Journal of Photochemistry & Photobiology, B: Biology 153 (2015) 240–246

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Journal of Photochemistry & Photobiology, B: Biology

journal homepage: www.elsevier.com/locate/jpb

Short Review

Effects of solar radiation on hair and photoprotection

Michelli F. Dario ⁎, André R. Baby, Maria Valéria R. Velasco
Departament of Pharmacy, University of São Paulo, 580 Prof. Lineu Prestes Avenue, Bl-13/15, 05508-000 São Paulo, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: In this paper the negative effects of solar radiation (ultraviolet, visible and infrared wavelengths) on hair proper-
Received 29 June 2015 ties like color, mechanical properties, luster, protein content, surface roughness, among others, will be discussed.
Received in revised form 15 September 2015 Despite knowing that radiation damages hair, there are no consensus about the particular effect of each segment
Accepted 21 September 2015
of solar radiation on the hair shaft. The hair photoprotection products are primarily targeted to dyed hair, special-
Available online xxxx
ly auburn pigments, and gray shades. They are usually based on silicones, antioxidants and quaternary chemical
Keywords:
UV filters that have more affinity for negatively charged hair surface and present higher efficacy. Unfortunately,
Hair there are no regulated parameters, like for skin photoprotection, for efficacy evaluation of hair care products,
Photodamage which makes impossible to compare the results published in the literature. Thus, it is important that researchers
UV radiation make an effort to apply experimental conditions similar to a real level of sun exposure, like dose, irradiance, time,
Keratin temperature and relative humidity.
Melanin © 2015 Published by Elsevier B.V.
Oxidation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
2. Hair Photodamage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
3. Hair Photoprotection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.1. Chemical Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.2. Silicones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
3.3. Antioxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
4. Efficacy Evaluation of Hair Photoprotective Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
4.1. Color Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245

1. Introduction
Hair fiber may be divided in three main layers: cuticles, cortex and
medulla [1,2]. The medulla is the innermost portion of hair shaft. The
cortex represents as much as 90% of the total weight of hair. This layer
gives the hair strength, flexibility, elasticity and color (due to natural
melanin and artificial pigments from hair dyes). The cortex is surronded
by a single layer of overlapping transparent, scalelike cells of cuticle (the
outermost layer of hair fiber) [3,4].
The hair is composed mainly of proteinaceous material (specially
keratin), lipids and other molecules like melanin that may be degraded
⁎ Corresponding author.
E-mail address: michelli.dario@usp.br (M.F. Dario).
by exposure to sun radiation. The impact of solar radiation on the hair
fibers are very discussed, but there is no consensus in the literature re-
garding the specific effects of different ranges of radiation (ultraviolet,
visible and infrared) on the characteristics of hair fiber, like color, me-
chanical properties, luster, protein content, surface roughness and
others. This difficulty is related to the lack of radiation exposure param-
eters harmonization such as dose, irradiance, temperature and relative
humidity, as will be discussed in the text.
Solar radiation comprises the ultraviolet (UV) radiation (280–
400 nm), visible (VIS) light (400–700 nm) and infrared (IR) (750–
2800 nm). The UV radiation can be divided into three groups, according
to the wavelength: UVA (315–400 nm), UVB (280–315 nm) and UVC
(100–280 nm). The ozone layer blocks the entry of UVC, allowing the
pass of 1–10% UVB and 90–99% UVA [5,6].

http://dx.doi.org/10.1016/j.jphotobiol.2015.09.025
1011-1344/© 2015 Published by Elsevier B.V.
Table 1
Effects of different radiation wavelengths on hair fiber characteristics. Legend: D = Radiation dose; I = irradiance; TEM = Transmission Electronic Microscopy; SEM = Scanning Electronic Microscopy; t = time; T = temperature; ROS = reactive
oxygen species; RH = relative humidity; VIS = visible radiation; UV = ultraviolet radiation; IR = Infrared radiation.

