1
It must be noted that the regiospecificity of the fatty acids on the triglycerides of Oil
2
C, Oil D, Oil E and Oil F were not determined. For this purpose, whenever a certain
3
triglyceride is reported, it must be assumed to refer to a group that contains the particular
4
triglyceride as well as all of its regio-isomers, hence the reference to a triglyceride “group”.
5
Triglycerides are also referred to by their carbon number, which is the added carbon number
6
of their fatty acid chains excluding the carbons from glycerol.
7
8
9
10
Oil C
Oil C – FA and TAG Composition
11
The fatty acid composition of Oil C is reported in Table 1. Oil C can be described as a
12
lauric oil consisting of a mixture of medium chain length fatty acids such as capric (12.6 %),
13
lauric (37.4 %) and myristic (9.84 %), with lauric acid making up the bulk of this fraction. A
14
considerable amount of palmitic acid is also present (8.11 %). The unsaturated component of
15
Oil C consists predominantly of oleic acid (22.5 %) and some linolenic acid (5.78 %). Oil C
16
has a very similar fatty acid composition to coconut oil1 although Oil C has slightly more
17
oleic acid and less lauric and myristic acid compared to coconut oil.
18
The triglyceride composition of Oil C is given in Table 2. The TAG analysis shows
19
that the distribution of TAGs according to carbon number is more varied in this fat. The
20
analysis shows that approximately 50 % of the TAGs in Oil C have a carbon number between
21
30 and 40. Roughly 75 % of the TAGs have a carbon number between 30 and 44. It can be
22
seen that 44.15 % area of the TAGs consist of trisaturated TAGs (groups A, C, D, H, J, O, X,
23
CC) while 38.23 % area of the TAGs consist of di-saturated TAGs. The TAGs containing
24
oleic acid (groups B, E, G, L, N, R, T, Z ) comprise 30.99 % area of the TAGs while a
25
smaller but significant portion of the TAGs containing linoleic acid (groups K, M, U, V)
26
comprise 7.24 % of the area. A sizable fraction (16.00 % area) consists of TAGs containing
1
1
two or three unsaturated fatty acids (groups I, F, P, Q, S, W, Y, AA, BB, DD). In this respect,
2
Oil C is very similar to Oil A in that it contains two solid fractions (trisaturates and oleic
3
acid-containing mono-unsaturate TAGs) although, in comparison, Oil C has significantly
4
more di- and tri-unsaturate “oil”. Presumably, the predominant TAGs (A, C and D from the
5
trisaturates and B and E from the disaturated TAG groups) from both types of TAGs
6
contribute to the structuring of the fat.
7
8
Oil C – Melting Behavior
9
A melting point estimation similar to that conducted for Oil A and Oil B can be
10
performed2,3. The melting point of the fat, to a certain extent, can be estimated from the
11
melting points of the pure triglycerides comprising the fat (shown to crystallize into a β’
12
polymorph). The melting points of the majority of the trisaturated group of TAGs can be
13
estimated to fall between 30 °C to 45 °C. Likewise, the melting points of most of the oleic
14
acid-containing di-saturated TAGs can be estimated to be between 15 °C to 25 °C.
15
Like the di- and tri- unsaturates of Oil B, the TAGs in the di- and tri-unsaturate group
16
of Oil C all appear to have very low melting points with the exception of oleic acid mono-
17
saturates containing a long chain fatty acid such as palmitic or stearic acid. As such, this lipid
18
class can be assumed to be predominantly liquid at ambient temperatures.
19
Examining the predominant TAGs in Oil C (% area > 6 %), it can be seen that these
20
consist of 5 groups, A, B, C, D and E. Groups A, C and D consist of trisaturated TAGs (and
21
their analogues) that have a carbon number of 34, 36 and 38, respectively. Group B is a di-
22
saturated TAG group that consists of either LaLaO or LaOLa. The melting points of these
23
groups is estimated to be as low as around 15 °C or as high as 50 °C for the trisaturates with
24
higher carbon numbers. In this light, it is highly likely that Oil C is structured by the high-
25
melting trisaturate groups mentioned above. Oil C may also be structured by oleic-acid
2
1
containing di-saturates, however, this is seemingly unlikely as the melting points of these
2
TAGs are below ambient temperatures due to the fact that the saturated fatty acids on these
3
TAGs are medium-chained unlike the long chain fatty acids in the oleic acid di-saturates in
4
Oil B.
5
Figure 1A shows that the melting trace of Oil C has two peak melting temperatures:
6
17.82 °C and 24.10 °C, suggesting only two melting fractions. The total melting enthalpy was
7
70.22 kJ/kg. The lower melting enthalpy reflects the fact that the solids content of Oil C is
8
less than the solids content of Oil A and Oil B. In all likelihood, the first melting peak at
9
17.82 °C can be attributed to the melting of the oleic acid-containing mono-unsaturate TAGs
10
as well as other low-melting components (most likely the linoleic acid-containing mono-
11
unsaturate TAGs). This is not inconceivable as the onset melting temperature of this peak is
12
1.2 °C. The second melting peak at 24.1 °C can most likely be attributed to the melting of the
13
higher-melting tri-saturated TAGs that structure the material. Although these TAGs, in their
14
pure form, have comparatively higher melting points (> 30 °C), it is possible that the melting
15
point may be depressed due to dilution and eutectic interactions between lipid phases.
16
Figure 2A shows that the melting profile of Oil C is gradual and starts at a temperature
17
of roughly 5 °C. The steepest decrease in the SFC occurs between 10 °C and 20 °C. This
18
melting profile is identical to the melting profile of Oil D. The initial solid fat content at 5 °C
19
is 52.24 %. Examining the TAG composition of Oil C and noting that the trisaturate groups
20
comprise roughly 44.15 % area of the TAG chromatogram, it can be safely assumed that the
21
solids in Oil C at the start of melting consist of the trisaturates as well as the higher-melting
22
TAGs of the oleic acid-containing mono-unsaturate class (with carbon number > 42).
23
Together, these fractions constitute 55.77 % of the area under the chromatogram. It is more
24
likely that LaLaO (carbon number = 40) and analogues thereof are present in the solid state at
25
the start of melting. In this case, the lower actual SFC observed (lower by about 10 %) at 5 °C
3
1
is perhaps due to eutectic effects. The lower-melting oleic acid-containing TAGs, as well as
2
the linoleic acid-containing di-saturates and the di- and tri- unsaturates constitute the oil phase
3
at 5 °C.
4
Like other fats previously discussed, the solid fat content of Oil C decreases in a linear
5
fashion as the temperature is increased. At 20 °C, the solid fat content is 11.8 %. This is
6
interesting considering that the four main trisaturate groups (groups A, C, D and H) all have
7
estimated melting points greater than 30 °C. This indicates that there may be eutectic or
8
solubilisation effects that depress the melting points of these TAGs considerably. Given that
9
these are the highest melting components, it is likely that the only fractions that have not
10
melted at 20 °C are these fractions. Melting is complete at 25 °C, which suggest that Oil C is
11
most likely an oil at ambient temperatures. As such, it has very limited functionality at
12
ambient temperatures as its plastic range is between 10 °C and 20 °C.
13
14
Oil C – Crystallization Behavior
15
The DSC crystallization trace for Oil C (Figure 1A) shows one peak crystallization
16
temperature at -2.59 °C. The onset of crystallization for this crystallization peak occurs
17
approximately at a temperature of 0 °C. A high undercooling of approximately 24 °C is
18
required to initiate crystallization of the fat (24 °C – 0°C). On the basis of the previous
19
discussion of melting points, this crystallization peak can be attributed to the crystallization of
20
tri-saturates as well as the high-melting components of the oleic acid-containing di-saturated
21
TAGs. It is highly unlikely that any of the lower-melting components crystallize given that
22
their melting points are significantly below 0 °C and that the experimental temperature does
23
not decrease sufficiently low to develop a supersaturation for these components.
24
The crystallization kinetics curve for Oil C is displayed in Figure 3A. Fit parameters
25
to the single or double Avrami equation are tabulated in Table 6. The plotted data suggests
4
1
only one crystallizing fraction. In addition, the kinetic data exhibited a long induction time
2
(approximately 900 seconds). The following result appears to agree with the DSC
3
crystallization curve for Oil C, which shows only one peak. A likely explanation for the long
4
induction time observed is that the high amount of liquid components decrease the
5
concentration of the crystallisable components. In turn, a higher undercooling is needed to
6
achieve supersaturation with the end result being that the rate of nucleation is not sufficient
7
for crystallization until a very low temperature is achieved.
8
The final SFC value as estimated from a single-Avrami fit is approximately 38.8 %.
9
This value is not altogether different from the solid fat content of the fat at 10 °C (44.5 %) as
10
obtained from the melting profile. Parameter estimates for the Avrami exponent for this
11
crystallization curve suggest that the crystallizing components grow either as a rod with
12
sporadic nucleation or as a disc with instantaneous nucleation4. Of the two, it is more likely
13
that the components grow as a disc with instantaneous nucleation, which suggests that all of
14
the crystallisable components nucleate at the beginning of crystallization and that no further
15
nucleation takes place during the course of the crystallization process. Examining the kinetics
16
curve, this is not inconceivable given the long lag time (presumably, the nuclei all form
17
within this long lag time).
18
19
Oil C – Crystal Structure and Microstructure
20
The XRD spectrum of Oil C is given in Figure 4A. A single long spacing peak at
21
32.93 Å can be observed in the small-angle region. Higher order reflections corresponding to
22
spacings of 16.73 Å and 11.18 Å are also present in the small-angle region. Similar to Oil A
23
and Oil B, the long spacing peaks suggest a bilayer stacking of triglyceride molecules. Using
24
the same calculation employed previously for Oil A and Oil B5, the number of carbons
25
comprising the length of the lamella detected via XRD can be estimated to be between 24 to
5
1
26. Given a 2L spacing, the lamella is most likely composed of glycerides with lauric acid on
2
both position 1 and position 2 (for a glyceride in the chair conformation) or with lauric acid
3
on positions 1 and 3 (for a tuning fork conformation). Given that there are significant amounts
4
of myristic and capric acid, it is also possible that the bilayer may be composed of
5
triglycerides containing these fatty acids at the positions specified previously. In light of this,
6
the TAG groups that compose these lamella are most likely groups A (LaLaLa or CaLaM),
7
C (LaLaCa), D (LaLaM) and H (MMLa).
8
No spacings suggestive of trilayer packing is evident in the XRD spectra. This is not
9
unreasonable as the triglycerides that commonly pack in the 3L arrangement usually contain a
10
fatty acid that is significantly different from the other two fatty acids on the triglyceride.
11
Examining the composition of Oil C, the triglyceride groups (in significant quantities) that
12
would presumably pack into the 3L arrangement is group B (LaLaO). However, this group
13
has an estimated melting point of about 15 °C, which would imply that it is liquid at the
14
temperatures at which the analysis is conducted and thus is not detected.
