Chapter 14 Seaweed Application in Cosmetics

CHAPTER
Seaweed Application
Cosmetics
in
14
C. Couteau, L. Coiffard
Universitv of Names, Nantes, France
INTRODUCTION
The skin is the most extensive and the heaviest organ in the human body, with a
surface area of around 2 m? and a mass of 2 kg for an adult Its essential role is one
of protection, Tt is a sense organ because of its role in sensory perception, It is at the
interface between the inside and the outside and plays a large part in the image that
we convey of ourselves, hence the importance of disciplines such as dermatology
and cosmetology,
The cosmetics industry is a key industrial sector, which is worth more than
€425 billion worldwide, In this context, Europe is the largest market in the world with
€72 billion, followed by the United States (€37,8 billion) and Japan (€29.3 billion), In
this context the cosmetics industry, with its turnover of €25 billion, is ranked fourth
in the French economy for its net trade balance, It is the second largest exporting
sector in the French economy after the aeronautics construction industry and in terms
of trade surplus (€7,6 billion in 2010), It is thus a dynamic sector governed by relatively recent regulations that were implemented after the dramatic "Talc Morhange
scandal" (Marrin-Bouyer et al., 1982), which led to the founding principle of "Do
not harm human health," Care must always be taken therefore to ensure that the raw
materials chosen for formulation are not toxic and to carry out thorough controls during successive phases in the production of industrial batches,
This industry is always searching for new ingredients, mainly for two reasons-the
first being for obvious marketing criteria, and the second being to replace raw materials that have been banned or have become distrusted by the consumer. The marine
world therefore constitutes a potential source of interesting substances because of its
richness and diversity (Pérez, 1997; Wang et al., 20] 5). Seaweeds arc rich in bioactive
compounds that could he exploited as functional ingredients for cosmetic applications. This review discusses the cosmetic potential of different bioactive compounds
found in seaweeds. Marine cosmetics, also known as phycocosmetics (Coiffard and
De Roeck-Holtzhauer, 1992), are an economic reality and specific ranges such as
Algothenn, Phytomer, Daniel Jouvance, Science & Mer, or Thalgo focus on marine
resources. Moreover, especially in the west of France, structures have been developed
that specialize in providing marine raw materials for industry. It often involves liquid
Seaweed in Health and Disease Prevention. http://dx.doi.orgllO.lOI61B978-0-12-802772-1.00014-Z
Copyright O ~Ol() Elsevier Inc. All rights reserved.
423
424
CHAPTER 14 Seaweed Application in Cosmetics
extracts in a mixture of water and propylene or butylène glycol. The main players in
this sector are Aleor (Lézardieux-e-Côtes
d' Armor, France), Ceva (Pleubian-Côtes
d' Armor, France), Codif International (Ile-et- Vilaine-France),
Secrna (PontrieuxCôtes d' Armor, France), and Gelyma (Bouches-du-Rhône-France).
GENERAL ASPECTS OF COSMETIC FORMULATION
-~~~~~--~~--i'l~embrafles
A cosmetic product is defined under European regulations as "any substance or mixture
intended to be placed in contact with the external parts of the human body (epidermis,
hair system, nails, lips and external genital organs) or with the teeth and the mucous
oHhe~oral cavity witjra--vtcw~erêltlsively
oF1ifâlfiITto-cleanmg
t1i~e~Jil.~,~--~~
perfuming them, changing their appearance, protecting them, keeping them in good
condition or correcting body odors" (Regulation (BC) 1223/2009). The Federal Food,
Drug and Cosmetic Act gives a fairly similar definition insofar as the functions mentioned are equivalent. The same is true in Japan. It can be noted therefore that unlike a
medicine, it is not possible for a cosmetic product to claim that it has any therapeutic
action. However, cosmetics are very often needed in the latter stages of dermatological
pathologies such as acne or atopic eczema. These cosmetics are used to combat the
acute drying out of the skin caused by treatment in the case of a patient with acne and
to act as a relay of dennocorticoids in the case of a patient with atopic eczema.
In terms of dosage forms, cosmetics can correspond to extremely diverse forms,
but a very general definition can be given that corresponds to all of them:
1 cosmetic
=
L
I or several Active ingredient(s) + 1 or several Excipient(s)
+ 1 or several Additive(s) + primary packaging
± secondary packaging
Where the active ingredient is responsible for the cosmetic's particular activity
(moisturizing, sli mming, antiaging, etc.), the excipient constitutes the vector of the
active ingredient and the additive is an ingredient intended to improve the product's
preservation or its organoleptic qualities (Couteau and Coiffard, 2014). We shall see
later that the marine world can provide us with molecules or extracts of interest for
these three categories of components.
