Marine plant extracts offer superior dermal protection

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Dr Helen J. Fitton, Tess Oddie, Dr Damien Stringer,
Dr Sam Karpiniec – Marinova, Australia
MARINE INGREDIENTS
Marine plant extracts offer
superior dermal protection
Marine plants, or macroalgae, have long
been recognised for their therapeutic ability
on the skin.1 Whole seaweed was
traditionally used in various cultures for
relieving joint pain, inflammation and burns
via direct application to skin, or the addition
to bath water and topical pastes. With
modern technology and the advancement
of extraction methods, certain components
of seaweed have been able to be isolated
for more targeted use in cosmetic
formulations. These components include
algae carbohydrates such as alginates
and fucoidans and pigments such as
polyphloroglucinol and fucoxanthin.
Carbohydrate components, while typically
used for stability, viscosity and conditioning
functions, have in more recent years gained
recognition for their extensive array of
bioactivities; particularly those of fucoidans.2
Fucoidans refer to a class of fucose-rich
polysaccharides found only in brown
macroalgae. They are highly branched and
heterodisperse compounds, which are both
sulfated and acetylated. Fucoidans differ
greatly in their molecular structure and
bioactivity, depending on the type of
macroalgae they are sourced from and the
extraction method that is used. For
example, fucoidan from Undaria pinnatifida
seaweed (as seen in Figure 1) is highly
sulfated and acetylated with a backbone
containing bith fucose and galactose, while
fucoidan extracted from Fucus vesiculosus
has a backbone made predominantly of
fucose with little acetylation.
In nature, fucoidans protect algae by
creating a barrier between plant cells and
the ocean, to provide strength and flexibility
and maintain correct ionic balance. They
also work together with pigment molecules,
such as polyphloroglucinol, to protect the
plant from other harsh elements of the
environment: UV rays, pathogens and
pollutants.
Fucoidans have been shown to have a
vast array of bioactivities once isolated from
their natural source, including anti-viral
activity, anti-inflammatory effects, UV
protection, enzyme inhibition and immune
modulating activity. Polyphloroglucinols
have potent antioxidant effects and are
ABSTRACT
Two specialty macroalgae-derived extracts have been developed by leading Australian
biotechnology company Marinova, for use in cosmetic formulations. Wild-grown Undaria
pinnatifida and Fucus vesiculosus macroalgae were sourced to extract two well
characterised, certified organic fucoidan compounds: Maritech® Reverse and Maritech®
Bright. Maritech® Reverse is a highly sulfated, high purity fucoidan, while Maritech
Bright is a high purity compound comprised of both fucoidan and marine polyphenols.
Extensive clinical and in vitro testing showed both extracts offer superior cosmeceutical
benefits, particularly through anti-glycation, immune boosting and enzyme inhibitory
mechanisms and UV protecting and soothing activity. Maritech Reverse was particularly
effective at increasing the expression of wound-healing genes, while Maritech Bright
was shown to clinically reduce age spot and wrinkle appearance. The demonstrated
bioactivity of the extracts at low concentrations, in addition to their certified organic
and environmentally sustainable status, position Maritech Bright and Maritech Reverse
as two highly valuable ingredients for cosmetic formulations.
fucoidan and polyphloroglucinol that
originates from the northern hemisphere
Fucus vesiculosus species, while Maritech®
Reverse (Undaria pinnatifida extract) is a
highly sulfated, concentrated fucoidan
sourced from the Undaria pinnatifida
macroalgae. A detailed description of both
of these extracts is displayed in Table 1.
CH3
OH
O
O
OSO3–Na+
OH
O
Na+–O3SO
O
CH3
OH
OCOCH3
O
O
Skin protective properties
OSO3–Na+ O
OH
OH
O
Figure 1: Graphic of
Undaria pinnatifida
fucoidan molecule.
OCOCH3
O
known for their ability to reduce damage
caused by UV, as well as inhibiting ageing
enzymes.
Commercial-scale extraction of both
of these compounds has been developed
by Australian biotechnology company,
Marinova Pty Ltd, which specialises in coldwater extraction of brown macroalgae
bioactive compounds without the use of
harsh, traditional solvents. This includes
two highly-purified and extensively
characterised extracts developed
specifically for cosmetic applications:
Maritech® Bright and Maritech® Reverse.
Maritech® Bright (Fucus vesiculosus
extract) is a complex compound of
The human skin plays a similar role to
fucoidan in marine plants. Being the largest
organ of the human body, skin plays a
fundamental role in our existence – not
only providing definition, character and
recognition, it is also the first line of
defence against foreign bodies, UV
radiation and other external hazards.
