Article

pubs.acs.org/JAFC

Biobased Fat Mimicking Molecular Structuring Agents for Medium-

Chain Triglycerides (MCTs) and Other Edible Oils
Julian R. Silverman†,§ and George John*,†,§
†
Department of Chemistry and Center for Discovery and Innovation (CDI), The City College of New York, 85 St. Nicholas Terrace,
New York, New York 10031, United States
§
Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, New York, New York 10016, United States
*
S Supporting Information

ABSTRACT: To develop sustainable value-added materials from biomass, novel small-molecule sugar ester gelators were
synthesized using biocatalysis. The facile one-step regiospecific coupling of the pro-antioxidant raspberry ketone glucoside and
unsaturated or saturated long- and medium-chain fatty acids provides a simple approach to tailor the structure and self-assembly
of the amphiphilic product. These low molecular weight molecules demonstrated the ability to self-assemble in a variety of
solvents and exhibited supergelation, with a minimum gelation concentration of 0.25 wt %, in numerous organic solvents, as well
as in a range of natural edible oils, specifically a relatively unstudied group of liquids: natural medium-chain triglyceride oils,
notably coconut oil. Spectroscopic analysis details the gelator structure as well as the intermolecular noncovalent interactions,
which allow for gelation. X-ray diffraction studies indicate fatty acid chain packing of gelators is similar to that of natural fats,
signifying the crystalline nature may lead to desirable textural properties and mouthfeel.
KEYWORDS: oleogels, coconut oil, molecular gelators, medium-chain triglycerides (MCTs), supergelators

■ INTRODUCTION
The recent ban of trans-fats and evolving discussion on the
safety of saturated fats have increased interest in healthful oils
and novel oil-structuring agents.1,2 Recently medium-chain
(C8−C12) triglyceride fats and oils have been demonstrated as
viable potential alternatives to long-chain fatty acyl oils in
creating functional gels and composites for food, medical, and
personal care applications.3,4 As edible, personal care, and
cosmetic oil mixtures depend greatly on the nature of the oil for
their organoleptic, rheological, and functional properties,
exploring applications of medium-chain triglyceride (MCT)
oils should result in viable value-added formulations.5
In an effort to design functional molecules from biobased
materials, much research has been focused on synthesizing
novel amphiphiles from biomass, including fatty acids and
sugars, as ester derivatives.6 Following a combined green
chemistry and biorefinery model approach (Figure 1A), it is
possible to develop sustainable and functional oil-structuring
agents from an array of natural products.7,8 By reversing the
equilibrium of lipase biocatalysis in nonaqueous solvents, it is
possible not only to design systems for rapid degradation in
aqueous environments9 but also to program amphiphile
functionality by selecting bioactive residues from nature.10
Since the 1960s, tasteless, odorless, and nontoxic sugar esters
have been used in a variety of industrial formulations as
nonionic surfactants in emulsions.11 The utilization of the
disparate hydrophobic fatty acid residues and hydrophilic
alcohol groups to spur gelation has been demonstrated with
sugar alcohol esters,12 monoacylglycerols,13 and hydroxylated
fatty acids, including 12-hydroxystearic acid.14
Toward the development of small-molecule solutions to
replace unhealthy trans-fat structuring agents, edible oil gels,
known as oleogels, have piqued researcher’s interests by
modifying formulation rheology with low molecular weight
gelators or, more simply, molecular gelators (MGs).12,15
Although natural and synthetic polymers, mostly methylated
and ethylated cellulose derivatives, have been demonstrated as
viable oil structuring agents,16 the serendipitous discovery of
small-molecule self-assembly as a method for structuring
solvents has led to the development and study of numerous
MGs.17−23 From gelator design to network assembly and
characterization, the variety of self-assembled networks of MGs
demonstrates an interdisciplinary effort to design functional
MG systems for myriad solvents and liquid mixtures. Despite
the popularity and functionality of MCT fats and oils, there are
relatively few efforts focused on developing MGs to specifically
gel this increasingly popular category of oils.24,25
A widely available MCT oil, coconut oil, is a major
component of South and Southeast Asian diets, deriving
antimicrobial, antifungal, and antiviral functionality from its
constituent 12-carbon lauric acid.3,26 Another versatile MCT
oil, palm kernel oil, extracted from the edible seed of the oil
palm tree, is often used after saponification in soapmaking due
to its quick lathering, which is also attributed to its lauric acid
content.27 By exploiting MCT-derived fatty acids in mixtures as
functional solvents for gels, MCT oleogels present interesting
multifunctional alternatives to conventional fat and oil mixtures.
In selecting components for the gelator, it may prove useful
to select similarly benign and functional components.
Following the biorefinery model and choosing from the wide
array of bioactive molecules, the study of artificial biobased
Received: September 5, 2015
Revised: November 17, 2015
Accepted: November 19, 2015
Published: December 1, 2015