Radiation Exposition parameters Hair/fiber Evaluated parameters Mainly results Ref. Year

UVA/UVB UVA — 20 W; UVB — 400 W, VIS — 575 W; IR — 600 W; Virgin black and light brown hair Color, amino acids and cysteine content VIS — color changed; UVA/UVB — changed amino acids in the cuticle, [36] 1995
VIS/IR Global — 600 W; t = 1008 h; RH N 70% reduced cystine, proline and valine in light brown hair; UVA/VIS — ↑
Global cysteic acid in the cuticle
UVA/UVB UVA — 20 W; UVB — 400 W, VIS — 575 W; IR — 600 W; Virgin black and light brown hair Color, melanin content VIS — color change; UVA — ↓ melanin content of light brown hair; [25] 1995
VIS/IR Global — 600 W; t = 1008 h; RH N 70% Irradiation did not affect black hair melanin; Photostabilty: eumelanin N
Global pheomelanin
UVA/UVB UVA — 48 W/m2; UVB — 2.5 W/m2; VIS — 463 W/m2; Brown hair submitted to Color, mechanical properties, lipid content UVA — ↓ protein content, ↓ mechanical resistance; VIS — color and [35] 1997
VIS/IR IR — 440 W/m2; permanent, bleaching or treated lipids changed
Global Global — 1037 W/m2 with auburn dye
UV UV = 5.06 mW/cm2 at 95% RH; Brown hair Fiber surface (MEV) High RH is essential to merge the cuticle layers in rigid and brittle [37] 2000
UV + VIS UV + VIS = 41.272 mW/cm2; RH = 95% structure, with loss of elasticity; melanin granules intact

M.F. Dario et al. / Journal of Photochemistry & Photobiology, B: Biology 153 (2015) 240–246
Natural and Natural (91 h): UVB (7 W/m2) + UVA Brown, blond, auburn, black and Protein loss, mechanical properties, fiber surface UVB — causes protein loss, UVA — color change [38] 2004
artificial (23 W/m2) + VIS (260 W/m2) curly brown virgin hair (MEV) Lighter hair — ↑ color changes, no effects on mechanical properties and
sunlight Artificial (56 to 448 h): UVB (9 W/m2) + cuticle aspect
UVA (27 W/m2) + VIS
(100 W/m2)/T = 30 ± 2 °C/RH = 50 ± 2%
UV/VIS I = 1600 W/m2 or 600 W/m2; 138.24 MJ/m2; Blond hair Mechanical properties, color 1600 W/m2 — structural damage; 600 W/m2 — color change; 85% RH — [39] 2004
T = 50 °C; RH = 85 or 20% ↑ color change
Artificial D = 220 kJ/m2; RH = 50%; T = Blond hair treated with auburn dye Color, combing Silicones (trimethylsiloxysilicate or propylphenylsilsesquioxane) [40] 2004
sunlight 55 ± 10 °C containing silicones protected color; dimethiconol and silicone resin gel improved combing
UV + VIS I = 149.7 J/h cm2 (400–800 nm); White, brown and bleached hair Color Melanin protected color [22] 2005
t = 8–32 h; RH = 35%; T = treated with light, medium and
45–50 °C dark auburn dye
VIS T = 25–35 °C; RH = 20–30% Red and blond hair Color, melanin granules (SEM) VIS — Blond hair lightened more than red [30] 2005
UV UV — Red hair lightened more than blond
Percentage of disappeared melanin granule higher in red hair
UV + VIS+ UV + VIS + IR Virgin white, dark brown, blond Color White hair: yellowing under IR [41] 2007
IR UVA + VIS + IR and auburn hair Auburn and dark brown ( UV + VIS + IR): yellowing
IR (oven) Blond (UV + VIS + IR): bleaching and melanin degradation
