It must be noted that the regiospecificity of the fatty acids on the triglycerides of Oil

C, Oil D, Oil E and Oil F were not determined. For this purpose, whenever a certain

triglyceride is reported, it must be assumed to refer to a group that contains the particular

triglyceride as well as all of its regio-isomers, hence the reference to a triglyceride “group”.

Triglycerides are also referred to by their carbon number, which is the added carbon number

of their fatty acid chains excluding the carbons from glycerol.

Oil C

Oil C – FA and TAG Composition

The fatty acid composition of Oil C is reported in Table 1. Oil C can be described as a

lauric oil consisting of a mixture of medium chain length fatty acids such as capric (12.6 %),

lauric (37.4 %) and myristic (9.84 %), with lauric acid making up the bulk of this fraction. A

considerable amount of palmitic acid is also present (8.11 %). The unsaturated component of

Oil C consists predominantly of oleic acid (22.5 %) and some linolenic acid (5.78 %). Oil C

has a very similar fatty acid composition to coconut oil1 although Oil C has slightly more

oleic acid and less lauric and myristic acid compared to coconut oil.

The triglyceride composition of Oil C is given in Table 2. The TAG analysis shows

that the distribution of TAGs according to carbon number is more varied in this fat. The

analysis shows that approximately 50 % of the TAGs in Oil C have a carbon number between

30 and 40. Roughly 75 % of the TAGs have a carbon number between 30 and 44. It can be

seen that 44.15 % area of the TAGs consist of trisaturated TAGs (groups A, C, D, H, J, O, X,

CC) while 38.23 % area of the TAGs consist of di-saturated TAGs. The TAGs containing

oleic acid (groups B, E, G, L, N, R, T, Z ) comprise 30.99 % area of the TAGs while a

smaller but significant portion of the TAGs containing linoleic acid (groups K, M, U, V)

comprise 7.24 % of the area. A sizable fraction (16.00 % area) consists of TAGs containing

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two or three unsaturated fatty acids (groups I, F, P, Q, S, W, Y, AA, BB, DD). In this respect,

Oil C is very similar to Oil A in that it contains two solid fractions (trisaturates and oleic

acid-containing mono-unsaturate TAGs) although, in comparison, Oil C has significantly

more di- and tri-unsaturate “oil”. Presumably, the predominant TAGs (A, C and D from the

trisaturates and B and E from the disaturated TAG groups) from both types of TAGs

contribute to the structuring of the fat.

Oil C – Melting Behavior

A melting point estimation similar to that conducted for Oil A and Oil B can be

performed2,3. The melting point of the fat, to a certain extent, can be estimated from the

melting points of the pure triglycerides comprising the fat (shown to crystallize into a β’

polymorph). The melting points of the majority of the trisaturated group of TAGs can be

estimated to fall between 30 °C to 45 °C. Likewise, the melting points of most of the oleic

acid-containing di-saturated TAGs can be estimated to be between 15 °C to 25 °C.

Like the di- and tri- unsaturates of Oil B, the TAGs in the di- and tri-unsaturate group

of Oil C all appear to have very low melting points with the exception of oleic acid mono-

saturates containing a long chain fatty acid such as palmitic or stearic acid. As such, this lipid

class can be assumed to be predominantly liquid at ambient temperatures.

Examining the predominant TAGs in Oil C (% area > 6 %), it can be seen that these

consist of 5 groups, A, B, C, D and E. Groups A, C and D consist of trisaturated TAGs (and

their analogues) that have a carbon number of 34, 36 and 38, respectively. Group B is a di-

saturated TAG group that consists of either LaLaO or LaOLa. The melting points of these

groups is estimated to be as low as around 15 °C or as high as 50 °C for the trisaturates with

higher carbon numbers. In this light, it is highly likely that Oil C is structured by the high-

melting trisaturate groups mentioned above. Oil C may also be structured by oleic-acid

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containing di-saturates, however, this is seemingly unlikely as the melting points of these

TAGs are below ambient temperatures due to the fact that the saturated fatty acids on these

TAGs are medium-chained unlike the long chain fatty acids in the oleic acid di-saturates in

Oil B.

Figure 1A shows that the melting trace of Oil C has two peak melting temperatures:

17.82 °C and 24.10 °C, suggesting only two melting fractions. The total melting enthalpy was

70.22 kJ/kg. The lower melting enthalpy reflects the fact that the solids content of Oil C is

less than the solids content of Oil A and Oil B. In all likelihood, the first melting peak at

17.82 °C can be attributed to the melting of the oleic acid-containing mono-unsaturate TAGs

as well as other low-melting components (most likely the linoleic acid-containing mono-

unsaturate TAGs). This is not inconceivable as the onset melting temperature of this peak is

1.2 °C. The second melting peak at 24.1 °C can most likely be attributed to the melting of the

higher-melting tri-saturated TAGs that structure the material. Although these TAGs, in their

pure form, have comparatively higher melting points (> 30 °C), it is possible that the melting

point may be depressed due to dilution and eutectic interactions between lipid phases.

Figure 2A shows that the melting profile of Oil C is gradual and starts at a temperature

of roughly 5 °C. The steepest decrease in the SFC occurs between 10 °C and 20 °C. This

melting profile is identical to the melting profile of Oil D. The initial solid fat content at 5 °C

is 52.24 %. Examining the TAG composition of Oil C and noting that the trisaturate groups

comprise roughly 44.15 % area of the TAG chromatogram, it can be safely assumed that the

solids in Oil C at the start of melting consist of the trisaturates as well as the higher-melting

TAGs of the oleic acid-containing mono-unsaturate class (with carbon number > 42).

Together, these fractions constitute 55.77 % of the area under the chromatogram. It is more

likely that LaLaO (carbon number = 40) and analogues thereof are present in the solid state at

the start of melting. In this case, the lower actual SFC observed (lower by about 10 %) at 5 °C

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is perhaps due to eutectic effects. The lower-melting oleic acid-containing TAGs, as well as

the linoleic acid-containing di-saturates and the di- and tri- unsaturates constitute the oil phase

at 5 °C.

Like other fats previously discussed, the solid fat content of Oil C decreases in a linear

fashion as the temperature is increased. At 20 °C, the solid fat content is 11.8 %. This is

interesting considering that the four main trisaturate groups (groups A, C, D and H) all have

estimated melting points greater than 30 °C. This indicates that there may be eutectic or

solubilisation effects that depress the melting points of these TAGs considerably. Given that

these are the highest melting components, it is likely that the only fractions that have not

melted at 20 °C are these fractions. Melting is complete at 25 °C, which suggest that Oil C is

most likely an oil at ambient temperatures. As such, it has very limited functionality at

ambient temperatures as its plastic range is between 10 °C and 20 °C.

Oil C – Crystallization Behavior

The DSC crystallization trace for Oil C (Figure 1A) shows one peak crystallization

temperature at -2.59 °C. The onset of crystallization for this crystallization peak occurs

approximately at a temperature of 0 °C. A high undercooling of approximately 24 °C is

required to initiate crystallization of the fat (24 °C – 0°C). On the basis of the previous

discussion of melting points, this crystallization peak can be attributed to the crystallization of

tri-saturates as well as the high-melting components of the oleic acid-containing di-saturated

TAGs. It is highly unlikely that any of the lower-melting components crystallize given that

their melting points are significantly below 0 °C and that the experimental temperature does

not decrease sufficiently low to develop a supersaturation for these components.

The crystallization kinetics curve for Oil C is displayed in Figure 3A. Fit parameters

to the single or double Avrami equation are tabulated in Table 6. The plotted data suggests

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only one crystallizing fraction. In addition, the kinetic data exhibited a long induction time

(approximately 900 seconds). The following result appears to agree with the DSC

crystallization curve for Oil C, which shows only one peak. A likely explanation for the long

induction time observed is that the high amount of liquid components decrease the

concentration of the crystallisable components. In turn, a higher undercooling is needed to

achieve supersaturation with the end result being that the rate of nucleation is not sufficient

for crystallization until a very low temperature is achieved.

The final SFC value as estimated from a single-Avrami fit is approximately 38.8 %.

This value is not altogether different from the solid fat content of the fat at 10 °C (44.5 %) as

obtained from the melting profile. Parameter estimates for the Avrami exponent for this

crystallization curve suggest that the crystallizing components grow either as a rod with

sporadic nucleation or as a disc with instantaneous nucleation4. Of the two, it is more likely

that the components grow as a disc with instantaneous nucleation, which suggests that all of

the crystallisable components nucleate at the beginning of crystallization and that no further

nucleation takes place during the course of the crystallization process. Examining the kinetics

curve, this is not inconceivable given the long lag time (presumably, the nuclei all form

within this long lag time).

Oil C – Crystal Structure and Microstructure

The XRD spectrum of Oil C is given in Figure 4A. A single long spacing peak at

32.93 Å can be observed in the small-angle region. Higher order reflections corresponding to

spacings of 16.73 Å and 11.18 Å are also present in the small-angle region. Similar to Oil A

and Oil B, the long spacing peaks suggest a bilayer stacking of triglyceride molecules. Using

the same calculation employed previously for Oil A and Oil B5, the number of carbons

comprising the length of the lamella detected via XRD can be estimated to be between 24 to

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26. Given a 2L spacing, the lamella is most likely composed of glycerides with lauric acid on

both position 1 and position 2 (for a glyceride in the chair conformation) or with lauric acid

on positions 1 and 3 (for a tuning fork conformation). Given that there are significant amounts

of myristic and capric acid, it is also possible that the bilayer may be composed of

triglycerides containing these fatty acids at the positions specified previously. In light of this,

the TAG groups that compose these lamella are most likely groups A (LaLaLa or CaLaM),

C (LaLaCa), D (LaLaM) and H (MMLa).

No spacings suggestive of trilayer packing is evident in the XRD spectra. This is not

unreasonable as the triglycerides that commonly pack in the 3L arrangement usually contain a

fatty acid that is significantly different from the other two fatty acids on the triglyceride.

