日本語
 
Help Privacy Policy ポリシー/免責事項
  詳細検索ブラウズ

アイテム詳細

  Flexible Biradicals in Liquid and Supercritical Carbon Dioxide:  The Exchange Interaction, the Chain Dynamics, and a Comparison with Conventional Solvents

Forbes, M., Dukes, K., Avdievich, N., Harbron, E., & DeSimone, J. (2006). Flexible Biradicals in Liquid and Supercritical Carbon Dioxide:  The Exchange Interaction, the Chain Dynamics, and a Comparison with Conventional Solvents. The Journal of Physical Chemistry A, 110(5), 1767-1774. doi:10.1021/jp053183q.

Item is

基本情報

表示: 非表示:
アイテムのパーマリンク: https://hdl.handle.net/21.11116/0000-0004-962C-2 版のパーマリンク: https://hdl.handle.net/21.11116/0000-0004-962D-1
資料種別: 学術論文

ファイル

表示: ファイル

関連URL

表示:

作成者

表示:
非表示:
 作成者:
Forbes, MDE, 著者
Dukes, KE, 著者
Avdievich, NI1, 著者           
Harbron, EJ, 著者
DeSimone, JM, 著者
所属:
1Max Planck Institute for Biological Cybernetics, Max Planck Society, ou_1497794              

内容説明

表示:
非表示:
キーワード: -
 要旨: X-band time-resolved electron paramagnetic resonance (TREPR) spectra of three flexible biradicals of varying chain length and structure were obtained in liquid and supercritical carbon dioxide (CO2) solutions and compared to conventional solvents. For C16 acyl−alkyl biradical 1a, an average spin exchange interaction between the radical centers, Javg, was obtained by spectral simulation using a simple model for spin-correlated radical pairs (SCRPs) and a small amount of T2 relaxation from a previously established J modulation mechanism. A large solvent effect on Javg was observed for the first time, varying by almost 1 order of magnitude from CO2 (Javg = −120 ± 10 MHz) to heavy mineral oil (−11 ± 3 MHz) for 1a. For C15 bis(alkyl) biradical 1b, spectra obtained under supercritical conditions are only slightly different from those detected in liquid CO2 but differ from spectra taken in benzene. For C10 acyl−alkyl biradical 2a, more emissive spin polarization due to S−T- mixing is observed in CO2 than in benzene. These results are discussed in terms of solvent properties such as dielectric constant, viscosity, and specific interactions. Both chain dynamics and changes to the equilibrium distribution of end-to-end distances can alter Javg and the observed ratio of S−T0 to S−T- mixing; however, faster chain dynamics is concluded to be the most likely cause of the observed effects in these systems.

資料詳細

表示:
非表示:
言語:
 日付: 2006-01
 出版の状態: 出版
 ページ: -
 出版情報: -
 目次: -
 査読: -
 識別子(DOI, ISBNなど): DOI: 10.1021/jp053183q
 学位: -

関連イベント

表示:

訴訟

表示:

Project information

表示:

出版物 1

表示:
非表示:
出版物名: The Journal of Physical Chemistry A
  その他 : J. Phys. Chem. A
種別: 学術雑誌
 著者・編者:
所属:
出版社, 出版地: Columbus, OH : American Chemical Society
ページ: - 巻号: 110 (5) 通巻号: - 開始・終了ページ: 1767 - 1774 識別子(ISBN, ISSN, DOIなど): ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4