JOURNAL OF OLEO SCIENCE

Copyright 2005 by Japan Oil Chemists Society

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

JOS

Effect of Static Magnetic Field Processing on Crystallization

Behavior of Triacylglycerols
Makoto MIURA1Ayako KUSANAGI1Shoichi KOBAYASHI1
Shigeru TOKAIRIN2 and Koichi TSURUMI2
1

Department of Agro-bioscience, Iwate University

(3-18-8 Ueda, Morioka, Iwate 020-8550, JAPAN)
2
Research Laboratory, Tsukishima Foods Industry Co., Ltd.
(3-17-9 Higashi Kasai, Edogawa-ku, Tokyo 134-8520, JAPAN)
Edited by M. Yonese, Nagoya City Univ., and accepted December 10, 2004 (received for review August 23, 2004)

Abstract: The influence of static magnetic field on crystallization of triacylglycerols

(TAGs) was investigated. Melted TAGs were solidified under static magnetic field of 5 T with a
superconductive magnet system. Polymorphic behavior of TAGs was examined by temperature
modulated differential scanning calorimetry (TMDSC) and X-ray diffraction (XRD). In TMDSC
experiment, saturated mono-acid TAGs (PPP and SSS) had no change in crystallization behavior
under static magnetic field. Static magnetic field processing suppressed the crystallization of a
form of SOS, PPO and POS. Furthermore, it suppressed the crystallization of sub-a form, a
form, and b form of POP. In case of SSO, the crystallization of a form and b form was
suppressed. On the other hand, in the XRD experiment the crystallization of a form in PPP and
POP was suppressed by static magnetic field processing. PPO had no change in crystallization
behavior under the static magnetic field. However, fluctuation in the ratio of the XRD peak area
(wide angle region/small angle region) of a form was increased. This change suggested that the
phase transition from a to b form had occurred. From these results, the following can be
considered as the influences of static magnetic field on crystallization of TAGs: (i) the effect of
static magnetic field on crystallization of saturated mono-acid TAGs depended on the fatty acid
chain length which constitutes TAG (PPP and SSS), (ii) the shorter the acyl chains of TAGs, the
more sensitive to static magnetic field it was in saturated-unsaturated mixed-acid TAGs (PPO
and SSO), and (iii) symmetrical type TAGs (POP and SOS) were more sensitive to static
magnetic field rather than asymmetrical type of TAG (POS). It is speculated that the effect of a
magnetic field on polymorphism of TAGs is due to the magnetic field gradient in a magnet and
the molecular orientation caused by magnetic anisotropy of a TAG molecule. Much work is
needed to clarify the mechanism of the polymorphic crystallization under static magnetic field.
Key words: triacylglycerol, crystallization, polymorphism, magnetic field

Introduction

Fats and oils are employed in food, cosmetics, pharmaceuticals, etc., as main bodies of end products, or as
matrices in which cosmetic and pharmacological fine

chemicals are dispersed. The molecular species of the

fats and oils are waxes, fatty acids, glycerols (mono-,
di- and tri-), phospholipids, and glycolipids etc., which
are categorized as long-chain compounds (1, 2). Triacylglycerols (TAGs) are employed in edible oil, butter,

Correspondence to: Makoto MIURA, Department of Agro-bioscience, Iwate University, 3-18-8 Ueda, Morioka, Iwate 020-8550, JAPAN
E-mail: mako@iwate-u.ac.jp
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://jos.jstage.jst.go.jp/en/

193

M. Miura, A. Kusanagi, S. Kobayashi et al.

margarine, cream, chocolate, and other edible oils and

fats products, and the fat structures are the major factors
to determine their physical properties, such as food texture, plasticity, morphology, and so on (3, 4). In chocolate manufacture, the solidification process significantly
influences the quality of the final product: gloss, snap,
food texture, heat resistance, fat bloom resistance, and
so on (5). The most troublesome problems are encountered in the occurrence of different crystal structures of
solid-fat components, mostly cocoa butter, called polymorphism.
The crystallization behavior of fats and oils has two
major industrial implications: (a) processing of the end
products made of fat crystals, such as chocolate, margarine and shortening, whipping cream, etc., and (b)
separation of specific fats and lipids materials from natural resources (6). The natural fats and oils resources
are vegetable and animal fats and oils, which contain
various molecular species having different chemical and
physical properties. It may be worth noting that there is
an increasing necessity to develop the fractionation
technology of high- and low-melting fats and oils put
forward by the following market demands: (a) obtaining
high melting fats by dry fractionation, instead of hydrogenation which produces trans-fatty acids as bi-products, (b) coping with new regulation standards of the
use of fat materials for confectionery end products, (c)
maintaining better functionality of physically refined
vegetable oils compared to conventional materials, etc.
The crystallization behavior of lipids is affected by
the presence of minor components. The crystallization
kinetics of palm stearin, a palm oil fraction, in blends
with sesame seed oil were investigated (7). The results
indicated that the crystallization behavior of palm
stearin in sesame oil was mainly associated with the
crystallization of tristearoylglycerol (SSS). Cocoa butter consists mainly of three symmetric TAGs, 1,3dipalmitoyl-2-oleoyl glycerol (POP), 1,3-distearoyl-2oleoyl glycerol (SOS), and 1-dipalmitoyl-2-oleoyl-3stearoyl glycerol (POS) (8). The polymorphism of
cocoa butter is an important physical aspect for the confectioner, especially for chocolate manufactures,
because the major fat in chocolate is cocoa butter. To
solidify chocolate in desired polymorphs, careful temperature treatment is needed because the polymorphism
of cocoa butter is quite complicated, and therefore its
crystallization phenomena are not easily controlled.
Monogalactosyldiacylglycerol (MGDG), digalacto-