© 2015 American Chemical Society 10536 DOI: 10.1021/acs.jafc.5b04236

J. Agric. Food Chem. 2015, 63, 10536−10542
Journal of Agricultural and Food Chemistry
Figure 1. (A) Schematic demonstration of the combined biorefinery model with green chemistry principles, extracting reagents from waste and
biomass resources to develop functional materials from value-added chemicals. (B) Synthetic scheme for the development of novel medium- and
long-chain triglyceride gelators following the model.
gelators may serve to aid in both the applied engineering of
materials and the fundamental study of biomolecules.
Devising a fatty acid glucoside variation on the fatty acid
sugar ester theme, the pro-antioxidant raspberry ketone
glucoside was coupled with saturated (caprylic and stearic)
and unsaturated (oleic) fatty acid tails (Figure 1B).28 To
explore the amphiphile’s gelation capability, medium- and long-
chain oils were mixed to form a variety of structured fats
depending on the gelator concentration. The individual fatty
acid, glucose, and phenol residue can be probed for further
functionality and their role in hierarchical 3D self-assembly to
better understand the complex phenomenon that is self-
assembled small-molecule gelation.
■
MATERIALS AND METHODS
Materials. Natural and refined vegetable oils were purchased from
local supermarkets. Unrefined (pressed) coconut oil (Keratech Ltd.,
Kerala, India; and Brad’s Organic Raw Oil, Sri Lanka), refined coconut
oil (Bedesse Imports, Thailand), palm kernel oil (Dr. Adorable Inc.,
Ghana), and hazelnut and grape seed oils (Trader Joe’s, Italy) were
obtained from the vendors noted. Raspberry ketone glucoside was
provided by Beijing Brilliance Bio, and fatty acid, methyl, and vinyl
esters were purchased from TCI America. Lipase acrylic resin
(Novozymes 435) from Candida antarctica (≥5000 U/g), recombi-
nant, expressed in Aspergillus niger was provided by Novozymes. Silica
gel (200−300 mesh), hexanes, ethyl acetate, and acetone were
purchased from Thermo Fisher (Waltham, MA, USA). Prior to use as
solvent for reactions, acetone was distilled over calcium chloride.
Raspberry Ketone Glucoside Fatty Acid Ester Synthesis. In a
500 mL screw-cap Erlenmeyer flask, solid Novozymes 435 lipase
catalyst (0.3 g/mmol glucoside) was added to mixture of raspberry
ketone glucoside (2.0 mmol, 0.652 g), and fatty acid, methyl ester, or
fatty acid vinyl ester (3:1 mmol acyl donor/glucoside ratio) containing
50 mL of dried acetone.12 The reaction proceeded in an orbital shaker
at 250 rpm and 50 °C. The reaction was monitored by thin-layer
chromatography (TLC) with an ethyl acetate eluent and visualized
using 5% sulfuric acid solution in water and gentle heating. After 24 h,
the bottom glucoside spot (Rf = 0.1) faded and a product spot
appeared (Rf = 0.4). Before the solution was allowed to cool to room
temperature, the enzymes were filtered out and rinsed with acetone
until the washings showed no further product on TLC before they
were air-dried and stored for reuse. Acetone was evaporated under
vacuum from the filtrate, leaving behind a crude solid mixture of
glucoside−ester product (% yield by acyl donor: methyl caprylate 87%
and 95% vinyl caprylate), unreacted acyl donor (Rf = 0.8) when run
with methyl or vinyl esters, and free fatty acid (Rf = 0.7). The solid
mixture was triturated three times with 50 mL of hexanes at 50 °C to
10537
Article
remove the excess fatty acid and derivatives from the opaque light
yellow bulk solid. For stearic and oleic acid derivatives the hexane−
product mixture was centrifuged in a Falcon tube at 3000 rpm for 5
min before decantation to avoid loss of suspended product. To remove
trace elements of unreacted sugar, ester, or acids, the product (0.85 g)
was dissolved in 25 mL of methanol and coated by evaporation onto
5.0 g of silica gel before being spread onto a short silica plug (40.0 g).
The column was twice eluted to dryness with 200 mL ethyl acetate,
and the solvent was evaporated from the second fraction via rotary
evaporation to afford the pure fatty acid glucoside ester product. Pure
glucoside ester was dissolved in deuterated solvent (20 mg in 1 mL
DMSO-d6, toluene-d8, or CDCl3), and the solution was filtered
through glass wool before a spectrum was recorded on a 300 MHz
Bruker NMR spectrometer.
Preparation and Characterization Molecular Gels. Gels were
prepared by adding the solid glassy glycosides (10.0−50.0 mg of
gelator) to the desired solvent (1 mL). The mixture was then heated
to disperse the gelator at 5 degrees below the boiling point of organic
solvents and at 125 °C for oils to produce a homogeneous sol. The sol
was kept at this temperature for 10 min under constant agitation to
fully disperse the gelator. The sol was then cooled to room
temperature to allow for self-assembly, and after a length of time
(between 2 and 24 h), the samples were inverted to confirm gel
formation.29 The efficacy of gel formation was examined by
determining the minimum gelation concentration (MGC) and gel-
to-sol transition temperature (Tgel). Gel samples were diluted with
solvent until after setting and vial inversion, when a gel, partial gel, or
sol was formed. The gel transition temperature was determined by
submersing a gel sample in an oil bath and increasing the temperature
until the gel flowed like a liquid, indicating the disassembly of the
gelator structure. MGC was determined beginning from 5 wt %
samples (50 mg of gelator in 1 mL of solvent) or below the
concentration of precipitation for gelators and diluting the samples
until a sol is formed.
FT-IR Spectroscopic Characterization. The infrared spectra
(FT-IR) of the neat bulk gelators and gel samples were measured
using a Thermo Scientific Nicolet iS 10 FT-IR spectrometer with an
ATR configuration in the range of 600−4000 cm−1.
Optical and Electron Microscopy. To study the self-assembled
gel structures, microscopic samples of oleogels were prepared via
multiple methods. For gels from volatile organic solvents the solvent
was removed by evaporation at ambient pressure and temperature,
under vacuum, and in liquid nitrogen by lyophilization. For oil samples
the gel network was extracted using hexanes (50:1 v solvent/ v oil) to
remove the oil.30 The gel structures were subsequently dried under
vacuum for 24 h. Each of the samples was coated with a thin layer of
carbon before images were recorded using a Zeiss Supra 55 field
emission scanning electron microscope. For polarized light micros-
copy, samples were gelled on microscope slides with a lam and imaged
DOI: 10.1021/acs.jafc.5b04236
J. Agric. Food Chem. 2015, 63, 10536−10542
Journal of Agricultural and Food Chemistry Article