Seawater
(International
Nomenclature
of Cosmetic
Ingredients
(INCl) name
It remains an
excipient, despite being frequently promoted in marketing because of the minerals
that it contains, and may therefore correspond to the definition of an active ingredient. In this respect, we are reminded of Quinton's marine plasma (Mariotti, 1952).
This is an isotonic dilution of seawater (pH 7.2) used since the beginning of the 20th
century as a medicine for treating various pathologies, some of them dermatological ones, such as eczema or psoriasis. The main example of the use of seawater by
the cosmetics industry is that of the Dead Sea, a saltwater lake in the Middle East
between Israel, Jordan, and Palestine. Its salt content of 275 giL is exceptionally
Aqua marisi itself is found in a certain number of phycocosrnetics.
Macroalgae as a Source of Active Ingredients
425
high (Katz et al., 2012). Bath salts as well as soaps and scrub products formulated
with Dead Sea salts are available. The main laboratory involved is Ahava Dead Sea
Laboratories.
MACROALGAE AS A SOURCE OF ACTIVE INGREDIENTS
Macroalgae can be classified by color into three main groups: brown (Phaeophyceae), red (Rhodophyceae), and green (Chlorophyceae). These can be of interest to
the cosmetics industry for a variety of reasons, not only as a source of minerals,
polysaccharides, proteins, and lipids, but also because of the secondary metabolites
~~~~~~~~SHGQ~s-r>heIlBli&-@0mfl0tlnds;-tel'pen()id~halügenated-comp('mndS';"'su1fur,tCTi:vati:Vc""',~, ~~~~~~~~~~~
and nitrogen derivatives that they can produce.
SEAWEED EXTRACTS AS ACTIVE INGREDIENTS FOR SLIMMING
PRODUCTS
Although they are seasonal, slimming products account for a turnover in France of
more than €100 million. Although the main active ingredient in this type of product
is caffeine, a xanthic base involved in the metabolism of cAMP (Franchi et aI., 2003),
it should be noted that a large number of formulations use algae extracts, mainly
Fucus or Laminaria. These algae are particularly rich in iodine, which justifies their
presence in these products. Iodine is known to be involved in thyroid metabolism and
that thyroid hormones promote lipolysis by increasing the penetration of fatty acids
in the mitochondria because of the increased synthesis of carnitine palmitoyl transferase (Kohn et aI., ] 993; Pocock and Richards, 2004; Leblanc et aI., 2006). Indeed,
algae have the property of concentrating the iodine from seawater. One such example
is Laminaria japonica. It contains 0.9% iodine as dry weight, while the seawater in
which it is found only contains 6.10-8 giL. The iodine content can vary tremendously
depending on the alga and where it was harvested (Table 14.1).
Table 14.1 Iodine Content of Some Species of Brown
Algae (Morita et ai., 2010)
Alga
Iodine Content (mg/kg Dry
Weight)
Codium fragile
U/va perfusa
Monostroma nitidum
Graci/aria conferoides
Sargassum kjellmanianum
Dictyopteris divaricata
154±9
12.9±O.2
63.6±2.5
353±24
273±6
28.8±O.5
Laminariajaponica
3040±32
426
CHAPTER 14 Seaweed Application in Cosmetics
Algae, above all Fucus and Laminaria, are traditionally used in slimming products although their efficacy has never been proven. This is no bad thing, as an action
targeting the thyroid falls out of the field of cosmetics! However, in this respect, it
should be remembered that iodine is prohibited from lise in cosmetics (Regulation
(EC) 1223/2009, Annex IL reference number 213).
A Jania rubens extract is being proposed for formulating slimming cosmetics. Tt
promotes the elimination of fats and the synthesis of collagen for smoothing out cellulite. This claim is not substantiated by the scientific literature. On the other hand,
a naturally occurring oxysterol, 16p-hydroxy-5a-cholestane-3,6-dione, was detected
in this red alga 15years ago. Its proven cytotoxic properties with regard to KB cells
(IDso 5Ilg/mL) demand that caution be exercised (Ktari et al., 2000).