syldiacylglycerol (DGDG) and trigalactosyldiacylglycerol (TGDG) were prepared from various natural materials (9). MGDG and DGDG significantly retarded the
polymorphic transformation from form V to VI on
cocoa butter compared with the control, with the addition of MGDG being the most effective.
Sophisticated food processing operations have been
developed to control crystallization in food lipids, particularly in the fields of chocolate, margarine, and
shortening manufacture. To produce good solid chocolate, it is necessary to crystallize it in a stable polymorphic form. This is achieved by a process of tempering
where the melt is exposed to a controlled-temperature
profile under shear, the aim being to create 1-3 % of the
desired crystals in an otherwise liquid continuum. Different processing factors, such as cooling rate and crystallization temperature as well as the supersaturation of
the system, may influence the crystallization behavior
of any system. The crystallization behavior of palm oil
and its thermal features were examined by differential
scanning calorimetry (DSC), X-ray diffractometry
(XRD) and infrared spectroscopy (IR) (10). When
using palm oil-based products, attention should be
directed to the effects of temperature on crystallization
of TAGs. The effects of cooling rate, degree of supercooling, and storage time on the micro-structure and
rheological properties of a vegetable shortening composed of soybean and palm oils were examined (11).
The morphology and size of the microstructural elements also affects the mechanical strength of the network. The induction times for the crystallization, under
isothermal conditions, of refined, and deodorized palm
oil from the melt were studied by viscometry (12). At
temperature below 295 K, the crystallization of palm oil
was observed to occur in a two-stage process. On the
other hand, only a single-stage crystallization process
was observed at temperatures higher than 295 K. The
effect of shear rate on the crystallization onset temperature of a confectionary coating fat was studied using a
rheometer incorporating ultrasonic sensors (13). The
onset temperature increased significantly with shear
rate, implying lipid crystallization can be accelerated by
mixing. Crystallization, polymorphic transformation,
and melting behavior of nanoparticles of trilauroylglycerol (LLL) in oil-in-water (O/W) emulsion were examined by simultaneous synchrotron radiation small-angle
(SAXS), wide-angle X-ray diffraction (WAXS) and
DSC (14). The forming nanoparticle of LLL in the O/W

194

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

Effect of Magnetic Field on Crystallization of TAGs

emulsion having the diameters of 42 to 120 nm reduced

the melting and crystallization temperatures and
increased the transformation rate of a b
b in
comparison to the LLL crystal formed in the bulk
phase.
Nowadays consumers are demanding prepared foods
devoid of any chemical additives, e.g., emulsifiers, and
with natural characteristics and natural flavor. Studying
the influence of parameters of reaction field such as
electric field, magnetic field, electromagnetic field and
extra-high pressure on lipid crystallization is quite
interesting since development of processing method for
crystallization control of lipids is needed in the food
industry without food additives. As for magnetic field
processing, an investigation of the influence of a magnetic field on selectivity ratio (SR) in the nickel-catalyzed hydrogenation process of sesame oil and soybean oil was reported (15). The SRs obtained were
higher than those without a magnetic field because the
magnetization of the nickel particles reduced the concentration of hydrogen on the catalyst surface.
New processing operations in controlling lipid crystallization have been developed. Therefore, the aim of
the present work was to investigate the effect of static
magnetic field on crystallization of lipids. In this study,
TAGs were chosen as model substances mainly because
their important properties of crystallization and polymorphic transformation in bulk state are well known.

