Supramolecular assembly properties of a mixed-sequence recognition-encoded melamine oligomer.

IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC
Mohit Dhiman, Joseph T Smith, Christopher A Hunter
{"title":"Supramolecular assembly properties of a mixed-sequence recognition-encoded melamine oligomer.","authors":"Mohit Dhiman, Joseph T Smith, Christopher A Hunter","doi":"10.1039/d5ob00769k","DOIUrl":null,"url":null,"abstract":"<p><p>Recognition-encoded melamine oligomers (REMO) are composed of an alternating piperazine-triazine backbone and side-chains equipped with either a H-bond donor (phenol, D) or a H-bond acceptor (phosphine oxide, A). Complementary homo-oligomers form stable duplexes in organic solvents, due to intermolecular base-pairing interactions between the phenol and phosphine oxide side-chains. For mixed-sequence oligomers, the major pathway that competes with duplex formation is folding due to intramolecular base-pairing interactions. Automated solid phase synthesis was used to prepare the self-complementary REMO DADA, and this oligomer was used to investigate the competition between intermolecular and intramolecular H-bonding interactions. Isothermal titration calorimetry in chloroform showed that DADA forms a dimeric complex, but with reduced stability compared with the duplexes formed by shorter oligomers. The results indicate that a folded state with intramolecular interactions between the two terminal recognition units is significantly populated. The dimeric complex formed at higher concentrations could involve the interaction of two folded oligomers in a kissing stem-loops structure, or the oligomer could unfold to give the duplex with four intermolecular base-pairs. One end of the oligomer was equipped with an azide and the other with an alkyne, so that the dimeric complex could be covalently trapped using copper-catalysed azide-alkyne cycloaddition reactions. The major product was the macrocyclic duplex with small amounts of the macrocyclic single-strand, which shows that the DADA·DADA duplex dominates at millimolar concentrations. Understanding the propensity of the REMO architecture to fold will help guide the future design principles for synthesis of more complex functional assemblies.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9000,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12227063/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5ob00769k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0

Abstract

Recognition-encoded melamine oligomers (REMO) are composed of an alternating piperazine-triazine backbone and side-chains equipped with either a H-bond donor (phenol, D) or a H-bond acceptor (phosphine oxide, A). Complementary homo-oligomers form stable duplexes in organic solvents, due to intermolecular base-pairing interactions between the phenol and phosphine oxide side-chains. For mixed-sequence oligomers, the major pathway that competes with duplex formation is folding due to intramolecular base-pairing interactions. Automated solid phase synthesis was used to prepare the self-complementary REMO DADA, and this oligomer was used to investigate the competition between intermolecular and intramolecular H-bonding interactions. Isothermal titration calorimetry in chloroform showed that DADA forms a dimeric complex, but with reduced stability compared with the duplexes formed by shorter oligomers. The results indicate that a folded state with intramolecular interactions between the two terminal recognition units is significantly populated. The dimeric complex formed at higher concentrations could involve the interaction of two folded oligomers in a kissing stem-loops structure, or the oligomer could unfold to give the duplex with four intermolecular base-pairs. One end of the oligomer was equipped with an azide and the other with an alkyne, so that the dimeric complex could be covalently trapped using copper-catalysed azide-alkyne cycloaddition reactions. The major product was the macrocyclic duplex with small amounts of the macrocyclic single-strand, which shows that the DADA·DADA duplex dominates at millimolar concentrations. Understanding the propensity of the REMO architecture to fold will help guide the future design principles for synthesis of more complex functional assemblies.

混合序列识别编码的三聚氰胺低聚物的超分子组装性质。
识别编码的三聚氰胺低聚物(REMO)由交替的哌嗪-三嗪主链和带有氢键供体(苯酚,D)或氢键受体(氧化膦,a)的侧链组成。在有机溶剂中,由于苯酚和氧化膦侧链之间的分子间碱基配对相互作用,互补的同质低聚物形成稳定的双相化合物。对于混合序列寡聚物,由于分子内碱基配对相互作用,与双相形成竞争的主要途径是折叠。采用自动固相合成技术制备了自互补的REMO DADA,并利用该低聚物研究了分子间和分子内氢键相互作用的竞争。氯仿等温滴定量热法表明,DADA形成二聚物,但与较短的低聚物形成的双聚物相比,其稳定性降低。结果表明,两个末端识别单元之间存在分子内相互作用的折叠态被显著填充。在较高浓度下形成的二聚体复合体可能涉及两个折叠的低聚物在接吻茎环结构中的相互作用,或者低聚物可能展开形成具有四个分子间碱基对的双聚体。该低聚物的一端配以叠氮化物,另一端配以炔,使得二聚物可以通过铜催化叠氮化物-炔环加成反应被共价捕获。主要产物为大环双链和少量的大环单链,表明在毫摩尔浓度下,DADA·DADA双链占主导地位。了解REMO架构的折叠倾向将有助于指导未来的设计原则,以综合更复杂的功能组件。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Organic & Biomolecular Chemistry
Organic & Biomolecular Chemistry 化学-有机化学
CiteScore
5.50
自引率
9.40%
发文量
1056
审稿时长
1.3 months
期刊介绍: Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信