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Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone

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Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone. / Berenbeim, Jacob A.; Wong, Natalie G.K.; Cockett, Martin C.R.; Berden, Giel; Oomens, Jos; Rijs, Anouk M.; Dessent, Caroline E.H.

In: Physical Chemistry Chemical Physics, Vol. 22, No. 35, 16.09.2020, p. 19522-19531.

Research output: Contribution to journalArticlepeer-review

Harvard

Berenbeim, JA, Wong, NGK, Cockett, MCR, Berden, G, Oomens, J, Rijs, AM & Dessent, CEH 2020, 'Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone', Physical Chemistry Chemical Physics, vol. 22, no. 35, pp. 19522-19531. https://doi.org/10.1039/D0CP03152F, https://doi.org/10.1039/d0cp03152f

APA

Berenbeim, J. A., Wong, N. G. K., Cockett, M. C. R., Berden, G., Oomens, J., Rijs, A. M., & Dessent, C. E. H. (2020). Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone. Physical Chemistry Chemical Physics, 22(35), 19522-19531. https://doi.org/10.1039/D0CP03152F, https://doi.org/10.1039/d0cp03152f

Vancouver

Berenbeim JA, Wong NGK, Cockett MCR, Berden G, Oomens J, Rijs AM et al. Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone. Physical Chemistry Chemical Physics. 2020 Sep 16;22(35):19522-19531. https://doi.org/10.1039/D0CP03152F, https://doi.org/10.1039/d0cp03152f

Author

Berenbeim, Jacob A. ; Wong, Natalie G.K. ; Cockett, Martin C.R. ; Berden, Giel ; Oomens, Jos ; Rijs, Anouk M. ; Dessent, Caroline E.H. / Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone. In: Physical Chemistry Chemical Physics. 2020 ; Vol. 22, No. 35. pp. 19522-19531.

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@article{a74bed7505c8415b87d370e8ac762269,
title = "Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone",
abstract = "A key decay pathway by which organic sunscreen molecules dissipate harmful UV energy involves excited-state hydrogen atom transfer between proximal enol and keto functional groups. Structural modifications of this molecular architecture have the potential to block ultrafast decay processes, and hence promote direct excited-state molecular dissociation, profoundly affecting the efficiency of an organic sunscreen. Herein, we investigate the binding of alkali metal cations to a prototype organic sunscreen molecule, oxybenzone, using IR characterization. Mass-selective IR action spectroscopy was conducted at the free electron laser for infrared experiments, FELIX (600-1800 cm-1), on complexes of Na+, K+ and Rb+ bound to oxybenzone. The IR spectra reveal that K+ and Rb+ adopt binding positions away from the key OH intermolecular hydrogen bond, while the smaller Na+ cation binds directly between the keto and enol oxygens, thus breaking the intramolecular hydrogen bond. UV laser photodissociation spectroscopy was also performed on the series of complexes, with the Na+ complex displaying a distinctive electronic spectrum compared to those of K+ and Rb+, in line with the IR spectroscopy results. TD-DFT calculations reveal that the origin of the changes in the electronic spectra can be linked to rupture of the intramolecular bond in the sodium cationized complex. The implications of our results for the performance of sunscreens in mixtures and environments with high concentrations of metal cations are discussed.",
author = "Berenbeim, {Jacob A.} and Wong, {Natalie G.K.} and Cockett, {Martin C.R.} and Giel Berden and Jos Oomens and Rijs, {Anouk M.} and Dessent, {Caroline E.H.}",
note = "{\textcopyright} the Owner Societies 2020.",
year = "2020",
month = sep,
day = "16",
doi = "10.1039/D0CP03152F",
language = "English",
volume = "22",
pages = "19522--19531",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "The Royal Society of Chemistry",
number = "35",

}

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TY - JOUR

T1 - Sodium cationization can disrupt the intramolecular hydrogen bond that mediates the sunscreen activity of oxybenzone

AU - Berenbeim, Jacob A.

AU - Wong, Natalie G.K.

AU - Cockett, Martin C.R.

AU - Berden, Giel

AU - Oomens, Jos

AU - Rijs, Anouk M.

AU - Dessent, Caroline E.H.

N1 - © the Owner Societies 2020.

PY - 2020/9/16

Y1 - 2020/9/16

N2 - A key decay pathway by which organic sunscreen molecules dissipate harmful UV energy involves excited-state hydrogen atom transfer between proximal enol and keto functional groups. Structural modifications of this molecular architecture have the potential to block ultrafast decay processes, and hence promote direct excited-state molecular dissociation, profoundly affecting the efficiency of an organic sunscreen. Herein, we investigate the binding of alkali metal cations to a prototype organic sunscreen molecule, oxybenzone, using IR characterization. Mass-selective IR action spectroscopy was conducted at the free electron laser for infrared experiments, FELIX (600-1800 cm-1), on complexes of Na+, K+ and Rb+ bound to oxybenzone. The IR spectra reveal that K+ and Rb+ adopt binding positions away from the key OH intermolecular hydrogen bond, while the smaller Na+ cation binds directly between the keto and enol oxygens, thus breaking the intramolecular hydrogen bond. UV laser photodissociation spectroscopy was also performed on the series of complexes, with the Na+ complex displaying a distinctive electronic spectrum compared to those of K+ and Rb+, in line with the IR spectroscopy results. TD-DFT calculations reveal that the origin of the changes in the electronic spectra can be linked to rupture of the intramolecular bond in the sodium cationized complex. The implications of our results for the performance of sunscreens in mixtures and environments with high concentrations of metal cations are discussed.

AB - A key decay pathway by which organic sunscreen molecules dissipate harmful UV energy involves excited-state hydrogen atom transfer between proximal enol and keto functional groups. Structural modifications of this molecular architecture have the potential to block ultrafast decay processes, and hence promote direct excited-state molecular dissociation, profoundly affecting the efficiency of an organic sunscreen. Herein, we investigate the binding of alkali metal cations to a prototype organic sunscreen molecule, oxybenzone, using IR characterization. Mass-selective IR action spectroscopy was conducted at the free electron laser for infrared experiments, FELIX (600-1800 cm-1), on complexes of Na+, K+ and Rb+ bound to oxybenzone. The IR spectra reveal that K+ and Rb+ adopt binding positions away from the key OH intermolecular hydrogen bond, while the smaller Na+ cation binds directly between the keto and enol oxygens, thus breaking the intramolecular hydrogen bond. UV laser photodissociation spectroscopy was also performed on the series of complexes, with the Na+ complex displaying a distinctive electronic spectrum compared to those of K+ and Rb+, in line with the IR spectroscopy results. TD-DFT calculations reveal that the origin of the changes in the electronic spectra can be linked to rupture of the intramolecular bond in the sodium cationized complex. The implications of our results for the performance of sunscreens in mixtures and environments with high concentrations of metal cations are discussed.

UR - http://www.scopus.com/inward/record.url?scp=85091191314&partnerID=8YFLogxK

U2 - 10.1039/D0CP03152F

DO - 10.1039/D0CP03152F

M3 - Article

C2 - 32840272

AN - SCOPUS:85091191314

VL - 22

SP - 19522

EP - 19531

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 35

ER -