~~~~~~~~~~~~~An0rheîe;)éampJe-t·hat-ca1'l-be-cited-js=é)Jsros'l?inrlnlT"lW"ll":'""Tlle-cüsmeti
cs in·âustry
chose to designate this brown alga by the INCl name Phyllacantha fibrosa. Somatoline Cosmetic 50 Plus Slimming Treatment", a product for women that has been on
the market for over 50years, contains a C. baccara extract in combination with a I.
rubens extract and caffeine. As is the case with Ionia, there is no scientific evidence
that justifies the presence of such extracts in a slimming product. Since this alga is
capable of absorbing mercury, cadmium, and lead dissolved in water (Herrero et al.,
2005; Lodeiro et al., 2006), caution should be exercised in this case as well.
ALGAE EXTRACTS AS ACTIVE INGREDIENTS FOR MOISTURIZING
AND ANTIAGING PRODUCTS
Water and Skin
The adult human body is made up of 60--65% water on average, of which 6-8 L
is contained in the skin, mainly in the dermis where it is fixed by proteoglycans
and glycoproteins. The epidermis only contains around 120mL of water (60% of
its mass) and the stratum corneum contains less than 20 mL (i 0-13 % of its mass).
The water is fixed thanks to hygroscopic substances known by the generic name of
NMF (natural moisturizing factor). NMF is made up of amino acids (40%), including
serine (20--30%), pyrrolidone carboxylic acid (12%), lactic acid (12%), urea (8%),
sugars, minerals, and a fraction that remains undetermined (Pashkovski et aI., 2009).
A transepidermal flux of water takes place, as the lower the relative humidity and the
higher the temperature of the surrounding area, the more water is lost by the skin.
This nonapparent diffusion is called insensible water loss. This is equivalent to about
5 g/m2/h. It is an indicator of skin barrier integrity. In atopical children, it can reach
13-18 g/m2/h, as in this case the skin is no longer working effectively as a barrier
(Marty, 2002; Roguenas-Contios and Lorette, 2007).
There are different types of dry skin. Congenital ichthyosis (from ictus, which
means "fish" in Greek) can be distinguished. This is a genetic skin disorder, the most
serious form of which is known as collodion baby (I in 300,000 births). Collodion
baby, also sometimes called harlequin-type ichthyosis, appears at birth in the form
of severe hyperkeratosis of the whole of the skin, which is crusty, hard, brownish,
and cracked, impeding movements and sucking. This disease can put the child's
Macroalgae as a Source of Active Ingredients
427
life at risk because of associated respiratory, infectious, and nutritional problems
(Akiyama, 1999; Bridoux et aI., 1999). Although this type of situation is unsuitable
for treatment with cosmetics, the same cannot be said for xerosis (from the Latin
word stringere, meaning "tight"), a phenomenon causing thin, rough, squamous. and
uncomfortable skin, described by the patient as feeling tight.
The Interest of Algae in the Field of Skin Moisturizing
Faced with this demand, oil/water emulsions are formulated that avoid excessive water
loss thanks to occlusive ingredients and fix the water in the skin thanks to moisturizing active ingredients. Although the extracts of Laminaria are the choice ingredient in
this case, a large number of algae can be used in this field. It is now known that NMf~
========~€el'a)'I1icleST-aflcl=aqt1aporins-are--the=key=etements~orski'n'1not1;"'tllrtztn-g~C[)rae~(}
15)'~.============
Seaweeds rich in amino acids, especially serine, such as Undaria pinnatifula. are therefore of particular interest here, as are those rich in polyunsaturated fatty acids (Cardozo
et aI., 2007; Kim et al., 2013). Fatty acids enable the reconstruction of the intercellular
cement and thus reinforce the skin barrier. Among the fatty acids, linoleic acid should
be mentioned; this is an omega 6 polyunsaturated fatty acid that is proving to be particularly effective. The increased transepidermal water loss (TEWL) may be returned
to normal by the introduction of linoleic acid to the diet or by the cutaneous application
of linoleic acid (Basnayake and Sinclair, 1956; Prottey et al., 1975). In general, the ability to restore TEWL to normal resides within the n-6 family of essential fatty acids and
specifically in the 18 carbon atom fatty acids, linoleic acid and v-Iinolenic acid (Hartop
and Prottey, 1974; Ziboh and Chapkin, 1987; Campos et al., 2006; Cano et al., 2007).
