92 FORMULATING FOR MILDNESS
Amino acid-based surfactants:
more than just ‘natural’!
n Dr Alexander T Wagner - Zschimmer & Schwarz, Germany
Amino acids are key components of the
human metabolism: Glutamate (Fig 1a), for O O- O O- O O-
instance, is the most important substance in
the brain to transport information from one
nerve cell to another. It is a
neurotransmitter. Additionally, amino acids + + +
can be linked together in different H3N H3N H2N
combinations to create shorter (peptides)
and longer (proteins) chains. Both fulfil a O-
variety of different vital functions in the
human body: Collagen, for instance, is the
most frequently occurring protein in the
O
human body. It is composed of three
intertwined chains (triple helix) to lend
structure to connective tissue. Simply for a b c
spatial arrangement reasons in this protein Figure 1: Examples for natural amino acids in aqueous solutions (pH 7):
the smallest amino acid, glycine (Fig 1b), is a) Glutamate, b) Glycine, c) Sarcosine
the main component.
The water solubility of amino acids also surfactants are an ideal choice for natural solutions, sensitivity to water hardness).2
makes them an attractive choice for the cosmetic applications. The ‘trick’ is to insert a suitable spacer
hydrophilic part of surfactants. When an Contrary to expectations, the between the hydrophobic part and the
amino acid is linked with a triglyceride- development of amino acid surfactants is carboxylate group (Fig 2). By the way, in the
derived fatty acid (e. g. from coconut oil), not a result of the current trend towards 1930s also another solution was found: To
surfactants (N-acyl derivatives, “amino acid ‘green’ surfactants. The first examples were introduce a sulfo-group and to “block” or
surfactants“, Fig 2a) exclusively based on patented in the 1930s.1 Already at that time replace the carboxylic group of fatty acids
natural components are created. When the one candidate, a derivative of sarcosine (e. g. acyl isethionates2 and fatty alcohol
amino acid is produced via a fermentation (Figs 1c, 2a), was introduced to the market. sulfates).3
process starting from glucose or its The original idea behind this development The attractiveness of amino acid
derivatives, the surfactants even are was to create surfactants alternative to surfactants for cosmetic applications is
completely composed of renewable raw soaps (Fig 2b) to overcome their drawbacks additionally based on two other aspects: At
materials (e. g. cocoyl glutamate). Those (precipitation in pH-neutral aqueous first, they are proven mild and well foaming
surfactants. Secondly, they are excellent
a
biodegradable. The linkage between the
O O- hydrophobic and the hydrophilic part of the
O surfactant is an amide bond (Fig 2a). This
type of bondage is frequently ‘used’ by
nature (e.g. in peptides and proteins) and
can therefore easily be cleaved by nature´s
N R
enzymes.
R* Acyl sarcosinates and acyl
glycinates: unequal siblings
The difference between sarcosine and
b O glycine is: In sarcosine one hydrogen atom
at the nitrogen atom is replaced by a
methyl group (Figs 1b,1c). The seemingly
small difference has an immense impact on
O- the physical properties of the
corresponding N-acyl derivatives. This can
Figure 2: a) Surfactants based on N-lauroyl amino acids (amino acid surfactants), R: Amino acid specific directly be traced back to the capability of
rest, R*: H for glutamates and glycinates, CH3 for sarcosinates b) Soap (laurate) acyl glycinates to create hydrogen bonds
PERSONAL CARE EUROPE April 2020
FORMULATING FOR MILDNESS 93
between the molecules.4 For acyl
Acyl glycinate Acyl sarcosinate
sarcosinates, however, this is not possible
(Fig 3). In the following some of the
O O
consequences are described.
