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Current Opinion in Colloid & Interface Science 6 2001.

148159

Natural surfactants
Krister HolmbergU
Sweden
Department of Applied Surface Chemistry, Chalmers Uni ersity of Technology, SE-412 96 Goteborg,

Abstract
The ever-increasing environmental concern about surfactants triggers an interest in natural surfactant. This review, which
has an emphasis on work published since 1998, covers three categories of natural surfactants: amphiphiles produced by yeast
or bacteria, amphiphiles containing a natural polar headgroup and amphiphiles containing a natural hydrophobic tail.
Microorganisms produce both high molecular weight and low molecular weight surfactants. Only the low molecular weight
compounds are included in the review. Sugars and amino acids are the two most important examples of surfactant polar
headgroups of natural origin. The research is particularly intense in the area of sugar surfactants and the review covers three
types: alkylglucosides, alkylglucamides and sugar esters. Surfactants based on two types of natural hydrophobic tails are
included: fatty acid monoethanolamides and sterol ethoxylates. Routes of preparation as well as physico-chemical properties
are discussed for the surfactants prepared by organic synthesis. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Surfactant; Natural; Biotechnology; Sugar; Polyol; Amino acid; Fatty acid; Sterol

1. Introduction
The term natural surfactant is not unambiguous.
Taken strictly a natural surfactant is a surfactant
taken directly from a natural source. The source may
be of either plant or animal origin and the product
should be obtained by some kind of separation procedure such as extraction, precipitation or distillation.
No organic synthesis should be involved, not even as
an after-treatment. There are in fact not many surfactants in use today that fulfil these requirements.
Lecithin, obtained either from soybean or from egg
yolk, is probably the best example of a truly natural
surfactant.
The main reason why natural surfactants in the real
sense of the word are so scarce is not a lack of
availability. Amphiphiles are abundant in both the

Tel.: q46-31-7722969; fax: q46-31-160062.


E-mail address: kh@surfchem.chalmers.se K. Holmberg..

plant and the animal kingdom where they are often


referred to as polar lipids. In biological systems the
surface active agents are used in very much the same
way as surfactants are employed in technical systems:
to overcome solubility problems, as emulsifiers, as
dispersants, to modify surfaces, etc.
The factor that works against production of truly
natural surfactants is the cost of work-up. The
products are usually present in small quantities and
the separation process tends to be tedious. In most
instances the cost of separationrisolation will by far
exceed the manufacturing cost of equivalent synthetic
surfactants.
The unfavorable cost situation for truly natural
surfactants may change if fermentation processes can
be developed that yield biosurfactants in high yields.
Both yeast and bacteria can be efficient producers of
surface active agents and there is considerable current interest in biotechnological processes for production of amphiphilic compounds. These substances can
be either low molecular weight, such as acylated

1359-0294r01r$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 0 2 9 4 0 1 . 0 0 0 7 4 - 7

K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

oligosaccharides, or high molecular weight, most often lipopolysaccharides. So far most interest has focused on the high molecular weight products, with

Emulsan, a highly charged heterolipopolysaccharide


with a molecular weight of approximately 10 6 , as the
prime example w1x.
The term natural surfactant is often used in a
broader sense than that discussed above, however.
Surfactants synthesized from natural raw materials
are usually referred to as natural surfactants. Proper
examples of surfactants belonging to this category are
fatty acid esters of sugars and fatty acid esters or
amides of amino acids. It is, in fact, common practice
to be even more generous in the use of the term
natural surfactant. A surfactant with one of the main
building blocks, the polar headgroup or the hydrophobic tail, obtained from a natural source is
often referred to as a natural surfactant. For example,
alkyl glucosides which are prepared from a natural
sugar unit and a non-natural fatty alcohol are often
regarded as natural surfactants. So-called natural
fatty alcohols should not be seen as natural starting
materials, although this is often done. Fatty alcohols
derived from coconut oil and other triglycerides are
made by two consecutive chemical reactions:
methanolysis of the triglyceride followed by reduction
of the methyl ester..
In this review the term natural surfactant is used
in its broadest sense. The paper covers true natural
surfactants prepared by fermentation, synthetic surfactants with a natural polar head group and synthetic
surfactants with a natural hydrophobic tail. Only low
molecular weight surfactants with a well-defined
structure are included. The natural surfactants used
to treat the respiratory distress syndrome, a chapter
of its own, are in reality mixtures of amphiphiles with
structures not fully elucidated w2x and are, hence, not
covered. The review is organized correspondingly.