Experimental

21 Materials
Seven kinds of TAGs were purchased from SigmaAldrich Corp. (St. Louis, MO, USA) with purity higher
than 99%. Tripalmitoyl glycerol (PPP) and tristearoyl
glycerol (SSS) were used as saturated mono-acid TAGs.
1,3-dipalmitoyl-2-oleoyl glycerol (POP) and 1,3-distearoyl-2-oleoyl glycerol (SOS) were used as symmetrical saturated-unsaturated mixed-acid TAGs. 1,2dipalmitoyl- 3-oleoyl glycerol (PPO), 1,2-distearoyl-3oleoyl glycerol (SSO), and 1-palmitoyl-2-oleoyl-3stearoyl glycerol (POS) were used as asymmetrical saturated-unsaturated mixed-acid TAGs. All the TAGs
were employed without further purification. Mercury
(Standard Reference Material 743, National Institute of
Standards and Technology, USA), biphenyl (Certified
Reference Material LGC2610, Laboratory of the Government Chemist, Middlesex, UK) and benzyl (Certi-

fied Reference Material LGC2604, Laboratory of the

Government Chemist, Middlesex, UK) were obtained
as reference materials for temperature calibration. Indium (Certified Reference Material LGC2601, Laboratory of the Government Chemist, Middlesex, UK) was
used as a reference material for enthalpy of fusion.
22 Static Magnetic Field Processing
The influence of static magnetic field on occurrence
of polymorphs of TAGs was examined by the simple
cooling of the melt from varying heating temperatures
(Th) to varying cooling temperatures (Tc). Two milligrams of the sample for temperature modulated differential scanning calorimetry (TMDSC) were weighted
into an aluminum sample pan and hermetically sealed.
The sample (200mg) was placed in the XRD sample
holder, which was temperature controlled. These samples were attached on the heating/cooling plate of Peltier type thermoelectric device (SL-10W, Nippon Blower
Co., Ltd., Tokyo, Japan) equipped with a platinum
resistance temperature sensor (f 2 mm L 30 mm,
Nippon Blower Co., Ltd.) and a temperature control
system (SL-CPP1206M, Nippon Blower Co., Ltd.). The
thermoelectric device was placed in a superconductive
magnet system (JMTD-5T300, central magnetic flux
density of 5 T, Japan Superconductor Technology Inc.,
Tokyo, Japan) as shown in Fig. 1 and temperature of the
samples controlled. Moreover, melted SOS was crystallized under static magnetic field of 2 T and 0.5 T. The
heating temperature (Th) were 60 for PPO and POS,
70 for SSO and POP, 80 for SOS, 90 for SSS,
and 100 for PPP at the heating rate of 2min1,
respectively. The cooling temperature (T c ) were
10 for POP, 0 for PPO, SSO, SOS and POS, and
20 for PPP and SSS at cooling rate of 5min1
except for SSS and POS at 2min1, respectively. All
the TMDSC and XRD measurements were performed
within 12 hours to avoid any crystal changes after static
magnetic field-processing of the samples.
23 Temperature Modulated Differential
Scanning Calorimetry
The crystallization and melting behaviors of the
TAGs were examined by TMDSC. Calorimetric analysis was performed with a MDSC Cell Base 2900
equipped with Thermal Analyst Controller TA-5200
(TA Instruments, Inc., New Castle, DE, USA). The
temperature calibration of the equipment was done with
195

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

M. Miura, A. Kusanagi, S. Kobayashi et al.

amplitude divided by the modulated heating rate amplitude. The reversing heat flow is determined by multiplying this heat capacity by the average heating rate.
The nonreversing heat flow is determined as the difference between the total and reversing heat flows.

Fig. 1 Experimental Setup for Heating-Cooling Processing

of Triacylglycerol under Static Magnetic Field: (A)
Schematic Diagram of Static Magnetic Field
Processing, (B) Heating-Cooling Unit with Peltier
Element.

mercury (melting temperature 38.83), biphenyl

(68.93) and benzyl (94.85). The baseline was
developed with an empty aluminum pan. The calibration for heat involved in phase changes (i.e., melting/
crystallization) was made only with indium (enthalpy
change for melting 28.71 Jg1). Nitrogen was used as
the purge gas to prevent condensation in the cell, and an
empty pan was used as reference.
For all scans, 10 min was allowed for insertion of the
sample, starting of scan, and for thermal equilibrium to
be established at initial temperature. For the heating
run, the sample was held at Tc for 10 min, then heated
at a constant rate from Tc to Th with the temperature
modulation amplitude of 0.125 and modulation period (frequency) of 100 s (0.01 Hz). The following heating rate was varied to assess the effect of static magnetic field-processing during the solidification stage and
thus the crystallization behavior of TAGs: at 0.8
min1 for SSO, 1min1 for POP and POS, 1.5
min 1 for PPO, 2min 1 for SOS, respectively.
Enthalpy change (DH), onset temperature (To), peak
temperature (Tp), and completion temperature (Tc) were
computed automatically.
Deconvolution of TMDSC signals provides not only
the total heat flow obtained from conventional DSC, but
also separates that total heat flow into its heat capacityrelated (reversible within the time scale of the perturbation) and kinetic (irreversible) components. Specifically, Fourier transformation analysis of the modulated
heat flow signal is used to continuously calculate an
average heat flow value which is equivalent to the total
heat flow signal in conventional DSC. Heat capacity is
calculated from the ratio of the modulated heat flow

