Illuminating Sunscreens:

Overview

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Key numbers

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Table 1. FDA-approved organic UV filters listed alongside their maximum approved
Table 2. FDA-approved inorganic (nanoparticulate) UV filters listed alongside their
Other notable components include: the Nd3+:YAG pumped OPO tunable laser source; a
for 95% of the total solar radiation incident on human skin. Contrary to earlier beliefs
harmful UV radiation into heat with almost 100% efficiency,(45) it is recognized that
ca. 30% of the total solar irradiance that reaches the surface of the Earth.(51,52) With most
a dose of 360-720 J/cm2 over 57-114 minutes, such dosages represent a range equivalent
Administration (FDA)-approved UV filters are outlined in Tables 1 and 2.(81,82)
Table 1. FDA-approved organic UV filters listed alongside their maximum approved
Table 2. FDA-approved inorganic (nanoparticulate) UV filters listed alongside their
sunscreen with an SPF of 25 will block out 96% of UV-B light etc. In an effort to uniform
wavelength at which > 90% of the sunscreen’s spectral coverage occurs and must value
Figure 3), a widely used UV-A absorber found in a range of sunscreens sold worldwide.
notoriously included in as many as ca. 45% of the sunscreens approved for sale in the US.
‘bulk’ effects can be fully assessed and manipulated.(114,126,129,182) A widespread range of
close conjunction with a range of the aforementioned (i.e., 2D-IR, TEAS, and TVAS) and
manipulated, and mass-analyzed via means of mass spectrometry.(197) This coupling of
the electronic configuration and vibrational dynamics of a range of systems, (197)
ground S0 state at a timescale beyond the means of the experiment (> 1 ns).(150)
shows ca. 20-40% of its population internally converting to the S1(*) state and conclude
U = 0). In this sense, as only ions with a selected m/z value exhibit a stable ion trajectory
03-F01, Thorlabs, Inc.) that reflects across the 200-2000 nm spectral range is conveniently
Other notable components include: the Nd3+:YAG pumped OPO tunable laser source; a
system (Eq. 1.4) are measured by means of “action spectroscopy” – a term notably coined
constant across the spectral range, Eq. 1.4 can be simplified and rearranged to give Eq. 1.5:
excited energy level (4F5/2). As this level is that of an unstable state, and exhibits a short
Appendices 1-4). Accordingly, once the targeted laser power is met, the adjustable prism
pulse power or shot stability is > 15%), the non-linear optics (NLOs) of the laser will need
(49) J. Krutmann, T. Passeron, Y. Gilaberte, C. Granger, G. Leone, M. Narda, S.
Table S1. Calculated relative energies and physical properties of OB dependent on pH.
Scheme S1. All the structures from Table S1. Arrows indicate the deprotonation site for
and 13.0, respectively. Basic mixture solutions > 10% MeOH are not shown due to the
ionic fragmentation, Table S1 provides ion counts measured in a typical experimental run
Table S1. Percent electron depletion of (PBSA–H)– calculated directly from precursor
giving ~0.3 mJ across the range 400-214 nm (3.1-5.8 eV). A laser step size of 2 nm was
USA) with an ESI source, run in the negative ion mode between 0-100% collisional
with m/z < 50 are not detectable in our mass spectrometer since low masses fall outside
respectively, illustrating a clear onset of thermal fragment production at 20% HCD energy.
thermal fragment ions are summarized in Table 1, and their postulated structures presented
proposed structural assignments outlined in Table S1. A condensed version is available in
Table S1. Proposed structures for the major ionic fragments of (BP4–H)– (m/z 307)
(HCD) at 40% and 70% HCD energies.

Methods (brief)

photolysis cells with electrospray ionization mass spectrometry, we use a model system
existing sunscreens and demonstrate the utility of laser-interfaced mass spectrometry for
1.3 Laser Photodissociation Mass Spectrometry … 32
1.3.1 Electrospray Ionization Mass Spectrometry … 33
1.3.2 Quadrupole Ion Trap Mass Spectrometry … 35
Phenylbenzimidazole‐5‐Sulfonic Acid via Laser‐Interfaced Mass Spectrometry … 80
Mass Spectrometry … 81
via Laser‐Interfaced Mass Spectrometry… 132
interfaced mass spectrometry experimental set up. … 48
Phenylbenzimidazole-5-Sulfonic Acid via Laser-Interfaced Mass Spectrometry”
ozone much more quickly than it could be replaced.(23–26) The signing of the landmark
photoprotection provided by a sunscreen when applied in vivo (i.e., on skin samples) at an
alter the IR pump pulse that imposes onto the sample.(135) After a specified delay time, the
IR probe pulse is overlapped spatially with the pump beam in the sample and a
small fraction of the sample molecules following their photoexcitation with a femtosecond
avoid multiphoton processes, weak probe pulses are usually used, led through the sample
laser-interfaced mass spectrometry (LIMS; see Chapter 1.3).
molecules. As a gas-phase method, samples are typically vaporized via heating and seeded

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Update history

The five most recent substantive edits to this page, classified major (evidence or structure moved), correction (a published value or statement was wrong and has been fixed), or minor (narrative rewritten without changing the underlying evidence). Each description is derived from what the edit did to this page; the linked commit is the authoritative record, routine regeneration passes are excluded, and the full version history lives in git. When DOI minting comes online (see schema docs), each entry below will also link to a version-pinned DataCite DOI.

Commit	Date	Change	Description
b01ec52c	2026-08-04	major	2 sections added
d49e450f	2026-08-03	major	5 sections added; narrative text revised