Blidingia minima is a species of the family of Ulvaceae, described by Johann
Kylin in 1947. A patent filed in 2009 by Jean-Noël Thorel, founder of the BiodermaEsthederm group, proposes the lise of an aqueous extract of this alga in order to
"improve the state of the skin." It apparently contains a polysaccharide with moisturizing properties.
Moreover, DNA extracted from algae can be used for skin moisturization, including extracts obtained from U. pinnatifida, Durvillaea antarctica, and Ascophyllum
nodosum.
It seems important to pay special attention to the harvesting locations and calendar, as seasonal variations of the compositions are now well known. The concentrations in molecules of interest fluctuate, as does the content in unwanted elements
such as heavy metals (Davis et al., 2003).
Algae Extracts as Active Ingredients for Antiaging Products
The antiaging products sector is in good shape. The reason for this is the present age
of the baby boomers, as evidenced by the wide range of products offered by cosmetics laboratories.
Reminders About Skin Aging
Aging is an unavoidable, slow, and complex phenomenon with intrinsic (mainly
genetic) as well as extrinsic or environmental
causes, with chronic exposure to
428
CHAPTER 14 Seaweed Application in Cosmetics
radiation playing a major role. Solar exposure (natural or in a tanning booth), tobacco,
and exposure to bad weather (wind, etc.) stand out among these causes. We cannot
speak about aging without talking about Dr Denham Hannan and his free-radical
theory of aging. This justifies the use of antioxidant substances such as vitamin C,
vitamin E, retinol, and coenzyme Q-I O.The use of ascorbic acid is all the more justified as this active ingredient is capable of stimulating the synthesis of type I and type
ITprocollagen by fibroblasts (Tajima and Pinnell, 1996; Thomas et al., 2013). These
antioxidant properties allow it to protect the natural antioxidant systems present in
the skin (superoxide dismutase, gluthatione peroxidase, etc.) (Jagetia et al., 2003).
Wrinkles, which are a visible sign of aging, are deemed age indicators. In 1985
they were classified by Kligman. He distinguished three types of wrinkle: crinkles,
~~~~~~~~~~~~!n0npermanent=wrinktenhât=disapp-e:arwhen=tln;-s1ITITis-strercl:reâ·
anël-aTe-liï1tS ââ'--'t""o========
the degradation of the elastic fibers of the dermis, which is a type of early-onset
degradation as it starts as early as 30 years of age; glyphic wrinkles, wrinkles that are
permanent and correspond to the accentuation of the cutaneous or dermatoglyphic
microrelief; and facial linear wrinkles, which are permanent wrinkles corresponding
to expression lines (Hatzisn, 2(04).
The Advantage of Algae in the Field of Antiaging
Stimulating collagen synthesis is still one of the mechanisms most frequently
employed to combat wrinkles. SEPPTC, a supplier of ingredients for the cosmetics
industry, is offering a lipophilic extract of an edible brown alga, Alaria esculenta
(Kalpariane= AD). A significant reduction of cutaneous progerin has been demonstrated (Verdy et al., 2011). The mutated form of the gene implicated in over 90% of
the known cases of progeria or Hutchinson-Gilford syndrome, which is characterized by accelerated aging, was identified in the early 2000s. The gene involved is
the LMNA gene, which is located on chromosome 1 and codes for the lamin A and
C proteins. The mutated form of this gene produces a truncated protein, progerin,
which remains anchored to the nuclear membrane in cells, where it accumulates
and causes dysfunctions (De Sander-Giovannoli et al., 2003; Eriksson et al., 2003;
Goldman et aI., 2(03). Tnaddition, the A. esculenta extract is apparently capable of
significantly reducing the expression of the Pmel l ? gene implicated in the transfer
of melanin to melanosomes, Hence applications in the area of age spot removal are
conceivable (Verdy et al., 2(12). The selling points of Kalpariane'" AD are limited
to claims that it increases the firmness and elasticity of the skin when used at a recommended dose of I % in the formulated product. A. esculenta extract is one of the
active ingredients of Algologie Firming Anti-Dark Spot Serum".
The matricines have potential for stimulating collagen synthesis. They are composed of short chains of amino acids «20 amino acids). These peptides are capable
of stimulating collagen synthesis. They are obtained by collagen proteolysis. The
(lysyl-threonyl-threonyl-lysyl-serine)
and (glycy I-L-histidyl-L-Iysine) sequences
are especially effective. It should be noted that the hydrophilic nature and therefore
the minimal skin penetration of these peptides makes them weak antiwrinkle agents
(Couteau and Coiffard, 2012). It is therefore essential to increase their lipophilicity by
Macroalgae as a Source of Active Ingredients
========~.