15
Several short spacing peaks characteristic of the β’ polymorph (3.808 Å and 4.223 Å)
16
are observable in the wide-angle region5. The crystallization of Oil C into a β’ polymorph is
17
interesting as the majority of triglycerides (mentioned previously as groups A, C, D and H)
18
typically crystallize into the β polymorph given that the length of the fatty acids is fairly
19
similar (does not differ by more than 4 carbons) and that the aforementioned TAGs do not
20
contain any unsaturated fatty acids.
21
The microstructure of Oil C as observed through a polarized light microscope is given
22
in Figure 5A. The microstructure is very similar to the microstructure of Oil A and Oil B.
23
From the micrograph, it can be seen that Oil C forms crystals with needle-like morphologies
24
(roundness = 0.61). The crystals appear to be much shorter and thinner than those of Oil A
25
and Oil B. The length of the crystals as given by the maximum Feret diameter is
6
1
approximately 2.8 ± 2.7 μm long. Like Oil A and Oil B, it is not unexpected that the fat
2
crystals in the β’ polymorph are small and needle-like6.
3
4
Oil C – Rheological Properties
5
The viscoelastic properties of Oil C are listed in Table 7. The rheological properties
6
are very similar to those of Oil A. The measured G’ was 6.05 ± 1.10 MPa. This G’ suggests a
7
relatively hard material similar to other hard fats commonly encountered in food manufacture.
8
As a standard of comparison, hardened cocoa butter has a G’ of approximately 20 MPa while
9
milkfat at 5 °C has a G’ between 1 to 10 MPa. The ratio of the loss modulus to the storage
10
modulus is 0.15, suggesting that the mechanical damping by the material is very minimal
11
although slightly higher than that for Oil A and Oil B. This is perhaps due to the higher liquid
12
content of Oil C compared to Oil A and Oil B.
13
Compared to Oil A and Oil B, the mechanical properties of Oil C are interesting in
14
that the hardness (using the G’ as a measure) is only slightly lower despite the relatively low
15
solid fat content of Oil C at the testing temperature (10 °C). Compared to Oil A and Oil B,
16
which both have a solid fat content of roughly 75 % at 10 °C, Oil C (as well as Oil D) only
17
has a solid fat content of roughly 50 %. These results suggest that it is possible to engineer fat
18
materials to have the same hardness despite differences in the solid fat content although a
19
more thorough elucidation of the structural factors that result in this is necessary.
20
7
1
Oil D
2
3
Oil D – FA and TAG Composition
4
The fatty acid composition of Oil D is reported in Table 1. Oil D can be described as a
5
high-oleic (44.8 %) oil containing high amounts of long chain fatty acids such as stearic acid
6
(14.8 %) and palmitic acid (28.1 %). A significant amount of linoleic acid (7.1 %) is also
7
present. Unlike Oil C, the medium-chain fatty acid content of Oil D is relatively low. Oil D
8
has a very similar fatty acid composition to cocoa butter7 although the stearic acid content of
9
Oil D is relatively low while the oleic acid content is relatively high.
10
The triglyceride composition of Oil D is given in Table 3. The TAG composition of
11
Oil D is unusual in that it contains very little trisaturates (comprising only 1.13 % area of the
12
chromatogram) and is very much like Oil B in that it contains predominantly oleic acid-
13
containing di-saturates. Unlike the other algal oils heretofore studied, the predominant TAG
14
groups in Oil D are the mono-saturates, comprising 52.73 % area of the chromatogram. The
15
mono-saturates consist of groups A, D, E, G, J, L, M, N, O, P, Q, R and X. The next largest
16
group of TAGs are the oleic acid-containing di-saturates, comprising 38.48 % area of the
17
chromatogram. This group consists of TAG groups B, C, F, K, Y and U. The linoleic acid-
18
containing di-saturates comprise 6.09 % area of the chromatogram and consist of TAG groups
19
H and I.
20
Oil D – Melting Behavior
21
The melting point of Oil D can be estimated using a methodology similar to that used
22
for Oil A, Oil B and Oil C. Given that the trisaturates comprise only a very small fraction of
23
Oil D, the melting behaviour of these TAGs can be ignored assuming that they will not
24
crystallize due to their low concentrations. Examining the TAG composition of Oil D, it is
25
obvious that the fat is structured by oleic acid-containing di-saturates, particularly groups B,
26
C, F and K. Together, these triglycerides have a melting point (for the β polymorph) of
8
1
approximately 35 °C to 40 °C. As well, it is possible that the linoleic acid-containing di-
2
saturates will contribute to the solids content of Oil D.
3
The TAGs in the mono-saturates group all have very low melting points with the
4
exception of oleic acid mono-saturates (such as OOS) containing a long-chain fatty acid such
5
as palmitic or stearic acid. The liquid component of the fat is most likely composed of these
6
mono-saturates.
7
Figure 1A shows that the melting trace of Oil D exhibits three peak melting points: 5.7
8
°C, 12.4 °C and 29.1 °C, suggesting three melting fractions. The total melting enthalpy is 21.8
9
kJ/kg. This is a comparatively low melting enthalpy when compared to Oil C, which has a
10
melting enthalpy of approximately 80 kJ/kg. The first melting peak at 5.69 °C can be
11
attributed to the melting of some of the di- and tri-unsaturated TAGs, which typically have
12
melting points between 0 °C to 5 °C. As well, the lower-melting components of the linoleic
13
and oleic acid-containing di-saturates (TAG groups H, I and K) may be undergoing a melting
14
transition in this peak. The second melting peak at 12.41 °C may likewise be assigned to the
15
melting of the oleic acid-containing di-saturated TAGs (groups B), which make up part of the
16
bulk of the solids in this fat. The third melting peak at 29.07 °C can be attributed to the
17
melting of the higher melting components of the oleic acid-containing groups (groups C and
18
F) as well as the tri-unsaturates. The melting enthalpy associated with this peak is miniscule,
19
suggesting that these high-melting components are relatively low in concentration.
20
Figure 2A shows that the melting profile of Oil D is gradual and starts at a temperature
21
of roughly 5 °C. The steepest decrease in the SFC occurs between 10 °C and 20 °C. This
22
melting profile is identical to the melting profile of Oil C. The initial solid fat content of Oil
23
D at 5 °C is 52.75 %. Unlike the TAG composition of Oil C, the bulk of the solids in Oil D
24
are composed of oleic acid-containing mono-unsaturate TAGs, which comprise 38.5 % area
25
of the chromatogram. As the solid fat content at beginning of melting is 52.8 %, it can be
9
1
assumed that the solid components at this temperature consist of both oleic acid and linoleic
2
acid-containing di-saturated TAGs as well as the tri-saturates and the higher melting
3
components of the di- and tri-unsaturates group. Taken together, these groups comprise
4
roughly 50 % area of the chromatogram, which would approximately be equal to the solids
5
content of Oil D. The lower-melting components of the mono-saturates constitute the oil
6
phase at 5 °C.
7
The solid fat content of Oil D decreases in a linear fashion as the temperature is
8
increased. The SFC decreases to 44.7 % as the temperature is increased to 10 °C. At this
9
temperature, the components in the first melting peak of the DSC curve (5.7 °C) have melted.
10
At this stage, the remaining solids are the higher-melting components of the oleic acid and
11
linoleic acid-containing TAGs. Increasing the temperature to 15 °C will melt the components
12
in the second peak of the DSC curve (12.4 °C). At this temperature, the remaining solids
13
content (28.6 %), are presumably the high-melting oleic acid-containing di-saturates (groups
14
C and F). Increasing the temperature to 20 °C will melt most of these components. While it is
15
unusual for these components to melt at 20 °C given that the melting point of the pure TAGs
16
is roughly in the region of 35 °C to 40 °C, the presence of a high amount of liquid
17
triglycerides at 20 °C will depress the melting point of these components either through a
18
eutectic or solubilisation effect.
19
Oil D – Crystallization Behavior
20
The DSC crystallization trace for Oil D (Figure 1A) shows one peak crystallization
21
temperature at 2.1 °C. The onset of crystallization for this crystallization peak occurs
22
approximately at a temperature of 10 °C. A high undercooling of approximately 19 °C is
23
required to initiate crystallization of the fat.
24
The crystallization kinetics curve for Oil D is displayed in Figure 3A. Fit parameters
25
to the single or double Avrami equation are tabulated in Table 6. Unlike Oil C, the plotted
10
1
data suggests two crystallizing fractions. The first crystallizing fraction has a maximum solid
2
fat content of 3.50 % as determined from a double Avrami fit. The low solids content suggest
3
that the concentration of TAGs crystallizing in this fraction is also relatively low. As such,
4
this crystallizing fraction is most likely composed of the trisaturates (groups S, T, V and W)
5
as well as the higher-melting components of the oleic acid-containing di-saturates (groups U
6
and Y). The second crystallizing component has a maximum solid fat content of 36.88 %.
7
This second crystallizing component likely consists of the oleic acid-containing di-saturates
8
(groups B, C, F and K) which constitute the bulk of the solids in the fat.
9
The final SFC value as estimated from a single-Avrami fit is approximately 41.6 %.
10
This value is not altogether different from the solid fat content of the fat at 10 °C (44.7 %) as
11
obtained from the melting profile. Parameter estimates for the Avrami exponent for the first
12
crystallizing components suggests that it grows either as a rod with sporadic nucleation or as a
13
disc with instantaneous nucleation. Of the two, it is more likely that growth is as a disc with
14
instantaneous nucleation. Parameter estimates for the Avrami exponent for the second
15
crystallizing component suggests that it grows either as a disc with sporadic nucleation or that
16
it grows as a sphere with instantaneous nucleation. Of the two, it is more likely that the
17
second crystallizing component grows as a sphere with instantaneous nucleation as fat crystal
18
particles typically grow as a sphere.
19
Oil D – Crystal Structure and Microstructure
20
The XRD spectrum of Oil D is given in Figure 4B. A single long spacing peak at
21
58.05 Å can be observed in the small-angle region. Higher-order reflections corresponding to
22
spacings of 40.85 Å and 30.03 Å are also present. Using the equations provided by Donald
23
Small5, each ethylene group or every two carbons can be approximated by a length of 2.27 Å
24
for a β polymorph. An allowance of 4.11 Å is made for the carbons on the glycerol backbone.
25
These factors are much smaller than those for the β’ polymorph to account for the tilting of
11
1
the glyceride chains for the β polymorph. From this, the number of carbons on the fatty acid
2
chains comprising the lamella can be calculated and this estimate stands at around 48 to 50
3
carbons in length. This suggests a 3L spacing within the lamella. The glycerides that comprise
4
these detected lamella are most likely the C50 and C52 oleic-acid containing di-saturates
5
(groups B and C). Assuming that the oleic acid in these glycerides is in position 2, the trilayer
6
packing is not unexpected. In this situation, the oleic acids are interdigitated in the middle of
7
the trilayer while the ends of the trilayer consist of either the palmitic or stearic acid chains. A
8
similar trilayer packing can still be achieved even if the oleic acid is in position 1 or 3 instead
9
of position 25.
