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Chap 4
Chap 4
Chap 4
Nucleation Behavior
The nucleation behavior affects numerous structural features including fiber size, fiber
morphology, number of crystal aggregates, and the spatial distribution of crystalline
Figure 4.1 Crystal conformation of DL 12-hydroxystearic acid (a, b, and c are the unit cell axis).
(Adapted from Kuwahara, T., Nagase, H., Endo, T., Ueda, H., Nakagaki, M., 1996. Crystal structure of
DL-12-hydroxystearic acid. Chem. Lett. 25, 435e436.)
mass (Marangoni and McGauley, 2003). Once the organogelatoresolvent melt is cooled
below the melting point of the gelator, the sol becomes supersaturated and causes the
gelator to assemble via nucleation events (Weiss and Terech, 2007). In industrial prac-
tices, crystallization typically occurs under nonisothermal cooling conditions (i.e., the
temperature changes as the material crystallizes).
To quantify the nucleation process, the number of crystals (N) may be counted on
polarized light micrographs and plotted as a function of time (t) for each cooling rate
(Fig. 4.2A and B). The first derivative of this curve corresponds to the rate of nucleation
(Fig. 4.2C and D). Further analysis of this data utilizes the peak nucleation rate (Jp)
derived from the first derivative of the nucleation rate curve corresponding to the
maximum value of the first derivative. A simple inverse relationship between the
rate of nucleation and the cooling rate was found for 12-HSA in the majority of
solvents (Fig. 4.2E and F) (Rogers and Marangoni, 2008). However, for certain
solvents that are capable of interacting with the growing fiber, an exponential relation-
ship is found leading to the development of spherulite crystals (Rogers and Marangoni,
2008, 2009).
Two dissimilar nucleation regimes with differing sensitivities to the cooling rate were
observed between Jp and the cooling rate and between Jp and the timeetemperature (b)
12-Hydroxystearic Acid Oleogels 87
Figure 4.2 The number of nuclei counted on bright-field micrographs as the sample was cooled
nonisothermally (A,B), the rate of nucleation determined by the change in the number of nuclei
per unit time (C, D), and Jmax, the maximum nucleation rate which is a fitted parameter that is a
function of the cooling rate (E,F). (Taken from Rogers, M.A., Marangoni, A.G., 2008. Non-isothermal
nucleation and crystallization of 12-HSA in vegetable oil. Cryst. Grow. Des. 8, 4596e4601.)
88 Edible Oleogels
Crystal Growth
The nucleation process requires highly specific interactions to induce preferential one-
dimensional growth. Following nucleation, fibers grow one-dimensionally (Fig. 4.3),
and the rate of branching, interpenetration, and entanglement depends on the degree
of supersaturation or undercooling (Wang et al., 2006). The ability for the self-
assembled fibrillar networks (SAFiNs) to self-assemble into rod-like structures requires
a balance between opposing parameters such as solubility and those parameters which
control epitaxial growth into axially symmetric elongated aggregates (Weiss and Terech,
2007; Suzuki et al., 2003).
The fiber growth rate was determined by monitoring the length of each fiber on the
polarized light micrographs as a function of time under different cooling rates (Fig. 4.3).
The data were fitted to a modified Avrami equation characterizing the crystal growth
12-Hydroxystearic Acid Oleogels 89
(B)
kinetics (Fig. 4.4A and B) (Rogers and Marangoni, 2009, Lam et al., 2010, Lam and
Rogers, 2011). The modified Avrami model has the form:
Y ¼ Ymax 1 ekapp ðxxo Þ
n
where Y is the fiber length, Ymax is the maximum length of the fiber, kapp is the apparent
rate constant of fiber elongation, x is the time, xo is the induction time, and n is the
dimensionality of growth.
