Unraveling the Structure-Affinity Relationship between Cucurbit[n]urils (n=7, 8) and Cationic Diamondoids

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00475010" target="_blank" >RIV/61388963:_____/17:00475010 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15310/17:73584589

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jacs.7b00056" target="_blank" >http://dx.doi.org/10.1021/jacs.7b00056</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.7b00056" target="_blank" >10.1021/jacs.7b00056</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Unraveling the Structure-Affinity Relationship between Cucurbit[n]urils (n=7, 8) and Cationic Diamondoids

Popis výsledku v původním jazyce

We report the measurement of the binding constants (K-a) for cucurbit[n]uril (n = 7, 8) toward four series of guests based on 2,6-disubstituted adamantanes, 4,9-disubstituted diamantanes, 1,6-disubstituted diamantanes, and 1-substituted adamantane ammonium ions by direct and competitive H-1 NMR spectroscopy. Compared to the affinity of CB[7]Diam(NMe3)(2), the adamantane diammonium ion complexes (e.g., CB[7]2,6-Ad(NH3)(2) and CB[7]2,6-Ad(NMe3)(2)) are less effective at realizing the potential 1000-fold enhancement in affinity due to ion-dipole interactions at the second ureidyl C=O portal. Comparative crystallographic investigation of CB[7]Diam(NMe3)(2), CB[7]DiamNMe(3), and CB[7]1-AdNMe(3) revealed that the preferred geometry positions the +NMe3 groups approximate to 0.32 above the C=O portal, the observed 0.80 spacing observed for CB[7]Diam(NMe3)(2) reflects the simultaneous geometrical constraints of CH2O=C close contacts at both portals. Remarkably, the CB[8]IsoDiam(NHMe2)2 complex displays femtomolar binding affinity, placing it firmly alongside the CB[7]Diam(NMe3)(2) complex. Primary or quaternary ammonium ion looping strategies lead to larger increases in binding affinity for CB[8] than for CB[7], which we attribute to the larger size of the carbonyl portals of CB[8], this suggests routes to develop CB[8] as the tightest binding host in the CB[n] family. We report that alkyl group fluorination (e.g., CB[7]1-AdNH(2)Et versus CB[7]1-AdNH(2)CH(2)CF(3)) does not result in the expected increase in Ka value. Finally, we discuss the role of solvation in nonempirical quantum mechanical computational methodology, which is used to estimate the relative changes in Gibbs binding free energies.

Název v anglickém jazyce

Unraveling the Structure-Affinity Relationship between Cucurbit[n]urils (n=7, 8) and Cationic Diamondoids

Popis výsledku anglicky

We report the measurement of the binding constants (K-a) for cucurbit[n]uril (n = 7, 8) toward four series of guests based on 2,6-disubstituted adamantanes, 4,9-disubstituted diamantanes, 1,6-disubstituted diamantanes, and 1-substituted adamantane ammonium ions by direct and competitive H-1 NMR spectroscopy. Compared to the affinity of CB[7]Diam(NMe3)(2), the adamantane diammonium ion complexes (e.g., CB[7]2,6-Ad(NH3)(2) and CB[7]2,6-Ad(NMe3)(2)) are less effective at realizing the potential 1000-fold enhancement in affinity due to ion-dipole interactions at the second ureidyl C=O portal. Comparative crystallographic investigation of CB[7]Diam(NMe3)(2), CB[7]DiamNMe(3), and CB[7]1-AdNMe(3) revealed that the preferred geometry positions the +NMe3 groups approximate to 0.32 above the C=O portal, the observed 0.80 spacing observed for CB[7]Diam(NMe3)(2) reflects the simultaneous geometrical constraints of CH2O=C close contacts at both portals. Remarkably, the CB[8]IsoDiam(NHMe2)2 complex displays femtomolar binding affinity, placing it firmly alongside the CB[7]Diam(NMe3)(2) complex. Primary or quaternary ammonium ion looping strategies lead to larger increases in binding affinity for CB[8] than for CB[7], which we attribute to the larger size of the carbonyl portals of CB[8], this suggests routes to develop CB[8] as the tightest binding host in the CB[n] family. We report that alkyl group fluorination (e.g., CB[7]1-AdNH(2)Et versus CB[7]1-AdNH(2)CH(2)CF(3)) does not result in the expected increase in Ka value. Finally, we discuss the role of solvation in nonempirical quantum mechanical computational methodology, which is used to estimate the relative changes in Gibbs binding free energies.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

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

Rok uplatnění

2017

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

139

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

3249-3258

Kód UT WoS článku

000395493400059

EID výsledku v databázi Scopus

2-s2.0-85014288032