Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance

William H. Woodruff; R. B. Dyer; Oloef Einarsdottir; Kristen A. Peterson; Page O. Stoutland; K. A. Bagley; Graham Palmer; J. R. Schoonover; David S. Kliger; Robert A. Goldbeck; T. D. Dawes; Jean Louis Martin; J. C. Lambry; Stephen J. Atherton; Stefan M. Hubig

Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance

William H. Woodruff
, R. B. Dyer
, Oloef Einarsdottir
, Kristen A. Peterson
, Page O. Stoutland
, K. A. Bagley
, Graham Palmer
, J. R. Schoonover
, David S. Kliger
, Robert A. Goldbeck
, T. D. Dawes
, Jean Louis Martin
, J. C. Lambry
, Stephen J. Atherton
, Stefan M. Hubig

MST-8, Los Alamos National Laboratory

Research output: Chapter in Book/Report/Conference proceeding › Conference contribution › peer-review

Abstract

Time-resolved electronic absorption, infrared, resonance Raman, and magnetic circular dichroism spectroscopies are applied to characterization of the intermediate which is formed within 20 ps after photodissociation of CO from cytochrome a₃ of reduced cytochrome oxidase. This intermediate decays with the same halflife (ca. 1 μs) as the post- photodissociation Cu_B+-CO species previously observed by time-resolved infrared. The transient UV-Vis spectra, kinetics, infrared, and Raman evidence suggest that an endogenous ligand is transferred from Cu_B to Fe_a3 when CO binds to Cu_B, forming a cytochrome a₃ species with axial ligation which differs from the reduced unliganded enzyme. The time-resolved magnetic circular dichroism results suggest that this transient is high spin and therefore five coordinate. Thus it is inferred that the ligand from Cu_B binds on the distal side of cytochrome a₃ and displaces the proximal histidine imidazole. This remarkable mechanistic feature is an additional aspect of the previously proposed 'ligand shuttle' activity of the Cu_B/Fe_a3 pair. The authors suggest that the ligand shuttle may play a functional role in redox-linked proton translocation by the enzyme. More detail on this work is presented elsewhere.

Original language	English
Title of host publication	Proceedings of SPIE - The International Society for Optical Engineering
Publisher	Publ by Int Soc for Optical Engineering
Pages	205-210
Number of pages	6
ISBN (Print)	0819405221
Publication status	Published - 1 Jan 1991
Externally published	Yes
Event	Biomolecular Spectroscopy II - Los Angeles, CA, USA Duration: 22 Jan 1991 → 23 Jan 1991

Publication series

Name	Proceedings of SPIE - The International Society for Optical Engineering
Volume	1432
ISSN (Print)	0277-786X

Conference

Conference	Biomolecular Spectroscopy II
City	Los Angeles, CA, USA
Period	22/01/91 → 23/01/91

Cite this

Woodruff, W. H., Dyer, R. B., Einarsdottir, O., Peterson, K. A., Stoutland, P. O., Bagley, K. A., Palmer, G., Schoonover, J. R., Kliger, D. S., Goldbeck, R. A., Dawes, T. D., Martin, J. L., Lambry, J. C., Atherton, S. J., & Hubig, S. M. (1991). Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance. In Proceedings of SPIE - The International Society for Optical Engineering (pp. 205-210). (Proceedings of SPIE - The International Society for Optical Engineering; Vol. 1432). Publ by Int Soc for Optical Engineering.

Woodruff, William H. ; Dyer, R. B. ; Einarsdottir, Oloef et al. / Ultrafast and not-so-fast dynamics of cytochrome oxidase : the ligand shuttle and its possible functional significance. Proceedings of SPIE - The International Society for Optical Engineering. Publ by Int Soc for Optical Engineering, 1991. pp. 205-210 (Proceedings of SPIE - The International Society for Optical Engineering).

@inproceedings{a6f765a0f07340d2b0d4dc19d0b00c98,

title = "Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance",

abstract = "Time-resolved electronic absorption, infrared, resonance Raman, and magnetic circular dichroism spectroscopies are applied to characterization of the intermediate which is formed within 20 ps after photodissociation of CO from cytochrome a3 of reduced cytochrome oxidase. This intermediate decays with the same halflife (ca. 1 μs) as the post- photodissociation CuB+-CO species previously observed by time-resolved infrared. The transient UV-Vis spectra, kinetics, infrared, and Raman evidence suggest that an endogenous ligand is transferred from CuB to Fea3 when CO binds to CuB, forming a cytochrome a3 species with axial ligation which differs from the reduced unliganded enzyme. The time-resolved magnetic circular dichroism results suggest that this transient is high spin and therefore five coordinate. Thus it is inferred that the ligand from CuB binds on the distal side of cytochrome a3 and displaces the proximal histidine imidazole. This remarkable mechanistic feature is an additional aspect of the previously proposed 'ligand shuttle' activity of the CuB/Fea3 pair. The authors suggest that the ligand shuttle may play a functional role in redox-linked proton translocation by the enzyme. More detail on this work is presented elsewhere.",

author = "Woodruff, \{William H.\} and Dyer, \{R. B.\} and Oloef Einarsdottir and Peterson, \{Kristen A.\} and Stoutland, \{Page O.\} and Bagley, \{K. A.\} and Graham Palmer and Schoonover, \{J. R.\} and Kliger, \{David S.\} and Goldbeck, \{Robert A.\} and Dawes, \{T. D.\} and Martin, \{Jean Louis\} and Lambry, \{J. C.\} and Atherton, \{Stephen J.\} and Hubig, \{Stefan M.\}",

year = "1991",

month = jan,

day = "1",

language = "English",

isbn = "0819405221",

series = "Proceedings of SPIE - The International Society for Optical Engineering",

publisher = "Publ by Int Soc for Optical Engineering",

pages = "205--210",

booktitle = "Proceedings of SPIE - The International Society for Optical Engineering",

note = "Biomolecular Spectroscopy II ; Conference date: 22-01-1991 Through 23-01-1991",

