دورية أكاديمية
أعرض في EDS

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

التفاصيل البيبلوغرافية
العنوان: Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air-water interface.
المؤلفون: Denton JK; Sterling Chemistry Laboratory, Yale University, New Haven, CT 06520., Kelleher PJ; Sterling Chemistry Laboratory, Yale University, New Haven, CT 06520., Johnson MA; Sterling Chemistry Laboratory, Yale University, New Haven, CT 06520; mark.johnson@yale.edu., Baer MD; Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352., Kathmann SM; Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352., Mundy CJ; Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352.; Department of Chemical Engineering, University of Washington, Seattle, WA 98195., Wellen Rudd BA; Department of Chemistry & Biochemistry, The Ohio State University, Columbus, OH 43210.; Department of Chemistry, Ohio Wesleyan University, Delaware, OH 43015., Allen HC; Department of Chemistry & Biochemistry, The Ohio State University, Columbus, OH 43210., Choi TH; Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260., Jordan KD; Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260.; Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15260.
المصدر: Proceedings of the National Academy of Sciences of the United States of America [Proc Natl Acad Sci U S A] 2019 Jul 23; Vol. 116 (30), pp. 14874-14880. Date of Electronic Publication: 2019 Jul 05.
نوع المنشور: Journal Article; Research Support, U.S. Gov't, Non-P.H.S.
اللغة: English
بيانات الدورية: Publisher: National Academy of Sciences Country of Publication: United States NLM ID: 7505876 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1091-6490 (Electronic) Linking ISSN: 00278424 NLM ISO Abbreviation: Proc Natl Acad Sci U S A Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة: Original Publication: Washington, DC : National Academy of Sciences
مستخلص: 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.
Competing Interests: The authors declare no conflict of interest.
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فهرسة مساهمة: Keywords: infrared; interface; metal complex; spectroscopy; surfactant
تواريخ الأحداث: Date Created: 20190707 Date Completed: 20200316 Latest Revision: 20231013
رمز التحديث: 20231013
مُعرف محوري في PubMed: PMC6660762
DOI: 10.1073/pnas.1818600116
PMID: 31278149
قاعدة البيانات: MEDLINE
الوصف
تدمد:1091-6490
DOI:10.1073/pnas.1818600116