A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F16%3A00467351" target="_blank" >RIV/61388963:_____/16:00467351 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/16:10332100 RIV/61989592:15310/16:73584922

Výsledek na webu

<a href="http://dx.doi.org/10.1002/chem.201601833" target="_blank" >http://dx.doi.org/10.1002/chem.201601833</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.201601833" target="_blank" >10.1002/chem.201601833</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions

Popis výsledku v původním jazyce

A training set of eleven X-ray structures determined for biomimetic complexes between cucurbit[n]uril (CB[7 or 8]) hosts and adamantane-/diamantane ammonium/aminium guests were studied with DFT-D3 quantum mechanical computational methods to afford G(calcd) binding energies. A novel feature of this work is that the fidelity of the BLYP-D3/def2-TZVPP choice of DFT functional was proven by comparison with more accurate methods. For the first time, the CB[n]guest complex binding energy subcomponents [for example, E-dispersion, E-electrostatic, G(solvation), binding entropy (-TS), and induced fit E-deformation(host), E-deformation(guest)] were calculated. Only a few weeks of computation time per complex were required by using this protocol. The deformation (stiffness) and solvation properties (with emphasis on cavity desolvation) of cucurbit[n]uril (n=5, 6, 7, 8) isolated host molecules were also explored by means of the DFT-D3 method. A high (2)=0.84 correlation coefficient between G(exptl) and G(calcd) was achieved without any scaling of the calculated terms (at 298K). This linear dependence was utilized for G(calcd) predictions of new complexes. The nature of binding, including the role of high energy water molecules, was also studied. The utility of introduction of tethered [-(CH2)(n)NH3](+) amino loops attached to N,N-dimethyl-adamantane-1-amine and N,N,N,N-tetramethyl diamantane-4,9-diamine skeletons (both from an experimental and a theoretical perspective) is presented here as a promising tool for the achievement of new ultra-high binding guests to CB[7] hosts. Predictions of not yet measured equilibrium constants are presented herein.

Název v anglickém jazyce

A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions

Popis výsledku anglicky

A training set of eleven X-ray structures determined for biomimetic complexes between cucurbit[n]uril (CB[7 or 8]) hosts and adamantane-/diamantane ammonium/aminium guests were studied with DFT-D3 quantum mechanical computational methods to afford G(calcd) binding energies. A novel feature of this work is that the fidelity of the BLYP-D3/def2-TZVPP choice of DFT functional was proven by comparison with more accurate methods. For the first time, the CB[n]guest complex binding energy subcomponents [for example, E-dispersion, E-electrostatic, G(solvation), binding entropy (-TS), and induced fit E-deformation(host), E-deformation(guest)] were calculated. Only a few weeks of computation time per complex were required by using this protocol. The deformation (stiffness) and solvation properties (with emphasis on cavity desolvation) of cucurbit[n]uril (n=5, 6, 7, 8) isolated host molecules were also explored by means of the DFT-D3 method. A high (2)=0.84 correlation coefficient between G(exptl) and G(calcd) was achieved without any scaling of the calculated terms (at 298K). This linear dependence was utilized for G(calcd) predictions of new complexes. The nature of binding, including the role of high energy water molecules, was also studied. The utility of introduction of tethered [-(CH2)(n)NH3](+) amino loops attached to N,N-dimethyl-adamantane-1-amine and N,N,N,N-tetramethyl diamantane-4,9-diamine skeletons (both from an experimental and a theoretical perspective) is presented here as a promising tool for the achievement of new ultra-high binding guests to CB[7] hosts. Predictions of not yet measured equilibrium constants are presented herein.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

22

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

13

Strana od-do

17226-17238

Kód UT WoS článku

000387854800019

EID výsledku v databázi Scopus

2-s2.0-84990975388