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ELSEVIER

The Effects of Detergents on


Hydration and Skin Surface Lipids
PER THUNE, MD

W
e all know that frequent use of soaps and influencing the hygroscopicity and water-holding ca-
synthetic detergents to cleanse the skin may pacity as well as the barrier function.5-7 Increases in
lead to a dry, chappy appearance and even to TEWL values as a result of a defective water barrier and
toxic reactions and eczema. We also know that there are reservoir function are associated with less hydration
individual differences in susceptibility and that various and water-holding capacity of the skin8 It has been
products are less well tolerated than others. assumed that the ability to take in water-that is, hy-
The barrier function of the stratum corneum is cru- groscopicity-is more dependent on natural moisturiz-
cial in protecting the skin against environmental influ- ing factor (NMF) components, which are hygroscopic
ences, including the use of detergents. In cases with substances of small molecular weight, while water re-
defective barrier function, transepidermal water loss tention requires a stratum corneum with an intact struc-
(TEWL) values increase, and the skin becomes drier ture.7 In one investigation the extraction of amino acids
with less water content. Water is the only plasticizer for by water did not affect the hydration status of the stra-
the stratum corneum, influencing the appearance, tum corneum sheet.’ It was assumed that amino acids
suppleness, and pliability of the skin. If the water con- are important for the suppleness of the skin and that
tent in the uppermost layers of the horny layer is less keratin fibers themselves are primarily involved in the
than lo%, the skin appears dry and chappy with fine water-holding capacity.
scales and feels rough to the touch. The stratum cor-
neum receives water from within but may also take Investigations
water from the environment, which is the basis for the
effect of hydrating or moisturizing agents. During the past 10 to 15 years, there have been several
The water content of the outer layers of the stratum reports on the effect of soaps and synthetic detergents
corneum fluctuates with the environmental humidity on the skin. Almost 15 years ago, Hassing et al. showed
level. Clinically occurring dry skin is actually a hetero- that measurements of skin vapor loss appear to be a
geneous group because we can distinguish between reliable method for assessing the damaging effect of
physiologically dry skin with a normal water content as low concentrations of soap.” They observed marked
seen in a dry environment and real dry skin with an effects by means of this method before morphologic
abnormal low water content due to structural and bio- changes in the epidermis could be visualized. They also
chemical abnormalities in the stratum corneum. questioned the widely held opinion that alkaline solu-
Characteristically, the “dry skin syndrome” is accen- tions of soap were prone to damage the skin. In fact,
tuated during the winter months in the presence of acid soaps initiated a marked increase in vapor loss.
cold, wind, and low humidity. It is also typical that The studies were performed on the volar side of the
aged skin has a lower water content than younger skin forearm. But one should keep in mind that there are
because it is thinner’ and perhaps also because it con- great differences in reactivity, amount of sebaceous lip-
tains fewer ceramides.’ So-called dry noneczematous ids, and skin thickness (stratum corneum) between
skin in people with atopic dermatitis contains less water various skin sites. Accordingly, it is impossible to com-
than normal-appearing skin and that of controls (Fig pare measurements of casual lipids performed on the
1).3 It also frequently feels rough to the touch. The cause face with a sebumeter with measurements of skin lipids
is probably a disorder of cornification and lack of cer- from the stratum corneum or to compare various TEWL
tain skin lipids.’ values from different skin areas. It may well be that a
The skin surface lipids consist of a mixture of sebum superfatted soap is preferred by people with “real” dry
and lipids derived from the stratum corneum. The stra- skin-atopics and elderly people, for example-but the
tum corneum lipids are produced by the keratinocytes4 effect might be other than that on the sebaceous lipids.”
and are of paramount importance as water modulators About 10 years ago, Fulmer and Kramer used a com-
mon surfactant, sodium dodecyl sulfate, to induce dry,
scaly conditions in human subjects.” These were
From the Department of Dermatology, Ulleuaa”l Hospital, Oslo, Norway.
Address correspondence to Per Thune, Professor M.D., Department of treated daily over a period of 2 weeks on one lower leg.
Dermatology, UIlevadl Hospital, 0407 Oslo, Norway. The contralateral leg was left untreated. The treatment