UVB + UVA T = 30 ± 2 °C; RH = 50 ± 2% Virgin or bleached dark brown hair Mechanical properties UVB — ↓ mechanical resistance [41] 2007
+ VIS/UVA t = 1344 h (mercury lamp); 200 h (xenon lamp)
+ VIS
UV UVA = 28.3 mW/cm2; UVB = Black and brown hair Melanin signal by electron spin resonance (ESR) UV generated melanin radical [7] 2008
9.6 mW/cm2 spectroscopy studies
UVA UVA = 6680 J; UVB 58.32 J; RH = 30% Virgin brown hair Cuticle integrity; protein and lipid content UVB — cuticle damage; UVA and UVB — ↓ lipids; UVA — ↑ protein loss [8] 2008
UVB
UVB I = 35337 W/m2; t = 48 h Wool Color; tryptophan content Tryptophan degradation mainly in cortex [14] 2010
UVA + VIS I = 283 W/m2 (t = 45 ou 90 min); Virgin auburn hair Protein loss; tryptophan content; lipid Protein loss; 283 W/m2 → ROS produced after 90 min of exposition; [13] 2012
I = 500 W/m2 (t = 9, peroxidation; ROS generated 500 W/m2 → tryptophan degradation and lipid peroxidation
18, 24, 36 and 48 h)
UV I = 500 W/m2; t = 18, 24, 36 and 48 h. Virgin brown and hair treated with Mechanical properties, protein loss, tryptophan After 18 h — protein loss, lipid peroxidation; [33] 2012
auburn dye degradation, lipid peroxidation, MEV, color 24 h — tryptophan degradation; 36 h — cuticle lifted (MEV), color
change
UVA UVA = 3.97 mW/m2; UVB = Black hair, eumelanin and Ration PTCA free/total (indicator of melanin UVA — ↓ eumelanin and pheomelanin [29] 2012
UVB 0.79 mW/m2 pheomelanin isolated degradation); ratio TTCA/4-AHP (indicator of
pheomelanin degradation)
UVB Doses from 0–4 J/cm2 Hair obtained from 20 females (25 Cuticles morphology and organic functional groups No significant cuticle damage, conversion of α-helix to β-sheet [42] 2012
to 31 years)
UVA/ UVB UVA = 20 J (t = 12 h); 40 J (t = Asian, Caucasian and African hair Hair surface (MEV), cuticle damage (MET); lipid UVB — cuticle damage and African hair is the most affected; [43] 2013
24 h); UVB = 8 J (t = 12 h); 16 J content UV — ↓ content of lipids except for Asian hair
(t = 24 h); RH = 30%; room temperature
UV + VIS + Artificial: VIS + IR; UV + VIS + IR — periods of 8 h, White hair Color VIS — photobleaching in white hair [26] 2014
IR followed by a Free radicals formed during the irradiation continues acting in the dark
VIS + IR periods of 16 h in the dark; t N period
200 h; T = 28 ± 2 °C; RH = 35 ± 9%. Yellowing after thermal degradation at 81 °C
Natural: from 10 am to 3 pm; VIS + IR; solar Sunlight — photoyellowing and photobleaching
full-spectrum (UV + VIS + IR; t = 50 h; T = UV and heat — yellowing
28 ± 2 °C; RH = 56 ± 14%

241
242 M.F. Dario et al. / Journal of Photochemistry & Photobiology, B: Biology 153 (2015) 240–246
The UVB radiation affects all layers of the hair [7] because it can pen-
etrate approximately 5 μm in the hair fiber but its intensity decays
below that. Thus, considering that intact hair cuticle have 6–10 layers,
each with 0.3–0.5 μm, this radiation is not able to fully reach the cortex,
but may cause structural changes in the cuticles, unlike UVA radiation,
which reaches deeply the cortex [8].
