Journal of Oleo Science

Copyright ©2012 by Japan Oil Chemists’ Society

J. Oleo Sci. 61, (6) 343-348 (2012)

Synthesis and Interfacial Properties of Monoacyl

Glyceric Acids as a New Class of Green Surfactants
Tokuma Fukuoka1, Shintaro Ikeda2, Hiroshi Habe1, Shun Sato1, Hideki Sakai2,
Masahiko Abe2, Dai Kitamoto1＊ and Keiji Sakaki1
1
Research Institute for Innovation in Sustainable Chemistry, National Institute of Advanced Industrial Science and Technology (AIST) (Tsukuba
Central 5-2, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, JAPAN)
2
Faculty of Science and Technology, Tokyo University of Science (Yamazaki 2641, Noda, Chiba 278-8510, JAPAN)

Abstract: Glyceric acid (GA) is one of the most promising functional hydroxyl acids, and it is abundantly
obtained from glycerol by a bioprocess using acetic acid bacteria. In this study, several monoacyl GAs were
synthesized by esterification of GA and saturated fatty acyl chlorides (C12, C14, C16, and C18), forming a
new class of bio-based surfactants. By the present method, a mixture of two isomers, namely 2-O-acyl and
3-O-acyl GAs, was produced, in which the 2-O-acyl derivatives were obtained as a major product. These
isomers were isolated, and their surface-active properties were investigated for the first time. The surface
tensions of 2-O-acyl GAs with different chain lengths were determined by the Wilhelmy method. At
concentrations below 10-4 M, the 2-O-acyl GAs exhibited higher surface-active properties compared to
commercially available synthetic surfactants. For example, 2-O-lauroyl GA reduced the surface tension of
water to around 25 mN/m above the critical micelle concentration (3.0×10-4 M). In addition, 2-O-acyl
derivatives showed higher surface-tension-lowering activity than 3-O-acyl GAs. The monoacyl GAs
synthesized herein can potentially be used as “green surfactants.”

Key words: glyceric acid, glycerol use, surfactant, green material, biorefinery

1 INTRODUCTION example, we have recently reported the synthesis of

Over the last decade, the production of biodiesel fuels branched poly （lactic acid） s containing GA and their poten-
based on fatty acid methyl esters from vegetable oils has tial use as novel bio-based modifiers for bioplastics. In ad-
dramatically increased. Glycerol is normally generated as a dition, we have synthesized several diacyl GAs and evaluat-
by-product of the transesterification of triglycerides in the ed their biological properties13, 14）.
biodiesel and oleochemical industry, and many projects are Previously, a mixture of GA esters biochemically pro-
under way to convert the surplus glycerol into various val- duced by Penicillium funiculosum was reported to
ue-added products1−4）. exhibit antitrypsin activity15）. We reported that chemically
Recently, we developed a new and effective technique to synthesized dioleoyl GAs also exhibit antitrypsin activity13）.
biocatalytically produce glyceric acid（GA）from raw crude Moreover, synthesized dilinoleoyl D-GA exhibited no signif-
glycerol using acetic acid bacteria5−8）. GA is a promising icant cytotoxic effects in normal human dermal fibroblasts
glycerol derivative because it can be used as a kind of or microvascular endothelial cells14）. These results suggest-
functional organic acid9）. In particular, D-GA has several bi- ed that acyl GAs could potentially be used as functional
ological actions, including diuresis10）, liver-stimulating and lipids in pharmaceuticals and cosmetics.
cholesterolytic activities11）, and the acceleration of ethanol In addition, acyl GAs are amphiphilic and can thus con-
and acetaldehyde oxidation12）. However, to promote the stitute a new class of bio-based surfactants. The design of
use of GA, further functional analysis of GA and GA deriva- bio-environmentally compatible surfactants based on
tives is necessary. natural renewable resources has become increasingly im-
We have thus focused our attention on the multifunc- portant; surfactants that are“greener,”milder, and more
tionality of GA and are developing GA-based functional efficient are now demanded for a wide variety of applica-
materials by using GA as a building block compound. For tions. Acyl GAs have great potential for use as“green sur-

＊
Correspondence to: Dai Kitamoto, Research Institute for Innovation in Sustainable Chemistry, National Institute of Advanced
Industrial Science and Technology (AIST) (Tsukuba Central 5-2, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, JAPAN)
E-mail: [email protected]
Accepted December 20, 2011 (received for review November 19, 2011)
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
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343
 T. Fukuoka, S. Ikeda, H. Habe et al.