Examining the composition of Oil C, the triglyceride groups (in significant quantities) that

would presumably pack into the 3L arrangement is group B (LaLaO). However, this group

has an estimated melting point of about 15 °C, which would imply that it is liquid at the

temperatures at which the analysis is conducted and thus is not detected.

Several short spacing peaks characteristic of the β’ polymorph (3.808 Å and 4.223 Å)

are observable in the wide-angle region5. The crystallization of Oil C into a β’ polymorph is

interesting as the majority of triglycerides (mentioned previously as groups A, C, D and H)

typically crystallize into the β polymorph given that the length of the fatty acids is fairly

similar (does not differ by more than 4 carbons) and that the aforementioned TAGs do not

contain any unsaturated fatty acids.

The microstructure of Oil C as observed through a polarized light microscope is given

in Figure 5A. The microstructure is very similar to the microstructure of Oil A and Oil B.

From the micrograph, it can be seen that Oil C forms crystals with needle-like morphologies

(roundness = 0.61). The crystals appear to be much shorter and thinner than those of Oil A

and Oil B. The length of the crystals as given by the maximum Feret diameter is

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approximately 2.8 ± 2.7 μm long. Like Oil A and Oil B, it is not unexpected that the fat

crystals in the β’ polymorph are small and needle-like6.

Oil C – Rheological Properties

The viscoelastic properties of Oil C are listed in Table 7. The rheological properties

are very similar to those of Oil A. The measured G’ was 6.05 ± 1.10 MPa. This G’ suggests a

relatively hard material similar to other hard fats commonly encountered in food manufacture.

As a standard of comparison, hardened cocoa butter has a G’ of approximately 20 MPa while

milkfat at 5 °C has a G’ between 1 to 10 MPa. The ratio of the loss modulus to the storage

modulus is 0.15, suggesting that the mechanical damping by the material is very minimal

although slightly higher than that for Oil A and Oil B. This is perhaps due to the higher liquid

content of Oil C compared to Oil A and Oil B.

Compared to Oil A and Oil B, the mechanical properties of Oil C are interesting in

that the hardness (using the G’ as a measure) is only slightly lower despite the relatively low

solid fat content of Oil C at the testing temperature (10 °C). Compared to Oil A and Oil B,

which both have a solid fat content of roughly 75 % at 10 °C, Oil C (as well as Oil D) only

has a solid fat content of roughly 50 %. These results suggest that it is possible to engineer fat

materials to have the same hardness despite differences in the solid fat content although a

more thorough elucidation of the structural factors that result in this is necessary.

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Oil D

Oil D – FA and TAG Composition

The fatty acid composition of Oil D is reported in Table 1. Oil D can be described as a

high-oleic (44.8 %) oil containing high amounts of long chain fatty acids such as stearic acid

(14.8 %) and palmitic acid (28.1 %). A significant amount of linoleic acid (7.1 %) is also

present. Unlike Oil C, the medium-chain fatty acid content of Oil D is relatively low. Oil D

has a very similar fatty acid composition to cocoa butter7 although the stearic acid content of

Oil D is relatively low while the oleic acid content is relatively high.

The triglyceride composition of Oil D is given in Table 3. The TAG composition of

Oil D is unusual in that it contains very little trisaturates (comprising only 1.13 % area of the

chromatogram) and is very much like Oil B in that it contains predominantly oleic acid-

containing di-saturates. Unlike the other algal oils heretofore studied, the predominant TAG

groups in Oil D are the mono-saturates, comprising 52.73 % area of the chromatogram. The

mono-saturates consist of groups A, D, E, G, J, L, M, N, O, P, Q, R and X. The next largest

group of TAGs are the oleic acid-containing di-saturates, comprising 38.48 % area of the

chromatogram. This group consists of TAG groups B, C, F, K, Y and U. The linoleic acid-

containing di-saturates comprise 6.09 % area of the chromatogram and consist of TAG groups

H and I.

Oil D – Melting Behavior

The melting point of Oil D can be estimated using a methodology similar to that used

for Oil A, Oil B and Oil C. Given that the trisaturates comprise only a very small fraction of

Oil D, the melting behaviour of these TAGs can be ignored assuming that they will not

crystallize due to their low concentrations. Examining the TAG composition of Oil D, it is

obvious that the fat is structured by oleic acid-containing di-saturates, particularly groups B,

C, F and K. Together, these triglycerides have a melting point (for the β polymorph) of

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approximately 35 °C to 40 °C. As well, it is possible that the linoleic acid-containing di-

saturates will contribute to the solids content of Oil D.

The TAGs in the mono-saturates group all have very low melting points with the

exception of oleic acid mono-saturates (such as OOS) containing a long-chain fatty acid such

as palmitic or stearic acid. The liquid component of the fat is most likely composed of these

mono-saturates.

Figure 1A shows that the melting trace of Oil D exhibits three peak melting points: 5.7

°C, 12.4 °C and 29.1 °C, suggesting three melting fractions. The total melting enthalpy is 21.8

kJ/kg. This is a comparatively low melting enthalpy when compared to Oil C, which has a

melting enthalpy of approximately 80 kJ/kg. The first melting peak at 5.69 °C can be

attributed to the melting of some of the di- and tri-unsaturated TAGs, which typically have

melting points between 0 °C to 5 °C. As well, the lower-melting components of the linoleic

and oleic acid-containing di-saturates (TAG groups H, I and K) may be undergoing a melting

transition in this peak. The second melting peak at 12.41 °C may likewise be assigned to the

melting of the oleic acid-containing di-saturated TAGs (groups B), which make up part of the

bulk of the solids in this fat. The third melting peak at 29.07 °C can be attributed to the

melting of the higher melting components of the oleic acid-containing groups (groups C and

F) as well as the tri-unsaturates. The melting enthalpy associated with this peak is miniscule,

suggesting that these high-melting components are relatively low in concentration.

Figure 2A shows that the melting profile of Oil D is gradual and starts at a temperature

of roughly 5 °C. The steepest decrease in the SFC occurs between 10 °C and 20 °C. This

melting profile is identical to the melting profile of Oil C. The initial solid fat content of Oil

D at 5 °C is 52.75 %. Unlike the TAG composition of Oil C, the bulk of the solids in Oil D

are composed of oleic acid-containing mono-unsaturate TAGs, which comprise 38.5 % area

of the chromatogram. As the solid fat content at beginning of melting is 52.8 %, it can be

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assumed that the solid components at this temperature consist of both oleic acid and linoleic

acid-containing di-saturated TAGs as well as the tri-saturates and the higher melting

components of the di- and tri-unsaturates group. Taken together, these groups comprise

roughly 50 % area of the chromatogram, which would approximately be equal to the solids

content of Oil D. The lower-melting components of the mono-saturates constitute the oil

phase at 5 °C.

The solid fat content of Oil D decreases in a linear fashion as the temperature is

increased. The SFC decreases to 44.7 % as the temperature is increased to 10 °C. At this

temperature, the components in the first melting peak of the DSC curve (5.7 °C) have melted.

At this stage, the remaining solids are the higher-melting components of the oleic acid and

linoleic acid-containing TAGs. Increasing the temperature to 15 °C will melt the components

in the second peak of the DSC curve (12.4 °C). At this temperature, the remaining solids

content (28.6 %), are presumably the high-melting oleic acid-containing di-saturates (groups

C and F). Increasing the temperature to 20 °C will melt most of these components. While it is

unusual for these components to melt at 20 °C given that the melting point of the pure TAGs

is roughly in the region of 35 °C to 40 °C, the presence of a high amount of liquid

triglycerides at 20 °C will depress the melting point of these components either through a

eutectic or solubilisation effect.

Oil D – Crystallization Behavior

The DSC crystallization trace for Oil D (Figure 1A) shows one peak crystallization

temperature at 2.1 °C. The onset of crystallization for this crystallization peak occurs

approximately at a temperature of 10 °C. A high undercooling of approximately 19 °C is

required to initiate crystallization of the fat.

The crystallization kinetics curve for Oil D is displayed in Figure 3A. Fit parameters

to the single or double Avrami equation are tabulated in Table 6. Unlike Oil C, the plotted

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data suggests two crystallizing fractions. The first crystallizing fraction has a maximum solid

fat content of 3.50 % as determined from a double Avrami fit. The low solids content suggest

that the concentration of TAGs crystallizing in this fraction is also relatively low. As such,

this crystallizing fraction is most likely composed of the trisaturates (groups S, T, V and W)

as well as the higher-melting components of the oleic acid-containing di-saturates (groups U

and Y). The second crystallizing component has a maximum solid fat content of 36.88 %.

This second crystallizing component likely consists of the oleic acid-containing di-saturates

(groups B, C, F and K) which constitute the bulk of the solids in the fat.

The final SFC value as estimated from a single-Avrami fit is approximately 41.6 %.

This value is not altogether different from the solid fat content of the fat at 10 °C (44.7 %) as

obtained from the melting profile. Parameter estimates for the Avrami exponent for the first

crystallizing components suggests that it grows either as a rod with sporadic nucleation or as a

disc with instantaneous nucleation. Of the two, it is more likely that growth is as a disc with

instantaneous nucleation. Parameter estimates for the Avrami exponent for the second

crystallizing component suggests that it grows either as a disc with sporadic nucleation or that

it grows as a sphere with instantaneous nucleation. Of the two, it is more likely that the

second crystallizing component grows as a sphere with instantaneous nucleation as fat crystal

particles typically grow as a sphere.

Oil D – Crystal Structure and Microstructure

The XRD spectrum of Oil D is given in Figure 4B. A single long spacing peak at

58.05 Å can be observed in the small-angle region. Higher-order reflections corresponding to

spacings of 40.85 Å and 30.03 Å are also present. Using the equations provided by Donald

Small5, each ethylene group or every two carbons can be approximated by a length of 2.27 Å

for a β polymorph. An allowance of 4.11 Å is made for the carbons on the glycerol backbone.