Amino acid surfactants are produced via
a two-step synthesis route starting from O O
fatty acid. This process leads to a salt N N
H
content of 5% and more in customary 30%
amino acid surfactant solutions. O- O-
Additionally, these solutions contain O
unreacted free amino acid. For some
consumer products, however, a high purity O O
grade is required. The reasons, for instance,
N O
can be reduced stabilities of ‘salty’ products H
or unwanted colour reactions of the free O- N
amino acid with other ingredients (e.g.
essential oils). Some customers therefore O-
prefer a limited content of salt and free
amino acid of maximum 0.5% or even
lower. For the purification process the Figure 3: Two amino acid surfactants: Hydrogen bonds (hashed line) can be created only in acyl
melting point of the protonated amino acid glycinates.
surfactant plays a major role. For
protonated lauroyl sarcosinate (lauroyl Disordered micellar structures: Low viscous Ordered structures: Viscous
sarcosine) the melting point is about 50°C
whereas for lauroyl glycine and lauroyl
glutamic acid it is about 120°C and 100°C.5
Protonated amino acid surfactants which
are liquid at a temperature below 80°C – Protonation of acyl sar-
90°C enable an easy purification step. So,
cosinate/acyl glycinate
this is only possible for lauroyl sarcosinate.
As a consequence, commercial aqueous
lauroyl sarcosinate solutions often have a
low salt concentration. In contrast to this,
there are only very few suppliers for highly
pure cocoyl glycinate and cocoyl glutamate Hydrophilic surfactant part
solutions on the world-wide market. To Hydrophobic surfactant part
desalt them a more sophisticated
procedure is necessary. Figure 4: Radical change of micellar structures: Thickening by lowering the pH.
Another significant difference between
the lauroyl derivatives of sarcosine and viscosity of sodium cocoyl glycinate solutions its ultra-mildness, which is proven in clinical
glycine is their solubility. Additional can be in the range of several thousand tests.10 In addition, the preferred pH-range
intermolecular hydrogen bonds stabilise mPa∙s. Therefore, already in the production to use acyl glycinates is the neutral to
the solid acyl glycinate form which reduces process problems can arise. Also, for some alkaline pH-range. These facts turn cocoyl
the water solubility. A suitable measure to applications (highly) viscous cocoyl glycinate glycinate into an ideal candidate for
prove this is the Krafft-temperature. It solutions are difficult to handle. Two very pH-neutral baby care applications as their
informs about the minimum temperature effective measures to reduce the viscosity of skin has a pH of about 7. As shown later in a
above which surfactants are water-soluble. cocoyl glycinate solutions will be suggested frame formulation, by adding suitable co-
For sodium lauroyl glycinate it is above when Zschimmer & Schwarz products are surfactants clear formulations can also be
room temperature even in weakly alkaline introduced. created in a pH-range of about 6.
solutions.6 In contrast, sodium lauroyl The capability of acyl glycinate to create
sarcosinate is easy to handle in aqueous intermolecular hydrogen bonds also has Acyl glutamates: completely
solutions. At pH 7.5 the deprotonated advantages. By these bonds, the stability of sustainable
anionic form is predominant 2,7 and the foam in comparison to acyl sarcosinate is With a longer carbon chain and an
Krafft-temperature is below room enhanced.4 It was shown that via additional carboxylate group the
temperature. Sodium lauroyl sarcosinate is intermolecular hydrogen bonds the foam derivatives of glutamates (Figs 1a,2a) have
soluble even in cold water and in slightly lamella elasticity is increased.8 This means some different properties than acyl
acidic solutions. In a solution of the soap that the bursting of foam bubbles is slowed glycinates and acyl sarcosinates. In the
sodium laurate, on the other hand, at down. In cosmetic applications consumers production process the additional
pH 7.5 already 50% of the soap is turned often perceive stable foam as a very creamy carboxylate group leads to side-reactions
into water-insoluble lauric acid. This foam. The stabilisation of foam by which reduce the yield of the target
confirms the statement that sodium lauroyl intermolecular hydrogen bonds is a general product. To avoid this, surfactants based on
sarcosinate is the “better soap“.2 phenomenon.9 In cosmetic products normally acidic amino acids like acyl glutamates
The different behaviour of acyl mixtures of different surfactants are used. usually are synthesised in aqueous solutions
sarcosinates and acyl glycinates can also be Acyl glycinates with their ability to create to which a solvent is added. This was
seen in the viscosity of their 30% aqueous hydrogen bonds are a smart choice to create already recommended in the patent of the
solutions. Whereas the viscosity of sodium a creamy foam also in surfactant mixtures. 1930s.1 When the solvent is volatile like
cocoyl sarcosinate solutions is water-like, the A unique property of cocoyl glycinate is acetone it is removed afterwards to avoid
April 2020 PERSONAL CARE EUROPE
94 FORMULATING FOR MILDNESS
its smell or other adverse effects. In case of
using the odourless propylene glycol the Lauroyl Sarcosinate Lauroyl Sarcosine
solvent usually remains in the product.
