Excited-State Properties of Protochlorophyllide Analogues and Implications for Light-Driven Synthesis of Chlorophyll

被引：8

作者：

Heyes, Derren J. ^{[1
,2
]}

Hardman, Samantha J. O. ^{[1
,2
]}

Mansell, David ^{[1
,2
]}

Ni Cheallaigh, Aisling ^{[1
,2
,4
]}

Gardiner, John M. ^{[1
,2
]}

Johannissen, Linus O. ^{[1
,2
]}

Greetham, Gregory M. ^{[3
]}

Towrie, Michael ^{[3
]}

Scrutton, Nigel S. ^{[1
,2
]}

机构：

[1] Univ Manchester, Manchester Inst Biotechnol, 131 Princess St, Manchester M1 7DN, Lancs, England

[2] Univ Manchester, Sch Chem, 131 Princess St, Manchester M1 7DN, Lancs, England

[3] Sci & Technol Facil Council, Cent Laser Facil, Res Complex Harwell, Didcot OX11 0QX, Oxon, England

[4] AstraZeneca UK, Charter Way,Silk Rd, Macclesfield SK10 2NA, Cheshire, England

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2017年 / 121卷 / 06期

基金：

英国工程与自然科学研究理事会; 英国生物技术与生命科学研究理事会;

关键词：

OXIDOREDUCTASE; DYNAMICS; INTERMEDIATE; MECHANISM;

D O I：

10.1021/acs.jpcb.7b00528

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Protochlorophyllide (Pchlide), an intermediate in the biosynthesis of chlorophyll, is the substrate for the light driven enzyme protochlorophyllide oxidoreductase. Pchlide has excited-state properties that allow it to initiate photochemistry in the enzyme active site, which involves reduction of Pchlide by sequential hydride and proton transfer. The basis of this photochemical behavior has been investigated here using a combination of time-resolved spectroscopies and density functional theory calculations of a number of Pchlide analogues with modifications to various substituent groups. A keto group on ring E is essential for excited-state charge separation in the molecule, which is the driving force for the photoreactivity of the pigment. Vibrational "fingerprints" of specific regions of the Pchlide chromophore have been assigned, allowing identification of the modes that are crucial for excited state chemistry in the enzyme. This work provides an understanding of the structural determinants of Pchlide that are important for harnessing light energy.

引用

页码：1312 / 1320

页数：9

共 30 条

[1] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].