Photochemical Degradation of the UV Filter Octyl Methoxy Cinnamate Probed via Laser-Interfaced Mass Spectrometry

TY - JOUR

T1 - Photochemical Degradation of the UV Filter Octyl Methoxy Cinnamate Probed via Laser-Interfaced Mass Spectrometry

AU - Wong, Natalie G.K.

AU - Sereli, Maria

AU - Anstöter, Cate S.

AU - Dessent, Caroline E.H.

N1 - Funding Information: We thank the University of York and the Department of Chemistry for the provision of funds for the OPO laser system. The York Centre of Excellence in Mass Spectrometry, used for the CID work, was created thanks to a major capital investment through Science City York, supported by Yorkshire Forward with funds from the Northern Way Initiative, and has more recently received additional support from the EPSRC and BBSRC. Funding Information: This work was funded through the Leverhulme Trust Research Project Grant RPG-2017-147. Publisher Copyright: © 2022 by the authors.

PY - 2022/12/12

Y1 - 2022/12/12

N2 - Octyl methoxycinnamate (OMC) is a common UVA and UVB filter molecule that is widely used in commercial sunscreens. Here, we used gas-phase laser photodissociation spectroscopy to characterise the intrinsic photostability and photodegradation products of OMC by studying the system in its protonated form, i.e., [OMC·H]+. The major photofragments observed were m/z 179, 161, and 133, corresponding to fragmentation on either side of the ether oxygen of the ester group (m/z 179 and 161) or the C–C bond adjacent to the ester carbonyl group. Additional measurements were obtained using higher-energy collisional dissociation mass spectrometry (HCD-MS) to identify fragments that resulted from the breakdown of the vibrationally hot electronic ground state. We found that the m/z 179 and 161 ions were the main fragments produced by this route. Notably, the m/z 133 ion was not observed through HCD-MS, revealing that this product ion is only produced through a photochemical route. Our results demonstrate that UV photoexcitation of OMC is able to access a dissociative excited-state surface that uniquely leads to the rupture of the C–C bond adjacent to the key ester carbonyl group.

AB - Octyl methoxycinnamate (OMC) is a common UVA and UVB filter molecule that is widely used in commercial sunscreens. Here, we used gas-phase laser photodissociation spectroscopy to characterise the intrinsic photostability and photodegradation products of OMC by studying the system in its protonated form, i.e., [OMC·H]+. The major photofragments observed were m/z 179, 161, and 133, corresponding to fragmentation on either side of the ether oxygen of the ester group (m/z 179 and 161) or the C–C bond adjacent to the ester carbonyl group. Additional measurements were obtained using higher-energy collisional dissociation mass spectrometry (HCD-MS) to identify fragments that resulted from the breakdown of the vibrationally hot electronic ground state. We found that the m/z 179 and 161 ions were the main fragments produced by this route. Notably, the m/z 133 ion was not observed through HCD-MS, revealing that this product ion is only produced through a photochemical route. Our results demonstrate that UV photoexcitation of OMC is able to access a dissociative excited-state surface that uniquely leads to the rupture of the C–C bond adjacent to the key ester carbonyl group.

KW - cinnamates

KW - lasers

KW - mass spectrometry

KW - photodegradation

KW - photodynamics

KW - sunscreens

UR - http://www.scopus.com/inward/record.url?scp=85144487535&partnerID=8YFLogxK

U2 - 10.3390/molecules27248796

DO - 10.3390/molecules27248796

M3 - Article

C2 - 36557928

AN - SCOPUS:85144487535

SN - 1420-3049

VL - 27

JO - MOLECULES

JF - MOLECULES

IS - 24

M1 - 8796

ER -