Premature ageing, physical damage and
diseases of the skin reduce its ability to
maintain such functions. This is why
application of effective anti-ageing,
protective and healing cosmetic ingredients
is so highly valued in today’s modern
world of densely populated, polluted and
stressful living conditions.3 The following
studies were undertaken to define the
likely cosmetic bioactivity of Undaria
pinnatifida extract and Fucus vesiculosus
extract.
Glycation inhibition
Glycation is a marker for ageing skin,
defined as a non-enzymatic reaction
March 2016 P E R S O N A L C A R E
51
MARINE INGREDIENTS
60
INCI name:
Fucus vesiculosus
extract
Undaria pinnatifida
extract
50
Trade Name:
Maritech Bright
Maritech Reverse
CAS number:
84696-13-9
223751-81-3
Soothing, smoothing,
emollient, skin
conditioning
Skin protecting
COSMOS, ACO,
NOP, Halal, Kosher
COSMOS, ACO,
NOP, Halal, Kosher
58.6%
89.6%
Polyphenol
33.7%
<2%
Neutral
Carbohydrates
43.7%
48.8%
Sulfate
10.1%
27.4%
3%
9%
Certifications:
Content: Fucoidan
Cations (approx.)
between amino acids and hydroxyl groups
of naturally occurring sugars (i.e. Maillard’s
reaction). When this reaction occurs in the
dermis, it stiffens the linkages between
certain elements within the extracellular
matrix, causing a loss of flexibility and
permanent damage. Glycation is a natural
process induced by ageing, with signs
appearing around the age of 30. External
factors, including UV damage, pollution and
smoking, can accelerate this process.4
Both Undaria pinnatifida extract and
Fucus vesiculosus extract were found to
be effective inhibitors of glycation. In vitro
testing based on the methods of Kiho5 and
Choi6 demonstrated the two extracts were
more effective than a standard glycation
inhibitor (amino-guanidine) at the low
concentration of 0.1 mg/mL. At 0.2 mg/mL,
Undaria pinnatifida extract was equally as
effective at inhibiting glycation as aminoguanidine, as seen in Figure 2.
UV protecting and soothing effects
Reduction in erythema (%)
25
n Fucus vesiculosis
n Undaria pinnatifida
n Placebo
33
30
20
Amino-guanidine
15
14.7
12.1
10.6
9
Undaria pinnatafida
extract
reduction in erythema and TEWL
(respectively) in the study group that
applied gel 30 minutes before and
20±4 hours after UV exposure. Both
extracts provided significantly reduced
erythema and TEWL compared to the
placebo. While both extracts proved to
be effective protective and soothing
agents, Fucus vesiculosus extract showed
marginally higher activity than Undaria
pinnatifida extract.
In addition, extracts were assessed
for their UV absorbance ability in vitro.
Fucus vesiculosus extract exhibited superior
UV radiation absorbance in the skindamaging UVA and UVB ranges, at the
low concentration of 0.1% w/v.
Enhanced wound-healing
gene expression
Undaria pinnatifida extract strongly
activated the gene expression of wound
healing genes in UVB and UVA irradiated
reconstructed human epidermis cells
n Fucus vesiculosis
n Undaria pinnatifida
n Placebo
22.1
21.9
19.8
19.6
18.3
17.1
15
10
7.6
7.9
7.3
5
5
Fucus vesiculosus
extract
Figure 2: Per cent of glycation inhibition of Undaria pinnatifida extract
and Fucus vesiculosus extract compared to standard glycation inhibitor,
amino-guanidine, at 0.1 mg/mL and 0.2 mg/mL.
20
18.5
31
24
Both Undaria pinnatifida extract and
Fucus vesiculosus extract are clinically
effective protecting and soothing agents.
In a placebo-controlled study, 25
Caucasian subjects tested the ability of a
0.3% w/v active gel formulation to protect
from and soothe damage caused by UV
radiation. UV radiation was administered
to subjects from a solar simulator at
1.25x the minimum erythemal dose.
Erythema (reddening of the skin) and
trans-epithelial water loss (TEWL) were
the indicators of damage assessed in the
study, which were measured at different
time points following UV exposure. The
evaluation of erythema was performed by
a Mexameter MX 18 (Courage+Khazaka
electronic GmbH) and TEWL was
assessed by a Tewameter 300R
(Courage+Khazaka electronic GmbH).
A quantity of 2 mg/cm2 of active or
placebo gel was applied to the skin,
before and/or after UV exposure.
Figures 3 and 4 display the per cent
19.6
10
45
40
0
22.6
21.6
50
50
25
20
n 0.2 mg/mL
n 0.1 mg/mL
10
Reduction in TEWL (%)
INCI listing functions:
Glycation inhibition (%)
Table 1: Description of Fucus vesiculosus extract and
Undaria pinnatifida extract for cosmetic use.
