Dermatol Clin 24 (2006) 105 – 117

Novel Emerging Sunscreen Technologies

Chanisada Tuchinda, MDa, Henry W. Lim, MDa,T, Uli Osterwalder, MSb,
André Rougier, PhDc
a
Department of Dermatology, Henry Ford Hospital, Detroit, MI, USA
b
Ciba Specialty Chemicals, Basel, Switzerland
c
La Roche-Posay Pharmaceutical Laboratories, Asnières, France

Because of increases in the number of skin can- 5. Diethylamino hydroxybenzoyl hexyl

cers diagnosed annually, adverse effects of ultravio- benzoate (DHHB)
let (UV) radiation are being recognized, and major 6. Drometrizole trisiloxane (DTS)
public education programs have been undertaken con- 7. Methylene-bis-benzotriazolyl tetramethylbutyl-
cerning photoprotection, including the use of sun- phenol (MBBT)
screen. In daily life, UV exposure is unavoidable; 8. Bis-ethylhexyloxyphenol methoxyphenyl tri-
therefore sunscreen should be used regularly. De- azine (BEMT)
velopment in sunscreen manufacturing has grown
tremendously in the last decade. Sunscreen active in- The absorption spectra of these filters are shown
gredients now are incorporated into cosmetics prod- in Fig. 1. TDSA, MBBT, and BEMT are at the
ucts to minimize photoaging changes. With the various stages of the approval process from the US
advances in technologies, many new UV filters have Food and Drug Administration (FDA). [1]
been developed recently. These have improved effi-
cacy and safety. This article reviews these new filters,
along with regulatory issues in the United States. Ultraviolet-B filters
The introduction of new sunscreen actives does
not occur frequently. Compared with the United Table 1 lists new active ingredients previously
States, there are more new filters available in Europe. approved for sunscreens in Europe or other coun-
In fact, eight new organic UV filters have been ap- tries but not yet available in the United States.
proved in Europe within the past 14 years: They are described in greater details in the follow-
ing paragraphs.
1. Diethylhexyl butamido triazone (DBT)
2. Benzylidene malonate polysiloxane (BMP) Ethylhexyl triazone
3. Terephthalylidene dicamphor sulphonic
acid (TDSA) Ethylhexyl triazone (EHT) is a UVB filter. In
4. Disodium phenyl dibenzimidazole tetrasulfo- Europe, EHT has been available for some time; in
nate (DPDT) fact, in 1996, it was listed as one of the top 10 most
frequently used filters in Germany [2]. EHT obtained
the status of ‘‘eligible to enter the sunscreen mono-
graph’’ through the FDA Time and Extent Applica-
T Corresponding author. Department of Dermatology, tion (TEA) process in 2003 [3]. It is now eligible
Henry Ford Hospital, 3031 West Grand Boulevard, Suite 800, to continue in the process to be added to the over-
Detroit, MI 48303. the-counter (OTC) monograph of active ingredients
E-mail address: hlim1@hfhs.org (H.W. Lim). approved for sunscreen in the United States, upon

0733-8635/06/$ – see front matter D 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.det.2005.09.003 derm.theclinics.com
106 tuchinda et al

1600
Benzylidene malonate polysiloxane
1400 S 71 (TDSA)
S 73 (DTS)
1200 S 74 (BMP) BMP is a new UVB filter that has a structure of
1000 S 78 (DBT) benzylidene malonate chromophore attached to a
E(1,1)*

S 79 (MBBT)
800
specific point on a polysiloxane chain (Fig. 4) [5].
S 80 (DPDT)
S 81 (BEMT) The molecular weight is about 6000 Da. Because of
600
the large molecular weight, it does not penetrate the
400 skin surface, thus providing improvement in safety.
200 Because the fraction of UV-absorbing moieties in
0 the overall mass of the molecule is small, however,
290 310 330 350 370 390 the efficiency in term of E1,1 is quite low [1]. E1,1
Wavelength (nm) is the extinction efficiency, and it refers to the theo-
retical extinction of a 1% solution of the substance
Fig. 1. Absorption spectrum of the new UV filters. measured at an optical path length of 1 cm. BMP can
be combined with nanopigments such as micron-
ized titanium dioxide (TiO2) or zinc oxide (ZnO) for
satisfactory presentation of data on safety and ef- broad-spectrum UV protection. It also photostabilizes
fectiveness to the FDA [3]. avobenzone; therefore, the combined product is pho-
The structure of EHT is comprised of the chromo- tostable and provides broad UV protection.
phore of para-amino benzoic acid (PABA) linking it
to a triazine ring. The peak absorption spectrum of
EHT is 314 nm (Fig. 2). Even though solubility is Ultraviolet-A filters
limited, EHT can be incorporated in sunscreen
formulations in substantial amounts [1]. Terephthalylidene dicamphor sulphonic acid

Diethylhexyl butamido triazone TDSA is a broad UV absorber, absorbing UV

radiation between 290 and 390 nm with a peak at
DBT is a very efficient UVB filter. It can be re- 345 nm (Fig. 5). It first was shown to be effective
garded as an improved version of EHT, which was against the effect of chronic UVA irradiation in ani-
considered to be the most efficient UVB filter before mal study in 1992 [6]. Unlike other UVA filters, such
the introduction of DBT. Besides the slight improve- as avobenzone, which is a photo-unstable filter, and
ment in efficacy, the solubility is increased compared benzophenone, which has poor UVA absorption,
with EHT [4]. The structure and absorption spectrum TDSA provides broad UVA absorption with photo-
of DBT are shown in Fig. 3. stable properties [7].

