An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates
α-Tocopheryl succinate (α-TOS) is a very promising anticancer agent; however, the mechanism of its action and the role of the succinic moiety in biological activity still remains unclear. This paper, presents the first determination of the X-ray structure of α-TOS and 2,2,5,7,8-pentamethylchroman-6-...
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doaj-c79e57fc65d94be1b3fee6509f92c41c2020-11-24T21:34:29ZengElsevierJournal of Saudi Chemical Society1319-61032019-03-01233365377An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinatesPiotr Wałejko0Łukasz Dobrzycki1Artur Ratkiewicz2Paweł Socha3Stanisław Witkowski4Michał K. Cyrański5University of Bialystok, Institute of Chemistry, Ciołkowskiego 1K, 15-245 Białystok, Poland; Corresponding author.University of Warsaw, Faculty of Chemistry, Czochralski Laboratory of Advanced Crystal Engineering, Zwirki i Wigury 101, 02-089 Warsaw, PolandUniversity of Bialystok, Institute of Chemistry, Ciołkowskiego 1K, 15-245 Białystok, PolandUniversity of Warsaw, Faculty of Chemistry, Czochralski Laboratory of Advanced Crystal Engineering, Zwirki i Wigury 101, 02-089 Warsaw, PolandUniversity of Bialystok, Institute of Chemistry, Ciołkowskiego 1K, 15-245 Białystok, PolandUniversity of Warsaw, Faculty of Chemistry, Czochralski Laboratory of Advanced Crystal Engineering, Zwirki i Wigury 101, 02-089 Warsaw, Polandα-Tocopheryl succinate (α-TOS) is a very promising anticancer agent; however, the mechanism of its action and the role of the succinic moiety in biological activity still remains unclear. This paper, presents the first determination of the X-ray structure of α-TOS and 2,2,5,7,8-pentamethylchroman-6-yl succinate (PMCS). The X-ray data indicated high out of planarity deformation of the aryl ring in the chroman-6-ol system. α-TOS and PMCS differed in angle θ value (28.4° vs. 21.5°, respectively) and in their heterocyclic ring conformations: 2-endo-3-exo in PMCS, and 2-endo-3-exo and 2-exo-3-endo in α-TOS. Due to their strong intermolecular hydrogen bonds, both succinates form cyclically repeated dimeric structures in well assembled crystal supramolecular structures.A population analysis of α-tocopherol (α-TOC), 2,2,5,7,8-pentamethylchroman-6-ol (PMC) and their acyl derivatives was performed at B3LYP/6-31G(d,p)/CPCM level of theory using a natural bond orbital (NBO) analysis within the Gaussian 09 program package. For all compounds, relaxed scans were performed along torsion angle γ, and for low-energy conformers the Fukui functions were calculated: electron donor (ƒ−(r)), electron acceptor (ƒ+(r)), free radical (ƒo(r)) and dual descriptor (ƒ2(r)).In general, the differences observed between α-TOC and its acyl derivative structures result from the non-bonding lone pair of the phenolic oxygen and its interaction with aromatic system π electrons. Keywords: α-Tocopheryl succinate, X-ray, Natural Bond Orbital, DFT calculation, Fukui functionhttp://www.sciencedirect.com/science/article/pii/S1319610318301029 |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Piotr Wałejko Łukasz Dobrzycki Artur Ratkiewicz Paweł Socha Stanisław Witkowski Michał K. Cyrański |
spellingShingle |
Piotr Wałejko Łukasz Dobrzycki Artur Ratkiewicz Paweł Socha Stanisław Witkowski Michał K. Cyrański An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates Journal of Saudi Chemical Society |
author_facet |
Piotr Wałejko Łukasz Dobrzycki Artur Ratkiewicz Paweł Socha Stanisław Witkowski Michał K. Cyrański |
author_sort |
Piotr Wałejko |
title |
An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates |
title_short |
An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates |
title_full |
An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates |
title_fullStr |
An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates |
title_full_unstemmed |
An X-ray and Natural Bond Orbital (NBO) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates |
title_sort |
x-ray and natural bond orbital (nbo) structural study of α-tocopheryl and 2,2,5,7,8-pentamethylchroman-6-yl succinates |
publisher |
Elsevier |
series |
Journal of Saudi Chemical Society |
issn |
1319-6103 |
publishDate |
2019-03-01 |
description |
α-Tocopheryl succinate (α-TOS) is a very promising anticancer agent; however, the mechanism of its action and the role of the succinic moiety in biological activity still remains unclear. This paper, presents the first determination of the X-ray structure of α-TOS and 2,2,5,7,8-pentamethylchroman-6-yl succinate (PMCS). The X-ray data indicated high out of planarity deformation of the aryl ring in the chroman-6-ol system. α-TOS and PMCS differed in angle θ value (28.4° vs. 21.5°, respectively) and in their heterocyclic ring conformations: 2-endo-3-exo in PMCS, and 2-endo-3-exo and 2-exo-3-endo in α-TOS. Due to their strong intermolecular hydrogen bonds, both succinates form cyclically repeated dimeric structures in well assembled crystal supramolecular structures.A population analysis of α-tocopherol (α-TOC), 2,2,5,7,8-pentamethylchroman-6-ol (PMC) and their acyl derivatives was performed at B3LYP/6-31G(d,p)/CPCM level of theory using a natural bond orbital (NBO) analysis within the Gaussian 09 program package. For all compounds, relaxed scans were performed along torsion angle γ, and for low-energy conformers the Fukui functions were calculated: electron donor (ƒ−(r)), electron acceptor (ƒ+(r)), free radical (ƒo(r)) and dual descriptor (ƒ2(r)).In general, the differences observed between α-TOC and its acyl derivative structures result from the non-bonding lone pair of the phenolic oxygen and its interaction with aromatic system π electrons. Keywords: α-Tocopheryl succinate, X-ray, Natural Bond Orbital, DFT calculation, Fukui function |
url |
http://www.sciencedirect.com/science/article/pii/S1319610318301029 |
work_keys_str_mv |
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