2 JOURNAL OF COSMETIC SCIENCE
of this phenomenon. This report presents equilibrium water sorption and desorption
isotherms for human nail, as well as interpretation thereof in terms of isotherm models.
Related reports will describe the effects of hydration on water diffusivity in nail and on
the permeability of nail to an antifungal drug, ketoconazole.
Equilibrium water sorption in nails from mixed mammalian species has been reported
by Baden (17). He found a maximum water uptake of 0.3 g H
2
O/g dry nail in studies
conducted at 26°C. No hysteresis between uptake and desorption curves was noted.
These data are discussed and quantitatively analyzed in this report, along with our own
observations. Comparisons are also made to equilibrium water uptake in other kerati-
nized tissues.
MATERIALS AND METHODS
Frozen intact cadaver nails were obtained from ScienceCare Anatomical (Phoenix, AZ).
Human nail clippings were collected from several donors in our facility. Demographic
information for each nail sample (nail clippings and intact cadaver finger and toe nails)
was obtained. Nail samples were washed with a mild liquid detergent (containing
sodium laureth sulfate and cocamidopropyl betaine) and dried at 45°C to a constant
weight (Mettler AE 100). Intact cadaver nails from three different donors were used with
n =4-6 nails per donor. Their average dry weight ranged from 0.08 g (for little finger
nails) to 0.50 g (for big toe nails). Nail clippings from multiple donors were pooled, then
divided into six samples ranging from 0.26-0.40 g dry weight. In the analysis they were
considered as from one donor, with n =6. The water-binding capacity of nail samples
was determined by transferring individual nail samples to a weighing dish and exposing
samples to the vapor phase of solutions of varying relative humidity (RH) in a glass
chamber maintained at 32°C. RH ranging from 11 %to 100% was maintained with
various concentrations of H
2
SO
4,
NaCl, K
2
CO
3, and Li Cl in water. Standard tabulations
of molal osmotic coefficients cp over a range of temperatures were interpolated to 32°C,
then converted to RH using the relationship RH =100 x exp(=vmcp/55.51), where vis
the number of ions per molecule of electrolyte and mis the molality of the solution (18).
Details may be found in (19). Sorption and desorption curves were obtained by sequen-
tially exposing the same nail to increasing and decreasing RH, respectively. At each RH
the samples came to constant weight in 3-5 days, which was taken as the measure of
equilibrium.
DATA ANALYSIS
The relative pressure of water vapor, x =plp0 ,was calculated as RH/100. This value is
essentially the water activity, aw (20). The amount of water absorbed by the nail samples
at each value of x was expressed as the adsorption volume, v, calculated as (g of water/ g
of dry tissue). The water uptake values in the plot are the mean values of nail clipping
data considered as from one donor (n =6) and three sets of intact cadaver nails (n =
4-5/donor). These variables were related according to equilibrium sorption isotherms
used previously to describe water uptake in other keratinized tissues. In particular we
have considered the D' Arey-Watt model (8), modified to exclude the linear term as
described in (21). This relationship is:
THE HUMAN NAIL: SORPTION ISOTHERMS
Bbx Ccx v=---+--
1 +bx 1 -ex
3
(1)
where B1 b1 C and c are disposable constants. The first term on the right hand side of
equation 1 is a Langmuir-like term describing primary adsorption in that sense B
corresponds to the monolayer volume, v
m
(20). The second term describes multilayer
sorption as discussed in (1). We also considered the Guggenheim-Anderson-deBoer
(GAB) model (equation 2):
V cKx
v
m (1 -Kx)(l -Kx +cKx) (2)
Equation 2 is a modified BET isotherm (20) indeed it was called just that in a previous
report from our group (21). The parameters c and vm are the binding constant and the
monolayer volume, respectively. The parameter K [equal to 1/a0 in (21)} is a positive
constant, with a value less than 1, that is associated with weakly bound water in the
second and successive layers surrounding the keratin fibers. The GAB model has found
wide applicability in hydrophilic polymer (22,23) and food (24) systems and has con-
siderable theoretical justification (25). In particular, non-unit values of K arise from a
phenomenon known as "jamming" that is physically more realistic than the unimpeded
sorption process inherent in the BET model (2 5 ).
The above sorption models were fit to individual data sets (nail clippings and intact
cadaver nails) for both the sorption and desorption phase, using nonlinear regression
(SigmaPlot®, Jandel Scientific). Values were compared by one-way ANOVA, and dif-
ferences having p 0.05 were considered significant.
RESULTS AND DISCUSSION
The results of human nail water sorption studies conducted in our laboratory are shown
in Figure 1, along with data from Baden (17). The results show that the human nail has
a maximum water uptake of �0.3 g H
2
O/g dry tissue at 100% RH. The magnitude of
water sorption in nail clippings was comparable to that of intact cadaver nails, but
showed less hysteresis, as discussed below.
The nail water sorption isotherm is a Type II isotherm with a characteristic hysteresis
between uptake and desorption, similar to that observed in wool, hair, and porcupine
quills (8). The hysteresis may be attributed to an unfolding of the keratin bundles on
adsorption that is not immediately reversed on desorption (5 ).The hysteresis was more
pronounced in some nail samples than in others. In particular, it was higher in intact
cadaver nails than in nail clippings. We postulate the observed difference may be related
to the differences in surface-to-volume ratio. The hydrostatic pressure exerted by the
adsorbed water on the samples having a higher surface-to-volume ratio (clippings) would
be less in comparison to those having a lower ratio (intact nails). Other explanations are
possible. El-Shimi and Princen (26) suggested that the hysteresis effect for human
stratum corneum was correlated with the process of aging and the associated change in
stratum corneum elasticity. Watt (8) argued that hysteresis in wool was associated with
relaxation processes taking place within the fibers and also discussel Lhe influence of the
drying process. All of these arguments invoke the concept of stress within the microfibril
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