Acyl glutamates have a hydrogen atom at
O- OH
the nitrogen atom so they should be able to
create intermolecular hydrogen bonds like
acyl glycinates (Fig 1). But because of the
‘bulkiness’ of the glutamate group these O O
hydrogen bonds play a minor role, if any.
Regarding solubility properties in aqueous R: C11 O N O N
solutions, for instance, cocoyl glutamate
behaves like cocoyl sarcosinate: It is easily
Hydrophilic part R
soluble in cold water even in weakly acidic R
solutions, so it is also a ‘better soap’.2
In comparison to the sarcosine and Hydrophobic part
glycine derivatives, cocoyl glutamates have
some further useful properties. For
instance, they are excellent oil-in-water Figure 5: Anionic and neutral form of an amino acid surfactant: Effective spatial arrangement within
(OW) emulsifiers for oils of different polarity micelles. For the position of the “border” between hydrophobic and hydrophilic parts see literature.11
like vegetable oils and paraffins. Emulsions
based on aqueous cocoyl glutamate Acyl glutamate
solutions are cold-processable. Further
‘add-on’ properties of acyl glutamates are
O- O-
discussed in the next section.
Acyl glutamates made from vegetable
oils are completely based on renewable raw
materials. When propylene glycol made
from glycerol is used in the production
process, this claim is still valid. O O
Nevertheless, some customers prefer
propylene glycol-free cocoyl glutamate
solutions. HN O
Surfactants in sulfate-free products for
the natural cosmetics market usually are
combinations of cocoyl glutamate and
sugar surfactants or their derivatives. As
cocoyl glutamate is a main surfactant in
R
these formulations the requirements in
terms of purity usually are very high.
The principle ‘thickening without
thickeners’ Figure 6: Schematic spatial arrangement of acyl glutamates within micelles.
To create viscous aqueous cleansing
formulations two different paths are taken. group of the lauryl sulfoacetate and the alkyl (ether) sulfates. The difference is the
Alkyl (ether) sulfate solutions are thickened carboxylic group of CAPB when it is trigger (here: pH-value, there: salt). Some
by adding salt. For other surfactant deprotonated. The disordered micelle examples of thickening amino acid
solutions the addition of thickeners is shape creates low-viscous solutions (Fig 4). surfactant solutions via pH-adjustement are
required which in some cases is unwanted. Now advantage is taken of the fact that by shown in the next section.
The usage of thickeners can be lowering the pH-value below 7 the The above-mentioned property applies
circumvented when lauroyl sarcosinate or carboxylate group of amino acid to lauroyl sarcosinate and cocoyl glycinate.
cocoyl glycinate are combined with surfactants is more and more discharged For cocoyl glutamate the situation is
suitable other surfactants. Via pH- via protonation.2 Figuratively speaking, the completely different as the hydrophilic
adjustment the viscosity of these surfactant ‘triangles’ are more and more turned to group here is inherently bulky (Figs 1,6).
solutions can easily be enhanced to 4.000 ‘rectangles’: ‘Ordered’ micelle structures In alkaline solutions acyl glutamates are
mPa∙s and more. In two formulations can arise at a pH-value of about 5 – 6 (Figs double negatively charged. This
introduced in the next section both amino 4,5). This can cause a drastic viscosity combination (molecular structure of the
acid surfactants are combined with lauryl increase of the formulation. The negative hydrophilic group plus two charges) can be
sulfoacetate and cocamidopropyl betaine charge of sulfonate groups does not used for the opposite effect: To ‘break’ the
(CAPB). Usually the surfactant change by lowering the pH3 whereas there viscosity of surfactant solutions (hydrotropic
concentration in aqueous cosmetic is probably also a contribution of CAPB’s surfactant).14,15 As an illustration of this
solutions is so high that they are associated carboxylic group to the viscosity increase. effect see Figure 4 from right to left
in micelles. A small part is shown in Figure As a consequence of its betaine structure (reverse arrow). In the next section an
4. The wedge-shape (‘triangle’-shape) for the pH-dependent behaviour of this example for the viscosity decreasing effect
lauroyl sarcosinate (Fig 5) is the result of carboxylic group (protonated or not of cocoyl glutamates as well as an example
repulsive forces between the carboxylate protonated) is very special. It is discussed for the viscosity increasing effect is
group of the amino acid surfactant and elsewhere.12,13 By the way, the basic introduced.