Table 1
New ultraviolet absorbers that are not yet approved in the United States
Sunscreen active
COLIPA Spectrum max (nm) Molecular
Type no./INCI name Trade name (supplier) (oil/water soluble) mass (Da) Approval (status)
UVB S69 EHT Uvinul T 150 (BASF) 314 (oil) 823 Europe, USA (TEAa)
S78 DBT Uvasorb HEB (3V Sigma) 312 (oil) 766 Europe
S74 BMP Parsol SLX (Roche/DSM) 312 (oil) 6000 Europe
UVA S71 TDSA Mexoryl SX (L’Oréal) 345 (water) 607 Europe, Japan, USA
(NDA)
S80 DPDT Neo Heliopan AP (Symrise) 334 (water) 675 Europe
DHHB Uvinul A Plus (BASF) 354 (oil) 398 Europe
UVB and UVA S73 DTS Mexoryl XL (L’Oréal) 303, 341 (oil) 501 Europe, Japan
S79 MBBT Tinosorb M (Ciba SC) 305, 360 659 Europe, Australia,
(water dispersible) USA (TEAa)
S81 BEMT Tinosorb S (Ciba SC) 310, 343 (oil) 629 Europe, USA (TEAa)
Abbreviations: COLIPA, European Cosmetic, Toiletry, and Perfumery Assocation; INCI, International Nomenclature Cos-
metic Ingredient.
a
With foreign marketing data.
 novel emerging sunscreen technologies 107

1500
O O

1200
NH

N N
900
E(1,1)

N H
N N
H
O O
600 O O

300

0
290 310 330 350 370 390
Wavelength / nm

Fig. 2. Structure and absorption spectrum of EHT (Uvinul T150). (*) Represents the extinction in efficacy referring to the
theoretical extinction of a 1% solution of the substance, measured at an optical path length of 1 cm.

Numerous studies of this agent showed promising and slowed UVA-induced skin pigmentation [8].
results for preventing photoaging, UV-induced skin Protection against pigmentation correlated with the
pigmentation, and UV-induced immunosuppression concentration of TDSA, and the level of protec-
and carcinogenesis. TDSA is also beneficial in photo- tion was synergistic when TDSA was associated with
dermatosis and photosensitivity conditions. DTS (a broad-spectrum UVB and UVA filter, dis-
In human study, TDSA applied before UVA ex- cussed later in this section). Level of pigmentation
posure decreased loss of skin hydration and elasticity protection essentially depends on UVA protection.

1500
NH

O
1200
NH

N N
H
N N N
900 H
E(1,1)

O O

O O

600

300

0
290 310 330 350 370 390
Wavelength / nm

Fig. 3. Structure and absorption spectrum of DBT (Uvasorb HEB).

108 tuchinda et al

500

Si O Si O Si
400 R n
n = approx. 60
R =
92.1 - 92.5% C H3 O
300 O
E(1,1)

approx. 6% O O O

200 O
O
approx. 1.5% O O O

100

0
290 310 330 350 370 390
Wavelength / nm

Fig. 4. Structure and absorption spectrum of BMP (Parsol SLX).

When sunscreens with the same sun protection fac- tum corneum [11]. In addition, sunscreen containing
tor (SPF) but different level of UVA protection were TDSA was shown to be more effective than 5% octyl
compared, only those with high UVA protection pro- methoxycinnamate at preventing photocarcinogene-
vided similar levels of protection against sunburn and sis and UV suppression of contact hypersensitivity
pigmentation [9,10]. reaction to allergens in mouse model [12,13].
Broad-spectrum sunscreen containing TDSA also This UVA filter was shown to be useful for pa-
may play a role in decreasing the degree of UV- tients with photodermatoses. A 1999 study evaluated
induced immunosuppression, which was evidenced a broad-spectrum SPF 60 sunscreen containing 5%
by its effect in decreasing UV-induced trans- to cis- 4-methylbenzylidene camphor (MBC), 3.3% TDSA,
photoisomerization of urocanic acid in human stra- 3.5% avobenzone, and 4.1% TiO2. This high UVA

1000
O
NaO 3 S
800 SO 3 Na
O

600
E(1,1)

400

200

0
290 310 330 350 370 390
Wavelength / nm

Fig. 5. Structure and absorption spectrum of TDSA (Mexoryl SX).