using a hot stage and Leica microscope (DFC280) to investigate the

gelation process.
X-ray Diffraction. To elucidate the packing of the gelator
molecules, some of the gel’s fibers were isolated from oleogel samples
via an extraction method similar to that described above. For bulk
gelator samples the gelator was ground to a fine powder and spread
over a clean glass slide before examination. Gel samples were prepared
by forming the gel directly on the slide. Crystal samples were
recrystallized from 1:1 acetone/water mixtures by slow evaporation of
the organic phase. Samples were recorded onto a PANalytical X’Pert
Pro Powder Diffraction X-ray diffractometer. The instrument was
operated under a voltage of 40 kV, a current of 40 mA, a 1/4° incident
slit width, and Cu Kα X-rays (λ = 1.54 Å). Small (1−10°) and wide
Figure 2. 1H NMR spectra of RKG8 mixtures in toluene: a closeup on
(5−45°) angle X-ray diffractograms were recorded for samples at 25
the shifting carbohydrate peaks. The bottom spectra (B−E) are in the
°C. The raw data were processed using X’Pert High Score Plus
software. gel state, and the top spectrum (A) is a solution. There is a shift in the
pyranose hydrogen at the C1 position ∼4.9 following stretched

■ RESULTS AND DISCUSSION

Gelator Synthesis and Characterization. Two saturated
hydrogen bond in the gel that then relaxes when the molecules are in
solution.

fatty acid glucoside esters, raspberry ketone glucoside caprylate Interestingly, NMR spectra of gelled toluene were recorded,
(RKG8) and raspberry ketone glucoside stearate (RKG18), and similar shifts were observed, highlighting the importance of
were prepared via heterogeneous lipase-mediated esterification hydrogen bonding in the gelled medium (Figure 2). The peaks
in nonaqueous media. Saturated caprylic and stearic acid, along shift continually downfield until the sample reaches the gel-to-
with derivative methyl and vinyl esters, were reacted with sol transition at ∼49 °C, at which point the peaks shift upfield
raspberry ketone glucoside in dried organic solvents. The with weaker hydrogen bonds.
monounsaturated raspberry ketone glucoside oleate (RKGO) RKG8, RKG18, and RKGO characterization is provided in
was synthesized from vinyl oleate. The facile workup allows for the SI.
simple catalyst regeneration, chromatographic solvent recycling, Effect of Gelator Structure in Gel Preparation. The
and monoacylated regiospecific product in high yields of 95% partial solubility of the glucoside gelator in oil solvents allows
for caprylic acid vinyl ester reactions. The versatility and an invisible nonpolar nanocrystalline network to form for a
specificity of the Novozym 435 catalyst allow the synthesis of variety of oil solvents (Figures 3 and 4). Clear, semisolid
gelators with a wide range of hydrophobic−lipophobic balance
values following a general biocatalytic coupling of reagents from
renewable resources. To compare the compatibility of medium-
and long-chain saturated fatty acid amphiphiles, gelator’s MGC
(Supporting Information (SI) Table 1) and melt temperatures
(SI Table 2) were tabulated. To study the effect of unsaturation
on self-assembly, the RKGO gels were compared to saturated
analogues, although gelation of RKGO derivatives indicated a Figure 3. Medium- and long-chain triglyceride oleogels (5% wt). Left
much higher MGC (>0.5 vs <0.5 wt %). This led the rheology to right: RKG8 and RKG18 in hazelnut oil, RKG8 and RKG18 in
and diffraction studies to focus on the robust saturated grape seed oil, RKG8 and RKG18 in red palm oil, RKG8 and RKG18
derivatives, specifically RKG8, due to exceedingly low MGC in coconut oil, gel of RKG8 in palm kernel oil, RKG8 in olive oil,
values. RKG8 in jojoba oil (comprising mainly wax esters), and RKG18
As many examples of molecular oil structurants exhibit soybean oil solution for comparison.
dissimilar properties between bulk samples and the self-
assembled structures, it serves to characterize the assembling
intermolecular forces in the gelators and their presence or
absence in the gelled samples.31
1
H NMR spectroscopy of the gelators in deuterated solvent
reveals the disparate hydrogen environments between the alkyl
(0.86−2.5 ppm), glucose (2.6−5.0 ppm), and phenolic
hydrogen nuclei (∼7 ppm) (Figure 2). As part of the planned
structural design, these spatially distinct hydrogens serve to
capitalize on their specific intermolecular interactions (van der
Waals dispersive forces and hydrogen-bonding interactions).
The role of hydrogen-bonding interactions was probed by
varying the concentration and temperature and following the
shift of the glucose’s hydrogen peaks.32 An increase in
concentration or decrease in temperature shifted the secondary
Figure 4. (A) Polarized optical microscopy images of neat coconut oil
alcohol doublets in chloroform-d downfield, the former at 1 h, (B) coconut oil R8 gel crystals at 1 h, (C) R8 coconut oil gel
indicating the prevalence of intermolecular hydrogen bonding, crystals after 72 h; (D) scanning electron microscopy images of R8
which is crucial in developing a robust gelator (SI).32 Similar xerogel; (E) sample after extracting a coconut oil gel in hexanes (a
shifts were seen in DMSO-d6 by varying the temperature, closeup of the fibrous network); and (F) an evaporated toluene
indicative of either inter- or intramolecular bonding (SI). organogel that displays sheet-like ribbons of gelator fibers.