factants”because they are readily synthesizable into firmed by 1H nuclear magnetic resonance
（NMR）analysis.
simple structures from cost-effective precursors that are
derived from waste products. However, the diacyl GAs syn- 2-O-lauroyl GA（2C12GA）: 1H NMR（CDCl3, 600 MHz）: δ
thesized in our previous study showed poor water solubility 5.19（t, 1H, J＝3.8 Hz, H-2）, 4.08（dd, 1H, J＝4.4, 12.5 Hz,
and evaluating their surface actions was difficult. In this H-3b）, 4.01（dd, 1H, J＝3.3, 12.1 Hz, H-3a）, 2.44（m, 2H,
study, we set out to selectively synthesize monoacyl GAs H-2’ ）, 1.66
（m, 2H, H-3’ ）, 1.20−1.40（br, 16H, -CH2-）, 0.88
and evaluate their interfacial properties since these are （t, 3H, J＝7.0, -CH3）; 13C NMR（CDCl3, 150 MHz）: δ 173.1
more hydrophilic than the diacyl derivatives. and 172.6（C＝O x2）, 72.6（C-2）, 62.1（C-3）, 33.8（C-2’ ）,
24.7（C-3’ ） （-CH2-）
, 31.9, 29.0−29.7, and 22.7 , 14.1（-CH3）.

3-O-lauroyl GA（3C12GA）: 1H NMR（CDCl3, 600 MHz）: δ

2 EXPERIMENTAL PROCEDURES 4.48（m, 1H, H-3b）, 4.47（s, 1H, H-2）, 4.36（dd, 1H, J＝5.5,
2.1 Materials 12.8 Hz, H-3a）, 2.35（t, 2H, J＝7.5 Hz, H-2’ ）, 1.61（m, 2H,
GA was obtained from the fermentation of glycerol using H-3’ ）, 1.20−1.40（ br, 16H, -CH 2-）, 0.88（ t, 3H, J＝7.0,
the acetic acid bacterium, Gluconobacter frateurii -CH3） ; 13C NMR
（CDCl3, 150 MHz） : δ 174.3 and 173.3（C＝O
NBRC103465. The standard procedure for the production x2）, 69.4（C-2）, 65.2（C-3）, 34.0（C-2’ ）, 24.8（C-3’ ）, 31.9,
of GA has previously been reported7）. The obtained GA was 29.0−29.7, and 22.7（-CH2-） , 14.1（-CH3） .
mainly composed of D-GA（73％ ee）. Other reagents and
solvents were commercially available and used as received. 2.4 Measurements
Structural analysis of the obtained fatty acyl GAs dis-
2.2 Synthesis of monoacyl GAs solved in deuterated chloroform （CDCl3） was performed by
1
The following standard procedure for the synthesis of H and 13C NMR using a JEOL JNM-LA600 （600 MHz）.
monolauroyl GA（C12GA）was adopted. A mixture of GA The surface tension of the purified acyl GA was deter-
（3.0 g, ca. 28 mmol）, triethylamine（10 mL, ca.72 mmol）, mined using a Krüss K100C Wilhelmy auto surface tensi-
and N,N-dimethyl-4-aminopyridine （0.25 g, ca. 2 mmol） was ometer with a platinum plate at 25℃. Continuous measure-
dissolved in acetone（100 mL）. Lauroyl chloride（2.4 g, ca. ments were carried out until the change in the surface
11 mmol）was added to the reaction mixture in small steps, tension became less than 0.01 mN/m per 90 s.
and the mixture was stirred at room temperature for 1 h. The emulsifying activity of the obtained monoacyl GA
Next, the reaction mixture was evaporated, and then 100 was determined using a modified colorimetric method as
mL of ethyl acetate, 20 mL of 7％ aqueous HCl, and 80 mL previously reported16）: 100 μL of soybean oil, which was
of water were added to the reaction mixture. The ethyl used as the hydrophobic phase, was added to a test tube of
acetate phase was extracted, washed twice with brine, 4 mL of distilled water containing the purified acyl GA（1
dried over MgSO 4, and then evaporated. The resulting mg）. The test tubes were then vortexed thoroughly for
white solid was purified by silica gel（Wako-Gel C-200） exactly 1 min and allowed to stand at room temperature.
column chromatography using elution with chloroform, After 3 h, the lower 1 mL of the mixture was transferred to
chloroform:acetone （80:20, vol/vol）, and acetone. The frac- a cuvette, and its turbidity was measured at 620 nm. The
tions containing the target compound were collected and emulsifying activity was expressed as the optical density; a
evaporated. Approximately 2.16 g of white solid was ob- solution containing no surfactant was used as a control.
tained（yield: ca. 68％） . Sodium dodecyl sulfate（SDS）and monolaurin were also
Similarly, monomyristoyl GA（C14GA）, monopalmitoyl used as references. All measurements reported herein are
GA（C16GA）, and monostearoyl GA （C18GA） were obtained mean values from at least three separate experiments.
at a yield of about 70％ each.