The Avrami index, n, is related to the mechanism of nucleation and the dimension-
ality of crystal growth. Hence, n is typically an integer between 1 and 4 for instantaneous
or sporadic nucleation and one-, two, or three-dimensional growth (Table 4.1). Upon
fitting the modified Avrami model to the experimental data (Fig. 4.4A and B), the
constants for Ymax, xo, and kapp were determined (Fig. 4.4CeE). The Avrami exponent
90 Edible Oleogels
Figure 4.4 Fiber length as a function of time/temperature supercooling trajectory measured using
ImageJ on bright-field micrograph (A, B) and the Avrami exponents; Ymax, maximum fiber length
(C); xo, induction time (D); and k, rate constant (E). (Taken from Rogers, M.A., Marangoni, A.G., 2008.
Non-isothermal nucleation and crystallization of 12-HSA in vegetable oil. Cryst. Grow. Des. 8, 4596e4601.)
Table 4.1 Possible forms of the Avrami model for the different modes of nucleation and their
associated dimensionality of crystal growth (Lam and Rogers, 2011)
Mode of nucleation Dimensionality of crystal growth Avrami equation n
1
Instantaneous Linear Ys
Ymax ¼ 1 eKt 1
2
Sporadic
Linear Ys
Ymax ¼ 1 eKt 2
2
Instantaneous
Platelet Ys
Ymax ¼ 1 eKt 2
3
Sporadic
Platelet Ys
Ymax ¼ 1 eKt 3
3
Instantaneous
Spherulitic Ys
Ymax ¼ 1 eKt 3
4
Sporadic
Spherulitic Ys
Ymax ¼ 1 eKt 4
depending on the cooling rate (Lam and Rogers, 2011). Cooling rates faster than
5e7 C/min produced short fibers suggesting a different mode of assembly for
12-HSA regardless of the solvent employed (Rogers and Marangoni, 2008, 2009, Lam
and Rogers, 2011). The Avrami constant, K, followed the same trends as the peak
nucleation rates (Fig. 4.2E and F). For fast cooling rates, the time-dependent thermody-
namic driving force leads to greater rates of both crystal growth and nucleation. This
regime of nucleation would be similar to that described by Wang et al.’s nucleatione
growthenoncrystallographic branchingegrowth mechanism (Wang et al., 2006).
Samples cooled faster and slower than 5e7 C/min indicate significant differences in
the morphology of the SAFiN (Marangoni and Rogers, 2009). Slow cooling rates
develop few nuclei, and the fibers have little branching and are several hundred microns
in length. This type of system does not effectively entrain liquid oil and exhibits syneresis
(Rogers and Marangoni, 2008). Conversely, under fast cooling rates, nucleation is a func-
tion of the supercooling-time exposure, leading to the creation of highly branched net-
works effective at entraining oil (Rogers et al., 2008). Therefore, in order to engineer the
oil-binding capacity and hardness/elasticity of an organogel, external fields, such as heat
and mass transfer, may be modified. The external fields not only dictate the number of
nuclei present but also define the degree of branching and fiber length of the SAFiN.
Future work should define those critical ranges of nucleation behavior.
Figure 4.5 Correlation length of 2.5 wt% 12-hydroxystearic acid fibers in mineral oil measured
from the micrographs obtained at 30 C after they had been cooled from 90 C at varying cooling rates
(Lam and Rogers, 2011).
these two peaks were observed, the modified Avrami model was applied (Rogers and
Marangoni, 2009). Upon fitting the data to the Avrami model, regardless of the cooling
rate, similar intensities of the peak area were measured (Fig. 4.6E). An exponential
decrease in the induction time was observed (Fig. 4.6G) (Lam and Rogers, 2011). The
Avrami exponent was found to be 1 for all samples, indicating that crystal growth
undergoes instantaneous nucleation and linear one-dimensional growth which corre-
sponds to Fig. 4.4 using polarized light microscopy (Fig. 4.6H). However, examining
the apparent rate constant of hydrogen bond formation between the 12-HSA carboxylic
acid groups and between the hydroxyl groups, a new insight into self-assembly and into
crystallographic mismatches were observed (Fig. 4.6F) (Lam et al., 2009). Previously,
branched fibers were thought to arise from molecules being incorporated into the lattice
in an imperfect manner. This would suggest that there is a significant decrease in the rate
of hydrogen bonding above 5 C/min, which corresponds to the significant change in
fiber length (Fig. 4.5). However, the rate of hydroxyl hydrogen bonding changes linearly
with the cooling rate and does not plateau as the cooling rate increases, which was
observed by a linear increase in the rate of hydroxyl interactions (Lam et al., 2009).