2. Hair Photodamage
The first event that occurs when hair is exposed to radiation is the
absorption of light by the fiber. As the most significant chromophores
of proteins (amino acid tryptophan, tyrosine, phenylalanine, and cyste-
ine/cystine) absorb in the range of UVB wavelengths [9], UVA and VIS
lights should not cause direct damage to proteins. Among all the chro-
mophores present in keratin only tryptophan absorbs significantly in
the UVB [10] and, for this reason, it has higher chances to be photolabile
[11,12]. Due to this characteristic, the tryptophan fluorescence can be
used as a marker of photodegradation of the hair fiber, especially the cu-
ticle, but also the cortex [13–15]. The tryptophan presents maximum
absorption at 280 nm, but the main product of tryptophan photooxida-
tion, N-formylkynurenin (a yellow compound) [12], that absorbs at
420 nm, can also be monitored [16].
The most significant effect of solar radiation is the reduction of me-
chanical strength of the hair fiber due to the breakage of disulfide
bonds, either R–S or S–S bonds [16,17] and protein degradation, produc-
ing carbonyl and amine groups [18]. Hair proteins absorb radiation be-
tween 200–380 nm [19] and the bond cleavage is related to protein
loss that may be measured by protein eluted from fiber [16,20].
Besides the direct interaction between UV radiation and hair compo-
nents, the formation of reactive oxygen species (ROS) is also related to
hair photodegradation. ROS are produced mainly by the action of UVA
radiation and are readily consumed in the oxidation of amino acids
such as tryptophan and cysteine [21]. Also, these species are related to
the production of oximelanin from the melanin as well as oxidation of
artificial pigments in dyed hair [22,23].
The ROS are generated by the reaction between molecular oxygen
(O2) and the melanin radical. Possible reactions include the following
[23]:
Melanin + hυ → Melanin*
Melanin* + O2 → Melanin oxidized + O−
2 However, according Signori [32], VIS radiation is most responsible
Melanin + O−
2 → Melanin oxidized + H2O2
Melanin, especially at low wavelengths, promotes photochemical
protection to certain proteins present in the cortex by absorbing, filter-
ing and dissipating the energy as heat. Its ability to absorb energy is re-
lated to the presence of carbonyl groups and conjugated double bonds,
property also observed in chemical filters [24]. In addition to retaining
part of the radiation, melanins immobilize many free radicals formed
during exposure to UV radiation, such as O− 2 , and H2O2 preventing
transport to the keratin matrix. However, during this process, melanin
is degraded or bleached [24,25].
In Table 1 are summarized some of the articles published in the last
years about the effects of sun radiation on the hair fiber. Besides that, it
is important to realize that the authors used different parameters of ra-
diation exposition, like irradiance, dose, temperature and relative hu-
midity, what makes the comparison among results difficult.
The white or gray hair have no melanin or reduced amount of the
natural pigment, respectively, and they are more susceptible to the
damage caused by UV radiation, presenting higher rate of disulfide
bonds break and therefore lower mechanical strength [17]. Thus, this
category of hair needs high photoprotection.
Richena et al. [26] observed that white hair irradiated with VIS plus
IR radiation displayed more pronounced photobleaching compared
with the hair undergoing full-spectrum lamp irradiation. On the other
hand, UV and heat tended to induce hair yellowing. Tryptophan oxida-
tion is a good candidate to explain the photoyellow observed under UV
exposure, but more conclusive studies are still necessary to explain the
mechanism of action [12].
Melanin is classified in two types: eumelanin (a dark brown-to-
black pigment) and pheomelanin (a yellow-to-reddish brown pigment)
[27]. Due to the variation of relative quantities of the two pigments
(eumelanin and pheomelanin) in the hair, the effect of radiation can
be different [7]. Eumelanin and pheomelanin are quantified in terms
of their degradation products, as PTCA (pyrrole-2,3,5-tricarboxylic
acid), a highly specific DHICA (5,6-dihydroxyindole-2-carboxylic
acid)-derived eumelanin, and TTCA (thiazole-2,4,5-tricarboxylic acid)
from pheomelanin [28,29]. The black hair has a higher amount of
eumelanin (340 ng PTCA·mg−1 hair) in relation to pheomelanin
(98 ng TTCA·mg−1 hair), as opposed to red hair, which have a higher
proportion of pheomelanin (62 ng PTCA·mg−1 hair; 89 ng TTCA·mg−1
hair), and blond hair that have small amounts of eumelanin and
pheomelanin (39 ng PTCA·mg− 1 hair; 38 ng TTCA·mg− 1 hair) [28].