 novel emerging sunscreen technologies 109

protection sunscreen prevented the development of Diethylamino hydroxybenzoyl hexyl benzoate

lesions that developed in all 23 patients with poly-
morphous light eruption (PMLE). Twenty patients DHHB was launched as a successor of avo-
(87%) using SPF 45 sunscreen containing 6% oxy- benzone. The UV-spectral properties are similar to
benzone and UVB filters (8% homosalate, 7.5% octyl avobenzone, but the photostability of DHHB is supe-
methoxycinnamate, 5% octyl salicylate) developed le- rior [1]. The structure and absorption spectrum of
sions on UV-tested areas [14]. DHHB are demonstrated in Fig. 7. DHHB is approved
Solar urticaria (SU) is a photodermatosis that has in Europe.
an action spectrum in the UVA and visible range.
Most sunscreen products may not be sufficient to
prevent the disease because of insufficient UVA pro- Broad-spectrum ultraviolet-B and -A filters
tection. A broad-spectrum sunscreen containing MBC,
TiO2, TDSA, and avobenzone has been shown to Drometriazole trisiloxane
prevent development of SU in patients whose action
spectrum was in the UVA and UVB range. This sun- A new UV filter, DTS, first was introduced in
screen preparation provided SU protection factors the European Academy of Dermatology and Venere-
(SU-PF) 75, 56, and 133, in the long UVA, short UVA, ology in 1998. It is the first photostable broad UV
and UVB ranges, respectively [15]. filter against UVA and UVB. DTS belongs to the
In a study of systemic absorption after topical photostable group of the hydroxybenzotriazoles.
application, it was shown that human systemic ab- Its structure is composed of two different chemi-
sorption of topical TDSA was less than 0.1% [16]. cal groups, hydroxyphenylbenzotriazol, which pro-
vides photostable UVA and UVB absorption, and
Disodium phenyl dibenzimidazole tetrasulfonate short siloxane chain, which provides liposolubility of
the molecule.
DPDT is a new water-soluble UVA filter, with DTS has two absorption spectra in UVB and
a peak absorption spectrum at 334 nm (Fig. 6) UVA range (290 – 320 nm, kmax 303 nm; and
[1,17,18]. Similar to TDSA, it shows synergistic ef- 320 – 360 nm, kmax 344 nm) (Fig. 8). By combining
fect when combined with filters in the oil phase. the lipophilic DTS with hydrophilic TDSA, a high
According to a formulator’s rule, higher SPF sun- level of photoprotection can be achieved [9]. Since
screens are most effective (ie, use less UV filter), if 1999, the combination of TDSA with the new filter
both the water and the oil phases of a sunscreen emul- DTS has been used in the Anthélios product line of
sion contain some UV filter. La Roche Posay.

1000
HO 3 S N N SO 3 H

N N
800 H H
SO 3 Na SO 3 Na

600
E(1,1)

400

200

0
290 310 330 350 370 390
Wavelength / nm

Fig. 6. Structure and absorption spectrum of DPDT (Neo Heliopan AP).

110 tuchinda et al

1000
O O
OH O

800
N

600
E(1,1)

400

200

0
290 310 330 350 370 390
Wavelength / nm

Fig. 7. Structure and absorption spectrum of DHHB (Uvinul A Plus).

Combination of TDSA and DTS was shown to DTS, avobenzone, TiO2 and octocrylene applied on a
be beneficial in different studies. Combination of half body, the other half body was treated by a
TDSA, DTS, avobenzone, TiO2, and octocrylene com- product affording a low UVA protection. Only four
pletely inhibited photoprovocation-induced lesion in subjects developed a PMLE with the potent broad-
100% of tested lupus erythematosus patients; in con- spectrum product, whereas 15 subjects developed a
trast, only 45% of patients were protected by a PMLE with the other product [20]. Moreover, it has
product that did not contain the two products [19]. been demonstrated that sunscreens with high and
In another study, 16 patients suffering from poly- comparable SPF values but not containing TDSA
morphous light eruption were exposed under the sun and DTS were not equivalent at protecting against
during 6 days with this combination of filters TDSA, UVA-induced polymorphous light eruption (PLE)

500

Si
400
N OH O
N Si
N
O
300
E(1,1)

Si

200

100

0
290 310 330 350 370 390
Wavelength / nm

Fig. 8. Structure and absorption spectrum of DTS (Mexoryl XL).

 novel emerging sunscreen technologies 111

500

400

300
E(1,1)

N OH OH N
200 N
N N
N

100

0
290 310 330 350 370 390
Wavelength / nm

Fig. 9. Structure and absorption spectrum of MBBT (Tinosorb M).