24 Powder X-ray Diffraction

The polymorphic forms of the TAG crystals were
assessed by powder XRD using a X-ray diffractometer
(M18XHF22, Bruker AXS K. K., Tsukuba, Japan). The
XRD patterns were obtained at X-ray tube voltage of 35
kV, X-ray tube current of 40mA, scanning rate of 5
degs1, measuring interval of 0.02 deg, and scanning
angle (2q) of 0 to 40 deg with Cu-Ka radiation. X-ray
diffraction spectrum of PPP was obtained at room temperature. As for POP and PPO, the spectra were measured at 0 using a cryostat.
The peak (2q 6 deg) reflecting a long spacing and
the peak (2q 21 deg) indicating a form crystal were
observed in all XRD patterns. Consequently, XRD peak
intensity was evaluated from the standardized peak area
of these peaks. And a peak ratio of the peak intensity of
2q 21 deg to that of 2q 6 deg was computed.
25 Statistical Analysis
Data were statistically analyzed by a one-way analysis of variance (ANOVA) using SPSS 12.0.2J for Windows (SPSS Inc., Tokyo, Japan). Significant difference
(P<0.05) between means were further determined by
Turkeys multiple range test.

Results and Discussions

31 Temperature Modulated Differential

Scanning Calorimetry
311 Saturated mono-acid TAGs
Tripalmitoyl glycerol (PPP) is known to crystallize in
three typical polymorphic forms: a, b
, and b in which
a is least stable, bis metastable, and b is most stable.
The melting points of these forms are 44.7, 56.6,
and 66.4, respectively (16). Rapid and slow cooling
scans crystallized the a and b forms, respectively.
After the formation of the two respective forms, the
DSC heating produced the melting of a and band successive crystallization of the b form which melted on
further heating (3). In TMDSC curves of PPP (Fig. 2),
reference sample in this experiment showed a small
endothermic peak at 43-45 , which was soon fol-

196

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

Effect of Magnetic Field on Crystallization of TAGs

lowed by an exothermic peak at 46-52 . These two

peaks corresponded to the melting of the a form and
rapid crystallization of the most stable b form. Further
heating showed an endothermic peak at 63-70 ,
which is due to the melting of b form. Figure 3 (A)
shows enthalpy changes of PPP on each peak in
TMDSC curves. No significant differences were
observed between the reference sample and the sample
processed with static magnetic field of 5 T regarding
the enthalpy changes accompanying the melting of a
form, the phase transition from a to b form, and the
melting of b form. Therefore, PPP was thought to have
no change in crystallization under static magnetic field

Fig. 2 TMDSC Curves of PPP without Static Magnetic

Field Processing (A) and with the Processing (B).
Deconvolution of TMDSC signals provides not only
the total heat flow (upper curve), but also separates
that total heat flow into its heat capacity-related
(middle curve) and kinetic (bottom curve) components. No significant differences were observed
between (A) and (B).

of 5 T.
SSS (tristearoyl glycerol) reveals three polymorphic
transformations, a, b
, and b. The melting temperatures
of a (55.0), b(61.64), and b (73.0) have been
reported (17, 18). Reference sample of SSS in this
experiment showed an endothermic peak at 52-56,
which was followed by an exothermic peak at 56-62
in TMDSC curve. These two peaks corresponded to the
melting of the a form and rapid crystallization of the
more stable b form. Further heating showed an
endothermic peak at 70-78, which is due to the melting of b form. The pattern of the obtained TMDSC
curve was in good agreement with the DSC curve
reported by Singh et al. (19). Figure 3 (B) shows
enthalpy changes of SSS on each peaks in the TMDSC
curves. No significant differences were observed

Fig. 3 Enthalpy Changes of Saturated Mono-Acid TAGs

Crystallized under Geomagnetism (white) and Static
Magnetic Field of 5 T (gray). (A) Enthalpy changes
of PPP : Mean values of six determinations (
standard deviation) are represented. (B) Enthalpy
changes of SSS : Mean values of eight determinations ( standard deviation) are represented.
197