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resulted in lower stratum corneum hydration and in- 120
1
creased surface scale and roughness. Excised skin from
the treated leg showed significant changes in stratum
corneum lipids with regard to the specific lipid classes
(ceramides), although the total quantities did not
change. The findings were interpreted in terms of per-
turbated stratum corneum formation and maturation-
that is, keratinization-rather than gross lipid extrac-
tion. group 1i group 2:
Froebe et al. measured the type and amount of lipid
l
extracted by two anionic surfactants known to be highly
irritant to skin.13 Very small amounts of lipids were
removed from the stratum corneum. They questioned .2 3 4 .5 6 7 8 0
the long-held belief that surfactants damage the skin by mgl+O/mgd.l
removing sizable quantities of lipids and speculated
that surfactant-protein and not only surfactant-lipid in- Figure 1. Measurements with the CM 430 corneometet
teractions were at work in the production of erythema. (hydration) correlated to the absolute amount of water within ihc
stratum corneum in vitro (mg H,O/mg dry tissue). Group 2:
As a matter of fact, it appeared that skin protein was the atopic dermatitis-dy skin. Group 2: atoprc dermatitis-normal
major site of surfactant binding. skin. (Reprinted with permission.)
The stratum corneum lipids are supposed to be ar-
ranged in an extracellular membrane network of mul- link between xerosis of the leg and the decline of the
tiple bilayers embedding the protein-enriched corneo- sebaceous function” has been reported.”
cytes. i4 If the surfactants bind to a small amount of The hydration data obtained in old, dry-appearing
stratum corneum lipid, they may impair the function ot skin were compared with those seen in old and young
the membrane and alter the interlayer spacing of the control subjects and with those from unaffected skin in
bilayer and damage the lipid structure, as mentioned by atopics. I8 The only sig nificant difference observed wilh
Froebe et alI3 The same authors also speculate that the that the atopic subjects had a lower hydration state than
feeling of “dryness” roughness, tightness, and scaling all the other groups. Water sorption-desorption tests
that is elicited by surfactants can be due primarily to demonstrated a lower prehydration state in atopic skin
keratin binding in addition to the lipid membrane per- and a lower hygroscopicity and water-holding capacity,
turbation.
Clinical dryness of the skin is a common problem Figure 2. Measurements of hydration. The shaded area indicate,
among elderly dermatologic patients. In one study, hy- the 95% conj+denccarea for the younger control group (n = 2.?!
dration and skin surface lipids (of sebaceous origin) Vertical range bars indicate the 95% confidence interval of the
median ualues in the dry-skin group (n = 40). f0 alkaline soap,
were studied together with the TEWL.15 A comparison l sebamed.)
of local effects of acid and alkaline cleansing products
was made. One arm was washed with an alkaline soap,
while the other arm was washed with an acid detergent,
followed by application of an acid lotion. After 1 weeks es- HYDRlsKmUmTS
topical therapy, the hydration values increased on both
sides (Fig 2). At the same time, the TEWL values de-
creased. The skin surface lipid readings showed a sig-
nificant increase on the side treated with acid products
but not on the other side (Fig 3). The increase in surface
lipids might have reflected the presence of compounds
that were derived from the lotion itself, but it could also
have been due to a modification of the NMF compo-
nents and epidermal lipids, manifested as an increase in
the stratum corneum hydration. No deleterious effects
were observed. Corresponding changes in TEWL and
hydration were observed on both sides-that is, also the
one treated with an alkaline soap. This indicates that
water was the main factor responsible and concurs with
other opinions regarding the minor importance of skin
surface lipids of sebaceous origin,i6 although “a close
Clinics in Dermatology l 1996;14:29-33 DETERGENT EFFECTS ON HYDRATION AND LIPIDS 31

