Volume 145, 2010
From the journal:

Faraday Discussions

Ultrafast time-resolved transient infrared and resonance Raman spectroscopic study of the photo-deprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates†

Qian Cao,a   Xiangguo Guan,b   Michael W. George,*a   David Lee Phillips,*b   Chensheng Ma,b   Wai Ming Kwok,c   Mingde Li,b   Yong Du,b   Xue-Zhong Suna  and  Jiadan Xueb  

* Corresponding authors

a School of Chemistry, University of Nottingham, University Park, Nottingham, United Kingdom

b Department of Chemistry, University of Hong Kong, Pokfulam Road, Hong Kong S.A.R., P. R. China

c Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong S.A.R., P. R. China

Abstract

This is a picosecond and nanosecond time-resolved infrared absorption spectroscopic study of p-hydroxphenacyl diethylphosphate (HPDP) in aqueous solution examining the deprotection reaction and subsequent evolution to produce the p-hydroxyphenylacetic acid (HPAA) rearrangement product. The data reported here support previous ultrafast fluorescence, Raman and transient UV/visible absorption studies and provide new insight into the role of water in the deprotection reaction. It also provides insight into the nature of the intermediate steps that take place following initial formation of the triplet state and its reaction with water to eventually produce the solvent-separated ions and solvolytic reaction product HPAA. In addition, density functional theory (DFT) calculations were performed to investigate the reactions of the triplet state of HPDP with water molecules to induce deprotection, the formation of a contact ion pair and the subsequent intermediates that lead to the HPAA rearrangement product. A more detailed reaction mechanism is proposed based on the time-resolved spectroscopy experiments and DFT computational results.

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Article information

DOI
https://doi.org/10.1039/B908188G
Article type
Paper
Submitted
23 Apr 2009
Accepted
23 Jun 2009
First published
20 Oct 2009

Faraday Discuss., 2010,145, 171-183

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Ultrafast time-resolved transient infrared and resonance Raman spectroscopic study of the photo-deprotection and rearrangement reactions of p-hydroxyphenacyl caged phosphates

Q. Cao, X. Guan, M. W. George, D. L. Phillips, C. Ma, W. M. Kwok, M. Li, Y. Du, X. Sun and J. Xue, Faraday Discuss., 2010, 145, 171 DOI: 10.1039/B908188G

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