These factors are much smaller than those for the β’ polymorph to account for the tilting of

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the glyceride chains for the β polymorph. From this, the number of carbons on the fatty acid

chains comprising the lamella can be calculated and this estimate stands at around 48 to 50

carbons in length. This suggests a 3L spacing within the lamella. The glycerides that comprise

these detected lamella are most likely the C50 and C52 oleic-acid containing di-saturates

(groups B and C). Assuming that the oleic acid in these glycerides is in position 2, the trilayer

packing is not unexpected. In this situation, the oleic acids are interdigitated in the middle of

the trilayer while the ends of the trilayer consist of either the palmitic or stearic acid chains. A

similar trilayer packing can still be achieved even if the oleic acid is in position 1 or 3 instead

of position 25.

A short spacing peak characteristic of the β polymorph (4.54 Å) is observable in the

wide-angle region suggesting the solid phase is in the β polymorph. This is a very unusual

observation given that Oil B (which is structured by TAGs similar to those found in Oil D)

crystallizes into the β’ polymorph. These TAGs are very similar to the TAGs found in cocoa

butter. It is well known that these TAGs (and those in cocoa butter) may crystallize into the β’

polymorph given sufficiently high undercoolings. These TAGs may also crystallize into the β

polymorph if the supersaturation is sufficiently low. The fact that these TAGs crystallized into

the β polymorph suggest that the supersaturation in this system was relatively low. While the

melting point of the pure TAGs will remain unchanged, the presence of a high amount of

liquid phase (which is considerably higher in Oil D than for cocoa butter and for Oil B) may

serve to promote the crystallization of the TAGs into the β polymorph by decreasing the

supersaturation at the crystallization temperature. In this manner, the high amount of liquid

phase essentially dilutes the crystallizing TAGs such that a lower supersaturation is achieved

at 10 °C when compared to Oil B.

The microstructure of Oil D as observed through a polarized light microscope is

shown in Figure 5B. The microstructure of Oil D is very much unlike the microstructure of

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Oil A, Oil B and Oil C. Oil D does not exhibit any needle-like crystals but instead exhibits

granular crystals (roundness = 0.69) with an average Feret diameter of roughly 2.2 ± 2.4 μm.

This unusual morphology, when compared to the other oils thus examined, may be due to the

fact that Oil D crystallizes into the β polymorph instead of the β’ polymorph.

Oil D – Rheological Properties

The viscoelastic properties of Oil D are listed in Table 7. The measured G’ was 3.32 ±

1.20 MPa. This G’ suggests a relatively hard material. As a standard of comparison, hardened

cocoa butter has a G’ of approximately 20 MPa while milkfat at 5 °C has a G’ between 1 to

10 MPa. The ratio of the loss modulus to the storage modulus is 0.20, suggesting that the

mechanical damping by the material is very minimal although slightly higher than that for Oil

A and Oil B. Like Oil C, this is perhaps due to the higher liquid content of Oil D.

As with Oil C, when compared to Oil A and Oil B, the mechanical properties of Oil D

are interesting in that the hardness (using the G’ as a measure) is only slightly lower despite

the relatively low solid fat content of Oil C at the testing temperature (10 °C). Compared to

Oil A and Oil B, which both have a solid fat content of roughly 75 % at 10 °C, Oil C (as well

as Oil D) only has a solid fat content of approximately 50 %.

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Oil E

Oil E – FA and TAG Composition

As can be seen from the fatty acid composition (Table 1), Oil E can be described as a

myristic-palmitic oil with a composition very similar to that of Oil A. The majority of the

fatty acids in Oil E are myristic (15.3 %) and palmitic (35.9 %) acid. Unlike Oil A, however,

Oil E contains very little capric acid (2.35 %) and significantly more oleic (29.50 %) and

linoleic acid (10.20 %). The fatty acid composition of Oil E does not appear to be found in

other known food oils. Palm kernel oil8 has a similar myristic acid content, however, it

contains relatively little palmitic acid, instead containing a high amount of lauric acid.

The triglyceride composition of Oil E is given in Table 4. The TAG analysis shows

that the vast majority (48.66 %) of the triglycerides are di-saturated TAGs containing a single

oleic acid. This TAG group consists of groups A, B, E, I, J, O, CC, GG and II. Of these, the

TAG groups A, B and J (total of 38.07 % area) are most likely responsible for structuring the

fat. The next largest group of TAGs are the TAGs containing two or more unsaturated fatty

acids, which comprise 27.07 % area of the chromatogram. This TAG group consists of groups

C, G, H, L, P, Q, T, X, Y, Z, AA, DD, EE and HH. The disaturated TAGs containing a

single linoleic acid are also present in appreciable quantities (14.48 %). These TAGs consist

of groups D, F, N, S, V and BB. The trisaturates constitute only a very small amount (7.86 %)

of the TAGs present in Oil A and as such, their contribution to the solids content is likely

minimal.

Oil E – Melting Behavior

As with previous examples of the algal oils, the melting point of the fat can be

estimated using literature values of the pure triglycerides present in Oil E. The melting points

of the disaturated TAGs containing a single oleic acid, for the β’ polymorph, are

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approximately between 25 °C to 35 °C. A like examination of the di-saturated TAGs

containing linoleic acid shows that the melting points of these TAGs are in the region

between 25 °C to 30 °C. While data is scarce for the pure component melting points of TAGs

containing more than one unsaturated fatty acid, it can be assumed that these TAGs are

predominantly in the liquid state at ambient temperatures, with the exception of TAG groups

C (OOP) and H (OOM). The high contents of these triglycerides in addition to their relatively

high melting points suggest that these TAGs may conceivably play a role in structuring the

fat. The trisaturated TAGs all have very high melting points in the region between 40 °C to 60

°C. Given that these TAGs are not present in appreciably high quantities, their contribution to

structuring is perhaps very minor.

Figure 1B shows that the melting trace of Oil E exhibits three peak melting

temperatures: 10.6 °C, 27.4 °C and 32.2 °C. The following DSC trace is very similar to the

DSC trace of Oil A. The total melting enthalpy is 63.305 kJ/kg. The first melting peak at 10.6

°C can most likely be attributed to the melting of the TAGs containing two or more

unsaturated fatty acids, particularly groups C and H. As well, it is possible that the disaturated

TAGs containing a single linoleic or oleic acid are also included in this peak, given the size of

the peak. The latter peak at 27.4 °C can be attributed to the melting of the remainder of the

disaturated TAGs containing linoleic acid. The last peak at 32.2 °C can be attributed to the

melting of the high-melting fractions of the disaturated TAGs containing oleic acid as well as

any trisaturated TAGs in the solid state.

The melting profile of Oil E is given in Figure 2B. The melting profile of Oil A shows

that melting is gradual and starts at a temperature of roughly 5 °C. This melting profile is

identical to the melting profile of Oil F. The initial solid fat content at 5 °C is 63.07 %. This

value is approximately equal to the sum of the trisaturated, oleic acid disaturated and the

higher-melting linoleic acid disaturated TAGs (groups D and F). As such, these groups can be

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assumed to form the solid phase of the fat. The liquid component of the fat can be assumed to

consist of the TAGs containing two or more unsaturated fatty acids as well as the di-saturated

TAGs containing linoleic acid.

As the temperature is increased, the solid fat content decreases in what appears to be a

linear fashion. The steep decrease in SFC after heating to 20 °C may be due to the dissolution

of the components with a peak melting temperature of 10.56 °C, which constitutes the largest

peak in the DSC trace. Of the major TAG groups in Oil E, the most likely TAGs that melt in

this region include TAG groups B, C and E. At this stage, the remaining solid components

consist of TAGs belonging to group A. Continued heating to 25 °C presumably results in the

melting of these oleic acid disaturated TAGs. This corresponds to the peak a peak melting

temperature of 27.4 °C in the DSC trace. Heating to 40 °C melts the components within the

32.2 °C peak in the DSC trace, which most likely consists of the high-melting trisaturated

TAG groups.

Oil E – Crystallization Behavior

The DSC crystallization trace (Figure 1B) for Oil E shows two peak crystallization

temperatures at -3.8 °C and 9.8 °C. The onset of crystallization for the first peak occurs

approximately at a temperature of 12 °C. Using the highest peak melting temperature at 32.2

°C as a reference, a high undercooling of approximately 20 °C is required to initiate

crystallization of the highest melting components as with other fats previously observed. On

the basis of the previous discussion of melting points and assuming a required undercooling

of ~15 °C, the first crystallization peak can be attributed to the crystallization of tri-saturates

as well as the high-melting components of the oleic acid-containing di-saturated TAGs.

Likewise, the second crystallization peak (onset of crystallization at approximately 0 °C) can

be attributed to the crystallization of the lower melting components such as the TAGs

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containing two or more unsaturates and the linoleic acid-containing di-saturated TAGs as well

as some of the lower-melting components of the oleic acid-containing di-saturated TAGs. The

TAGs crystallizing in this peak are typically liquid at ambient temperatures and constitute the

liquid phase of the fat.

The crystallization kinetics curve for Oil E is displayed in Figure 3B. Fit parameters to

the single or double Avrami equation are tabulated in Table 6. The final SFC value was

estimated from a single-Avrami fit to be approximately 57.0 %. This value is not altogether

different from the solid fat content at 10 °C (54.0 %) as obtained from the melting profile.

Parameter estimates for the Avrami exponent for this crystallization curve suggest that the

initial crystallizing components grow in a disc-like fashion with sporadic nucleation

nucleation or as a sphere with instantaneous nucleation4. Of the two, it is more likely that

growth occurs as a sphere. The estimates for the second component suggest that growth

occurs in a like manner, i.e. as a disc with sporadic nucleation or as a sphere with

instantaneous nucleation. Of the two, it is more likely that growth occurs as a sphere.

