Direct Measurement of the Isomerization Barrier of the Isolated Retinal Chromophore

被引:18
作者
Dilger, Jonathan [1 ]
Musbat, Lihi [2 ]
Sheves, Mordechai [3 ]
Bochenkova, Anastasia V. [4 ,5 ]
Clemmer, David E. [6 ]
Toker, Yoni [2 ]
机构
[1] Spectrum Warfare Syst Dept, NSWC Crane Div, Crane, IN 47522 USA
[2] Bar Ilan Univ, Inst Nanotechnol & Adv Mat, IL-290002 Ramat Gan, Israel
[3] Weizmann Inst Sci, Dept Chem, IL-978007 Rehovot, Israel
[4] Aarhus Univ, Dept Phys & Astron, DK-8000 Aarhus C, Denmark
[5] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia
[6] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
关键词
chromophores; gas-phase reactions; ion mobility spectroscopy; isomerization; proteins; PROTONATED SCHIFF-BASE; VISUAL PIGMENTS; GAS-PHASE; PHOTORECEPTORS; BRADYKININ; ACTIVATION; MECHANISM; TRANS; NOISE; LIGHT;
D O I
10.1002/anie.201411894
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Isomerizations of the retinal chromophore were investigated using the IMS-IMS technique. Four different structural features of the chromophore were observed, isolated, excited collisionally, and the resulting isomer and fragment distributions were measured. By establishing the threshold activation voltages for isomerization for each of the reaction pathways, and by measuring the threshold activation voltage for fragmentation, the relative energies of the isomers as well as the energy barriers for isomerization were determined. The energy barrier for a single cis-trans isomerization is (0.64 +/- 0.05)eV, which is significantly lower than that observed for the reaction within opsin proteins.
引用
收藏
页码:4748 / 4752
页数:69
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