10538 DOI: 10.1021/acs.jafc.5b04236

J. Agric. Food Chem. 2015, 63, 10536−10542
Journal of Agricultural and Food Chemistry Article

oleogels were formed by the dispersion of the derived gelators

in oils up to exceedingly low nanomolar concentrations (<0.25
wt % v/v), comparable to other supergelators.33 Surprisingly,
gelled samples of coconut and palm kernel oils are clear
oleogels despite the opaque nature of the oil. The clarity of the
coconut oleogels at 25 °C remained for up to and beyond 1
week, whereas palm kernel oil crystallized out in the gel
samples, forming an opaque gel within 1 h of gel setting. The
MGC of the caprylate gelator was determined by vial inversion
Figure 5. (Left) FTIR spectra of oleogel and bulk gelators samples;
to be 798 nM or 0.27 wt %, comparable to the stearate
(right) hydrogen-bonding region displays weak O−H peaks in the gel
derivative at 515 nM or 0.29 wt % (SI Table 1). The oleate spectrum, comparable to those noted in oleogel samples.29
gelator exhibited similarly low, but higher, MGC values in oils.
The comparable MGC values may be explained as the
percolation threshold determining the minimum amount of Waals forces, serve to stabilize the solid crystalline network
gelator to bridge a specified domain and represents the region dispersed throughout the oil. This corresponds with the
of the phase diagram in which binary gelator solvent mixture to gelator’s solubility in polar protic solvents; the intermolecular
the sol phase.34 The melt temperatures of the gels (Tgel) were solvent−gelator hydrogen bonding disrupts gelator−gelator
similar between oils with varied triglyceride profiles, including a interactions, preventing network formation.36 Indicative of
high percentage of monounsaturated oleic acid in olive oil and increased hydrogen bonding and weakened O−H bonds is a
medium-chain triglyceride coconut oil as demonstrated in SI decrease in the absorption frequency relating to increased
Table 2. Palm kernel oil formulations could not be tested for inductive effects. In addition to the shift between the gel and its
MGC at room temperature, as the component oil is a solid fat. components, comparing the two neat RKG8 and RKG18
Comparable MGC and Tgel values indicate the universal oleogel gelator’s hydrogen-bonding peaks, respectively, 3493 and 3206
character of the solid gelator network that assembles in many cm−1 and 3489 and 3247 cm−1, indicates subtle changes in the
types of edible oils, relatively independent of the fatty acid intermolecular hydrogen bonding. The difference between
profile. RKG8 and RKG18’s FTIR spectra indicates the ability to tailor
Polarized Optical and Scanning Electron Microscopy the gel’s intermolecular hydrogen bonding forces by varying
of Oleogels and Xerogels. Examining the gel samples under gelator structure, but not necessarily adding or removing
polarized light indicated the formation of birefringent networks hydrogen bonding functional groups, instead affecting inter-
(Figure 4A−C). Gels were prepared directly on slides to study molecular interactions by merely changing saturated fatty acid
the crystallization of coconut oil samples over time. Because a chain length.
low-temperature transition between an opaque and translucent Powder X-ray Diffraction Analysis. By examining peak
gel phase (25−30 °C) corresponds to the crystallization of the location of the bulk gelator, neat gels, and extracted fibers from
medium-chain triglycerides (specifically the 12-carbon lauric gel samples, it is possible to classify the structure of the gel
acid), it was evident that the RKG8, RKG18, and RKGO network. Small-angle powder diffraction (1−10°) probes
nanometer length longitudinal molecular packing, indicative
samples crystallized from a higher number of nucleation sites,
in lipidic systems of bilayer thickness.12 Wide-angle powder
compared to neat coconut oil, which melts between 24 and 32
diffraction (5−45°) reveals information on crystal polymorphs,
°C. Under 50× magnification, gel networks were still not
short-range structuring, and the maximum intermolecular
visible; thus, samples for electron microscopy were prepared by
distance. Polymorphs of the RKG8 gelator from clear crystal
evaporating solvents from organogels and by extraction of the
samples grown in water/acetone mixtures and opaque bulk
oil with solvent. Solvent-extracted fibers from oil demonstrate
gelator precipitated from methanol exhibit distinctive curves
tubular shapes, whereas evaporated samples from toluene yield
(Figure 6). Whereas all self-assembled gels and extracted fibers
ribbon-like fibers (Figure 4E,F). Both samples indicate the
diffract at short angles indicating spacings of 2.98 ± 0.02 nm,
presence of fibrils, which comprise the vast network spanning
and entrapping the solvent.
Infrared Spectroscopy. The infrared spectroscopic char-
acterization of neat oils, gelators, and composite gels high-
lighted the role of hydrogen-bonding interactions in the gels.
Characteristic of the oils, gelators, and oleogels is the strong
saturated fatty acid carbonyl stretch at 1740 cm−1. Oils,
gelators, and the composite oleogels present intense methylene
stretches at 2918 and 2850 cm−1, which dwarf the methyl
stretch at 2955 cm−1 as the fatty acid chain length increases
(Figure 5). Present in both the gelator and gel samples, and
expectedly absent in the oil sample, were broad O−H
absorptions indicating intermolecular hydrogen bonding. Of
the two broad O−H stretches in RKG8 and RKG18 samples at
3500 and 3200 cm−1, only the higher frequency peak appears as
a weak and broad band in the oleogel spectrum (Figure 5,
right). Absorbing between 3504 and 3442 cm−1, the oleogel’s
O−H stretch indicated the presence of hydrogen bonding in
the gel network similar to those in the bulk form.35 Figure 6. XRD spectra of gelators and gels. Dotted lines highlight
Intermolecular hydrogen bonds, along with dispersive van der location of peaks indicative of β′ crystal polymorph.

