Chemistry Everyday for Everyone
edited by
applications & analogies
The Photochemistry of Sunscreens
Doris R. Kimbrough
Chemistry Department, Box 194, University of Colorado at Denver, P.O. Box 173364, Denver, CO 80217-3364
There is a new public awareness of the damaging
effects of overexposure to the sun. Many of us take ad-
vantage of the effects of chemical sunscreens to lengthen
the time we can safely spend outdoors without risking
short-term skin damage in the form of sunburn or long-
term damage in the form of skin cancer. The action of
sunscreens to prevent the harm that can be caused by
excess exposure to ultraviolet radiation offers an inter-
esting application of molecular excited states and pho-
tochemistry.
The harmful effects of solar radiation are caused
predominantly by the ultraviolet region of the electro-
magnetic spectrum, which can be divided into three re-
gions. UV-A is the least biologically harmful type of ul-
traviolet light, as it corresponds to the low-energy re-
gion of the UV, between 320 and 400 nm. Most of the
UV-A in sunlight reaches the earth’s surface (1). Much
of the higher-energy UV-B (280–320 nm) and all of the
highest-energy UV-C (200–280 nm) is filtered out by the
earth’s atmosphere, although continued deterioration of
the ozone layer could change that (1). Overexposure to
UV-B causes most skin cancer and has also been linked
to a suppression of the human immune system, although
recent research has shown that sunscreens that block
only UV-B (and not UV-A) do not adequately protect us
from the risk of skin cancer (1–3).
To understand how sunscreens work, one must un-
derstand how molecules interact with light energy. Ab-
sorption of light by a molecule is associated with the part
of its structure called a chromophore, which may or may
not encompass the whole molecule (4). For organic mol-
ecules the chromophores that are responsible for absorp-
tion of ultraviolet light are generally associated with
delocalized π-electrons in conjugated systems. In general,
when a molecule absorbs a photon whose energy is high
enough, an electron is promoted from a lower energy
level to a higher energy level. The molecule is said to go
from its ground state to an excited state (see Fig. 1). The
most common excited state for organic molecules is the
first singlet excited state, in which the promoted elec-
Figure 1. Simplified
Jablonski diagram in-
dicating the energies
associated with
ground and photo-
chemically excited
states. The wavy
lines represent vibra-
tional relaxation
commonly seen
among sunscreens.
DNA damage results
from photochemical
reactions from the
lower energy excited
state ( 3).
Vol. 74 No. 1 January 1997 • Journal of Chemical Education
Ron DeLorenzo
Middle Georgia College
Cochran, GA 31014
tron is still spin-paired with the one left in the lower
energy level.
Once in the excited state, the molecule has several
available pathways, which are outlined in Figure 1.
1. The molecule can emit a photon and return to the
ground state; this process is called fluorescence.
2. The molecule can return to the ground state by
emitting the energy thermally through a series of
vibrational transitions; this is called nonradiative
decay or vibrational relaxation (4, 5).
3. The molecule can undergo some type of reaction
from the excited state, which is generally termed
photochemistry.
4. Finally, the molecule can convert to a lower energy
excited state—typically the triplet state, in which
the electrons cease to be spin paired. The lower
energy excited state can in turn revert to ground
state in either a radiative (phosphorescence) or
nonradiative (vibrational) decay, or it can also un-
dergo photochemistry.
Which of the many pathways described above predomi-
nates depends on the relative rates of each process, the
favored path being the one with the most rapid rate. The
relative rates depend on the nature of the chromophore
and the particular structure of the molecule in question.
The photochemistry and photoproducts of DNA, as
well as their resulting mutagenic potential, have been
discussed in great detail by Taylor (3). The majority of
products result from a photochemical reaction of the
lower-energy excited state described above. Humans’
natural protection mechanism against the effects of ex-
posure to UV light involves specialized skin cells called
melanocytes (6, 7). When skin is irritated by exposure
to UV light, melanocytes produce a black pigment called
melanin and distribute it through the skin. The pres-
ence of melanin results in a tanned appearance and pro-
tects the skin by absorbing ultraviolet radiation, thus
preventing the type of photochemical reactions that pro-
duce skin damage.
Protection against UV
light can also be accom-
plished through the use of
topically applied chemical
sunscreens. The sunscreens
that are commercially avail-
able function in one of two
ways. Substances such as zinc
oxide and titanium dioxide
offer physical protection in
that they are opaque enough
to reflect and scatter the in-
cident radiation. Photon-ab-
sorbing agents function by
absorbing radiation in the ul-
traviolet region and then un-
dergoing very rapid vibra-
51
Chemistry Everyday for Everyone

Table 1. Structures and Examples of the Substances Most Commonly Used in Commercial Sunscreen Preparations.