However, it was observed that at cooling rates greater than 5e7 C/min, the rate of
dimerization between carboxylic acid groups plateaued (Fig. 4.6F). This suggests that
the crystallographic mismatch for 12-HSA is a result of the inability of the 12-HSA
monomers to effectively dimerize at rapid cooling rates. When incorporated into the
crystal lattice, monomers prevent the uninterrupted longitudinal growth observed at
slower cooling rates.
The elastic properties of 12-HSA organogels result from the formation of both per-
manent and transient junction zones within these soft materials. The permanent junction
zones arise from crystallographic mismatches while the transient junction zones are a
consequence of fiber entanglement. The noncovalent interactions responsible for the
occurrence of transient junction zones in 12-HSA arise due to hydroxylehydroxyl
hydrogen bonding. This may result from the preferential arrangement of carboxylic
acid groups to dimerize within the fiber, resulting in a reduction of the fiberesolvent
interfacial tension (Roger et al., 2009a). As well, synchrotron infrared spectromicroscopy
indicates that the crystallization process of SAFiNs efficiently displaces solvent from the
interface of the growing crystals contributing to the epitaxial growth into axially symmet-
ric elongated aggregates (Rogers et al., 2009a). The periodicity in the density of
hydrogen bonding resolves the supramolecular chirality of 12-HSA fibers (Fig. 4.7).
For 12-HSA in mineral oil, the area of the peak at 3200 cm1, corresponding to the
hydroxyl-hydroxyl interactions between molecules (Fig. 4.7A), and the area (Fig. 4.7B)
and intensity (Fig. 4.7C) of the dimerization of carboxylic acid groups on 12-HSA at
1700 cm1 were mapped. The two-dimensional maps for 12-HSA/mineral oil revealed
two distinct fibers with an approximate width of w8e10 mm (Rogers et al., 2009a). The
width corresponds well with previously obtained cryo-scanning electron microscopy
12-Hydroxystearic Acid Oleogels 95
(A) (D)
(B) (E)
(C) (F)
Figure 4.7 Fourier-transform infrared maps of the relative change in hydroxyl hydrogen bonding area
(A,D), carboxylic acid dimerization area (B), carboxylic acid dimerization intensity (C), ester band area
(E), and intensity (F) for mineral oil (AeC) and methyl oleate (DeF). (Taken from Rogers, M.A., Pederson,
T., Quaroni, L., 2009. Hydrogen bonding density of supramolecular structures for self-assembled fibrillar
networks probed using synchrotron infrared spectromicroscopy. Cryst. Grow. Des. 9, 3621e3625.)
images (Rogers et al., 2007). Fig. 4.7AeC presents the same field of view and is
superimposable. Strands of 12-HSA have a helical nature due to the supramolecular
arrangement of fibers arising from the chirality at position 12 on 12-HSA (Dumas
et al., 2004; Tachibana and Kambara, 1968; Uzu and Sugiura, 1975; Fuhrhop et al.,
96 Edible Oleogels
1987; Terech et al., 1994). Previously, 12-HSA strands in mineral oil were shown to be
approximately 100 mm long and 3e8 mm wide (Rogers et al., 2009a). 12-HSA in methyl
oleate has shorter fibers ranging in length from 5 to 75 mm, and these are approximately
the same width as observed in mineral oil (Rogers et al., 2009a). The supramolecular
helical configuration instilled from the chiral carbon may be observed via the hydrogen
bonding periodicity within the fibers illustrated by the reddish-pink zones containing
concentrated dimerization in the crystalline structure (Fig. 4.7B).
