BIOMAT Database Logo BIOMAT Database Logo

Excited-State Properties of Protochlorophyllide Analogues and Implications for Light-Driven Synthesis of Chlorophyll. 2017

Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Manchester Institute of Biotechnology and School of Chemistry, The University of Manchester , 131 Princess Street, Manchester M1 7DN, U.K.

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.

UI MeSH Term Description Entries
D008027 Light That portion of the electromagnetic spectrum in the visible, ultraviolet, and infrared range. Light, Visible,Photoradiation,Radiation, Visible,Visible Radiation,Photoradiations,Radiations, Visible,Visible Light,Visible Radiations
D009942 Organometallic Compounds A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed) Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D011521 Protochlorophyllide A photo-active pigment localized in prolamellar bodies occurring within the proplastids of dark-grown bean leaves. In the process of photoconversion, the highly fluorescent protochlorophyllide is converted to chlorophyll. Protochlorophyllide A,MV-PChlide,Monovinyl Protochlorophyllide,MV PChlide,Protochlorophyllide, Monovinyl
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D002734 Chlorophyll Porphyrin derivatives containing magnesium that act to convert light energy in photosynthetic organisms. Phyllobilins,Chlorophyll 740
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular

Related Publications

Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Excited state dynamics and catalytic mechanism of the light-driven enzyme protochlorophyllide oxidoreductase.
July 2012, Physical chemistry chemical physics : PCCP,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Protein-induced excited-state dynamics of protochlorophyllide.
July 2011, The journal of physical chemistry. A,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Protochlorophyll and protochlorophyllide as precursors for chlorophyll synthesis in vitro.
December 1974, FEBS letters,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
New Excited State of Chlorophyll.
October 1958, Science (New York, N.Y.),
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Switching light with light in chlorophyll-A molecules based on excited-state absorption.
March 2009, IEEE transactions on nanobioscience,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Light-driven deracemization enabled by excited-state electron transfer.
October 2019, Science (New York, N.Y.),
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Excited state absorption spectrum of chlorophyll a obtained with white-light continuum.
April 2007, The Journal of chemical physics,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Excited-state dynamics of protochlorophyllide revealed by subpicosecond infrared spectroscopy.
January 2011, Biophysical journal,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Properties of Protochlorophyllide and Chlorophyll(ide) Holochromes from Etiolated and Greening Leaves.
March 1974, Plant physiology,
Derren J Heyes, and Samantha J O Hardman, and David Mansell, and Aisling Ní Cheallaigh, and John M Gardiner, and Linus O Johannissen, and Gregory M Greetham, and Michael Towrie, and Nigel S Scrutton
Protochlorophyllide oxidoreductase: "dark" reactions of a light-driven enzyme.
January 2003, Biochemistry,
Copied contents to your clipboard!