Spontaneous Generation of Hydrogen Peroxide from Aqueous Microdroplets

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2019 Aug 28

PMID 31451646

Citations 114

Authors

Jae Kyoo Lee

Katherine L Walker

Hyun Soo Han

Jooyoun Kang

Fritz B Prinz

Robert M Waymouth

Hong Gil Nam

Richard N Zare

Affiliations

Soon will be listed here.

Abstract

We show HO is spontaneously produced from pure water by atomizing bulk water into microdroplets (1 μm to 20 µm in diameter). Production of HO, as assayed by HO-sensitve fluorescence dye peroxyfluor-1, increased with decreasing microdroplet size. Cleavage of 4-carboxyphenylboronic acid and conversion of phenylboronic acid to phenols in microdroplets further confirmed the generation of HO The generated HO concentration was ∼30 µM (∼1 part per million) as determined by titration with potassium titanium oxalate. Changing the spray gas to O or bubbling O decreased the yield of HO in microdroplets, indicating that pure water microdroplets directly generate HO without help from O either in air surrounding the droplet or dissolved in water. We consider various possible mechanisms for HO formation and report a number of different experiments exploring this issue. We suggest that hydroxyl radical (OH) recombination is the most likely source, in which OH is generated by loss of an electron from OH at or near the surface of the water microdroplet. This catalyst-free and voltage-free HO production method provides innovative opportunities for green production of hydrogen peroxide.

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References

Gaiduk A, Pham T, Govoni M, Paesani F, Galli G . Electron affinity of liquid water. Nat Commun. 2018; 9(1):247. PMC: 5770385. DOI: 10.1038/s41467-017-02673-z. View

Noyori R, Aoki M, Sato K . Green oxidation with aqueous hydrogen peroxide. Chem Commun (Camb). 2003; (16):1977-86. DOI: 10.1039/b303160h. View

Ben-Amotz D . Unveiling Electron Promiscuity. J Phys Chem Lett. 2015; 2(10):1216-22. DOI: 10.1021/jz2002875. View

Zhong J, Kumar M, Francisco J, Zeng X . Insight into Chemistry on Cloud/Aerosol Water Surfaces. Acc Chem Res. 2018; 51(5):1229-1237. DOI: 10.1021/acs.accounts.8b00051. View

Kumar M, Zhong J, Zeng X, Francisco J . Reaction of Criegee Intermediate with Nitric Acid at the Air-Water Interface. J Am Chem Soc. 2018; 140(14):4913-4921. DOI: 10.1021/jacs.8b01191. View

Dumitrescu I, Anand R, Fosdick S, Crooks R . Pressure-driven bipolar electrochemistry. J Am Chem Soc. 2011; 133(13):4687-9. DOI: 10.1021/ja111050h. View

Collin F . Chemical Basis of Reactive Oxygen Species Reactivity and Involvement in Neurodegenerative Diseases. Int J Mol Sci. 2019; 20(10). PMC: 6566277. DOI: 10.3390/ijms20102407. View

Miller E, Albers A, Pralle A, Isacoff E, Chang C . Boronate-based fluorescent probes for imaging cellular hydrogen peroxide. J Am Chem Soc. 2005; 127(47):16652-9. PMC: 1447675. DOI: 10.1021/ja054474f. View

Nam I, Lee J, Nam H, Zare R . Abiotic production of sugar phosphates and uridine ribonucleoside in aqueous microdroplets. Proc Natl Acad Sci U S A. 2017; 114(47):12396-12400. PMC: 5703324. DOI: 10.1073/pnas.1714896114. View

10.

Yamanaka I, Murayama T . Neutral H2O2 synthesis by electrolysis of water and O2. Angew Chem Int Ed Engl. 2008; 47(10):1900-2. DOI: 10.1002/anie.200704431. View

11.

Reeves C, Penkett S . Measurements of peroxides and what they tell us. Chem Rev. 2003; 103(12):5199-218. DOI: 10.1021/cr0205053. View

12.

Floyd R, Henderson R, Watson J, Wong P . Use of salicylate with high pressure liquid chromatography and electrochemical detection (LCED) as a sensitive measure of hydroxyl free radicals in adriamycin treated rats. J Free Radic Biol Med. 1986; 2(1):13-8. DOI: 10.1016/0748-5514(86)90118-2. View

13.

Huang M, Hsu H, Lee J, Jeng J, Shiea J . Direct protein detection from biological media through electrospray-assisted laser desorption ionization/mass spectrometry. J Proteome Res. 2006; 5(5):1107-16. DOI: 10.1021/pr050442f. View

14.

Du S, Francisco J, Kais S . Study of electronic structure and dynamics of interacting free radicals influenced by water. J Chem Phys. 2009; 130(12):124312. DOI: 10.1063/1.3100549. View

15.

Lee J, Samanta D, Nam H, Zare R . Spontaneous formation of gold nanostructures in aqueous microdroplets. Nat Commun. 2018; 9(1):1562. PMC: 5908806. DOI: 10.1038/s41467-018-04023-z. View

16.

Edwards J, Pritchard J, Lu L, Piccinini M, Shaw G, Carley A . The direct synthesis of hydrogen peroxide using platinum-promoted gold-palladium catalysts. Angew Chem Int Ed Engl. 2014; 53(9):2381-4. DOI: 10.1002/anie.201308067. View

17.

Lee J, Kim S, Nam H, Zare R . Microdroplet fusion mass spectrometry for fast reaction kinetics. Proc Natl Acad Sci U S A. 2015; 112(13):3898-903. PMC: 4386409. DOI: 10.1073/pnas.1503689112. View

18.

Lee J, Nam H, Zare R . Microdroplet fusion mass spectrometry: accelerated kinetics of acid-induced chlorophyll demetallation. Q Rev Biophys. 2017; 50:e2. PMC: 5729759. DOI: 10.1017/S0033583517000014. View

19.

Rivas L, Soares C, Baptista A, Simaan J, Di Paolo R, Murgida D . Electric-field-induced redox potential shifts of tetraheme cytochromes c3 immobilized on self-assembled monolayers: surface-enhanced resonance Raman spectroscopy and simulation studies. Biophys J. 2005; 88(6):4188-99. PMC: 1305649. DOI: 10.1529/biophysj.104.057232. View

20.

Landon P, Collier P, Papworth A, Kiely C, Hutchings G . Direct formation of hydrogen peroxide from H2/O2 using a gold catalyst. Chem Commun (Camb). 2002; (18):2058-9. DOI: 10.1039/b205248m. View