429
grafting them to a fatty chain. The palmitoylated peptides, for example, are obtained
in this manner (Chirita et aI., 2009). A combination of Meristotheca dakarensis and
J. rubens is being offered on the market, with the claim of restructuring the epidermis
by stimulating the synthesis of keratin K14, glycosaminoglycans (GAGs), and collagens I and m. More particularly the red alga M. dakarensis (Solieriaceae, Gigartinales) has the feature of being endemic to Senegal (Faye et aI., 2004).
An aqueous extract of Macrocystis pyrifera, a brown alga in the family Laminariaceae, is available on the market. It supposedly stimulates the synthesis of
hyaluronic acid. Hyaluronic acid was first used in 1968 for treating a burn victim. It
is a principal component of the extracellular matrix of the skin (Price et al., 2007).
In the 1990s, plastic surgeons began exploiting the volume properties of this mol€Ule=f0f-StHt)cthing-wrinkles-a1Td-tortreatin-g\Toillme~hYSl>~(A-s-c:lrerët-al-:-;=2004--'F.===========
Twenty years later, hyaluronic acid is still being used (Park et al., 2011) in both the
medical field and in the cosmetics field. While the efficacy of this active ingredient
in plastic surgery is an established fact, this is not the case in the cosmetics field.
For maximum efficacy, hyaluronic acid must penetrate the dermis. In order to do so
it must be applied to the skin in the "right" carrier (Kong et al., 20 11). M. pyrifera
extract may also stimulate the synthesis of syndecan-a, a protein encoded by the
SDC4 gene. Humans contain four SDC genes: SDC1, SDC2, and SDC3, which are
expressed in a tissue-specific manner, and SDC4, which is expressed in a variety
of cell types (Xian et aI., 20 10). Its influence on life expectancy may be linked to
its role in lipid homeostasis (Rose et aI., 20 J 5). It is still too early to say whether
the topical application of a syndecan-4 stimulating molecule or extract could have
observable effects on skin aging.
Another interesting line of research lies in metalloproteinase inhibition. The matrix
metalloproteinases (MMPs), a family of endopeptidases capable of breaking down
the constituents of the extracellular matrix, playa key role in biological processes
(Sternlicht and Werb, 200 I). These roles are linked to the fact that MMPs intervene
in the regulation of the synthesis and secretion of cytokines and growth factors. In the
skin, they apparently playa substantial role in wrinkle formation (Hu et aI., 2002; Sang
et al., 2006). Discovering an extract of algal origin with inhibitory properties toward
MMPs is thus a major scientific and economic challenge. The brown alga Ecklonia
cava has already proven to be an interesting candidate because of the phlorotannins
(eckol and dieckol) (Fig. 14.1) that it contains (Kim et al., 2006; Joe et al., 2006).
Since they are also able to inhibit tyrosinase (Soo-Jin et al., 2009) these molecules are all the more interesting. We shall return to this aspect later. Also worth
investigating is the red alga Corallina pilulifera. A methanol extract of this species
reduced the expression of UV-induced MMP-2 and -9 in human dermal fibroblast
(Ryu et al., 2009). However, it is important to point out that such an extract cannot
have direct applications in a cosmetic because methanol is on the list of substances
prohibited for this type of use (Annex II of EC Regulation no. 1223/2009).
A strengthening of the dermoepidermaI junction by stimulating the synthesis of
laminin-5 and collagen IV in conjunction with stimulating the synthesis of GAGs
and collagen I by means of an aqueous extract of Caulerpa leruillifera. a seaweed
430
CHAPTER 14 Seaweed Application in Cosmetics
OH
(A)
O~OH
HOhOA
yoVO>I
OH
OH
h0*:'h
(8)
HO
.
0
'?',
HO*OH
OH
HO
OH
OH
0
OH
~~
b~O
JlÂ_OH
HO
FIGURE 14.1
Chemical structure of eckol (A) and dieckol (B).
used in Japanese cuisine, is conceivable. C. lentillifera is known for its polyphenol,
sterol, vitamin, and mineral content (Matanjun et al., 2010), but no scientific study
has documented that it has any special properties for the skin.