2. Surfactants prepared by fermentation


2.1. Acylpolyols

149

Fig. 1. A trehalose ester.

hydroxy fatty acids connected to disaccharides by ester bonds. They are extracellular compounds produced by actinomycetes such as Mycobacterium,
Corynebacterium and Bre ibacterium w3x. The acylpolyols are abundant in bacterial cell walls. A typical
example of an acylpolyol is the trehalose ester shown
in Fig. 1.
2.2. Glycolipids
Glycolipids are usually hydroxy fatty acids attached
to a sugar via a glycosidic bond. Sophorolipids and
rhamnolipids are well known examples, produced by
Candida and by Pseudomonas, respectively w4,5x. Fig. 2
shows a cyclic and an acyclic sophorolipid. Rhamnolipids are attractive in that they can be efficiently
produced during growth on either hydrocarbon or
carbohydrates as the sole carbon source. There has
been considerable interest in the molecular genetics
of rhamnolipids and this topic has recently been reviewed in this journal w6x.
A sucrose lipid produced by Serratia marcescens has
recently been isolated and characterized w7 x. The
product was found to be an excellent emulsifier for a

Acylpolyols prepared by fermentation are usually

Fig. 2. A cyclic and an acyclic sophorolipid.

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K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

Fig. 3. Surfactin from Bacillus subtilis.

wide range of hydrocarbons including crude oil. It has


been suggested as a surfactant for cleaning of oil
tanks.

3. Surfactants based on a natural polar headgroup

2.3. Acylpeptides

Various types of sugars or polyols derived from


sugar have been used as surfactant polar headgroup
for many years. Sorbitane alkanoates and ethoxylated
sorbitane alkanoates, well known under the trade
names of Span and Tween, respectively, have been
around for a long time. In recent years there has been
a focus on three classes of surfactants with sugar or a
polyol derived from sugar as polar headgroup: alkyl
polyglucosides APGs., alkyl glucamides and sugar
esters. Representative structures of the three surfactant types are shown in Fig. 4.
There is currently a very strong interest in exploring alkyl polyglucosides APGs. as surfactant for
several types of applications. APGs are synthesized by
direct reaction of glucose with fatty alcohol, using a
large excess of alcohol in order to minimize sugar
oligomerization. Alternatively, they are made by
transacetalization of a short chain alkyl glucoside,
such as ethyl or butyl glucoside, with a long chain
alcohol. An acid catalyst is used in both processes.
Either glucose or a degraded starch fraction is used as
starting material. Fig. 5 illustrates the synthesis. Alkyl

Acylpeptides or lipopeptides, are usually cyclic


compounds based on a hydroxy acid and a short
peptide chain. By far the most studied compound is

Surfactin, produced from Bacillus subtilis w8,9x.


Acylpeptides, such as Surfactin and Lichenysin produced by Bacillus licheniformis, are efficient amphiphiles when it comes to surface tension reduction,
etc. Surfactin is one of the few biosurfactants that has
found commercial use. It is used in a variety of
pharmacological applications w10x. The formula of
Surfactin is shown in Fig. 3. Surfactin and rhamnolipids are the only two biosurfactants for which
there is any regulatory information and the molecular
genetics of Surfactin has recently been reviewed w6x.

Fig. 4. Examples of polyol surfactants. From top to bottom: an


alkyl glucoside, an alkylglucamide, and the ethyl acetal of a fatty
acid glucose ester.

3.1. Sugar as polar headgroup

Fig. 5. Pathway for APG synthesis from von Rybinski and Hill w18x
with permission..

