Sunteți pe pagina 1din 9

International Journal of Cosmetic Science, 2012, 34, 502510

doi: 10.1111/j.1468-2494.2012.00744.x

Review Article

Emollients are more than sensory ingredients: the case of


Isostearyl Isostearate
J. C. Dederen*, B. Chavan and A. V. Rawlings
*Croda Consumer Care Europe, Dorpsstraat 144a, B-3078, Meerbeek, Belgium, Croda Consumer Care Europe, Goole, East Yorkshire, U.K. and AVR
Consulting Ltd, Northwich, Cheshire, U.K.

Received 8 July 2012, Accepted 18 July 2012

Keywords: emollient, isostearates, lipid packing, moisturization, sensory

Synopsis
In order to understand the skin benefits of emollient oil ingredients
in topical skin moisturizers, one single highly popular in vivo
method (corneometry), even when executed to perfection, does not
suffice. A systematical exploration using a combination of bioengineering techniques shows how a previously unaccounted for mechanism of moisturization by internal occlusion was discovered. As a
result, Isostearyl Isostearate turns out to be a highly functional
moisturizer when several methodologies are used.
sume

Re
Pour comprendre les benefices des huiles emollientes dans des
hydratants cutanes topiques, il ne suffit pas dutiliser une seule
methode in vivo pourtant tre`s populaire (corneometrie), meme si
elle est executee a` la perfection. Une exploration systematique utilisant une combinaison de techniques de bio-ingenierie montre comment un mecanisme dhydratation par occlusion interne jusque-la`
inconnu a ete decouvert. En consequence, lisostearyl-isostearate
save`re etre un hydratant hautement fonctionnel quand on utilise
plusieurs methodes danalyse.

Introduction
As a contribution to this commemorative issue, we have chosen to
review 10 years of research by Johann Wiechers on the function of
emollients in skin care emulsions.
Moving from a fundamental science environment into a cosmetic ingredients research position in 1995, the pharmacist
Wiechers was struck by the limited understanding of the effect and
performance on skin by so-called inert oil ingredients offered in
hundreds of different chemical flavours. He therefore undertook an
ambitious journey into unravelling step by step the functional
contributions of individual ingredients to a complete skin care
formulation.
Employed by a lipid-producing oleochemical company (Unichema,
now Croda), he started by studying the effect of emollients trying
to understand what exactly moisturizes the skin meant as a
Correspondence: Joseph C. Dederen, Croda Consumer Care Europe, Dorpsstraat 144a, B-3078 Meerbeek, Belgium. Tel.: +3227598951; fax:
+3227598953; e-mail: chris.dederen@croda.com

502

cosmetic claim. The objective was to put more objective science in


selection, design and formulation of lipids.
Emollients, multifunctional cosmetic ingredients
Wiechers has always been concerned with the functional claims
that are made on skin care cosmetics and he was very aware of
the multitude of claim substantiation methods that are being put
forward by product developers [1, 2].
Through a holistic approach, he studied the effect of individual,
blended and formulated emollients in two major segments of cosmetic formulation:
(i) the delivery of (oil soluble) actives [3, 4], which became his
main area of focus in the recent past and (ii) the mechanical properties of the skin resulting in a defined tactile sensory perception [5
7] and fundamentally defined by moisturization and elasticity
effects induced by cosmetic ingredients.
Because the methodological and innovative approach Wiechers
chose to follow, it is these latter effects we would like to relate in
this review.
In this paper, emollients are defined as the liquid oily components of skin care formulations (O/W, W/O, oleogels, ointments).
This is the cosmetic definition; in a health care context, often the
whole formulation is called emollient in reference to the plasticizing and smoothing effect on a rough and dry skin surface.
Emollients are multifunctional ingredients supporting multiple
formulation claims: skin-feel agents, solvents for numerous active
ingredients and skin benefit agents, permeation enhancers, particle
coating and suspension stabilizers, skin protectants against damaging environments, gloss and shine control agents in make-up formulations or essential skin lipid supplements.
Adjusted to individual skin conditions, all these functions and
claims must meet different standards of chemical preferences, of
real or perceived safety and sustainability and of availability and
cost-effectiveness.
No wonder hundreds of emollients have been commercialized
over the past 60 years and their number keeps on growing.
A formulators first-line approach in selecting emollients is by
subjective judgment of the tactile sensory properties of the neat oils
[8, 9]. This is because the most obvious function of an emollient is
its lubricating and friction-reducing skin surface effect: it reduces
friction forces exerted on the skin surface through contacts with the