[21]. The same observations have been made in the Methylene-bis-benzotriazolyl tetramethylbutylphenol
protection against UVA – induced phototoxicity fol-
lowing topical antibiotherapy [22]. MBBT is a photostable UVA filter that also has
Under intensive sunlight exposure and realistic a strong absorption in UVB (kmax 305 and 360 nm)
application conditions, the use of the same highly (Fig. 9) [1,25]. It is the in the first class of sunscreens
protective filter combination prevented the photo- that combine the benefits of organic and inorganic
induced skin immunosuppression [23,24]. filters. It comes as microfine organic particles with a

1000

800

600
E(1,1)

OCH3

400
OH N N OH

N
200 O O

0
290 310 330 350 370 390
Wavelength / nm

Fig. 10. Structure and absorption spectrum of BEMT (Tinosorb S).

112 tuchinda et al

diameter of 100 to 200 nm; therefore it not only available for avobenzone or by an energy transfer
absorbs UV, but also scatters and reflects it [26]. from avobenzone to the stabilizing molecule. In the
MBBT is intended for use in aqueous dispersion. The case of UV-absorbers, both mechanisms are possible,
microfine organic particles are dispersed in the water but with DEHN, which shows only negligible ab-
phase, leading to a synergistic effect with oil-soluble sorption in the UVB and none in the UVA, the latter
filters. Because MBBT is relatively large, its systemic one applies.
absorption following topical application is small.
Sun protection factor boosters by the use of
Bis-ethylhexyloxyphenol methoxyphenyl triazine nonabsorbing materials
The technique to increase an SPF of sunscreen
BEMT is a new broad-band UV filter. Because was introduced by adding new nonabsorbing mate-
of its hydroxyphenyltriazine structure, it exhibits rial to sunscreen [31]. Sunspheres is a nonabsorbing
both UVB and UVA absorptions (kmax 310 nm and material, developed by Rohm and Haas (Philadelphia,
343 nm) (Fig. 10). BEMT is oil-soluble and photo- Pennsylvania). It is a styrene/acrylates copolymer
stable. It has been shown to improve photostability of manufactured by means of emulsion polymerization.
avobenzone, and the combination of avobenzone and The polymer itself does not absorb UV radiation;
octyl methoxycinnamate (OMC) [27]. Both MBBT therefore is not an active sunscreen agent. It was
and BEMT were reported to have no estrogenic or designed to enhance the effectiveness of the active
androgenic activities [28]. ingredients present in the formula [32]. When Sun-
spheres are manufactured, they are filled with water.
When the product is applied to the skin, the internal
Update on US Food and Drug Administration water migrates out of the sphere, leaving microscopic
approval of new filters hollow beads. When UV hits these hollow beads, the
UV radiation is scattered and begins to travel side-
A United States clinical trial with TDSA has ways instead of straight down into skin. The spheres
been completed; data have been submitted to the act as efficient scattering centers that increase the
FDA as part of a new drug application (NDA) probability of UV radiation coming into contact with
process. MBBT and BEMT have fulfilled the 5-year the UV active ingredients present in the sunscreen
foreign marketing criterion; they are being submitted formulation. Sunspheres polymer was claimed to
for FDA TEA for inclusion in the FDA sun- boost a sunscreen’s SPF by 50% to 70%, making it
screen monograph. possible to reduce the amount of active ingredients in
sunscreen products while providing the same level of
photoprotection [32]. With a tiny external diameter of
Development of UV filters for sunscreens approximately 325 nm, the particle is nearly invisible
and cannot be felt during the application of sunscreen
Some of the new technologies to improve the ef- on the skin. Sunspheres function well with UVB and
ficacy or safety of UV filters developed in recent UVA filters. Examples of products containing sty-
years are summarized. rene/acrylates copolymer include facial care products
of Nivea Vital, Dove, and Yves Saint Laurent.
New development with respect to conventional UV
filters Micronization of inorganic sunscreen
Because of the efficacy and safety of inorganic
Stabilizing agents for butyl sunscreen, the initial purpose of its development was
methoxydibenzoylmethane for the use in children and individuals with sensi-
Avobenzone is a broad UVA absorber; however, tive skin. Because of the whitening effect, however, it
its drawback is photoinstability. After exposed to was not cosmetically acceptable to most individuals.
1 hour of sunlight, it was estimated that it would UV attenuation performance of inorganic sunscreen is
degrade by 36% [29]. Avobenzone/OMC combina- influenced by its particle size. When particle size is
tion is known as a photounstable formulation. The not sufficiently small (ie, < 100 nm), it can cause whit-
photoinstability of avobenzone can be avoided by ening of skin [33]. With the development in sun-
combining it with octocrylene, MBC [30], BEMT, or screen technology, inorganic particle size now can be
with non-UV filters such as diethylhexyl 2,6 naph- decreased into micronized form (10 – 50 nm), com-
thalate (DEHN) [1,27]. This stabilization is either pared with 200 to 500 nm of the nonmicronized form,
caused by a reduction of the number of photons resulting in less scattering of visible light. This im-
 novel emerging sunscreen technologies 113

