Liquid-jet photoemission spectroscopy (LJ-PES) directly probes the electronic structure of solutes and solvents. It also emerges as a novel tool to explore chemical structure in aqueous solutions, yet the scope of the approach has to be examined. Here, we present a pH-dependent liquid-jet photoelectron spectroscopic investigation of ascorbic acid (vitamin C). We combine core-level photoelectron spectroscopy and ab initio calculations, allowing us to site-specifically explore the acid-base chemistry of the biomolecule. For the first time, we demonstrate the capability of the method to simultaneously assign two deprotonation sites within the molecule. We show that a large change in chemical shift appears even for atoms distant several bonds from the chemically modified group. Furthermore, we present a highly efficient and accurate computational protocol based on a single structure using the maximum-overlap method for modeling core-level photoelectron spectra in aqueous environments. This work poses a broader question: to what extent can LJ-PES complement established structural techniques such as nuclear magnetic resonance? Answering this question is highly relevant in view of the large number of incorrect molecular structures published.

Department of Chemistry Graduate School of Science Kyoto University Kitashirakawa Oiwakecho Sakyo Ku 606 8502 Kyoto Japan

Department of Physical Chemistry University of Chemistry and Technology Technická 5 16628 Prague Czech Republic

Molecular Physics Fritz Haber Institut der Max Planck Gesellschaft Faradayweg 4 6 14195 Berlin Germany

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Faubel M. Steiner B. Toennies J. P. J. Chem. Phys. 1997;106:9013–9031. doi: 10.1063/1.474034. DOI

Winter B. Faubel M. Chem. Rev. 2006;106:1176–1211. doi: 10.1021/cr040381p. PubMed DOI

Winter B. Nucl. Instrum. Methods Phys. Res., Sect. A. 2009;601:139–150. doi: 10.1016/j.nima.2008.12.108. DOI

Seidel R. Winter B. Bradforth S. E. Annu. Rev. Phys. Chem. 2016;67:283–305. doi: 10.1146/annurev-physchem-040513-103715. PubMed DOI

Siegbahn K., ESCA. Atomic, Molecular and Solid State Structure Studied by Means of Electron Spectroscopy, Almqvist & Wiksells Uppsala, Uppsala, 1967

Signorell R. Winter B. Phys. Chem. Chem. Phys. 2022;24:13438–13460. doi: 10.1039/D2CP00164K. PubMed DOI PMC

Dupuy R. Richter C. Winter B. Meijer G. Schlögl R. Bluhm H. J. Chem. Phys. 2021;154:060901. doi: 10.1063/5.0036178. PubMed DOI

Perrine K. A. Parry K. M. Stern A. C. Spyk M. H. C. V. Makowski M. J. Freites J. A. Winter B. Tobias D. J. Hemminger J. C. Proc. Natl. Acad. Sci. U. S. A. 2017;114:13363–13368. doi: 10.1073/pnas.1707540114. PubMed DOI PMC

Ghosal S. Hemminger J. C. Bluhm H. Mun B. S. Hebenstreit E. L. Ketteler G. Ogletree D. F. Requejo F. G. Salmeron M. Science. 2005;307:563–566. doi: 10.1126/science.1106525. PubMed DOI

Wu C. H. Weatherup R. S. Salmeron M. B. Phys. Chem. Chem. Phys. 2015;17:30229–30239. doi: 10.1039/C5CP04058B. PubMed DOI

Malmgren S. Ciosek K. Hahlin M. Gustafsson T. Gorgoi M. Rensmo H. Edström K. Electrochim. Acta. 2013;97:23–32. doi: 10.1016/j.electacta.2013.03.010. DOI

Reuss T. Nair Lalithambika S. S. David C. Döring F. Jooss C. Risch M. Techert S. Acc. Chem. Res. 2023;56:203–214. doi: 10.1021/acs.accounts.2c00525. PubMed DOI PMC