The area (Fig. 4.7B) and intensity (Fig. 4.7C) of the carboxylic acid interactions were
used to visualize the fibers. Fig. 4.7B and C indicates a reduction in the amount of
COOHeCOOH interactions between fibers. This suggests that upon formation of
the fiber, the COOH groups are effectively excluded from the fiberesolvent interface
reducing the interfacial tension. Fig. 4.7A indicates that the fibers’ nonpermanent
junction zones interact via hydrogen bonding of the hydroxyl groups while preferentially
excluding the carboxylic acid groups from the surface of the fiber (Rogers et al., 2009a).
As a result, the hydroxyl groups at position 12 are exposed to the surface. The idea that
nanofibers interact to form the supramolecular network via van der Waals interactions
alone, in certain cases, may be over simplified.
12-HSA in methyl oleate produced very few long fibers resulting in small densely
packed crystals (Fig. 4.7D). Both Fig. 4.7D and E show numerous 5e10 mm crystals.
The areas elevated in hydroxylehydroxyl interactions (Fig. 4.2D, reddish nuclei) corre-
spond to the areas depleted of the ester band for methyl oleate (Fig. 4.7E and F, blue
solvent), suggesting that the development of 12-HSA fibers is extremely efficient at dis-
placing the solvent from the growing fiber surface and as a result develops densely packed
crystals. However, numerous other crystallization processes, as in the case of triacylgly-
cerides (TAGs), often entrain liquid TAGs during the formation of large diffusion-
limited clusters.
OIL-BINDING CAPACITY
Organogels have tremendous potential for topical applications in drug delivery
(Giorgano et al., 1998). The rate of delivery is governed by the pore size distribution
within a gel and therefore understanding the fiber nanostructure is of utmost importance
(Kantaria et al., 1999). The rate of release is governed by the rate of syneresis, which is the
expulsion of oil from a matrix due to shrinkage. This results in the solvent (oil) being
expelled from the organogel matrix. Thus, to modify the rate of release, the fiber branch-
ing/interactions must be adjustable. To prevent syneresis in a gel, the interfacial tension
between the solvent and SAFiN must exceed or balance the gravitational force. It has
been postulated that if the interfacial area between the oil and 12-HSA network is larger,
a corresponding higher interfacial tension will occur, which if it exceeds the gravitational
forces, the network will retain oil. However, if the interfacial area is smaller than the
12-Hydroxystearic Acid Oleogels 97
average capillary dimensions, with an even distribution of mass, the network will entrain
the oil and prevent syneresis. Several authors have observed differences in the oil-binding
capacity of organogels (Markovic et al., 2004; Tamura and Ichikawa, 1997).
Samples of 12-HSA in canola oil were prepared by isothermally cooling them to 5
and 30 C; they were removed from the incubators after 24 h and were equilibrated at
20 C for 1 h before being placed on Whatman filter papers (Whatman, Number 5,
15 cm diameter) for 1 h (Rogers et al., 2008). The distance the oil front moved on
the Whatman filter paper was measured and plotted as a function of time (Fig. 4.8A).
Fig. 4.8A indicates that the oil mobility is significantly greater for the sample stored at
30 C than for the sample stored at 5 C. The ratio of the rates of syneresis (D) at the
two temperatures studied, D30 C/D5 C, was 1.35 0.02 (Rogers et al., 2008).
Samples were subjected to T2 relaxation measurements on a Bruker mq20 series
nuclear magnetic resonance analyzer (Bruker, Milton, ON, Canada). A Carr-Purcell-
Meiboom-Gill pulse sequence was used to determine the spinespin relaxation times
for the liquid relaxations. The data underwent a Laplace transformation and were solved
using a constrained regularization method for data inversion (Provencher, 1982a, 1982b).
Three main distributions of liquid relaxations are distinguished in Fig. 4.7B as having T2
in the range of 50e70 ms, 80e130 ms, and 200e500 ms, respectively. The 50e70 ms
relaxation was attributed to the immobilized or entrained oil (less mobile oil) and the
200e500 ms relaxation to the more mobile liquid oil. With increasing crystallization
temperature, the immobilized or entrained oil at 50e70 ms becomes part of the
80e130 ms relaxation, and the 200e500 ms relaxation shifts to higher relaxations.