10539 DOI: 10.1021/acs.jafc.5b04236

J. Agric. Food Chem. 2015, 63, 10536−10542
Journal of Agricultural and Food Chemistry
crystal samples display another long-range peak at 3.30 nm,
indicating multidimensional long-range crystal growth com-
pared to the single-dimension growth specific to self-assembled
systems.37 Neat samples of the oils and fats absorbed broadly
between 15 and 25°, as did the bulk RKG8 and RKG18
gelators, indicative of short-range ordering.38
Between RKG8 and RKG18 spectra, the expected increase in
the longitudinal spacing of 11 Å corresponds to the increase in
chain length between caprylic and stearic acid. In comparing
oleogel samples to structured oils and fats, it is possible to
classify the gel network’s polymorphic phase.
Typified by peaks at 4.2 and 3.8 Å, a β′ conformation of the
gelled lipidic amphiphiles indicates a kinetically controlled
metastable structure compared to more and less stable forms, β
and α, respectively.21,39 Similar to lamellar arrangements of
glyceride systems,13 a β′ classification combined with the
longitudinal spacing indicates a collection of angled amphi-
philes stacking to form a bilayer structure. This indicates that
the gelators pack in a manner similar to natural fats structuring
the oils like a fat mimic. This may represent the first step in
creating oil-structuring agents with desirable mouthfeel or
texture, as dissimilar polymorphs may dissolve differently and
influence taste.
Due to the relatively low signal given by the dispersed gel
network, much work was done on neat gel structures from air-
dried gels, xerogels, and extracted gel fibers. Extracting clear
oleogels with hexanes yields a solution of self-assembled
structures with peaks corresponding to those found in the bulk
gelator sample, such being artifacts of precipitation. Compared
to the oleogel samples, extracted fibers diffracted at slightly
higher 2θ values, indicating a more compact bilayer structure.
Hexanes, a nonpolar mixture of structural isomers, may serve to
form compact bulk structures due to hydrophobic effects with
the glucoside’s secondary hydroxyl groups. The resultant fibers
lack the 4.2 Å diffraction peaks, indicating a change in
conformation of assembly, perhaps to a more compact
polymorph (SI Table 3).
Effect of Concentration and Oil Type on Mechanical
Gel Properties. Oscillatory rheometry elucidated an expected
increase in gel strength corresponding to an increase in gelator
concentration. Although it has been demonstrated that the gel
point does not always correspond with the crossover point of
the elastic and viscous moduli, which more accurately
represents the beginning of stochastic nucleation, oscillatory
strain sweep rheometry of the coconut oil gels demonstrates a
marked increase in the position (% strain) of the crossover
point corresponding to an increased gel concentration (SI
Figure 2A).40 This indicates that the concentrated gels require
greater deformations to disrupt the gel network than more
dilute gels. It can also been seen that the storage modulus
increases with an increase in gel concentration, indicating the
elastic and stability properties of the gel depend of the
concentration of the gel (SI Figure 2B).
The storage moduli of coconut oil gels are seen to scale as a
function of frequency. To examine the firmness or tolerance of
the gel to external forces, a frequency sweep was conducted
within the linear viscoelastic region.4 Indicating that the
samples remain in a gel state, the larger magnitude of the
storage modulus was seen to increase with an increase in
frequency, whereas the viscous moduli remained relatively
unchanged (SI Figure 2B). Indicative of junction zones
between fibers in the gel network, the relatively unscaled
curves for the dilute gels indicate fewer junction nodes. Their
10540
Article
gel network therefore consists of fewer entangled nanostruc-
tures.41
Gel Stability and Shelf Life. As the gelator molecules self-
assemble to form a crystalline network, the cooling rate of the
gel can greatly affect the microstructure of this self-assembly.13
By controlling the cooling rate as the mixture transitions from
sol to gel, the crystalline architecture may be controlled. It has
been previously demonstrated that slower cooling rates favor
epitaxial growth, which leads to a finer monodisperse crystalline
system.13 Particular to the coconut gel samples, the gel phase is
composed of two distinct phases, a clear gel and a white opaque
gel, which are separated by a broad melting point (22−27 °C).
In the transparent gels, coconut oil triglycerides crystallize
trapped within the gel network and bloom to form an opaque
structure below room temperature. This thermoreversible
coconut oil crystallization is kinetically delayed compared to
neat oil samples, which become translucent but remain liquid