proves the cosmetic acceptability and allows easier cause there is no chemical interaction of these two
incorporation into formulations. Microfine TiO2 and UV filters [37,38].
microfine ZnO are used widely for daily wear sun-
screen and traditional recreational products. To maxi- Microfine organic particles
mize the UV attenuation without causing whitening
of skin, inorganic particle size needs to be controlled. Microfine organic particle is a new form of UV
TiO2 with particle size smaller than 100 nm will de- filters providing characters of organic and inorganic
crease scattering effects, resulting in a decrease in filters. Its unique property includes absorbing UV
UVA attenuation, but an increase in UVB absorption. radiation similar to an organic filter, and scattering
Therefore, by reducing the particle size, the peak and reflecting UV similar to an inorganic filter [26].
of the absorption spectrum is shifted to the shorter MBBT is the first agent in this new class using mi-
wavelength. ZnO absorbs UV more uniformly than crofine particle technology. Colorless UV-absorbing
TiO2. UV absorption curve of ZnO has a sharp cut- organic solid has been micronized to particles below
off around 375 nm; similar to TiO2, as the particle 200 nm in diameter. The physical properties of mi-
size gets smaller, the UV absorption will shift to crofine organic particles strongly depend on the par-
slightly shorter wavelengths [34]. Because microfine ticle size. At 160 nm particle size, about 85% of the
ZnO has better absorption at longer wave of UVA transmitted UV is absorbed; 10% to 15% is forward
(340 – 380 nm) than TiO2, there has been a shift of scattered and 3% to 5% is backward scattered (re-
sunscreen use from TiO2 to ZnO in the past few years flected) [39]. It is inherently photostable and highly
[1,34]. Because of possible photocatalytic activity efficient because of its triple actions: UV absorption
of inorganic sunscreen, inorganic particles frequently (by photostable organic molecules), scattering, and
are coated with dimethicone or silica for maintenance reflection (by microfine particles).
of their efficacy [35].

Requirements for sunscreen active ingredients

New product forms
Three basic requirements on sunscreen active in-
Encapsulation of conventional UV absorbers gredients must be fulfilled before they can be incor-
porated into a final product [1].
By using a technique called micro-encapsulation,
the organic sunscreen actives can be entrapped within Efficacy
a silica shell [36]. This silica glass is produced at
room temperature so the sunscreen is not destroyed. The sunscreen active ingredients must demon-
The little glass spheres are only one-hundredth of the strate good UV absorption at least in parts of the UV
width of a human hair in diameter, extremely stable. range of 290 to 400 nm. Efficacy also includes good
They form a protective film on the skin. By using this solubility. UV filters must be incorporated easily
technique, the organic filter does not contact with the to any kind of formulation. Lastly, photostability of
skin directly, therefore decreasing the probability of UV filters also influence efficacy of sunscreen ac-
allergic or irritant reaction. This microencapsulation tive ingredients.
technique is not limited to UV filters but is applicable
to many other cosmetic ingredients. Safety/registration
Eusolex UV-Pearls is the first sunscreen product
using this technique. The first commercially available In Europe, South America, Asia, and Africa,
product contains octyl methoxycinnamate [36]. It is sunscreens are considered as cosmetics. Therefore,
supplied as aqueous dispersions containing approxi- the approval is possible within 1 to 2 years of filling.
mately 37% (w/w) of the UV absorber. The white Sunscreen actives should have no adverse effect on
liquids contain Eusolex UV-Pearls of about 1.0 mm people or the environment. The toxicological studies
diameter on average. They are sufficiently small to generally required for a global registration include
be transparent when applied to the skin and to give acute and chronic toxicity, fertility, embryofetal tox-
a pleasant skin feeling. Using this technique for en- icity, and peri-/postnatal effects, in vitro and in vivo
capsulation of UV filters, the incompatibility prob- percutaneous absorption, genetic toxicity, and carci-
lem between sunscreen active ingredients can be nogenicity [40]. In Australia and Japan, specific data
solved. Photostability of the avobenzone/OMC is im- on a complete formulation are required in addition to
proved after segregate encapsulation technique, be- the European Union dossier. In the United States,
114 tuchinda et al

1000
Patent freedom
800
Patent freedom means the free use of sunscreen
600 active ingredient by any sunscreen manufacturer,
E(1,1)

avoiding the infringement of any third-party rights.

400

200
Sunscreen regulation by the US Food and Drug
0 Administration
290 310 330 350 370 390
Wavelength / nm Twenty-eight, 26, and 21 active ingredients are
approved for UVA and UVB sunscreens in Europe,
Fig. 11. Absorption spectrum of IMC (amiloxate).

