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Host-Guest Complexation of Amphiphilic Molecules at the Air-Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen

Geng, Wen-Chao and Zhang, Dongmei and Gong, Chu and Liu, Zhihao and Barraza, Kevin M. and Beauchamp, J. L. and Guo, Dong-Sheng and Zhang, Xinxing (2020) Host-Guest Complexation of Amphiphilic Molecules at the Air-Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen. Angewandte Chemie International Edition . ISSN 1433-7851. (In Press) https://resolver.caltech.edu/CaltechAUTHORS:20200408-085116537

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Abstract

The paradox of antioxidants is that they protect other more valuable molecules by sacrificial reactions with oxidizers. Their consequential loss in efficacy imposes great challenges to both living organisms and the food industry. Here we show that the host‐guest complexation of the carefully designed positively charged amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A‐12C) and negatively charged oleic acid (OA), a well‐known cell membrane antioxidant, prevents the oxidation of a monolayer of the complex at the air‐water interface from two potent oxidizers, hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field‐induced droplet ionization mass spectrometry results have demonstrated that the host‐guest complexation is able to achieve steric shielding and to prevent both types of oxidation as a result of the tight and “sleeved in” physical arrangement, rather than the chemical reactivity, of the complexes.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.202001355DOIArticle
ORCID:
AuthorORCID
Barraza, Kevin M.0000-0003-1849-5219
Beauchamp, J. L.0000-0001-8839-4822
Additional Information:© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Accepted manuscript online: 06 April 2020; Manuscript accepted: 06 April 2020; Manuscript revised: 20 March 2020; Manuscript received: 27 January 2020. X.Z. acknowledges the National Key R&D Program of China (2018YFE0115000) and the NSF of Tianjin City (19JCYBJC19600). This work was supported by the Beckman Institute at Caltech and by NSF grant CHE-1508825 (J.L.B.). NSFC (51873090 and 21672112) and the Fundamental Research Funds for the Central Universities are gratefully acknowledged.
Funders:
Funding AgencyGrant Number
National Key Research and Development Program of China2018YFE0115000
National Science Foundation of Tianjin City19JCYBJC19600
Caltech Beckman InstituteUNSPECIFIED
NSFCHE-1508825
National Natural Science Foundation of China51873090
National Natural Science Foundation of China21672112
Fundamental Research Funds for the Central UniversitiesUNSPECIFIED
Subject Keywords:Mass spectrometry; supramolecular chemistry; Host-guest complex; Calixarene; Air-water interface
Record Number:CaltechAUTHORS:20200408-085116537
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200408-085116537
Official Citation:Geng, W., Zhang, D., Gong, C., Li, Z., Barraza, K., Beauchamp, J., Guo, D. and Zhang, X. (2020), Host‐Guest Complexation of Amphiphilic Molecules at the Air‐Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen. Angew. Chem. Int. Ed.. Accepted Author Manuscript. doi:10.1002/anie.202001355
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102395
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 Apr 2020 16:50
Last Modified:08 Apr 2020 16:50

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