other anionic head groups: the sulfonate thickening mechanism is the same as for
PERSONAL CARE EUROPE April 2020
FORMULATING FOR MILDNESS 95
Amino acid surfactants
Zschimmer & Schwarz offers amino acid 18000
surfactant solutions under the brand name
Protelan: LS 9011/SL (INCI: Sodium Lauroyl
Sarcosinate), AGL 95 (INCI: Disodium Lauroyl
Glutamate), AGL 95/C (INCI: Disodium
Cocoyl Glutamate) and GC (INCI: Sodium 13500
Cocoyl Glycinate).
Additionally, in our portfolio there are
Viscosity in mPa·s
some very special products based on amino
acid surfactants. Lumorol K 5601 (INCI: 9000
Cocamidopropyl Betaine, Sodium Lauroyl
Sarcosinate, Sodium Lauryl Sulfoacetate) is
an example for the thickening principle
described in the last section. It is a sulfate-
4500
free ready-to-use blend which enables the
formulator to reversibly create an end-
product viscosity of about 4.000 mPa∙s via
pH-adjustment to about 5.5.3 In Sebumol S
1000 (INCI: MIPA-Cocoyl Sarcosinate, 0
Polyglyceryl-3 Polyricinoleate, Polyglyceryl-3 7.0 6.0 5.5 5.3 5.0 4.7
Diisostearate, Polyglyceryl-3 Caprate) pH
advantage of the liquid form of cocoyl
sarcosine and its alcohol amine salts is taken: Figure 7: Thickening by lowering the pH.
It is a clear, liquid and (nearly)
water-free product. The surfactants in this derivative with additional bacteriostatic and ‘natural’ counterpart of K 5601 from the
product are completely made from natural deodorising properties. same series. It was also introduced at the
building blocks. Mixtures of S 1000 with For some customers propylene glycol- in-cosmetics Global 2017 in London and is
different oils can be used for PEG-free free cocoyl glutamate solutions are of a ready-to-use-blend. A 40% aqueous
shower oil applications. Additionally, they are particular interest for natural cosmetic solution of K Natural can be thickened via
excellent PEG-free makeup removers.16 Table applications. Propylene glycol-free pH-adjustment (Fig 7). Via lowering the pH
1 shows an example formulation. The Protelan-Types are AG 915 SF (INCI: the glutamate carboxylate groups are
ingredient Sebumol ODPC was introduced Disodium Cocoyl Glutamate) and AG 37 more and more discharged by
earlier.16 It is a special moisturising ester with (INCI: Disodium Cocoyl Glutamate, Sodium protonation. By this, the strong viscosity
a completely natural basis. Cocoyl Glutamate). Both products are decreasing effect of acyl glutamates is
Aqueous cocoyl glycinate solutions like COSMOS approved and in the process of steadily reduced towards a (partial)
Protelan GC tend to be viscous. They can NATRUE certification. The properties of AG “knock-out”: The ‘wedge’-effect is
have a viscosity of several thousand mPa∙s. 915 SF were already discussed in detail weakened which is equal to a viscosity
Some customers prefer low viscous products. earlier.16 AG 37 was presented at increase. The additional trigger ‘salt’ for
As mentioned before, cocoyl glutamate is an in-cosmetics Global 2019 in Paris. It coco sulfate can be used to support the
excellent hydrotropic surfactant to reduce the matches the high requirements of natural viscosity increase in lower concentrated
viscosity of surfactant solutions. So, we cosmetic products concerning purity. With solutions of K Natural: The viscosity of a
added small amounts of cocoyl glutamate to AG 37 we succeeded in developing a 28% solution at pH 4.9 is about 8.000
