Ultrafast Tryptophan-to-Heme Electron Transfer in Myoglobins Revealed by UV 2D Spectroscopy

Consani, Cristina; Auböck, Gerald; Mourik, Frank van; Chergui, Majed

doi:10.1126/science.1230758

Cited by 131 publications

(147 citation statements)

References 41 publications

Supporting

Mentioning

138

Contrasting

Order By: Relevance

“…[1][2][3][4] The extra information accessible by measuring 2D spectra when compared to the traditional 1D nonlinear techniques, such as pumpprobe spectroscopy, have become apparent in the last couple of years. 5 One example of an important process probed by 2D spectroscopy is energy transfer dynamics.…”

Section: Introductionmentioning

confidence: 99%

Two-dimensional electronic spectroscopy based on conventional optics and fast dual chopper data acquisition

Heisler

Moca

Camargo

et al. 2014

Review of Scientific Instruments

View full text Add to dashboard Cite

We report a new experimental scheme for two-dimensional electronic spectroscopy (2D-ES) based solely on conventional optical components and fast data acquisition. This is accomplished by working with two choppers synchronized to a 10 kHz repetition rate amplified laser system. We demonstrate how scattering and pump-probe contributions can be removed during 2D measurements and how the pump probe and local oscillator (LO) spectra can be generated and saved simultaneously with each population time measurement. As an example the 2D ES spectra for cresyl violet were obtained. The resulting 2D spectra show a significant oscillating signal during population evolution time which can be assigned to an intramolecular vibrational mode.

show abstract

Section: Introductionmentioning

confidence: 99%

Two-dimensional electronic spectroscopy based on conventional optics and fast dual chopper data acquisition

Heisler

Moca

Camargo

et al. 2014

Review of Scientific Instruments

View full text Add to dashboard Cite

show abstract

“…Recently, charge transfer has also been investigated (12,13). Here we are interested in photochemical processes leading to ground-state product species with a molecular configuration that is different from the initial reactant.…”

mentioning

confidence: 99%

Multidimensional spectroscopy of photoreactivity

Ruetzel¹,

Diekmann²,

Nuernberger³

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

Coherent multidimensional electronic spectroscopy is commonly used to investigate photophysical phenomena such as light harvesting in photosynthesis in which the system returns back to its ground state after energy transfer. By contrast, we introduce multidimensional spectroscopy to study ultrafast photochemical processes in which the investigated molecule changes permanently. Exemplarily, the emergence in 2D and 3D spectra of a cross-peak between reactant and product reveals the cis-trans photoisomerization of merocyanine isomers. These compounds have applications in organic photovoltaics and optical data storage. Cross-peak oscillations originate from a vibrational wave packet in the electronically excited state of the photoproduct. This concept isolates the isomerization dynamics along different vibrational coordinates assigned by quantum-chemical calculations, and is applicable to determine chemical dynamics in complex photoreactive networks.photoreactive processes | ultrafast spectroscopy | 2D spectroscopy | vibrational coherence A basic objective of physical chemistry is to determine the mechanisms underlying chemical reactions. Fundamental insights into these are provided by femtosecond time-resolved spectroscopy, even below the timescale of molecular vibrations (1). The major challenge of ultrafast photochemistry is to identify isolated signatures of reactants, intermediates, and products, whose spectral bands often overlap. Here we show that such ambiguities are unraveled by coherent multidimensional electronic spectroscopy, e.g., 2D and 3D spectroscopy, where the correlation of a system's excitation and emission frequencies is measured separating features that otherwise superpose. We detect photoreactivity directly via cross-peaks in multidimensional spectra. This opens the broad field of femtochemistry (1) to the multidimensional concept.Two-dimensional electronic spectroscopy (2-5) was primarily implemented for studying photophysical phenomena such as energy transfer in multichromophore light-harvesting systems or other excitonically coupled systems (6-11). Recently, charge transfer has also been investigated (12, 13). Here we are interested in photochemical processes leading to ground-state product species with a molecular configuration that is different from the initial reactant. As a general extension of 2D spectroscopy, 3D representations provide an even more detailed picture. Coherent 3D spectroscopy has been introduced to infrared spectroscopy (14, 15), and recently to electronic spectroscopy for isolating excitonic coherences (16, 17), for liquid-and gas-phase model systems (18)(19)(20), and for analyzing photosynthetic lightharvesting (21,22). Regarding these approaches, one has to differentiate between fifth-order experiments (14, 15, 19) for effects of higher nonlinearity (e.g., three-point frequency-fluctuation correlation functions) (14) and third-order techniques (20)(21)(22)(23)(24), as demonstrated here to unravel photochemical reactions.The principal idea of multidimensional spectrosc...

show abstract

“…Coherent 2D experiments in the UV region are now possible, but require state of the art technology. [30,31] By directly connecting 2D spectroscopy experiments with molecular simulations, we can uncover the underlying mechanisms of folding and see how the folding process actually occurs in time by monitoring the folding pathways. Our work provides a general approach to connect 2DUV experiments with MD simulations by theoretical calculations.…”

Section: Discussionmentioning

confidence: 99%

Exploring the Protein Folding Dynamics of Beta3s with Two‐Dimensional Ultraviolet (2DUV) Spectroscopy

Lai

Jiang

Mukamel

et al. 2014

Israel Journal of Chemistry

View full text Add to dashboard Cite

Ultraviolet (UV) spectra of proteins originate from electronic excitations of their backbone chromophore and aromatic side chains and provide a sensitive probe of the secondary structure. Recently developed femtosecond lasers allow multidimensional spectroscopy to be extended into the UV regime. Two‐dimensional UV (2DUV) techniques, with short pulses, provide a promising tool to study the structures and dynamics of proteins. We combined 2DUV spectroscopy and molecular dynamics generated free energy profiles to simulate the protein electronic transitions and UV photon echo signals to monitor the protein folding process of the small protein Beta3s. Near‐ultraviolet (NUV) and far‐ultraviolet (FUV) signals illustrate the variation of the 2D correlation plots when the protein evolves along the underlying free energy landscape. Chiral polarization configurations of the NUV and FUV pulses are sensitive to protein structural evolution. This work provides a protocol for applying multidimensional UV spectroscopy to study protein folding.

show abstract

Ultrafast Tryptophan-to-Heme Electron Transfer in Myoglobins Revealed by UV 2D Spectroscopy

Cited by 131 publications

References 41 publications

Two-dimensional electronic spectroscopy based on conventional optics and fast dual chopper data acquisition

Two-dimensional electronic spectroscopy based on conventional optics and fast dual chopper data acquisition

Multidimensional spectroscopy of photoreactivity

Exploring the Protein Folding Dynamics of Beta3s with Two‐Dimensional Ultraviolet (2DUV) Spectroscopy

Contact Info

Product

Resources

About