DOI: 10.1073/pnas.0800181105. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

10.1073/pnas.0800181105

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

Bibliography

Uejio, J. S., Schwartz, C. P., Duffin, A. M., Drisdell, W. S., Cohen, R. C., & Saykally, R. J. (2008). Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets. Proceedings of the National Academy of Sciences, 105(19), 6809â6812.

Authors 6

Janel S. Uejio (first)
Craig P. Schwartz (additional)
Andrew M. Duffin (additional)
Walter S. Drisdell (additional)
Ronald C. Cohen (additional)
Richard J. Saykally (additional)

References 29 Referenced 121

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W Kutzelnigg, U Fleischer, M Schindler, The IGLO Method: ab initio calculation and interpretation of NMR chemical shifts and magnetic susceptibilities. NMR—Basic Principles and Progress, ed P Diehl (Springer, New York) Vol 23, 165–262 (1991). / NMR—Basic Principles and Progress by Kutzelnigg W (1991)
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Dates

Type	When
Created	17 years, 3 months ago (May 7, 2008, 9:10 p.m.)
Deposited	3 years, 4 months ago (April 12, 2022, 5:04 p.m.)
Indexed	2 months, 1 week ago (June 17, 2025, 4:09 a.m.)
Issued	17 years, 3 months ago (May 13, 2008)
Published	17 years, 3 months ago (May 13, 2008)
Published Online	17 years, 3 months ago (May 13, 2008)
Published Print	17 years, 3 months ago (May 13, 2008)

Funders 0

None

BibTeX

@article{Uejio_2008, title={Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets}, volume={105}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.0800181105}, DOI={10.1073/pnas.0800181105}, number={19}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Uejio, Janel S. and Schwartz, Craig P. and Duffin, Andrew M. and Drisdell, Walter S. and Cohen, Ronald C. and Saykally, Richard J.}, year={2008}, month=may, pages={6809–6812} }

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