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie

J. C. Dederen et al.

Emollients are more than sensory ingredients

environment (skin-to-skin, clothing-to-skin, etc.) and thereby alleviates possible sources of discomfort and irritation. Residual film thickness, dynamic spreading and oil viscosity can explain many but not
all of these lubrication effects. But skin is not an inert, rigid surface.
The compliant and elastic nature of living human skin tissue complicates the picture and the act of applying emollients introduces a
time dependence of the intrinsic friction properties: emollients
directly and indirectly modify the mechanical properties of skin and
adapted measuring methods had to be developed [1016].
By simply placing a dried piece of stratum corneum in different
liquid environments, Blank [17] realized already 60 years ago that
water is the most effective skin plasticizer and that neat emollient
oils do not have any plasticizing effect on dry skin (or on hair,
which is chemically comparable [18]). However, Blanks conclusions were erroneous at that time as he had not considered the
natural flux of water through the skin namely transepidermal
water loss (TEWL).
Because oil and water are sparingly miscible, it seemed logical
that applying a thin layer of oil on the skin surface could contribute to skin water-loss prevention by simple occlusion. Hence, by
reducing the water gradient in the upper layers of the skin, emollients can be considered as indirect skin moisturizers.
Moisturization is the most basic consumer expectation of a cosmetic skin care emulsion and therefore the most common functional cosmetic claim [19, 20]. The core challenge for any cosmetic
chemist is to master the water-binding capacity in the upper layers
of the skin and at the same time respect tactile sensory aesthetics
thereby delivering an improvement in the signs and symptoms of
dry skin. Again, the connection between skin mechanical properties, moisture gradient and individual classes of cosmetic ingredients was realized long time ago [21].
Emollients are not created equal
Starting from this simple physical water-barrier model of occlusion,
many authors devised equally simple tests to rank lipids and formulations [2227]. The general principle of an occlusivity measurement method is to determine the rate of evaporation from a
water-saturated closed compartment through a membrane upon
which a standardized amount of lipid or formulation is placed. The
rate of evaporation is typically determined gravimetrically or with
a transepidermal water-loss measuring tool.
From such a simple test, it appeared already decades ago that
different emollient oils exhibit different occlusive effects. Neat semisolid petrolatum always seems to come out on top of the occlusivity
ranking. However, as soon as other lipids are admixed to it, the
effectiveness of stopping water vapour transmission drops. Other
than a speculative judgment on the molecular packing density (or
porosity) in the oil film, there does not seem to be an apparent
structural chemistry logic in the ranking. Nor is the ranking order
the same in different studies: choice of membrane, emollient
concentration and detection method seem to introduce artefacts
[28, 29].
Although Wiechers recognized the existence of occlusivity as a
moisture-control mechanism, he did not pursue this simple in vitro
methodology as an emollient ranking strategy. Instead, he chose to
measure effects in vivo [30, 31].
Because of the novel and unusual approach, the size and cost of
this multi-year project, Wiechers paid great attention to the experimental detail of the testing methodology, its repeatability and statistical interpretation.

Wiechers decided to work with 20-person human panels and


characterize and rank 50 emollients by their moisturization (M,
enhanced SC water content), elasticity (E, plasticizing effect on SC)
and substantivity (S, mobility of the emollient on the SC surface)
performance relative to industry-accepted and well-documented
gold standards of performance.
These 100% performance references were respectively glycerine
for moisturization, water (applied 30 min under occlusion) for elasticity and petrolatum for substantivity. The negative control was
untreated skin.
The chosen measuring tools were the Corneometer CM820 for
moisturization, the Dermal Torque Meter for skin elasticity and the
Sebumeter 820PC for substantivity.
The choice of the Corneometer has been questioned frequently:
others would have preferred a TEWL measurement. Wiechers
defended his choice by defining moisturization performance as a
more direct measure of the moisture present in the top layers of
the skin (with a Corneometer) rather than estimating it from measuring the rate of moisture loss from the skin (with a TEWLmeasuring device). Furthermore, at the time of the study, accuracy
of TEWL equipment required larger test panels and even tighter
controlled testing protocols.
The relative performance of product P is expressed as
RP% 100  Pt  Ut=Ct  Ut
with P, U and C the measured value for product, untreated skin
and the control product at time t. The time variable was recognized
and RP% values were determined at 0.5, 1, 2, 4 and 6 h. The 6-h
value for the moisturization and elasticity readings and the 1-h
reading for substantivity gave the best product differentiation.
The applied product volume was 2.24l cm2; to avoid artefacts
from product-specific probe interactions, the treated skin measuring
site was gently wiped before the first measurement was taken and
the probe was wiped between each of the three repeat readings.
The advantage of working with a relative performance is that
the ranking is much less depending on intra- and interpersonal
variability, provided environmental conditions are kept standardized (tests carried out during U.K. winter season, and panellists
acclimatized at 21 1 C and 45 5 %RH).
As a result, individual emollients could be ranked by their M, E
and S relative performance as illustrated in Fig. 1.
The M, E and S ranking orders were different for different emollients. M performance was found to gradually improve from poor
to very good, whereas E and S performance offered only a few high
performers and many mediocre or poor performers, with most of
the time very little overlap between good M, E and S performers.
Using PCA multivariate statistical analysis, no correlation was
found between in vivo M and S and in vitro occlusivity data (see
Fig. 2) indicating that the mechanism of moisturization was not
(only) correlated to the skin occlusivity of the oil tested. Similarly, no
correlation was found between M-RP% and water absorbance or the
calculated skin penetration of the tested emollients (results not
shown). From this, Wiechers concluded that moisturizing emollients
do not operate through an occlusion or moisture-carrier mechanism.
More surprisingly, examining M- and E-RP% results, Wiechers
concluded that an increased moisturization performance does not
necessarily result in increased skin elasticity and that therefore a
combination of mechanisms had to be influencing what is
perceived by consumers as a positive skin response to emollient
application [33].