Thürmer S. Malerz S. Trinter F. Hergenhahn U. Lee C. Neumark D. M. Meijer G. Winter B. Wilkinson I. Chem. Sci. 2021;12:10558–10582. doi: 10.1039/D1SC01908B. PubMed DOI PMC

Winter B. Hergenhahn U. Faubel M. Björneholm O. Hertel I. V. J. Chem. Phys. 2007;127:094501. doi: 10.1063/1.2770457. PubMed DOI

Winter B. Aziz E. F. Ottosson N. Faubel M. Kosugi N. Hertel I. V. J. Am. Chem. Soc. 2008;130:7130–7138. doi: 10.1021/ja8009742. PubMed DOI

Hollas D. Pohl M. N. Seidel R. Aziz E. F. Slavček P. Winter B. Sci. Rep. 2017;7:756. doi: 10.1038/s41598-017-00756-x. PubMed DOI PMC

Li J. Lu J. Chew A. Han S. Li J. Wu Y. Wang H. Ghimire S. Chang Z. Nat. Commun. 2020;11:2748. doi: 10.1038/s41467-020-16480-6. PubMed DOI PMC

Barreau L. Ross A. D. Garg S. Kraus P. M. Neumark D. M. Leone S. R. Sci. Rep. 2020;10:5773. doi: 10.1038/s41598-020-62461-6. PubMed DOI PMC

Nishitani J. West C. W. Suzuki T. Struct. Dyn. 2017;4:044014. doi: 10.1063/1.4979857. PubMed DOI PMC

Yin Z. Chang Y.-P. Balčiūnas T. Shakya Y. Djorović A. Gaulier G. Fazio G. Santra R. Inhester L. Wolf J.-P. Wörner H. J. Nature. 2023;619:749–754. doi: 10.1038/s41586-023-06182-6. PubMed DOI PMC

Ernst R. R., Bodenhausen G. and Wokaun A., Principles of Nuclear Magnetic Resonance in One and Two Dimensions, Oxford University Press, 1990

Yoo H.-D. Nam S.-J. Chin Y.-W. Kim M.-S. Arch. Pharm. Res. 2016;39:143–153. doi: 10.1007/s12272-015-0649-9. PubMed DOI

Shen S.-M. Appendino G. Guo Y.-W. Nat. Prod. Rep. 2022;39:1803–1832. doi: 10.1039/D2NP00023G. PubMed DOI

Nicolaou K. C. Snyder S. A. Angew. Chem., Int. Ed. 2005;44:1012–1044. doi: 10.1002/anie.200460864. PubMed DOI

Suyama T. L. Gerwick W. H. McPhail K. L. Bioorg. Med. Chem. 2011;19:6675–6701. doi: 10.1016/j.bmc.2011.06.011. PubMed DOI PMC

Aziz E. F. Ottosson N. Faubel M. Hertel I. V. Winter B. Nature. 2008;455:89–91. doi: 10.1038/nature07252. PubMed DOI

Ottosson N. Børve K. J. SpÅngberg D. Bergersen H. Sæthre L. J. Faubel M. Pokapanich W. Öhrwall G. Björneholm O. Winter B. J. Am. Chem. Soc. 2011;133:3120–3130. doi: 10.1021/ja110321q. PubMed DOI

He L. Tomaník L. Malerz S. Trinter F. Trippel S. Belina M. Slavíček P. Winter B. Küpper J. J. Phys. Chem. Lett. 2023;14:10499–10508. doi: 10.1021/acs.jpclett.3c01763. PubMed DOI PMC

Mudryk K. Lee C. Tomaník L. Malerz S. Trinter F. Hergenhahn U. Neumark D. M. Slavíček P. Bradforth S. Winter B. J. Am. Chem. Soc. 2024;146:16062–16075. doi: 10.1021/jacs.4c03174. PubMed DOI PMC

Thürmer S. Seidel R. Winter B. Ončák M. Slavíček P. J. Phys. Chem. A. 2011;115:6239–6249. doi: 10.1021/jp111674s. PubMed DOI