2.3 Separation of 2-O-acyl and 3-O-acyl GAs

The following standard procedure for the separation of 3 RESULTS AND DISCUSSION
2-O-lauroyl GA（2C12GA） and 3-O-lauroyl GA （3C12GA） was 3.1 Synthesis and purification of monoacyl GAs
adopted. The obtained C12GA mixture described above Very recently, we synthesized diacyl GAs via the esterifi-
was subjected to precise silica gel column chromatography cation of GA under the condition of excess acyl chloride. In
using elution with chloroform:acetone （80:20, vol/vol）. The the present study, to preferentially synthesize monoacyl
fractions were analyzed by high-performance thin-layer GAs, we performed the esterification of GA using lauroyl
chromatography（HPTLC）on silica plates（silica gel 60F254, （C12） （C14）
, myristoyl （C16）
, palmitoyl （C18）
, and stearoyl
Merck）with chloroform:methanol（90:10, vol/vol）. The chloride under the GA-rich condition（Fig. 1）. After a 1 h
upper spot was identified as 2C12GA and the lower spot as reaction time, as determined by thin layer chromatography,
3C12GA. The purity of the separated lauroyl GA was con- the hydrophilic monoacyl GA was obtained as a major com-
344
J. Oleo Sci. 61, (6) 343-348 (2012)
 Synthesis and Interfacial Properties of Monoacyl Glyceric Acids as a New Class of Green Surfactants

Fig. 1 Synthesis of monoacyl glyceric acids.

ponent in the reaction mixture, and the spots derived from

a free fatty acid and diacyl GA were observed at the same
time. We were unable to reduce the incidence of these by-
products by changing the reaction conditions, but these
more hydrophobic compounds could be removed by silica
gel column chromatography by elution with chloroform.
As an example of the obtained monoacyl GA, a 1H NMR
spectrum of the easily separated monolauroyl GA is shown
in Fig. 2. The spectrum confirmed that the product is a
mixture of 2-O-lauroyl GA（2C12GA）and 3-O-lauroyl GA Fig. 3 1H NMR spectra of the purified monolauroyl
（3C12GA）. Two clearly distinguishable peaks were detect- glyceric acids: (a) 2-O-lauroyl glyceric acid
ed between the peaks derived from 2C12GA （peak a: H-2 at (2C12GA) and (b) 3-O-lauroyl glyceric acid
5.19 ppm, b: H-3 at 3.99−4.09 ppm, and c: H-2’at 2.44 (3C12GA).
ppm）and 3C12GA（a’: H-2 at 4.47 ppm, b’: H-3 at 4.35−
4.49 ppm, and c’: H-2’at 2.35 ppm）. The relative propor- rin18）. In contrast, herein, we preferentially prepared and
tions of 2C12GA and 3C12GA were estimated to be 81％ characterized 2-O-acyl GAs for the first time. We next in-
and 19％, respectively, as based on the area ratio of these vestigated the interfacial properties of these monoacyl GA
peaks on the 1H NMR chart. homologs.
These isomers could be precisely separated by column
chromatography using elution with chloroform:acetone 3.2 Surface-active properties of monoacyl GAs
（80:20, vol/vol）. By HPTLC using elution with chloroform: We determined the surface tension of aqueous solutions
methanol（90:10, vol/vol）, the purified 2C12GA showed a of purified monoacyl GAs by the Wilhelmy method. First,
higher R f value compared to 3C12GA（Fig. 3）. 1H NMR we evaluated the surface activities between 2-O-acyl GAs
spectra of the purified isomers are shown in Fig. 3, and the with different chain lengths（C12-C18）because 2-O-acyl
chemical shifts of these compounds are summarized in derivatives can be obtained as a major product in the
Section 2. 3. present reaction. Figure 4 shows the surface（air-water）
In the case of C14, C16, and C18GA, 2-O-acyl derivatives tension versus concentration plots for 2C12GA, 2C14GA,
were also preferentially obtained（＞80％）, which was esti- and 2C16GA in distilled water at 25℃. The estimated criti-
mated by NMR. The 2- and 3-O-acyl derivatives were puri- cal micelle concentrations（CMCs）and surface tensions at
fied using the same method. the CMC（γCMC）of these compounds are summarized in
A 3-O-acyl GA was previously isolated from plants17）. In Table 1. The surface tension of 2C18GA was not measured
addition, Ahn et al. reported the synthesis of 3C12GA by because of its poor water solubility.
selective oxidation of the primary alcohol in 1-monolau- The CMC values for these compounds decreased with in-
creasing chain length. This surface behavior, based on the
increase in hydrophobic interactions, corresponds well
with the general rules of synthetic surfactants. The surface
tension of these compounds, however, had a tendency to
decrease with decreasing chain length. In particular,
2C12GA reduced the surface tension to around 25 mN/m
above the CMC. These results indicate that the present
2-O-acyl GAs show excellent interfacial activity compared
to commercially available synthetic surfactants such as sat-
urated fatty acid sodium salts（fatty acid soaps）19）, SDS20）,
and 1-O-monolauroyl glycerol（1-monolaurin）21）. CMC and
γCMC values for these surfactants were as follows: C12
Fig. 2 1H NMR spectrum of a mixture of monolauroyl soap（2.0×10−2 M, ca. 36 mN/m）, C14 soap（4.0×10−3 M,
glyceric acids. ca. 36 mN/m） , C16 soap（1.8×10−4 M, ca. 36 mN/m）, mea-
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J. Oleo Sci. 61, (6) 343-348 (2012)
 T. Fukuoka, S. Ikeda, H. Habe et al.