K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

glucosides can also be made by enzymatic synthesis,


using -glucosidase as catalyst which yields only the
-anomer and gives low yield.. The corresponding
-anomer can more readily be obtained by -glucosidase catalyzed hydrolysis of the racemate. There are
considerable differences between the mixture obtained by organic synthesis and the pure enantiomers
obtained by the bio-organic route. The -anomer of
n-octyl glucoside has found use as a surfactant in
biochemical work.
Alkyl glucosides are stable at high pH and sensitive
to low pH where they hydrolyze to sugar and fatty
alcohol. A sugar unit is more water-soluble and less
soluble in hydrocarbons than the corresponding polyoxyethylene unit; hence, APGs and other polyol-based
surfactants are more lipophobic than their polyoxyethylene-based surfactant counterparts w11x. This
makes the physico-chemical behavior of APG surfactants in oilwater systems distinctly different from
that of conventional non-ionics. Furthermore, APGs
do not show the pronounced inverse solubility vs.
temperature relationship that normal non-ionics do.
This makes an important difference in solution behavior between APGs and polyoxyethylene-based surfactants. The main attractiveness of APGs lies in their
favorable environmental profile: the rate of biodegradation is usually high and the aquatic toxicity is low
w12,13x. In addition, APGs exhibit favorable dermatological properties, being very mild to skin and eye
w14x. The mildness makes this surfactant class attractive for personal care products but APGs have also
found a range of technical applications.
APGs have been the topic of several excellent
overviews w1518x. In addition, the physico-chemical
properties of APGs, as well as other polyhydroxylbased surfactants, have recently been reviewed in this
journal w19x. Only a few brief notes on recent developments in the field will therefore be given here.
The solution behavior of APGs, both anomeric
mixtures, prepared by organic synthesis, and pure
enantiomers have been studied in detail w20 ,2123x.
The micellar phase region is usually large and at
higher concentrations the normal pattern of liquid
crystalline phases appears. It interesting to note, as
was described in a previous review w19x, that some
APG surfactants exhibit a miscibility gap in the micellar region. As with polyoxyethylene-based non-ionics
two micellar phases appear in this region, one dilute
and one concentrated. For a pure decyl glucoside
surfactant it was found that the dilute phase consisted
of micelles of aggregation number in the range
200400 while the concentrated phase contained
larger aggregates, probably branched micelles that
formed a network through entanglement w20x. A characteristic feature of the liquid crystalline region which
appears at higher surfactant concentration is that the

151

borders between the different crystalline phases in a


temperature vs. surfactant concentration diagram are
almost vertical, indicating a temperature-independent
behavior. This is very different from the behavior of
polyoxyethylene-based non-ionics.
Mixed micelle formation of two APGs with different length of the alkyl chain with both anionic and
cationic surfactants have been studied w24 x. The experimental data were fitted to Rubinghs model for
non-ideal mixed micelle formation w25x. A value of the
interaction parameter, is obtained and the value of
, positive or negative, indicates whether there is a
repulsive or an attractive interaction involved in the
formation of mixed micelles between the two surfactant types. Combination of an APG with the cationic
surfactant dodecyltrimethylammonium bromide gave
a value of the -parameter of y4.1 indicating rather
strong attractive interaction. The combination of the
same APG with the anionic surfactant sodium dodecylsulfate gave a -value of y2.3, indicative of a
smaller attraction. These results are interesting and
not easily explained. They tend to support the view,
proposed by several workers, that APGs carry a negative net charge, the origin of which is unclear w24 x. It
is interesting that whereas a combination of an APG
and an alcohol ethoxylate gave a value of the parameter of zero, the same APG when combined
with another alkyl glycoside, an alkyl maltoside of the
same alkyl chain length C10. gave a -value of y2.0.
This attractive interaction was tentatively explained as
due to favorable packing of the headgroups of the two
surfactants w24 x.
The majority of work on glycoside surfactants has
been made on alkyl glucosides, i.e. surfactants based
on glucose or slightly oligomerized glucose as polar
headgroup. Recently, alkyl maltosides have been studied with a specific focus on its behavior in mixed
micelles together with anionic and non-ionic surfactants w26,27x. A combination of a decyl maltoside with
sodium dodecylbenzene sulfonate gave a value of the
-parameter of y2.1 which can be compared with the
value of y3.3 for a combination of an alcohol ethoxylate, octaethylene glycol.monodecyl ether C10E8.
with the same anionic surfactant. A combination of
the alkyl maltoside with the alcohol ethoxylate gave a
very small -value y0.3.. A synergistic effect with
regard to surface tension reduction was also found for
combinations of either of the non-ionic surfactants
and sodium dodecylbenzene sulfonate. Thus, the results obtained with the maltoside surfactant agree
very well with those previously obtained with glucoside surfactants of the same alkyl chain length. A full
explanation of the results still remains, however.
Alkylglucamides see Fig. 4., or more strictly named
as N-alkanoyl-N-metylglucamines, are commercially
important products. The product sold in large quanti

