Calculated and observed isotope effects with easily polarizable hydrogen and deuterium bonds

Janoschek, Rudolf; Hayd, A.; Weidemann, E. G.; Leuchs, Martin; Zuńdel, Georg

doi:10.1039/f29787401238

Cited by 31 publications

(12 citation statements)

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“…Its intensity decreases to about 50% with deuteration. From experimental results as well as theoretical treatments (Zundel et al, 1993;Zundel, 1969;Janoschek, et al, 1978), it is well known that the infrared continua caused by polarizable deuterium bonds begin at the (----) DCCD-blocked, after H2O0D2O exchange.…”

Section: Resultsmentioning

confidence: 99%

The F0 complex of the ATP synthase of Escherichia coli contains a proton pathway with large proton polarizability caused by collective proton fluctuation

Bartl¹,

Deckers-Hebestreit²,

Altendorf³

et al. 1995

Biophysical Journal

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The F0 complex of the Escherichia coli ATP synthase embedded into cardiolipin liposomes was studied by FT-IR spectroscopy. For comparison, respective studies were performed with dried F0 liposomes and with F0 liposomes treated with N,N'-dicyclohexyl-carbodiimide (DCCD), which binds to Asp-61 of subunit c. Furthermore, the effect of H2O-->D2O exchange on the infrared spectrum was investigated. With F0 liposomes an infrared continuum is observed beginning at about 3000 cm-1 and extending toward smaller wavenumbers. In the DCCD-treated sample, this continuum is no longer observed. It vanishes also with drying of the liposomes. After H2O-->D2O exchange, this infrared continuum begins at about 2350 cm-1 and is less intense. All of these results demonstrate that a proton pathway in native F0 is present, in which the protons are shifted in a hydrogen-bonded chain with large proton polarizability due to collective proton tunneling. With the D2O-hydrated system, deuteron polarizability due to collective deuteron motion is observed, but the polarizability due to collective deuteron motion is smaller. Such pathways are very efficient, because they conduct protons or deuterons within picoseconds. These pathways lose their polarizability if the F0 complex is blocked by DCCD or if the liposomes are dried. On the basis of our results on the proton polarizability of hydrogen bonds and hydrogen-bonded systems and on the basis of structural data from the literature, the nature of the proton pathway of the F0 complex of E. coli is discussed.

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Section: Resultsmentioning

confidence: 99%

The F0 complex of the ATP synthase of Escherichia coli contains a proton pathway with large proton polarizability caused by collective proton fluctuation

Bartl¹,

Deckers-Hebestreit²,

Altendorf³

et al. 1995

Biophysical Journal

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“…Thus, the proton potential in the NO-H+*ON bonds is narrow and hence, the proton polarizability due to proton shifts within this hydrogen bond is small. 12 In Table 1 all systems studied are summarized. First we consider the complexes formed by compound 1 with phenols (ratio 1 : 1) as a function of the pKa of the phenols.…”

Section: Resultsmentioning

confidence: 99%

Complex formation and proton transfer in the polarizable hydrogen bonds of two N,N′-dioxides + substituted phenol systems as a function of the pK_aof the phenols. An FTIR study

Brzeziński¹,

Schroeder²,

Zuńdel³

et al. 1992

J. Chem. Soc., Perkin Trans. 2

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“…The calculations performed by Zundel er 01. (23) showed, that in the case of broad "continuous" protonic absorption the total effect consists of the narrowing on both sides of the band and a drop of intensity.…”

Section: Resultsmentioning

confidence: 99%

Infrared spectra of hydrogen bonded adducts of 2,6-dichlorophenols and oxygen bases

Wolny¹,

Koll²,

Sobczyk³

1985

Can. J. Chem.

