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Title: Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface

Abstract

We exploit gas-phase cluster ion techniques to provide insight into the local interactions underlying divalent metal ion-driven changes in the spectra of carboxylic acids at the air–water interface. This information clarifies the experimental findings that the CO stretching bands of long-chain acids appear at very similar energies when the head group is deprotonated by high subphase pH or exposed to relatively high concentrations of Ca 2+ metal ions. To this end, we report the evolution of the vibrational spectra of size-selected [Ca 2+ ·RCO 2 − ] + ·(H 2 O) n =0 to 12 and RCO 2 − ·(H 2 O) n =0 to 14 cluster ions toward the features observed at the air–water interface. Surprisingly, not only does stepwise hydration of the RCO 2 − anion and the [Ca 2+ ·RCO 2 − ] + contact ion pair yield solvatochromic responses in opposite directions, but in both cases, the responses of the 2 (symmetric and asymmetric stretching) CO bands to hydration are opposite to each other. The result is that both CO bands evolve toward their interfacial asymptotes from opposite directions. Simulations of the [Ca 2+ ·RCO 2 − ] + ·(H 2 O)more » n clusters indicate that the metal ion remains directly bound to the head group in a contact ion pair motif as the asymmetric CO stretch converges at the interfacial value by n = 12. This establishes that direct metal complexation or deprotonation can account for the interfacial behavior. We discuss these effects in the context of a model that invokes the water network-dependent local electric field along the C–C bond that connects the head group to the hydrocarbon tail as the key microscopic parameter that is correlated with the observed trends.« less

Authors:
ORCiD logo; ; ORCiD logo; ; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Pittsburgh, PA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); Univ. of California, Berkeley, CA (United States)
OSTI Identifier:
1531201
Alternate Identifier(s):
OSTI ID: 1598780
Grant/Contract Number:  
FG02-00ER15066; CHE-1801971; FA9550-17-1-0267; AC05-76RL01830; AC02-05CH11231; FG02-06ER15800
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 30; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; interface; spectroscopy; infrared; surfactant; metal complex

Citation Formats

Denton, Joanna K., Kelleher, Patrick J., Johnson, Mark A., Baer, Marcel D., Kathmann, Shawn M., Mundy, Christopher J., Wellen Rudd, Bethany A., Allen, Heather C., Choi, Tae Hoon, and Jordan, Kenneth D.. Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface. United States: N. p., 2019. Web. doi:10.1073/pnas.1818600116.
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Denton, Joanna K., Kelleher, Patrick J., Johnson, Mark A., Baer, Marcel D., Kathmann, Shawn M., Mundy, Christopher J., Wellen Rudd, Bethany A., Allen, Heather C., Choi, Tae Hoon, & Jordan, Kenneth D.. Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface. United States. https://doi.org/10.1073/pnas.1818600116
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Denton, Joanna K., Kelleher, Patrick J., Johnson, Mark A., Baer, Marcel D., Kathmann, Shawn M., Mundy, Christopher J., Wellen Rudd, Bethany A., Allen, Heather C., Choi, Tae Hoon, and Jordan, Kenneth D.. Fri . "Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface". United States. https://doi.org/10.1073/pnas.1818600116.
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@article{osti_1531201,
title = {Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface},
author = {Denton, Joanna K. and Kelleher, Patrick J. and Johnson, Mark A. and Baer, Marcel D. and Kathmann, Shawn M. and Mundy, Christopher J. and Wellen Rudd, Bethany A. and Allen, Heather C. and Choi, Tae Hoon and Jordan, Kenneth D.},
abstractNote = {We exploit gas-phase cluster ion techniques to provide insight into the local interactions underlying divalent metal ion-driven changes in the spectra of carboxylic acids at the air–water interface. This information clarifies the experimental findings that the CO stretching bands of long-chain acids appear at very similar energies when the head group is deprotonated by high subphase pH or exposed to relatively high concentrations of Ca 2+ metal ions. To this end, we report the evolution of the vibrational spectra of size-selected [Ca 2+ ·RCO 2 − ] + ·(H 2 O) n =0 to 12 and RCO 2 − ·(H 2 O) n =0 to 14 cluster ions toward the features observed at the air–water interface. Surprisingly, not only does stepwise hydration of the RCO 2 − anion and the [Ca 2+ ·RCO 2 − ] + contact ion pair yield solvatochromic responses in opposite directions, but in both cases, the responses of the 2 (symmetric and asymmetric stretching) CO bands to hydration are opposite to each other. The result is that both CO bands evolve toward their interfacial asymptotes from opposite directions. Simulations of the [Ca 2+ ·RCO 2 − ] + ·(H 2 O) n clusters indicate that the metal ion remains directly bound to the head group in a contact ion pair motif as the asymmetric CO stretch converges at the interfacial value by n = 12. This establishes that direct metal complexation or deprotonation can account for the interfacial behavior. We discuss these effects in the context of a model that invokes the water network-dependent local electric field along the C–C bond that connects the head group to the hydrocarbon tail as the key microscopic parameter that is correlated with the observed trends.},
doi = {10.1073/pnas.1818600116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 30,
volume = 116,
place = {United States},
year = {2019},
month = {7}
}
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https://doi.org/10.1073/pnas.1818600116
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Cited by: 33 works
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Figures / Tables:

Figure 1 Figure 1: IRRAS spectra of monolayers (20.5 Å2/molecule) of (a) d31-palmitic acid (d31-PA) on neat H2O, (b) d35-stearic acid (d35-SA) on D2O with a subphase pH of 10.5, and (c) d31-PA on D2O with a subphase CaCl2 concentration of 0.3 M. Features assigned to the two carbon-oxygen stretching modes ofmore » the intact carboxylic acid are denoted $ν^{C-OH}$ and $ν^{C=0}$ in trace (a), along with the water bending mode ($ν^{H_2O}_{bend}$ ). Peaks assigned to the symmetric and asymmetric stretching modes of the deprotonated carboxylate head group are denoted $ν ^{COO}_{a}$and $ν ^{COO}_{as}$), respectively, in trace (b). Note that with the exception of the H2O bend peaks appear as negative bands due to the experimental geometry.« less
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