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Femtochemistry of orange II in solution and in chemical and biological nanocavities.

Abstract：

:In this work, we report on studies of the nature of the dynamics and hydrophobic binding in cyclodextrins and human serum albumin protein complexes with orange II. With femtosecond time resolution, we examined the proton-transfer and trans-cis isomerization reactions of the ligand in these nanocavities and in pure solvents. Because of confinement at the ground state, the orientational motion in the formed phototautomer is restricted, leading to a rich dynamics. Therefore, the emission lifetimes span a large window of tens to hundreds of picoseconds in the cavities. Possible H-bond interactions between the guest and cyclodextrin do not affect the caged dynamics. For the protein-ligand complexes, slow diffusional motion ( approximately 630 ps) observed in the anisotropy decay indicates that the binding structure is not completely rigid, and the embedded guest is not frozen with the hydrophobic pocket. The ultrafast isomerization and decays are explained in terms of coupling motions between N-N and C-N stretching modes of the formed tautomer. We discuss the role of confinement on the trans-cis isomerization with the cavities and its relationships to frequency and time domains of nanostructure emission.

journal_name

Proc Natl Acad Sci U S A

journal_title

Proceedings of the National Academy of Sciences of the United States of America

authors

Douhal A,Sanz M,Tormo L

doi

10.1073/pnas.0507459102

keywords:

subject

Has Abstract

pub_date

2005-12-27 00:00:00

pages

18807-12

issue

52

eissn

0027-8424

issn

1091-6490

pii

0507459102

journal_volume

102

pub_type

杂志文章

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