10
A short spacing peak characteristic of the β polymorph (4.54 Å) is observable in the
11
wide-angle region suggesting the solid phase is in the β polymorph. This is a very unusual
12
observation given that Oil B (which is structured by TAGs similar to those found in Oil D)
13
crystallizes into the β’ polymorph. These TAGs are very similar to the TAGs found in cocoa
14
butter. It is well known that these TAGs (and those in cocoa butter) may crystallize into the β’
15
polymorph given sufficiently high undercoolings. These TAGs may also crystallize into the β
16
polymorph if the supersaturation is sufficiently low. The fact that these TAGs crystallized into
17
the β polymorph suggest that the supersaturation in this system was relatively low. While the
18
melting point of the pure TAGs will remain unchanged, the presence of a high amount of
19
liquid phase (which is considerably higher in Oil D than for cocoa butter and for Oil B) may
20
serve to promote the crystallization of the TAGs into the β polymorph by decreasing the
21
supersaturation at the crystallization temperature. In this manner, the high amount of liquid
22
phase essentially dilutes the crystallizing TAGs such that a lower supersaturation is achieved
23
at 10 °C when compared to Oil B.
24
The microstructure of Oil D as observed through a polarized light microscope is
25
shown in Figure 5B. The microstructure of Oil D is very much unlike the microstructure of
12
1
Oil A, Oil B and Oil C. Oil D does not exhibit any needle-like crystals but instead exhibits
2
granular crystals (roundness = 0.69) with an average Feret diameter of roughly 2.2 ± 2.4 μm.
3
This unusual morphology, when compared to the other oils thus examined, may be due to the
4
fact that Oil D crystallizes into the β polymorph instead of the β’ polymorph.
5
Oil D – Rheological Properties
6
The viscoelastic properties of Oil D are listed in Table 7. The measured G’ was 3.32 ±
7
1.20 MPa. This G’ suggests a relatively hard material. As a standard of comparison, hardened
8
cocoa butter has a G’ of approximately 20 MPa while milkfat at 5 °C has a G’ between 1 to
9
10 MPa. The ratio of the loss modulus to the storage modulus is 0.20, suggesting that the
10
mechanical damping by the material is very minimal although slightly higher than that for Oil
11
A and Oil B. Like Oil C, this is perhaps due to the higher liquid content of Oil D.
12
As with Oil C, when compared to Oil A and Oil B, the mechanical properties of Oil D
13
are interesting in that the hardness (using the G’ as a measure) is only slightly lower despite
14
the relatively low solid fat content of Oil C at the testing temperature (10 °C). Compared to
15
Oil A and Oil B, which both have a solid fat content of roughly 75 % at 10 °C, Oil C (as well
16
as Oil D) only has a solid fat content of approximately 50 %.
17
13
1
Oil E
2
Oil E – FA and TAG Composition
3
As can be seen from the fatty acid composition (Table 1), Oil E can be described as a
4
myristic-palmitic oil with a composition very similar to that of Oil A. The majority of the
5
fatty acids in Oil E are myristic (15.3 %) and palmitic (35.9 %) acid. Unlike Oil A, however,
6
Oil E contains very little capric acid (2.35 %) and significantly more oleic (29.50 %) and
7
linoleic acid (10.20 %). The fatty acid composition of Oil E does not appear to be found in
8
other known food oils. Palm kernel oil8 has a similar myristic acid content, however, it
9
contains relatively little palmitic acid, instead containing a high amount of lauric acid.
10
The triglyceride composition of Oil E is given in Table 4. The TAG analysis shows
11
that the vast majority (48.66 %) of the triglycerides are di-saturated TAGs containing a single
12
oleic acid. This TAG group consists of groups A, B, E, I, J, O, CC, GG and II. Of these, the
13
TAG groups A, B and J (total of 38.07 % area) are most likely responsible for structuring the
14
fat. The next largest group of TAGs are the TAGs containing two or more unsaturated fatty
15
acids, which comprise 27.07 % area of the chromatogram. This TAG group consists of groups
16
C, G, H, L, P, Q, T, X, Y, Z, AA, DD, EE and HH. The disaturated TAGs containing a
17
single linoleic acid are also present in appreciable quantities (14.48 %). These TAGs consist
18
of groups D, F, N, S, V and BB. The trisaturates constitute only a very small amount (7.86 %)
19
of the TAGs present in Oil A and as such, their contribution to the solids content is likely
20
minimal.
21
22
Oil E – Melting Behavior
23
As with previous examples of the algal oils, the melting point of the fat can be
24
estimated using literature values of the pure triglycerides present in Oil E. The melting points
25
of the disaturated TAGs containing a single oleic acid, for the β’ polymorph, are
14
1
approximately between 25 °C to 35 °C. A like examination of the di-saturated TAGs
2
containing linoleic acid shows that the melting points of these TAGs are in the region
3
between 25 °C to 30 °C. While data is scarce for the pure component melting points of TAGs
4
containing more than one unsaturated fatty acid, it can be assumed that these TAGs are
5
predominantly in the liquid state at ambient temperatures, with the exception of TAG groups
6
C (OOP) and H (OOM). The high contents of these triglycerides in addition to their relatively
7
high melting points suggest that these TAGs may conceivably play a role in structuring the
8
fat. The trisaturated TAGs all have very high melting points in the region between 40 °C to 60
9
°C. Given that these TAGs are not present in appreciably high quantities, their contribution to
10
structuring is perhaps very minor.
11
Figure 1B shows that the melting trace of Oil E exhibits three peak melting
12
temperatures: 10.6 °C, 27.4 °C and 32.2 °C. The following DSC trace is very similar to the
13
DSC trace of Oil A. The total melting enthalpy is 63.305 kJ/kg. The first melting peak at 10.6
14
°C can most likely be attributed to the melting of the TAGs containing two or more
15
unsaturated fatty acids, particularly groups C and H. As well, it is possible that the disaturated
16
TAGs containing a single linoleic or oleic acid are also included in this peak, given the size of
17
the peak. The latter peak at 27.4 °C can be attributed to the melting of the remainder of the
18
disaturated TAGs containing linoleic acid. The last peak at 32.2 °C can be attributed to the
19
melting of the high-melting fractions of the disaturated TAGs containing oleic acid as well as
20
any trisaturated TAGs in the solid state.
21
The melting profile of Oil E is given in Figure 2B. The melting profile of Oil A shows
22
that melting is gradual and starts at a temperature of roughly 5 °C. This melting profile is
23
identical to the melting profile of Oil F. The initial solid fat content at 5 °C is 63.07 %. This
24
value is approximately equal to the sum of the trisaturated, oleic acid disaturated and the
25
higher-melting linoleic acid disaturated TAGs (groups D and F). As such, these groups can be
15
1
assumed to form the solid phase of the fat. The liquid component of the fat can be assumed to
2
consist of the TAGs containing two or more unsaturated fatty acids as well as the di-saturated
3
TAGs containing linoleic acid.
4
As the temperature is increased, the solid fat content decreases in what appears to be a
5
linear fashion. The steep decrease in SFC after heating to 20 °C may be due to the dissolution
6
of the components with a peak melting temperature of 10.56 °C, which constitutes the largest
7
peak in the DSC trace. Of the major TAG groups in Oil E, the most likely TAGs that melt in
8
this region include TAG groups B, C and E. At this stage, the remaining solid components
9
consist of TAGs belonging to group A. Continued heating to 25 °C presumably results in the
10
melting of these oleic acid disaturated TAGs. This corresponds to the peak a peak melting
11
temperature of 27.4 °C in the DSC trace. Heating to 40 °C melts the components within the
12
32.2 °C peak in the DSC trace, which most likely consists of the high-melting trisaturated
13
TAG groups.
14
15
Oil E – Crystallization Behavior
16
The DSC crystallization trace (Figure 1B) for Oil E shows two peak crystallization
17
temperatures at -3.8 °C and 9.8 °C. The onset of crystallization for the first peak occurs
18
approximately at a temperature of 12 °C. Using the highest peak melting temperature at 32.2
19
°C as a reference, a high undercooling of approximately 20 °C is required to initiate
20
crystallization of the highest melting components as with other fats previously observed. On
21
the basis of the previous discussion of melting points and assuming a required undercooling
22
of ~15 °C, the first crystallization peak can be attributed to the crystallization of tri-saturates
23
as well as the high-melting components of the oleic acid-containing di-saturated TAGs.
24
Likewise, the second crystallization peak (onset of crystallization at approximately 0 °C) can
25
be attributed to the crystallization of the lower melting components such as the TAGs
16
1
containing two or more unsaturates and the linoleic acid-containing di-saturated TAGs as well
2
as some of the lower-melting components of the oleic acid-containing di-saturated TAGs. The
3
TAGs crystallizing in this peak are typically liquid at ambient temperatures and constitute the
4
liquid phase of the fat.
5
The crystallization kinetics curve for Oil E is displayed in Figure 3B. Fit parameters to
6
the single or double Avrami equation are tabulated in Table 6. The final SFC value was
7
estimated from a single-Avrami fit to be approximately 57.0 %. This value is not altogether
8
different from the solid fat content at 10 °C (54.0 %) as obtained from the melting profile.
9
Parameter estimates for the Avrami exponent for this crystallization curve suggest that the
10
initial crystallizing components grow in a disc-like fashion with sporadic nucleation
11
nucleation or as a sphere with instantaneous nucleation4. Of the two, it is more likely that
12
growth occurs as a sphere. The estimates for the second component suggest that growth
13
occurs in a like manner, i.e. as a disc with sporadic nucleation or as a sphere with
14
instantaneous nucleation. Of the two, it is more likely that growth occurs as a sphere.
15
16
Oil E - Crystal Structure and Microstructure
17
The XRD spectrum of Oil E is given in Figure 4C. A single long spacing peak at
18
39.78 Å can be observed in the small-angle region. Higher-order reflections corresponding to
19
spacings of 20.44 Å (second order) and 13.71 Å (third order) can also be identified.
20
The long spacings suggest a 2L packing9. For the β’ polymorph, an estimate of 2.32 Å
21
for every two carbons/ethylene group (taking into account the tilt of the glyceride chain in the
22
lamella) and an allowance of 4.43 Å for the carbons on the glycerol backbone can be used to
23
estimate the number of carbons on the fatty acid chains comprising the lamella5. Using these
24
calculations, it can be seen that the long spacing corresponds to a lamella that is roughly 28 to
25
30 carbons in length, excluding the glycerol. Given a 2L spacing and the fatty acid
17
1
composition of Oil E, this lamella most likely consists of a bilayer of either myristic acid or
2
palmitic acid or a mixed bilayer consisting of both myristic acid and palmitic acid much like
3
Oil A.
4
It is interesting to note that despite the high content of disaturated TAGs containing
5
oleic acid, a 3L structure was not observed. This is highly unusual as the vast majority of
6
TAGs in Oil E contain at least one oleic acid and that the trisaturated TAGs consisting only
7
of myristic and/or palmitic acid are not present in sufficient quantities to be able to attribute
8
this peak to these trisaturated TAGs. Given that the X-ray spectra for Oil E also contains
9
peaks characteristic of the β polymorph, the thickness of the bilayer can be recalculated using
10
different factors to account for the tilting of the chains. Every two carbons can be
11
approximated by a length of 2.27 Å for a β polymorph with an allowance of 4.11 Å made for
12
the carbons on the glycerol backbone. Using these parameters, the new estimate for the
13
thickness of the bilayer is 30 to 32 carbons. This bilayer thickness is possible from a bilayer
14
formed by a myristic acid and oleic acid. As well, it must be noted that because of the kink of
15
the oleic acid chain, the actual number of carbons comprising the layer may be
16
underestimated, which would suggest that a bilayer formed by oleic acid and palmitic acid is
17
also possible.
