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International Journal of Cosmetic Science 21: 437447 (1999)

Horse chestnut Aesculus hippocastanum:


potential applications in cosmetic skin-care
products
J . A . W I L K I N S O N * and A . M . G . B R O W N
Herbal Research Laboratories, School of Health, Biological and Environmental Sciences, Middlesex
University, Queensway, Enfield, Middlesex EN3 4SF, UK

Received 12 March 1999


Accepted 22 April 1999
Keywords: anti-inflammatory, cosmoceutical, herbal, phytochemistry, saponin
Synopsis
In addition to the well reported beneficial effects of horse chestnut (Aesculus hippocastanum) extracts on venous
insufficiency and associated conditions, such preparations also have many potential positive pharmacological
effects on the skin. Extracts from this species, and in particular, those based on horse chestnut seeds, contain
saponins, known collectively as aescin, which have a gentle soapy feel, and are potent anti-inflammatory
compounds. Saponins, such as escin, also reduce capillary fragility, and therefore help to prevent leakage of
fluids into surrounding tissues, which can cause swelling. An extract of horse chestnut has recently been shown
to have one of the highest active-oxygen scavenging abilities of 65 different plant extracts tested. Such extracts
are more powerful anti-oxidants than vitamin E, and also exhibit potent cell-protective effects, which are linked
to the well-known anti-ageing properties of anti-oxidants.
The extract is also rich in a number of flavonoids, such as derivatives of quercetin and kaempferol.
Flavonoids also have protective effects on blood vessels, and are well-known, powerful anti-oxidants.
Resume
En plus des effets benefiques bien connus des extraits de marron dInde (Aesculus hippocastanum) sur
linsuffisance veineuse et les troubles associes, de telles preparations ont aussi de nombreux effets
pharmacologiques potentiels positifs sur la peau. Des extraits de cette esp`ece, et en particulier, ceux a` base de
graines de marron dInde, contiennent des saponines, collectivement connues comme aescine, qui ont un
toucher savonneux doux, et sont des composes anti-inflammatoires puissants. Les saponines, telles que
laescine, reduisent aussi la fragilite capillaire, et aident par consequent a` empecher la fuite des fluides dans les
tissus environnants, ce qui peut causer un gonflement. Un extrait de marron dInde sest recemment avere avoir
une capacite de capture de loxyg`ene actif parmi les plus e levees de 65 extraits de plantes differentes testes.
De tels extraits sont des anti-oxydants plus puissants que la vitamine E, et presentent aussi des effets potentiels
de protection de la cellule, qui sont lies aux proprietes anti-vieillissement bien connues des anti-oxydants.
Lextrait est aussi riche en un certain nombre de flavonodes, tels que des derives de la quercetine et du
kaempferol. Les flavonodes ont aussi des effets protecteurs sur les vaisseaux sanguins, et sont des anti-oxydants
puissants bien connus.

Introduction
In recent years, the cosmetic industry has become increasingly interested in using plantderived natural products in cosmetic formulations. This is not merely a marketing tool, but
* To whom correspondence should be addressed: (T) 144 181 362 6425; (F) 144 181 805 0702. E-mail:
J.Wilkinson@mdx.ac.uk
01425463 1999 International Journal of Cosmetic Science

438

Wilkinson and Brown

a result of the plant material itself having biological activity that is beneficial to skin [1].
The use of horse chestnut preparations as herbal medicines has been adequately described
elsewhere, so this paper therefore focuses on the biological potential of extracts from this
species as cosmoceuticals and for skin-care products.