Different values are found in literature and discrepancies come from
different measuring methods and also from the samples used since
hair is a biological material [30].
Hoting, Zimmermann & Hocker [25] have shown that black hair
have their hair color changed (are bleached) when exposed to VIS or
the total radiation (UVB + UVA + VIS + IR). However, light brown
tresses (that have high amounts of pheomelanin in relation to
eumelanin) color changed for all types of radiation, except IR, particu-
larly UVA and VIS. These results indicate that the eumelanin has greater
photostability in relation to pheomelanin probably due to the quinone
group present in the structure of this polymer, and also melanin of irra-
diated red hair produces more ROS than the black one [21]. Chemically,
the photobleaching observed in natural hair exposed to solar radiation
is related to the oxidation of indolquinon portion of eumelanin
and the conversion of benzothiazine portion of pheomelanin to
benzothiazole [29].
Thus, it is known that melanins can present both photoreactive char-
acteristics, through the production of superoxide and hydrogen perox-
ide and also photoprotective due to the combined screening and
scavenging of reactive free radicals [31].
for changing the natural color of the hair fiber due to the degradation
of melanin granules, while the UV radiation causes changes in proteins,
which affect the mechanical properties. Fernandez et al. [33] stated the
UVA radiation promotes the generation of ROS, while UVB degrades
melanin pigments and modifies the mechanical properties by promot-
ing breakage of disulfide bonds of cystine present in keratin, which
weakens the hair fiber.
Indeed, the solar radiation causes damage to the hair fiber, altering
its color characteristics, protein content and consequently affects its
mechanical properties such as strength at break and elasticity [34].
However, the color changes are more noticeable in the dyed hair fiber
because the radiation dose required to promote this effect is about 20
times lower than that needed for natural fiber, since the melanin is a
photoprotective substance. The auburn dye shades (light, medium
and dark auburn) are those with the most pronounced changes in
color [22].
According to Locke & Jachowicz [22], white hair treated with auburn
dye showed higher changes of color that bleached brown hair which, in
turn, showed greater damage than natural brown hair when exposed to
artificial sun radiation. These results were observed because of the pres-
ence of the natural photoprotective melanin discolored or natural hair,
in comparison to white hair.
 M.F. Dario et al. / Journal of Photochemistry & Photobiology, B: Biology 153 (2015) 240–246
Therefore, the damage found depends on several factors, such as
natural hair color submitted to the dyeing process (persistent natural
pigments in dyed or bleached hair promote photoprotection), number
of washing procedures and wavelength ranges studied (UVA, UVB,
VIS, IR or total solar radiation) [26,35].
In addition to the color changes, UV rays cause changes in the senso-
ry properties of hair, such as texture, promoting drying of the fiber, an
increase in porosity and loss of flexibility. The penetration of radiation
in the hair shaft affects the structure of keratin, including photo-
oxidation of amino acids, sterols and fatty acids, resulting in the rupture
of disulfide bonds, decomposition of lipids, decreased melanin, as well
as numerous micro-molecular lesions [7].
3. Hair Photoprotection
As already discussed, the natural pigments are an important mecha-
nism of hair photoprotection. Also, hair dyes have demonstrated to be
interesting [44,45]. Besides these pigments, other substances may
used to improve protection to UV radiation effects, as chemical filters,
silicones, and antioxidants.