The absence of the highly immobilized oil at 30 C suggests that the SAFiN is not
entraining the liquid oil efficiently.
Figure 4.8 Oil syneresis from a 2-cm diameter disk of 0.5% hydroxystearic acid (HSA)/canola oil on a
Whatman 5 filter paper (A) and pulse nuclear magnetic resonance T2 relaxation distributions
2.5%HSA/canola oil stored at different temperatures (B). (Adapted from Rogers, M.A., Wright, A.J.,
Marangoni, A.G., 2009b. Nanostructuring fiber morphology and solvent inclusions for 12 hydroxystearic
acid/canola oil organogels. Curr. Opin. Coll. Inter. Sci. 14, 33e42.)
98 Edible Oleogels
T2 relaxations in porous systems have been related to both the time it takes for the
molecule to diffuse to the surface of the pore (Strange et al., 1993) as well as to the levels
of confinement in a pore (Baba et al., 1999). Regardless of this assumption, if there is a
change in the level of confinement or a change in the pore size, it should affect the T2
relaxation time. If T2 is directly related to the pore size, then the T2(30 C)/T2(5 C) ratio
should be numerically similar to D30 C/D5 C (1.35 0.02). The ratios of the three T2
relaxations at 30 C (51 ms, 113 ms, and 326 ms) and 5 C (39 ms, 90 ms, and 250 ms)
were determined to be, on average, 1.30 0.03. This suggests that the ratio of the T2
relaxations compared to the ratio of the rates of syneresis is similar.
The 12-HSA matrix is composed of capillaries where the solvent interacts with the
surface of a fiber. Thus the force entraining the liquid oil will be a function of the radius
of the pore r and the contact angle a. The Laplace pressure (Pc) that arises from these
interactions is expressed as:
2Ts cosa
Pc ¼ .
r
For flow to occur, the capillary pressure must be overcome, Poiseuille’s equation de-
scribes the pressure required to cause a material to flow with viscosity h, though a capil-
lary of radius r, length l, at a rate n as:
y8hl
Pf ¼
r2
For syneresis to occur in a capillary, a minimum value of Pf must equal to or exceed
Pc, and the length will be replaced with a variable diffusion distance c0 (Vesely, 2001). If
Pc is equal to Pf, then the minimum force required for flow to occur is overcome and the
following expression for the flow velocity can be obtained:
Ts rcosa
y ¼ .
4hc0
It is assumed that the interfacial tension, contact angle, and diffusion distance remains
constant for samples stored at 30 C and 5 C, since they are essentially the same system.
Therefore, to determine the relative differences between the rates of syneresis, our
expression simplifies to:
y30 C r30 C h5 C
¼
y5 C r5 C h30 C
The complex viscosity was determined using small deformation rheology, while
the pore radius was determined by microscopy at different magnifications (Fig. 4.9,
Table 4.2). Using the pore radius and complex viscosity (17 kPa at 30 C and 8 kPa at
12-Hydroxystearic Acid Oleogels 99
Figure 4.9 Cryogenic scanning electron micrographs of 2% 12-hydroxystearic acid/canola oil organo-
gels stored for 24 h. After storing for 24 h at 5 C (A,C) and 30 C (B,D), the samples were treated with
80/20 (v:v) hexane/acetone. Error bars for A,B ¼ 30 mm and C,D ¼ 3 mm. (Taken from Rogers, M.A.,
Wright, A.J., Marangoni, A.G., 2009b. Nanostructuring fiber morphology and solvent inclusions for 12
hydroxystearic acid/canola oil organogels. Curr. Opin. Coll. Inter. Sci. 14, 33e42.)
5 C), a relative change in the flow rate may then be determined. The ratio was found
to be 1.35 0.14. Analysis of variance was used to compare the ratio of the flow rate
determined using radius and viscosity to the T2 relaxations and the oil mobility. It was
found that there was no significant difference in the ratio of mobility regardless of the
method used. This confirms that changes in oil syneresis may be directly measured using
both the T2 relaxation times as well as the ratio of the viscosity to pore radius.