GC. The resulting product is Protelan GG product with a salt content (sodium mPa∙s when 0.6% salt (sodium chloride) is
(INCI: Sodium Cocoyl Glycinate, Disodium chloride plus sodium glutamate) below added. The other blend, Zetesap 915 CS,
Cocoyl Glutamate) which has an easy-to- 0.2%. Table 3 shows a shower gel is a suitable raw material to prepare natural
handle viscosity of about 100 mPa∙s. It still formulation which is suitable for natural syndet wash pieces. The surfactants in this
has all the positive properties of cocoyl cosmetics. product are coco sulfate and cocoyl
glycinate. Table 2 shows a body shampoo Two surfactant blends containing cocoyl glutamate. The advantages of using this
formulation which takes advantage of the glutamate were developed for natural product were described earlier.2 Both
mentioned principle to enhance viscosity by cosmetic applications. Lumorol K Natural blends are ideal candidates for natural
pH-adjustment. The viscosity of this (INCI: Sodium Coco-Sulfate, Lauryl cosmetic products. In each of them cocoyl
formulation is about 10.000 mPa∙s at pH 6. Glucoside, Disodium Cocoyl Glutamate, glutamate is able to reduce the ‘harshness’
Another way to decrease the viscosity of Alcohol, Caprylyl/Capryl Glucoside) is the of coco sulfate.
cocoyl glycinate solutions is to reduce the
salt content drastically. The salt content
Table 1: PEG-free luxurious facial Cleansing Oil
(sodium chloride) of conventional 30% cocoyl
glycinate solutions like GC is about 5%. In Ingredients INCI w/w%
GC-D (INCI: Sodium Cocoyl Glycinate), the
Almond oil Prunus Amygdalus Dulcis (Sweet Almond) Oil 53.75
desalted version of GC, it is below 0.2%. This
product has a viscosity of about 100 mPa∙s. MIPA-Cocoyl Sarcosinate, Polyglyceryl-3 Polyricinoleate, Poly-
SEBUMOL S 1000 30.0
Some Protelan-Types are ideal candidates glyceryl-3 Diisostearate, Polyglyceryl-3 Caprate
for natural cosmetic applications. AG 8-EC Isopropyl palmitate Isopropyl Palmitate 10.0
(INCI: Disodium Capryloyl Glutamate) and Macadamia nut oil Macadamia Ternifolia Seed Oil 4.0
AGE-C (INCI: Disodium Cocoyl Glutamate)
SEBUMOL ODPC Octyldodecyl PCA 2.0
are COSMOS and Ecocert Cosmetics
Perfume Parfum (Fragrance) 0.25
approved. AG 8-EC is a short-chain (C8)
April 2020 PERSONAL CARE EUROPE
96 FORMULATING FOR MILDNESS
Conclusion Table 2: Very mild and creamy foaming Body Shampoo
The growing awareness of environmental
aspects increases the focus on the raw Ingredients INCI w/w%
materials used in cosmetic products. More
PROTELAN GG Sodium Cocoyl Glycinate, Disodium Cocoyl Glutamate 20.0
and more, ingredients are preferred that are
AMPHOTENSID B 5 Cocamidopropyl Betaine 15.0
made from natural substances. For
surfactants this applies to the hydrophobic Sodium Lauryl Sulfoacetate Sodium Lauryl Sulfoacetate 3.0
and the hydrophilic part. The amino acid Polyquaternium-47 (20%) Polyquaternium-47 1.0
surfactants shown in Figures 1 and 2a are an Perfume Parfum (Fragrance) 0.5
ideal choice as their components - fatty Water Aqua (Water) 60.5
acids and amino acids - are part of nature.
Procedure:
The linkage between them is also ‘natural’.
1. Stir to homogeneity until the solution is clear.
Therefore, amino acid surfactants are 2. Adjust the pH value with citric acid to 6.0.
excellent biodegradable. They are proven
to be mild with good foaming properties.