18
These observations notwithstanding, the observation of a 39.78 Å peak has been
19
reported10 for POP, the predominant TAG group in Oil E. POP, by itself, exhibits a long
20
spacing peak of approximately 31 Å. However, when POP is mixed with PPO at equimolar
21
amounts, a molecular compound in the β polymorph is formed which exhibits a long spacing
22
of approximately 41 Å. As the observed long spacing peak very closely approximates the
23
reported long spacing, it suggests that the predominant TAG group (A) in Oil E is actually a
24
mixture of POP and PPO, which forms a molecular compound.
18
1
Several short spacing peaks characteristic of both the β’ polymorph (3.904 Å and 4.21
2
Å) and the β polymorph (4.59 Å) are observable in the wide-angle region, which suggests that
3
some TAGs crystallize into the β’ polymorph while others crystallize into the β polymorph.
4
The presence of a β polymorph is unusual in that by examining the majority of TAGs
5
in the fat, one can conclude that the TAGs will crystallize into the β’ polymorph given the
6
fatty acid diversity in the TAGs present. Indeed, some TAGs have crystallized into the β’
7
polymorph. The β polymorph is most likely due to the formation of the molecular compound
8
between POP and PPO mentioned above. As such, the remainder of the TAGs, particularly
9
those that contain at least one oleic or linoleic acid, crystallize into the β’ form.
10
The microstructure of Oil E as examined through a polarized light microscope is
11
shown in Figure 5C. The micrograph shows several crystals with a needle-like morphology
12
(roundness = 0.63). The average Feret diameter of the crystals is 2.9 ± 3.2 μm. Like Oil A,
13
Oil B and Oil C, Oil E crystallizes into the β’ polymorph, in which crystals are small and
14
needle-like6.
15
Oil E- Rheological Properties
16
The measured rheological properties for Oil E are presented in Table 7. The measured
17
G’ was 5.37 ± 3.01MPa. Judging by the scale previously established, this fat is relatively
18
hard. The ratio of the loss modulus to the storage modulus is 0.12, suggesting that the
19
mechanical damping by the material is very limited and is similar in magnitude to that of Oil
20
A and Oil B.
21
19
1
Oil F
2
Oil F – FA and TAG Composition
3
The fatty acid composition of Oil F is reported in Table 1. The fatty acid composition
4
of Oil F is very similar to that of Oil D. Like Oil D, Oil F can be described as a high-oleic
5
(44.00 %) oil containing high amounts of long chain fatty acids such as stearic acid (21.39 %)
6
and palmitic acid (23.24 %). A significant amount of linoleic acid (7.17 %) is also present.
7
Much like Oil D, the medium-chain fatty acid content of Oil F is relatively low. Oil F has a
8
very similar fatty acid composition to cocoa butter7. It is much more like cocoa butter than
9
Oil D is. However, like Oil D, the oleic acid content of Oil F is approximately 25 % more
10
than what is normally found in cocoa butter. The stearic acid content of Oil F is marginally
11
higher than that in Oil D but compared to the levels normally found in cocoa butter, the
12
stearic acid content is still relatively low.
13
The triglyceride composition of Oil F is given in Table 5. The TAG composition of
14
Oil F is almost identical to the TAG composition of Oil D. Like Oil D, the TAG composition
15
of Oil F contains very little trisaturates (comprising only 2.10 % area of the chromatogram)
16
but is composed predominantly of oleic acid-containing di-saturates. Like Oil D, the
17
predominant TAG groups in Oil F are the di- and tri-unsaturates, comprising 49.17 % area of
18
the chromatogram. The di- and tri-unsaturates consist of groups B, C, F, G, I, U, L, M, N, R,
19
T and AA. The next largest group of TAGs are the oleic acid-containing di-saturates, which
20
presumably are responsible for structuring the fat. This group of TAGs comprise 39.28 % area
21
of the chromatogram and consists of TAG groups A, D, E, K, O, P, X and Z. The linoleic
22
acid-containing di-saturates comprise 8.94 % area of the chromatogram and consist of TAG
23
groups H, J, K and Y.
24
Oil F – Melting Behavior
20
1
The melting point of Oil F can be estimated by examining the TAG composition. As
2
with Oil D, the trisaturates comprise only a very small fraction of Oil F. As such, the melting
3
behaviour of these TAGs can be ignored assuming that their contribution to the solid content
4
is negligible. Examining the TAG composition of Oil F, it is obvious that the fat is structured
5
by oleic acid-containing di-saturates, particularly groups A, D and E. As a group, these
6
triglycerides have a melting point (for the β polymorph) of approximately 35 °C to 40 °C. The
7
sum of the % area of these triglycerides (37.23 %) falls short of the expected solid fat content
8
for Oil F. As such, it is highly likely that other triglycerides in the fat are present in the solid
9
phase. It is highly likely that the TAGs containing two oleic acids and a saturated fatty acid
10
such as palmitic or stearic acid (groups B and C) are also present in the solid phase as these
11
have relatively high melting points considering they are TAGs with an appreciable amount of
12
unsaturates.
13
Figure 1B shows that the melting trace of Oil F exhibits three peak melting points:
14
27.34 °C, 23.37 °C and 12.00 °C, suggesting three melting fractions. The total melting
15
enthalpy is 63.52 kJ/kg. The first melting peak at 12.0 °C can be attributed to the melting of
16
some of the di- and tri-unsaturated TAGs (with the exception of groups B and C), which
17
typically have melting points between 0 °C to 5 °C. As well, the lower-melting components of
18
the linoleic and oleic acid-containing di-saturates are presumably melting in this peak as well.
19
The second melting peak at 23.4 °C may be attributed to the melting of the TAGs that contain
20
palmitic acid, such as those belonging to groups D and B. The latter peak at 27.3 °C may be
21
assigned to the melting of the TAGs that contain stearic acid such as those belonging to
22
groups A, C and E.
23
Figure 2B shows that the melting profile of Oil F is gradual and starts at a temperature
24
of roughly 5 °C. As with previous fats, the steepest decrease in the SFC occurs between 10 °C
25
and 20 °C. This melting profile is identical to the melting profile of Oil E. The initial solid fat
21
1
content of Oil F at 5 °C is 58.0 %. The solid components that melt between 5 °C and 20 °C
2
are most likely the TAGs with two oleic acids and a single saturated fatty acid such as those
3
belonging to groups B and C. As well, it is highly likely that some of the higher melting oleic
4
acid disaturated TAGs such as those belonging to groups D and A are melting at this stage.
5
The melting components within this range are those that are present in the melting peaks at
6
12.0 °C and 23.4 °C. As the temperature is increased past 20 °C all the way to 40 °C, the
7
remainder of the TAGs in group A as well as the TAGs in group E melt. This last stage of
8
melting corresponds to the melting peak and 27.3 °C.
9
10
.
Oil F – Crystallization Behavior
11
The DSC crystallization trace for Oil F (Figure 1B) shows two peak crystallization
12
temperatures at 12.1 °C and 3.6 °C. The onset of crystallization for the first crystallization
13
peak occurs approximately at a temperature of 16 °C. A relatively modest undercooling of
14
approximately 16 °C is required to initiate crystallization of the fat (32 °C – 16°C). This first
15
peak can most likely be attributed to the crystallization of TAGs such as SOS and POS
16
(groups E and A, respectively). The onset of the second and much larger peak occurs at a
17
temperature of approximately 8 °C. This peak can perhaps be attributed to the crystallization
18
of the lower melting TAGs such as those belonging to groups B, D and C as well as those
19
TAGs that are normally liquid at ambient temperature.
20
The crystallization kinetics curve for Oil F is displayed in Figure 3B. Fit parameters to
21
the double Avrami equation are tabulated in Table 6. The crystallization kinetics curve for Oil
22
F suggests two crystallizing fractions. Both crystallizing fractions have approximately the
23
same solids content at roughly 25 % each. The first crystallizing component is most likely
24
TAGs belonging to groups A, D and E. Much like in cocoa butter, these TAGs crystallize
25
initially and act as a seed for the crystallization of the remaining TAGs in the second
22
1
crystallizing component, which most likely consist of the lower-melting TAGs that belong to
2
groups B and C.
3
The final SFC value as estimated from a single-Avrami fit is approximately 48.68 %.
4
This value is not altogether different from the solid fat content of the fat at 10 °C (52.2 %) as
5
obtained from the melting profile. Parameter estimates for the Avrami exponent for the first
6
crystallizing components suggests that it grows as a rod with instantaneous nucleation
7
Parameter estimates for the Avrami exponent for the second crystallizing component suggests
8
that it grows as a sphere with sporadic nucleation. The presence of sporadic nucleation
9
suggests that the second crystallizing component has a sufficiently low melting point such
10
that the undercooling is not sufficient to promote a high nucleation rate.
11
Oil F – Crystal Structure and Microstructure
12
The XRD spectrum of Oil F is given in Figure 4D and contains many similarities to
13
the XRD spectrum of Oil D. No single predominant long spacing can be observed in the X-
14
ray spectra. A long spacing peak at 60.94 Å can be observed with higher-order reflections
15
corresponding to spacings of 42.03 Å and 31.51 Å also present. Using the equations provided
16
by Donald Small5, each ethylene group or every two carbons can be approximated by a length
17
of 2.27 Å for a β polymorph. An allowance of 4.11 Å is given for the carbons on the glycerol
18
backbone. From this, the number of carbons on the fatty acid chains comprising the lamella
19
can be calculated and this estimate stands at around 48 to 50 carbons in length. This suggests
20
a 3L spacing within the lamella. The glycerides that comprise these lamella are most likely
21
the C50 and C52 oleic-acid containing di-saturates (groups A, D and E) as well as the TAGs
22
containing two or more oleic acids with a single saturated fatty acid (groups B and C). By
23
assuming that the oleic acid in these glycerides is in position 2, the trilayer packing is not
24
unexpected. In this situation, the oleic acids are interdigitated in the middle of the trilayer
25
while the ends of the trilayer consist of either the palmitic or stearic acid chains. A similar
23
1
trilayer packing can still be achieved even if the oleic acid is in position 1 or 3 instead of
2
position 25.
3
A short spacing peak characteristic of the β polymorph (4.54 Å) is observable in the
4
wide-angle region suggesting the solid phase is in the β polymorph as was found in Oil D.
5
Like Oil D, it is interesting to note that Oil F crystallizes into the β polymorph while a similar
6
fat such as Oil B crystallizes into the β’ polymorph. The TAGs in Oil F as well as Oil D may
7
crystallize into either the β’ or β polymorph under the right undercoolings. The fact that these
8
TAGs crystallized into the β polymorph suggest that the supersaturation in this system was
9
relatively low. As well, given that Oil F has a relatively high amount of liquid phase, the β
10
polymorph may be promoted by decrease in the effective supersaturation at the start of
11
crystallization. In this manner, the high amount of liquid phase essentially dilutes the
12
crystallizing TAGs such that a lower supersaturation is achieved at 10 °C when compared to
13
Oil B.