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This paper is dedicated to Professor Camille Sandorfy on the occasion of his 65th birthdayR. WOLNY, A. KOLL, and L. SOBCZYK. Can. J. Chem. 63, 3568 (1985). Infrared spectra of hydrogen bonded complexes of 2,6-dichlorophenol derivatives and oxygen bases have been studied over a broad ApK, range (from -10.55 to + 1.69). For the complexes of I : I stoichiometry typical evolution of spectra, similar to those for other hydrogen bonded systems, have been found. With an increase of ApK.,, the hydroxyl group stretching vibration band shifts to lower frequencies until the inversion region is reached, where hydrogen bonded (HB) and proton transfer (PT) forms occur in equilibrium, then a broad background absorption is observed. The centre of gravity of the broad protonic bands, v,,, calculated from the integrated intensity over the whole infrared region have been correlated with ApK. and the contribution of the PT form. It has been shown that the minimum on the plot v,, vs. ApK;, is reached close to the inversion point, where K, = I. The observed correlations and the change in the shape of the broad protonic absorption are consistent with expectations of theories based on the concept of the double minimum potential function and the stochastic mechanisms of band broadening.R. WOLNY, A. KOLL et L. SOBCZYK. Can. J. Chem. 63, 3568 (1985).Utilisant un large intervalle de ApK, (allant de -10,55 a + 1,69), on a etudie les spectres infrarouges des complexes des dCrivCs du dichloro-2,6 phCnol et des bases oxygCntes lies par des liaisons hydrogknes. Dans le cas des complexes du type I : I, on a trouvC une Cvolution typique des spectres semblable a celle des autres systkmes lies par des liaisons hydrogknes. Lorsque le ApK. augmente, la bande de vibration d'tlongation du groupe hydroxyle glisse vers les basses frequences jusqu'ii atteindre la rCgion d'inversion ob les formes hydrogkne liC (HL) et transfert de proton (TP) existent ii I'Cquilibre; on observe alors une large absorption de fond. On a Ctabli une correlation entre le centre de gravitC des bandes protoniques larges, v,,, calculC a partir de I'intensitC intCgrCe sur toute la rCgion infrarouge, avec le ApK;, et la contribution de la forme TP. On montre que I'on atteint le minimum de la courbe v,, en fonction du ApK;, prks du point d'inversion ob K,, = I . Les corrClations observCes et le changement de forme de I'absorption protonique large sont en accord avec les attentes des theories fondees sur le concept de la fonction de potentiel du minimum double et sur le mCcanisme stochastique de I'Clargissement de la bande.[Traduit par le journal]

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Calculated and observed isotope effects with easily polarizable hydrogen and deuterium bonds

Cited by 31 publications

References 0 publications

The F0 complex of the ATP synthase of Escherichia coli contains a proton pathway with large proton polarizability caused by collective proton fluctuation

The F0 complex of the ATP synthase of Escherichia coli contains a proton pathway with large proton polarizability caused by collective proton fluctuation

Complex formation and proton transfer in the polarizable hydrogen bonds of two N,N′-dioxides + substituted phenol systems as a function of the pK_aof the phenols. An FTIR study

Infrared spectra of hydrogen bonded adducts of 2,6-dichlorophenols and oxygen bases

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Calculated and observed isotope effects with easily polarizable hydrogen and deuterium bonds

Cited by 31 publications

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The F0 complex of the ATP synthase of Escherichia coli contains a proton pathway with large proton polarizability caused by collective proton fluctuation

The F0 complex of the ATP synthase of Escherichia coli contains a proton pathway with large proton polarizability caused by collective proton fluctuation

Complex formation and proton transfer in the polarizable hydrogen bonds of two N,N′-dioxides + substituted phenol systems as a function of the pKaof the phenols. An FTIR study

Infrared spectra of hydrogen bonded adducts of 2,6-dichlorophenols and oxygen bases

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Complex formation and proton transfer in the polarizable hydrogen bonds of two N,N′-dioxides + substituted phenol systems as a function of the pK_aof the phenols. An FTIR study