View in EDS

Nitroxoline Molecule: Planar or Not? A Story of Battle between π-π Conjugation and Interatomic Repulsion.

Saved in:
Bibliographic Details
Title: Nitroxoline Molecule: Planar or Not? A Story of Battle between π-π Conjugation and Interatomic Repulsion.
Authors: Tikhonov, Denis S.1 dentix@phys.chem.msu.ru, Sharapa, Dmitry I.2 dmitriy.sharapa@fau.de, Otlyotov, Arseniy A.3 arseney_otlyotov@mail.ru, Solyankin, Peter M.4,5, Rykov, Anatolii N.1, Shkurinov, Alexander P.4,5, Grikina, Olga E.1, Khaikin, Leonid S.1
Source: Journal of Physical Chemistry A. 2/15/2018, Vol. 122 Issue 6, p1691-1701. 11p.
Subjects: Bioconjugates, Interatomic angles, Conformational analysis, Electron diffraction, Solid state chemistry
Abstract: The conformational properties of the nitro group in nitroxoline (8-hydroxy-5-nitroquinoline, NXN) were investigated in the gas phase by means of gas electron diffraction (GED) and quantum chemical calculations, and also with solid-state analysis performed using terahertz time-domain spectroscopy (THz-TDS). The results of the GED refinement show that in the equilibrium structure the NO2 group is twisted by angle φ = 8 ± 3° with respect to the 8-hydroxyoquinoline plane. This is the result of interatomic repulsion of oxygen in the NO2 group from the closest hydrogen, which overcomes the energy gain from the π-π conjugation of the nitro group and aromatic system of 8-hydroxyoquinoline. The computation of equilibrium geometry using MP2/cc-pVXZ (X = T, Q) shows a large overestimation of the φ value, while DFT with the cc-pVTZ basis set performs reasonably well. On the other hand, DFT computations with double-ζ basis sets yield a planar structure of NXN. The refined potential energy surface of the torsion vibration the of nitro group in the condensed phase derived from the THz-TDS data indicates the NXN molecule to be planar. This result stays in good agreement with the previous X-ray structure determination. The strength of the π-system conjugation for the NO2 group and 8-hydroxyoquinoline is discussed using NBO analysis, being further supported by comparison of the refined semiexperimental gas-phase structure of NXN from GED with other nitrocompounds. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 128142714
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Nitroxoline Molecule: Planar or Not? A Story of Battle between π-π Conjugation and Interatomic Repulsion.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Tikhonov%2C+Denis+S%2E%22">Tikhonov, Denis S.</searchLink><relatesTo>1</relatesTo><i> dentix@phys.chem.msu.ru</i><br /><searchLink fieldCode="AR" term="%22Sharapa%2C+Dmitry+I%2E%22">Sharapa, Dmitry I.</searchLink><relatesTo>2</relatesTo><i> dmitriy.sharapa@fau.de</i><br /><searchLink fieldCode="AR" term="%22Otlyotov%2C+Arseniy+A%2E%22">Otlyotov, Arseniy A.</searchLink><relatesTo>3</relatesTo><i> arseney_otlyotov@mail.ru</i><br /><searchLink fieldCode="AR" term="%22Solyankin%2C+Peter+M%2E%22">Solyankin, Peter M.</searchLink><relatesTo>4,5</relatesTo><br /><searchLink fieldCode="AR" term="%22Rykov%2C+Anatolii+N%2E%22">Rykov, Anatolii N.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Shkurinov%2C+Alexander+P%2E%22">Shkurinov, Alexander P.</searchLink><relatesTo>4,5</relatesTo><br /><searchLink fieldCode="AR" term="%22Grikina%2C+Olga+E%2E%22">Grikina, Olga E.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Khaikin%2C+Leonid+S%2E%22">Khaikin, Leonid S.</searchLink><relatesTo>1</relatesTo>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. 2/15/2018, Vol. 122 Issue 6, p1691-1701. 11p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Bioconjugates%22">Bioconjugates</searchLink><br /><searchLink fieldCode="DE" term="%22Interatomic+angles%22">Interatomic angles</searchLink><br /><searchLink fieldCode="DE" term="%22Conformational+analysis%22">Conformational analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+diffraction%22">Electron diffraction</searchLink><br /><searchLink fieldCode="DE" term="%22Solid+state+chemistry%22">Solid state chemistry</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The conformational properties of the nitro group in nitroxoline (8-hydroxy-5-nitroquinoline, NXN) were investigated in the gas phase by means of gas electron diffraction (GED) and quantum chemical calculations, and also with solid-state analysis performed using terahertz time-domain spectroscopy (THz-TDS). The results of the GED refinement show that in the equilibrium structure the NO2 group is twisted by angle φ = 8 ± 3° with respect to the 8-hydroxyoquinoline plane. This is the result of interatomic repulsion of oxygen in the NO2 group from the closest hydrogen, which overcomes the energy gain from the π-π conjugation of the nitro group and aromatic system of 8-hydroxyoquinoline. The computation of equilibrium geometry using MP2/cc-pVXZ (X = T, Q) shows a large overestimation of the φ value, while DFT with the cc-pVTZ basis set performs reasonably well. On the other hand, DFT computations with double-ζ basis sets yield a planar structure of NXN. The refined potential energy surface of the torsion vibration the of nitro group in the condensed phase derived from the THz-TDS data indicates the NXN molecule to be planar. This result stays in good agreement with the previous X-ray structure determination. The strength of the π-system conjugation for the NO2 group and 8-hydroxyoquinoline is discussed using NBO analysis, being further supported by comparison of the refined semiexperimental gas-phase structure of NXN from GED with other nitrocompounds. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=128142714
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1021/acs.jpca.7b11364
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 11
        StartPage: 1691
    Subjects:
      – SubjectFull: Bioconjugates
        Type: general
      – SubjectFull: Interatomic angles
        Type: general
      – SubjectFull: Conformational analysis
        Type: general
      – SubjectFull: Electron diffraction
        Type: general
      – SubjectFull: Solid state chemistry
        Type: general
    Titles:
      – TitleFull: Nitroxoline Molecule: Planar or Not? A Story of Battle between π-π Conjugation and Interatomic Repulsion.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Tikhonov, Denis S.
      – PersonEntity:
          Name:
            NameFull: Sharapa, Dmitry I.
      – PersonEntity:
          Name:
            NameFull: Otlyotov, Arseniy A.
      – PersonEntity:
          Name:
            NameFull: Solyankin, Peter M.
      – PersonEntity:
          Name:
            NameFull: Rykov, Anatolii N.
      – PersonEntity:
          Name:
            NameFull: Shkurinov, Alexander P.
      – PersonEntity:
          Name:
            NameFull: Grikina, Olga E.
      – PersonEntity:
          Name:
            NameFull: Khaikin, Leonid S.
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 15
              M: 02
              Text: 2/15/2018
              Type: published
              Y: 2018
          Identifiers:
            – Type: issn-print
              Value: 10895639
          Numbering:
            – Type: volume
              Value: 122
            – Type: issue
              Value: 6
          Titles:
            – TitleFull: Journal of Physical Chemistry A
              Type: main
ResultId 1