3.1. Chemical Filters
Chemical UV filters have the capacity to absorb short UV wavelengths
and transform photons into heat-emitting long-wavelength (infrared) ra-
diation [46]. It is known that UVA and UVB chemical filters used in skin
care products such as ethylhexyl methoxycinnamate, ethylhexyl salicy-
late, terephthalylidene dicamphor sulfonic acid, drometrizole trisiloxane,
4-methylbenzylidene camphor, phenylbenzimidazole sulfonic acid,
ethylhexyl triazone, butyl methoxydibenzoylmethane, TEA-salicylate or
some benzophenones are incorporated mainly in “leave-on” products
like gels and sprays, but also in hair shampoos and conditioners, with
the aim of protecting hair structure from sunlight [47–49]. However,
most of these non-ionic filters does not have substantivity to the hair,
i.e., they do not form a film and do not adhere well to the fiber, which fa-
cilitates its removal and reduces the photoprotective capacity [50].
Hair tends to have negative charges on its surface due to the isoelec-
tric point of keratin (around 3.7) [51] and other environmental factors
and management of the hair fiber. Thus, nowadays, quaternary mole-
cules (positively charged), which have a higher affinity for the negative-
ly charged hair fibers, have been developed with the aim of protecting
the photo-oxidative damage caused by solar radiation. these molecules
present substantivity to the hair shaft and tend to be more efficient than
the non-ionic chemical filters, since during washing procedures, the
non-ionic chemical filter is removed quickly from the fiber, unlike the cat-
ionic one [52]. The most used quaternary substances nowadays are
cinnamidopropyltrimonium chloride (INCI: Cinnamidopropyltrimonium
chloride) and dimethylpabamidopropyl laurdimonium tosylate (INCI:
Dimethylpabamidopropyl laurdimonium tosylate), both UVB absorbers
[50,53], but other molecules have also shown photoprotective
efficacy, as quaternium-95 (and) propanediol [15], dodecyl dimethyl-
aminobenzamidopropyl dimethyl ammonium tosylate (DDABDT) [54].
Cationic chromone derivatives with high affinity to hair shaft have
shown potential to absorb in UV region and present antioxidant
activity [55].
3.2. Silicones
Silicones are polymers of silicon, carbon, hydrogen, and oxygen,
sometimes also including nitrogen or sulfur [56]. This group of molecules
has many applications mainly in hair care products due to the film-
formation properties that provides several benefits to the hair fiber, as
combability and luster. Also, these polymers have been studied and mod-
ified to make them useful as hair photoprotective substances. Maillan
[48] showed that the polymeric organosiloxane sunscreen protected
color and lightness of semipermanent hair dyed and brightness of
243
permanent dyed hair while ethylhexyl methoxycinnamate did not
have any positive effect.
Film formers such as silicones can be added to either the hair dye as
for products intended for the post-dye application (treatment products)
for the purpose of photoprotection. According to Schlosser [40],
trimethylsiloxysilicate and propyl–phenyl silsesquioxane were able to
preserve the color of blond hair treated with auburn dye in approxi-
mately 11% when exposed to artificial solar radiation. A non-ionic sili-
cone emulsion protected the color of auburn dyed hair in 83.5% and
brightness in 72.0% [57].
The silicon adherence to the hair shaft depends on its chemical struc-
ture (presence of charges, length of the hydrophobic tail) and health
conditions of the fiber. Chemically-treated hair shaft has more negative
charges on the surface due to the 18-methyleicosanoic acid of F-layer
removal during the chemical process. Thus, the sun protective product
for dyed hair must present positively charged silicones or the formula-
tion has to be enhanced in order to improve the adherence of silicone
to charged hair, as the liquid crystals colloidal structures developed by
Brown et al. [57].
3.3. Antioxidants
In addition to the substances mentioned above, it has been invested
in the study of antioxidants, natural or synthetic molecules that could
prevent the formation of free radicals or to protect the hair structures
(pigments, proteins and lipids) from oxidation. These compounds
could be incorporated to dye formulation or pre-sun formulations, and
to be efficient, they must penetrate deeply into the hair structure and in-
teract with melanin in the cortex [7,58].
Among these natural substances, the potent antioxidants polyphe-
nols are of great interest because they are obtained from fruits and veg-
etables in high concentrations.