UV Absorption
Category Structure Examples
λmax (nm)
CO2R1 PABA 283–289
R1=R2=H
2-ethylhexyl-p-dimethylaminobenzoate (Padimate O) 310
PABA derivatives C2H5

N R 1 = –CH2CH–C4H9
R2 R2 R 2 = –CH3

O 2-ethylhexyl-p-methoxycinnamate (Parsol MCX, Neo-Heliopan AV) 310

C2H5
Cinnamates OR
R = –CH2CH–C4H9
2-ethoxyethyl-p-methoxycinnamate (Giv Tan F) 310
CH3O
R = –C2H4–O–C2H5

(2-hydroxy-4-methoxy)-benzophenone 288–290
Oxybenzone
oxybenzone 325
CH3O OH

Homomenthyl salicylate (homosalate, Heliophan) 309

CH3

CO2R H C CH3
R=
Salicylates
OH CH3

Octyl salicylate 310

R = –C8H17

OH O
Avobenzone (Parsol 1789) 358
R = –C(CH3)3
Dibenzoylmethanes
4-isopropyldibenzoylmethane (Eusolex 8020) 315
R = –CH(CH3)2
R

tional relaxation back to the ground state (8–11). Once
in the ground state, these molecules can absorb another
photon to repeat the process, thereby effectively shield-
ing the skin from damage by UV radiation. Any molecule
for which vibrational relaxation to the ground state is
the fastest pathway can act as a sunscreen. However,
only 14 different substances are commonly used in sun-
screen preparations in the United States. Structures for
the most common ones can be found in Table 1 (8–10).
The structural similarities of these compounds are
evident. All are substituted aromatic compounds with a
high degree of conjugation, which allows them to absorb
in the appropriate region for protection against ultra-
violet radiation (4, 5, 8). Historically the first commer-
cially available photon absorbing chemical sunscreen
was para-aminobenzoic acid (PABA), which absorbs
strongly in the UV-B region of the spectrum (11). PABA
itself is not especially oil soluble, thus making it unap-
pealing for the formulations normally associated with
skin lotions. Therefore various PABA esters (which are
more oil soluble) are used. Both PABA and PABA esters
cause a photoallergic response in 1–2% of the popula-
tion (10), so PABA-free sunscreen preparations typically
have one or more of the other substances found in Table
1 as their active ingredient. The cinnamate esters,
oxybenzone, and avobenzone are also highly oil soluble
and have the additional protective advantage that they
also absorb strongly in the UV-A range, offering better
overall protection (8, 11). The salicylates tend to have a
low molecular absorptivity coefficient, meaning that a
higher concentration is needed in order to obtain the
same protection afforded by a lower concentration of a
different substance (9).
The efficacy of a sunscreen is described on the label
by the “sun protection factor” or SPF, which is defined
as the UV energy required to produce a minimal
erythema (sunburn) dose (MED) on protected skin di-
vided by the UV energy required to produce an MED on
unprotected skin (9, 10):
MED protected
SPF =
MED unprotected
The “dose” can be measured in intensity of light or in
length of exposure. The latter is the more common
method of SPF determination (9, 12). In this manner,

52 Journal of Chemical Education • Vol. 74 No. 1 January 1997


each individual’s particular sensitivity to ultraviolet ra- Literature Cited
diation is taken into account in the generalized SPF
number. There are two ways in which to increase the SPF 1.
of a particular sunscreen preparation. One can increase 2.
3.
the concentration of the active photon-absorbing ingre- 4.
dient. As is evident from Beer’s law, the higher the con- 5.
centration, the greater the number of photons absorbed.
One can only take this so far, however, before the con- 6.
centration becomes high enough to be irritating to the
7.
skin. Combining two or more of the substances in Table
1 in the formulation is a common way to increase the
SPF value of a sunscreen preparation because the effec- 8.
tive photon absorption is roughly additive.
Most of us have experienced a sunburn, and most 9.
of us have relied upon sunscreens to prevent it. The 10.
chemistry involved in the action of sunscreens, particu- 11.
larly when coupled to the photochemistry of DNA (3), is
a relevant introduction to the interaction of light energy
with molecules, the behavior of molecular excited states, 12.
and the effects of concentration and absorption.
Vol. 74 No. 1 January 1997 • Journal of Chemical Education
Chemistry Everyday for Everyone
Baird, C. Environmental Chemistry; Freeman: New York, 1995.
Madronich, S.; de Gruijl, F. R. Nature 1993, 366, 23.
Taylor, J.-S. J. Chem. Educ. 1990, 67, 835.
Isaacs, N. S. Physical Organic Chemistry; Wiley: New York, 1987.
Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic
Chemistry, 3rd ed.; Harper & Row: New York, 1987.
Guyton, A. C.; Hall, J. E. Textbook of Medical Physiology, 9th ed.;
Saunders: Philadelphia, 1996.
Wilmott, J. M.; Duggan, M. C.; Znaidin, A. P. In Physician’s Guide
to Sunscreens; Lowe, N. J., Ed.; Dekker: New York, 1991; Chapter
6.
Scott, A. I. Interpretation of the Ultraviolet Spectra of Natural Prod-
ucts; Macmillan: New York, 1964.
Pittet, G. H.; Givaudan, S. A. Drug Cosmetic Ind. 1988, 143(3), 24.
Dromgoole, S. H.; Maibach, H. I. In Physician’s Guide to Sun-
screens; Lowe, N. J., Ed.; Dekker: New York, 1991; Chapter 8.
Harber, L. C.; DeLeo, V. A.; Prystowsky, J. H. In Physician’s Guide
to Sunscreens; Lowe, N. J., Ed.; Dekker: New York, 1991; Chapter
10.
Lowe, N. J. In Physician’s Guide to Sunscreens; Lowe, N. J., Ed.;
Dekker: New York, 1991; Chapter 11.
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