Existing uses of Aesculus hippocastanum


Extracts of the seeds of Aesculus hippocastanum (horse chestnut) are a well established
treatment for conditions such as varicose veins, haemorrhoids, phlebitis (inflammation of
the veins), diarrhoea, fever, enlargement of the prostate gland [2], rheumatism, neuralgia
and rectal complaints [3]. Such treatments are usually administered orally, at a dose of
0.51.2 ml of liquid seed extract per day.
In addition to these uses for seed extracts, preparations from both the bark and the leaves
of A. hippocastanum are also used as therapeutic agents. The bark is no longer in common
use, but has a folk medicinal application as a febrifuge, and as an astringent in cases of
diarrhoea and haemorrhoids [4]. Decoctions of the bark are also used, albeit rarely, for the
topical treatment of skin disorders, such as sores, lupus and ulcers [4]. The bark has also
previously been used as an anti-malarial agent, as a cinchona substitute, but this practice
is no longer continued [3]. Horse chestnut leaf preparations are used in folk medicine to
treat coughs, rheumatism and arthritis, although the underlying phytochemical basis for
these applications has not been determined [3].

Chemical constituents of Aesculus hippocastanum seeds


Saponins
The total saponin content of seeds, often expressed as (a)escin (Figure 1), actually
consists of -escin and -escin, the latter of which is, in turn, composed of more than 30
derivatives of the triterpenoids, protoaescigenin and barringtogenol C. These compounds
are primarily found in the seed cotyledons (they can constitute up to 28% of the weight of
the dry seeds), but have also been detected in the seed integument, the bark, buds, leaves
and the immature fruit pericarp of A. hippocastanum [5].
Flavonoids
A number of flavonoids (mainly glycoside derivatives of quercetin and kaempferol) have
been detected in A. hippocastanum (Figure 2), including astragalin (kaempferol 3-Oglucoside), isoquercitrin (quercetin-3 -glucoside), leucocyanidin (3,3',4,4',5,7 hexahydroxyflavone) and rutin (quercetin 3-rutinoside) [3]. Most of these compounds are found in
the seeds (not including the integument), but have also been found in the fruit pericarp,
bark, leaves and buds. Results concerning quercitrin are contradictory, with different
authors reporting that this compound is present either in the leaves or in the seeds of
A. hippocastanum. [5]
In addition to these flavones, epicatechin and its dimer proanthocyanidin A2 (Figure 3)
have been reported in A. hippocastanum. These compounds are primarily found in the
bark, leaves buds and fruit pericarp, but have also been found in the seed integument.
Previously, this latter tissue has been eliminated from extracts used in the preparation of
drugs [6], but, if included, it would provide a valuable additional source of bioactive
compounds.

A. hippocastanum: potential applications in cosmetic skin-care products

escin Ia
escin Ib
desacylescin I
escin IIa
escin IIb
desacylescin II

R1
Tig
Ang
H
Tig
Ang
H

R2
Ac
Ac
H
Ac
Ac
H

439

R3
CH2OH
CH2OH
CH2OH
H
H
H

Figure 1. Selected components of the saponin mixture escin.

R 5 Rutinoside: Rutin
R 5 Rhamnoside: Quercitrin
R 5 Glucose: Isoquercitrin
R 5 Arabinoside: Quercetin 3-arabinoside

R1 5 Rutinoside: Kaempferol 3-O-rutinoside


R1 5 Rhamnoside: Kaempferol 3-O-rhamnoside
R1 5 Glucose: Astragalin
R1 5 Arabinoside: Kaempferol 3-arabinoside

Figure 2. Selected flavonoids found in Aesculus hippocastanum.

440

Wilkinson and Brown

Figure 3. Structure of proanthocyanidin A2.

Other constituents
Seeds of A. hippocastanum have also been described as containing starch (4050% weight)
[6], sugars, proteins (specifically the globulin, hippocastanine, containing L-(1)lysine and
L-(1)-tryptophan), a fatty oil (containing oleic, linoleic, linolenic, stearic and palmitic
acids) and purines (adenosine, adenine and guanine). [5]

Bark
The bark of Aesculus hippocastanum, in common with the seeds, has been described as
containing the saponin mixture escin [3]. Coumarin glycosides, including esculin,
scopolin and fraxin, and their respective aglycones, esculetin, scopoletin and fraxetin, are
also present in the bark of A. hippocastanum (Figure 4), in contrast to seed tissues, in
which these compounds have not been detected. The flavonoid glycoside quercitrin (Figure
2), and its corresponding aglycone have also been detected in bark tissues. Additional
compounds, including allantoin, sterols, leucocyanidin, leucodelphinidin, catechol tannins
and alkanes have also been described as occurring in bark tissues. [3]

R1 5 H: Aesculetin, R 5 Glucose: Aesculin


R2 5 H: Scopoletin, R 5 Glucose: Scopolin
R3 5 H: Fraxetin, R 5 Glucose: Fraxin

Figure 4. Coumarins and coumarin glycosides present in the leaves and bark of Aesculus
hippocastanum.