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

M. Miura, A. Kusanagi, S. Kobayashi et al.

between the reference sample and the sample treated

with static magnetic field of 5 T in regard to enthalpy
changes accompanying the melting of a form, the phase
transition from a to b form, and the melting of b form.
From these results, it can be concluded that static
magnetic field processing during solidification had no
significant effect on crystallization behavior of PPP and
SSS.
312 Saturated-unsaturated mixed-acid TAGs
In 1,3-dipalmitoyl-2-oleoyl glycerol (POP), six polymorphs, a (melting point 15.2), g (27.0), pseudob2 (30.3), pseudo-b1 (33.5), b2 (35.1) and b1
(36.7) were identified with XRD, DSC and Raman
spectroscopy by Sato et al. (20). Additionally, POP
exhibited two transformation pathways; a g pseudo-b2 ( pseudo-b1 ) b2 b1 in the sample with
99% purity, and d (melting point 29.2) pseudob1
b2 b1 in the sample with 99.2% purity, implying subtle influences of the impurity. Sub-a form was
observed in SOS, AOA(1,3-diarachidoyl-2-oleoyl glycerol) and BOB (1,3-dibehenoyl-2-oleoyl glycerol) as a
less stable form than a form (21). An exothermic peak
which indicated solid-state transition from the sub-a to
a form was observed in the present TMDSC curve of a
reference sample at 11-17. Thereafter the sample
showed a endothermic peak at 26-29 followed by an
exothermic peak at 29-31. These two peaks corresponded to the melting of the a form and the rapid
crystallization of a form to the more stable b form.
Further heating showed an endothermic peak at 3134 which indicate the melting of bform. Figure 4
(A) displayed enthalpy changes of each peaks in the
TMDSC curves of POP. As for solidified POP under
static magnetic field of 5 T, the exothermic peak which
indicated solid-state transition from the sub-a to a form
could not be observed. Consequently, static magnetic
field processing suppressed the crystallization of the a
form (ca. 73% compared with the reference sample),
the transformation from the a form to the bform (ca.
35%) and the crystallization of the bform (ca. 76%).
Five polymorphs, a, g, pseudo-b
, b2, and b1 were
isolated in SOS (1,3-distearoyl-2-oleoyl glycerol) (20).
The melting points of these crystal forms are 23.5,
35.4, 36.5, 41.0, and 43.0, respectively. There
was one transformation pathway in SOS; a g
pseudo-b
b2 b1. On TMDSC curves, reference
sample of SOS showed a small endothermic peak at 2123 soon followed by an exothermic peak at 24-29.

These two peaks corresponded to the melting of the a

form and rapid crystallization of a form to the more
stable bform. Further heating showed an endothermic
peak at 35-42 which was due to the melting of b
form.
TMDSC curves of SOS solidified under static magnetic
field of 5 T showed disappearance of a thermopeak
indicating the melting of a form or the thermopeaks
indicating the melting of a form and the transformation

Fig. 4 Enthalpy Changes of 1, 3-disaturated-2-unsaturated

Mixed Acid TAGs Crystallized under Geomagnetism
(white) and Static Magnetic Field (gray). Data are
taken from the mean standard deviation. (A)
Enthalpy changes of POP crystallized under and
static magnetic field of 5 T (n=6). (B) Enthalpy
changes of SOS crystallized under and static
magnetic field of 2 T (n=4). (C) Enthalpy changes of
SOS crystallized under static magnetic field of 0.5 T
(n=4).

198

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

Effect of Magnetic Field on Crystallization of TAGs

from the a form to the b form. This result indicated

that static magnetic field processing suppressed the
crystallization of the a form of SOS. Since the exothermic peak of the phase transition was observed in three
of the processed sample but not the others, magnetic
flux density of 5 T would be near the critical value
affecting the polymorphic behavior of SOS. Accordingly, static magnetic field processing of 2 T and 0.5 T to
this TAG was also tried. TMDSC curves of the samples
processed under static magnetic field of 2 T and 0.5 T
showed the same patterns as the reference sample. Static magnetic field of 2 T accelerated the crystallization
of the a form (ca. 126% compared with the reference
sample) as shown in Fig. 4 (B). There was no appreciable difference between the reference sample and the
sample processed with static magnetic field of 0.5 T as
shown in Fig. 4 (C). It appears that SOS would not be
influenced by the static magnetic field processing of 0.5
T.
The results described above suggest that both POP
and SOS were influenced by static magnetic field processing of 5 T, and it became clear that a form of these
TAGs were suppressed. Polymorphic behavior of SOS
would be more sensitive to static magnetic field and
have a critical magnetic flux density.
1,2-dipalmitoyl-3-oleoyl glycerol (PPO) shows two
kinds of polymorph: a (melting point 18.5) and
b(35.2) forms (6). Reference sample of PPO in this
experiment showed an endothermic peak at 17-19
soon followed by an exothermic peak at 20-23 in
TMDSC curve. These two peaks corresponded to the
melting of the a form and rapid crystallization of the
more stable b form, respectively. Further heating
showed an endothermic peak at 31-36 which is due
to the melting of b form. Figure 5 (A) shows the
enthalpy changes of each peaks in a TMDSC curve.
Thermopeaks indicating the melting of the a form and
the transformation from the a form to the bform could
not be observed. This suggests that static magnetic field
processing at 5 T suppressed the crystallization of the a
form of PPO.
1,2-distearoyl-3-oleoyl glycerol (SSO) is similar with
PPO in chain length structure, and exhibits simpler
transformation from a form to bform, maintaining the
triple chain length structure (22). The melting points of
these form are 26 and 41.4, respectively (23). Reference sample of SSO in this experiment showed an
endothermic peak at 30-33 which was soon followed

by an exothermic peak at 32-36 in TMDSC curve.