The moisturizing active ingredients are of just as much interest here as we know
that skin aging is accompanied by drying of the epidermis. Carotenoids, first of all,
are yellow/orange liposoluble pigments. These linear polyenes derived from isoprene
are composed of eight units to five carbon atoms in which single and double bonds
alternate (Fig. 14.1). Their role is to inhibit the formation of reactive oxygen species. ~-Carotene tops this family of pigments. It is the main carotenoid produced by
the halotolerant microalga Dunaliella salina, which is capable of producing more
than 10% in relation to its dry weight (de Jesus Raposo et al., 2013). ~-Carotene is
known to have a large provitamin A activity, hence its interest for use in antiaging
products. Fucoxanthin (Fig. 14.2) is the molecule responsible for the color of kelp
and of certain diatoms. It has an original structure, including an unusual allenic bond
and 5,6-monoepoxide (Lorenz and Cysewski, 2000; Ratih and Se-Kwon, 2011).
Macroalgae as a Source of Active Ingredients
(A)
OH
0
:::tt)__
(C)
HO
(D)
iX~
~
OH
~
~
~
~
~
~
HO
OH
(E)
~
~
~
~
~
~
~
~
FIGURE 14.2
Some imoortant carotenoids produced by algae. (A) Astaxanth!n, (B) ~-carotene, (C) fucoxanthin, (0) zeaxanthin, (E) violaxanthin.
Astaxanthin (Fig. 14 2) has applications in the field of antiaging thanks to its
remarkable antioxidant properties, which are much greater than a-tocopherol
(Terao, 1989).
Fucoxanthin has been identified as the predominant carotenoid in the brown
algae. Its concentration is greater than that of ~-carotene. In the red and green algae,
lutein and zeaxanthin are the carotenoids that predominate over ~-carotene.
431
432
CHAPTER 14 Seaweed Application in Cosmetics
Algae Extracts as Active Ingredients in the Field of Topical
Photoprotection
uv radiation is one of the major stress factors for most phototrophic organisms found in
land and sea ecosystems. When confronted with this type of aggression these organisms
develop means of protecting themselves, which can be used to protect human skin. The
substances of interest in this field are first and foremost mycosporine-like amino acids
(MAAs) (palythine, shinorine, usujirene, etc.) found in numerous matine organisms and
characterized by a maximum absorption of between 310 and 360mn, in the UVA region
(Ramjee et al., 2010). Certain red algae (ie, Porphyra umbilicalisi are already exploited
on an industrial scale because of their high MAA content. An aqueous extract of P
umbilicalis (Helionori'", Gelyma) has been on the market for a number of years. The
===========~abs0rptiEm-m:aximum=i
-;:,'3t)nm7'Manyo1lrcrulgaecould a'lso o·e-a resource roD~e=ta~p""'p~e""'â~======~
in the future (Carrero and Carignan, 20 I 1). This applies to Pa/maria palmata (Yuan
et al., 2009), for example, and also Solieria chordalis, a proliferous alga that causes
recurrent problems because of its accumulation on French beaches (Stengel et al., 2011).
The potential level of protection in the UVB and UVA domains, indicated by the sun
protection factor and the UVAprotection factor, respectively, still has to be quantified.
Indeed molecules such as fucosterol (Fig. 14.3) are of real interest given that they
are likely to decrease the UVB-induced expression of matrix metalloproteinase-l ,
interleukin-ô, phospho-c-Jun, and phospho-c-Fos significantly (Kim et al., 2013;
Hwang et al., 2014).
Algae Extracts as Active Ingredients in the Field of Skin Whitening
Skin lightening is a widespread practice, especially in Asia (Numata et al., 2005). In
Western countries there is a greater focus on the search for an "antispot" effect, Special
products are required for this. Most of them are formulated using tyrosine inhibitors
such as kojic acid or arbutin (Hu et al., 2009; Noh et al., 2009). Indeed tyrosinase
catalyzes two distinct significant reactions in melanin synthesis: the hydroxylation of
t-tyrosine to 3,4-dihydroxY-L-phenylalanine (ï.-dopa) and the oxidation of r.-dopa to
dopaquinone, followed by further conversion to melanin. Sun exposure increases the
synthesis of both tyrosinase and melanosornes. Tthas been reported that the fucoxanthin extract of L. japonica acts as a tyrosinase inhibitor (Thomas and Kim, 2013).
HO
FIGURE 14.3
Chemical structure of fucosterol.