A. hippocastanum: potential applications in cosmetic skin-care products

441

Leaves
In common with the bark of A. hippocastanum, leaf tissues contain the coumarin
glycosides scopolin, fraxin and esculin (Figure 4) [3]. A range of flavonoid glycosides
of quercetin (e.g. quercitrin, rutin, isoquercitrin and quercetin 3-arabinoside) and the
corresponding glycosides of kaemperfol have also been detected in leaf tissues (Figure 2).
In addition to these glycosides, escin has been detected (but only in trace amounts), as well
as leucanthocyans, cis,trans-polyprenols, amino acids, fatty acids and sterols (sitosterol,
stigmasterol and campesterol).

Biological activities of horse chestnut phytochemicals


Saponins
Isolated components of the escin complex have been demonstrated to have potent antiinflammatory effects, especially on the early stages of induced inflammation [7, 8] and can
also reduce ethanol absorption and display hypoglycaemic actions when taken orally [9].
Escin also has positive therapeutic effects on the microvasculature and its surrounding
connective tissues. Such tissues are composed of cellular and fibrous components in a fluid
ground substance or extracellular matrix, which consists of proteoglycans and glucosaminoglycans, and provides support and cushioning to blood vessels and fibrous tissues.
One of the key components of this ground substance is hyaluronic acid, a proteoglycan,
which gives the extracellular matrix its viscosity.
The activity of hyaluronidase, the enzyme which breaks down hyaluronic acid, reduces
the viscosity of the ground substance [10], thus reducing its supporting and cushioning
capacity. An additional effect of this activity is that there is reduced resistance to fluid
leakage from capillary vessels, as a result of the compromised integrity of the extracellular
matrix, and hence there is an increased exchange of fluids across the microvasculature
membranes (Figure 5) [11]. Whilst this activity can be associated with pathogenic
infections (e.g. Staphylococcus aureus secretes hyaluronidase, allowing the bacterium to
move more freely through the connective tissues [10]), it has also been exploited for
beneficial effect, as injection of hyaluronidase prior to drug administration can be used to
deliberately increase capillary permeability, thus facilitating easier access of the therapeutic agent to the blood stream. One hypothesis for the oedematous symptoms associated
with venous insufficiency is that hyaluronidase activity results in increased vascular
leakage from the capillaries [11]. This hypothesis could certainly be used to explain
the beneficial effects of horse chestnut extracts on conditions resulting from venous
insufficiency, as more than one component of these extracts have been demonstrated to
display anti-hyaluronidase activity [11, 5].
The saponin mixture, escin, is one component of horse chestnut extracts capable of
inhibiting hyaluronidase activity (another is proanthocyanidin A2; see later). In the case
of escin, however, inhibition of hyaluronidase has been determined to be insufficient
to account for the powerful venotonic properties of A. hippocastanum extracts on the
microvasculature, and it has been suggested that inhibition of other enzymes, including
collagenase, elastase and -glucuronidase, all of which are involved in defining the
integrity of the extravascular matrix, might explain why extracts of A. hippocastanum were
markedly more effective than escin alone [11].

442

Wilkinson and Brown

1
Ground tissue consists of proteoglycans and glucosaminoglycans, including hyaluronic acid.
Cellular components (fibroblasts, macrophages, plasma cells, adipocytes and mast cells) and tissues
(collagen, elastic and reticular fibres) omitted for clarity.
2
Fluid leakage due to capillary permeability and density of surrounding ground substance. Increased
capillary permeability can result in oedema typical of diseases resulting from venous insufficiency.