Box 1. Sunscreens approved in European

sunscreen actives are considered as OTC drugs; as
countries
such, they need to be included in the FDA sunscreen
monograph before they could be used. Starting in
1. Benzophenone-4 (sulisobenzone)
January 2002, there was a new procedure (TEA)
2. 3-Benzylidene camphor
introduced by the FDA. It is a two-step process. After
3. Benzylidene camphor sulfonic acid
a minimum of 5 continuous years of experience in
4. BEMT (bemotrizinol [Tinosorb S])
the same countries as OTC products, new sunscreen
5. Bisymidazylate
actives can be considered for TEA approval [41]. In
6. Butyl methoxydibenzoylmethane
the next step, data on efficacy and safety have to
(avobenzone [Parsol 1789])
be submitted. TEA provides an alternative to filling
7. Camphor benzalkonium methosulfate
an NDA, which requires significantly more time
8. DHHB
and cost. Three UVB filters widely used outside the
9. DBT
United States have received the status of ‘‘eligibility
10. Dimethicodiethylbenzal malonate
to enter the sunscreen monograph’’ in the United
11. DTS (silatriazole [Mexoryl XL])
States [42]. These are
12. Ethoxylated ethyl 4-aminobenzoic
acid (PEG-25 PABA)
1. Isoamyl p-methoxycinnamate (IMC), US drug
13. Ethylhexyl methoxycinnamate
name: amiloxate (absorption spectrum is
(octyl methoxycinnamate
shown in Fig. 11)
and octinoxate)
2. 4-Methylbenzylidene camphor (MBC), US
14. 2-Ethylhexyl p-dimethyl amino
drug name: enzacamene (absorption spectrum
benzoate (octyl dimethyl PABA)
is shown in Fig. 12)
15. Ethylhexyl salicylate (octyl salicy-
3. Ethylhexyl triazone (EHT), US drug name:
late; Octisalate)
octyl triazone
16. Homomenthyl salicylate (homosalate)
17. IMC (Amiloxate)
18. MBC (enzacamene)
1000
19. MBBT (bisoctrizole [Tinosorb M])
800 20. Octocrylene
21. Octyl triazone
600 22. Oxybenzone
E(1,1)

23. PABA
400 24. Phenylbenzimidazole sulfonic
acid (ensulizole)
200
25. Polyacrylamidomethyl
0 benzylidene camphor
290 310 330 350 370 390 26. TDSA (ecamsule [Mexoryl SX])
Wavelength / nm 27. TiO2
28. ZnO
Fig. 12. Absorption spectrum of MBC (enzacamene).
 novel emerging sunscreen technologies 115

Table 2 and safety of sun protective products. In the near

Sixteen sunscreens approved in the United States future, new sunscreen products with even better in
Max concentration efficacy and safety should become available all over
Approved sunscreens (%) the world.
PABA 15
Avobenzone 3
Cinoxate 3
Dioxybenzone 3
References
Ensulizole 4
Homosalate 15 [1] Herzog B, Hueglin D, Osterwalder U. New sunscreen
Meradimate (menthyl anthranilate) 5 actives. In: Shaath NA, editor. Sunscreen: regulations
Octinoxate 7.5 and commercial development. 3rd edition. New York7
Octisalate 5 Marcel Dekker; 2005. p. 291 – 320.
Octocrylene 10 [2] Finkel P. Formulierung kosmetischer Sonnen-
Octyl dimethyl PABA 8 schutzmittel—Trends und Tendenzen [Formulating
Oxybenzone 6 cosmetic sun protection products—trends and tenden-
Salisobenzone 10 cies]. Parf ümerie Kosmetik 1999;80:10 – 6 [in German].
TiO2 25 [3] BASF The Chemical Company. BASF is one of first to
Trolamine salicylate 12 receive initial TEA approval from FDA. Available at:
ZnO 25 http://www.basf.com/corporate/news2003/newsinfo_
tea_approval.html. Accessed May 2005.
[4] Malpede A, Fumagalli S. Diethylhexyl butamido
triazone-nuovo filtro per la protezione cutanea [Dieth-
ylhexyl butamide triazone—a new filter for skin
protection]. Cosmet Technol 2000;3:33 – 8 [in Italian].
Australia, and Canada, respectively [26]. A list of [5] Parsol SLX: a new possibility to combine with nano-
28 active ingredients approved in the European Union pigments. Available at: http://www.dsm.com/en_us/
is shown in Box 1. In the United States, there are downloads/dnp/news_rel_2004_08.pdf. Accessed Oc-
16 filters included in the FDA sunscreen monograph tober 2005.
(Table 2). Some of the permitted filters are not broad [6] Fourtanier A, Labat-Robert J, Kern P, et al. In vivo
evaluation of photoprotection against chronic ultra-
UVA filters; some are not photostable or are difficult
violet-A irradiation by a new sunscreen Mexoryl SX.
to incorporate into formulations. All permitted UV Photochem Photobiol 1992;55:549 – 60.
filters can be used with any other permitted UV filters [7] Diffey BL, Strokes RP, Forestier S, et al. Suncare
except avobenzone. Current FDA rules do not allow product phostability: a key for more realistic in vitro
formulators to combine avobenzone with inorganic efficacy evaluation. In: Rougier A, Schaefer H, editors.
sunscreen [26]. Avobenzone is allowed to be used Protection of the skin against ultraviolet radiation.
only with cinoxate, dioxybenzone, octinoxate, octi- Paris7 John Libbey; 1998. p. 137 – 42.
salate, homosalate, oxybenzone, octocrylene, suliso- [8] Seite S, Moyal D, Richard S, et al. Mexoryl SX:
benzone, and trolamine salicylate. Microfine oxides a broad absorption UV-A filter protects human skin
are allowed in the United States, Europe, and Aus- from the effects of repeated suberythemal doses of
UVA. J Photochem Photobiol B 1998;44:69 – 76.
tralia [43]. Because of their safety, they are probably
[9] Moyal D. Prevention of ultraviolet-induced skin pig-
the most common choice for children’s and high mentation. Photodermatol Photoimmunol Photomed
SPF products. 2004;20:243 – 7.
[10] Moyal D, Dutei L, Queille-Roussel C, et al. Compari-
son of UV-A protection afforded by sunscreens with
a high sun protection factor. Eur J Dermatol 2002;12:
Summary 2 – 3.
[11] Krien P, Moyal D, Rougier A. Influence of high pro-
To improve the efficacy and safety of sun- tective sunscreens on photoisomerization of urocanic
screen products, UV filters and efficient photostable acid in human skin. In: Rougier A, Schaefer H, editors.
Protection of the skin against ultraviolet radiation.
UVA and broadband UVB/UVA filters have been
Paris7 John Libbey; 1998. p. 183 – 8.
developed. Other new technologies, including a non- [12] Fourtanier A. Mexoryl SX protects against solar-
absorbing material to boost SPF, coating/modifications simulated UVR-induced photocarcinogenesis in mice.
of inorganic sunscreen, stabilizing avobenzone by Photochem Photobiol 1996;64:688 – 93.
photostabilizers, encapsulation of UV absorbers, and [13] Gueniche A, Fourtanier A. Mexoryl SX protects
microfine organic particles also may improve efficacy against photoimmunosuppression. In: Altmeyer P, Hoff-
116 tuchinda et al