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

503

J. C. Dederen et al.

Emollients are more than sensory ingredients

A Moisturization
Relative performance (%)

120
Y

Measurements

100

W
V
U
S

80

Q
P
O
N
M

60

L
K
J
I
H
G

40

F
E
D
C
B
A

20
0

B Elasticity
Relative performance (%)

100

80

V
U

60

Q
P
O

N
M

40

L
K
J
I
H
G
F

20

E
D
C
B
A

C Substantivity
Relative performance (%)

120
AA

100
Z
Y

80

N
W

L
U

60

J
S

I
R

H
Q

G
P

F
E

40

D
C
B

20

Figure 1 Emollients ranked by their relative moisturization (a; 6-h reading), elasticity (b; 6-h reading) and substantivity (c; 1-h reading) performance. Arrows indicate statistical differences (P < 0.05) between individual
products.

The formulation corollary was that multiple emollients are


needed to obtain multiple effects. This was confirmed by testing
blends of good M- and E-performing emollients [34].
The impact of emollient rankings in formulation
What these M, E and S rankings meant to practical formulation
design was examined on (i) binary blends of good- and bad-performing emollients and (ii) on emollients formulated into emulsions
using the same experimental in vivo methodology [35, 36].
For each performance criterion (M, E or S) 1:0, 1:3, 1:1 and 0:1
blends of a high- and low-performing emollient were tested and the
dose effect was confirmed. The same oil blends were incorporated
at a 25% level in O/W and W/O emulsions stabilized by emulsifiers
operating by seven different stabilizing system (polymeric, liquid

504

crystal phase, anionic, non-ionic, silicone). Two emulsion systems


were also tested with an additional 6% glycerine.
The surprising results were:
1 The same functional M, E and S performance ranking order of
neat emollient blends was found for the emulsions, independent
from the emulsifier type. This meant that the clinical performance of the emollients dominated the effect of the emulsifier.
2 The choice of the emulsifier type added in a similar extent to the
performance of a good or a bad emollient. From this observation, it was concluded that an emulsifier has its particular clinical signature.
3 Six per cent glycerine addition had only a measurable benefit for
the emulsions that contained a poorly performing moisturizing
emollient.
The conclusion was that a good moisturizing (or E or S) performance depends principally on the choice of the emollients and can
be further enhanced by choosing the right emulsifier [37]. Under
the specific conditions of this experiment, the common wisdom
that W/O and liquid crystal phase containing emulsions performed
measurably better was supported.
Being aware that all these very interesting observations were
made in a clinical context devoid from any consumer perception
considerations, Wiechers also tested the connection between
sensory properties of emollients and formulations and 6-h RP%
moisturization.
Sensory testing was performed using Tragon Quantitative
Descriptive Analysis. A 13-women consumer panel, pre-screened for
high sensory acuity, developed its own set of common sensory attributes and scored them against an individual, internalized intensity
scale during and a few minutes after emollient application.
The panel did also spontaneously generate the my skin feels
moisturized descriptor for both the rub-in and afterfeel phase of
application. This descriptor correlated strongly with another sensory descriptor: skin smoothness.
Alas, no correlation could be found between clinical and sensory
moisturization, which serves as a warning that in effective formulation both clinical and sensory performance must be considered and
combined [38, 39]. This has also been observed by others [40].
And therefore, again, there is no perfect emollient combining
best clinical and sensory attributes and multiple emollients are
needed to obtain multiple effects.
A new mechanism of skin moisturization
At this point in time, Wiechers formulation research splits into
two parts: (i) a continuation of practical understanding the sensory
preference of emollient-emulsifier combinations taking also clinical
results into account [41, 42] and (ii) trying to find a fundamental
explanation of the observed M, E and S behaviour or emollients
[43, 44].
Eventually, Wiechers concentrated on the latter and more specifically on the emollient moisturizing effect by working with the
team of Bouwstra at Leiden University (Holland). They could deploy
much more sophisticated techniques than the Corneometer. For
cost and time management reasons, it was, however, no longer
possible to work with 50 emollients.
Therefore, research efforts focused on key hydrophilic and lipophilic benchmarks and structurally similar and cosmetically relevant emollients notably Isopropyl Isostearate (IPIS), which has an
M-RP% nearly identical to the benchmark glycerine and Isostearyl

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

J. C. Dederen et al.

Emollients are more than sensory ingredients

X-loadings
-Y

PC3

0.8
0.6

Ln(Substantivity)

0.4

Moisturisation

0.2
PC2

0
0.2
Occlusivity

0.4
0.4
0.2
0
0.2
0.4
0.6
0.8

PC1

0.4

0.2

0.2

0.4

0.6

0.8

Figure 2 Principal component analysis of moisturization (M-RP%), occlusivity and substantivity (S-RP%) data. Occlusivity data were obtained by testing emollients by the method described by de Vringer [32]. M, S and O vectors are nearly orthogonal indicating no correlation exists.

