Sunscreens
Sunscreens
Sunscreens
edited by
applications & analogies Ron DeLorenzo
Middle Georgia College
Cochran, GA 31014
There is a new public awareness of the damaging tron is still spin-paired with the one left in the lower
effects of overexposure to the sun. Many of us take ad- energy level.
vantage of the effects of chemical sunscreens to lengthen Once in the excited state, the molecule has several
the time we can safely spend outdoors without risking available pathways, which are outlined in Figure 1.
short-term skin damage in the form of sunburn or long- 1. The molecule can emit a photon and return to the
term damage in the form of skin cancer. The action of ground state; this process is called fluorescence.
sunscreens to prevent the harm that can be caused by 2. The molecule can return to the ground state by
excess exposure to ultraviolet radiation offers an inter- emitting the energy thermally through a series of
esting application of molecular excited states and pho- vibrational transitions; this is called nonradiative
tochemistry. decay or vibrational relaxation (4, 5).
The harmful effects of solar radiation are caused 3. The molecule can undergo some type of reaction
predominantly by the ultraviolet region of the electro- from the excited state, which is generally termed
magnetic spectrum, which can be divided into three re- photochemistry.
gions. UV-A is the least biologically harmful type of ul- 4. Finally, the molecule can convert to a lower energy
traviolet light, as it corresponds to the low-energy re- excited state—typically the triplet state, in which
gion of the UV, between 320 and 400 nm. Most of the the electrons cease to be spin paired. The lower
UV-A in sunlight reaches the earth’s surface (1). Much energy excited state can in turn revert to ground
of the higher-energy UV-B (280–320 nm) and all of the state in either a radiative (phosphorescence) or
highest-energy UV-C (200–280 nm) is filtered out by the nonradiative (vibrational) decay, or it can also un-
earth’s atmosphere, although continued deterioration of dergo photochemistry.
the ozone layer could change that (1). Overexposure to
UV-B causes most skin cancer and has also been linked Which of the many pathways described above predomi-
to a suppression of the human immune system, although nates depends on the relative rates of each process, the
recent research has shown that sunscreens that block favored path being the one with the most rapid rate. The
only UV-B (and not UV-A) do not adequately protect us relative rates depend on the nature of the chromophore
from the risk of skin cancer (1–3). and the particular structure of the molecule in question.
To understand how sunscreens work, one must un- The photochemistry and photoproducts of DNA, as
derstand how molecules interact with light energy. Ab- well as their resulting mutagenic potential, have been
sorption of light by a molecule is associated with the part discussed in great detail by Taylor (3). The majority of
of its structure called a chromophore, which may or may products result from a photochemical reaction of the
not encompass the whole molecule (4). For organic mol- lower-energy excited state described above. Humans’
ecules the chromophores that are responsible for absorp- natural protection mechanism against the effects of ex-
tion of ultraviolet light are generally associated with posure to UV light involves specialized skin cells called
delocalized π-electrons in conjugated systems. In general, melanocytes (6, 7). When skin is irritated by exposure
when a molecule absorbs a photon whose energy is high to UV light, melanocytes produce a black pigment called
enough, an electron is promoted from a lower energy melanin and distribute it through the skin. The pres-
level to a higher energy level. The molecule is said to go ence of melanin results in a tanned appearance and pro-
from its ground state to an excited state (see Fig. 1). The tects the skin by absorbing ultraviolet radiation, thus
most common excited state for organic molecules is the preventing the type of photochemical reactions that pro-
first singlet excited state, in which the promoted elec- duce skin damage.
Protection against UV
light can also be accom-
Figure 1. Simplified
plished through the use of
Jablonski diagram in-
topically applied chemical
dicating the energies
sunscreens. The sunscreens
associated with
that are commercially avail-
ground and photo-
able function in one of two
chemically excited
ways. Substances such as zinc
states. The wavy
oxide and titanium dioxide
lines represent vibra-
offer physical protection in
tional relaxation
that they are opaque enough
commonly seen
to reflect and scatter the in-
among sunscreens.
cident radiation. Photon-ab-
DNA damage results
sorbing agents function by
from photochemical
absorbing radiation in the ul-
reactions from the
traviolet region and then un-
lower energy excited
dergoing very rapid vibra-
state ( 3).
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
(2-hydroxy-4-methoxy)-benzophenone 288–290
Oxybenzone
oxybenzone 325
CH3O OH
CO2R H C CH3
R=
Salicylates
OH CH3
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 have one or more of the other substances found in Table
in the ground state, these molecules can absorb another 1 as their active ingredient. The cinnamate esters,
photon to repeat the process, thereby effectively shield- oxybenzone, and avobenzone are also highly oil soluble
ing the skin from damage by UV radiation. Any molecule and have the additional protective advantage that they
for which vibrational relaxation to the ground state is also absorb strongly in the UV-A range, offering better
the fastest pathway can act as a sunscreen. However, overall protection (8, 11). The salicylates tend to have a
only 14 different substances are commonly used in sun- low molecular absorptivity coefficient, meaning that a
screen preparations in the United States. Structures for higher concentration is needed in order to obtain the
the most common ones can be found in Table 1 (8–10). same protection afforded by a lower concentration of a
The structural similarities of these compounds are different substance (9).
evident. All are substituted aromatic compounds with a The efficacy of a sunscreen is described on the label
high degree of conjugation, which allows them to absorb by the “sun protection factor” or SPF, which is defined
in the appropriate region for protection against ultra- as the UV energy required to produce a minimal
violet radiation (4, 5, 8). Historically the first commer- erythema (sunburn) dose (MED) on protected skin di-
cially available photon absorbing chemical sunscreen vided by the UV energy required to produce an MED on
was para-aminobenzoic acid (PABA), which absorbs unprotected skin (9, 10):
strongly in the UV-B region of the spectrum (11). PABA
itself is not especially oil soluble, thus making it unap- MED protected
SPF =
pealing for the formulations normally associated with MED unprotected
skin lotions. Therefore various PABA esters (which are
more oil soluble) are used. Both PABA and PABA esters The “dose” can be measured in intensity of light or in
cause a photoallergic response in 1–2% of the popula- length of exposure. The latter is the more common
tion (10), so PABA-free sunscreen preparations typically method of SPF determination (9, 12). In this manner,