for hours at room temperature. Whereas long-chain oleate and
stearate derivatives only formed translucent gels, the clear
transparent coconut oil gels at low concentrations (∼0.5%)
were stable over long periods at room temperature (>6
months). Gels with higher gelator concentration (2.5−5 wt %)
were stored at an elevated temperature and displayed a
tendency to aggregate to the air−gel interface, forming a solid
sponge-like disk, whereas lower concentration gels (0.25−2.0
wt %) remained stable.
The versatility of the raspberry ketone glucoside derivatives
to gelate a variety of aprotic liquids suggests small-molecule
gelation may prove to be a powerful alternative to current oil-
processing methods. By programming functionality into
bioderived surfactants, it may be possible to tailor formulations
from the bottom up. Because consumer products exist as
complex mixtures of raw materials, the exceedingly low
concentration of gelator needed to solidify large quantities of
oil may serve to allow products to contain less filler and more
active ingredients. Of the utmost importance will be developing
protocols to determine the safety of novel species, focusing
especially on their nanosized components. Although the
materials are derived from nature, any artificial ingredient
must undergo rigorous testing to avoid complications
developed with comparable structuring agents.
We have demonstrated the exploitation of van der Waals
forces and hydrogen bonding in the end-goal of making a
versatile organogelator from biobased reagents. By exploiting a
relatively unexplored class of solvents, MCT oils, we propose
these gelators may be used in next-generation formulations for
multifunctional materials. As the structure serves to structure
oils in a fat-mimicking fashion, they may present themselves as
viable edible oil structuring agents for a host of applications.
As more and more chemicals generally recognized as unsafe
continue to be removed from consumer products, it is
important that their replacements, the next generation of
functional chemicals, serve to improve upon economic and,
importantly, environmental costs. Developing soft functional
materials from biomass serves not to limit the variety of
chemical progress but rather to use biomimesis as inspiration.
Structured oils and fats, long at the forefront of the battle
against trans-fats and in favor of healthy hearts, represent the
continued need for research into soft matter. Furthermore, by
studying natural products and their derivatives, research may
serve to inform us on the chemistry of natural systems and
subsequently help to develop healthful eco-friendly alternatives
to conventional rheology modifiers.
DOI: 10.1021/acs.jafc.5b04236
J. Agric. Food Chem. 2015, 63, 10536−10542
Journal of Agricultural and Food Chemistry
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jafc.5b04236.
1 agents. J. Agric. Food Chem. 2013, 61, 12005−12011.
H NMR data and synthesis data of coconut oil gelators
along with rheological curves, MGC, XRD peak, and Tgel
data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*(G.J.) E-mail: gjohn@ccny.cuny.edu. Phone: (212) 650-8353.
Fax: (212) 650-6107. Homepage: http://www.sci.ccny.cuny.
edu/~john/index.html.
Funding
This work was partially supported by the GoMRI Grant SA 12-
05/GoMRI-003 (subcontract TUL-626-11/12).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
G.J. thanks Chemical and Biological Engineering, Princeton
University, where part of this manuscript was written, for a
visiting faculty position (sabbatical) in 2014. We thank Dr. A.
Bykov for help with X-ray measurements and Amit Ahuja for
his help with rheological measurements.
■
ABBREVIATIONS USED
TLC, thin-layer chromatography; MG, molecular gelators;
MCT, medium-chain triglyceride; XRD, X-ray diffraction;
RKG, raspberry ketone glucoside; RKG8, raspberry ketone
glucoside caprylate; RKG18, raspberry ketone glucoside
stearate; RKGO, raspberry ketone glucoside oleate
■
REFERENCES
(1) McCarthy, M. US gives food manufacturers three years to ban
trans fats. Br. Med. J. 2015, DOI: 10.1136/bmj.h3315.
(2) Bier, D. M. Saturated fats and cardiovascular disease:
interpretations not as simple as they once were. Crit. Rev. Food Sci.
Nutr. 2015, 0.
(3) Watson, R. R. Nutrients and Foods in AIDS; CRC: Boca Raton,
FL, USA, 1998.
(4) O Brien, R. D.; Timms, R. E. Fats and oils - formulating and
processing for applications. Eur. J. Lipid Sci. Technol. 2004, 106, 451.
(5) Marina, A. M.; Che Man, Y. B.; Amin, I. Virgin coconut oil:
emerging functional food oil. Trends Food Sci. Technol. 2009, 20, 481−
487.
(6) Gumel, A. M.; Annuar, M. S. M.; Heidelberg, T.; Chisti, Y. Lipase
mediated synthesis of sugar fatty acid esters. Process Biochem. 2011, 46,
2079−2090.
(7) John, G.; Vijai Shankar, B.; Jadhav, S. R.; Vemula, P. K.