Table 3: Shower Gel for natural cosmetics
For natural cosmetics, cocoyl glutamate is
of special interest as it is completely based Phase Ingredients INCI w/w%
on renewable raw materials. For some A Water Aqua (Water) 50.5
customers in particular propylene glycol-
B Xanthan Gum Xanthan Gum 0.5
free cocoyl glutamate solutions are ideal
C ZUTELAN GL 810 Caprylyl/Capryl Glucoside 15.0
candidates for natural cosmetic
applications. ZUTELAN GL 124 Lauryl Glucoside 5.0
The N-acyl derivatives of glutamate, Perfume Parfum (Fragrance) 0.4
sarcosine and glycine are the most popular Disodium Cocoyl Glutamate / Sodium Cocoyl
D PROTELAN AG 37 20.0
amino acid surfactants in Europe. Glutamate
Zschimmer & Schwarz offers surfactants
Sodium Cocoyl Hydrolyzed
based on these amino acids for all needs of Sodium Cocoyl Hydrolyzed Wheat Protein 1.25
Wheat Protein
customers. The latest developments are the
propylene glycol-free Protelan AG 37 (INCI: Sodium PCA Sodium PCA 1.2
Disodium Cocoyl Glutamate, Sodium Glycerin Glycerin 4.2
Cocoyl Glutamate) and Protelan GC-D Lactic acid (80 %) Lactic Acid 1.5
(INCI: Sodium Cocoyl Glycinate). Both have Sodium Benzoate Sodium Benzoate 0.3
a very low content of salt and free amino Potassium Sorbate Potassium Sorbate 0.15
acids (in sum: below 0.2%). AG 37 is
approvable for natural cosmetic labels. All Procedure:
Zschimmer & Schwarz products mentioned 1. Add B to A and stir to a homogeneous gel.
in this article are preservative-free and also 2. Combine C and stir until it is clear and homogenous.
3. Add all components of D to C in the indicated sequence and stir to homogeneity.
available in RSPO-MB quality.
4. Combine AB and CD and stir to homogeneity.
The usage of amino acid surfactants in 5. Control the pH value and adjust if necessary to 5.3 - 5.5 (original).
combination with other suitable surfactants
is a highly attractive way to create viscous
cosmetic products without using thickeners: The better “Soaps”?, Personal Care Magazine foam stability, Advances in Colloid and
Lowering the pH-value starting from about 2019; 13(3): 111 – 114 Interface Science 2017, 247: 435 – 443
7 causes a steady protonation of the anionic 3 Wagner AT. Sulfate-free Surfactants: What 10 Regan J, Mollica LM, Ananthapadmanabhan
carboxylate group(s) of amino acid about Sulfonates?, Personal Care Magazine KP. A novel glycinate-based body wash, J. Clin.
surfactants. As a result of the neutral 2018; 12(2): 61 – 65 Aesthet Dermatol 2013, 6(6): 23 – 30
carboxylic function the micelle architecture 4 Raykundaliya N, Bordes R, Holmberg K, Wu J, 11 Zhang Y, Romsted LS, Zhuang L, de Jong S.
changes completely. By this, viscous Somasundaran P, Shah DO. The effect on Simultaneous Determination of Interfacial
aqueous surfactant solutions can be solution properties of replacing a hydrogen atom Molarities of Amide Bonds, Carboxylate
created. This is the case in the particularly with a methyl group in a surfactant. Tenside Groups, and Water by Chemical Trapping
attractive pH-range at around 5-6. Besides Surfactants Detergents 2015; 52(5): 369 – 374. Micelles of Amphiphiles Containing Peptide
this, cocoyl glutamates can additionally 5 Jungermann E, Gerecht JF, and Krems IJ, The Bond Models, Langmuir 2013; 29: 534−544
serve as viscosity reducer and are excellent preparation of Long Chain N-Acylamino Acids. 12 Rosen MJ, Zhu BY. Synergism in binary
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one percent of what nature has revealed to Langmuir 2010, 26 (5): 3077 – 3083. amphoteric surfactants, Journal of Colloid and
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are even more attractive possibilities for dodecanoyl sarcosinate solution at different surfactants. CESIO World Surfactant
them in cosmetic applications which we do pH, Colloid Polymer Sci 2012, 290: 323 – 330 Conference 2019.
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