Isostearate (ISIS), which had been found to be a very poor moisturizer by the Corneometer measuring method [45], see Fig. 3.
Contrary to corneometry, near infra-red spectroscopy (NIR) can
take a direct look at the presence of water, albeit over a much
greater (1020 times) depth down into the dermis [46]. With NIR,
no water-content difference was observed between IPIS and ISIS,
indicating that the cause for the moisturizing difference between
IPIS and ISIS had to be sought much nearer to the skin surface
(Fig. 4).
Together with Bouwstra, the moisturizing effect of the selected
emollients was examined at cellular level [4749]. The distribution
of water in cross-sections of isolated skin could be visualized indirectly with cryo-scanning electron microscopy: zones with different
water content in swollen and flat layers are visible as contrast densities (see Fig. 5). The number of cell layers in the swollen and
non-swollen regions could be counted. The swollen region in the
cryo-SEM picture coincides with the NMF-rich (natural moisturizing factor) region of the SC.
In contrast to the oils, it was found that glycerine permeates easily through all layers of the SC and it creates a large region of
swollen corneocytes, an indication of more water being present in
the skin. Applying emollients does not increase the total amount of
water but can change the water gradient in the skin. Applied ISIS
and petrolatum showed a smaller upper non-swollen region than
IPIS, which was interpreted as a greater water content closer to
the skin surface, in contrast to the Corneometer findings.
Then, an even closer look at molecular organization of the skin
moisture barrier lipids was taken.
The layered lamellar phases in the SC consist of a mix of ceramides CER, cholesterols CHOL and free fatty acids FFA.
Two structural dimensions of this layered lipid phase need considering: a cross-sectional and a planar.
In cross-section, the sandwich model has gained wide acceptance [50]. Lamellar liquid bilayers in healthy human SC show a
dual periodicity: a short periodicity phase with a repeat distance of
approximately 6 nm and a long periodicity phase LPP with a
repeat distance of about 13 nm. Very long-chain ceramides (CER
EO types) are key to this LPP. In the centre of the LPP, a fluid
domain can be observed. It is also known that the quality of the

Figure 3 Isopropyl isostearate (IPIS) and Isostearyl Isostearate (ISIS) compared on the scale of corneometer relative moisturization performance.

LPP dominates the barrier quality in terms of moisture loss. The


periodicity of these multi-bilayer lipid stacks was studied with small
angle X-ray diffraction SAXD using an intense synchrotron radiation source.
With a lipid CER : CHOL : FFA : emollient in a 2:1:1:1 molar
ratio, lamellar lipid stacks were built up in vitro by a spraying technique (for availability reasons, pig CER are used) [51]. It did show
that at 20 molar%, the emollients got incorporated into the LPP and
induced more of the LPP in these in vitro lipid stacks. At 5 molar%,
there was no difference with the control. When a similar SAXD
experiment was carried out on tape-stripped SC, dried and immersed
in neat emollient for 24 h, no significant differences were noticed,
but the measurement resolution is much lower owing to the reduced
number of lipid bilayers compared with the in vitro method.
In the planar dimension, the density of the lateral packing of the
C-chains of the barrier lipids hand is a natural mixture of weak liquid
structures, a hexagonal packing of intermediate density and a dense
orthorhombic structure (Fig. 6). Each of these packing modes is present in a ratio depending on skin health and temperature. In healthy
skin, SC lipids are predominantly present in a dense orthorhombic
packing with very low water permeability [52].
Fourier transform infra-red spectroscopy is used to study lateral
organization of the lipid matrix and looks at shifts in C-H stretching

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

505

J. C. Dederen et al.

Emollients are more than sensory ingredients

Female, non-smoking, 45% RH, 6 h

0.002

Average untreated skin


Average IPIS-treated skin

Abs

0.001

Difference

0.001

0.002

0.003

IPIS
1650

1700

1750

1800

1850

1900

1950

2000

Female, non-smoking, 45% RH, 6 h

0.002

Average untreated skin


Average ISIS-treated skin

Abs

0.001

Difference

0.001

0.002

0.003

ISIS
1650

1700

1750

1800

1850

1900

1950

2000

Wavelength nm
Figure 4 Near infra-red spectroscopy (NIR) spectra of untreated skin and isopropyl isostearate (IPIS)-treated skin as well as a difference spectrum (top figure)
and of untreated skin, Isostearyl Isostearate (ISIS)-treated skin as well as a difference spectrum (bottom figure). Note that IPIS and ISIS can hardly be distinguished; their moisturization signal is effectively the same.

and scissoring vibrations. Below 32C, the packed lipid chains are
visible as the doublet of an orthorhombic phase and above that
temperature as the singlet of a hexagonal phase. To separate the
IR absorption signals of skin lipids from those of the applied test
lipid emollient, perdeuterated emollients, that is, d-IPIS and d-ISIS,
had to be prepared.
An in vitro experiment with a CER : CHOL : FFA : emollient in a
1:1:1:0.75 molar ratio mixture showed a clear increase in
orthorhombic packing with both IPIS and ISIS, persisting well
above 32C (Fig. 7).
Such moisturizing mechanism of barrier improvement to a denser
lipid packing had not been shown before and can be considered as a
new mechanism in addition to occlusion, with petrolatum as best
performer, and humectancy, with glycerine as industry reference.
Wiechers called it the internal occlusion mechanism [53, 54].