14
The microstructure of Oil D as observed through a polarized light microscope is
15
shown in Figure 5D. The microstructure of Oil D is unlike the microstructure of Oil A, Oil B,
16
Oil C and Oil E but is relatively similar to the microstructure of Oil D. Like Oil D, Oil F
17
exhibits granular crystals (roundness = 0.86) with an average Feret diameter of roughly 1.7 ±
18
2.5 μm. This unusual morphology, when compared to the other oils thus examined, may be
19
due to the fact that Oil F crystallizes into the β polymorph instead of the β’ polymorph.
20
Oil F – Rheological Properties
21
The viscoelastic properties of Oil F are given in Table 7. The measured G’ was 4.93 ±
22
1.47 MPa. As with the other algal fats, this G’ suggests a relatively hard material. The ratio of
23
the loss modulus to the storage modulus is 0.20, suggesting that the mechanical damping by
24
the material is very minimal although slightly higher than that for Oil A and Oil B. Like Oil
25
C, this is perhaps due to the higher liquid content of Oil D.
24
1
Conclusion: A Comparison of Oil C/Oil D
2
A similar explanation for the melting profile similarities between Oil C and Oil D as
3
that for Oil A and Oil B can also be made. Oil C consists mainly of medium chain fatty acids
4
(and oleic acid) and is structured by trisaturate TAGs containing these fatty acids. Oil D, on
5
the other hand, consists mainly of oleic acid as well as long chain saturated fatty acids. Oil D
6
is structured by TAGs that contain a single oleic acid and two long chain saturated fatty acids.
7
As with Oil A and Oil B, these TAGs have very similar melting ranges and SFC. Both Oil C
8
and Oil D contain similar proportions of these structurant TAGs and as such, it is not
9
surprising that these fats have very similar melting profiles and SFC.
10
Oil C and Oil D have similar mechanical properties despite the difference in the
11
distribution of the crystalline mass as given by the fractal dimension as well as the difference
12
in the crystal morphologies between Oil C (which crystallizes into needle-like crystals in the
13
β’ polymorph) and Oil D (which crystallizes into granular crystals in the β polymorph). As
14
well, the Avrami exponents of most of the crystallizing components in Oil C and Oil D are
15
different, which suggests the morphology of the microstructural elements is different. Most of
16
the TAGs in Oil C grow as a disk (presumably needle-like crystals) while the TAGs in Oil D
17
grow as a sphere. However, Oil C and Oil D have similar solid fat contents. As well, Oil C
18
and Oil D have very similar crystal sizes, which would suggest that similarities in this
19
microstructural feature is sufficient to result in similar mechanical properties despite the
20
differences in the fractal dimension and crystal morphology. The similarities in the
21
mechanical properties between Oil C and Oil D can therefore be ascribed to the similarity in
22
the size of the microstructural elements of the fats despite the differences in the polymorphic
23
form and morphology of the crystals.
24
25
1
Conclusion: A Comparison of Oil E/Oil F
2
Like Oil A/Oil B and Oil C/Oil D, Oil E and Oil F all have very similar functional
3
properties such as melting profiles and rheological properties despite the differences in their
4
chemical compositions. The saturated fatty acids in Oil E consists predominantly of myristic
5
and palmitic acids while the fatty acids in Oil F consists primarily of palmitic and stearic
6
acid. On this basis, it would have been reasonable to conclude that Oil F will exhibit
7
behaviour more characteristic of a high-saturates fat, i.e. higher melting point and higher solid
8
fat content. However, Oil F contains relatively more unsaturated fatty acids than Oil E. Oil F
9
consists of approximately 50 % unsaturates while Oil E consists of only 40 % unsaturates. As
10
such, Oil E contains more saturates even though these saturates are shorter than those found
11
in Oil F.
12
The TAG composition of Oil E and Oil F are relatively similar. Both contain high
13
amounts of oleic acid di-saturated TAGs and relatively little trisaturates. The trisaturate
14
content of Oil E is marginally higher than that of Oil F. With regards to the nature of the
15
TAGs in each fat, Oil F has relatively higher melting TAGs such as SOS (group E) while Oil
16
E contains more of the lower melting TAGs such as MOP (group B) and MOM (group E).
17
Despite this slight difference, the reason why Oil E and Oil F have similar melting profiles
18
can perhaps be explained by dilution of the solid phase. Despite having high-melting fatty
19
acids and TAGs, Oil F contains relatively less of these high-melting TAGs than does Oil E,
20
which, while possessing relatively low-melting TAGs, contain more of these TAGs. In
21
essence, the presence of higher-melting TAGs in Oil F is balanced by the presence of more
22
lower-melting TAGs in Oil E. This can perhaps explain the similarity in the melting profiles.
23
Were the saturated fatty acid content of Oil F to match that of Oil E, it is possible that the
24
melting profiles would be different.
26
1
The similarity in the mechanical properties of Oil E and Oil F is not obvious from
2
examining the microstructural features of both fats. Oil E and Oil F contain the same solids
3
content although this is where the similarities end. Oil E contains relatively larger and more
4
needle-like crystals than Oil F. As well, the fractal dimensions of both fats are different. As
5
with Oil C and Oil D, the Avrami exponents are also very different, which reflects the fact
6
that the microstructure is different. Despite the differences, both Oil E and Oil F have very
7
similar hardness as given by the G’.
8
The observed similarities can be explained by a balance of the microstructural features
9
previously mentioned. As a general rule, the box counting fractal dimension, roundness and
10
particle size are all inversely proportional to the hardness of a fat. Examining the data, Oil E
11
will be much harder than Oil F if the magnitude of the box counting fractal dimension and the
12
particle morphology are both considered. However, if the particle size is considered, Oil F
13
will be much harder than Oil E due to the smaller particle size. As such, the similarity in
14
hardness between the two fats is due to the competing effects of all three microstructural
15
quantities. By virtue of the box-counting fractal dimension and the particle morphology, Oil
16
E will be much harder while considering the particle size, Oil F will be much harder. These
17
competing trends result in similar hardnesses for the fats.
18
27
1
Figures
2
3
4
5
6
7
8
9
10
11
12
Figure 1. Melting (negative heat flow) and crystallization (positive heat flow) DSC traces for (A) Oil C (—) and
Oil D (---) and (B) Oil E (—) and Oil F (---). Peak temperatures corresponding to melting and crystallization
transitions are listed.
28
1
2
3
4
5
6
7
8
9
10
11
12
Figure 2. The melting profiles of algal fats crystallized at 10 °C: (A) Oil C (●) and Oil D (■), (B) Oil E(●) and
Oil F (■).
29
1
2
3
4
5
6
7
8
9
10
Figure 3. Crystallization kinetic curves showing the evolution of the solid fat content under isothermal
crystallization at 10 °C for (A) Oil C (●) and Oil D (■) and (B) Oil E (●) and Oil F (■). The Avrami parameter
estimates are listed in Table 6.
30
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
Figure 4. X-ray spectra of four different algal fats: (A) Oil C, (B) Oil D, (C) Oil E and (D) Oil F. Spacings
corresponding to a diffraction peak are described.
31
1
2
3
4
5
6
7
8
9
10
Figure 5. The microstructure of (A) Oil C, (B) Oil D, (C) Oil E and (D) Oil F as examined through a polarized
light microscope. Scale bar = 50 μm.
32
1
Tables
2
3
Table 1. Fatty Acid Composition (in % wt/wt) of six algal oils (Oil C, Oil D, Oil E and Oil
F) as determined using GLC.
C8:0 (Cy)
C10:0 (C)
C12:0 (La)
C14:0 (M)
C16:0 (P)
C18:0 (S)
C18:1 (O)
C18:2 (L)
C18:3 (Ln)
Oil C
0.15
12.6
37.4
9.84
8.11
1.67
22.5
5.78
0.36
Oil D
0.00
0.08
0.06
1.5
28.1
14.78
44.81
7.1
0.35
4
5
33
Oil E
0.00
2.35
0.93
15.3
35.9
3.46
29.5
10.2
0.2
Oil F
0.00
0.01
0.03
0.7
23.24
21.39
44.0
7.17
0.14
1
Table 2. The Triglyceride Composition of Oil C.
Triglyceride
CC: MMP
O: LaMP + LaLaS
H: MMLa + CaMP + LaLaP
D: LaLaM + LaPCa
A: LaLaLa + CaLaM
C: LaLaCa
J: CaCaLa
X: CaCaCa
Z: POS
N: POP + (MOS)
R: LaSO + MOP
L: MOM + LaOP
G: LaOM + CaOP
B: LaLaO
E: CaOLa
T: CaOCa
U: LaLP + MLM
V: LaLM
K: LaLaL (+ CaLM)
M: CaLLa + LaLnLa
I: OOO
P: OOL
W: OOS
Y: LLO
F: OOP
Q: POL
AA: OOM
S: OOLa
BB: LaOL
DD: CaOO
n
44
42
40
38
36
34
32
30
52
50
48
46
44
42
40
38
46
44
42
40
54
54
54
54
52
52
50
48
48
46
Group
T
T
T
T
T
T
T
T
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-L
DS-L
DS-L
DS-L
MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
2
3
4
34
% Area
0.47
1.80
4.58
8.11
13.15
11.54
3.73
0.78
0.57
1.95
1.08
2.83
5.20
11.91
6.53
0.93
0.90
0.88
3.00
2.45
4.06
1.51
0.80
0.65
5.22
1.29
0.54
0.97
0.51
0.45
1
2
Table 3. The Triglyceride Composition of Oil D.
Triglyceride
V:SSP
S:PPS + SSM
T:MPS
W:PPM
Y:SOLg
U:LgOP
F:SOS (+ POA)
C: POS
B: POP
K:MOP
I:PLS
H:PLP
X:OOLg
O:OOA
D: OOS
G:OOO
J:SOL
L:OOL
N:SOL
Q:LLS
R:LLO
A: OOP
E:POL
P:LLP
M:OOM (+ POPo)
n
52
50
48
46
60
58
54
52
50
48
52
50
60
56
54
54
54
54
54
54
54
52
52
52
50
Group
T
T
T
T
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-L
DS-L
MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
3
4
35
% Area
0.18
0.42
0.35
0.18
0.06
0.21
4.87
14.71
16.58
2.05
2.88
3.21
0.08
0.75
10.70
4.68
2.87
1.89
0.94
0.67
0.53
21.15
6.09
0.74
1.64
1
2
Table 4. The Triglyceride Composition of Oil E.