Oil E - Crystal Structure and Microstructure

The XRD spectrum of Oil E is given in Figure 4C. A single long spacing peak at

39.78 Å can be observed in the small-angle region. Higher-order reflections corresponding to

spacings of 20.44 Å (second order) and 13.71 Å (third order) can also be identified.

The long spacings suggest a 2L packing9. For the β’ polymorph, an estimate of 2.32 Å

for every two carbons/ethylene group (taking into account the tilt of the glyceride chain in the

lamella) and an allowance of 4.43 Å for the carbons on the glycerol backbone can be used to

estimate the number of carbons on the fatty acid chains comprising the lamella5. Using these

calculations, it can be seen that the long spacing corresponds to a lamella that is roughly 28 to

30 carbons in length, excluding the glycerol. Given a 2L spacing and the fatty acid

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composition of Oil E, this lamella most likely consists of a bilayer of either myristic acid or

palmitic acid or a mixed bilayer consisting of both myristic acid and palmitic acid much like

Oil A.

It is interesting to note that despite the high content of disaturated TAGs containing

oleic acid, a 3L structure was not observed. This is highly unusual as the vast majority of

TAGs in Oil E contain at least one oleic acid and that the trisaturated TAGs consisting only

of myristic and/or palmitic acid are not present in sufficient quantities to be able to attribute

this peak to these trisaturated TAGs. Given that the X-ray spectra for Oil E also contains

peaks characteristic of the β polymorph, the thickness of the bilayer can be recalculated using

different factors to account for the tilting of the chains. Every two carbons can be

approximated by a length of 2.27 Å for a β polymorph with an allowance of 4.11 Å made for

the carbons on the glycerol backbone. Using these parameters, the new estimate for the

thickness of the bilayer is 30 to 32 carbons. This bilayer thickness is possible from a bilayer

formed by a myristic acid and oleic acid. As well, it must be noted that because of the kink of

the oleic acid chain, the actual number of carbons comprising the layer may be

underestimated, which would suggest that a bilayer formed by oleic acid and palmitic acid is

also possible.

These observations notwithstanding, the observation of a 39.78 Å peak has been

reported10 for POP, the predominant TAG group in Oil E. POP, by itself, exhibits a long

spacing peak of approximately 31 Å. However, when POP is mixed with PPO at equimolar

amounts, a molecular compound in the β polymorph is formed which exhibits a long spacing

of approximately 41 Å. As the observed long spacing peak very closely approximates the

reported long spacing, it suggests that the predominant TAG group (A) in Oil E is actually a

mixture of POP and PPO, which forms a molecular compound.

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Several short spacing peaks characteristic of both the β’ polymorph (3.904 Å and 4.21

Å) and the β polymorph (4.59 Å) are observable in the wide-angle region, which suggests that

some TAGs crystallize into the β’ polymorph while others crystallize into the β polymorph.

The presence of a β polymorph is unusual in that by examining the majority of TAGs

in the fat, one can conclude that the TAGs will crystallize into the β’ polymorph given the

fatty acid diversity in the TAGs present. Indeed, some TAGs have crystallized into the β’

polymorph. The β polymorph is most likely due to the formation of the molecular compound

between POP and PPO mentioned above. As such, the remainder of the TAGs, particularly

those that contain at least one oleic or linoleic acid, crystallize into the β’ form.

The microstructure of Oil E as examined through a polarized light microscope is

shown in Figure 5C. The micrograph shows several crystals with a needle-like morphology

(roundness = 0.63). The average Feret diameter of the crystals is 2.9 ± 3.2 μm. Like Oil A,

Oil B and Oil C, Oil E crystallizes into the β’ polymorph, in which crystals are small and

needle-like6.

Oil E- Rheological Properties

The measured rheological properties for Oil E are presented in Table 7. The measured

G’ was 5.37 ± 3.01MPa. Judging by the scale previously established, this fat is relatively

hard. The ratio of the loss modulus to the storage modulus is 0.12, suggesting that the

mechanical damping by the material is very limited and is similar in magnitude to that of Oil

A and Oil B.

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Oil F

Oil F – FA and TAG Composition

The fatty acid composition of Oil F is reported in Table 1. The fatty acid composition

of Oil F is very similar to that of Oil D. Like Oil D, Oil F can be described as a high-oleic

(44.00 %) oil containing high amounts of long chain fatty acids such as stearic acid (21.39 %)

and palmitic acid (23.24 %). A significant amount of linoleic acid (7.17 %) is also present.

Much like Oil D, the medium-chain fatty acid content of Oil F is relatively low. Oil F has a

very similar fatty acid composition to cocoa butter7. It is much more like cocoa butter than Oil

D is. However, like Oil D, the oleic acid content of Oil F is approximately 25 % more than

what is normally found in cocoa butter. The stearic acid content of Oil F is marginally higher

than that in Oil D but compared to the levels normally found in cocoa butter, the stearic acid

content is still relatively low.

The triglyceride composition of Oil F is given in Table 5. The TAG composition of

Oil F is almost identical to the TAG composition of Oil D. Like Oil D, the TAG composition

of Oil F contains very little trisaturates (comprising only 2.10 % area of the chromatogram)

but is composed predominantly of oleic acid-containing di-saturates. Like Oil D, the

predominant TAG groups in Oil F are the di- and tri-unsaturates, comprising 49.17 % area of

the chromatogram. The di- and tri-unsaturates consist of groups B, C, F, G, I, U, L, M, N, R,

T and AA. The next largest group of TAGs are the oleic acid-containing di-saturates, which

presumably are responsible for structuring the fat. This group of TAGs comprise 39.28 % area

of the chromatogram and consists of TAG groups A, D, E, K, O, P, X and Z. The linoleic

acid-containing di-saturates comprise 8.94 % area of the chromatogram and consist of TAG

groups H, J, K and Y.

Oil F – Melting Behavior

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The melting point of Oil F can be estimated by examining the TAG composition. As

with Oil D, the trisaturates comprise only a very small fraction of Oil F. As such, the melting

behaviour of these TAGs can be ignored assuming that their contribution to the solid content

is negligible. Examining the TAG composition of Oil F, it is obvious that the fat is structured

by oleic acid-containing di-saturates, particularly groups A, D and E. As a group, these

triglycerides have a melting point (for the β polymorph) of approximately 35 °C to 40 °C. The

sum of the % area of these triglycerides (37.23 %) falls short of the expected solid fat content

for Oil F. As such, it is highly likely that other triglycerides in the fat are present in the solid

phase. It is highly likely that the TAGs containing two oleic acids and a saturated fatty acid

such as palmitic or stearic acid (groups B and C) are also present in the solid phase as these

have relatively high melting points considering they are TAGs with an appreciable amount of

unsaturates.

Figure 1B shows that the melting trace of Oil F exhibits three peak melting points:

27.34 °C, 23.37 °C and 12.00 °C, suggesting three melting fractions. The total melting

enthalpy is 63.52 kJ/kg. The first melting peak at 12.0 °C can be attributed to the melting of

some of the di- and tri-unsaturated TAGs (with the exception of groups B and C), which

typically have melting points between 0 °C to 5 °C. As well, the lower-melting components of

the linoleic and oleic acid-containing di-saturates are presumably melting in this peak as well.

The second melting peak at 23.4 °C may be attributed to the melting of the TAGs that contain

palmitic acid, such as those belonging to groups D and B. The latter peak at 27.3 °C may be

assigned to the melting of the TAGs that contain stearic acid such as those belonging to

groups A, C and E.

Figure 2B shows that the melting profile of Oil F is gradual and starts at a temperature

of roughly 5 °C. As with previous fats, the steepest decrease in the SFC occurs between 10 °C

and 20 °C. This melting profile is identical to the melting profile of Oil E. The initial solid fat

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content of Oil F at 5 °C is 58.0 %. The solid components that melt between 5 °C and 20 °C

are most likely the TAGs with two oleic acids and a single saturated fatty acid such as those

belonging to groups B and C. As well, it is highly likely that some of the higher melting oleic

acid disaturated TAGs such as those belonging to groups D and A are melting at this stage.

The melting components within this range are those that are present in the melting peaks at

12.0 °C and 23.4 °C. As the temperature is increased past 20 °C all the way to 40 °C, the

remainder of the TAGs in group A as well as the TAGs in group E melt. This last stage of

melting corresponds to the melting peak and 27.3 °C.

.

Oil F – Crystallization Behavior

The DSC crystallization trace for Oil F (Figure 1B) shows two peak crystallization

temperatures at 12.1 °C and 3.6 °C. The onset of crystallization for the first crystallization

peak occurs approximately at a temperature of 16 °C. A relatively modest undercooling of

approximately 16 °C is required to initiate crystallization of the fat (32 °C – 16°C). This first

peak can most likely be attributed to the crystallization of TAGs such as SOS and POS

(groups E and A, respectively). The onset of the second and much larger peak occurs at a

temperature of approximately 8 °C. This peak can perhaps be attributed to the crystallization

of the lower melting TAGs such as those belonging to groups B, D and C as well as those

TAGs that are normally liquid at ambient temperature.

The crystallization kinetics curve for Oil F is displayed in Figure 3B. Fit parameters to

the double Avrami equation are tabulated in Table 6. The crystallization kinetics curve for Oil

F suggests two crystallizing fractions. Both crystallizing fractions have approximately the

same solids content at roughly 25 % each. The first crystallizing component is most likely

TAGs belonging to groups A, D and E. Much like in cocoa butter, these TAGs crystallize

initially and act as a seed for the crystallization of the remaining TAGs in the second

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crystallizing component, which most likely consist of the lower-melting TAGs that belong to

groups B and C.

The final SFC value as estimated from a single-Avrami fit is approximately 48.68 %.