8
2.6
1.4
0
2.2
2
1.6
0.2
0
0
1
2
24
Time after UV exposure (hours)
Figure 3: Per cent reduction in erythema relative to placebo
in subjects who applied gel 30 minutes prior and 20±4 hours
after UV exposure.
52
P E R S O N A L C A R E March 2016
0
1
2
24
Time after UV exposure (hours)
Figure 4: Per cent reduction in transepithelial water loss (TEWL)
relative to placebo in subjects who applied gel 30 minutes prior
and 20±4 hours after UV exposure.
MARINE INGREDIENTS
400
Singlet oxygen
387
Peroxyl
3%
4%
Hydroxyl
Peroxynitrite
7%
1%
Change (%)
300
233
229
200
226
202
100
85%
0
TLR2
TLR3
MMP1
MMP3
MMP9
Genes
Figure 5: Per cent change of gene expression in UVB and UVA irradiated
reconstructed human epidermis cells treated with Undaria pinnatifida
extract at 100 μg/mL (relative to irradiated control, after 4 hours of
exposure). TLR: Toll-like receptor; MMP: matrix metalloproteases.
in vitro, confirming previous research
observations for Undaria pinnatifida
extracts.7 Toll-like receptors (TLR) are
critical to innate immune system function.
They are expressed by keratinocytes (the
most populated cells in the epidermis) in
response to invading pathogens, aiding in
the body’s first line of defence.8 Matrix
metalloproteases (MMP) are a group of
enzymes that are involved in a wide range
of proteolytic circumstances, including
inflammation, wound healing and
angiogenesis.9
In the study, Undaria pinnatifida extract
was used to topically treat reconstructed
human keratinocytes at 30 and 100 μg/mL
concentrations and incubated for 24 hours
in vitro, to replicate histologically very
similar cultures to those that are observed
in vivo. Results were compared to placebo
treated cells. After incubation, cells were
topically treated again (with Undaria
pinnatifida extract or placebo) and
irradiated with UVB and UVA, using a
SOL500 sun simulator equipped with an
H2 filter. Cells were then topically retreated
(with active or placebo) and incubated
for a further 4 or 24 hours and frozen
at –80˚C. mRNA was extracted and
analysed on a dedicated PCR array
containing 64 target genes.
Genes for TLR2 and TLR3 were strongly
activated in the 100 μg/mL Undaria
pinnatifida extract treated assay, at 387%
and 229% respectively. In addition, there
was a substantial increase in expression
of certain extra cellular MMP genes.
Gene expression of MMP1, MMP3 and
MMP9 more than doubled in the Undaria
pinnatifida extract treated group compared
to the control at 4 hours. These results,
as seen in Figure 5, indicate an enhanced
immune system response and ‘woundhealing’ signal in UV-irradiated human
keratinocytes.
Superoxide free radical
Figure 6: ORAC 5.0 assay results for Fucus vesiculosus extract,
as per cent of total antioxidant power of 27,187μmol TE/g.
Enzyme inhibition
Enzyme stimulation is a fundamental
component of ageing.10 Elastase,
collagenase and tyrosinase are three
extracellular matrix enzymes, which cause
degradation of the skin when stimulated.
It is believed that degraded collagen fibrils
actually induce further collagenase activity
and prevent new tissue formation.
Inhibiting collagenase activity is seen as
an effective way to slow the skin ageing
process and promote new tissue formation.
Previous studies have noted the inhibitory
effects of fucoidan fractions on matrix
degrading enzymes.11,12
Both Fucus vesiculosus extract and
Undaria pinnatifida extract were effective
elastase and collagenase inhibitors in vitro,
with 99% inhibition at concentrations of
0.1 mg/mL. In addition, Fucus vesiculosus
extract was a highly effective inhibitor
of tyrosinase, with 99% inhibition at a
concentration of 0.2 mg/mL in vitro.
While in vitro findings cannot be directly
inferred to in vivo activity, this provides
positive indicative data in combination
with earlier clinical findings.
Powerful antioxidant ability
Fucus vesiculosus extract was found to
have superior antioxidant capability, due to
its high content of the marine polyphenol,
polyphloroglucinol. Fucus vesiculosus
extract was tested using the ORAC 5.0
assay, which involves measuring the
antioxidant activity of the extract in
reference to five common free radicals:
peroxyl, hydroxyl, superoxide, singlet
oxygen and peroxynitrite. Superoxide is of
particular interest in a cosmetic setting, as
it is a precursor of other free radicals and
is highly toxic to cells, contributing to DNA
damage. ORAC 5.0 assay results showed
the extract to have a total antioxidant
power of 27,187 μmol TE/g, with
particularly high activity towards the
superoxide free radical (85% of total
antioxidant activity), as seen in Figure 3.