Malerz S. Mudryk K. Tomaník L. Stemer D. Hergenhahn U. Buttersack T. Trinter F. Seidel R. Quevedo W. Goy C. Wilkinson I. Thürmer S. Slavíček P. Winter B. J. Phys. Chem. A. 2021;125:6881–6892. doi: 10.1021/acs.jpca.1c04695. PubMed DOI PMC

Szent-Györgyi A., Nobel Lecture, Nobel Foundation, 1937, https://www.nobelprize.org

Institute of Medicine, Dietary Reference Intakes for Vitamin C, Vitamin E, Selenium, and Carotenoids, The National Academies Press, Washington, DC, 2000 PubMed

Davies M., Partridge D. and Austin J., Vitamin C: Its Chemistry and Biochemistry, Royal Society of Chemistry, 2007

Ems T., St Lucia K. and Huecker M. R., Biochemistry, Iron Absorption, StatPearls Publishing, Treasure Island (FL), 2022 PubMed

Martıénez-Navarrete N. Camacho M. Martıénez-Lahuerta J. Martıénez-Monzó J. Fito P. Food Res. Int. 2002;35:225–231. doi: 10.1016/S0963-9969(01)00189-2. DOI

Hirst E. L., in The Structure and Synthesis of Vitamin C (Ascorbic Acid) and its Analogues, ed. L. Zechmeister, Y. Asahina, C. Dhéré, K. Freudenberg, C. R. Harington, E. L. Hirst, F. Kuffner, H. Rudy, E. Spath, G. Tóth and G. Zemplén, Springer, Vienna, Vienna, 1939, pp. 132–159

Berger S. Tetrahedron. 1977;33:1587–1589. doi: 10.1016/0040-4020(77)80166-X. DOI

Birch T. W. Harris L. J. Biochem. J. 1933;27:595. PubMed PMC

Viefhaus J. Scholz F. Deinert S. Glaser L. Ilchen M. Seltmann J. Walter P. Siewert F. Nucl. Instrum. Methods Phys. Res., Sect. A. 2013;710:151–154. doi: 10.1016/j.nima.2012.10.110. DOI

Malerz S. Haak H. Trinter F. Stephansen A. B. Kolbeck C. Pohl M. Hergenhahn U. Meijer G. Winter B. Rev. Sci. Instrum. 2022;93:015101. doi: 10.1063/5.0072346. PubMed DOI

Nguyen-Truong H. T. J. Phys.: Condens. Matter. 2018;30:155101. doi: 10.1088/1361-648X/aab40a. PubMed DOI

Sodhi R. N. Brion C. J. Electron Spectrosc. Relat. Phenom. 1984;34:363–372. doi: 10.1016/0368-2048(84)80050-X. DOI

Pluhařová E. Slavíček P. Jungwirth P. Acc. Chem. Res. 2015;48:1209–1217. doi: 10.1021/ar500366z. PubMed DOI

Runge E. Gross E. K. U. Phys. Rev. Lett. 1984;52:997–1000. doi: 10.1103/PhysRevLett.52.997. DOI

Muchová E. Slavček P. J. Phys.: Condens. Matter. 2018;31:043001. doi: 10.1088/1361-648X/aaf130. PubMed DOI

Salzner U. Baer R. J. Chem. Phys. 2009;131:231101. doi: 10.1063/1.3269030. PubMed DOI

Krylov A. I. Annu. Rev. Phys. Chem. 2008;59:433–462. doi: 10.1146/annurev.physchem.59.032607.093602. PubMed DOI

Feng X. Epifanovsky E. Gauss J. Krylov A. I. J. Chem. Phys. 2019;151:014110. doi: 10.1063/1.5100022. PubMed DOI

Ghosh D. Roy A. Seidel R. Winter B. Bradforth S. Krylov A. I. J. Phys. Chem. B. 2012;116:7269–7280. doi: 10.1021/jp301925k. PubMed DOI PMC

Aryasetiawan F. Gunnarsson O. Rep. Prog. Phys. 1998;61:237. doi: 10.1088/0034-4885/61/3/002. DOI