These two peaks corresponded to the melting of the a
form and rapid crystallization of the more stable
b form. Further heating showed an endothermic peak
at 40-44 indicating the melting of bform. In SSO,
static magnetic field processing suppressed the crystallization of the a form (ca. 92% compared with the reference sample), the transformation from the a form to
the b form (ca. 89%) and the crystallization of the
bform (ca. 91%) as shown in Fig. 5 (B).
1-palmitoyl-2-oleoyl-3-stearoyl glycerol (POS),
which is the major component of cocoa butter, has four
polymorphs, a (19.5), d (28.3), pseudo-b
(31.6),
and b (35.5) (21). There are two pathways of polymorphic transformations in POS : a pseudo-b b
and d pseudo-b b. a form directly transformed

Fig. 5 Enthalpy Changes of 1, 2-disaturated-3-unsaturated

Mixed-Acid TAGs Crystallized under Geomagnetic
Field (white) and Static Magnetic Field of 5 T (gray).
(A) Enthalpy changes of PPO : Mean values of four
determinations ( standard deviation) are represented. (B) Enthalpy changes of SSO : Mean values
of five determinations ( standard deviation) are
represented.
199

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

M. Miura, A. Kusanagi, S. Kobayashi et al.

to pseudo-b
, not through the d form. The pattern of the
obtained TMDSC curve of POS was in good agreement
with the DSC curve reported by Arishima et al. (24).
Reference sample of POS in this experiment showed an
endothermic peak at 19-21 which was soon followed
by an exothermic peak at 22-24. These two peaks
corresponded to the melting of the a form and rapid
crystallization of the more stable bform, respectively.
Further heating showed an endothermic peak at 3135 corresponding to the melting of bform. Figure 6
shows enthalpy changes of each peaks in TMDSC
curves of POS. Static magnetic field processing suppressed the crystallization of the a form (ca. 69% compared with the reference sample), and the transformation from the a form to the bform (ca. 82%).

field processing suppressed the crystallization of the a

form (ca. 90% compared with the reference sample).
This result seems to be in conflict with the result
obtained by TMDSC. However, it can be explained as
follows: TMDSC is a thermodynamic measurement
technique which measures the incoming and outgoing
heat capacity during melting and crystallization of a
substance. Differences in XRD patterns between the
reference and static magnetic field processed samples
could not be detected by TMDSC due to limited detection of the present calorimeter. The result obtained by
XRD suggests that effect of static magnetic field processing on crystallization behavior of saturated monoacid TAGs depends on the kind of fatty acid chain

32 X-ray Diffraction
The XRD patterns of reference sample and magnetic
field processed samples of PPP were shown in Fig. 7
(A). In wide angle region, the a form crystal is characterized by a single strong reflection at diffraction angle
(2q) of 21.4 deg (25). The wide angle spacings are
related to the cross sectional arrangement of the carbon
atoms, i.e. the crystal structure on the atomic level: they
are independent of the triacylglycerol composition. In
the small angle region, XRD provides additional information with respect to the overall molecular arrangement. In this study, the ratio of the XRD peak area in
the wide angle region ( 2q 21 deg) to the peak area
in the small angle region (2q 6 deg) was defined to
quantify the magnetic field effect. The ratios of PPP,
POP, and PPO were shown in Table 1. Static magnetic

Fig. 6 Enthalpy Changes of POS Crystallized under Geomagnetism (white) and Static Magnetic Field of 5 T
(gray). Mean values of four determinations (
standard deviation) are represented.

Fig. 7 X-ray Diffraction Patterns of TAGs Crystallized

under Geomagnetic Field for Control (solid black
line) and Static Magnetic Field of 5 T (solid gray
line): (A) PPP, (B) POP, (C) PPO.

200

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

Effect of Magnetic Field on Crystallization of TAGs

Table 1 The Ratio of the Peak Area of a form Crystal of

TAGs.
Ratio of the peak areaa

Magnetic field
processing

PPP

POP

PPO

35.5 2.3a

26.7 0.5c

27.9 1.3e

Processed under 5 T 31.9 1.5b

18.4 1.1d

26.1 3.4f

Without

Values are mean and standard deviations for triplicates, means with
different letters within a column differ signigicantly (P<0.05).

length which constitutes TAGs.

Characteristic peak of a form crystal was observed at
2q 21 deg in XRD pattern of POP (Fig. 7 (B)) (26).
Static magnetic field processing suppressed the crystallization of the a form of POP (ca. 69% compared with
the reference sample) as shown in Table 1. It is likely
that static magnetic field processing suppressed the
crystallizations of the a form in symmetrical saturatedunsaturated mixed-acid TAGs. Also, the characteristic
peak of a form crystal was observed at 2q 21 deg in
the XRD pattern (Fig. 7 (C)) of PPO (22). No significant differences were observed in XRD patterns
between the reference sample and the static magnetic
field processed sample (5 T) as shown in Table 1. However, PPO exhibited suppressed crystallization of a
form. The coefficient of variation (13%) of the peak
area which shows the a form in static magnetic field
processed sample was larger than that (5-8%) of the reference sample. The diffraction peak of b form might
have overlapped on the peak of a form crystal, thus
explaining the reason for the higher variation. Therefore, polymorphic transition from a form to b form
would be caused by static magnetic field processing in
PPO.