Biorefinery: a design tool for molecular gelators. Langmuir 2010, 26,
17843−17851.
(8) Clark, J. H.; Budarin, V.; Deswarte, F. E. I.; Hardy, J. J. E.; Kerton,
F. M.; Hunt, A. J.; Luque, R.; Macquarrie, D. J.; Milkowski, K.;
Rodriguez, A.; Samuel, O.; Tavener, S. J.; White, R. J.; Wilson, A. J.
Green chemistry and the biorefinery: a partnership for a sustainable
future. Green Chem. 2006, 8, 853.
(9) Ducret, A.; Giroux, A.; Trani, M.; Lortie, R. Characterization of
enzymatically prepared biosurfactants. J. Am. Oil Chem. Soc. 1996, 73, ,
109.
(10) Balachandran, V. S.; Jadhav, S. R.; Pradhan, P.; De Carlo, S.;
John, G. Adhesive vesicles through adaptive response of a biobased
surfactant. Angew. Chem., Int. Ed. 2010, 49, 9509−9512.
10541
Article
(11) Bhattacharya, C.; Kumar, N.; Sagiri, S. S.; Pal, K.; Ray, S. S.
Development of Span 80-Tween 80 based fluid-filled organogels as a
matrix for drug delivery. J. Pharm. BioAllied Sci. 2012, 4, 155−163.
(12) Jadhav, S. R.; Hwang, H.; Huang, Q.; John, G. Medium-chain
sugar amphiphiles: a new family of healthy vegetable oil structuring
(13) Ojijo, N. K.; Neeman, I.; Eger, S.; Shimoni, E. Effects of
monoglyceride content, cooling rate and shear on the rheological
properties of olive oil/monoglyceride gel networks. J. Sci. Food Agric.
2004, 84, 1585−1593.
(14) Terech, P.; Rodriguez, V.; Barnes, J. D.; McKenna, G. B.
Organogels and aerogels of racemic and chiral 12-hydroxyoctadecanoic
acid. Langmuir 1994, 10, 3406−3418.
(15) Rogers, M. A.; Marangoni, A. G. Non-isothermal nucleation and
crystallization of 12-hydroxystearic acid in vegetable oils. Cryst. Growth
Des. 2008, 8, 4596−4601.
(16) Dey, T.; Kim, D. A.; Marangoni, A. G.; Garti, N. Edible oleogels.
In Ethylcellulose Oleogels; 2011; pp 295−309, DOI: 10.1016/B978-0-
9830791-1-8.50016-4.
(17) John, G.; Vemula, P. K. Design and development of soft
nanomaterials from biobased amphiphiles. Soft Matter 2006, 2, 909−
914.
(18) Yu, H.; Liu, B.; Wang, Y.; Wang, J.; Hao, Q. Gallic ester-based
phase-selective gelators. Soft Matter 2011, 7, 5113.
(19) Johnson, E. K.; Adams, D. J.; Cameron, P. J. Peptide based low
molecular weight gelators. J. Mater. Chem. 2011, 21, 2024.
(20) Marangoni, A. Organogels: an alternative edible oil-structuring
method. J. Am. Oil Chem. Soc. 2012, 89, 749−780.
(21) Abdallah, D. J.; Sirchio, S. A.; Weiss, R. G. Hexatriacontane
organogels. The first determination of the conformation and molecular
packing of a low-molecular-mass organogelator in its gelled state.
Langmuir 2000, 16, 7558−7561.
(22) Vidyasagar, A.; Handore, K.; Sureshan, K. M. Soft optical
devices from self-healing gels formed by oil and sugar-based
organogelators. Angew. Chem., Int. Ed. 2011, 50, 8021−8024.
(23) Patel, A. R.; Babaahmadi, M.; Lesaffer, A.; Dewettinck, K.
Rheological profiling of organogels prepared at critical gelling
concentrations of natural waxes in a triacylglycerol solvent. J. Agric.
Food Chem. 2015, 63, 4862−4869.
(24) Phaechamud, T.; Katewongsa, P.; Chuekaew, A.;
Saengthongpinit, W. Non-aqueous virgin coconut oil hair gel. Adv.
Mater. Res. 2012, 506, 347−350.
(25) Al-Edresi, S.; Baie, S. Formulation and stability of whitening
VCO-in-water nano-cream. Int. J. Pharm. 2009, 373, 174−178.
(26) Enig, M. G. Lauric Oils as Antimicrobial Agents: Theory of Effect,
Scientific Rationale, and Dietary Applications as Adjunct Nutritional
Support for HIV-Infected Individuals; CRC Press: Boca Raton, FL, USA,
1998.
(27) Chen, C. W.; Chong, C. L.; Ghazali, H. M.; Lai, O. M.
Interpretation of triacylglycerol profiles of palm oil, palm kernel oil and
their binary blends. Food Chem. 2007, 100, 178−191.
(28) Storozhok, N. M.; Gureeva, N. V.; Khalitov, R. A.; Storozhok, A.
S.; Krysin, A. P. Antioxidant activity of synthetic analogs and pure
active principles of Rhodiola rosea and raspberry ketone. Pharm. Chem.
J. 2012, 45, 732−735.
(29) Weiss, R. G., Terech, P., Eds. Molecular GelsMaterials with
Self-Assembled Fibrillar Networks; Springer: Berlin, Germany, 2006.
(30) Zetzl, A. K. Microstructure and Mechanical Properties of
Ethylcellulose Oleogels and Their Fat Substitution Potential in the Meat
Industry; University of Guelph: Guelph, Canada, 2013.
(31) Yılmaz, E.; Ö ğütcü, M. Properties and stability of hazelnut oil
organogels with beeswax and monoglyceride. J. Am. Oil Chem. Soc.
2014, 91, 1007−1017.
(32) Jing, P.; Yan, J.; Cai, X.; Liu, J.; Hu, B.; Fang, Y. Solvent-induced
molecular gel formation at room temperature and the preparation of
related gel-emulsions. Sci. China: Chem. 2013, 56, 982−991.
(33) Zhang, S.; Yang, S.; Lan, J.; Tang, Y.; Xue, Y.; You, J.
Ultrasound-induced switching of sheetlike coordination polymer
DOI: 10.1021/acs.jafc.5b04236
J. Agric. Food Chem. 2015, 63, 10536−10542
Journal of Agricultural and Food Chemistry Article