The exceptional antioxidant power of Fucus
vesiculosus extract towards the superoxide
anion measures at 23,025 μmol TE/g,
which, to put into perspective, is
considerably higher than that of other wellknown antioxidant compounds such as
green tea extract (14,000 μmol TE/g )
and cocoa extract (406 μmol TE/g).
Reduction in wrinkles and age spots
Fucus vesiculosus extract was used in a
double-blind, placebo-controlled hemi-face
clinical trial to assess its effect on wrinkle
depth and the appearance of age spots.
The study was carried out over 60 days with
20 Caucasian participants, who applied
either a 0.3 % w/v formulation containing
Fucus vesiculosus extract or a placebo,
morning and night. Subjects were assessed
on days 0, 15, 30 and 60 for wrinkle depth
(by Primos 3D) and the melanin index of
age spots (by a Mexameter MX 18 probe).
Results of the study found the extract to
be an effective active ingredient, reducing
wrinkles and age spot appearance, as seen
in Figures 7 and 8.
Organic and
sustainable extracts
The demand for organic, sustainable, plantbased cosmetic ingredients is increasing
throughout the globe, with organics
being the fastest growing segment of the
personal care industry. Increased consumer
awareness of personal health and hygiene
and rising concerns towards environmental
pollutants is driving growth in this area.
The Asia Pacific region is the fastestgrowing region in the world in regards to
demand for organic cosmetics, with the
sector expected to grow at a CAGR of
9.5% by 2020.13
March 2016 P E R S O N A L C A R E
53
MARINE INGREDIENTS
300
n Active
n Placebo
n Active
n Placebo
280
6
6.6
Melanin index
Reduction in wrinkle depth (%)
8
5.1
4
2.8
260
240
2
1.9
220
1.2
0
0.6
15
30
60
200
0
15
Figure 7: Per cent reduction in wrinkle depth after treatment with
Fucus vesiculosus extract at 0.3% w/v.
In order to receive organic certification,
extracts must derive from organic
agriculture that respect biodiversity, use
natural resources responsibly and utilise
manufacturing processes that respect
human health and the environment. They
must also integrate ‘Green Chemistry’ –
methods that involve minimal waste and
exclude harsh chemical use. This rigorous
set of rules is stringently monitored
through comprehensive inspections and
auditing processes by the certifying body.
Both Fucus vesiculosus extract and
Undaria pinnatifida extract are the only
fucoidan compounds in the world that are
certified organic with Australian Certified
Organic (ACO), Cosmetic Organic and
Natural Standard (Cosmos) and the
United States National Organic Program
(NOP).
Wild growing Fucus vesiculosus and
Undaria pinnatifida macroalgae are
sourced to produce these cosmetic
ingredients, from the purest ocean waters
of Nova Scotia and Patagonia respectively.
All seaweed is hand harvested at their
peak growth cycle to ensure minimal
environmental impact and is then
immediately sun-dried. Dried seaweed
then undergoes a unique cold-water
extraction process to produce the isolated
ingredients, in cGMP and ISO 9001
accredited facilities. All by-products of
this process are utilised in nutrient-rich
horticultural products, thus making this
unique process zero-waste and
environmentally sustainable.
Safe and non-sensitising
All clinical tests have shown Undaria
pinnatifida extract and Fucus vesiculosus
extract to be non-sensitising and nonallergenic. Both extracts are safe to
apply topically at high concentrations,
although clinical testing demonstrate their
bioactivity at the very low concentration
of 0.3 % w/v.
54
P E R S O N A L C A R E March 2016
30
60
Time (days)
Time (days)
Figure 8: Age spot intensity after treatment with Fucus vesiculosus
extract at 0.3% w/v.
Conclusion
Maritech Reverse, an extract of Undaria
pinnatifida macroalgae and Maritech
Bright, an extract of Fucus vesiculosus
macroalgae, are two certified organic and
effective anti-ageing cosmetic ingredients.
Sourced from marine plants grown in
the purest ocean waters, Maritech Bright
and Maritech Reverse have demonstrated
anti-glycation activity and were highly
effective collagenase and elastase
inhibitors in vitro. Maritech Reverse
increased the expression of wound-healing
genes in vitro and demonstrated clinical
UV protecting and soothing effects at
0.3% w/v. Maritech Bright demonstrated
marginally higher UV protecting and
soothing effects than Maritech Reverse,
as well as reducing the appearance of
age spots and wrinkles in clinical testing.
This is most likely due to its high
polyphenol content and demonstrated
antioxidant ability.
Clinically active at the very low
concentration rate of 0.3% w/v with
organic certification and a ‘pure source’
guarantee, Maritech Reverse and Maritech
Bright combine the best elements of
science, sustainability and marketability.
These two extracts are novel bioactive
ingredients that exceed the ever-increasing
global demand for natural, sustainable,
safe and effective cosmeceutical
PC
formulations.
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