This value is not altogether different from the solid fat content of the fat at 10 °C (52.2 %) as

obtained from the melting profile. Parameter estimates for the Avrami exponent for the first

crystallizing components suggests that it grows as a rod with instantaneous nucleation

Parameter estimates for the Avrami exponent for the second crystallizing component suggests

that it grows as a sphere with sporadic nucleation. The presence of sporadic nucleation

suggests that the second crystallizing component has a sufficiently low melting point such

that the undercooling is not sufficient to promote a high nucleation rate.

Oil F – Crystal Structure and Microstructure

The XRD spectrum of Oil F is given in Figure 4D and contains many similarities to

the XRD spectrum of Oil D. No single predominant long spacing can be observed in the X-

ray spectra. A long spacing peak at 60.94 Å can be observed with higher-order reflections

corresponding to spacings of 42.03 Å and 31.51 Å also present. Using the equations provided

by Donald Small5, each ethylene group or every two carbons can be approximated by a length

of 2.27 Å for a β polymorph. An allowance of 4.11 Å is given for the carbons on the glycerol

backbone. From this, the number of carbons on the fatty acid chains comprising the lamella

can be calculated and this estimate stands at around 48 to 50 carbons in length. This suggests

a 3L spacing within the lamella. The glycerides that comprise these lamella are most likely

the C50 and C52 oleic-acid containing di-saturates (groups A, D and E) as well as the TAGs

containing two or more oleic acids with a single saturated fatty acid (groups B and C). By

assuming that the oleic acid in these glycerides is in position 2, the trilayer packing is not

unexpected. In this situation, the oleic acids are interdigitated in the middle of the trilayer

while the ends of the trilayer consist of either the palmitic or stearic acid chains. A similar

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trilayer packing can still be achieved even if the oleic acid is in position 1 or 3 instead of

position 25.

A short spacing peak characteristic of the β polymorph (4.54 Å) is observable in the

wide-angle region suggesting the solid phase is in the β polymorph as was found in Oil D.

Like Oil D, it is interesting to note that Oil F crystallizes into the β polymorph while a similar

fat such as Oil B crystallizes into the β’ polymorph. The TAGs in Oil F as well as Oil D may

crystallize into either the β’ or β polymorph under the right undercoolings. The fact that these

TAGs crystallized into the β polymorph suggest that the supersaturation in this system was

relatively low. As well, given that Oil F has a relatively high amount of liquid phase, the β

polymorph may be promoted by decrease in the effective supersaturation at the start of

crystallization. In this manner, the high amount of liquid phase essentially dilutes the

crystallizing TAGs such that a lower supersaturation is achieved at 10 °C when compared to

Oil B.

The microstructure of Oil D as observed through a polarized light microscope is

shown in Figure 5D. The microstructure of Oil D is unlike the microstructure of Oil A, Oil B,

Oil C and Oil E but is relatively similar to the microstructure of Oil D. Like Oil D, Oil F

exhibits granular crystals (roundness = 0.86) with an average Feret diameter of roughly 1.7 ±

2.5 μm. This unusual morphology, when compared to the other oils thus examined, may be

due to the fact that Oil F crystallizes into the β polymorph instead of the β’ polymorph.

Oil F – Rheological Properties

The viscoelastic properties of Oil F are given in Table 7. The measured G’ was 4.93 ±

1.47 MPa. As with the other algal fats, this G’ suggests a relatively hard material. The ratio of

the loss modulus to the storage modulus is 0.20, suggesting that the mechanical damping by

the material is very minimal although slightly higher than that for Oil A and Oil B. Like Oil

C, this is perhaps due to the higher liquid content of Oil D.

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Conclusion: A Comparison of Oil C/Oil D

A similar explanation for the melting profile similarities between Oil C and Oil D as

that for Oil A and Oil B can also be made. Oil C consists mainly of medium chain fatty acids

(and oleic acid) and is structured by trisaturate TAGs containing these fatty acids. Oil D, on

the other hand, consists mainly of oleic acid as well as long chain saturated fatty acids. Oil D

is structured by TAGs that contain a single oleic acid and two long chain saturated fatty acids.

As with Oil A and Oil B, these TAGs have very similar melting ranges and SFC. Both Oil C

and Oil D contain similar proportions of these structurant TAGs and as such, it is not

surprising that these fats have very similar melting profiles and SFC.

Oil C and Oil D have similar mechanical properties despite the difference in the

distribution of the crystalline mass as given by the fractal dimension as well as the difference

in the crystal morphologies between Oil C (which crystallizes into needle-like crystals in the

β’ polymorph) and Oil D (which crystallizes into granular crystals in the β polymorph). As

well, the Avrami exponents of most of the crystallizing components in Oil C and Oil D are

different, which suggests the morphology of the microstructural elements is different. Most of

the TAGs in Oil C grow as a disk (presumably needle-like crystals) while the TAGs in Oil D

grow as a sphere. However, Oil C and Oil D have similar solid fat contents. As well, Oil C

and Oil D have very similar crystal sizes, which would suggest that similarities in this

microstructural feature is sufficient to result in similar mechanical properties despite the

differences in the fractal dimension and crystal morphology. The similarities in the

mechanical properties between Oil C and Oil D can therefore be ascribed to the similarity in

the size of the microstructural elements of the fats despite the differences in the polymorphic

form and morphology of the crystals.

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Conclusion: A Comparison of Oil E/Oil F

Like Oil A/Oil B and Oil C/Oil D, Oil E and Oil F all have very similar functional

properties such as melting profiles and rheological properties despite the differences in their

chemical compositions. The saturated fatty acids in Oil E consists predominantly of myristic

and palmitic acids while the fatty acids in Oil F consists primarily of palmitic and stearic

acid. On this basis, it would have been reasonable to conclude that Oil F will exhibit

behaviour more characteristic of a high-saturates fat, i.e. higher melting point and higher solid

fat content. However, Oil F contains relatively more unsaturated fatty acids than Oil E. Oil F

consists of approximately 50 % unsaturates while Oil E consists of only 40 % unsaturates. As

such, Oil E contains more saturates even though these saturates are shorter than those found

in Oil F.

The TAG composition of Oil E and Oil F are relatively similar. Both contain high

amounts of oleic acid di-saturated TAGs and relatively little trisaturates. The trisaturate

content of Oil E is marginally higher than that of Oil F. With regards to the nature of the

TAGs in each fat, Oil F has relatively higher melting TAGs such as SOS (group E) while Oil

E contains more of the lower melting TAGs such as MOP (group B) and MOM (group E).

Despite this slight difference, the reason why Oil E and Oil F have similar melting profiles

can perhaps be explained by dilution of the solid phase. Despite having high-melting fatty

acids and TAGs, Oil F contains relatively less of these high-melting TAGs than does Oil E,

which, while possessing relatively low-melting TAGs, contain more of these TAGs. In

essence, the presence of higher-melting TAGs in Oil F is balanced by the presence of more

lower-melting TAGs in Oil E. This can perhaps explain the similarity in the melting profiles.

Were the saturated fatty acid content of Oil F to match that of Oil E, it is possible that the

melting profiles would be different.

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The similarity in the mechanical properties of Oil E and Oil F is not obvious from

examining the microstructural features of both fats. Oil E and Oil F contain the same solids

content although this is where the similarities end. Oil E contains relatively larger and more

needle-like crystals than Oil F. As well, the fractal dimensions of both fats are different. As

with Oil C and Oil D, the Avrami exponents are also very different, which reflects the fact

that the microstructure is different. Despite the differences, both Oil E and Oil F have very

similar hardness as given by the G’.

The observed similarities can be explained by a balance of the microstructural features

previously mentioned. As a general rule, the box counting fractal dimension, roundness and

particle size are all inversely proportional to the hardness of a fat. Examining the data, Oil E

will be much harder than Oil F if the magnitude of the box counting fractal dimension and the

particle morphology are both considered. However, if the particle size is considered, Oil F

will be much harder than Oil E due to the smaller particle size. As such, the similarity in

hardness between the two fats is due to the competing effects of all three microstructural

quantities. By virtue of the box-counting fractal dimension and the particle morphology, Oil

E will be much harder while considering the particle size, Oil F will be much harder. These

competing trends result in similar hardnesses for the fats.

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Figures

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.

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3456789

101112

Figure 2. The melting profiles of algal fats crystallized at 10 °C: (A) Oil C (●) and Oil D (■), (B) Oil E(●) and Oil F (■).

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101112

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.

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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.

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101112131415161718192021222324252627282930313233

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.

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Tables

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.

Oil C Oil D Oil E Oil FC8:0 (Cy) 0.15 0.00 0.00 0.00C10:0 (C) 12.6 0.08 2.35 0.01C12:0 (La) 37.4 0.06 0.93 0.03C14:0 (M) 9.84 1.5 15.3 0.7C16:0 (P) 8.11 28.1 35.9 23.24C18:0 (S) 1.67 14.78 3.46 21.39C18:1 (O) 22.5 44.81 29.5 44.0C18:2 (L) 5.78 7.1 10.2 7.17

C18:3 (Ln) 0.36 0.35 0.2 0.14

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Table 2. The Triglyceride Composition of Oil C.Triglyceride n Group % Area

CC: MMP 44 T 0.47O: LaMP + LaLaS 42 T 1.80H: MMLa + CaMP + LaLaP 40 T 4.58D: LaLaM + LaPCa 38 T 8.11A: LaLaLa + CaLaM 36 T 13.15C: LaLaCa 34 T 11.54J: CaCaLa 32 T 3.73X: CaCaCa 30 T 0.78Z: POS 52 DS-O 0.57N: POP + (MOS) 50 DS-O 1.95R: LaSO + MOP 48 DS-O 1.08L: MOM + LaOP 46 DS-O 2.83G: LaOM + CaOP 44 DS-O 5.20B: LaLaO 42 DS-O 11.91E: CaOLa 40 DS-O 6.53T: CaOCa 38 DS-O 0.93U: LaLP + MLM 46 DS-L 0.90V: LaLM 44 DS-L 0.88K: LaLaL (+ CaLM) 42 DS-L 3.00M: CaLLa + LaLnLa 40 DS-L 2.45I: OOO 54 MS 4.06P: OOL 54 MS 1.51W: OOS 54 MS 0.80Y: LLO 54 MS 0.65F: OOP 52 MS 5.22Q: POL 52 MS 1.29AA: OOM 50 MS 0.54S: OOLa 48 MS 0.97BB: LaOL 48 MS 0.51DD: CaOO 46 MS 0.45