Govoni M. Galli G. J. Chem. Theory Comput. 2015;11:2680–2696. doi: 10.1021/ct500958p. PubMed DOI

Vidal M. L. Feng X. Epifanovsky E. Krylov A. I. Coriani S. J. Chem. Theory Comput. 2019;15:3117–3133. doi: 10.1021/acs.jctc.9b00039. PubMed DOI

Vidal M. L. Krylov A. I. Coriani S. Phys. Chem. Chem. Phys. 2020;22:2693–2703. doi: 10.1039/C9CP03695D. PubMed DOI

Gilbert A. T. B. Besley N. A. Gill P. M. W. J. Phys. Chem. A. 2008;112:13164–13171. doi: 10.1021/jp801738f. PubMed DOI

Herbert J. M. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021;11:e1519.

Cammi R. Tomasi J. Int. J. Quantum Chem. 1995;56:465–474. doi: 10.1002/qua.560560850. DOI

Jagoda-Cwiklik B. Slavíček P. Cwiklik L. Nolting D. Winter B. Jungwirth P. J. Phys. Chem. A. 2008;112:3499–3505. doi: 10.1021/jp711476g. PubMed DOI

Pliego J. R. Riveros J. M. J. Phys. Chem. A. 2001;105:7241–7247. doi: 10.1021/jp004192w. DOI

Bryantsev V. S. Diallo M. S. Goddard III W. A. J. Phys. Chem. B. 2008;112:9709–9719. doi: 10.1021/jp802665d. PubMed DOI

Tomaník L. Muchová E. Slavíček P. Phys. Chem. Chem. Phys. 2020;22:22357–22368. doi: 10.1039/D0CP02768E. PubMed DOI

Pluhařová E. Ončák M. Seidel R. Schroeder C. Schroeder W. Winter B. Bradforth S. E. Jungwirth P. Slavíček P. J. Phys. Chem. B. 2012;116:13254–13264. doi: 10.1021/jp306348b. PubMed DOI

Gordon M. S. Fedorov D. G. Pruitt S. R. Slipchenko L. V. Chem. Rev. 2012;112:632–672. doi: 10.1021/cr200093j. PubMed DOI

Herbert J. M. J. Chem. Phys. 2019;151:170901. doi: 10.1063/1.5126216. PubMed DOI

Yanai T. Tew D. P. Handy N. C. Chem. Phys. Lett. 2004;393:51–57. doi: 10.1016/j.cplett.2004.06.011. DOI

Mennucci B. Tomasi J. J. Chem. Phys. 1997;106:5151–5158. doi: 10.1063/1.473558. DOI

Cancès E. Mennucci B. Tomasi J. J. Chem. Phys. 1997;107:3032–3041. doi: 10.1063/1.474659. DOI

Rappe A. K. Casewit C. J. Colwell K. S. Goddard W. A. I. Skiff W. M. J. Am. Chem. Soc. 1992;114:10024–10035. doi: 10.1021/ja00051a040. DOI

Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery, Jr. J. A., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas Ö., Foresman J. B., Ortiz J. V., Cioslowski J. and Fox D. J., Gaussian 09 Revision D.01, Gaussian Inc., Wallingford CT, 2009

Barca G. M. J. Gilbert A. T. B. Gill P. M. W. J. Chem. Theory Comput. 2018;14:1501–1509. doi: 10.1021/acs.jctc.7b00994. PubMed DOI

Dunning T. H. J. Chem. Phys. 1989;90:1007–1023. doi: 10.1063/1.456153. DOI

Kendall R. A. Dunning T. H. Harrison R. J. J. Chem. Phys. 1992;96:6796–6806. doi: 10.1063/1.462569. DOI

Woon D. E. Dunning T. H. J. Chem. Phys. 1995;103:4572–4585. doi: 10.1063/1.470645. DOI