mechanism but at different observation times. The ex-


cess water uptake was related to a conformational
change of stratum corneum keratin proteins in the pres-
ence of the alkyl sulfate. After evaporation, it is con-
ceivable that the tertiary structure of the protein cannot
be totally restored but is left with some functional de-
fects. The ensuing reduction in water-binding capacity
after repeated applications of SLS is accordingly due to
a denaturation of keratin protein.
A low quantity of ceramides has been demonstrated
in atopic skin,2 in addition to small corneocytes25 and
abnormal lamellar bodies.26 These are findings that can
certainly be related to the low water content and the
appearance of rough, dry skin, which is more than nor-
mally vulnerable to the effect of various surfactants.
This also implies an abnormal cohesion of the cells.
Yamamura and Tezuka investigated the water-
holding capacity of the stratum corneum in the hairless
sari Anuomwak
oftmebnmt rat by means of nuclear magnetic resonance.*’ The
bound water content remained unchanged by the ace-
Figure 3. Measurements of the skin lipids. (Symbols are as in ton-ether extraction treatment. This also means that wa-
Fig 2.)
ter-soluble components like NMF as amino acids and
pyrrolidone-carboxylate help to enhance the bound wa-
Control skin and old, dry skin did not differ. In another ter content. Lipid analysis showed that chloroform-
study, Berardesca et al., using analogous equipment, methanol extraction consisted of polar lipids like sphin-
showed a reduced water content and increased TEWL gomyelin in addition to a large amount of free amino
in atopics who were free from all signs of skin disease, acids. Aceton-ether extraction consisted of nonpolar lip-
compared to sex- and age-matched controls and psori- ids such as sebaceous gland lipids and a small amount
atics. Also, the water retention capacity, as measured by of polar lipids such as ceramides. It is probable that the
the plastic occlusion stress test, was significantly lower NMF components are ionized in the water in intercel-
in atopics.” lular spaces and form complexes with the lipids, which
Abnormal hygroscopicity and water-retaining capac- are then arranged in a lamellar structure.27
ity have been demonstrated in xerotic skin of the Application of aceton-ether to the human forearm for
legs, 1,2,20,21
while other studies on the arms have shown extremely long periods showed that sebaceous lipids
normal skin conductance. 15,i8 The discrepancies are were extracted for the first 10 minutes, followed by ex-
probably due to different sensitivities of the methods traction of stratum corneum lipids during the next 20
applied and the variation in skin sites examined. For minutes.28 Application of sebaceous lipids on deli-
instance, one study described no change in stratum cor- pidized skin did not alter the induced defect in water-
neum lipids in elderly, xerotic skin compared with the holding properties, while application of a ceramide
data obtained in younger persons,l’ whereas other in- fraction on delipidized skin induced a recovery in wa-
vestigators have reported a decline and relative change ter-holding properties.
in composition in stratum corneum ceramides with in- Also, Berardesca et al. investigated the effects of de-
creasing age.21,22 A decreasing activity of the ceramide- lipidization on the water-holding capacity of the stra-
producing enz me sphingomyelinase has also been tum corneum using the plastic occlusion stress test pro-
demonstrated? Y cedure.30 They observed a sig nificant effect of
Wilhelm et al. showed that anionic surfactants can chloroform-methanol treatment versus ether-aceton
increase stratum corneum hydration in vivo.24 The in- and concluded that polar lipids have a profound role in
duction of hydration was closely correlated with the modulating the barrier function and water-holding
irritation potential of the investigated compounds. The properties of the stratum corneum.
maximum effect was obtained for sodium lauryl sulfate
(SLS). It is interesting to note that the same authors also Conclusions
indicated that the initial SLSinduced increase in stra- The water content of the stratum corneum has been
tum corneum water content was reversed to a dramatic estimated at approximately 30% by weight. About 10%
drying several days after exposure. They speculated of this is lipid associated, while the remaining 20% is
whether the initial statum corneum hyperhidrosis and resistant to solvents and water extraction and is attrib-
subsequent dryness could be a result of the same uted to keratin components.2
32 THIJNE.