Fig. 4 Surface tension-concentration plots of the pu-

rified 2-O-acyl glyceric acids (C12, C14, and Fig. 5 Surface tension-concentration plots of the puri-
C16). fied monomyristoyl glyceric acids.
Table 1 Physicochemical properties of 2-O-
those of 3C14GA were 7.0×10−5 M and 35.0 mN/m. Both
acyl GAs
C14GA isomers showed higher water solubility and surface-
CMC (M) γCMC (mN/m) tension-lowering activity compared to similarly structured
2C12GA 3.0×10 −4
25.6 1-O-monomyristoyl glycerol（1-monomyristin; CMC＝5.8×
−5 10−6 M, γCMC＝48.0 mN/m）21）. The increase in hydrophi-
2C14GA 9.3×10 28.7
−5
licity is attributable to the presence of a carboxyl group in
2C16GA 2.9×10 34.1 the hydrophilic domain. In addition, the 2-O-acyl derivative
exhibited higher surface tension-lowering activity com-
sured in 0.01 M NaOH solution; SDS（8.1×10−3 M, ca. 38 pared to the 3-O-acyl derivative. The data suggest that the
mN/m）; and 1-monolaurin（4.4×10−5 M, 36.2 mN/m）. The 2-O-acyl derivative has stronger intermolecular polar head
remarkable surface-tension-lowering activity of these GA- interactions compared to the 3-O-acyl derivative. On the
based surfactants compared to commercially available ma- other hand, based on a molecular dynamics study of mono-
terials is attributable to strong intermolecular hydrophilic acyl GAs（data not shown）, the 2-O-acyl derivative has
interactions（i.e., hydrogen bonding）between the bulky more sterically bulky hydrophilic groups on the hydropho-
polar carboxyl and hydroxyl head groups of GA and water bic acyl chain compared to the 3-O-acyl derivative. The dif-
at the surface. ferences in the molecular configuration of monoacyl GAs
In addition, by carefully observing the surface tension may also significantly contribute to their excellent surface-
curves of these 2-O-acyl GAs, a biphasic change of surface tension-lowering activities.
tension seemed to occur （Fig. 4） . This behavior suggests a Meanwhile, we also examined the surface activities of
rather complicated molecular event in the surfactant solu- the unpurified mixture of monoacyl GA isomers. The
tion; however, in this study, we could not demonstrate the mixture was confirmed to exhibit surface-tension-lowering
morphology changes of the aggregates by dynamic light activity comparable to those of the corresponding 2-O-acyl
scattering and pyrene fluorescence. Further investigations GAs described above. Therefore, from a practical point of
are needed to clarify this surface behavior of monoacyl view, the mixture of the present GA-based surfactants is
GAs. more easily available since it is capable of being used
without separation and purification.
We then compared the surface activities of 2- and We next examined the emulsifying activity of monoacyl
3-O-acyl GAs. For example, Fig. 5 shows the surface-ten- GAs by simple turbidity measurements as previously re-
sion-lowering activities of 2C14GA and 3C14GA. The esti- ported16）. The activity of C12GA was comparatively evalu-
mated CMC and γCMC of 2C14GA were 9.3×10−5 M and ated using synthetic surfactants bearing lauric acid as a hy-
28.7 mN/m, respectively, and the respective values for drophobic chain. With respect to soybean oil, the present
346
J. Oleo Sci. 61, (6) 343-348 (2012)
 Synthesis and Interfacial Properties of Monoacyl Glyceric Acids as a New Class of Green Surfactants

cation of GAs contributes to the development of a new

technology for utilizing surplus glycerol.

ACKNOWLEDGEMENT
This work was partly supported by Japan-U.S. coopera-
tion project for research and standardization of Clean
Energy Technologies（ heisei 22・05・20 zai-san the first
number） .

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