506

The conclusion that Wiechers eventually reached was that


lipid emollients can modify the moisture gradient in SC by operating two mechanisms simultaneously at different depths and
that the measuring method can define the performance ranking
depending on which mechanism the measuring device preferentially looks at.
To explain the IPIS > petrolatum > ISIS order of accumulated
water visible to the Corneometer, Wiechers speculated that the
smaller IPIS molecule (40% lower molar volume) penetrates easier,
more and deeper than ISIS and therefore introduces more orthorhombic packing with less moisture loss from the SC and therefore
a higher Corneometer reading [53]. Although the large, highly
apolar hydrocarbon molecules of viscous petrolatum stay at the SC
surface and cannot measurably modify the lateral packing of skin
lipids, its residual occlusive effect makes it still a better performer

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

J. C. Dederen et al.

Emollients are more than sensory ingredients

Low hydration

High
hydration
Viable
epidermis

Figure 5 Cryo-SEM of untreated human full-thickness skin demonstrating


three distinct layers within the stratum corneum: an upper non-swelling
region (dark), a swelling region (lighter) and a lower non-swelling region
(dark).

Figure 7 Fourier transform infra-red (FTIR) spectra at 32C with a ceramides (CER) : cholesterols (CHOL) : free fatty acids (FFA) (control) and
CER : CHOL : FFA + 20% isopropyl isostearate (IPIS) or Isostearyl Isostearate (ISIS) mixtures. In presence of the emollients, the characteristic orthorhombic phase doublet is still visible suggesting they induce an increased
orthorhombic lipid packing.

Figure 6 From Ref [53]: Schematic representation of the skin lipid packing:
(a) In the liquid crystalline (La or fluid) phase, the lipids display lateral and
rotational movements. In the hexagonal (Lb or gel) phase and the orthorhombic (crystalline) phase, the lateral movements are reduced. (b) The circles represent the acyl chains of the lipids. In the liquid phase, their position
is not well defined in contrast to the hexagonal and orthorhombic packing.
In the hexagonal packing, the hydrocarbon chains can freely rotate around
their axes. In the orthorhombic packing, the lipids are in a solid state and
are packed more closely in one direction indicated by the 0.37 nm spacing.
The orthorhombic packing is considered the least permeable structure,
whereas the liquid crystalline phase is highly permeable to compounds [52].

than ISIS. But the total moisture content is negligibly different


when NIR is used [53, 54].
This internal occlusion hypothesis of course now begged for
transepidermal water-loss testing: a more effective barrier to water
loss must translate in a reduced transepidermal water-loss signal.
A first attempt was made by Caussin et al. [49]. However, when
she carried out a small-scale study (four subjects, 3-h duration)
with the standard open cell Tewameter 210 apparatus, no significant benefit on TEWL could be observed.
At this point, emollient IPIS/ISIS moisturization research was
taken over by Croda, after it acquired Uniqema.
First, it was confirmed that the isostearates were not working
via simple occlusion, in line with old publications. It was reasoned
that if IPIS or ISIS could function as moisturizers by Wiechers postulated internal occlusion mechanism, these changes would probably be non-detectable by standard TEWL measurements owing to
lack of sensitivity of the standard TEWL method or instrument.
Therefore, plastic occlusion stress testing (POST) [55, 56] using
a sensitive closed cell Biox AquaFlux apparatus [57] was opted for.
By occluding the skin for 24 h after 2 mg cm2 product application and then measuring the skin surface water loss over a defined

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

507

J. C. Dederen et al.

Emollients are more than sensory ingredients

Figure 8 Two milligrams per square centimetre of Isostearyl Isostearate


(ISIS), isopropyl isostearate (IPIS) or petrolatum are applied under occlusion
for 24 h. After removing the occluding patch and removing visible surface
water under standardized conditions, skin surface water loss is followed during 5 min using an AquaFlux apparatus. The area under the curve AUC,
corrected for baseline values for each panellist, indicates if any changes of
the moisture barrier have occurred in the 24-h occlusion phase. If the AUC
is reduced compared with the control, the moisture barrier has improved.

time interval after removal of the occluding patch, the total waterholding capacity of the skin can be determined by the amount of
water accumulated behind the patch. If less water is lost through the
skin, then it is reasonable to assume a more robust SC barrier is present. By this POST method, the more performing barrier-reinforcing
emollient could effectively be identified by Pennick et al. [58].
Surprisingly, IPIS was shown to have no benefit reducing skin
surface water loss as TEWL readings after 24 hours of occlusion were
the same as the untreated site (Fig. 8). Petrolatum fared slightly better than IPIS but the best performer was ISIS, which reduced skin
surface water loss significantly compared with both petrolatum and
IPIS, P < 0.01 and P < 0.001, respectively. Albeit less distinctly, this
was still shown to be the case when the application dose was lowered, even down to 0.25 mg cm2 (three repeat applications over
3 days under occlusion).
This time only comparing ISIS to petrolatum, the in vivo performance difference with neat emollients was also confirmed in an
11-panellist 7-day application study applying a 10% O/W formulation; the POST method was applied on day 6 of the study and the
AUC determined on day 7 [59]. The AUC values of ISIS-treated
skin areas were significantly lower than the control or petrolatum,
which did not differ.

