u03b2f<\/i>\u00a0that may have led to its emergence out of multiple possibilities as the sugar scaffold for \u201clife\u2019s code\u201d and suggest a mechanism by which the resulting freedom of OH-3\u2032 (and hence accessibility as a nucleophile) in \u03b2f<\/i> may drive preferential processing and complex structure formation, such as replicative propagation of DNA from 5\u2032-to-3\u2032.<\/p>\n

The paper has been accepted by\u00a0ACS Central Science<\/strong><\/em><\/p>\n","protected":false},"excerpt":{"rendered":"

The constitution, configuration, and flexibility of the core sugars of DNA molecules alter their function in diverse roles. Conformational itineraries of the ribofuranosides (fs) have long been known to finely determine rates of processing, yet we also know that, strikingly, semifunctional DNAs containing pyranosides (ps) or other configurations can be created, suggesting sufficient but uncompletely …<\/p>\n","protected":false},"author":1,"featured_media":1908,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":[],"categories":[1],"tags":[],"acf":[],"aioseo_notices":[],"_links":{"self":[{"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/posts\/1906"}],"collection":[{"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/comments?post=1906"}],"version-history":[{"count":5,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/posts\/1906\/revisions"}],"predecessor-version":[{"id":1912,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/posts\/1906\/revisions\/1912"}],"wp:featuredmedia":[{"embeddable":true,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/media\/1908"}],"wp:attachment":[{"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/media?parent=1906"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/categories?post=1906"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/grupodeespectroscopia.es\/MW\/wp-json\/wp\/v2\/tags?post=1906"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}