Terahertz Raman Optical Activity Reveals Emergent Supramolecular Chirality in Mononucleotide G-quadruplexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F25%3A73631306" target="_blank" >RIV/61989592:15310/25:73631306 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11320/25:10499295

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cmtd.202500070" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cmtd.202500070</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cmtd.202500070" target="_blank" >10.1002/cmtd.202500070</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Terahertz Raman Optical Activity Reveals Emergent Supramolecular Chirality in Mononucleotide G-quadruplexes

Popis výsledku v původním jazyce

Raman optical activity (ROA) provides unique chiroptical insights into biomolecular structure but suffers from inherently weak signals. A substantial enhancement in the low-wavenumber/THz region (50–250 cm−1/1.5–7.5 THz) of ROA spectra upon the formation of mononucleotide G-quadruplexes (mG4) from guanosine-5′-monophosphate (5′rGMP) is reported. Using concentration-dependent Raman and ROA measurements, a nearly 100-fold increase in ROA intensity upon aggregation is identified, with spectral features highly sensitive to cation-mediated structural variations. These effects can be traced to long-range chiral interactions and distinct stacking arrangements within mG4. While strong terahertz Raman optical activity (THz-ROA) signals have previously been observed in globular proteins and α-helical polypeptides, the findings of this study represent the first evidence of this phenomenon in nucleotides, demonstrating that noncovalent self-assembly into supramolecular helices can give rise to intense low-frequency chiroptical responses. This establishes THz-ROA as a powerful background-free tool for studying supramolecular chirality and nucleotide self-assembly, with potential applications in characterizing biologically relevant G-quadruplex structures. © 2025 The Author(s). Chemistry - Methods published by Chemistry Europe and Wiley-VCH GmbH.

Název v anglickém jazyce

Terahertz Raman Optical Activity Reveals Emergent Supramolecular Chirality in Mononucleotide G-quadruplexes

Popis výsledku anglicky

Raman optical activity (ROA) provides unique chiroptical insights into biomolecular structure but suffers from inherently weak signals. A substantial enhancement in the low-wavenumber/THz region (50–250 cm−1/1.5–7.5 THz) of ROA spectra upon the formation of mononucleotide G-quadruplexes (mG4) from guanosine-5′-monophosphate (5′rGMP) is reported. Using concentration-dependent Raman and ROA measurements, a nearly 100-fold increase in ROA intensity upon aggregation is identified, with spectral features highly sensitive to cation-mediated structural variations. These effects can be traced to long-range chiral interactions and distinct stacking arrangements within mG4. While strong terahertz Raman optical activity (THz-ROA) signals have previously been observed in globular proteins and α-helical polypeptides, the findings of this study represent the first evidence of this phenomenon in nucleotides, demonstrating that noncovalent self-assembly into supramolecular helices can give rise to intense low-frequency chiroptical responses. This establishes THz-ROA as a powerful background-free tool for studying supramolecular chirality and nucleotide self-assembly, with potential applications in characterizing biologically relevant G-quadruplex structures. © 2025 The Author(s). Chemistry - Methods published by Chemistry Europe and Wiley-VCH GmbH.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10306 - Optics (including laser optics and quantum optics)

Projekt

<a href="/cs/project/GA25-15726S" target="_blank" >GA25-15726S: Prozkoumání nových forem Ramanovy optické aktivity</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

CHEMISTRY-METHODS

ISSN

2628-9725

e-ISSN

2628-9725

Svazek periodika

5

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

"e202500070-1"-"e202500070-7"

Kód UT WoS článku

001518981400001

EID výsledku v databázi Scopus

2-s2.0-105009441747