References
1. Wiechers, J.W. and Wortel, V.A.L. Creating
effective claim support packages. Cosm. Toilet. 114, 5157 (1999).
2. Wiechers, J.W. Mind over matter: cosmetic
claim substantiation issues facing the future.
Cosm. Toilet. 120, 5764 (2005).

508

Wiechers explanation of the Corneometer M-RP% ranking


(IPIS > petrolatum > ISIS) was based on greater depth of penetration of IPIS compared with ISIS owing to size differences. If correct,
this could possibly also explain why IPIS was not performing in the
POST TEWL test. Closer to the surface, the SC has a higher ratio of
hexagonal- to orthorhombic-packed lipids [60]. ISIS could be influencing this transition more effectively at the surface compared with
IPIS, which would be active further down the SC where a higher
proportion of orthorhombic-packed lipids exist and hence additional
lipid transition would not constitute much of a benefit.
Regrettably, without sufficiently sensitive techniques that look at
the effect in a direct way in vivo, the exact explanation why Corneometer and TEWL give opposing results remains unclear. Both
techniques are, however, frequently used and readily accepted as
valid in cosmetic moisturizing claim substantiation [56].
Nevertheless, ISIS together with self-assembled amphiphilic lipids
has been shown to reduce the signs and symptoms of dry skin in a
Kligman regression test. Not only did they alleviate the dryness
more quickly than a comparable mineral oil emulsion but they also
reduced the reappearance of the dry skin [61].
Conclusion
Our main conclusion from this brief review is that the skin is such
a unique and complex multilayered heterogeneous material that
trying to characterize it with the purpose of making claims on cosmetic product performance using just one measuring technique, no
matter how carefully executed, is quite risky.
In the particular example reviewed here, we could see that a
material rejected as functional by one still very popular and convenient technique (ISIS by corneometry) turns out very functional if
measured by other, more complex and refined detection methods
together with clinical testing.
Whatever the perfect emollient may be, Wiechers critical analysis of own experiments has put a third moisturization mechanism,
internal occlusion, thus far unknown to cosmetic chemists, in the
spotlight.
Last but not least, the lack of correlation when comparing the clinical vs. sensory testing results of these emollients serves as warning
that ultimately the consumer will decide which formulation is perceived to satisfy best his or her very situational skin needs.
Acknowledgement
This paper is dedicated to our deceased friend and colleague, Prof.
Dr. Johann Wiechers, whose scientific mindset made us all think
harder and more critically about experimental evidence in a cosmetic research environment. The review paper was fully funded by
Croda Consumer Care Europe. Tony Rawlings is a consultant to
Croda.

3. Wiechers, J.W., Kelly, L.K., Blease, T.G. and


Dederen, J.C. Formulating for efficacy. Int. J.
Cosm. Sci. 26, 173182 (2004).
4. Wiechers, J.W. Clinical proof for validity of
the Formulating for Efficacy concept:
enhanced skin delivery results in enhanced
skin efficacy and both can be predicted. IFSCC Magazine 12, 2937 (2001).

5. Wortel, V.A.L. and Wiechers, J.W. Skin sensory performance of individual personal care
ingredients and marketed personal care product. Food Qual. Prefer. 11, 121127 (2000).
6. Wiechers, J.W. and Wortel, V.A.L. Bridging
the language gap between cosmetic formulators and consumers. Cosm. Toilet. 115, 33
41 (2000).