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Table 3. The Triglyceride Composition of Oil D.Triglyceride n Group % Area

V:SSP 52 T 0.18S:PPS + SSM 50 T 0.42T:MPS 48 T 0.35W:PPM 46 T 0.18Y:SOLg 60 DS-O 0.06U:LgOP 58 DS-O 0.21F:SOS (+ POA) 54 DS-O 4.87C: POS 52 DS-O 14.71B: POP 50 DS-O 16.58K:MOP 48 DS-O 2.05I:PLS 52 DS-L 2.88H:PLP 50 DS-L 3.21X:OOLg 60 MS 0.08O:OOA 56 MS 0.75D: OOS 54 MS 10.70G:OOO 54 MS 4.68J:SOL 54 MS 2.87L:OOL 54 MS 1.89N:SOL 54 MS 0.94Q:LLS 54 MS 0.67R:LLO 54 MS 0.53A: OOP 52 MS 21.15E:POL 52 MS 6.09P:LLP 52 MS 0.74M:OOM (+ POPo) 50 MS 1.64

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Table 4. The Triglyceride Composition of Oil E.TAG n Group % Area

FF: PPS + SSM + (MPA) 50 T 0.17R: PPP +MPS 48 T 1.08K: PPM + (MMS) 46 T 2.70M:MMP + (LaMS) 44 T 2.07U: MMM + LaMP 42 T 0.94W: CaMP 40 T 0.90II: SOLg + POHx 60 DS-O 0.05GG: SOB + LgOP 58 DS-O 0.17CC: SOS + POA 54 DS-O 0.39J: POS ( + MOA) 52 DS-O 3.22A: POP + (MOS) 50 DS-O 19.47B: MOP + (LaSO) 48 DS-O 15.38E: MOM + LaOP 46 DS-O 5.23I: LaOM + CaOP 44 DS-O 3.44O: CaOM 42 DS-O 1.33N: MLM + LaLP 46 DS-L 1.59S: PLS 52 DS-L 1.06D:PLP + (MLS) 50 DS-L 5.57F: MLP 48 DS-L 4.80V: CaLP 44 DS-L 0.91BB: CaLM 42 DS-L 0.55X: OOL 56 M 0.81Q: OOO 54 M 1.20Y: OOS 54 M 0.76AA: LOL 54 M 0.61DD: SOL 54 M 0.35C: OOP 52 M 9.14G: POL 52 M 4.42P: LLP 52 M 1.26H: OOM (+ POPo) 50 M 4.10L: MOL + PoOL + PoPPo 50 M 2.49T: LLM 50 M 0.96Z: CaOO 46 M 0.61EE: CaOL 46 M 0.33HH: CaLL 46 M 0.13

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Table 5. The Triglyceride Composition of Oil F.Triglyceride n Group % Area

BB: SSA 56 T 0.06W: SSS 54 T 0.30S:SSP 52 T 0.64Q:PPS + SSM 50 T 0.73V:MPS 48 T 0.37Z:SOLg 60 MO 0.11X:LgOP 58 MO 0.27P: SOA + POB 56 MO 0.79E:SOS (+ POA) 54 MO 8.88A: POS 52 MO 17.27D: POP 50 MO 11.08O:MOP 48 MO 0.89K: SLS + (PLA) 54 ML 2.15H:PLS 52 ML 4.24J:PLP 50 ML 2.37Y: PPL 50 ML 0.19AA:OOLg 60 D 0.10N:OOA 56 D 0.95C: OOS 54 D 12.95F:OOO 54 D 5.57I:SOL 54 D 3.55L:OOL 54 D 1.96R:LLS 54 D 0.69T:LLO 54 D 0.59B: OOP 52 D 16.59G:POL 52 D 4.65U:LLP 52 D 0.47M:OOM (+ POPo) 50 D 1.11

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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.

Ymax,1(%) k1(s-n) n1 Ymax,2(%) k2(s-n) n2

Oil C 38.8 ± 0.20 7.54 x 10-5 ± 9.99 x 10-12 1.60 ± 0.01

Oil D 3.50 ± 1.52 (4.64 ± 62.37) x 10-5 1.97 ± 278 37.4 ± 1.85 (6.71 ± 23.99) x 10-9 2.53 ± 0.48Oil E 9.92 ± 0.50 (1.48 ± 5.30) x 10-5 2.36 ± 0.78 34.81 ± 0.84 (7.48 ± 14.93) x 10-9 2.43 ± 0.26Oil F 26.9 ± 3.00 (6.48 ± 6.05) x 10-3 0.68 ± 0.17 25.5 ± 4.76 (1.71 ± 22.25) x 10-13 4.00 ± 1.92

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.

G’ (106Pa) G” (105Pa) δ (°) tan δOil C 6.05±1.10 9.05±1.01 8.57±0.65 0.15Oil D 3.32±1.20 6.35±1.42 11.20±1.51 0.20Oil E 5.37±3.01 5.87±2.21 6.89±2.14 0.12Oil F 4.93±1.47 7.66±2.94 8.65±1.07 0.15

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.

Dbox Feret Diameter (μm) RoundnessOil C 1.41 ± 0.06 2.8 ± 2.7 0.61 ± 0.22Oil D 1.62 ± 0.07 2.2 ± 2.4 0.69 ± 0.23Oil E 1.34 ± 0.05 2.9 ± 3.2 0.63 ± 0.23Oil F 1.64 ± 0.06 1.7 ± 2.5 0.86 ± 0.25

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Supplementary Material: Melting point assignments

TAG Composition of Oil A.TAG n Group % Area Tm (β’, °C)

Y: PPS/PSP + (SSM/SMS) 50 T 0.44 58.7/67.7 + (58.3/58.8)Q: PPP + MPS/PMS/PSM 48 T 2.04 55.7 + > 52.0q1/56.1/55.2-58.3q2

G:PPM/PMP + (MMS/MSM) 46 T 5.52 52.0/48.5-56.1g1 + (49.3/55.2)E:MMP/MPM + (LaMS) 44 T 8.01 48.5/59.5 + (45.5)D:LaMP + LaLaS/LaSLa 42 T 9.03 ~42.0-48.5d1 + 39.8/43.0A:MMLa/MLaM + CaMP + LaLaP/LaPLa 40 T 9.92 42.0/~40.0-45.9a1 + ~38.0-42.0a2 + 43.0/42.5H:LaLaM/LaMLa + LaPCa 38 T 5.39 37.8/49.8 + ~45.3h1

J:CaLaM/CaMLa/LaCaM + PCaCa/CaPCa 36 T 3.55 36.7/30.0-38.0j1/31.0-40.0j2 + ~31.0-38.0j3/36.0N: CaCaM/CaMCa 34 T 2.45 31.0/30.0Z: CaCaLa/CaLaCa 32 T 0.32 26.0/37.7DD: CaCaCa 30 T 0.24 16.8CC: SOS/SSO + (POA) 54 MO 0.25 37.0/41.9 + (?)O: POS/PSO/SPO 52 MO 2.27 33.2-37.0o1/40.0/< 34.6o2

C:POP/PPO + (MOS) 50 MO 9.11 33.2/34.6 + (?)B:MOP/PMO/MPO 48 MO 9.47 ~26.4-34.8b1/< 34.6b2/< 34.6b2

I:MOM/MMO + LaOP/LaPO/PLaO 46 MO 4.70 26.4/< 23.9i1 + 27.0i2/< 29.5i3/?F:CaOP 44 MO 5.77 ?M: CaOM 42 MO 3.15 < ~26.4m1

X: CyOP 42 MO 0.48 ?U: CaOCa/CaCaO 38 MO 0.84 -4.8/4.4V: PLS/SPL/PSL 52 ML 0.82 24.5v1/> 26.5v2/ > 26.5v2

K:PLP/PPL + (MLS) 50 ML 3.50 < ~27.1k1/26.5 + ?L: MLP/MPL/PML + (LaLS) 48 ML 3.41 < ~27.1l1/< ~26.5l2/< ~26.5l2+ ?R: MLM/LMM + LaLP 46 ML 1.80 ?/? + ?P: CaLP/CaPL/PCaL 44 ML 2.23 ?/?/?S: CaLM 42 ML 1.10 ?T: OOP/OPO 52 D 0.85 < 18.5t1/< 19.6t2

BB: POL/PLO/LPO 52 D 0.29 ?/?/?W: OOM/OMO + POPo (?) 50 D 0.55 12.8w1/< 19.6w2+ ?AA: CaOO/OCaO 46 D 0.30 < -0.3aa1/?q1Melting point for MPS not available. Melting point of MPP used as estimate.q2Melting point for PSM not available. Melting point estimated to be between melting points of MSM and MSS.g1Melting point for PMP not available, melting point estimated to be between melting point of PMM and PMS.d1Melting point for LaMP not available, melting point estimated to be between melting point of LMM and PMM.a1Melting point for MLM not available, melting point estimated to be between melting point of MCM and MMM.a2Melting point for CaMP not available, melting point estimated to be between melting point of CaMM and CMS.h1Melting point for LaPCa not available, melting point of LPL used as estimate.j1Melting point for CaMLa not available, melting point estimated to be between melting point of CMC and CMM.j2Melting point LaCaM not available, melting point estimated to be between melting point of CCM and MCM.j3Melting point for PCC not available, melting point estimated to be between melting point of MCC and SCC.o1Melting point for POS not available. Melting point estimated to be between melting point of POP and POS.o2Melting point for SPO not available. Estimate provided is for PPO.b1Melting point for MOP not available, melting point estimated to be between melting point of MOM and POP.b2Melting point for PMO and MPO not available. Melting point of PPO used as an estimate.