Epifanovsky E. Gilbert A. T. B. Feng X. Lee J. Mao Y. Mardirossian N. Pokhilko P. White A. F. Coons M. P. Dempwolff A. L. Gan Z. Hait D. Horn P. R. Jacobson L. D. Kaliman I. Kussmann J. Lange A. W. Lao K. U. Levine D. S. Liu J. McKenzie S. C. Morrison A. F. Nanda K. D. Plasser F. Rehn D. R. Vidal M. L. You Z.-Q. Zhu Y. Alam B. Albrecht B. J. Aldossary A. Alguire E. Andersen J. H. Athavale V. Barton D. Begam K. Behn A. Bellonzi N. Bernard Y. A. Berquist E. J. Burton H. G. A. Carreras A. Carter-Fenk K. Chakraborty R. Chien A. D. Closser K. D. Cofer-Shabica V. Dasgupta S. de Wergifosse M. Deng J. Diedenhofen M. Do H. Ehlert S. Fang P.-T. Fatehi S. Feng Q. Friedhoff T. Gayvert J. Ge Q. Gidofalvi G. Goldey M. Gomes J. González-Espinoza C. E. Gulania S. Gunina A. O. Hanson-Heine M. W. D. Harbach P. H. P. Hauser A. Herbst M. F. Hernández Vera M. Hodecker M. Holden Z. C. Houck S. Huang X. Hui K. Huynh B. C. Ivanov M. Jász Á. Ji H. Jiang H. Kaduk B. Kähler S. Khistyaev K. Kim J. Kis G. Klunzinger P. Koczor-Benda Z. Koh J. H. Kosenkov D. Koulias L. Kowalczyk T. Krauter C. M. Kue K. Kunitsa A. Kus T. Ladjánszki I. Landau A. Lawler K. V. Lefrancois D. Lehtola S. Li R. R. Li Y.-P. Liang J. Liebenthal M. Lin H.-H. Lin Y.-S. Liu F. Liu K.-Y. Loipersberger M. Luenser A. Manjanath A. Manohar P. Mansoor E. Manzer S. F. Mao S.-P. Marenich A. V. Markovich T. Mason S. Maurer S. A. McLaughlin P. F. Menger M. F. S. J. Mewes J.-M. Mewes S. A. Morgante P. Mullinax J. W. Oosterbaan K. J. Paran G. Paul A. C. Paul S. K. Pavošević F. Pei Z. Prager S. Proynov E. I. Rák Á. Ramos-Cordoba E. Rana B. Rask A. E. Rettig A. Richard R. M. Rob F. Rossomme E. Scheele T. Scheurer M. Schneider M. Sergueev N. Sharada S. M. Skomorowski W. Small D. W. Stein C. J. Su Y.-C. Sundstrom E. J. Tao Z. Thirman J. Tornai G. J. Tsuchimochi T. Tubman N. M. Veccham S. P. Vydrov O. Wenzel J. Witte J. Yamada A. Yao K. Yeganeh S. Yost S. R. Zech A. Zhang I. Y. Zhang X. Zhang Y. Zuev D. Aspuru-Guzik A. Bell A. T. Besley N. A. Bravaya K. B. Brooks B. R. Casanova D. Chai J.-D. Coriani S. Cramer C. J. Cserey G. DePrince I. Eugene A. DiStasio J. Robert A. Dreuw A. Dunietz B. D. Furlani T. R. Goddard I. William A. Hammes-Schiffer S. Head-Gordon T. Hehre W. J. Hsu C.-P. Jagau T.-C. Jung Y. Klamt A. Kong J. Lambrecht D. S. Liang W. Mayhall N. J. McCurdy C. W. Neaton J. B. Ochsenfeld C. Parkhill J. A. Peverati R. Rassolov V. A. Shao Y. Slipchenko L. V. Stauch T. Steele R. P. Subotnik J. E. Thom A. J. W. Tkatchenko A. Truhlar D. G. Van Voorhis T. Wesolowski T. A. Whaley K. B. Woodcock I. Lee H. Zimmerman P. M. Faraji S. Gill P. M. W. Head-Gordon M. Herbert J. M. Krylov A. I. J. Chem. Phys. 2021;155:084801. doi: 10.1063/5.0055522. PubMed DOI PMC

Crespo-Otero R. Barbatti M. Theor. Chem. Acc. 2012;131:1237.

