Short but Weak: The Z-DNA lone-pair...Pi Conundrum Challenges Standard Carbon Van der Waals Radii

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F20%3A00116488" target="_blank" >RIV/00216224:14310/20:00116488 - isvavai.cz</a>

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/ange.202004201" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/ange.202004201</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/anie.202004201" target="_blank" >10.1002/anie.202004201</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Short but Weak: The Z-DNA lone-pair...Pi Conundrum Challenges Standard Carbon Van der Waals Radii

Popis výsledku v původním jazyce

Current interest in lone-pair center dot center dot center dot pi (lp center dot center dot center dot pi) interactions is gaining momentum in biochemistry and (supramolecular) chemistry. However, the physicochemical origin of the exceptionally short (ca. 2.8 angstrom) oxygen-to-nucleobase plane distances observed in prototypical Z-DNA CpG steps remains unclear. High-level quantum mechanical calculations, including SAPT2 + 3 interaction energy decompositions, demonstrate that lp center dot center dot center dot pi contacts do not result from n -&gt;pi* orbital overlaps but from weak dispersion and electrostatic interactions combined with stereochemical effects imposed by the locally strained structural context. They also suggest that the carbon van der Waals (vdW) radii, originally derived for sp(3) carbons, should not be used for smaller sp(2) carbons attached to electronwithdrawing groups. Using a more adapted carbon vdW radius results in these lp center dot center dot center dot pi contacts being no longer of the sub-vdW type. These findings challenge the whole lp center dot center dot center dot pi concept that refers to elusive orbital interactions that fail to explain short interatomic contact distances.

Název v anglickém jazyce

Short but Weak: The Z-DNA lone-pair...Pi Conundrum Challenges Standard Carbon Van der Waals Radii

Popis výsledku anglicky

Current interest in lone-pair center dot center dot center dot pi (lp center dot center dot center dot pi) interactions is gaining momentum in biochemistry and (supramolecular) chemistry. However, the physicochemical origin of the exceptionally short (ca. 2.8 angstrom) oxygen-to-nucleobase plane distances observed in prototypical Z-DNA CpG steps remains unclear. High-level quantum mechanical calculations, including SAPT2 + 3 interaction energy decompositions, demonstrate that lp center dot center dot center dot pi contacts do not result from n -&gt;pi* orbital overlaps but from weak dispersion and electrostatic interactions combined with stereochemical effects imposed by the locally strained structural context. They also suggest that the carbon van der Waals (vdW) radii, originally derived for sp(3) carbons, should not be used for smaller sp(2) carbons attached to electronwithdrawing groups. Using a more adapted carbon vdW radius results in these lp center dot center dot center dot pi contacts being no longer of the sub-vdW type. These findings challenge the whole lp center dot center dot center dot pi concept that refers to elusive orbital interactions that fail to explain short interatomic contact distances.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10603 - Genetics and heredity (medical genetics to be 3)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Angewandte Chemie International Edition

ISSN

1433-7851

e-ISSN

1521-3773

Svazek periodika

59

Číslo periodika v rámci svazku

38

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

8

Strana od-do

16553-16560

Kód UT WoS článku

000548319500001

EID výsledku v databázi Scopus

2-s2.0-85087864327