mann K, Stucker M, editors. Skin cancer and UV UV-A testing protocols that are still waiting FDA de-
radiation. Berlin: Springer Verlag; 1997. p. 249 – 62. cisions. Chemical and Engineering News 2005;
[14] Allas S, Lui H, Moyal D, et al. Comparison of the 83(15):18 – 22. Available at: http://pubs.acs.org/cen/
ability of 2 sunscreens to protect against polymor- coverstory/83/print/8315sunscreens.html.
phous light eruption induced by a UV-A/UV-B metal [27] Chatelain E, Gabard B. Photostabilization of butyl
halide lamp. Arch Dermatol 1999;135:1421 – 2. methoxydibenzoylmethane (Avobenzone) and ethyl-
[15] Nocera T, Peyron JL, Moyal D, et al. Protection contre hexyl methoxycinnamate by bis-ethylhexyloxyphenol
l’urticaire solaire par les filtres : Une méthode de methoxyphenyl triazine (Tinosorb S), a new UV
détermination du coefficient de photoprotection UVA broadband filter. Photochem Photobiol 2001;74:
[Protection of solar urticaria using broad spectrum 401 – 6.
sunscreen and determination of solar urticaria protec- [28] Ashby J, Tinwell H, Plautz J, et al. Lack of bind-
tion factor]. Les Nouvelles Dermatologiques 1998; ing to isolated estrogen or androgen receptors, and
17(5):301 – 4 [in French]. inactivity in the immature rat uterotrophic assay, of
[16] Benech-Kieffer F, Meuling WJ, Leclerc C, et al. the ultraviolet sunscreen filters Tinosorb M-active
Percutaneous absorption of Mexoryl SX in human and Tinosorb S. Regul Toxicol Pharmacol 2001;34:
volunteer: comparison with in vitro data. Skin Phar- 287 – 91.
macol Appl Skin Physiol 2003;16:343 – 55. [29] Deflandre A, Lang G. Photostability assessment of
[17] Symrise GmbH & Co. Neo heliopan AP product and sunscreens: benzylidene camphor and dibenzoylme-
brochure. Holzminden (Germany)7 Symrise; 2002. thane derivatives. Int J Cosmet Sci 1988;10:53 – 62.
[18] Johncock W, Langner R. Advance in UVA photo- [30] Forestier S, Mazillier C, Richard A, et al. Suncare
protection via a novel water soluble UV-A – absorbing product photostability: a key parameter for a more
bis-phenylimidazole derivative. 21st International Fed- realistic in vitro efficacy evaluation. Part II: chromato-
eration of Societies of Cosmetic Chemists Congress graphic analysis. In: Rougier A, Schaefer H, editors.
Congress. Berlin, Germany, September 11 – 14, 2000. Protection of the skin against ultraviolet radiation.
Augsburg (Germany)7 Verlag für Chemische Indus- Paris7 John Libbey; 1998. p. 143 – 7.
trie; 2000. p. 372 – 7. [31] Jones CE. A new polymeric additive for sunscreen.
[19] Stege H, Budde MA, Grether-Beck S, et al. Evaluation SÖFW 1995;121:561 – 5.
of the capacity of sunscreens to photoprotect lupus [32] SunSpheres Hollow Sphere Technology. Available at:
erythematosus patients by employing the photoprovo- http://www.rhpersonalcare.com/pdf/sunspheres_personal
cation test. Eur J Dermatol 2002;12:7 – 9. care.pdf. Accessed October 2005.
[20] Moyal D, Binet O, Richard A, et al. Prevention of [33] Shaath NA, Walele IL. Inorganic particulate ultraviolet
polymorphous light eruption by a new broad spectrum filters in commerce. In: Shaath NA, editor. Sunscreen:
sunscreen: a need for a high UVA protecting factor. regulations and commercial development. 3rd edition.