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i1Melting point for MMO, β’ polymorph not available. Melting point of β polymorph used as estimate.i2Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph used as estimate.i3Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given as estimate.mlMelting point for CaOM not available. Estimate provided is for MOM.v1Melting point for PLS, β’ polymorph not available. Estimate provided is for the β polymorph.v2Melting point for both SPL and PSL not available. Melting point of PPL used as an estimate.k1Melting point for PLP, β’ polymorph not available. Estimate provided is for β polymorph.l1Melting point for MLP not available. Estimate provided is for PLP, β polymorph.l2Melting point for MPL and PML not available. Estimate provided is the melting point of PPL.t1Melting point for OOP, β’ polymorph not available. Estimate provided is for the β polymorph.t2Melting point for OPO, β’ polymorph not available. Estimate provided is for the β polymorph.w1Melting point for OOM, β’ polymorph not available. Estimate provided is for the β polymorph.w2Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β polymorph.aa1Melting point for CaOO, β’ polymorph not available. Estimate provided is for the β polymorph.

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TAG Composition of Oil B.Triglyceride n Group % Area Tm (β’, °C)

S: PPS/PSP + (MPA) 50 T 0.59 58.7/67.7 + (?)H: PPP + MPS/PMS/PSM 48 T 2.85 55.7 + > 52.0h1/56.1/55.2-58.3h2

I: PPM/PMP + (MMS/MSM) 46 T 2.75 52.0/48.5-56.1i1 + (49.3/55.2)P: SOS/SSO + (POA) 54 MO 0.91 37.0/41.9 +E: POS/SPO/PSO 52 MO 7.34 33.2-37.0e1/40.0/< 34.6e2

A: POP/PPO + (MOS) 50 MO 35.60 33.2/34.6 +D: MOP/PMO/MPO 48 MO 8.44 ~26.4-34.8d1/< 34.6d2/< 34.6d2

N: MPPo + LaOP/LaPO/PLaO 46 MO 1.11 + 27.0n1/< 29.5n2/?U: SSL/SLS + (PLA) 54 ML 0.32 < 35.8u1/< 37.0u2 +J: PLS/SPL/PSL 52 ML 2.24 24.5j1/> 26.5j2/ > 26.5j2

B: PLP/PPL + (MLS) 50 ML 12.94 < 27.1b1/26.5G: MLP/MPL/PML + PoOPo 48 ML 3.33 < ~27.1g1/< ~26.5g2/< ~26.5g2+ ?V: LOL/OLL 54 D 0.25 -39.0/~ -12.3v1

T: SOL/OLS/OSL 54 D 0.48 -3.5/-10.4/?Q: OOO 54 D 0.83 -10.0M: OOS/OSO 54 D 1.16 < 23.5m1/20.5L: OOL/OLO + MMP/MPM 54 D 1.19 < -10.0l1/< -9.5l2 + 48.5/59.5C: OOP/OPO 52 D 8.71 < 18.5c1/< 19.6c2

F: POL/PLO/LPO 52 D 4.02 < -3.5f1/< -10.4f2/R: LLP/LPL 52 D 0.75 -4.2/-3.0K: OOM/OMO + POPo (?) 50 D 1.47 12.8k1/< 19.6k2

O: MOL + PLPo 50 D 1.02 ?

h1Melting point for MPS not available. Melting point of MPP used as estimate.h2Melting point for PSM not available. Melting point estimated to be between melting points of MSM and MSS.i1Melting point for PMP not available, melting point estimated to be between melting point of PMM and PMS.e1Melting point for POS not available. Melting point estimated to be between melting point of POP and POS.e2Melting point for SPO not available. Estimate provided is for PPO.d1Melting point for MOP not available, melting point estimated to be between melting point of MOM and POP.d2Melting point for PMO and MPO not available. Melting point of PPO used as an estimate.n1Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph used as estimate.n2Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given as estimate.u1Melting point for SSL, β’ polymorph not available. Melting of β polymorph used as estimate.u2Melting point for SLS not available. Melting point of SOS used as estimate.j1Melting point for PLS, β’ polymorph not available. Estimate provided is for the β polymorph.j2Melting point for both SPL and PSL not available. Melting point of PPL used as an estimate.b1Melting point for PLP, β’ polymorph not available. Estimate provided is for the β polymorph.g1Melting point for MLP not available. Estimate provided is for PLP, β polymorph.g2Melting point for MPL and PML not available. Estimate provided is the melting point of PPL.v1Melting point for OLL not available. Melting point of LLL used a estimate.m1Melting point for OOS, β’ polymorph not available. Estimate provided is for the β polymorph.l1Melting point for OOL not available. Estimate provided is for OOO.l2Melting point for OLO, β’ polymorph not available. Estimate provided is for the β polymorph.

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c1Melting point for OOP, β’ polymorph not available. Estimate provided is for the β polymorph.c2Melting point for OPO, β’ polymorph not available. Estimate provided is for the β polymorph.f1Melting point for POL not available. Estimate provided is for SOL.f2Melting point for PLO not available. Estimate provided is for SLO.k1Melting point for OOM, β’ polymorph not available. Estimate provided is for the β polymorph.k2Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β polymorph.

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TAG Composition of Oil C.Triglyceride n Group % Area Tm (β’, °C)

CC: MMP/MPM + LaMS 44 T 0.47 48.5/59.5 + 45.5O: LaMP + LaLaS/LaSLa 42 T 1.80 ~42.0-48.5o1 + 39.8/43.0H: MMLa/MLaM + CaMP + LaLaP/LaPLa 40 T 4.58 42.0/~40.0-45.9a1 + ~38.0-42.0a2 +

43.0/42.5D: LaLaM/LaMLa + LaPCa 38 T 8.11 37.8/49.8 + ~45.3h1

A: LaLaLa + CaLaM/CaMLa/LaCaM 36 T 13.15 35.1 + 36.7/30.0-38.0j1/31.0-40.0j2

C: LaLaCa/LaCaLa 34 T 11.54 31.0/> 26.0c1

J: CaCaLa/CaLaCa 32 T 3.73 26.0/37.7X: CaCaCa 30 T 0.78 16.8Z: POS/PSO/SPO 52 MO 0.57 33.2-37.0o1/40.0/< 34.6o2

N: POP/PPO+ (MOS) 50 MO 1.95 33.2/34.6 + (?)R: LaSO/LaOS/OLaS + MOP/PMO/MPO 48 MO 1.08 ?/?/? + ~26.4-34.8b1/< 34.6b2/<

34.6b2

L: MOM/MMO + LaOP/LaPO/PLaO 46 MO 2.83 26.4/< 23.9i1 + 27.0i2/< 29.5i3/?

G: LaOM + CaOP 44 MO 5.20 ? + ?B: LaLaO/LaOLa 42 MO 11.91 15.7/< 16.5b1

E: CaOLa/CaLaO/LaCaO 40 MO 6.53 > -4.8e1/4.4-18.0e2/4.4-18.0e2

T: CaOCa 38 MO 0.93 -4.8U: LaLP + MLM 46 ML 0.90 ?V: LaLM 44 ML 0.88 ?K: LaLaL/LaLLa (+ CaLM) 42 ML 3.00 > 15.5k1/<< 27.1k2+ ?M: CaLLa + LaLnLa 40 ML 2.45 ?I: OOO 54 D 4.06 -10.0P: OOL/OLO 54 D 1.51 > -2.2p1/< -9.5p2

W: OOS/OSO 54 D 0.80 < 23.5w1/20.5Y: LLO 54 D 0.65F: OOP/OPO 52 D 5.22 < 18.5f1/< 19.6f2

Q: POL/PLO/LPO 52 D 1.29 ?/?/?AA: OOM/OMO 50 D 0.54 12.8w1/< 19.6w2

S: OOLa/OLaO 48 D 0.97 < 5.1s1/?BB: LaOL 48 D 0.51 ?DD: CaOO 46 D 0.45 ?

o1Melting point for LaMP not available, melting point estimated to be between melting point of LMM and PMM.

a1Melting point for MLM not available, melting point estimated to be between melting point of MCM and MMM.a2Melting point for CaMP not available, melting point estimated to be between melting point of CaMM and CMS.h1Melting point for LaPCa not available, melting point of LPL used as estimate.j1Melting point for CaMLa not available, melting point estimated to be between melting point of CMC and CMM.j2Melting 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.o1Melting point for POS not available. Melting point estimated to be between melting point of POP and POS.o2Melting point for SPO not available. Estimate provided is for PPO.b1Melting point for MOP not available, melting point estimated to be between melting point of MOM and POP.b2Melting point for PMO and MPO not available. Melting point of PPO used as an estimate.i1Melting point for MMO, β’ polymorph not available. Melting point of β polymorph used as estimate.i2Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph used as estimate.

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i3Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given as estimate.b1Melting point for LaOLa, β’ polymorph not available. Melting point of β polymorph is given as estimate.e1Melting point for CaOLa not available. Melting point estimated to be slightly higher than melting point of CaOCa.e2Melting point for CaLaO not available. Melting point estimated to be between melting point of CaCaO and LaLaO.k1Melting 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.k2Melting 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.p1Melting 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.p2Melting 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.w1Melting 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.f1Melting 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.f2Melting 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.w1Melting point for OOM, β’ polymorph not available. Estimate provided is for the β polymorph.w2Melting point for OMO, β’ polymorph not available. Estimate provided is for OPO, β polymorph.s1Melting point for OOLa, β’ polymorph not available. Estimated provided is for OOLa, β polymorph.