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K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

ties for the detergent sector is N-dodecanoyl-N-methylglucamines, i.e. the C12-derivative. The product is
prepared from glucose, metyl amine, hydrogen and
methyl laurate by a two-step reaction.
Alkylglucamides have been the subject of an extensive review recently w28x. Few major investigations on
this surfactant class seem to have been made recently.
In a paper by Zhu et al. a glucamide was compared
with polyol surfactants of similar structure, a xylamide
and a glyceramide, all having a C12 alkyl chain w29 x.
The glucamide has four hydroxyl groups in the polar
head, the xylamide three and the glyceramide one.
This was reflected both in the area per molecule
values and the CMC values which were 30, 28 and 26
2 and 0.347, 0.331 and 0.234 mM, respectively.
A
There is considerable current interest in sugar esters see Fig. 4. and a recent review covers the topic
until 1998 w30x. Esters of glucose can be made either
by enzymatic synthesis, using a lipase catalyst, or by
an organic chemical route. Using the right enzyme
the bio-organic route can give esterification almost
exclusively at the 6-position of the sugar moiety. The
organic synthesis requires extensive use of protecting
groups to obtain high selectivity. Selective enzymatic
synthesis of other sugar esters than glucose esters
have been difficult to achieve without the use of
protective groups. Starting from sugar acetals and
fatty acids, monoesters of sugars were obtained in
good yield, after a deprotection step, from several
starting materials, both mono- and disaccharides
w31,32x.
The advantage of the organic synthesis over the
enzymatic route is that the sugar unit can be varied at
will. The group of Drummond has recently made
important contributions in this area with a specific
focus on degradation mechanisms w33 ,34 ,35x but
also covering physico-chemical behavior w36 x. A series of sugar ester surfactants were synthesized having
different headgroup size glucose, sucrose and raffinose, consisting of one, two and three anhydroglucose
rings, respectively. and with C12 and C16 acyl chains.
Sulfonated sugar esters were also prepared. It was
found that all unsubstituted sugar esters degraded
rapidly. Variations in the sugar headgroup size or the
acyl group chain length did not significantly affect the
biodegradability. The anionic derivatives degraded
more slowly, however w33 x.
A detailed study on the mechanism of biodegradation of the unmodified and the sulfonated sugar esters
showed that sucrose laurate biodegradation occurs via
initial ester hydrolysis. The sucrose -sulfonyl laurate,
on the other hand, degrades by initial alkyl chain
oxidation. This indicates that the ester hydrolysis
pathway is blocked by the sulfonyl group adjacent to
the ester bond so that biodegradation is forced to
proceed via the slower alkyl chain oxidation pathway

w34 x. An ethyl substituent in -position instead of


the sulfonate group also slowed down the biodegradation rate, probably for the same reason. The two
degradation routes are shown in Fig. 6.
Base catalyzed hydrolysis was also investigated.
Similar to the results from the biodegradation, the
unsubstituted sugar esters degraded faster than the
derivatives with either a sulfonate or an ethyl group in
the -position. The difference in hydrolysis rate
between the three surfactants sucrose laurate, sucrose
-sulfonyl laurate and sucrose -ethyl laurate, varied
with temperature. It was concluded that at higher
temperature, when steric hindrance is the dominant
factor, hydrolysis of -sulfonyl laurate is slowest. By
contrast, at lower temperature, when activation energy is more important, hydrolysis is faster in the
presence of an electron-withdrawing -sulfonyl group
than in the presence of an electron-attracting -ethyl
group w35x.
Dimeric and trimeric sugar ester surfactants have
been synthesized by a combination of enzymatic and
organic chemical methods w37 x. An impressive series of products were prepared with different spacer
units between the sugar rings. For instance, a dimeric
gemini. glucose ester with C12 acyl chains attached
at positions 6 of the two anhydroglucose units and
with the two moieties connected via a six carbon
spacer was prepared in high yield. The product is
shown in Fig. 7.

