一种“超级”光碱的超快动力学
Ultrafast Dynamics of a "Super" Photobase.
作者信息
Sheng Wei, Nairat Muath, Pawlaczyk Patrick D, Mroczka Elizabeth, Farris Benjamin, Pines Ehud, Geiger James H, Borhan Babak, Dantus Marcos
机构信息
Department of Chemistry, Michigan State University, E. Lansing, MI, 48824, USA.
Department of Chemistry, Ben-Gurion University of the Negev, POB 653, Beer Sheva, 84105, Israel.
出版信息
Angew Chem Int Ed Engl. 2018 Nov 5;57(45):14742-14746. doi: 10.1002/anie.201806787. Epub 2018 Oct 12.
Abstract
Molecular reactivity can change dramatically with the absorption of a photon due to the difference of the electronic configurations between the excited and ground states. Here we report on the discovery of a modular system (Schiff base formed from an aldehyde and an amine) that upon photoexcitation yields a more basic imine capable of intermolecular proton transfer from protic solvents. Ultrafast dynamics of the excited state conjugated Schiff base reveals the pathway for proton transfer, culminating in a 14-unit increase in pK to give the excited state pK >20 in ethanol.
摘要
由于激发态和基态之间电子构型的差异，分子反应性会因光子吸收而发生显著变化。在此，我们报告了一种模块化体系（由醛和胺形成的席夫碱）的发现，该体系在光激发时会产生一种碱性更强的亚胺，能够从质子溶剂中进行分子间质子转移。激发态共轭席夫碱的超快动力学揭示了质子转移的途径，最终使pK增加14个单位，在乙醇中激发态pK>20。
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1
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2
Enantioselective Protonation of Silyl Enol Ether Using Excited State Proton Transfer Dyes.使用激发态质子转移染料对硅基烯醇醚进行对映选择性质子化。
Org Lett. 2016 Oct 21;18(20):5416-5419. doi: 10.1021/acs.orglett.6b02820. Epub 2016 Oct 10.
3
Photobasicity in Quinolines: Origin and Tunability via the Substituents' Hammett Parameters.喹啉中的光碱度：通过取代基的哈米特参数探究其起源及可调控性
J Phys Chem Lett. 2016 Jun 2;7(11):2093-9. doi: 10.1021/acs.jpclett.6b00790. Epub 2016 May 23.
4
A photochromic-acidochromic HCl fluorescent probe. An unexpected chloride-directed recognition.一种光致变色-酸致变色的 HCl 荧光探针。一种意想不到的氯离子导向识别。
Analyst. 2016 Jun 20;141(13):4108-20. doi: 10.1039/c6an00509h.
5
Manipulating and Monitoring On-Surface Biological Reactions by Light-Triggered Local pH Alterations.通过光触发的局部 pH 变化来操控和监测表面上的生物反应。
Nano Lett. 2015 Jul 8;15(7):4758-68. doi: 10.1021/acs.nanolett.5b01578. Epub 2015 Jun 30.
6
Comprehensive study of ultrafast excited-state proton transfer in water and D2O providing the missing RO(-)···H(+) ion-pair fingerprint.对水和重水中超快激发态质子转移的综合研究提供了缺失的RO(-)···H(+)离子对指纹。
J Phys Chem A. 2014 Jun 26;118(25):4425-43. doi: 10.1021/jp5002435. Epub 2014 Jun 12.
7
Acid effect on photobase properties of curcumin.酸对姜黄素光致碱性质的影响。
J Phys Chem A. 2014 Apr 3;118(13):2470-9. doi: 10.1021/jp501061p. Epub 2014 Mar 24.
8
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Nat Commun. 2013;4:2611. doi: 10.1038/ncomms3611.
9
Extended Stokes shift in fluorescent proteins: chromophore-protein interactions in a near-infrared TagRFP675 variant.荧光蛋白中的扩展斯托克斯位移：近红外 TagRFP675 变体中的发色团-蛋白相互作用。
Sci Rep. 2013;3:1847. doi: 10.1038/srep01847.
10
Ultrafast photochemistry in liquids.液体中的超快光化学。
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