The beneficial effects of antioxidants in the protection of blond
hair color, after exposition to UV/VIS radiation, was demonstrated
[39]. The commercially available antioxidant complex that combines
procyanidins from grape seeds, tocopherol and rosemary were incorpo-
rated into a pre-sun formulation. The results showed that the formula-
tion was effective in protecting the hair fiber.
Artichoke extract (Cynara scolymus L.), rich in hydroxycinnamic de-
rivatives, protected hair tresses exposed to UV radiation from the lipid
peroxidation and protein degradation, while the rice extract (Oryza
sativa L.) preserved the strength, color and luster [33]. Pomegranate ex-
tract (Punica granatum L.), rich in tannins, incorporated to a leave-in
hair conditioner protected the color of dyed red tresses exposed to UV
radiation [59]. Similar results were observed for honeysuckle extract
(Lonicera japonica Thunb.), that presents high amounts of flavonoids
such as quercetin, a recognized antioxidant molecule [60].
4. Efficacy Evaluation of Hair Photoprotective Products
There are no regulated methods for evaluating photoprotective hair
efficacy, as the SPF (Sun Protection Factor) for sunscreens [61–63], for
this reason, the claim “hair sunscreen” in commercial products should
be replaced by “prevents color and brightness change”, among other
similar claims [64]. However, this has become necessary due to the
high number of publications regarding this area (some are shown in
Table 1) as well as several patents.
The Hair Protection Factor (HPF) concept, firstly proposed by Nacht
[65] in 1996, is based on the mechanical properties changes of protected
and unprotected hair fiber, upon exposure to UV radiation [45]. The typ-
ical stress–strain curve of a single hair fiber observed during extension
presents three characteristic parts: elastic, yield and post-yield regions
(Fig. 1).
During extension, hair is progressively damaged, initially in a revers-
ible way but then irreversibly. Firstly, the hydrogen bonds are affected
(elastic region), and then the α-helical content is unfolded to β-sheet
244 M.F. Dario et al. / Journal of Photochemistry & Photobiology, B: Biology 153 (2015) 240–246
(yield region) followed by breaks of the covalently bonded network in-
volving cystine (post-yield region) [66]. The yield slope θ obtained in
the second phase indicates the hair damage and can be used to calculate
the HPF, according to Eq. 1 [65].
ðyield slope; nonirradiated − yield slope; irradiatedÞ unprotected hair
HPF ¼
ðyield slope; nonirradiated − yield slope; irradiatedÞ protected hair
Besides the mechanical property, another possible parameter used
to assess the efficacy of a photoprotective hair product is the Radical
Hair Protection Factor (RHF) proposed by Jung et al. [58]. The RHF is a
factor that characterize the cosmetic product according to its ability to
prevent the generation of free radicals induced by UV radiation, a pa-
rameter clearly measured by ESR (Eq. 2) [7]. The intensity of melanin*
radical signal is related to the free radicals/ROS generated upon expo-
sure to UV [67–69].
RH F ¼ Nðfree radicalsÞ unprotected= Nðfree radicalsÞ protected
The COLIPA (European Cosmetics Trade Association) publishes
guidelines for SPF and UVA-PF (Protection Factor UVA) in vitro or
in vivo determination of sunscreens as well as photostability tests.
Some parameters indicated for sunscreens could also be applied to
hair products, as irradiance, since hair is exposed to sun radiation as
skin. According to COLIPA, total UV irradiance should be in the range
of 50–140 W/m2 (290–400 nm) and irradiance ratio of UVA
(315–400 nm) to UVB (290–315 nm) between 8 to 22 [70]. The radia-
tion dose necessary to observed the mainly changes such as lipid oxida-
tion, tryptophan degradation, disulfide bond cleavage and color fading
is about 10,000 J/cm2 [22] at 500 W/m2 (300–800 nm), the irradiation
equivalent to 2 days in June in Catalonia [33].