}

Woodruff, WH, Dyer, RB, Einarsdottir, O, Peterson, KA, Stoutland, PO, Bagley, KA, Palmer, G, Schoonover, JR, Kliger, DS, Goldbeck, RA, Dawes, TD, Martin, JL, Lambry, JC, Atherton, SJ & Hubig, SM 1991, Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance. in Proceedings of SPIE - The International Society for Optical Engineering. Proceedings of SPIE - The International Society for Optical Engineering, vol. 1432, Publ by Int Soc for Optical Engineering, pp. 205-210, Biomolecular Spectroscopy II, Los Angeles, CA, USA, 22/01/91.

Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance. / Woodruff, William H.; Dyer, R. B.; Einarsdottir, Oloef et al.
Proceedings of SPIE - The International Society for Optical Engineering. Publ by Int Soc for Optical Engineering, 1991. p. 205-210 (Proceedings of SPIE - The International Society for Optical Engineering; Vol. 1432).

Research output: Chapter in Book/Report/Conference proceeding › Conference contribution › peer-review

TY - GEN

T1 - Ultrafast and not-so-fast dynamics of cytochrome oxidase

T2 - Biomolecular Spectroscopy II

AU - Woodruff, William H.

AU - Dyer, R. B.

AU - Einarsdottir, Oloef

AU - Peterson, Kristen A.

AU - Stoutland, Page O.

AU - Bagley, K. A.

AU - Palmer, Graham

AU - Schoonover, J. R.

AU - Kliger, David S.

AU - Goldbeck, Robert A.

AU - Dawes, T. D.

AU - Martin, Jean Louis

AU - Lambry, J. C.

AU - Atherton, Stephen J.

AU - Hubig, Stefan M.

PY - 1991/1/1

Y1 - 1991/1/1

N2 - Time-resolved electronic absorption, infrared, resonance Raman, and magnetic circular dichroism spectroscopies are applied to characterization of the intermediate which is formed within 20 ps after photodissociation of CO from cytochrome a3 of reduced cytochrome oxidase. This intermediate decays with the same halflife (ca. 1 μs) as the post- photodissociation CuB+-CO species previously observed by time-resolved infrared. The transient UV-Vis spectra, kinetics, infrared, and Raman evidence suggest that an endogenous ligand is transferred from CuB to Fea3 when CO binds to CuB, forming a cytochrome a3 species with axial ligation which differs from the reduced unliganded enzyme. The time-resolved magnetic circular dichroism results suggest that this transient is high spin and therefore five coordinate. Thus it is inferred that the ligand from CuB binds on the distal side of cytochrome a3 and displaces the proximal histidine imidazole. This remarkable mechanistic feature is an additional aspect of the previously proposed 'ligand shuttle' activity of the CuB/Fea3 pair. The authors suggest that the ligand shuttle may play a functional role in redox-linked proton translocation by the enzyme. More detail on this work is presented elsewhere.

AB - Time-resolved electronic absorption, infrared, resonance Raman, and magnetic circular dichroism spectroscopies are applied to characterization of the intermediate which is formed within 20 ps after photodissociation of CO from cytochrome a3 of reduced cytochrome oxidase. This intermediate decays with the same halflife (ca. 1 μs) as the post- photodissociation CuB+-CO species previously observed by time-resolved infrared. The transient UV-Vis spectra, kinetics, infrared, and Raman evidence suggest that an endogenous ligand is transferred from CuB to Fea3 when CO binds to CuB, forming a cytochrome a3 species with axial ligation which differs from the reduced unliganded enzyme. The time-resolved magnetic circular dichroism results suggest that this transient is high spin and therefore five coordinate. Thus it is inferred that the ligand from CuB binds on the distal side of cytochrome a3 and displaces the proximal histidine imidazole. This remarkable mechanistic feature is an additional aspect of the previously proposed 'ligand shuttle' activity of the CuB/Fea3 pair. The authors suggest that the ligand shuttle may play a functional role in redox-linked proton translocation by the enzyme. More detail on this work is presented elsewhere.

M3 - Conference contribution

AN - SCOPUS:0025795344

SN - 0819405221

T3 - Proceedings of SPIE - The International Society for Optical Engineering

SP - 205

EP - 210

BT - Proceedings of SPIE - The International Society for Optical Engineering

PB - Publ by Int Soc for Optical Engineering

Y2 - 22 January 1991 through 23 January 1991

ER -

Woodruff WH, Dyer RB, Einarsdottir O, Peterson KA, Stoutland PO, Bagley KA et al. Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance. In Proceedings of SPIE - The International Society for Optical Engineering. Publ by Int Soc for Optical Engineering. 1991. p. 205-210. (Proceedings of SPIE - The International Society for Optical Engineering).

Ultrafast and not-so-fast dynamics of cytochrome oxidase: the ligand shuttle and its possible functional significance

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