3.2. Amino acid as polar headgroup


Amino acids and short peptides constitute an alternative to sugars as a natural polar headgroup for
surfactants. Several amino acids have been investigated for this purpose with the majority of papers
dealing with basic amino acids such as arginine and
lysine from which cationic surfactants can easily be
prepared. Most synthetic procedures are based on
organic synthesis but enzymatic processes have also
been explored w38,39x. Arginine-based surfactants have
recently been reviewed w40x.
Arginine surfactants, such as N-dodecanoylarginine
metyl ester salt are conveniently prepared by reaction
between the oil soluble dodecanoic acid and the water
soluble arginine methyl ester hydrochloride using dicyclohexylcarbodiimide as condensing agent. The reaction is normally carried out in an aprotic, polar
solvent such as dimethylformamide DMF.. The reaction is performed at room temperature and works
well in a laboratory scale. However, DMF is an unsuitable solvent for large scale operations, partly due
to cost and toxicity and partly due to difficulties in
removing it from the product by simple vacuum evaporation. An alternative process, using a highinternal-phase-ratio emulsion, has been investigated

K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

153

Fig. 6. Degradation pathways of a sugar fatty acid ester from Baker et al. w34x with permission..

for the synthesis w41 x. Such emulsions can be formulated with a large amount, sometimes above 99%, of
internal phase and with very low amount of surfactant, often less than 0.5%. The structure of water-inoil emulsions of this type is that of closed-packed

Fig. 7. A sugar fatty acid gemini surfactant from Gao et al. w37x
with permission..

water droplets of a broad size distribution separated


by a thin film of the continuous oil phase. The viscosity is usually high and such emulsions are
sometimes referred to as gel emulsions. It was demonstrated that the concentrated emulsions were
good reaction media with yields equivalent to those
obtained in DMF. The yield depended on the waterto-oil ratio. Too high water content at constant surfactant concentration gave large water droplets with
corresponding small interfacial area which was found
to be unfavorable.
A papain-catalyzed synthesis of arginine-based surfactants have been reported w42,43x. Papain deposited
on a solid support was used as catalyst for the amide
and ester bond formation between arginine methyl
ester and various long-chain alkyl amines and fatty

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K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

Fig. 8. Route of preparation of a tryptophan-based surfactant from Pegiaduo et al. w46x with permission..

alcohols in organic solvent. High yield of arginine


amide was obtained from reaction in acetonitrile. For
the synthesis of the arginine fatty acid ester the best
yield was obtained in a solvent-free system kept at a
temperature above the melting temperature of the
fatty alcohol.
Using a combination of organic and bioorganic
synthesis arginine-based gemini surfactants have been
synthesized by the group of Infante w44x and the
solution properties have been investigated w45x. The
gemini surfactants consisted of two N-acylarginine
moieties connected via the arginine carboxyl groups
by a diamino spacer molecule, such as 1,3-diaminopropane or 1,3-diamino-2-hydroxypropane. A
N-acyl-L-arginine alkyl ester was used as starting
material. This compound was first reacted with the
diamino spacer to form the amino-amide, i.e. the
spacer reacted with one of its amino group to form a
N-acyl-L-arginine amide. In a second step, catalyzed
by papain, the free amino group reacted with another
molecule of N-acyl-L-arginine alkyl ester to form the
diamide product. Overall yields of the order of 65%
were reported.

A series of tryptophan-based surfactants have been


synthesized w46 x. The surfactants were synthesized by
reaction of tryptophan with the epichlorohydrine
adduct of a fatty alcohol, as shown in Fig. 8. The
series of surfactants based on fatty alcohols with from
9 to 16 carbon atoms was evaluated with respect to
CMC, surface tension at CMC and area per molecule
at the airwater interface. The results are summarized in Table 1. As can be seen, the CMC values are
low, considerably lower than for simple alkanoate
surfactants of the same hydrocarbon chain length. For
instance, sodium laurate has a CMC of 20 mM to be
compared with the value of 0.038 mM of the C12
surfactant of Table 1. The surface tension values are
generally low, as expected for these hydrophobic surfactants. The areas per molecule are within the expected range, the increase in area for the shorter
chain length surfactants most probably reflecting a
less ordered packing at the surface.
The amino acid-based surfactants are possible candidates for pharmaceutical applications and the
hemolytic action of some lysine-based anionic surfactants has been investigated. The surfactants were salts

K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

155

Table 1
Physico-chemical data for arginine-based surfactants having the structure given in Fig. 8 data taken from Pegiaduo et al. w46x.
Compound

CMC
mM.

