Time-Resolved and Mechanistic Study of the Photochemical Uncaging Reaction of the o-Hydroxycinnamic Caged Compound
文献类型：期刊论文
| 作者 | Yu, Youqing; Wu, Lidan; Zou, Xiaoran; Dai, Xiaojuan; Liu, Kunhui; Su, Hongmei |
| 刊名 | journal of physical chemistry a
 |
| 出版日期 | 2013-08-22 |
| 卷号 | 117期号:33页码:7767-7775 |
| 英文摘要 | the o-hydroxycinnamic derivatives represent efficient caged compounds that can realize quantification of delivery upon uncaging, but there has been lack of time-resolved and mechanistic studies. we used time-resolved infrared (trir) spectroscopy to investigate the photochemical uncaging dynamics of the prototype o-hydroxycinnamic compound, (e)-3-(2-hydroxyphenyl)-acrylic acid ethyl ester (haaee), leading to coumarin and ethanol upon uncaging. taking advantage of the specific vibrational marker bands and the ir discerning capability, we have identified and distinguished two key intermediate species, the cis-isomers of haaee and the tetrahedral intermediate, in the transient infrared spectra, thus providing clear spectral evidence to support the intramolecular nucleophilic addition mechanism following the trans-cis photoisomerization. moreover, the product yields of coumarin upon uncaging were observed to be greatly affected by the solvent polarity, suppressed in ch2cl2 but enhanced in d2o/ch3cn with the increasing volume ratio of d2o. the highly solvent-dependent behavior indicates e1 elimination of the tetrahedral intermediate to give rise to the final uncaging product coumarin. the photorelease rate of coumarin was directly characterized from trir (3.6 x 10(6) s(-1)), revealing the promising application of such o-hydroxycinnamic compound in producing fast alcohol jumps. the trir results provide the first time-resolved detection and thus offer direct dynamical information about this photochemical uncaging reaction. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, physical ; physics, atomic, molecular & chemical |
| 研究领域[WOS] | chemistry ; physics |
| 关键词[WOS] | photoremovable protecting group ; coumarinic acids ; spectroscopy ; phototriggers ; lactonization ; photorelease ; phosphates ; absorption ; molecules ; dynamics |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000323593700013 |
| 公开日期 | 2015-11-10 |
| 源URL | [http://159.226.238.44/handle/321008/137957]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, BNLMS, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yu, Youqing,Wu, Lidan,Zou, Xiaoran,et al. Time-Resolved and Mechanistic Study of the Photochemical Uncaging Reaction of the o-Hydroxycinnamic Caged Compound[J]. journal of physical chemistry a,2013,117(33):7767-7775. |
| APA | Yu, Youqing,Wu, Lidan,Zou, Xiaoran,Dai, Xiaojuan,Liu, Kunhui,&Su, Hongmei.(2013).Time-Resolved and Mechanistic Study of the Photochemical Uncaging Reaction of the o-Hydroxycinnamic Caged Compound.journal of physical chemistry a,117(33),7767-7775. |
| MLA | Yu, Youqing,et al."Time-Resolved and Mechanistic Study of the Photochemical Uncaging Reaction of the o-Hydroxycinnamic Caged Compound".journal of physical chemistry a 117.33(2013):7767-7775. |
入库方式： OAI收割
来源：大连化学物理研究所
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