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TAG Composition of Oil D.Triglyceride n Group % Area Tm (β, °C)

V:SSP/SPS 52 T 0.18 64.4/68.0S:PPS/PSP + SSM/SMS 50 T 0.42 62.6/65.3 + 60.9/63.3T:MPS/MSP/PMS 48 T 0.35 58.5/ < 65.3t1/59.6W:PPM/PMP 46 T 0.18 55.8/59.9Y:SOLg 60 MO 0.06 ?U:LgOP 58 MO 0.21 ?F:SOS/OSS (+ POA) 54 MO 4.87 43/> 41.9f1 +C: POS/PSO/SPO 52 MO 14.71 37.1/?/40.2B: POP/PPO 50 MO 16.58 37.2/> 34.6b1

K:MOP/MPO/PMO 48 MO 2.05 27/> 23.9k1/> 23.9k1

I:PLS/PSL/SPL 52 ML 2.88 24.5/< 35.8i1/< 35.8i1

H:PLP/PPL 50 ML 3.21 27.1/>26.5h1

X:OOLg 60 D 0.08 ?O:OOA 56 D 0.75 ?D: OOS/OSO 54 D 10.70 23.5/23.9G:OOO 54 D 4.68 4.8J:SOL/SLO/OSL 54 D 2.87 > -3.5j1/> -10.4j2/?L:OOL/OLO 54 D 1.89 >> -2.2l1/-9.5N:SOL 54 D 0.94 ?Q:LLS 54 D 0.67 ?R:LLO 54 D 0.53 ?A: OOP/OPO 52 D 21.15 18.5/19.6E:POL/PLO/LPO 52 D 6.09 >> 13.3e1/>> 13.2 e2/>> 11.7 e3

P:LLP 52 D 0.74 ?M:OOM (+ POPo) 50 D 1.64 ?

t1Melting point for MSP not available. Melting point estimated to be slightly lower than melting point of PSP.f1Melting 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.b1Melting 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.k1Melting point of MPO not available. Melting point estimated to be slightly higher than the melting point of MMO.i1Melting point of PSL not available. Melting point estimated to be slightly lower than the melting point of SSL.h1Melting 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.j1Melting 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.j2Melting 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.l1Melting 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.e1Melting 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.e2Melting 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.e3Melting 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.

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TAG Composition of Oil E.Oil E

TAG % Area n Group Tm (β’, °C)FF: PPS/PSP + SSM/SMS + (MPA) 0.17 50 T 58.7/67.7 + 58.3/58.8 + (?)R: PPP +MPS/PMS/PSM 1.08 48 T 55.7 + > 52.0r1/56.1/55.2-58.3r2

K: PPM/PMP + (MMS/MSM) 2.70 46 T 52.0/48.5-56.1k1 + (49.3/55.2)M:MMP/MPM + (LaMS) 2.07 44 T 48.5/59.5 + (45.5)U: MMM + LaMP 0.94 42 T 45.9 + ~42.0-48.5u1

W: CaMP 0.90 40 T ~38.0-42.0w1

II: SOLg + POHx 0.05 60 MOGG: SOB + LgOP 0.17 58 MOCC: SOS/SSO + POA 0.39 54 MO 37.0/41.9 + (?)J: POS ( + MOA) 3.22 52 MO 33.2-37.0j1/40.0/< 34.6j2 + (?)A: POP/PPO + (MOS) 19.47 50 MO 33.2/34.6 + (?)B: MOP/MPO/PMO+ (LaSO/LaOS/OLaS) 15.38 48 MO 27/> 23.9b1/> 23.9b1 + (?/?/?)E: MOM/MMO + LaOP/LaPO/PLaO 5.23 46 MO 26.4/< 23.9e1 + 27.0e2/< 29.5e3/?I: LaOM + CaOP 3.44 44 MO ? + ?O: CaOM 1.33 42 MO < ~26.4o1

N: MLM + LaLP 1.59 46 ML ? + ?S: PLS/SPL/PSL 1.06 52 ML 24.5s1/> 26.5s2/ > 26.5s2

D:PLP/PPL + (MLS) 5.57 50 ML < ~27.1d1/26.5 + ?F: MLP/MPL/PML 4.80 48 ML < ~27.1f1/< ~26.5f2/< ~26.5f2

V: CaLP/CaPL/PCaL 0.91 44 ML ?/?/?BB: CaLM 0.55 42 ML ?X: OOL/OLO 0.81 56 D < -10.0x1/< -9.5x2

Q: OOO 1.20 54 D -10.0Y: OOS/OSO 0.76 54 D < 23.5y1/20.5AA: LOL/OLO 0.61 54 D -39.0/~ -12.3aa1

DD: SOL/OLS/OSL 0.35 54 D -3.5/-10.4/?C: OOP/OPO 9.14 52 D < 18.5c1/< 19.6c2

G: POL 4.42 52 D ?P: LLP/LPL 1.26 52 D -4.2/-3.0H: OOM/OMO (+ POPo) 4.10 50 D 12.8h1/< 19.6h2

L: MOL + PoOL + PoPPo ? 2.49 50 D ?T: LLM 0.96 50 D < -4.2t1

Z: CaOO 0.61 46 D < -0.3z1/?EE: CaOL 0.33 46 D ?HH: CaLL 0.13 46 D ?

r1Melting point for MPS not available. Melting point of MPP used as estimate.r2Melting point for PSM not availabe. Melting point estimated to be between melting points of MSM and MSS.k1Melting point for PMP not available, melting point estimated to be between melting point of PMM and PMS.u1Melting point for LaMP not available, melting point estimated to be between melting point of LMM and PMM.w1Melting point for CaMP not available, melting point estimated to be between melting point of CaMM and CMS.j1Melting point for POS not available. Melting point estimated to be between melting point of POP and POS.j2Melting point for SPO not available. Estimate provided is for PPO.

b1Melting point of MPO not available. Melting point estimated to be slightly higher than the melting point of MMO.e1Melting point for MMO, β’ polymorph not available. Melting point of β polymorph used as estimate.e2Melting point for LaOP, β’ polymorph not available. Melting point of MOP, β polymorph used as estimate.

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e3Melting point for LaPO, β’ polymorph not available. Melting point of β polymorph is given as estimate.olMelting point for CaOM not available. Estimate provided is for MOM.s1Melting point for PLS, β’ polymorph not available. Estimate provided is for the β polymorph.s2Melting point for both SPL and PSL not available. Melting point of PPL used as an estimate.d1Melting point for PLP, β’ polymorph not available. Estimate provided is for β polymorph.f1Melting point for MLP not available. Estimate provided is for PLP, β polymorph.f2Melting point for MPL and PML not available. Estimate provided is the melting point of PPL.x1Melting point for OOL not available. Estimate provided is for OOO.x2Melting point for OLO, β’ polymorph not available. Estimate provided is for the β polymorph.y1Melting point for OOS, β’ polymorph not available. Estimate provided is for the β polymorph.aa1Melting point for OLL not available. Melting point of LLL used a estimate.c1Melting 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.c2Melting 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.h1Melting point for OOM, β’ polymorph not available. Estimate provided is for the β polymorph.h2Melting 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.z1Melting point for CaOO, β’ polymorph not available. Estimate provided is for the β polymorph.

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TAG Composition of Oil FTriglyceride n Group % Area Tm (β, °C)

BB: SSA/SAS 56 T 0.06 ~70.7bb1

W: SSS 54 T 0.30 72.5S:SSP/SPS 52 T 0.64 64.4/68.0Q:PPS/PSP + SSM/SMS 50 T 0.73 62.6/65.3 + 60.9/63.3V:MPS/MSP/PMS 48 T 0.37 58.5/ < 65.3v1/59.6Z:SOLg 60 MO 0.11 ?X:LgOP 58 MO 0.27 ?P: SOA + POB 56 MO 0.79 41.5 + ?E:SOS/OSS (+ POA) 54 MO 8.88 43/> 41.9e1 +A: POS/PSO/SPO 52 MO 17.27 37.1/?/40.2D: POP/PPO 50 MO 11.08 37.2/> 34.6d1

O:MOP/MPO/PMO 48 MO 0.89 27/> 23.9o1/> 23.9o1

K: SLS/SSL + (PLA) 54 ML 2.15 < 35.8k1/< 37.0k2+ ?H:PLS/PSL/SPL 52 ML 4.24 24.5/< 35.8h1/< 35.8h1

J:PLP 50 ML 2.37 27.1Y: PPL 50 ML 0.19 >26.5y1

AA:OOLg 60 D 0.10 ?N:OOA 56 D 0.95 ?C: OOS/OSO 54 D 12.95 23.5/23.9F:OOO 54 D 5.57 4.8I:SOL/SLO/OSL 54 D 3.55 > -3.5i1/> -10.4i2/?L:OOL/OLO 54 D 1.96 >> -2.2l1/-9.5R:LLS 54 D 0.69 ?T:LLO 54 D 0.59 ?B: OOP/OPO 52 D 16.59 18.5/19.6G:POL/PLO/LPO 52 D 4.65 >> 13.3g1/>> 13.2 g2/>> 11.7 g3

U:LLP 52 D 0.47 ?M:OOM (+ POPo) 50 D 1.11 ?

bb1Melting point for MSP not available. Melting point estimated to be slightly lower than melting point of PSP.v1Melting point for MSP not available. Melting point estimated to be slightly lower than melting point of PSP.e1Melting 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.d1Melting 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.o1Melting point of MPO not available. Melting point estimated to be slightly higher than the melting point of MMO.k1Melting point for SSL, β’ polymorph not available. Melting of β polymorph used as estimate.k2Melting point for SLS not available. Melting point of SOS used as estimate.h1Melting point of PSL not available. Melting point estimated to be slightly lower than the melting point of SSL.y1Melting 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.i1Melting 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.i2Melting 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.l1Melting 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.g1Melting 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.g2Melting 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.

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g3Melting 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.

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References

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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, 2ndedn. CRC Press LLC, Boca Raton, Florida, United States of America, 518 p.

5 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.

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 97-138.

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.

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