Surface tension at CMC


mNrm.

Area per molecule


2 .
A

Rs C9H19
Rs C10H21
Rs C11H23
Rs C12H25
Rs C13H27
Rs C14H29
Rs C15H31
Rs C16H33

0.5
0.36
0.065
0.038
0.022
0.020
0.017
0.012

35
33
32
32
32
31
30
30

78
67
53
51
64
64
66
68

of N ,N-dialkanoyl lysine. In one series of experiments the alkyl chain lengths were varied w47x. In
another work the surfactant was N ,N-octanoyl lysine and the counterion was varied w48x. As expected,
the hemolytic activity depended on the alkyl chain
length and on the choice of counterion. With lysine as
counterion to the lysine-based anionic surfactant a
protective effect against hypotonic hemolysis was obtained.

4. Surfactants based on a natural hydrophobic tail


4.1. Fatty acid as hydrophobic tail
Fatty amide ethoxylates are easily prepared by
ethoxylation of the fatty amide monoethanolamide.
The ethanolamide, in turn, is prepared by aminolysis
of the fatty acid metyl ester by ethanolamine. The
fatty amide ethoxylates are of interest as an alternative to fatty alcohol ethoxylates for several reasons: i.
they biodegrade readily to fatty acid and aminoterminated polyethylene glycol.; ii. the amide bond
in the structure may improve surfactant packing due
to hydrogen bond formation; and iii. double bonds in
the fatty acid chain can be preserved in the product
although during the ethoxylation step 1,3-cis,cis-double bonds undergo migration to conjugated trans,cis
structures ..
A series of fatty amid ethoxylates, all based on C18
fatty acids but with varying number of double bonds,
has been synthesized and evaluated with regard to the
effect of the amide bond and the double bonds on
physico-chemical properties w49 ,50 x. Surfactants
with different polyoxyethylene chain lengths were prepared and the corresponding saturated fatty alcohol
ethoxylates, stearyl ethoxylates, were used as references. It was found that the presence of the amide
group led to a decrease in CMC, possibly due to
hydrogen bond formation. The surface tension at the
CMC was higher when an amide bond was present,
however, which was assumed to reflect the increase in

size of the polar group decrease in the critical packing parameter value. which is unfavorable for close
alignment of surfactant molecules at the airwater
interface. The same effect was seen in adsorption at a
hydrophobic, solid surface, as studied by ellipsometry.
The presence of unsaturations in the hydrophobic
tail gave an increase in CMC. This may partly be due
to the surfactants becoming more hydrophilic and
partly to the increased bulkiness of the chains rendering packing into closed aggregates and formation of
hydrogen bonds between amide groups more difficult.
The presence of one double bond, cis oleyl. or trans
elaidyl., did not much affect the molecular cross-sectional area at the surface. Two double bonds gave
much larger areas, as can be seen from Fig. 9.
Self-diffusion NMR was used to study the effect of
temperature and surfactant concentration on the size
of the surfactant aggregates. It was found that at both

Fig. 9. Area per molecule for a series of fatty amide ethoxylates


with 10, 15 or 20 oxyethylene units. The number of double bonds in
the acyl chain vary from zero stearyl. to one, cis oleyl. and one,
trans elaidyl. to two linoleyl.. Stearyl alcohol erhoxylates C18En.
are included as references.