Figure 5. Simplified representations of capillary vessel permeability in connective tissues.


Left: Permeability in tissue containing normal amounts of hyaluronic acid in ground
substance. Right: Increased permeability, as a result of reduced hyaluronic acid content
(due to hyaluronidase activity).

Flavonoids
As a class of phytochemicals, flavonoids are widely accepted as possessing a range of
biological activities [12] which may be of relevance in the context of topical application of
flavonoid-containing preparations. Some of these activities are listed in Table I.
In the specific case of horse chestnut flavonoids, rutin has been described as possessing
radical scavenging, anti-bacterial and anti-viral activities, and is also used medicinally in
the treatment of varicosis and capillary fragility [13]. Quercitrin and isoquercitrin are also
antibacterial (e.g. against Pseudomonas maltophilia), and the former additionally possesses
anti-haemorrhagic activity [13].
Proanthocyanidin A2 has been demonstrated to possess a range of biological activities,
similar to those of escin, which would be beneficial in cosmetic applications [5, and refs.
Table I. General biological activities of flavonoids
Activity
Reduction of capillary fragility and permeability
Anti-inflammatory
Anti-allergenic
Anti-bacterial
Anti-viral
Enzyme inhibitory
Activities as described in Bruneton (1995) [6]

A. hippocastanum: potential applications in cosmetic skin-care products

443

therein]. These activities are primarily venotonic and vasoprotective, such as depermeabilisation of capillaries, but also include wound healing, powerful antioxidant, antiinflammatory, and anti-enzymatic properties. In a similar manner to escin, proanthocyanidin
A2 has been shown to be able to inhibit lipid peroxidation, which is indicative of cellularprotective effects of this compound. Similarly, proteolytic enzymes in the extravascular
matrix are inhibited by proanthocyanidin A2, with -glucuronidase, elastase and collagenase all being more strongly inhibited than hyaluronidase. Compounds such as proanthocyanidin A2 may well be at least partly responsible for the differences between the
venotonic effects of escin (which inhibits hyaluronidase [11]), and the more powerful
effects of crude A. hippocastanum extracts.

Existing cosmetic applications


In 1980, the applications of horse chestnut and escin to cosmetic products were described
for treating the following areas: scalp, oral cavity, face, body, hands, legs and feet, body
hygiene, foot hygiene, intimate hygiene and prevention of haemorrhoids [14]. Recently, it
has been reported that extracts of horse chestnut [or escin at 0.250.5% (w/v)] have been
included in a range of commercial products which apply to these areas, including
shampoos, shower foams, foam baths, creams, lotions and toothpastes [15]. Horse chestnut
seeds are on the Medicines Control Agencys General Sales List in the UK [2] for external
use only. In Germany, they are the subject of a positive therapeutic monograph, indicated
for venous insufficiency, although in the United States, they are of undetermined
regulatory status [15].

Additional cosmetic applications


Recent pharmacological studies suggest that there is, in addition to the uses described
above, considerable potential for use of these extracts in cosmetic preparations in the
following categories:
Anti-ageing effects
Many reports suggest a link between skin ageing and active oxygen species, especially
when combined with ultra-violet radiation. Recently, an extract of A. hippocastanum has
been shown to be highly effective in reducing the production and damaging effects of
active oxygen species in vitro, using both biochemical and biological assays [16].
In vitro active-oxygen-scavenging properties of A. hippocastanum. An extract of A.
hippocastanum has been demonstrated to be a potent scavenger of active oxygen, being
almost 20 times more effective at absorbing superoxide anions than ascorbic acid, a
recognised anti-oxidant [16; Table II]. Similarly, the extract of A. hippocastanum reduced
the release of hydroxyl radicals and singlet oxygens in vitro, demonstrating a broad
spectrum of active oxygen scavenging properties (Table II). As these oxygen species are
associated with cellular damage and inflammation, their absorption by cosmetic preparations containing horse chestnut phytochemicals has great potential to alleviate damage to
the skin, which could ultimately be manifested as an anti-ageing effect.
In vitro cell-protective effects of A. hippocastanum. Lipid peroxidation, a process indicative
of damage to cellular membranes, was induced in vitro, under controlled conditions, and