In general, the efficacy of hair sun care products is measured in terms
of color and luster changes, microscopic characteristics (scale thickness,
porosity, and split ends), mechanical strength, combing, degradation of
amino acids and lipids [58] and melanin* radical signal by ESR [67]. The
most analyzed parameter is hair color because it is one of the first
changes observed and a useful indicator of sun exposure, especially for
dyed hair, and it is easily quantified in numerical terms. Thus, this pa-
rameter will be discussed in more detail in this paper.
Fig. 1. Typical stress–strain curve of a human hair fiber.
4.1. Color Measurement
The exposition of hair fibers to sun radiation causes color variation
that may be measured by quantitative analysis that allows a more accu-
rate and non-subjective assessment of color [71]. The diffuse reflectance
spectrophotometry, the most used technique for this purpose, usually
provides the results in terms of the CIE L*a*b* system, a model devel-
ð1Þ oped by the International Commission on Illuminants (CIE — Commis-
sion Internationale de l'Eclairage).
In this model, the color measure is based on three vectors:
dL*parameter represents the difference in brightness (0 for black and
100 for white), da* defines the difference in color-coordinated green–
red (redness if positive coordinate or greenness if negative coordinate)
and db* defines the difference in color-coordinated blue–yellow
(yellowness if positive coordinate or blueness if negative coordinate)
[72,73].
The total color change or dE parameter is calculated, in this system,
through Eq. (3) [26]. The dC parameter or chromaticity difference is cal-
culated according to Eq. (4). A dE value higher than 1.0 is considered
ð2Þ significant and perceptive to human eyes [74].
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2 2
dE ¼ ðdaÞ þ ðdbÞ þ ðdLÞ ð3Þ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2
dC ¼ ðdaÞ þ ðdbÞ : ð4Þ
There are three factors that affect the color perception by the eyes:
the illuminant, the object being illuminated and the observer (visual
physiology). The CIE standard illuminants comprise A, B, C and D65.
But with the aim of making comparisons among results described in
the literature, CIE recommends, wherever possible, the use of the Stan-
dard Illuminant A (SA) or D65. SA is convenient for tungsten lamps sim-
ulation and D65 is an excellent representation of daylight. Thus, for hair
color assessment, D65 illuminant is the most used because it is more
representative of daylight including the ultraviolet region [75].
According to Scanavez et al. [73], the viewing angle (2° or 10°) did
not affect the hair color parameters (L*a*b*) although most of the re-
searchers prefer to use 10o viewing angle, that does the results more
reliable.
Another important aspect related to color measurement is the inclu-
sion of specular reflectance component of light on measurements. Color
parameters (L*a*b*) of smooth surfaces are substantially influenced by
the inclusion of specular components, unlike the hair fiber that has a cy-
lindrical shape [75]. Thus, the specular component may be excluded
during analysis. Also, the color measure must always be done in the
same portion of hair, and the fibers should be straight and fixed to a
support to avoid experimental mistakes [38] and to ensure the
reproducibility.
5. Conclusions
Sun radiation affects hair properties as color, luster, mechanical re-
sistance, the content of proteins and others. The dyed and white hair
are the most damaged under radiation exposure due to the lack of mel-
anin, the natural photoprotective substance. These types of hair must be
protected from radiation by using products containing mainly silicones,
quaternized UV chemical filters, and antioxidants. Nowadays, the indus-
try challenge is to develop an effective product that covers the whole
hair surface. Despite the considerable number of articles regarding
hair photodamage and photoprotection, there is no consensus about
the effect of the different solar radiation wavelengths on hair fiber.
This may be explained by the absence of exposure parameter harmoni-
zation such as dose, irradiance, temperature and relative humidity.
Thus, it is crucial to establish defined exposure parameters as well as ef-
fectiveness evaluation methods.
 M.F. Dario et al. / Journal of Photochemistry & Photobiology, B: Biology 153 (2015) 240–246
Acknowledgments
We thank Fundação de Amparo à Pesquisa do Estado de São Paulo
(Fapesp) for the financial support (grant numbers: 2013/16070-8 and
2013/16265-3).
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