TAG
FF: PPS + SSM + (MPA)
R: PPP +MPS
K: PPM + (MMS)
M:MMP + (LaMS)
U: MMM + LaMP
W: CaMP
II: SOLg + POHx
GG: SOB + LgOP
CC: SOS + POA
J: POS ( + MOA)
A: POP + (MOS)
B: MOP + (LaSO)
E: MOM + LaOP
I: LaOM + CaOP
O: CaOM
N: MLM + LaLP
S: PLS
D:PLP + (MLS)
F: MLP
V: CaLP
BB: CaLM
X: OOL
Q: OOO
Y: OOS
AA: LOL
DD: SOL
C: OOP
G: POL
P: LLP
H: OOM (+ POPo)
L: MOL + PoOL + PoPPo
T: LLM
Z: CaOO
EE: CaOL
HH: CaLL
n
50
48
46
44
42
40
60
58
54
52
50
48
46
44
42
46
52
50
48
44
42
56
54
54
54
54
52
52
52
50
50
50
46
46
46
3
4
36
Group
T
T
T
T
T
T
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-O
DS-L
DS-L
DS-L
DS-L
DS-L
DS-L
M
M
M
M
M
M
M
M
M
M
M
M
M
M
% Area
0.17
1.08
2.70
2.07
0.94
0.90
0.05
0.17
0.39
3.22
19.47
15.38
5.23
3.44
1.33
1.59
1.06
5.57
4.80
0.91
0.55
0.81
1.20
0.76
0.61
0.35
9.14
4.42
1.26
4.10
2.49
0.96
0.61
0.33
0.13
1
Table 5. The Triglyceride Composition of Oil F.
Triglyceride
BB: SSA
W: SSS
S:SSP
Q:PPS + SSM
V:MPS
Z:SOLg
X:LgOP
P: SOA + POB
E:SOS (+ POA)
A: POS
D: POP
O:MOP
K: SLS + (PLA)
H:PLS
J:PLP
Y: PPL
AA:OOLg
N:OOA
C: OOS
F:OOO
I:SOL
L:OOL
R:LLS
T:LLO
B: OOP
G:POL
U:LLP
M:OOM (+ POPo)
n
56
54
52
50
48
60
58
56
54
52
50
48
54
52
50
50
60
56
54
54
54
54
54
54
52
52
52
50
Group
T
T
T
T
T
MO
MO
MO
MO
MO
MO
MO
ML
ML
ML
ML
D
D
D
D
D
D
D
D
D
D
D
D
2
3
4
5
6
37
% Area
0.06
0.30
0.64
0.73
0.37
0.11
0.27
0.79
8.88
17.27
11.08
0.89
2.15
4.24
2.37
0.19
0.10
0.95
12.95
5.57
3.55
1.96
0.69
0.59
16.59
4.65
0.47
1.11
1
2
3
Table 6. Parameter estimates obtained by fitting the Avrami equation to the crystallization
kinetics data for Oil C, Oil D, Oil E and Oil F.
k1(s-n)
Ymax,1(%)
n1
Ymax,2(%)
k2(s-n)
n2
37.4 ± 1.85
34.81 ± 0.84
25.5 ± 4.76
(6.71 ± 23.99) x 10-9
(7.48 ± 14.93) x 10-9
(1.71 ± 22.25) x 10-13
2.53 ± 0.48
2.43 ± 0.26
4.00 ± 1.92
-5
Oil C
Oil D
Oil E
Oil F
4
5
6
7
8
9
38.8 ± 0.20
3.50 ± 1.52
9.92 ± 0.50
26.9 ± 3.00
7.54 x 10 ± 9.99 x
10-12
(4.64 ± 62.37) x 10-5
(1.48 ± 5.30) x 10-5
(6.48 ± 6.05) x 10-3
1.60 ± 0.01
1.97 ± 278
2.36 ± 0.78
0.68 ± 0.17
Table 7. The elastic modulus (G’), loss modulus (G”), phase angle (δ) and tan δ of Oil C, Oil
D, Oil E and Oil F crystallized at 10 °C obtained via a stress sweep using dynamic rheology.
Oil C
Oil D
Oil E
Oil F
G’ (106Pa)
6.05±1.10
3.32±1.20
5.37±3.01
4.93±1.47
G” (105Pa)
9.05±1.01
6.35±1.42
5.87±2.21
7.66±2.94
δ (°)
8.57±0.65
11.20±1.51
6.89±2.14
8.65±1.07
tan δ
0.15
0.20
0.12
0.15
10
11
12
13
Table 8. Box-counting fractal dimension, Feret (caliper) diameter and roundness of the
microstructure in polarized light micrographs of Oil C, Oil D, Oil E and Oil F.
Oil C
Oil D
Oil E
Oil F
Dbox
1.41 ± 0.06
1.62 ± 0.07
1.34 ± 0.05
1.64 ± 0.06
Feret Diameter (μm)
2.8 ± 2.7
2.2 ± 2.4
2.9 ± 3.2
1.7 ± 2.5
14
38
Roundness
0.61 ± 0.22
0.69 ± 0.23
0.63 ± 0.23
0.86 ± 0.25
Supplementary Material: Melting point assignments
1
TAG Composition of Oil A.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
TAG
Y: PPS/PSP + (SSM/SMS)
Q: PPP + MPS/PMS/PSM
G:PPM/PMP + (MMS/MSM)
E:MMP/MPM + (LaMS)
D:LaMP + LaLaS/LaSLa
A:MMLa/MLaM + CaMP + LaLaP/LaPLa
H:LaLaM/LaMLa + LaPCa
J:CaLaM/CaMLa/LaCaM + PCaCa/CaPCa
N: CaCaM/CaMCa
Z: CaCaLa/CaLaCa
DD: CaCaCa
CC: SOS/SSO + (POA)
O: POS/PSO/SPO
C:POP/PPO + (MOS)
B:MOP/PMO/MPO
I:MOM/MMO + LaOP/LaPO/PLaO
F:CaOP
M: CaOM
X: CyOP
U: CaOCa/CaCaO
V: PLS/SPL/PSL
K:PLP/PPL + (MLS)
L: MLP/MPL/PML + (LaLS)
R: MLM/LMM + LaLP
P: CaLP/CaPL/PCaL
S: CaLM
T: OOP/OPO
BB: POL/PLO/LPO
W: OOM/OMO + POPo (?)
AA: CaOO/OCaO
q1
n
50
48
46
44
42
40
38
36
34
32
30
54
52
50
48
46
44
42
42
38
52
50
48
46
44
42
52
52
50
46
Group
T
T
T
T
T
T
T
T
T
T
T
MO
MO
MO
MO
MO
MO
MO
MO
MO
ML
ML
ML
ML
ML
ML
D
D
D
D
% Area
0.44
2.04
5.52
8.01
9.03
9.92
5.39
3.55
2.45
0.32
0.24
0.25
2.27
9.11
9.47
4.70
5.77
3.15
0.48
0.84
0.82
3.50
3.41
1.80
2.23
1.10
0.85
0.29
0.55
0.30
Tm (β’, °C)
58.7/67.7 + (58.3/58.8)
55.7 + > 52.0q1/56.1/55.2-58.3q2
52.0/48.5-56.1g1 + (49.3/55.2)
48.5/59.5 + (45.5)
~42.0-48.5d1 + 39.8/43.0
42.0/~40.0-45.9a1 + ~38.0-42.0a2 + 43.0/42.5
37.8/49.8 + ~45.3h1
36.7/30.0-38.0j1/31.0-40.0j2 + ~31.0-38.0j3/36.0
31.0/30.0
26.0/37.7
16.8
37.0/41.9 + (?)
33.2-37.0o1/40.0/< 34.6o2
33.2/34.6 + (?)
~26.4-34.8b1/< 34.6b2/< 34.6b2
26.4/< 23.9i1 + 27.0i2/< 29.5i3/?
?
< ~26.4m1
?
-4.8/4.4
24.5v1/> 26.5v2/ > 26.5v2
< ~27.1k1/26.5 + ?
< ~27.1l1/< ~26.5l2/< ~26.5l2+ ?
?/? + ?
?/?/?
?
< 18.5t1/< 19.6t2
?/?/?
12.8w1/< 19.6w2+ ?
< -0.3aa1/?
Melting point for MPS not available. Melting point of MPP used as estimate.
Melting point for PSM not available. Melting point estimated to be between melting points
of MSM and MSS.
g1
Melting point for PMP not available, melting point estimated to be between melting point of
PMM and PMS.
d1
Melting point for LaMP not available, melting point estimated to be between melting point
of LMM and PMM.
a1
Melting point for MLM not available, melting point estimated to be between melting point
of MCM and MMM.
a2
Melting point for CaMP not available, melting point estimated to be between melting point
of CaMM and CMS.
h1
Melting point for LaPCa not available, melting point of LPL used as estimate.
j1
Melting point for CaMLa not available, melting point estimated to be between melting point
of CMC and CMM.
j2
Melting point LaCaM not available, melting point estimated to be between melting point of
CCM and MCM.
j3
Melting point for PCC not available, melting point estimated to be between melting point of
MCC and SCC.
o1
Melting point for POS not available. Melting point estimated to be between melting point of
POP and POS.
o2
Melting point for SPO not available. Estimate provided is for PPO.
b1
Melting point for MOP not available, melting point estimated to be between melting point
of MOM and POP.
b2
Melting point for PMO and MPO not available. Melting point of PPO used as an estimate.
q2
39
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Melting point for MMO, β’ polymorph not available. Melting point of β polymorph used as
estimate.
i2
Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph
used as estimate.
i3
Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given
as estimate.
ml
Melting point for CaOM not available. Estimate provided is for MOM.
v1
Melting point for PLS, β’ polymorph not available. Estimate provided is for the β
polymorph.
v2
Melting point for both SPL and PSL not available. Melting point of PPL used as an
estimate.
k1
Melting point for PLP, β’ polymorph not available. Estimate provided is for β polymorph.
l1
Melting point for MLP not available. Estimate provided is for PLP, β polymorph.
l2
Melting point for MPL and PML not available. Estimate provided is the melting point of
PPL.
t1
Melting point for OOP, β’ polymorph not available. Estimate provided is for the β
polymorph.
t2
Melting point for OPO, β’ polymorph not available. Estimate provided is for the β
polymorph.
w1
Melting point for OOM, β’ polymorph not available. Estimate provided is for the β
polymorph.
w2
Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β
polymorph.
aa1
Melting point for CaOO, β’ polymorph not available. Estimate provided is for the β
polymorph.
i1
28
40
TAG Composition of Oil B.
1
Triglyceride
S: PPS/PSP + (MPA)
H: PPP + MPS/PMS/PSM
I: PPM/PMP + (MMS/MSM)
P: SOS/SSO + (POA)
E: POS/SPO/PSO
A: POP/PPO + (MOS)
D: MOP/PMO/MPO
N: MPPo + LaOP/LaPO/PLaO
U: SSL/SLS + (PLA)
J: PLS/SPL/PSL
B: PLP/PPL + (MLS)
G: MLP/MPL/PML + PoOPo
V: LOL/OLL
T: SOL/OLS/OSL
Q: OOO
M: OOS/OSO
L: OOL/OLO + MMP/MPM
C: OOP/OPO
F: POL/PLO/LPO
R: LLP/LPL
K: OOM/OMO + POPo (?)
O: MOL + PLPo
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
n
50
48
46
54
52
50
48
46
54
52
50
48
54
54
54
54
54
52
52
52
50
50
Group
T
T
T
MO
MO
MO
MO
MO
ML
ML
ML
ML
D
D
D
D
D
D
D
D
D
D
h1
% Area
0.59
2.85
2.75
0.91
7.34
35.60
8.44
1.11
0.32
2.24
12.94
3.33
0.25
0.48
0.83
1.16
1.19
8.71
4.02
0.75
1.47
1.02
Tm (β’, °C)
58.7/67.7 + (?)