Presented at the 57th Annual Meeting of the American New York7 Marcel Dekker; 2005. p. 281 – 90.
Academy of Dermatology. New Orleans, Louisiana, [34] Schlossman D, Shao Y. Inorganic sunscreens. In:
March 19 – 24, 1999. Shaath NA, editor. Sunscreen: regulations and com-
[21] Stege H, Budde M, Grether-Beck S, et al. Sunscreen mercial development. 3rd edition. New York7 Marcel
with high SPF values are not equivalent in protection Dekker; 2005. p. 239 – 79.
from UV-A – induced polymorphous light eruption. [35] Lademann J, Weigmann H, Schafer H, et al. Inves-
Eur J Dermatol 2002;12:4 – 6. tigation of the stability of coated titanium micro-
[22] Duteil L, Queille-Roussel C, Rougier A, et al. High particles used in sunscreens. Skin Pharmacol Appl
protective effect of a broad-spectrum sunscreen Skin Physiol 2000;13:258 – 64.
against tetracycline toxicity. Eur J Dermatol 2002;12: [36] Merck. Eusolex UV-Pearls. Available at: http://www.
10 – 1. merck.de/servlet/PB/menu/1322070/index.html.
[23] Moyal D, Duteil L, Queille-Roussel C, et al. Pre- Assessed May 2005.
vention of solar-induced immunosuppression by a [37] Schwack W, Rudolph T. Photoreaction of chemical
new highly protective broad-spectrum sunscreen. Pre- UVA filters in cosmetics. GIT Lab J 1997;1:17 – 20.
sented at the 57th Annual Meeting of the American [38] Chadorowski S, Quinn FX, Sanchez C, inventors.
Academy of Dermatology. New Orleans, Louisiana, L’Oreal, assignee. Method for improving UV radiation
March 19 – 24, 1999. stability of photosensitive sunscreen filters. US Patent
[24] Schiller M, Brzoska T, Bohm M, et al. Solar-simulated 6,607,713. August 19, 2003.
ultraviolet radiation induced upregulation of the [39] Müller S, Herzog B, Osterwalder U. Microfine organic
melanocortin-1 receptor, proopiomelanocortin, and particles—a new type of physical sunscreen actives.
alpha-melanocyte stimulating hormone in human epi- Presented at the 63th Annual Meeting of the American
dermis in vivo. J Invest Dermatol 2004;122:468 – 76. Academy of Dermatology. New Orleans, Louisiana,
[25] Ciba Specialty Chemical Inc. EC0746305. Basel (Swit- February 18 – 23, 2005.
zerland): Ciba Specialty Chemicals. [40] Nohynek G, Schaefer H. Benefit and risk of organic
[26] Reisch MC. New-wave sunscreens active ingredient ultraviolet filters. Regul Toxicol Pharmacol 2001;33:
makers are frustrated by the long list of sunscreesn and 1 – 15.
 novel emerging sunscreen technologies 117

[41] United States Food and Drug Administration. Addi- the-counter drugs products; safety and efficacy re-
tional criteria and procedures for classifying over- view; additional sunscreen ingredients. In: Notices.
the-counter drugs as, generally recognized as safe [docket no. 2003N – 0233] Fed Regist 2003;68(133):
and effective and not misbranded. In: Rules and 41386 – 7.
regulations. [21 CFR, part 330, docket no. 96N – [43] Steinberg DC. Regulation of sunscreens worldwide.
0277, Rin 0910 – AA01] Fed Regist 2002;67(15): In: Shaath NA, editor. Sunscreen: regulations and
3060 – 76. commercial development. 3rd edition. New York7 Mar-
[42] United States Food and Drug Administration. Over- cel Dekker; 2005. p. 173 – 98.