Hydrogen Bond Migration between Molecular Sites Observed with Ultrafast 2D IR Chemical Exchange Spectroscopy

Kwak, Kyungwon; Gengeliczki, Zsolt; Fayer, M. D.

doi:10.1021/jp911452z

Cited by 25 publications

(16 citation statements)

References 40 publications

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“…In an interesting solution-phase experiment Rosenfeld et al observed a switching of the interaction site for phenol from the p-electron density of the acetylenic CC bond to the p-electron density of the benzene ring within a 5 ps timescale. [115] This indicates the dynamic behavior of the hydrogen-bonding pattern in phenylacetylene. The fact that the leading contribution switches from electrostatics to dispersion can explain the difference in the intermolecular structures of the water and methanol complexes.…”

Section: The Chameleonmentioning

confidence: 87%

Phenylacetylene: A Hydrogen Bonding Chameleon

et al. 2010

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Molecules with multiple hydrogen bonding sites offer the opportunity to investigate competitive hydrogen bonding. Such an investigation can become quite interesting, particularly when the molecule of interest has neither lone-pair electrons nor strongly acidic/basic groups. Phenylacetylene is one such molecule with three hydrogen bonding sites that cannot be ranked into any known hierarchical pattern. Herein we review the structures of several binary complexes of phenylacetylene investigated using infrared optical double-resonance spectroscopy in combination with high-level ab initio methods. The diversity of intermolecular structures formed by phenylacetylene with various reagents is remarkable. The nature of intermolecular interaction with various reagents is the result of a subtle balance between various configurations and competition between the electrostatic and dispersion energy terms, while trying to maximize the total interaction strength.

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Section: The Chameleonmentioning

confidence: 87%

Phenylacetylene: A Hydrogen Bonding Chameleon

et al. 2010

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“…26–28 In addition, phenol group is a proton donor that can establish hydrogen bonding interactions with proton acceptors such as phenolate ion, aromatic ring, and carboxylic acid or carboxylate groups. 29, 30 The immobilized tyramine moieties are pendent on the PGS backbone with succinate as a spacer. In this way, the tyramine moieties are more accessible and more flexible and it is easier to establish physical interactions between them.…”

Section: Introductionmentioning

confidence: 99%

Tyramine functionalization of poly(glycerol sebacate) increases the elasticity of the polymer

Ding

Gao

et al. 2017

J. Mater. Chem. B

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Poly(glycerol sebacate) (PGS) is an elastomer used widely in tissue engineering studies due to good biocompatibility. Hereby we report a tyramine functionalized PGS called PGS-TA. Tyramine adds a stronger physical bonding capability to PGS-TA. Tensile tests showed that the softness and toughness of the material were similar to PGS. However, PGS-TA demonstrated 16-folds increase of elastic deformations compared to PGS processed under identical conditions. The in vitro studies demonstrated that the viability, and metabolic activity of baboon smooth muscle cells were the same as those on tissue culture polystyrene. Porous subcutaneous implants of PGS-TA substantially degraded in vivo over two weeks, showing good biodegradability and biocompatibility. We expect PGS-TA to be useful for applications in tissues and organs that are subjected to large reversible mechanical deformations.

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“…11 2D IR spectroscopy has been extremely successful in understanding spectral diffusion in bulk water [6][7][8][12][13][14][15] and other hydrogen bonding systems, 11,16,17 protein and other biological systems, [18][19][20][21][22][23][24][25][26] as well as systems that undergo chemical exchange or isomerization. [27][28][29][30][31][32] Through a time-ordered series of three input electric fields (ultrafast laser pulses), 2D IR spectroscopy can manipulate the quantum pathways by which a system evolves. The first pulse excites a coherent superposition of the ground (0) and first excited (1) vibrational states.…”

Section: Introductionmentioning

confidence: 99%

Extracting 2D IR frequency-frequency correlation functions from two component systems

Fenn

Fayer²

2011

The Journal of Chemical Physics

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The center line slope (CLS) method is often used to extract the frequency-frequency correlation function (FFCF) from 2D IR spectra to delineate dynamics and to identify homogeneous and inhomogeneous contributions to the absorption line shape of a system. While the CLS method is extremely efficient, quite accurate, and immune to many experimental artifacts, it has only been developed and properly applied to systems that have a single vibrational band, or to systems of two species that have spectrally resolved absorption bands. In many cases, the constituent spectra of multiple component systems overlap and cannot be distinguished from each other. This situation creates ambiguity when analyzing 2D IR spectra because dynamics for different species cannot be separated. Here a mathematical formulation is presented that extends the CLS method for a system consisting of two components (chemically distinct uncoupled oscillators). In a single component system, the CLS corresponds to the time-dependent portion of the normalized FFCF. This is not the case for a two component system, as a much more complicated expression arises. The CLS method yields a series of peak locations originating from slices taken through the 2D spectra. The slope through these peak locations yields the CLS value for the 2D spectra at a given T(w). We derive analytically that for two component systems, the peak location of the system can be decomposed into a weighted combination of the peak locations of the constituent spectra. The weighting depends upon the fractional contribution of each species at each wavelength and also on the vibrational lifetimes of both components. It is found that an unknown FFCF for one species can be determined as long as the peak locations (referred to as center line data) of one of the components are known, as well as the vibrational lifetimes, absorption spectra, and other spectral information for both components. This situation can arise when a second species is introduced into a well characterized single species system. An example is a system in which water exists in bulk form and also as water interacting with an interface. An algorithm is presented for back-calculating the unknown FFCF of the second component. The accuracy of the algorithm is tested with a variety of model cases in which all components are initially known. The algorithm successfully reproduces the FFCF for the second component within a reasonable degree of error.

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Hydrogen Bond Migration between Molecular Sites Observed with Ultrafast 2D IR Chemical Exchange Spectroscopy

Cited by 25 publications

References 40 publications

Phenylacetylene: A Hydrogen Bonding Chameleon

Phenylacetylene: A Hydrogen Bonding Chameleon

Tyramine functionalization of poly(glycerol sebacate) increases the elasticity of the polymer

Extracting 2D IR frequency-frequency correlation functions from two component systems

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