55.7 + > 52.0h1/56.1/55.2-58.3h2
52.0/48.5-56.1i1 + (49.3/55.2)
37.0/41.9 +
33.2-37.0e1/40.0/< 34.6e2
33.2/34.6 +
~26.4-34.8d1/< 34.6d2/< 34.6d2
+ 27.0n1/< 29.5n2/?
< 35.8u1/< 37.0u2 +
24.5j1/> 26.5j2/ > 26.5j2
< 27.1b1/26.5
< ~27.1g1/< ~26.5g2/< ~26.5g2+ ?
-39.0/~ -12.3v1
-3.5/-10.4/?
-10.0
< 23.5m1/20.5
< -10.0l1/< -9.5l2 + 48.5/59.5
< 18.5c1/< 19.6c2
< -3.5f1/< -10.4f2/
-4.2/-3.0
12.8k1/< 19.6k2
?
Melting point for MPS not available. Melting point of MPP used as estimate.
Melting point for PSM not available. Melting point estimated to be between melting points
of MSM and MSS.
i1
Melting point for PMP not available, melting point estimated to be between melting point of
PMM and PMS.
e1
Melting point for POS not available. Melting point estimated to be between melting point of
POP and POS.
e2
Melting point for SPO not available. Estimate provided is for PPO.
d1
Melting point for MOP not available, melting point estimated to be between melting point
of MOM and POP.
d2
Melting point for PMO and MPO not available. Melting point of PPO used as an estimate.
n1
Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph
used as estimate.
n2
Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given
as estimate.
u1
Melting point for SSL, β’ polymorph not available. Melting of β polymorph used as
estimate.
u2
Melting point for SLS not available. Melting point of SOS used as estimate.
j1
Melting point for PLS, β’ polymorph not available. Estimate provided is for the β
polymorph.
j2
Melting point for both SPL and PSL not available. Melting point of PPL used as an estimate.
b1
Melting point for PLP, β’ polymorph not available. Estimate provided is for the β
polymorph.
g1
Melting point for MLP not available. Estimate provided is for PLP, β polymorph.
g2
Melting point for MPL and PML not available. Estimate provided is the melting point of
PPL.
v1
Melting point for OLL not available. Melting point of LLL used a estimate.
m1
Melting point for OOS, β’ polymorph not available. Estimate provided is for the β
polymorph.
l1
Melting point for OOL not available. Estimate provided is for OOO.
l2
Melting point for OLO, β’ polymorph not available. Estimate provided is for the β
polymorph.
h2
41
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Melting point for OOP, β’ polymorph not available. Estimate provided is for the β
polymorph.
c2
Melting point for OPO, β’ polymorph not available. Estimate provided is for the β
polymorph.
f1
Melting point for POL not available. Estimate provided is for SOL.
f2
Melting point for PLO not available. Estimate provided is for SLO.
k1
Melting point for OOM, β’ polymorph not available. Estimate provided is for the β
polymorph.
k2
Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β
polymorph.
c1
42
TAG Composition of Oil C.
1
Triglyceride
CC: MMP/MPM + LaMS
O: LaMP + LaLaS/LaSLa
H: MMLa/MLaM + CaMP +
LaLaP/LaPLa
D: LaLaM/LaMLa + LaPCa
A: LaLaLa +
CaLaM/CaMLa/LaCaM
C: LaLaCa/LaCaLa
J: CaCaLa/CaLaCa
X: CaCaCa
Z: POS/PSO/SPO
N: POP/PPO+ (MOS)
R: LaSO/LaOS/OLaS +
MOP/PMO/MPO
L: MOM/MMO +
LaOP/LaPO/PLaO
G: LaOM + CaOP
B: LaLaO/LaOLa
E: CaOLa/CaLaO/LaCaO
T: CaOCa
U: LaLP + MLM
V: LaLM
K: LaLaL/LaLLa (+ CaLM)
M: CaLLa + LaLnLa
I: OOO
P: OOL/OLO
W: OOS/OSO
Y: LLO
F: OOP/OPO
Q: POL/PLO/LPO
AA: OOM/OMO
S: OOLa/OLaO
BB: LaOL
DD: CaOO
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
n
44
42
Group
T
T
% Area
0.47
1.80
40
T
4.58
38
T
8.11
36
T
13.15
34
32
30
52
50
T
T
T
MO
MO
11.54
3.73
0.78
0.57
1.95
48
MO
1.08
46
MO
2.83
44
42
40
38
46
44
42
40
54
54
54
54
52
52
50
48
48
46
MO
MO
MO
MO
ML
ML
ML
ML
D
D
D
D
D
D
D
D
D
D
5.20
11.91
6.53
0.93
0.90
0.88
3.00
2.45
4.06
1.51
0.80
0.65
5.22
1.29
0.54
0.97
0.51
0.45
Tm (β’, °C)
48.5/59.5 + 45.5
~42.0-48.5o1 + 39.8/43.0
42.0/~40.0-45.9a1 + ~38.0-42.0a2 +
43.0/42.5
37.8/49.8 + ~45.3h1
35.1 + 36.7/30.0-38.0j1/31.0-40.0j2
31.0/> 26.0c1
26.0/37.7
16.8
33.2-37.0o1/40.0/< 34.6o2
33.2/34.6 + (?)
?/?/? + ~26.4-34.8b1/< 34.6b2/<
34.6b2
i1
26.4/< 23.9 + 27.0i2/< 29.5i3/?
?+?
15.7/< 16.5b1
> -4.8e1/4.4-18.0e2/4.4-18.0e2
-4.8
?
?
> 15.5k1/<< 27.1k2+ ?
?
-10.0
> -2.2p1/< -9.5p2
< 23.5w1/20.5
< 18.5f1/< 19.6f2
?/?/?
12.8w1/< 19.6w2
< 5.1s1/?
?
?
o1
Melting point for LaMP not available, melting point estimated to be between melting point
of LMM and PMM.
a1
Melting point for MLM not available, melting point estimated to be between melting point
of MCM and MMM.
a2
Melting point for CaMP not available, melting point estimated to be between melting point
of CaMM and CMS.
h1
Melting point for LaPCa not available, melting point of LPL used as estimate.
j1
Melting point for CaMLa not available, melting point estimated to be between melting point
of CMC and CMM.
j2
Melting point for LaCaM not available, melting point estimated to be between melting point
of CCM and MCM.
c1
Melting point for LaCaLa not available, melting point estimated to be slightly higher than
CaCaLa.
o1
Melting point for POS not available. Melting point estimated to be between melting point of
POP and POS.
o2
Melting point for SPO not available. Estimate provided is for PPO.
b1
Melting point for MOP not available, melting point estimated to be between melting point
of MOM and POP.
b2
Melting point for PMO and MPO not available. Melting point of PPO used as an estimate.
i1
Melting point for MMO, β’ polymorph not available. Melting point of β polymorph used as
estimate.
i2
Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph
used as estimate.
43
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given
as estimate.
b1
Melting point for LaOLa, β’ polymorph not available. Melting point of β polymorph is
given as estimate.
e1
Melting point for CaOLa not available. Melting point estimated to be slightly higher than
melting point of CaOCa.
e2
Melting point for CaLaO not available. Melting point estimated to be between melting point
of CaCaO and LaLaO.
k1
Melting point for LaLaL, β’ polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the α polymorph of LaLaL.
k2
Melting point for LaLLa, β’ polymorph not available. Melting point estimated to be
significantly lower than the provided melting point for the β’ polymorph of PLP.
p1
Melting point for OOL, β’ polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the α polymorph of OOL.
p2
Melting point for OLO, β’ polymorph not available. Melting point estimated to be slightly
lower than the provided melting point for the β polymorph of OLO.
w1
Melting point for OOS, β’ polymorph not available. Melting point estimated to be slightly
lower than the provided melting point for the β polymorph of OOS.
f1
Melting point for OOP, β’ polymorph not available. Melting point estimated to be slightly
lower than the provided melting point for the β polymorph of OOP.
f2
Melting point for OPO, β’ polymorph not available. Melting point estimated to be slightly
lower than the provided melting point for the β polymorph of OPO.
w1
Melting point for OOM, β’ polymorph not available. Estimate provided is for the β
polymorph.
w2
Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β
polymorph.
s1
Melting point for OOLa, β’ polymorph not available. Estimated provided is for OOLa, β
polymorph.
i3
44
1
2
TAG Composition of Oil D.
Triglyceride
V:SSP/SPS
S:PPS/PSP + SSM/SMS
T:MPS/MSP/PMS
W:PPM/PMP
Y:SOLg
U:LgOP
F:SOS/OSS (+ POA)
C: POS/PSO/SPO
B: POP/PPO
K:MOP/MPO/PMO
I:PLS/PSL/SPL
H:PLP/PPL
X:OOLg
O:OOA
D: OOS/OSO
G:OOO
J:SOL/SLO/OSL
L:OOL/OLO
N:SOL
Q:LLS
R:LLO
A: OOP/OPO
E:POL/PLO/LPO
P:LLP
M:OOM (+ POPo)
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
n
52
50
48
46
60
58
54
52
50
48
52
50
60
56
54
54
54
54
54
54
54
52
52
52
50
Group
T
T
T
T
MO
MO
MO
MO
MO
MO
ML
ML
D
D
D
D
D
D
D
D
D
D
D
D
D
t1
% Area
0.18
0.42
0.35
0.18
0.06
0.21
4.87
14.71
16.58
2.05
2.88
3.21
0.08
0.75
10.70
4.68
2.87
1.89
0.94
0.67
0.53
21.15
6.09
0.74
1.64
Tm (β, °C)
64.4/68.0
62.6/65.3 + 60.9/63.3
58.5/ < 65.3t1/59.6
55.8/59.9
?
?
43/> 41.9f1 +
37.1/?/40.2
37.2/> 34.6b1
27/> 23.9k1/> 23.9k1
24.5/< 35.8i1/< 35.8i1
27.1/>26.5h1
?
?
23.5/23.9
4.8
> -3.5j1/> -10.4j2/?
>> -2.2l1/-9.5
?
?
?
18.5/19.6
>> 13.3e1/>> 13.2 e2/>> 11.7 e3
?
?
Melting point for MSP not available. Melting point estimated to be slightly lower than
melting point of PSP.
f1
Melting point for OSS, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point of the β’ polymorph of OSS.
b1
Melting point of PPO, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point of the β’ polymorph of PPO.
k1
Melting point of MPO not available. Melting point estimated to be slightly higher than the
melting point of MMO.
i1
Melting point of PSL not available. Melting point estimated to be slightly lower than the
melting point of SSL.
h1
Melting point of PPL, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the β’ polymorph of PPL.
j1
Melting point for SOL, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the β’ polymorph of SOL.
j2
Melting point for SLO, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the β’ polymorph of SLO.
l1
Melting point for OOL, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of OOL.
e1
Melting point of POL, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of POL.
e2
Melting point of PLO, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of PLO.
e3
Melting point of LPO, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of LPO.