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

J. C. Dederen et al.

Emollients are more than sensory ingredients

7. Wiechers, J.W., Taelman, M.-C., Wortel, V.


A.L., Verboom, C. and Dederen, J.C. Emollients and emulsifiers exert their sensory
impact in different phases of the sensory
evaluation process but how does one demonstrate the absence of such an influence?.
IFSCC Magazine 5, 99105 (2001).
8. Goldemberg, R.L. and De la Rosa, C.P.
Correlation of skin feel of emollients to their
chemical structure. J. Soc. Cosmet. Chem.
22, 635654 (1971).
9. Zeidler, U. Ueber den taktilen Eigenschaften
kosmetischer Oele. SOFW 118, 10011007
(1992).
10. Naylor, P.F. The skin surface and friction.
Br. J. Dermatol. 67, 239248 (1955).
11. Comaish, S. and Bottoms, E. The skin and
friction: deviations from Amontons laws
and the effects of hydration and lubrication.
Br. J. Dermatol. 84, 3743 (1971).
12. El-Shimi, A.F. In-vivo skin friction measurements. J. Soc. Cosmet. Chem. 28, 3751
(1977).
13. Highley, D.R., Coomey, M., DenBeste, M.
and Wolfram, L.J. Frictional properties of
the skin. J. Invest. Dermatol. 69, 303305
(1977).
14. Nakajima, K. and Narasaka, H. Evaluation
of skin surface associated with morphology
and coefficient of friction. Int. J. Cosm. Sci.
15, 135151 (1993).
15. Koudine, A.A., Barquins, M., Anthoine, P.,
Aubert, L. and Leveque, J.-L. Frictional properties of skin: proposal of a new approach.
Int. J. Cosm. Sci. 22, 1120 (2000).
16. Kusakari, K., Yoshida, M., Matsuzaki, F.,
Yanaki, T., Fukui, H. and Date, M.
Evaluation of post-application rheological
changes in cosmetics using a novel measuring device: relationship to sensory evaluation. J. Soc. Cosmet. Chem. 54, 321333
(2003).
17. Blank, I.H. Factors which influence the
water content of the stratum corneum.
J. Invest. Dermatol. 18, 433440 (1952).
18. Gamez-Garcia, M. Effects of some oils, emulsions and other aqueous systems on the
mechanical properties of hair at small deformations. J. Soc. Cosmet. Chem. 44, 6987
(2000).
19. Loden, M. and Maibach, H.I., eds. Dry Skin
and Moisturizers. CRC Press, Boca Raton
(2000).
20. Rawlings, A.V. and Leyden, J.J., eds. Skin
Moisturization. Informa healthcare, New
York (2009).
21. Takahashi, M., Yamada, M. and Machida,
Y. A new method to evaluate the softening
of cosmetic ingredients on skin. J. Soc. Cosmet. Chem. 35, 171181 (1983).

22. Hauser, M. Penetration and occlusion


properties of paraffin oil and vegetable oils
a comparison of cosmetic oils. Cossma (English edition on line) 13, 2628 (2012).
23. Hildebrandt, M. and Tannert, U. Die
Messung der okklusiven Wirkung bei
Lipidphasen. SOFW 121, 846849 (1995).
24. Cubero-Robles, E. In search of the ideal
emollient. IFSCC Conference Platja dAro
(Spain), Proceedings 2, 275295 (1993).
25. Handjani-Vila, R.M., Rondot, B. and LaChampt, F. Measurement of the moisturizing
effect. Cosm. Toilet. 91, 2530 (1976).
26. Tsutsumi, H. Effect of the residual states of
occlusive films on the skin surface upon
emolliency. IFSCC Congress Melbourne
(Australia), Proceedings 1, 38 (1978).
27. Hu, Y., Topolkaraev, V., Hiltner, A. and
Baer, E. Measurement of water vapour
transmission rate in highly permeable films.
J. Appl. Polym. Sci. 81, 16241633 (2001).
28. Tsutumi, H., Utsugi, T. and Hayashi, S.
Study on occlusivity of oil films. J. Soc. Cosmet. Chem. 30, 345356 (1979).
29. Jacobi, O. Nature of cosmetic films on the
skin. J. Soc. Cosmet. Chem. 18, 149160
(1967).
30. Wiechers, J.W. Testing relative performance.
Cosm. Toilet. 112, 7984 (1997).
31. Wiechers, J.W. A suppliers contribution to
performance testing of personal care ingredients. SOFW 123, 981990 (1997).
32. de Vringer, T. Topical preparation containing a suspension of solid lipid particles.
European Patent 0506197, Yamanouchi
Europe (1992).
33. Wiechers, J.W. and Barlow, T. Skin moisturization and elasticity originate from at least
two different mechanisms. Int. J. Cosm. Sci.
21, 425435 (1999).
34. Wiechers, J.W., Verboom, C., Wortel, V.A.L.
and Starmans, W.A. Multifunctionality:
from One in More to More in One.
Cosm. Toilet. 117, 7378 (2002).
35. Wiechers, J.W., Groenhof, F.G. and Barlow,
T. Relative performance testing of formulations. Emollients 115, 2937 (2000).
36. Wiechers, J.W., Taelman, M.-C., Barlow, T.
and Dederen, J.C. Relative performance testing of formulations: emulsifiers. Cosm. Toilet.
115, 3742 (2000).
37. Wiechers, J.W. The EEE concept: how emulsifiers and emollients work together to create more efficacious cosmetic products.
SOFW 129, 25 (2003).
38. Wiechers, J.W. Comparing instrumental and
sensory measurements of skin moisturization. Cosm. Toilet. 114, 2932 (1999).
39. Wiechers, J.W. Verbraucher messen etwas
anders. Parfuem. Kosmet 80, 5056 (1999).

