Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether

Two novel β-cyclodextrin (β -CD) derivatives possessing azobenzene functional groups as a spectral probe, i.e., mono{6-O-[4-(phenylazo)phenyl]}- β -cyclodextrin (1) and mono{6-O-[4-((4-nitrophenyl)azo)phenyl]}- β-cyclodextrin (2), were synthesized in high yields, and their complexation behaviors wit...

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Main Authors: Liu, Yu, Zhao, Yanli, Zhang, Heng Yi, Fan, Zhi, Wen, Guo Dong, Ding, Fei
Format: Article
Published: 2011
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Online Access:https://hdl.handle.net/10356/94279
http://hdl.handle.net/10220/6972
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spelling sg-ntu-dr.10356-942792020-03-07T12:37:19Z Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether Liu, Yu Zhao, Yanli Zhang, Heng Yi Fan, Zhi Wen, Guo Dong Ding, Fei DRNTU::Science::Chemistry::Organic chemistry::Aliphatic compounds DRNTU::Engineering::Chemical technology Two novel β-cyclodextrin (β -CD) derivatives possessing azobenzene functional groups as a spectral probe, i.e., mono{6-O-[4-(phenylazo)phenyl]}- β -cyclodextrin (1) and mono{6-O-[4-((4-nitrophenyl)azo)phenyl]}- β-cyclodextrin (2), were synthesized in high yields, and their complexation behaviors with aliphatic alcohols were evaluated by using UV-vis, circular dichroism, and 1H NMR spectroscopy. The induced circular dichroism (ICD) and 2D NMR spectroscopy investigations revealed that azobenzene groups attached to the β-CD rim can be deeply embedded to the β-CD cavity to form the intramolecular inclusion complexes in 10% DMSO aqueous solution. Increasing the ratio of DMSO in solution results in the gradual exclusion of the azobenzene sidearm from the β-CD cavity. Upon complexation with guest adamantanols, modified β-CD 1 or 2 displays two different binding models, that is, the competitive inclusion model for 2-adamantanol and the co-inclusion model for 1-damantanol. These two different models reasonably explain the different binding behaviors and molecular selectivities of host β-CDs toward guests. Therefore, besides acting as a spectral probe, azobenzene modified β-CDs can also effectively recognize the size/shape of guest molecules, giving good molecular selectivity up to 91 for 2-adamantanol/(+)-borneol pair by 1 and the modeate enantioselectivity (K-/K+ = 2.1) for (-)-/(+)-borneol pair by 2. None of the above 2011-09-05T04:09:33Z 2019-12-06T18:53:38Z 2011-09-05T04:09:33Z 2019-12-06T18:53:38Z 2004 2004 Journal Article Liu, Y., Zhao, Y. L., Zhang, H. Y., Fan, Z., Wen, G. D., & Ding, F. (2004). Spectrophotometric Study of Inclusion Complexation of Aliphatic Alcohols by β-Cyclodextrins with Azobenzene Tether. The Journal of Physical Chemistry B, 108(26), 8836-8843. https://hdl.handle.net/10356/94279 http://hdl.handle.net/10220/6972 10.1021/jp0380024 159672 Journal of physical chemistry B © 2004 American Chemical Society. 8 p.
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
topic DRNTU::Science::Chemistry::Organic chemistry::Aliphatic compounds
DRNTU::Engineering::Chemical technology
spellingShingle DRNTU::Science::Chemistry::Organic chemistry::Aliphatic compounds
DRNTU::Engineering::Chemical technology
Liu, Yu
Zhao, Yanli
Zhang, Heng Yi
Fan, Zhi
Wen, Guo Dong
Ding, Fei
Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
description Two novel β-cyclodextrin (β -CD) derivatives possessing azobenzene functional groups as a spectral probe, i.e., mono{6-O-[4-(phenylazo)phenyl]}- β -cyclodextrin (1) and mono{6-O-[4-((4-nitrophenyl)azo)phenyl]}- β-cyclodextrin (2), were synthesized in high yields, and their complexation behaviors with aliphatic alcohols were evaluated by using UV-vis, circular dichroism, and 1H NMR spectroscopy. The induced circular dichroism (ICD) and 2D NMR spectroscopy investigations revealed that azobenzene groups attached to the β-CD rim can be deeply embedded to the β-CD cavity to form the intramolecular inclusion complexes in 10% DMSO aqueous solution. Increasing the ratio of DMSO in solution results in the gradual exclusion of the azobenzene sidearm from the β-CD cavity. Upon complexation with guest adamantanols, modified β-CD 1 or 2 displays two different binding models, that is, the competitive inclusion model for 2-adamantanol and the co-inclusion model for 1-damantanol. These two different models reasonably explain the different binding behaviors and molecular selectivities of host β-CDs toward guests. Therefore, besides acting as a spectral probe, azobenzene modified β-CDs can also effectively recognize the size/shape of guest molecules, giving good molecular selectivity up to 91 for 2-adamantanol/(+)-borneol pair by 1 and the modeate enantioselectivity (K-/K+ = 2.1) for (-)-/(+)-borneol pair by 2.
format Article
author Liu, Yu
Zhao, Yanli
Zhang, Heng Yi
Fan, Zhi
Wen, Guo Dong
Ding, Fei
author_facet Liu, Yu
Zhao, Yanli
Zhang, Heng Yi
Fan, Zhi
Wen, Guo Dong
Ding, Fei
author_sort Liu, Yu
title Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
title_short Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
title_full Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
title_fullStr Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
title_full_unstemmed Spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
title_sort spectrophotometric study of inclusion complexation of aliphatic alcohols by β-cyclodextrins with azobenzene tether
publishDate 2011
url https://hdl.handle.net/10356/94279
http://hdl.handle.net/10220/6972
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