45
1
2
TAG Composition of Oil E.
TAG
FF: PPS/PSP + SSM/SMS + (MPA)
R: PPP +MPS/PMS/PSM
K: PPM/PMP + (MMS/MSM)
M:MMP/MPM + (LaMS)
U: MMM + LaMP
W: CaMP
II: SOLg + POHx
GG: SOB + LgOP
CC: SOS/SSO + POA
J: POS ( + MOA)
A: POP/PPO + (MOS)
B: MOP/MPO/PMO+ (LaSO/LaOS/OLaS)
E: MOM/MMO + LaOP/LaPO/PLaO
I: LaOM + CaOP
O: CaOM
N: MLM + LaLP
S: PLS/SPL/PSL
D:PLP/PPL + (MLS)
F: MLP/MPL/PML
V: CaLP/CaPL/PCaL
BB: CaLM
X: OOL/OLO
Q: OOO
Y: OOS/OSO
AA: LOL/OLO
DD: SOL/OLS/OSL
C: OOP/OPO
G: POL
P: LLP/LPL
H: OOM/OMO (+ POPo)
L: MOL + PoOL + PoPPo ?
T: LLM
Z: CaOO
EE: CaOL
HH: CaLL
% Area
0.17
1.08
2.70
2.07
0.94
0.90
0.05
0.17
0.39
3.22
19.47
15.38
5.23
3.44
1.33
1.59
1.06
5.57
4.80
0.91
0.55
0.81
1.20
0.76
0.61
0.35
9.14
4.42
1.26
4.10
2.49
0.96
0.61
0.33
0.13
Oil E
n
50
48
46
44
42
40
60
58
54
52
50
48
46
44
42
46
52
50
48
44
42
56
54
54
54
54
52
52
52
50
50
50
46
46
46
Group
T
T
T
T
T
T
MO
MO
MO
MO
MO
MO
MO
MO
MO
ML
ML
ML
ML
ML
ML
D
D
D
D
D
D
D
D
D
D
D
D
D
D
Tm (β’, °C)
58.7/67.7 + 58.3/58.8 + (?)
55.7 + > 52.0r1/56.1/55.2-58.3r2
52.0/48.5-56.1k1 + (49.3/55.2)
48.5/59.5 + (45.5)
45.9 + ~42.0-48.5u1
~38.0-42.0w1
37.0/41.9 + (?)
33.2-37.0j1/40.0/< 34.6j2 + (?)
33.2/34.6 + (?)
27/> 23.9b1/> 23.9b1 + (?/?/?)
26.4/< 23.9e1 + 27.0e2/< 29.5e3/?
?+?
< ~26.4o1
?+?
24.5s1/> 26.5s2/ > 26.5s2
< ~27.1d1/26.5 + ?
f1
< ~27.1 /< ~26.5f2/< ~26.5f2
?/?/?
?
< -10.0x1/< -9.5x2
-10.0
< 23.5y1/20.5
-39.0/~ -12.3aa1
-3.5/-10.4/?
< 18.5c1/< 19.6c2
?
-4.2/-3.0
12.8h1/< 19.6h2
?
< -4.2t1
< -0.3z1/?
?
?
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
r1
Melting point for MPS not available. Melting point of MPP used as estimate.
Melting point for PSM not availabe. Melting point estimated to be between melting points of
MSM and MSS.
k1
Melting point for PMP not available, melting point estimated to be between melting point of
PMM and PMS.
u1
Melting point for LaMP not available, melting point estimated to be between melting point
of LMM and PMM.
w1
Melting point for CaMP not available, melting point estimated to be between melting point
of CaMM and CMS.
j1
Melting point for POS not available. Melting point estimated to be between melting point of
POP and POS.
j2
Melting point for SPO not available. Estimate provided is for PPO.
r2
b1
Melting point of MPO not available. Melting point estimated to be slightly higher than the
melting point of MMO.
e1
Melting point for MMO, β’ polymorph not available. Melting point of β polymorph used as
estimate.
e2
Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph
used as estimate.
46
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given
as estimate.
ol
Melting point for CaOM not available. Estimate provided is for MOM.
s1
Melting point for PLS, β’ polymorph not available. Estimate provided is for the β
polymorph.
s2
Melting point for both SPL and PSL not available. Melting point of PPL used as an estimate.
d1
Melting point for PLP, β’ polymorph not available. Estimate provided is for β polymorph.
f1
Melting point for MLP not available. Estimate provided is for PLP, β polymorph.
f2
Melting point for MPL and PML not available. Estimate provided is the melting point of
PPL.
x1
Melting point for OOL not available. Estimate provided is for OOO.
x2
Melting point for OLO, β’ polymorph not available. Estimate provided is for the β
polymorph.
y1
Melting point for OOS, β’ polymorph not available. Estimate provided is for the β
polymorph.
aa1
Melting point for OLL not available. Melting point of LLL used a estimate.
c1
Melting point for OOP, β’ polymorph not available. Melting point estimated to be slightly
lower than the provided melting point for the β polymorph of OOP.
c2
Melting point for OPO, β’ polymorph not available. Melting point estimated to be slightly
lower than the provided melting point for the β polymorph of OPO.
h1
Melting point for OOM, β’ polymorph not available. Estimate provided is for the β
polymorph.
h2
Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β
polymorph.
t1
Melting point for LLM, β’ polymorph not available. Estimate provided is for LLP, β
polymorph.
z1
Melting point for CaOO, β’ polymorph not available. Estimate provided is for the β
polymorph.
e3
47
TAG Composition of Oil F
1
Triglyceride
BB: SSA/SAS
W: SSS
S:SSP/SPS
Q:PPS/PSP + SSM/SMS
V:MPS/MSP/PMS
Z:SOLg
X:LgOP
P: SOA + POB
E:SOS/OSS (+ POA)
A: POS/PSO/SPO
D: POP/PPO
O:MOP/MPO/PMO
K: SLS/SSL + (PLA)
H:PLS/PSL/SPL
J:PLP
Y: PPL
AA:OOLg
N:OOA
C: OOS/OSO
F:OOO
I:SOL/SLO/OSL
L:OOL/OLO
R:LLS
T:LLO
B: OOP/OPO
G:POL/PLO/LPO
U:LLP
M:OOM (+ POPo)
n
56
54
52
50
48
60
58
56
54
52
50
48
54
52
50
50
60
56
54
54
54
54
54
54
52
52
52
50
Group
T
T
T
T
T
MO
MO
MO
MO
MO
MO
MO
ML
ML
ML
ML
D
D
D
D
D
D
D
D
D
D
D
D
% Area
0.06
0.30
0.64
0.73
0.37
0.11
0.27
0.79
8.88
17.27
11.08
0.89
2.15
4.24
2.37
0.19
0.10
0.95
12.95
5.57
3.55
1.96
0.69
0.59
16.59
4.65
0.47
1.11
Tm (β, °C)
~70.7bb1
72.5
64.4/68.0
62.6/65.3 + 60.9/63.3
58.5/ < 65.3v1/59.6
?
?
41.5 + ?
43/> 41.9e1 +
37.1/?/40.2
37.2/> 34.6d1
27/> 23.9o1/> 23.9o1
< 35.8k1/< 37.0k2+ ?
24.5/< 35.8h1/< 35.8h1
27.1
>26.5y1
?
?
23.5/23.9
4.8
> -3.5i1/> -10.4i2/?
>> -2.2l1/-9.5
?
?
18.5/19.6
>> 13.3g1/>> 13.2 g2/>> 11.7 g3
?
?
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
bb1
Melting point for MSP not available. Melting point estimated to be slightly lower than
melting point of PSP.
v1
Melting point for MSP not available. Melting point estimated to be slightly lower than
melting point of PSP.
e1
Melting point for OSS, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point of the β’ polymorph of OSS.
d1
Melting point of PPO, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point of the β’ polymorph of PPO.
o1
Melting point of MPO not available. Melting point estimated to be slightly higher than the
melting point of MMO.
k1
Melting point for SSL, β’ polymorph not available. Melting of β polymorph used as
estimate.
k2
Melting point for SLS not available. Melting point of SOS used as estimate.
h1
Melting point of PSL not available. Melting point estimated to be slightly lower than the
melting point of SSL.
y1
Melting point of PPL, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the β’ polymorph of PPL.
i1
Melting point for SOL, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the β’ polymorph of SOL.
i2
Melting point for SLO, β polymorph not available. Melting point estimated to be slightly
higher than the provided melting point for the β’ polymorph of SLO.
l1
Melting point for OOL, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of OOL.
g1
Melting point of POL, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of POL.
g2
Melting point of PLO, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of PLO.
48
1
2
3
Melting point of LPO, β polymorph not available. Melting point estimated to be
significantly higher than the provided melting point for the α polymorph of LPO.
g3
49
1
References
1
Marina AM, Che Man YB, Nazimah SAH, Amin I (2009) Chemical Properties of Virgin Coconut Oil. J Am
Oil ChemSoc 86: 301-307.
2
Wesdorp LH (1990) Liquid–Multiple Solid Phase Equilibria in Fat - Theory and Experiments, Ph.D. Thesis,
Technical University of Delft, Delft, The Netherlands, 258 p.
3
Hagemann JW (1988) Thermal Behavior and Polymorphism of Acylglycerides. In: Garti N, Sato K (eds)
Crystallization and Polymorphism of Fats and Fatty Acids. Marcel Dekker, New York, New York, United States
of America, pp 9-96.
4
Marangoni AG, Wesdorp L (2013) Structure and Properties of Fat Crystal Networks, 2 ndedn. CRC Press LLC,
Boca Raton, Florida, United States of America, 518 p.
Small D (1986) Glycerides. In: Small D (ed) The Physical Chemistry of Lipids – From Alkanes to
Phospholipids. Plenum Press, New York, New York, United States of America, pp 345-394.
5
6
Narine SS, Marangoni AG (2002) Structure and Mechanical Properties of Fat Crystal Networks. In: Marangoni
AG, Narine SS (eds) Physical Properties of Lipids. Marcel Dekker, New York, New York, United States of
America, pp 63-83.
7
Lipp M, Simoneau C, Ulberth F, Anklam E, Crews C, Brereton P, de Greyt W, Schwackd W, Wiedmaier C
(2001) Composition of Genuine Cocoa Butter and Cocoa Butter Equivalents. J Food Compos Anal 14:399-408.
8
Bereaua D, Benjelloun-Mlayaha B, Banoubb J and Bravoc R (2003) FA and Unsaponifiable Composition of
Five Amazonian Palm Kernel Oils. J Am Oil ChemSoc 80:49-83.
9
Hernqvist L (1988) Crystal Structures of Fats and Fatty Acids. In: Garti N, Sato K (eds) Crystallization and
Polymorphism of Fats and Fatty Acids. Marcel Dekker, New York, New York, United States of America, pp 97138.
10
Minato A, Ueno S, Smith K, Amemiya Y, Sato K (1997 Thermodynamic and Kinetic Study on Phase
Behavior of Binary Mixtures of POP and PPO Forming Molecular Compound Systems. J PhysChem B
101:3498-3505.
50