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

40. Stanzl, K. Efficacy how does a regular


consumer perceive clinical test results?
Parfuem. Kosmet 77, 696699 (1996).
41. Wiechers, J.W. Molecular modeling of personal care ingredients to create specific skin
sensory characteristics. IFSCC Magazine 4,
171177 (2001).
42. Wiechers, J.W., Wortel, V.A. and Taelman,
M.-C. Formulating with a lot of sense. IFSCC
Congress Orlando (USA), CD-ROM Proceedings Poster 219 (2004).
43. Wiechers, J.W., Bouwstra, J., Burgess, A.N.
et al. A multifaceted approach to elucidating
skin moisturization and elasticity. IFSCC
Congress Edinburg (UK), CD-ROM Proceedings Poster 133 (2002).
44. Ren, X.J., Smith, C.W., Evans, K.E. et al.
Experimental testing and numerical modeling of human skin. IFSCC Magazine 8, 95
98 (2005).
45. For reference, the Corneometer M-RP% readings were: 100 for glycerin, 99 for IPIS, 50
for petrolatum and 15 for ISIS. In-vitro, IPIS
was found 3 times less efficient in stopping
the evaporation of water through a cellulosic membrane (and ISIS less than half as
efficient as petrolatum). Its worth noting
here that when a similar test was done ref.
[58] using In-Vitro Skin TM the effect of
membrane choice was clearly evidenced: the
occlusivity order was the same, with petrolatum being much more occlusive, but the
difference between IPIS and ISIS was considerably smaller.
46. Wiechers, J.W., Snieder, M., Dekker, N.A.G.
and Hansen, W.G. Factors influencing skin
moisturization signal using near-infrared
spectroscopy. IFSCC Magazine 6, 1926
(2003).
47. Bouwstra, J.A., de Graaf, A., Gooris, G.S.,
Nijsse, J., Wiechers, J.W. and van Aelst, A.C.
Water distribution and related morphology
in human stratum corneum at different
hydration levels. J. Invest. Dermatol. 120,
750758 (2003).
48. Caussin, J. Stratum Corneum Hydration, Mode
of Action of Moisturizers on a Molecular Level.
PhD Thesis. University Leiden, The Netherlands (2009).
49. Caussin, J., Gooris, G.S., Groenink, H.W.W.,
Wiechers, J.W. and Bouwstra, J.A. Interaction of lipophilic moisturizers on stratum corneum lipid domains in vitro and in vivo. Skin
Pharmacol. Physiol. 20, 175186 (2007).
50. Bouwstra, J.A., Dubbelaar, F.E.R., Gooris, G.
S. and Ponec, M. The lipid organisation in
the skin barrier. Acta Derm. Venereol. Suppl.
(Stockh) 208, 2330 (2000).
51. Groen,
D.
Stratum
Corneum
Model
Membranes: Molecular Organization in Relation

509

J. C. Dederen et al.

Emollients are more than sensory ingredients

to Skin Barrier Function. PhD Thesis, University Leiden, The Netherlands (2011).
52. Pilgram, G.S.K., Vissers, D.C.J., van der
Meulen, H., Pavel, S., Lavrijsen, S.P.M.,
Bouwstra, J.A. and Koerten, H.K. Aberrant
lipid organization in SC of patients with atopic dermatitis and lamellar ichthyosis.
J. Invest. Dermatol. 117, 710717 (2001).
53. Wiechers, J.W., Dederen, J.C. and Rawlings,
A.V. Moisturization mechanisms: internal
occlusion by orthorhombic lipid phase
stabilisers a novel mechanism of action in
Skin Moisturization. see reference 20,
Chapter 19, 309333 (2009).
54. Wiechers, J.W. Orthorhombic phase stabilization: a new mechanism for skin moisturization. Cosm. Toilet. 124, 4550 (2009).

510

55. Berardesca, E. and Maibach, H.I. Monitoring


the water-holding capacity in visually nonirritated skin by plastic occlusion stress test
(POST). Clin. Exp. Dermatol. 15, 107110
(1990).
56. Pinto, P.C., Pereira, L.M., Minhos, R. and
Rodrigues, L.M. Discriminative capacity of
compartmental modeling for the analysis of
the in-vivo epidermal water content changes
following topical application under occlusion. IFSCC Magazine 5, 8792 (2002).
57. Detailed information and literature references on the AquaFlux equipment can be
found on http://www.biox.biz/Home/Biox
KeyPubs.php, accessed Xx June 2012.
58. Pennick, G., Harrison, S., Jones, D. and
Rawlings, A.V. Superior effect of isostearyl

isostearate on improvement in stratum corneum water permeability barrier function as


examined by the plastic occlusion stress test.
Int. J. Cosm. Sci. 32, 304312 (2010).
59. Croda Crodamol ISIS product information
bulletin DC200 (2009).
60. Pilgram, G.S., Engelsma-Van Pelt, A.M.,
Bouwstra, J.A. and Koerten, H.K. Electron diffraction provides new information on human
stratum corneum lipid organization studied
in relation to depth and temperature. J.
Invest. Dermatol. 113, 403409 (1999).
61. See paper by Pennick elsewhere in this
issue.

2012 Society of Cosmetic Scientists and the Societe Francaise de Cosmetologie


International Journal of Cosmetic Science, 34, 502510

S-ar putea să vă placă și