100 Edible Oleogels
Table 4.2 The Length of 12-Hydroxystearic Acid Strands and Size of Pores in Canola Oil
Were Determined Using Different Magnifications of the Xerogel and the Osmium
Tetroxide/Isobutanol-Treated Samples
58C 308C
300 1000 10,000 300 1000 10,000
Figure 4.10 Release profiles of ibuprofen from organogel including (B) 0%, (C) 2%, (6) 3%, (:) 5%,
and (,) 10% of 12-hydroxystearic acid in simulated intestinal fluid. Each value represents the mean -
SE of three experiments. (Take from Iwanaga, K., Sumizawa, T., Miyazaki, M., and Kakemi, M., 2010.
Characterization of organogel as a novel oral controlled release formulation for lipophilic compounds. Int.
J. Pharm. 3888, 123e128.)
REFERENCES
Baba, M., Gardette, J.-I., Lacoste, J., 1999. Crosslinking on ageing of elastomers II. Comparison of solvent
freezing point depression and conventional crosslinking evaluation. Polym. Degrad. Stab. 65, 415.
Dumas, P., Jamin, N., Teillaud, J.L., Miller, L.M., Beccard, B., 2004. Imaging capabilities of synchrotron
infrared microspect-roscopy. Faraday Discuss 126, 289e302.
Elliger, C.A., Guadagni, D.G., Dunlap, C.E., 1972. Thickening action of hydroxytearates in peanut butter.
J. Am. Oil Chem. Soc. 1972 (49), 536e537.
Fuhrhop, J.-H., Schnieder, P., Rosenberg, J., Boekema, E., 1987. The chiral Bilayer effect stabilizes micellar
fibers. J. Am. Chem. Soc. 109, 3387e3390.
Giorgano, J., Daleo, C., Stacks, S.M., 1998. Topical ondansetron attenuates nociceptive and inflammatory
effects of intradermal capsaicin in humans. Eur. J. Pharmacol. 354, R13eR141.
Hughes, N.E., Marangoni, A.G., Wright, A.J., Rogers, M.A., Rush, J.W., 2010. Potential food applications
of edible oil organogels. Trends Food Sci. 2009 (20), 470e480.
Iwanaga, K., Sumizawa, T., Miyazaki, M., Kakemi, M., 2010. Characterization of organogel as a novel oral
controlled release formulation for lipophilic compounds. Int. J. Pharm. 3888, 123e128.
Kantaria, S., Rees, G.D., Lawrence, M.J., 1999. Gelatin-Stabilised microemulsion-based organogels:
rheology and application in iontophoretic transdermal drug delivery. J. Control. Rel. 60, 355e365.
Kirilov, P., Gauffre, F., Franceschi-Messant, S., Perez, E., Rico-Lattes, I., 2009. Rheological characterization
of a new type of colloidal dispersion based on nanoparticles of gelled oil. J. Phys. Chem. B 113,
11101e11108.
Kuwahara, T., Nagase, H., Endo, T., Ueda, H., Nakagaki, M., 1996. Crystal structure of DL-12-
hydroxystearic acid. Chem. Lett. 25, 435e436.
Lam, R., Rogers, M.A., 2011. Experimental Validation of the modified Avrami model for non-isothermal
crystallization condition. CrystEngComm. https://doi.org/10.1039/C0CE00532C.
102 Edible Oleogels
Lam, R., Pederson, T., Quaroni, L., Rogers, M.A., 2010. A molecular insight into the nature of crystallo-
graphic mismatches in self-assembled fibrillar networks under non-isothermal crystallization conditions.
Soft Matter 6, 404e408.
Liu, X.Y., Sawant, P.D., 2001. Formation kinetics of fractal nanofiber networks in organogels. App. Phys.
Lett. 79, 3518e5320.
Liu, X.Y., Sawant, P.D., 2002. Mechanism of the formation of self-organized microstructures in soft
functional materials. Adv. Mater 14, 421e426.
