Interactions of easily polarizable hydrogen bonds with polar solvents and anions.  Theoretical considerations.  1.  Interactions of a single bond

Pfeiffer, H. G.; Zuńdel, Georg; Weidemann, E. G.

doi:10.1021/j100482a024

Cited by 20 publications

(4 citation statements)

References 2 publications

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“…Ep + Ei = (ípCp + qc¡ )d (20) From the combination of the eq 8-10, 12, and 13 and by elimination of cb, ch, and cc the following relation for the equilibrium concentration c¡ of the free anion is obtained: The absorptivity c¡ can be determined from a pure solution of a salt with the respective anion A™. If cB is varied again, the constants Kpj, KB, and ep result from the fit to the measured points.…”

Section: Methodsmentioning

confidence: 99%

Proton potentials and proton polarizability in carboxylic acid-trimethylamine oxide hydrogen bonds as a function of the donor and acceptor properties: IR investigations

Boehner¹,

Zuńdel²

1986

J. Phys. Chem.

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Section: Methodsmentioning

confidence: 99%

Proton potentials and proton polarizability in carboxylic acid-trimethylamine oxide hydrogen bonds as a function of the donor and acceptor properties: IR investigations

Boehner¹,

Zuńdel²

1986

J. Phys. Chem.

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“…In ref. 21, the interaction of a structurally symmetrical hydrogen bond with a polar environment was treated theoretically with the result that if the proton is in the ground state, the proton potentials usually become more and more asymmetrical due to polar environments. The intensity of the Rayleigh scattering in the Raman spectra near the excitation line is a direct measure of the anisotropy of the proton or deuteron polarizabilities and thus, since these polarizabilities occur only in bond direction, of the polarizabilities.…”

Section: Discussionmentioning

confidence: 99%

Influence of stereochemistry, screening, and deuteration of long and short intramolecular easily polarizable hydrogen bonds on their infrared continua

Brzeziński¹,

Zuńdel²

1981

Can. J. Chem.

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HClO4 salts of N,N′-tetramethylalkanes (compounds 1–6) and of N,N′-tetraalkyl-o-xylildiamines (compounds 7–11) and HAuCl4 salts of N,N′-tetramethyl-o-xylildiamine-di-N-oxide (compound 12) and of o-xylildipiperidyl-di-N-oxides (compounds 13–14) were studied by nmr and ir spectroscopy. It is shown that in the compounds 3, 4, 5, and 7–11, long intramolecular [Formula: see text] hydrogen bonds with large proton polarizability and in compounds 12–14, short intramolecular [Formula: see text] hydrogen bonds with large proton polarizability are formed. The study of the compounds 1–6 shows that the most favorable conditions for the formation of the intramolecular easily polarizable hydrogen bonds occur with compound 4, i.e., if these hydrogen bonds are present in the 7-membered rings. In the case of compounds 7–14 it is shown that the continua usually observed with easily polarizable hydrogen bonds vanish when these bonds become screened from their solvent environments. Then, instead of continua only bands of the fundamental transitions are observed, with the long [Formula: see text] bonds in the region 2800–1800 cm−1 and with the short [Formula: see text] bonds in the region 1200–850 cm−1. This result demonstrates that for the occurrence of the ir continua, the interaction of the easily polarizable hydrogen bonds with their solvent environments is absolutely necessary. Furthermore, it is shown with the long as well as the short hydrogen bonds that the intensity of the continua decreases strongly with deuteration, demonstrating that in both cases the deuteron polarizabilities are much smaller than the proton polarizabilities of the hydrogen or deuterium bonds, respectively. From this observation it is concluded that the proton potentials of these structurally symmetrical hydrogen bonds are considerably deformed by their molecular surroundings.

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“…These hydrogen bonds are extremely and therefore, the barrier in the proton potential is high and the proton polarizability very large.5y6 Caused by the strong interaction with their environment, however, the proton potentials become deformed. 34 In a 50% proton-transfer system this happens to the same degree toward both sides of the bonds.…”

Section: U S Hmentioning

confidence: 99%

Proton transfer and polarizability of hydrogen bonds formed between cysteine and lysine residues

Kristof

Zuńdel

1982

Biopolymers

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(L‐Cys)n + N‐base systems and (L‐Cys)n + (L‐Lys)n systems were studied by ir spectroscopy. It is shown that in the water‐free systems, SH ⃛N ⇌ S− ⃛H+N hydrogen bonds are formed. With the (L‐Cys)n + N‐base systems, both proton‐limiting structures in the SH ⃛N ⇌ S− ⃛H+N bonds have equal weight when the pKa of the protonated N‐base is 2 pKa units larger than that of (L‐Cys)n. The same is true with the water‐free (L‐Cys)n + (L‐Lys)n system. Thus, with regard to the type of proton potentials present, these hydrogen bonds are proton‐transfer hydrogen bonds showing very large proton polarizabilities. This is confirmed by the occurrence of continua in the ir spectra. Small amounts of water open these hydrogen bonds and increase the transfer of the proton to (L‐Lys)n. In the (L‐Lys)n + N‐base systems, with increasing proton transfer the backbone of (L‐Cys)n changes from antiparallel β‐structure to coil. In (L‐Cys)n + (L‐Lys)n, the conformation is determined by the (L‐Lys)n conformation and changes depending on the chain length of (L‐Lys)n. Finally, the reactivity increase in the active center of fatty acid synthetase, which should be caused by the shift of a proton, is discussed on the basis of the great proton polarizability of the cysteine–lysine hydrogen bonds.

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Interactions of easily polarizable hydrogen bonds with polar solvents and anions. Theoretical considerations. 1. Interactions of a single bond

Cited by 20 publications

References 2 publications

Proton potentials and proton polarizability in carboxylic acid-trimethylamine oxide hydrogen bonds as a function of the donor and acceptor properties: IR investigations

Proton potentials and proton polarizability in carboxylic acid-trimethylamine oxide hydrogen bonds as a function of the donor and acceptor properties: IR investigations

Influence of stereochemistry, screening, and deuteration of long and short intramolecular easily polarizable hydrogen bonds on their infrared continua

Proton transfer and polarizability of hydrogen bonds formed between cysteine and lysine residues

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