Seaweeds as a Source of Excipients
Table 14.2 Examples of Some Lightening Ingredients
Trade Name
Supplier
Algal Species
Claimed Properties
Algowhite
Codif Recherche&
Nature
Gelyma
Ascophyl/um
nodosum
Inhibitionof melaninsynthesis
Lightoceane
Halidrys
siliquosa
Melanogenesiscontrol, decrease
of tyrosinaseactivity,decrease of
melaninsynthesis,reduction of
melanosometransfer to keratinocytes, protection against free
radicals,protection against UVAl
UVB radiations,protection of the
=~~~~~~~~~~~~~~I~=~~~~~~II~~~~~~i~.deLOlaLmatljx_agaiQSLp[oteases,~=~~~~~~~~~==
Sea Shine
Seppic
Undaria
Significantreduction of the
pinnatifida
expressionof severalgenes,
enzymes,and proteins involved
in melanosomesynthesis, in the
migration of melanocytesto keratinocytes, and in the absorption
of melanosomesby keratinocytes
This effect is linked to its antioxidant activity. A large number of species were screened
in an effort to find new ingredients or extracts suitable for use as skin lighteners. Extracts
of Endarachne binghamiae.Schizymenia dubyi, E. cava, and Sargassum siliquastrum
have already proven to be good candidates. In terms of tyrosinase inhibition, results
equivalent to those of the standard molecule, kojic acid, have been obtained. A Dietyopteris membranacea extract is available from Codif. It is one of the active ingredients
of the product Algoblanc®~Dark Spot Intensive Corrector (Algotherm).
Given that kojic acid was once suspected of being mutagenic but has since evidently been cleared of all suspicion (Wei et al., 1991; Burnett et al., 2010) and that
arbutin (a hydroquinone beta-glucoside) can pose certain toxicological problems
because of its nature (Blaut et al., 2006), this search turns out to be even more important. Table 14.2 lists extracts currently sold in France and their selling points.
Much research still needs to be done in view of the fact that it is very often difficult to extrapolate from results obtained in vitro. Indeed, in actual practice it turns
out that not all of the extracts shown to be tyrosine inhibitors in vitro necessarily have
an effect in vivo on skin spots.
SEAWEEDS AS A SOURCE OF EXCIPIENTS
Carrageenans are gelling or thickening agents of algal origin obtained from various
Rhodophyceae of the genera Eucheuma, Chondrus, and Gigartina where they are
constituents of the cell walls. They are polyholosides (more precisely o-galactans)
and are more or less sulfated. The common pattern is an alternation of a (I ->3) and ~
433
434
CHAPTER 14 Seaweed Application in Cosmetics
(1-4) bonds between the residues of n-galactose (Bellion ct al., 1983). The proportion of groups of sulfates that arc present conditions the solubility of the molecule.
Four types of carrageenan can be distinguished, called K, l"~ À (Fig. 14.4), and fJ..
Their name seems to come from the region of Carragheen, on the south coast of
Ireland, whose inhabitants used these red seaweed extracts for food and medicine
more than 600years ago (Prajapari et al., 2014)
Their way of gelling was demonstrated by Rees about 40years ago. Indeed the study
of the diffraction spectra of X-rays showed that l- and x-carrageenates could form single
or double helices. The double helix is stabilized by the interchain hydrogen bonds. The
constitution of the three-dimensional network is attributed to the presence of galactose6-sulfate and galactose-2,6-disulfate,
which breaks the stereoregularity of the chain.
These patterns form "bends" forcing each chain to combine In a double helix with several
neighboring chains. The association of the double helices between themselves (which
leads to aggregates) is limited because of electrostatic repulsion, giving an elastic gel,
without syneresis. A divalent cation is necessary for gelation CRees, 1963, 1972).
À-Carrageenates are considered more as thickeners and K- and z-carrageenates as
gelling agents.
These gelling agents are used in the field of oral and dental care to formulate
toothpaste. They are used specifically in the field of topically applied dental care
products. but they should be used more widely by the cosmetics industry because of
their interesting psychosensory and moisturizing properties.
In addition, alginates should be mentioned. Sodium alginate is a polymer of
L-guluronic acid and n-mannuronic acid (Fig. 14.5), which is obtained from various
brown algae, mainly Laminaria digitata (Ahmed et al., 2014).