Marangoni, A.G., McGauley, S.E., 2003. Relationship between crystallization behavior and structure in
Cocoa butter. Cryst. Grow. Des. 3, 95e102.
Markovic, N., Ginic-Markovic, M., Dutta, M.K., 2004. Benzene physical and chemical organogels: effect of
network scaffolding on the thermodynamic behavior of entrapped solvent molecules. J. App. Polym. Sci.
94, 1253.
Maskaev, A.K., Man’Kovskaya, N.K., Lend’el, I.V., Fedorvskii, V.T., Simurova, E.I., Terent’eva, V.N.,
1971. Preparation of 12-hydroxystearic acid, the raw material for plastic greases. Chem. Techn. Fuels
Oil 1971 (7), 109e112.
Provencher, S.W., 1982a. A contstrained regularization method for inverting data represented by linear
algebraic or integral equations. Comp. Phys. Comm. 27, 213e217.
Provencher, S.W., 1982b. Contin: a general purpose constrained regularization program for inverting noisy
linear algebraic and integral equations. Comp. Phys. Comm 27, 229e242.
Rogers, M.A., Marangoni, A.G., 2008. Non-isothermal nucleation and crystallization of 12HSA in
vegetable oil. Cryst. Grow. Des. 8, 4596e4601.
Rogers, M.A., Marangoni, A.G., 2009. Solvent modulated nucleation and crystallization kinetics of
12-hydroxystearic acid: a non-isothermal approach. Langmuir 25, 5886e5896.
Rogers, M.A., Smith, A.S., Wright, A.J., Marangoni, A.G., 2007. A novel imaging technique for vegetable
based organogels. J. Am. Oil Chem. Soc. 84, 899e906.
Rogers, M.A., Pederson, T., Quaroni, L., 2009a. Hydrogen bonding density of supramolecular structures for
self-assembled fibrillar networks probed using synchrotron infrared spectromicroscopy. Cryst. Grow.
Des. 9, 3621e3625.
Rogers, M.A., Wright, A.J., Marangoni, A.G., 2009b. Nanostructuring fiber morphology and solvent
inclusions for 12 hydroxystearic acid/canola oil organogels. Curr. Opin. Coll. Inter. Sci. 14, 33e42.
Strange, J.H., Rahman, M., Smith, E.G., 1993. Characterization of porous solids by NMR. Phys. Rev. Lett.
71, 3589e3591.
Suzuki, M., Nakajima, Y., Yumoto, M., Kimura, M., Shirai, H., Hanabusa, K., 2003. Effects of hydrogen
bonding and van der Waals interactions on organogelation using designed Low-molecular-weight
gelators and gel formation at room temperature. Langmuir 19, 8622e8624.
Tachibana, T., Kambara, H., 1968. The sense of twist in the fibrous aggregates from 12-hydroxystearic acid
and its alkali metal soaps. J. Colloid Sci. 28, 173e174.
Tamura, T., Ichikawa, M., 1997. Effect of lecithin on organogel formation of 12-hydroxystearic acid. J. Am.
Oil Chem. Soc. 74, 491e495.
Terech, P., Rodigues, V., Barns, J.D., McKenna, G.B., 1994. Organogels and aerogels of racemic and chiral
12-hydroxyoctadecanoic acid. Langmuir 10, 3406e3418.
Uzu, Y., Sugiura, T., 1975. Electron microscopic and thermal studies of optically active 12-hydroxystearic
acids in soap formation. J. Colloid Int. Sci. 51, 346e349.
Vesely, D., 2001. Molecular sorption mechanism of solvent diffusion in polymers. Polymer 42, 4417.
Wang, R., Lui, X.Y., Xiong, J., Li, J., 2006. Real-time observation of fiber network formation in molecular
organogel: supersaturation-dependent microstructure and its related rheological property J. Phys. Chem.
B 110, 7275.
Weiss, R.G., Terech, P., 2007. In: Weiss, R.G., Terech, P. (Eds.), Introduction. Molecular Gels Materials
with Self-assembled Fibrillar Networks. Springer, Dordrecht, Netherlands, pp. 1e13.