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A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions
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SYSNO ASEP 0467351 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název A Nexus between Theory and Experiment: Non-Empirical Quantum Mechanical Computational Methodology Applied to Cucurbit[n]urilGuest Binding Interactions Tvůrce(i) Hostaš, Jiří (UOCHB-X) RID
Sigwalt, D. (US)
Šekutor, M. (HR)
Ajani, Haresh (UOCHB-X) ORCID, RID
Dubecký, M. (CZ)
Řezáč, Jan (UOCHB-X) RID, ORCID
Zavalij, P. Y. (US)
Cao, L. (US)
Wohlschlager, Ch. (AT)
Mlinaric-Majerski, K. (HR)
Isaacs, L. (US)
Glaser, R. (IL)
Hobza, Pavel (UOCHB-X) RID, ORCIDZdroj.dok. Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 22, č. 48 (2016), s. 17226-17238Poč.str. 13 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova adamantane-/diamantane-skeleton guests ; biomimetic complexes ; BLYP-D3 quantum mechanical calculations ; cucurbit[n]uril ; host-guest complexes ; primary ammonium loops Vědní obor RIV CF - Fyzikální chemie a teoretická chemie CEP GBP208/12/G016 GA ČR - Grantová agentura ČR Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 000387854800019 EID SCOPUS 84990975388 DOI 10.1002/chem.201601833 Anotace 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. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2017
Počet záznamů: 1