,~--:_J.:~ "
~o~
HJF);"
o
H
H ~
À
FIGURE 14.4
Structure of carrageenans
FIGURE 14.5
Chemical structure of sodium alginate
:::ro\
H
It
OSO,
H
K
Seaweeds as a Source of Additives
SEAWEEDS AS A SOURCE OF ADDITIVES
SEAWEEDS AS A SOURCE OF PRESERVATIVES
The preservatives that are authorized for use in cosmetics in Europe are listed in
Regulation (EC) 1223/2009, Annex V. They include parabens. They are a family of
antimicrobial preservatives derived from p-hydroxybenzoic acid that were at the center of controversy about 10years ago. Although the first publication that reported a
certain estrogenic effect of parabens was published in 1998 (Routledge et al., 1998),
the controversy started in earnest six years later when Philippa Darbre established a
link, hastily to say the least between the occurrence of breast cancer and the use of
deodorants containing parabens (Dm'bre et al., 2004). The information, which was
~~~~~~~~=q;'-;uccl:-;:c"kr.ly7:s""'p"-"r=eaâl3y
teme ia, caused panic among the users of these products and the
cosmetics industry was forced to formulate paraben-free products. However, paraben free does not mean preservative free and substitutes had to be found. Some of
them failed quickly in terms of skin tolerance. This included methylisothiazolinone,
previously known for its sensitizing properties (de Groot et al., 1988; de Groot and
Herxheimer, 1989; Bruze et al., 1989; Larsen, 1989; Aerts et al., 2014) and it is
surprising that this had been thought of as a replacement for parabens. In this context, seaweed extracts with a high antibacterial and/or antifungal activity should be
considered with interest. Even though certain molecules were isolated over 40years
ago, it is clear that concrete applications are currently nonexistent because of the
other properties of these molecules. For example, pachydictyol A (Fig. 14.6), which
is a diterpene alcohol isolated by Hirschfeld at the beginning of the 1970s from
the brown seaweed called Pachydictyon coriaceum, cannot be used in the cosmetics industry because of its significant cytotoxic properties (Hirschfeld et al., 1973;
Caamal-Fuentes et al., 2014).
Studies have highlighted the inhibiting properties of extracts of Himanthalia
elongata and Synechocystis spp, regarding Escherichia coli and Staphylococcus
aureus (Plaza et al., 2010; Gyawali et al., 2014). It remains to be seen whether such
extracts are compatible with use in cosmetics.
FIGURE 14.6
Chemical structure of pachydictyol A.
435
436
CHAPTER 14 Seaweed Application in Cosmetics
FIGURE 14.7
Phycocyanin.
SEAWEEDS AS A SOURCE OF DYES
We previously mentioned carotenoids as antiaging active ingredients. Another group
of pigments found in algae are phycobil iproteins. These are water-soluble fluorescent
proteins that are the main light-harvesting pigments of photosystem II in Cyanobacteria and Rhodophyta. The phycobiliproteins include phycoerythrin (Fig. 14.7), a
blue molecule known for its antioxidant and anti free radical properties (Gunjan et al.,
2009; Ratih and Se-Kwon, 2011; Dumay et aL, 2014; Hsiao- Wei et al., 2014).
The main sources of phycoerythrin and phycocyanin are currently PorphyridiUI17 cruentum, a red microalga, and Spiruline platensis, a cyanobacterium (de Jesus
Raposo et al., 2013).
SEAWEEDS AS A SOURCE OF AROMAS AND FRAGRANCES
Although the perfume industry has used ambergris. an intestinal concretion produced
by sperm whales (Rice, 2009), as a fixative for a long time, nowadays it has been
replaced by a synthetic substitute, Ambrox" (Snowden and Linder, 199 I). Despite
fairly intense research in this field, there are few raw materials of this type in the
marine world. We can, however, mention Algarol, an extract of Fucus vesiculosus,
used to bring a marine note to fragrance compositions.
CONCLUSION
Algae are easily accessible resources and can be used for innovative formulations by
the cosmetics industry. Excipients, active ingredients, and additives, all categories
of raw materials that go into cosmetics, can come from the sea. Numerous concrete
applications already exist, while only a few currently concern the field of photoprotection. It would seem, however, that extracts may turn out to be very promising in
the future.
In keeping with the Nagoya Protocol, the quality of the source material must
always be ensured by verifying the absence of contaminants (in particular heavy
metals) and the compatibility of the selected extraction solvent with a cosmetic use.
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