Conclusion

and SSO) were to static magnetic field and (iii) symmetrical type TAGs (POP and SOS) were more sensitive to static magnetic field rather than asymmetrical
type of TAGs (POS). It is speculated that the effect of a
magnetic field on polymorphism of TAGs is due to the
magnetic field gradient in a magnet and the molecular
orientation caused by magnetic anisotropy of a TAG
molecule. Magnetic anisotropy is defined as a property
in which magnetic internal energy changes with magnetized directions of substances. Crystalline materials have
a magnetic anisotropy whose magnetic susceptibility
changes with direction of crystal growth.
The present findings will be useful in tempering fats
and oils, such as shortening and chocolate. However, in
order to confirm the conclusion (i), it is necessary to
conduct the same experiments on more saturated monoacid TAGs (e.g., LLL, MMM, AAA, BBB: M, myristic
acid; A, arachidic acid; B, behenic acid) which consist
of a fatty acid chain length of 12-22. It is also necessary
to examine the polymorphic behavior of asymmetrical
saturated-unsaturated mixed-acid TAGs (e.g., LLO,
MMO, LMO, LPO, LSO) which consist of a fatty acid
chain length of 12-18 for confirmation of conclusion
(ii). Further, in order to prove conclusion (iii), it is necessary to execute the same experiments for more symmetrical saturated-unsaturated mixed-acid TAGs (e.g.,
LOL, MOM, AOA, BOB), and the asymmetrical saturated-unsaturated mixed-acid TAGs (e.g., MOL, MOP,
MOS, MOA, MOB) which consist of a fatty acid chain
length of 12-22. There are many problems left unsolved
both theoretically and experimentally. These include an
energetic consideration of the occurrence and stabilization of the diversified polymorphism of TAGs. Much
work is needed to clarify the mechanism of the polymorphic crystallization under static magnetic field.

Acknowledgement

In order to clarify the effect of static magnetic field

on polymorphic behavior of TAGs and to provide a
crystal control technique using magnetic field to food
industries, melted TAGs were cooled and crystallized
under the static magnetic field. The main results are as
follows: (i) the effect of static magnetic field on crystallization of saturated mono-acid TAGs depended on acyl
chain length which constitutes TAGs (PPP and SSS),
(ii) the shorter the acyl chains of TAGs, the more sensitive the saturated-unsaturated mixed-acid TAGs ( PPO

The authors are deeply indebted to Dr. Kiyotaka

Sato, Hiroshima University for providing constructive
comments and helpful suggestions. Dr. Toru Takahashi
of Akita Research Institute of Food and Brewing for his
kind assistance in XRD measurements and valuable discussion. We thank Dr. Zhe Jin of Iwate Industry Promotion Center for his instruction on superconducting magnet system. Advanced Applications of Magnetic Field
- The creation of industries based on magnetic fields
application - program supported by Collaboration of
201

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)

M. Miura, A. Kusanagi, S. Kobayashi et al.

Regional Entities for the Advancement of Technological Excellence (CREATE) and Japan Science and
Technology Agency (JST) are greatly acknowledged for
their financial support.

References

14.

15.

1. D.M. SMALL, Glycerides, in The Physical Chemistry of Lipids,

from Alkanes to Phospholipids, Handbook of Lipid Research
Series (D.J. HANAHAN, ed.), Vol. 4, Plenum Press, New York,
pp. 475-522 (1986).
2. J. YANO and K. SATO, FT-IR Studies on Polymorphism of
Fats: Molecular Structures and Interactions, Food Res. Int., Vol.
32, 249-259 (1999).
3. K. SATO, S. UENO and J. YANO, Molecular Interactions and
Kinetic Properties of Fats, Progr. Lipid Res., Vol. 38, 91-116
(1999).
4. K. SATO, Solidification and Phase Transformation Behavior of
Food Fats - a Review, Fett/Lipid, Vol. 101, 467-474 (1999).
5. I. HACHIYA, T. KOYANO and K. SATO, Seeding Effects on
Crystallization Behavior of Cocoa Butter, Agric. Biol. Chem.,
Vol. 53, 327-332 (1989).
6. K. SATO, Crystallization Behavior of Fats and Lipids - a
Review, Chem. Eng. Sci., Vol. 56, 2255-2265 (2001).
7. J.F. TORO-VAZQUEZ, M. BRICENO-MONTELONGO, E.
DIBILDOX-ALVARADO, M. CHARO-ALONSO and J.
REYES-HERNANDEZ, Crystallization Kinetics of Palm Stearin
in Blends with Sesame Seed Oil, J. Am. Oil Chem. Soc., Vol. 77,
297-310 (2000).
8. T. KOYANO, I. HACHIYA, T. ARISHIMA, N. SAGI and K.
SATO, Polymorphism of POS. II. Kinetics of Melt Crystallization, J. Am. Oil Chem. Soc., Vol. 68, 716-718 (1991).
9. T. NAKAE, T. KOMETANI, T. NISHIMURA, H. TAKII and S.
OKADA, Effects of Glyceroglycolipids Prepared from Various
Natural Materials on Polymorphic Transformation of Cocoa
Butter, Food Sci. Technol. Res., Vol. 6, 320-323 (2000).
10. H. MIHARA, T. ISHIGURO, H. FUKANO, S. TANIUCHI and
K. OGINO, Effect of Crystallization Temperature of Palm Oil
on Its Crystallization, J. Oleo Sci., Vol. 53, 231-238 (2004).
11. J.W. LITWINENKO, A.M. ROJAS, L.N. GERCHENSON and
A.G. MARANGONI, Relationship Between Crystallization
Behavior, Microstructure, and Mechanical Properties in a Palm
Oil-Based Shortening, J. Am. Oil Chem. Soc., Vol. 79, 647-654
(2002).
12. C.W. CHEN, O.M. LAI, H.M. GHAZALI and C.L. CHONG,
Isothermal Crystallization Kinetics of Refined Palm Oil, J. Am.
Oil Chem. Soc., Vol. 79, 403-410 (2002).
13. C. GARBOLINO, G.R. ZIEGLER and J.N. COUPLAND, Ultra-