microparticles to nanofibers capable of gelating solvents. J. Am. Chem.

Soc. 2009, 131, 1689−1691.
(34) Rogers, M. A.; Wright, A. J.; Marangoni, A. G. Nanostructuring
fiber morphology and solvent inclusions in 12-hydroxystearic acid/
canola oil organogels. Curr. Opin. Colloid Interface Sci. 2009, 14, 33−
42.
(35) Suzuki, M.; Nakajima, Y.; Yumoto, M.; Kimura, M.; Shirai, H.;
Hanabusa, K. Effects of hydrogen bonding and van der Waals
interactions on organogelation using designed low-molecular-weight
gelators and gel formation at room temperature. Langmuir 2003, 19,
8622−8624.
(36) Sawalha, H.; den Adel, R.; Venema, P.; Bot, A.; Flöter, E.; van
der Linden, E. Organogel-emulsions with mixtures of β-sitosterol and
γ-oryzanol: influence of water activity and type of oil phase on gelling
capability. J. Agric. Food Chem. 2012, 60, 3462−3470.
(37) Cui, G.-H.; Li, J.-R.; Tian, J.-L.; Bu, X.-H.; Batten, S. R.
Multidimensional metal−organic frameworks constructed from flexible
bis(imidazole) ligands. Cryst. Growth Des. 2005, 5, 1775−1780.
(38) Spaar, A.; Salditt, T. Short range order of hydrocarbon chains in
fluid phospholipid bilayers studied by X-ray diffraction from highly
oriented membranes. Biophys. J. 2003, 85, 1576−1584.
(39) AOCS. Official Methods and Recommended Practices of the AOCS;
Champaign, IL, USA, 1998; Cj-2-95.
(40) Wang, R.-Y.; Liu, X.-Y.; Narayanan, J.; Xiong, J.-Y.; Li, J.-L.
Architecture of fiber network: from understanding to engineering of
molecular gels. J. Phys. Chem. B 2006, 110, 25797−25802.
(41) Lescanne, M.; Grondin, P.; d’Aléo, A.; Fages, F.; Pozzo, J.-L.;
Monval, O. M.; Reinheimer, P.; Colin, A. Thixotropic organogels
based on a simple N-hydroxyalkyl amide: rheological and aging
properties. Langmuir 2004, 20, 3032−3041.

10542 DOI: 10.1021/acs.jafc.5b04236

J. Agric. Food Chem. 2015, 63, 10536−10542