Picosecond transient circular dichroism of the photoreceptor protein of the light-adapted form of Blepharisma japonicum

Hache, F.; Khuc, Mai-Thu; Brazard, Johanna; Plaza, Pascal; Martin, Monique M.; Checcucci, Giovanni; Lenci, Francesco

doi:10.1016/j.cplett.2009.10.059

Cited by 12 publications

(8 citation statements)

References 22 publications

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“…For this reason, circular dichroisms (CDs) in absorption spectroscopies are typically very weak effects in the range of normal10−6 to normal10−3 relative signal changes. Nevertheless, time-resolved CD (TRCD) techniques have gained increasing attention over the last 15 y (4) and nowadays cover the infrared (5, 6), visible (7), and ultraviolet (UV) (8–11) spectral regions. The promise of extending such measurements to the X-ray domain has recently been predicted (12–14).…”

mentioning

confidence: 99%

Real-time probing of chirality during a chemical reaction

Baykusheva

Zindel

Svoboda

et al. 2019

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

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Chiral molecules interact and react differently with other chiral objects, depending on their handedness. Therefore, it is essential to understand and ultimately control the evolution of molecular chirality during chemical reactions. Although highly sophisticated techniques for the controlled synthesis of chiral molecules have been developed, the observation of chirality on the natural femtosecond time scale of a chemical reaction has so far remained out of reach for isolated molecules.Here, we demonstrate a general experimental technique, based on high-harmonic generation in tailored laser fields, and apply it to probe the time evolution of molecular chirality during the photodissociation of 2-iodobutane. These measurements show a change in sign and a pronounced increase in the magnitude of the chiral response over the first 100 fs, followed by its decay within less than 500 fs, revealing the photodissociation to achiral products. The observed time evolution is explained in terms of the variation of the electric and magnetic transition-dipole moments between the lowest electronic states of the cation as a function of the reaction coordinate. These results open the path to investigations of the chirality of molecular reaction pathways, light-induced chirality in chemical processes and the control of molecular chirality through tailored laser pulses. SIGNIFICANCE STATEMENTChiral molecules interact and react differently, depending on their handedness (left vs. right). This chiral recognition is the basic principle governing most biomolecular interactions, such as the activity of drugs or our perception of scents. Inspite of this fundamental importance, a real-time (femtosecond) observation of chirality during a chemical reaction has remained out of reach for isolated molecules. In the present work, we report this fundamental breakthrough with a seemingly unlikely technique: high-harmonic generation (HHG) in tailored intense near-infrared laser fields. Combining the powerful transient-grating technique with HHG in counter-rotating circularly-polarized laser fields, we follow the temporal evolution of molecular chirality during a chemical reaction from the unexcited electronic ground state through the transition-state region to the final achiral products.

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mentioning

confidence: 99%

Real-time probing of chirality during a chemical reaction

Baykusheva

Zindel

Svoboda

et al. 2019

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

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“…We assume the pump and probe pulses are of the form given in Eq. (11), with E(t) a Gaussian envelope. Using the labels r for the probe and u for the pump, the above requires the definition of a carrier frequency ω r/u , polarization p r/u and FWHM √ 8 ln(2)σ r/u for each pulse.…”

Section: A Pump-probe Spectroscopy In the Doorway Window Formulationmentioning

confidence: 99%

“…Linear CD and ORD spectroscopy have been used extensively to determine more accurately the structure of proteins [2][3][4] and the excitonic states in photosynthetic antennae including the Fenna-Matthews-Olson complex (FMO) from Green Sulfur bacteria 5 , and light harvesting complex I 6 and II 7,8 . Transient circular dichroism (TRCD), that is, the time-domain CD spectra of a system away from equilibrium, has been used within the infra-red 9,10 and ultra-violet frequency ranges 11,12 . This technique has proved useful in measuring protein conformation and lipid structure 13,14 .…”

Section: Introductionmentioning

confidence: 99%

Coherence specific signal detection via chiral pump-probe spectroscopy

Holdaway

Collini

Olaya-Castro

2016

The Journal of Chemical Physics

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We examine transient circular dichroism spectroscopy (TRCD) as a technique to investigate signatures of exciton coherence dynamics under the influence of structured vibrational environments. We consider a pump-probe configuration with a linearly polarized pump and a circularly polarized probe, with a variable angle θ between the two directions of propagation. In our theoretical formalism the signal is decomposed in chiral and achiral doorway and window functions. Using this formalism, we show that the chiral doorway component, which beats during the population time, can be isolated by comparing signals with different values of θ. As in the majority of time-resolved pump-probe spectroscopy, the overall TRCD response shows signatures of both excited and ground state dynamics. However, we demonstrate that the chiral doorway function has only a weak ground state contribution, which can generally be neglected if an impulsive pump pulse is used. These findings suggest that the pump-probe configuration of optical TRCD in the impulsive limit has the potential to unambiguously probe quantum coherence beating in the excited state. We present numerical results for theoretical signals in an example dimer system.

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“…Very few examples of time-resolved optical activity measures can be found in the literature. After the pioneering work of Kliger's group, [12] time-dependent chiral signals have been used to investigate the dynamic of structural changes in molecules and biomolecules [13], and vibrational optical activity [14]. There has also been a great deal of theoretical interest in using full chiral two-dimensional spectroscopy to better resolve cross peaks [15], study vibrational optical activity [16], geometric fluctuations [17] and coherence beating [18].…”

Section: Introductionmentioning

confidence: 99%

Isolating the chiral contribution in optical two-dimensional chiral spectroscopy using linearly polarized light

Holdaway,

Collini,

Olaya-Castro

2017

Preprint

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The full development of mono-or multi-dimensional time-resolved spectroscopy techniques incorporating optical activity signals has been strongly hampered by the challenge of identifying the small chiral signals over the large achiral background. Here we propose a new methodology to isolate chiral signals removing the achiral background from two commonly used configurations for performing two dimensional optical spectroscopy, known as BOXCARS and GRadient Assisted Photon Echo Spectroscopy (GRAPES). It is found that in both cases an achiral signal from an isotropic system can be completely eliminated by small manipulations of the relative angles between the linear polarizations of the four input laser pulses. Starting from the formulation of a perturbative expansion of the signal in the angle between the beams and the propagation axis, we derive analytic expressions that can be used to estimate how to change the polarization angles of the four pulses to minimize achiral contributions in the studied configurations. The generalization to any other possible experimental configurations has also been discussed.

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Picosecond transient circular dichroism of the photoreceptor protein of the light-adapted form of Blepharisma japonicum

Cited by 12 publications

References 22 publications

Real-time probing of chirality during a chemical reaction

Real-time probing of chirality during a chemical reaction

Coherence specific signal detection via chiral pump-probe spectroscopy

Isolating the chiral contribution in optical two-dimensional chiral spectroscopy using linearly polarized light

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