444

Wilkinson and Brown

Table II. Superoxide-anion, hydroxyl radical and singlet oxygen scavenging activities of Aesculus
hippocastanum and antioxidants
IC50 mg (dry material) ml21
Treatment

Superoxide anions

Hydroxyl radicals

Singlet oxygens

Aesculus hippocastanum
L-Ascorbic acid
dl-a-Tocopherol
DMSO
Sodium azide

0.24 6 0.01
4.10 6 0.39
576.20 6 38.70

7.79 6 0.26
3.30 6 0.03
253.70 6 38.70
(2.55 6 0.1) 3 105

72.98 6 6.20
21.18 6 0.39

43.75 6 8.99

Data represent mean 6 standard deviation (n 5 3).


Data using L-Ascorbic acid, dl-a-Tocopherol, DMSO and Sodium azide are included as reference values,
IC50 values for these compounds are expresed as mgml21
Modified from Masaki et al., 1995 [16].

was found to be significantly reduced in experiments using A. hippocastanum extracts


[16]. Such inhibition was comparable to that obtained by including the anti-oxidant
-tocopherol in the assay. Cultured fibroblasts, which are cells usually found in the
connective tissue secreting a matrix associated with the repair and isolation of wounded
tissues, were also strongly protected by the extract of A. hippocastanum from damage
caused by active oxygen species in vitro. Almost four times the number of these cells
survived damage induced by oxygen species, generated using the hypoxanthine/xanthineoxidase system, in the presence of the A. hippocastanum extract than when the extract was
absent.
Solar protective effects
Closely linked to the anti-ageing effects of A. hippocastanum are its potential applications
in cosmetics with sun-screen properties. A recent study [17] has investigated the potential
use of plant extracts, including A. hippocastanum seed extract, as novel anti-solar agents,
based on their ability to absorb light. Such absorption is of particular interest in the ultraviolet region of the spectrum, as UV radiation has been linked with a number of cutaneous
conditions, including sunburn, photosensitivity, actinic elastosis, cutaneous degeneration
and perhaps most importantly, skin cancer [10, 17].
Although an extract of A. hippocastanum did not display significant UV-absorbing
properties when studied in isolation [in which it had a sun protection factor (SPF) of 0],
when combined with a synthetic sunscreen, octylmethoxyciunamate, significant increases
in the effectiveness of the synthetic compound were demonstrated (SPF rose from 4 to 6
on the addition of the A. hippocastanum extract; Table III). Whilst the precise reasons for
this improvement of SPF remain unresolved, the authors speculated that such an increase
may be as a result of synergistic interactions between components of the A. hippocastanum
extract and octylmethoxycinnamate [17].
Venous effects
One of the most widely used applications of A. hippocastanum is in the treatment of poor
circulation, and its associated conditions. Whilst many of these studies rely on oral
delivery of the extracts to improve circulation, conditions such as varicose veins, phlebitis

A. hippocastanum: potential applications in cosmetic skin-care products

445

Table III. Sun protection factors and UV absorptions of dry extracts


of Aesculus hippocastanum (prepared by maceration) alone, and in
combination with 2% solution of octylmethoxycinnamate.
Absorbance
Wavelength (nm)

10% dry extract

10% dry extract 1 2%


octylmethoxycinnamate

290
295
300
305
310
315
320
SPFa

0.091
0.079
0.065
0.053
0.045
0.038
0.034
0

0.528
0.569
0.598
0.625
0.651
0.625
0.553
6b

SPF 5 Sun protection factor


2% octylmethoxycinnamate has an SPF rating of 4
Modified from Ramos et al., 1996 [17].
a