16.

17.

18.

19.

20.

21.

22.

23.
24.

25.

26.

sonic Determination of the Effect of Shear on Lipid Crystallization, J. Am. Oil Chem. Soc., Vol. 77, 157-162 (2000).
M. HIGAMI, S. UENO, T. SEGAWA, K. IWANAMI and K.
SATO, Simultaneous Synchrotron Radiation X-ray Diffraction
DSC Analysis of Melting and Crystallization Behavior of Trilauroyl- glycerol in Nanoparticles of Oil-in-Water Emulsion, J.
Am. Oil Chem. Soc., Vol. 80, 731-739 (2003).
A. JART, The Magnetic Field as an Additional Selectivity
Parameter in Fat Hydrogenation, J. Am. Oil Chem. Soc., Vol. 74,
615-617 (1997).
E.S. LUTTON and A.J. FEHL, The Polymorphism of Odd Even
Saturated Single Acid Triglycerides C8-C22, Lipids, Vol. 5, 91-99
(1969).
M. OLLIVON and R. PERRON, Measurements of Enthalpies
and Entropies of Unstable Crystalline Forms of Saturated Even
Monoacid Triglycerides, Thermochim. Acta, Vol. 53, 183-194
(1982).
J.W. HAGEMANN and J.A. ROTHFUS, Polymorphism and
Transformation Energetics of Saturated Monoacid Triglycerides
from Differential Scanning Calorimetry and Theoretical Modeling, J. Am. Oil Chem. Soc., Vol. 60, 1123-1131 (1983).
S.K. SINGH, A.F. JALALI and M. ALDEN, Modulated Temperature Differential Scanning Calorimetry for Examination of
Tristearin Polymorphism: 1. Effect of Operational Parameters, J.
Am. Oil Chem. Soc., Vol. 76, 499-505 (1999).
K. SATO, T. ARISHIMA, Z.H. WANG, K. OJIMA, N. SAGI
and H. MORI, Polymorphism of POP and SOS. I. Occurrence
and Polymorphic Transformation, J. Am. Oil Chem. Soc., Vol.
66, 664-674 (1989).
Z.H. WANG, K. SATO, N. SAGI, T. IZUMI and H. MORI,
Polymorphism of 1, 3-Di(saturated acyl)-2-oleoylglycerols:
POP, SOS, AOA and BOB, Yukagaku, Vol. 36, 671-679 (1987).
K. SATO, Newest Understandings of Molecular Structures and
Interactions of Unsaturated Fats and Fatty Acids, Progr. Colloid
Polym. Sci., Vol. 108, 58-66 (1998).
L. ENGSTROM, Triglyceride Systems Forming Molecular
Compounds, J. Fat Sci. Technol., Vol. 94, 173-181 (1992).
T. ARISHIMA, N. SAGI, H. MORI and K. SATO, Polymorphism of POS. I. Occurrence and Polymorphic Transformation,
J. Am. Oil Chem. Soc., Vol. 68, 710-715 (1991).
M. KELLENS, W. MEEUSSEN, R. GEHRKE and H. REYNAERS, Synchrotron Radiation Investigations of the Polymorphic Transitions of Saturated Monoacid Triglycerides. Part 1:
Tripalmitin and Tristearin, Chem. Phys. Lipids, Vol. 58, 131-144
(1991).
T. KOYANO, I. HACHIYA and K. SATO, Fat Polymorphism
and Crystal Seeding Effects on Fat Bloom Stability of Dark
Chocolate, Food Structure, Vol. 9, 231-240 (1990).

202

J. Oleo Sci., Vol. 54, No. 4, 193-202 (2005)