Echoes of a salty exchange

Laage, Damien; Hynes, James T.

doi:10.1073/pnas.0812306106

Cited by 6 publications

(7 citation statements)

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“…[20–22] and they measure the equilibrium hydrogen-bond exchange kinetics in a non-perturbative manner [5, 22–27]. The uniqueness and power of 2D IR exchange methods in clarifying hydrogen bond dynamics have been highlighted in a recent PNAS Commentary[28]. …”

Section: Introductionmentioning

confidence: 99%

A peptide’s perspective of water dynamics

Ghosh

Hochstrasser

2011

Chemical Physics

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This Perspective is focused on amide groups of peptides interacting with water. The 2D IR spectroscopy has already enabled structural aspects of the peptide backbone to be determined through its ability to measure the coupling between different amide-I modes. Here we describe why nonlinear IR is emerging as the method of choice to examine the fast components of the water dynamics near peptides and how isotopically edited peptide links can be used to probe the local water at a residue level in proteins. This type of research necessarily involves an intimate mix of theory and experiment. The description of the results is underpinned by relatively well established quantum-statistical theories that describe the important manifestations of peptide vibrational frequency fluctuations.

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Section: Introductionmentioning

confidence: 99%

A peptide’s perspective of water dynamics

Ghosh

Hochstrasser

2011

Chemical Physics

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“…This change of jump component is suggested to be caused by ions strengthening or weakening the hydrogen bonding structure of the surrounding water molecules. 19 , 23 , 26 , 27 , 37 , 38 , 41 …”

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confidence: 99%

The opposite effects of sodium and potassium cations on water dynamics

Zhang

Chen

et al. 2017

Chem. Sci.

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“…10 ps at room temperature. 16,17 The study of the kinetic of the methanol attack to tetrafluoro-substituted benzhydryl carbocations in methanol solution, conducted by Riedle et al 18 using femtosecond transient spectroscopy and on-the-fly molecular dynamics methods, also affords a very important experimental proof against the concerted mechanism for the hydration reaction. Thus, the found typical reaction trajectory shows that, at ca.…”

Section: ■ Discussion and Resultsmentioning

confidence: 99%

“…On the other hand, it was also shown by ultrafast IR spectroscopy that the breaking/formation of hydrogen bonds in bulky water, corresponding to the Grotthuss mechanisms in neutral water, occurs on a time scale of ca. 10 ps at room temperature. , …”

Section: Discussion and Resultsmentioning

confidence: 99%

“…30,43−46 Moreover, the formation of continuous water wires, needed for a collective proton transfer (soliton mechanisms), is an energetically disfavored process mainly due to the low entropy of the wire structures. 47 Hence, the Grotthuss proton transfer reaction is by no means "instantaneous", [13][14][15][16][17][18]39,47,48 as wrongly assumed by Cox. 4,5 On the other hand, we are convinced that, nowadays, Grothuss himself would not qualify his pioneering proton propagation mechanism 49 as instantaneous.…”

Section: ■ Conclusionmentioning

confidence: 99%

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About the Existence of Organic Oxonium Ions as Mechanistic Intermediates in Water Solution

2016

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This paper is aimed to show overwhelming experimental and theoretical evidence supporting the existence of organic oxonium ions (ROH2 +) as mechanistic intermediates in water solution, which should be taken into account when describing important reactions, like hydrations of carbocations or C–O cleavages under acidic conditions. For the hydration reaction of tert-butyl (t-Bu+) cation, we have calculated the reaction rate between the intermediate hydrated cation t-BuOH2 + and water, showing that the concerted proton/electron transfer reaction (CPET) is very slow in comparison with experimental data. Much better accordance is achieved by assuming a sequential electron transfer/proton transfer reaction (ETPT). Thus, there is an excellent accordance between the calculated relaxation time (τ = 2.14 ps) for the ETPT process in water and experimentally determined τ values (1.0–1.5 ps) for related reactions. Moreover, there is also an excellent agreement between the potential energy of activation (ΔV TS ≠ = 3.17 kcal/mol) for the proton transfer in gas-phase, computed with the B3LYP/6-31G(d) method following the variational transition state theory (VTST), with the analogous ΔV(Q EQ)≠ value (3.09 kcal/mol), calculated using methods based on single electron transfer (SET) reactions.

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Echoes of a salty exchange

Cited by 6 publications

References 19 publications

A peptide’s perspective of water dynamics

A peptide’s perspective of water dynamics

The opposite effects of sodium and potassium cations on water dynamics

About the Existence of Organic Oxonium Ions as Mechanistic Intermediates in Water Solution

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