and post-thrombotic syndrome have all been treated using gels containing escin [5, and
refs. therein], suggesting that the topical administration of extracts, as would be the case
in the application of cosmetics, is potentially an equally valid delivery system.
The positive effects of A. hippocastanum extracts on circulation are due to a range of
complex interactions with veins, the lymphatic system, capillaries and connective tissue.
Extracts of A. hippocastanum have been demonstrated to possess venotonic effects in vitro
and in vivo, in both animal and human systems [5, and refs. therein]. For example, A.
hippocastanum extract led to an increase in pressure of flow through both normal and
constricted isolated veins, and an increased effect of noradrenaline on increasing the blood
pressure (and consequently flow) through such vessels [18]. Similarly, capillaries have
been shown to be strengthened by administration of A. hippocastanum extract.
In addition to the direct effects of A. hippocastanum extract on blood vessels, benefit
may also be gained from the protective effects of the extract on connective tissues which
surround the capillary vessels. In chronic venous insufficiency, the capillaries become
highly permeable, resulting in water and proteins leaving the vascular system, which in
turn cause swelling; this may be as a result of the degradation of the extracellular matrix
surrounding the microvasculature (Figure 5). The main component of this extracellular
matrix is hyaluronic acid, a simple glucosaminoglycan consisting of up to several thousand
sugar residues; levels of this compound are usually regulated by the enzyme hyaluronidase,
which promotes the degradation of hyaluronic acid. Recently, escin and its aglycone,
escinol, have been demonstrated to possess non-competitive antihyaluronidase activity
(Table IV), even at concentrations well below that expected as a result of topical
application of these compounds [11].
This inhibition of hyaluronidase should lead to the recovery of the integrity of
hyaluronic acid, and consequently the extracellular matrix surrounding the microvasculature, and may therefore be responsible for some of the beneficial effects of A.
hippocastanum extracts.

446

Wilkinson and Brown


Table IV. Anti-hyaluronidase activity of selected sapogenins and saponins
IC50 (Hyaluronidase)
Sapogenins
Hederagenina (from Hedera helixc)
Oleanolic acida (from H. helixc)
Ruscogeninb (from Ruscus aesculeatusd)
Escinola (from Aesculus hippocastanume)
Saponins
Hederacoside C (from H. helixc)
a-hederin (from H. helixc)
Escin (from A. hippocastanume)
a

Triterpene sapogenin
Steroidal sapogenin
c
Obtained from leaf tissues
Modified from Facino et al., 1995 [11].

280.4 6 2.7 mM
300.2 6 3.1 mM
. 5 mM
1.65 6 0.03 mM
. 5 mM
. 5 mM
149.9 6 2.6 mM

Obtained from rhizome tissues


Obtained from seed tissues

One of the conditions associated with venous insufficiency is the development of


oedematous panniculopathies (inflammation of the sub-cutaneous layer of fat, leading to
tender nodules, typically on the thighs and breasts), and this condition has recently been
treated with phytochemicals from horse chestnut. Application of an emulsion containing
escin and biological carriers, such as -sitosterol and phosphatidylcholine, over a 30 day
treatment period, led to significant improvements to both thigh and breast pauniculopathies
in human volunteers. These improvements were ascribed to improvements in microcirculation, as recorded by Laser Doppler Flowmetry, resulting in reduced swelling and
normalisation of skin temperature [5, and refs. therein].

Conclusions
In addition to the existing uses of extracts of horse chestnut as treatments for venous
insufficiency, preparations containing phytochemicals from horse chestnut have considerable potential for inclusion in a range of cosmetic formulations. Inclusion of horse chestnut
extracts (especially those from the seeds of the plant, rather than the more poorlycharacterised extracts from leaf and bark tissue) could result in a number of beneficial
actions on the skin after topical administration. Such effects would include potent antioxidative activity, which could help decrease the visible signs of skin ageing, anti-bacterial
and anti-viral properties (largely due to flavonoids), reduction in skin reddening and
cutaneous swelling as a result of effects on capillary vessels and their surrounding connective tissues (due to saponins and the epicatechin dimer proanthocyanidin A2) and also
the potential synergistic enhancement of the efficacy (SPF) of sun screens.

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Note added in proof: Extracts of Aesculus Hippocastanum referred to in Tables II and III were
prepared in 50% ethanol [16] and ethanol [17] respectively.

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