Structural Dynamics of Hydrated Phospholipid Surfaces Probed by Ultrafast 2D Spectroscopy of Phosphate Vibrations

Costard, René; Heisler, Ismael A.; Elsaesser, Thomas

doi:10.1021/jz402493b

Cited by 59 publications

(62 citation statements)

References 33 publications

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“…26 The phospholipid-water interface is subject to very strong electrostatic fields originating from the phosphate-choline dipole moments of approximately 20 D. Such fields have a strong in-plane component at the interface and orient the much smaller water dipoles. Molecular dynamics simulations found that water molecules connect different phospholipids and that the lifetime of these water bridges is up to 50 ps.…”

Section: Discussionmentioning

confidence: 99%

“…[24][25][26] Interestingly, there is a universal 300 fs lifetime of ν AS (PO − 2 ) that is independent of the studied system and the water content around the phosphate groups. Such a behavior suggests a common relaxation mechanism that involves low-frequency vibrations of the PO 4 tetrahedron.…”

Section: Vibrational Lifetimesmentioning

confidence: 93%

“…2D spectra, we calculate 2D spectra using density matrix theory 43,44 and the response functions detailed in Ref. 26. This approach considers dephasing of vibrational polarizations due to frequency fluctuations and takes into account broadening by the finite vibrational lifetimes.…”

Section: A 2d Ir Spectroscopymentioning

confidence: 99%

“…6,26 Briefly, tunable mid-IR pulses with a center frequency between 1000 and 1300 cm −1 , a spectral bandwidth of 200 cm −1 , and a duration of 100 fs are generated by nonlinear parametric frequency conversion. 48 2D spectra are acquired with a noncollinear 3-pulse photon echo experiment.…”

Section: A Experimentalmentioning

confidence: 99%

“…[24][25][26] In phospholipids, the 2D lineshapes of phosphate stretching vibrations display a pronounced inhomogeneous broadening that persists on a time scale on the order of 10 ps and points to minor structural fluctuations of interfacial water.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast phosphate hydration dynamics in bulk H2O

Costard

Tyborski

Fingerhut

et al. 2015

The Journal of Chemical Physics

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Phosphate vibrations serve as local probes of hydrogen bonding and structural fluctuations of hydration shells around ions. Interactions of H2PO4− ions and their aqueous environment are studied combining femtosecond 2D infrared spectroscopy, ab-initio calculations, and hybrid quantum-classical molecular dynamics (MD) simulations. Two-dimensional infrared spectra of the symmetric (νS(PO2−)) and asymmetric (νAS(PO2−)) PO2− stretching vibrations display nearly homogeneous lineshapes and pronounced anharmonic couplings between the two modes and with the δ(P-(OH)2) bending modes. The frequency-time correlation function derived from the 2D spectra consists of a predominant 50 fs decay and a weak constant component accounting for a residual inhomogeneous broadening. MD simulations show that the fluctuating electric field of the aqueous environment induces strong fluctuations of the νS(PO2−) and νAS(PO2−) transition frequencies with larger frequency excursions for νAS(PO2−). The calculated frequency-time correlation function is in good agreement with the experiment. The ν(PO2−) frequencies are mainly determined by polarization contributions induced by electrostatic phosphate-water interactions. H2PO4−/H2O cluster calculations reveal substantial frequency shifts and mode mixing with increasing hydration. Predicted phosphate-water hydrogen bond (HB) lifetimes have values on the order of 10 ps, substantially longer than water-water HB lifetimes. The ultrafast phosphate-water interactions observed here are in marked contrast to hydration dynamics of phospholipids where a quasi-static inhomogeneous broadening of phosphate vibrations suggests minor structural fluctuations of interfacial water.

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Section: Discussionmentioning

confidence: 99%

Section: Vibrational Lifetimesmentioning

confidence: 93%

Section: A 2d Ir Spectroscopymentioning

confidence: 99%

Section: A Experimentalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ultrafast phosphate hydration dynamics in bulk H2O

Costard

Tyborski

Fingerhut

et al. 2015

The Journal of Chemical Physics

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Size‐Dependent Water Structures in Carbon Nanotubes

Ohba

2014

Angewandte Chemie

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Water surrounded by hydrophobic interfaces affects a variety of chemical reactions and biological activities. Carbon nanotubes (CNTs) can be used to investigate the behavior of water at hydrophobic interfaces. Here, we determined the fundamental unit of water by evaluating the ice‐like cluster formation of water in the limited hydrophobic nanospaces of CNTs, using X‐ray diffraction and molecular simulation analysis. The water in CNTs with a diameter of 1 nm had fewer hydrogen bonds than bulk water under ambient conditions. In CNTs with diameters of 2 and 3 nm, water formed nanoclusters even under ambient conditions, because of prolific hydrogen bonding; predominant ice‐like cluster formation was induced in the 2–3 nm nanospaces. The results confirming the cluster formation in the CNTs also demonstrated that the critical cluster size was 0.8–3.4 nm. The fundamental cluster size was 0.8 nm; these results indicated that 0.8 nm clusters are the fundamental units of water assemblies.

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Femtosecond Hydrogen Bond Dynamics of Bulk‐like and Bound Water at Positively and Negatively Charged Lipid Interfaces Revealed by 2D HD‐VSFG Spectroscopy

et al. 2016

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Interfacial water in the vicinity of lipids playsa n important role in many biological processes,s uch as drug delivery,i on transportation, and lipid fusion. Hence, molecular-level elucidation of the properties of water at lipid interfaces is of the utmost importance.W er eport the two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) study of the OH stretch of HOD at charged lipid interfaces,w hich shows that the hydrogen bond dynamics of interfacial water differ drastically,d epending on the lipids.T he data indicate that the spectral diffusion of the OH stretch at apositively charged lipid interface is dominated by the ultrafast (<~ 100 fs) component, followed by the minor sub-picosecond slow dynamics,w hile the dynamics at a negatively charged lipid interface exhibit sub-picosecond dynamics almost exclusively,i mplying that fast hydrogen bond fluctuation is prohibited. These results reveal that the ultrafast hydrogen bond dynamics at the positively charged lipid-water interface are attributable to the bulk-like property of interfacial water,w hereas the slowd ynamics at the negatively charged lipid interface are due to bound water, which is hydrogen-bonded to the hydrophilic head group.

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Structural Dynamics of Hydrated Phospholipid Surfaces Probed by Ultrafast 2D Spectroscopy of Phosphate Vibrations

Cited by 59 publications

References 33 publications

Ultrafast phosphate hydration dynamics in bulk H2O

Ultrafast phosphate hydration dynamics in bulk H2O

Size‐Dependent Water Structures in Carbon Nanotubes

Femtosecond Hydrogen Bond Dynamics of Bulk‐like and Bound Water at Positively and Negatively Charged Lipid Interfaces Revealed by 2D HD‐VSFG Spectroscopy

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