Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes

Asplund, Matthew C.; Zanni, Martin T.; Hochstrasser, Robin M.

doi:10.1073/pnas.140227997

Cited by 492 publications

(404 citation statements)

References 28 publications

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“…These studies also suggest the possibility of expanding FSRS to multiple dimensions, as has been done in NMR, IR, and electronic spectroscopies (12,44). Many research labs are building FSRS setups, and their progress will be interesting to watch (45,46).…”

Section: Prospectsmentioning

confidence: 91%

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Femtosecond Stimulated Raman Spectroscopy

Kukura

Yoon²,

Mathies³

2006

Anal. Chem.

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R aman spectroscopy is a powerful analytical technique for revealing vibrational structure. It is widely used in biology, chemistry, and studies of molecular reaction dynamics (1-3). One of the technique's greatest advantages is that a single spectrum contains a wealth of vibrational structural information about the sample. The large number of well-resolved vibrational bands provides unique information analogous to a human fingerprint, and the technique is very sensitive to molecular structure. Changes in bond lengths of as little as 0.01 Å can produce clear differences in the vibrational spectrum. This specificity and sensitivity make Raman an excellent tool for trace analysis and for studies of chemically induced structural changes.Although a wide variety of Raman techniques have been developed over the years and applied to analytical problems, significant room for improvement still exists. FT Raman methods are often used in industrial applications to avoid background fluorescence-via intense laser radiation in the NIR-and to exploit the FT multiplex advantage. Clinical applications of FT Raman range from identification of cancerous tissues to microscopic imaging (4). However, it can suffer from weak resonance enhancement and intense Rayleigh scattering caused by the noise distribution of the FT (5). In surface-enhanced Raman spectroscopy, spectra of molecules adsorbed to roughened metallic surfaces or nanostructures can be taken with extreme sensitivity; however, the technique relies on the not-easily-controlled interaction of the metallic substrates with the analyte (6). Raman imaging has recently been advanced through the use of nonlinear Raman techniques, in particular coherent anti-stokes Raman scattering (CARS), which has been used, for example, to monitor biological processes in real time (7,8). Despite these advances, limitations exist that prevent these methods from exploiting the full potential of Raman scattering. We asked: Can an analytical resonance Raman technique be developed that can produce high-S/N spectra that are immune to background fluorescence, with short data-acquisition times?Time-resolved vibrational spectroscopies are also extensively used in structural studies of dynamics of chemical and biological reactions. The earliest (<50-fs) events in photochemical and photophysical processes are best studied by resonance Raman intensity analysis, an extremely powerful technique that can provide detailed excited-state structural information (9, 10). Spontaneous time-resolved resonance A new approach for obtaining vibrational Raman spectra and for studying chemical reaction dynamics. 9 4 A N A LY T I C A L C H E M I S T R Y / S E P T E M B E R 1 , 2 0 0 6Raman spectroscopy is limited to the picosecond time domain because of the transform limit; this prevents the technique from being applied to chemical reactions that occur on the order of 10 f s-1 ps. This limitation has recently been overcome by the availability of femtosecond pulses in the IR. As a consequence, pump-probe approaches for measu...

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Section: Prospectsmentioning

confidence: 91%

“…This limitation has recently been overcome by the availability of femtosecond pulses in the IR. As a consequence, pump-probe approaches for measuring ultrafast vibrational kinetics and multidimensional techniques that provide structural information on the picosecond timescale have emerged (11)(12)(13).…”

mentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy

Kukura

Yoon²,

Mathies³

2006

Anal. Chem.

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“…Consequently, the multidimensional spectroscopy has been proven to be valuable and versatile tools for diverse topics in condensed-phase chemical dynamics. Especially, objects under study in two-dimensional infrared (2D-IR) spectroscopy have definitely spread very wide: structures and dynamics of peptides, [9][10][11][12][13][14][15] conformational changes in protein, [16][17][18] water dynamics, 19 hydrogen-bond dynamics, 20-25 solute-solvent interactions, 26,27 quantum tunneling processes, [28][29][30] and fast chemical exchange in molecular complexes. [31][32][33] Multidimensional vibrational spectroscopy is the optical counterpart of multidimensional NMR such as COSY and NOESY, which are powerful tools for organic structural analysis and structural biology.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of a Multimode System Coupled to Multiple Heat Baths Probed by Two-Dimensional Infrared Spectroscopy

2007

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Reduced equation of motion for a multimode system coupled to multiple heat baths is constructed by extending the quantum Fokker-Planck equation with low-temperature correction terms (J. Phys. Soc. Jpn. 2005, 74, 3131). Unlike such common approaches used to describe intramolecular multimode vibration as a BlochRedfield theory and a stochastic theory, the present formalism is defined by the molecular coordinates. To explore the correlation among different modes through baths, we consider two cases of system-bath couplings. One is a correlated case in which two modes are coupled to a single bath, and the other is an uncorrelated case in which each mode is coupled to a different bath. We further classify the correlated case into two cases, the plus-and minus-correlated cases, according to distinct correlation manners. For these, one-dimensional and two-dimensional infrared (2D-IR) spectra are calculated numerically by solving the equation of motion. It is demonstrated that 2D-IR spectroscopy has the ability to analyze the correlation of fluctuation-dissipation processes among different modes.

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“…Improvements were realized by implementing Fourier-Transform 2DIR (FT-2DIR), 5 which is analogous to modern methods of 2D-NMR. In FT-2DIR, the narrow-bandwidth pump pulse is replaced by two ultrafast broadband pulses separated by a time delay t1 (the coherence time); these pulses provide the two pump interactions of the 3 rd order molecular response, while retaining high time resolution.…”

Section: Introductionmentioning

confidence: 99%

Distinguishing Population and Coherence Transfer Pathways in a Metal Dicarbonyl Complex Using Pulse-Shaped Two-Dimensional Infrared Spectroscopy

Marroux

Orr-Ewing

2016

J. Phys. Chem. B

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Collection of two dimensional infrared (2DIR) spectra using two ultrafast, broadband infrared pump pulses followed by an ultrafast probe pulse optimizes the experimental time and frequency resolution, but can also introduce quantum beat and coherence transfer pathways. The associated coherent dynamics create intensity oscillations and add extra features to 2DIR spectra.We describe a method to suppress these pathways using pump-pulse shaping, without significantly degrading the time and spectral resolution. We illustrate the method for a rhodium dicarbonyl complex, acetylacetonato dicarbonyl rhodium, to establish the relative importance of coherence and population transfer between carbonyl symmetric and asymmetric stretching modes. Our technique effectively suppresses the quantum beats. Comparison of peak intensities obtained with shaped and unshaped pump pulses demonstrates that coherence transfer does not play a significant role in the 2DIR spectrum of RDC in this spectral region.

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Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes

Cited by 492 publications

References 28 publications

Femtosecond Stimulated Raman Spectroscopy

Femtosecond Stimulated Raman Spectroscopy

Dynamics of a Multimode System Coupled to Multiple Heat Baths Probed by Two-Dimensional Infrared Spectroscopy

Distinguishing Population and Coherence Transfer Pathways in a Metal Dicarbonyl Complex Using Pulse-Shaped Two-Dimensional Infrared Spectroscopy

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