K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

156

high and low surfactant concentration the hydrodynamic radius of a stearyl amide ethoxylate was somewhat larger than the radius of the stearyl alcohol
ethoxylate with the same number of oxyethylene units.
For the higher surfactant concentration, where the
micelles are non-spherical, this may be due to the
larger polar headgroup size of the amide surfactants
see discussion above. giving slightly less elongated
micelles. The results are more difficult to rationalize
for the low surfactant concentration where both amphiphiles give spherical micelles.
4.2. Sterol as hydrophobic tail
Sterol-based surfactants have been reviewed recently w51x and a new review is in progress w52x.
Sterol-based surfactants are of interest because of the
large hydrophobic group of fully natural origin which,
due to its rather planar four ring structure, may
induce good packing at interfaces. Two recent papers
deal with phytosterol ethoxylates w53 ,54x. Phytosterols are sterols of plant origin and their structure is
similar to that of cholesterol, the prime example of
sterols from animal sources. The sterols contain a
secondary hydroxyl group that can be ethoxylated.
The alcohol is sterically hindered, however, and the
reaction with ethylene oxide is not straightforward.
The best procedure seems to be to start the ethoxylation with a Lewis acid catalyst, cease the reaction
after 35 mol of ethylene oxide have been added, and
continue with KOH as initiator w55x. The structure of
a representative sterol ethoxylate is shown in Fig. 10.
Surface tension plots of a series of phytosterol
ethoxylates with 10, 20 and 30 oxyethylene units
showed that i. the CMC values were very low; and
ii. the CMC increased with increasing polyoxyethylene chain length. The latter, which has previously
been observed by others as accounted for in Folmer
et al. w53 x, is unexpected and is difficult to explain.
The values are collected in Table 2. Another interesting observation is that the time to reach surface
tension equilibrium is very long, more than 2 h. The
decay of surface tension with time is shown in Fig. 11.
Most likely, the long equilibrium time is due to ex

Table 2
Physico-chemical data for sterol-based surfactants having the
structure given in Fig. 10 data taken from Folmer et al. w53x.
Number of
oxyethylene

CMC
M.

Surface
tenstion at
CMC mNrm.

10
20
30

10
7
3

31
34
42

change reactions of sterol ethoxylates with varying


polyoxyethylene chain length at the airwater interface and to slow conformational changes of individual
molecules at the surface. The multiring structure of
sterols is rigid and the time required to adapt a
favorable conformation at an interface may be long.
The phase behavior of the sterol ethoxylates has
been studied in some detail w53 ,54x. Fig. 12 shows
phase diagrams for phytosterols with 5, 10, 20 and 30
oxyethylene units. The surfactant having 10 oxyethylene units gives a lamellar phase over a very wide
concentration range at elevated temperature. The
phase diagrams of the more hydrophilic surfactants
with large headgroups are dominated by hexagonal
and cubic phases. The high thermal stability of the
liquid crystalline phases is noteworthy. It is particularly striking to see a cubic phase for a non-ionic
surfactant that extends above 100C. Cubic phases are
normally seen as being trapped in a three-dimensional lattice with no possibility of movement. Usually
when the temperature is increased a cubic structure
therefore melts at a relatively low temperature. The
high thermal stability of the cubic phase formed by
the ethoxylated sterols is probably related to an efficient packing of the sterol moieties. Self-diffusion
NMR measurements of samples from within the cubic

Fig. 10. -Sitosterol ethoxylates.

Fig. 11. Surface tension for phytosterol with 20 oxyethylene units


as a function of time at fixed concentration 3.44= 10y6 M9 from
Folmer et al. w53x with permission..

K. Holmberg r Current Opinion in Colloid & Interface Science 6 (2001) 148159

157

Acknowledgements
Dan Lundberg at Chalmers University of Technology is acknowledged for help with the literature
search. This review on natural surfactants and some
of the work referred to are part of the activities
within SNAP, the Centre for Surfactants from Natural Products which is sponsored by VINNOVA and by
several companies.
References and recommended reading

Fig. 12. Phase diagrams for phytosterol with a. five oxyethylene


units; b. 10 oxyethylene units; c. 20 oxyethylene units; and d. 30
oxyethylene units. L1, L2, L , L , I1, Nc , and H1 indicate the
following phases: micellar, reversed micellar, lamellar, gel, closedpacked micellar cubic, nematic, and hexagonal, respectively from
Folmer et al. w53x with permission..

phase has shown the presence of elongated aggregates with an axial ratio of 1.6 w54x.

5. Conclusions

The review has covered work performed in recent


years in three areas, i.e. surfactants produced from
bacteria and yeast, surfactants based on either sugar
or amino acid as polar headgroup, and surfactants
based on either fatty acid or sterol as hydrophobic
tail. All three areas are important and subject to
considerable research activity. The natural surfactants
obtained by these approaches are generally well characterized and the performance are up to the standards of conventional surfactants. The biotechnologically produced surfactants suffer from high cost due
to relatively low yield in the fermentation and cumbersome work-up procedures. The surfactants based
on either a natural polar headgroup or a natural
hydrophobic tail show great promise for the future.

of special interest
of outstanding interest

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