Sršeň Š. Sita J. Slavíček P. Ladányi V. Heger D. J. Chem. Theory Comput. 2020;16:6428–6438. doi: 10.1021/acs.jctc.0c00579. PubMed DOI

Prlj A. Marsili E. Hutton L. Hollas D. Shchepanovska D. Glowacki D. R. Slavíček P. Curchod B. F. E. ACS Earth Space Chem. 2022;6:207–217. doi: 10.1021/acsearthspacechem.1c00355. PubMed DOI PMC

Dierking C. W. Zurheide F. Zeuch T. Med J. Parez S. Slavíček P. J. Chem. Phys. 2017;146:244303. doi: 10.1063/1.4986520. PubMed DOI

Sršeň Š. Slavíček P. J. Chem. Theory Comput. 2021;17:6395–6404. doi: 10.1021/acs.jctc.1c00749. PubMed DOI

Grimme S. J. Comput. Chem. 2006;27:1787–1799. doi: 10.1002/jcc.20495. PubMed DOI

Jorgensen W. L. Chandrasekhar J. Madura J. D. Impey R. W. Klein M. L. J. Chem. Phys. 1983;79:926–935. doi: 10.1063/1.445869. DOI

Nosé S. J. Chem. Phys. 1984;81:511–519. doi: 10.1063/1.447334. DOI

Hoover W. G. Phys. Rev. A: At., Mol., Opt. Phys. 1985;31:1695–1697. doi: 10.1103/PhysRevA.31.1695. PubMed DOI

Rubešová M. Jurásková V. Slavíček P. J. Comput. Chem. 2017;38:427–437. doi: 10.1002/jcc.24696. PubMed DOI

Martínez L. Andrade R. Birgin E. G. Martínez J. M. J. Comput. Chem. 2009;30:2157–2164. doi: 10.1002/jcc.21224. PubMed DOI

Hollas D., Suchan J., Svoboda O., Ončák M. and Slavíček P., ABIN, v1.0, 2020

Ufimtsev I. S. Martinez T. J. J. Chem. Theory Comput. 2009;5:2619–2628. doi: 10.1021/ct9003004. PubMed DOI

Titov A. V. Ufimtsev I. S. Luehr N. Martinez T. J. J. Chem. Theory Comput. 2013;9:213–221. doi: 10.1021/ct300321a. PubMed DOI

Jahnke T. Hergenhahn U. Winter B. Dörner R. Frühling U. Demekhin P. V. Gokhberg K. Cederbaum L. S. Ehresmann A. Knie A. Dreuw A. Chem. Rev. 2020;120:11295–11369. doi: 10.1021/acs.chemrev.0c00106. PubMed DOI PMC

Sadybekov A. Krylov A. I. J. Chem. Phys. 2017;147:014107. doi: 10.1063/1.4990564. PubMed DOI

Bondi A. J. Phys. Chem. 1964;68:441–451. doi: 10.1021/j100785a001. DOI

Thürmer S. Seidel R. Faubel M. Eberhardt W. Hemminger J. C. Bradforth S. E. Winter B. Phys. Rev. Lett. 2013;111:173005. doi: 10.1103/PhysRevLett.111.173005. PubMed DOI

Pohl M. N. Muchová E. Seidel R. Ali H. Sršeň Š. Wilkinson I. Winter B. Slavíček P. Chem. Sci. 2019;10:848–865. doi: 10.1039/C8SC03381A. PubMed DOI PMC

Pauling L. Science. 1968;160:265–271. doi: 10.1126/science.160.3825.265. PubMed DOI

Pauling L., How to Live Longer and Feel Better, Avon, 1987

Pauling L., Nobel Lecture, Nobel Foundation, 1954, https://www.nobelprize.org

Pauling L., The Nature of the Chemical Bond, Cornell University Press, Ithaca, NY, 1960

From Gas to Solution: The Changing Neutral Structure of Proline upon Solvation