The skin of the legs and forearms has been the site of
many investigations, because it has a tendency to de-
velop signs of xerosis with cracking of the horny layer, 1. Potts RO, Buras EM, Chrisman DA. Changes with age iri
desquamation, and a feeling of roughness and dryness. the moisture content of human skin. J invest Dermatol
1984;82:97--100.
In addition, sebaceous glands are sparse, particularly
on the legs. 2. Imokawa G, Abe A, Jin K. Decreased level ot ceramic& in
stratum corneum of atopic dermatitis: An etiologic factor
Several factors may influence the measurement of in atopic dry skin? J Invest Dermatol 1991;96:523-6.
stratum corneum lipids. With aging, the turnover rate .3 Werner Y. The water content of the stratum corneum in
of the epidermal cells is prolonged, there is a decline in patients with atopic dermatitis: Measurement with the
epidermal proliferative activity, and the number of stra- corneometer CM 420. Acta Derm Venereol (Stockh) 1886;
tum granulosum cells decreases. The biosynthesis of 66:2814.
sphingolipids is influenced by epidermal proliferation, 4. Elias PM. Dynamics of the epidermal barrier: New imph-
and changes in sphingolipid composition may reflect a cations for percutaneous drug deiivery, topical therapeu-~
decline in the sphingomyelinase activity with aging.“’ tics and disease pathogenesis. Dermatology Foundation
The ceramides have been supposed to play a crucial 1992;26:1-8.
role in water barrier function and perhaps also in the 5. ‘Tagami H, Ohi M, iwatsuki K, et al. Evaluation of the skm
water-holding capacity of the stratum corneum.“,‘” surface hydration in vivo by electrical measurement 1
Menon et al. demonstrated a “clear dynamic relation- Invest Dermatol 1980;75:500-7.
ship between the host’s water-barrier requirements and 6. lmokawa G, Hattori M. A possible function of structuraf
epidermal sterol metabolism.“2” They showed that lipids in the water-holding properties of the stratum ,!
damage to the barrier with either detergents or solvents Invest Dermatol 1985;84:282-4.
resulted in a burst of lipid synthetic activity in the epi- 7. Tagami H, Kanamuru Y, moue K, et al. Water sorption
dermis, The time course of this activity paralleled bar- desorption test of the skin in vivo for functional assess
ment of the stratum corneum. J Invest Dermatol 1982:78:
rier repair. The lipid synthesis could be partly blocked 425-B.
by the application of a membrane impermeable to water 8. Tagami H, Yoshikuni K. Inter-relationship between \**a.
vapor that imitated fully restored stratum corneum bar- ter-barrier and reservoir functions of pathologic stratum
rier function. The regulatory factors and second mes- corneum. Arch Dermatol 1985;121:642-5.
sengers at work in the repair process are only partly 9. Imokawa G, Kuno H, Kawai M. Stratum corneum lipids
known. According to Elias, the lipid biosynthetic re- serve as a bound-water modulator. J Invest Dermatol
sponse to barrier disruption is “differentially regulated 1991;96:845-51.
in the lower nucleated (basal/spinous) versus outer 10. Hassing jW, Nater JP, Bleumink E. lrritancy of low con-
nucleated (granular) cell layers of the epidermis.““ centrations of soap and synthetic detergents as measureci
Also, DNA synthesis is regulated by barrier require- by skin water loss. Dermatologica 1982;164:374-21.
ments.” Il. Bechor R, Zlotogorski A, Dikstein S. Effect of soaps and
It was assumed until recently that the ceramides detergents on the pH and casual lipid levels of the skin
were of paramount importance for the water-holding surface. J Appl Cosmetol 1988;6:123-8.
capacity of the stratum corneum and for barrier func- 12. Fulmer AW, Kramer GJ. Stratum corneum lipid abnor-
tion.2,27b8 This was shown with of extraction methods malities in surfactant-induced dry scaly skin. J InvestmDer-
by which the skin was delipidized and also by local matol 1986;86:598-602.
application of ceramides on delipidized skin--in which 13. Froebe CL, Simion FA, Rhein LD, et al. Stratum corneum
case, the barrier can be restored. lipid removal by surfactants: Relation to in vivo irritation
Recent investigations performed with surfactants Dermatologica 1990;181:277-83.
such as SDS and SLS indicate no gross lipid extraction 14. Wertz PW. Epidermal lipids. Semin Dermatol 1992;I 1.
106-13.
if the application time is not extremely prolonged, but
15. Thune l’, Nilsen T, Hanstad IK, et al. The water barrier
there is a change in ceramide biosynthesis.i2,‘” At the
function of the skin in relation to the water content of
same time, the cholesterol and free fatty acid profile is stratum corneum, pH and skin lipids: The effect of alka,
altered. These findings are interpreted as SDS alter- line soap and syndets on dry skin in elderly, non-atopic
ations in the keratinization process, while total sterol patients. Acta Derm Venereol (Stockh) 1988;68:277-83.
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process. corneum lipids in skin xerosis. Dermatologica 1989;;178:
The role of the sebaceous lipids in dry skin has been ISI--5.
much debated.16 In fact, there has been no correlation 18. Thune I’. Evaluation of the hydration and the water-
between sebaceous gland activity and the presence or holding capacity in atopic skin and so-called dry skin.
severity of dry skin or hydrationa’-“” Acta Derm Venereol (Stockh) 1989(SuppI 144):133-5.
Clinics in Dermatoology l 1996;14:29-33 DETERGENT EFFECTS ON HYDRATION AND LIPIDS 33

19. Berardesca E, Fideli D, Borroni G, et al. In vivo hydration atopic dermatitis: A quantitative electron microscopic
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bound water. J Invest Dermatol 1986;87:574-6. of deranged water-holding properties by stratum cor-
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and asteatotic eczema. J Dermatol 1993;20:1-6. rologenesis in the skin: II. Regulation by cutaneous barrier
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requirements. J Lipid Res 1985;26:418-27.
change in stratum corneum sphingolipids. Arch Dermatol
30. Berardesca E, Herbst R, Maibach H. Plastic occlusion
Res 1993;285:415-7.
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