Dynamics of Nanoscopic Water:  Vibrational Echo and Infrared Pump−Probe Studies of Reverse Micelles

Piletic, Ivan R.; Tan, Howe‐Siang; Fayer, M. D.

doi:10.1021/jp051837p

Cited by 114 publications

(179 citation statements)

References 84 publications

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“…This form has been used previously for the analysis of pure water (7) and nanoscopic water pools in AOT reverse micelles (22,37). The FFCF has the form…”

Section: Resultsmentioning

confidence: 99%

Hydrogen bond dynamics in aqueous NaBr solutions

Park

Fayer

2007

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

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294

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Hydrogen bond dynamics of water in NaBr solutions are studied by using ultrafast 2D IR vibrational echo spectroscopy and polarization-selective IR pump-probe experiments. The hydrogen bond structural dynamics are observed by measuring spectral diffusion of the OD stretching mode of dilute HOD in H2O in a series of high concentration aqueous NaBr solutions with 2D IR vibrational echo spectroscopy. The time evolution of the 2D IR spectra yields frequency-frequency correlation functions, which permit quantitative comparisons of the influence of NaBr concentration on the hydrogen bond dynamics. The results show that the global rearrangement of the hydrogen bond structure, which is represented by the slowest component of the spectral diffusion, slows, and its time constant increases from 1.7 to 4.8 ps as the NaBr concentration increases from pure water to Ϸ6 M NaBr. Orientational relaxation is analyzed with a wobbling-in-a-cone model describing restricted orientational diffusion that is followed by complete orientational randomization described as jump reorientation. The slowest component of the orientational relaxation increases from 2.6 ps (pure water) to 6.7 ps (Ϸ6 M NaBr). Vibrational population relaxation of the OD stretch also slows significantly as the NaBr concentration increases.ultrafast 2D IR spectroscopy ͉ water dynamics in ionic solutions W ater plays an important role in chemical and biological processes. In aqueous solutions, water molecules dissolve ionic compounds, charged chemical species, and biomolecules by forming hydration shells (layers) around them. Pure water undergoes rapid structural evolution of the hydrogen bond network that is responsible for water's unique properties (1). A question of fundamental importance is how the dynamics of water in the immediate vicinity of an ion or ionic group differ from those of pure water. For monatomic ions, molecular ions, charged groups of large molecules, or charged amino acids on the surfaces of proteins, the basic structure of hydration shells is determined by ion-dipole interactions between water molecules and the charged group (2, 3). Such ion-dipole interactions will influence both the structure and dynamics of water in the proximity of ions. Water dynamics in ion hydration shells play a significant role in the nature of systems such as proteins and micelles (3) and in processes such as ion transport through transmembrane proteins (4).Over the last several years, the application of ultrafast IR vibrational echo spectroscopy (5, 6), particularly 2D IR vibrational echo experiments, (7, 8) combined with molecular dynamics (MD) simulations (9-12) have greatly enhanced understanding of the hydrogen bond dynamics in pure water. These experiments directly examine the dynamics of water rather than study the indirect influence of water dynamics on a probe molecule (13). The ultrafast 2D IR vibrational echo experiments on water (7, 8) and other hydrogen-bonded systems (14) build upon earlier IR pump-probe experiments that have been extensively used to study ...

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“…This form has been used previously for the analysis of pure water (7) and nanoscopic water pools in AOT reverse micelles (22,37). The FFCF has the form…”

Section: Resultsmentioning

confidence: 99%

Hydrogen bond dynamics in aqueous NaBr solutions

Park

Fayer

2007

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

Self Cite

294

403

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“…The confinement of water in biological structures does not represent a single pattern of behavior. For example, water confined in reverse micelles [5][6][7][8][9] differs from water confined in phospholipid membranes [10] or in DNA interfaces [3].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen bonds of interfacial water in human breast cancer tissue compared to lipid and DNA interfaces

Abramczyk¹,

Brożek-Płuska²,

Surmacki³

et al. 2011

JBPC

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The paper presents the results for water confined in a human breast cancerous tissue, a single stranded DNA, a double stranded DNA and in phospholipids (DPPC-D--Phosphatidylcholine, dipalmitoyl). The interfacial water in DNA and lipids is represented by a double band in the region of the OH stretching mode of water corresponding to the symmetric and asymmetric vibrational modes, in contrast to water confined in the cancerous breast tissue where only one band at 3311 cm -1 has been recorded. The marked red-shift of the maximum peak position of the OH stretching mode confirms that the vibrational properties of the interfacial water observed in restricted biological environment differ drastically from those in bulk water. The change of vibrational pattern of behavior may be due to the decoupling of the vibrations of the OH bonds in water molecule or change of the vibrational selection rules at biological interfaces. According to our knowledge Raman vibrational properties of water confined in the normal and cancerous breast tissue of the same patient have not been reported in literature yet. Here we have also presented the first Raman 'optical biopsy' images of the non-cancerous and cancerous (infiltrating ductal cancer) human breast tissues.

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“…Both neat water and HOD were studied in bulk water 3,[20][21][22][23][24][29][30][31] and in confined environment. [25][26][27][28]32,34 One interesting challenge of nonlinear spectroscopy of water is how to disentangle the influence of orientational dynamics, population relaxation, frequency fluctuations, and wave function delocalization. Using the NEP, we investigate the sensitivity of nonlinear techniques to both the excitonic coupling and the two-exciton coherence in liquid water.…”

Section: Introductionmentioning

confidence: 99%

Coherent infrared multidimensional spectra of the OH stretching band in liquid water simulated by direct nonlinear exciton propagation

Falvo

Palmieri

Mukamel

2009

The Journal of Chemical Physics

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The two-dimensional vibrational response of the disordered strongly fluctuating OH exciton band in liquid water is investigated using a new simulation protocol. The direct nonlinear exciton propagation generalizes the nonlinear exciton equations to include nonadiabatic time dependent Hamiltonian and transition dipole fluctuations. The excitonic picture is retained and the large cancellation between Liouville pathways is built-in from the outset. The sensitivity of the photon echo and double-quantum-coherence techniques to frequency fluctuations, molecular reorientation, intermolecular coupling, and the two-exciton coherence is investigated. The photon echo is particularly sensitive to the frequency fluctuations and molecular reorientation, whereas the double-quantum coherence provides a unique probe for intermolecular couplings and two-exciton coherence.

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Dynamics of Nanoscopic Water: Vibrational Echo and Infrared Pump−Probe Studies of Reverse Micelles

Cited by 114 publications

References 84 publications

Hydrogen bond dynamics in aqueous NaBr solutions

Hydrogen bond dynamics in aqueous NaBr solutions

Hydrogen bonds of interfacial water in human breast cancer tissue compared to lipid and DNA interfaces

Coherent infrared multidimensional spectra of the OH stretching band in liquid water simulated by direct nonlinear exciton propagation

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