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To cite this document: Gerbaud, Vincent and Teles dos Santos, Moises and Carrillo Le Roux, Galo Vegetable oil modeling applied for the formulation of structured lipids. (2012) In: Journées chevreul 2012 : Chimie du végétal et lipochimie, 5-6 Jun 2012, Maison Alfort, France.
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Vegetable oil modeling applied for
the formulation of structured lipids
Vincent Gerbaud
Laboratoire de Génie Chimique, Toulouse
Moises Teles Dos Santos, Galo Carillo Le Roux
Universidad de Sao Paulo (Brasil)
Journées Chevreul 2012 : chimie du végétal et lipochimie
Outline
- Motivations
- SFC : Solid fat content : the core property
- Vegetable Oil modeling• Analysis• Development
- Results• Binary TAGs mixture• Four TAGs mixture• Vegetable oil: 17 TAGs and more..• Oil blends, interesterified or not• Structured lipids application
- Conclusions
Journées Chevreul 2012 : chimie du végétal et lipochi mie2
Motivations
- Growing need for TAG based products = more systematic tools for their design
Journées Chevreul 2012 : chimie du végétal et lipoch imie3
ROSILLO-CALLE, F. et al. A global overview of vegetable oils with reference to biodiesel. Report for the IEA Bioenergy Task 40 (2009)
Our model concerns
food & industrial
uses
Foods
Cosmetics
Lubricants
Cutting fluids
Waxes
Solvents
Vegetable Oil
Solid Fat Content: the core property
- Many evidences that end-user attributes are correlatedwith Solid Fat Content
Journées Chevreul 2012 : chimie du végétal et lipoch imie
Flöter. The role of physical properties data in product development. Eur. J. Lipid Sci. Technol. 2009, 111, 219–226
4
Solid Fat Content: the core property
Journées Chevreul 2012 : chimie du végétal et lipoch imie
Physical Chemical
Attributes (end-user perception)
Macroscopic properties
Microstructure
ProcessingStorage
SFC Polymorphism
CompositionFA TAGs Veg.Oil / Fat
stabilityspreadability texture shine Flavor
Natural sources
End-user
The molecular scale
5
Vegetable Oil modeling
- Datas are not uniform and consistent across the scales.
- Predictive models did not exist so far.
Journées Chevreul 2012 : chimie du végétal et lipoch imie
Physical Chemical
Attributes (end-user perception)
Macroscopic properties
Microstructure
ProcessingStorage
SFC Polymorphism
CompositionFA TAGs Veg.Oil / Fat
stabilityspreadability texture shine Flavor
Natural sources
Data (SP, Tm)
Data (FAME) Data Data
Data
Data (NMR) Data
QSPRcorrelations
6
(IV)
- A predictive model for the missing links: • SFC vs Veg. Oil composition
• By using FA distribution or TAGs composition
Vegetable Oil modeling
Journées Chevreul 2012 : chimie du végétal et lipoch imie7
SFC Polymorphism
CompositionFA TAGs Veg.Oil / Fat
? SFC vs Veg. Oilcomposition
Vegetable Oil modeling
Journées Chevreul 2012 : chimie du végétal et lipoch imie
- Model analysis• SFC calculation
• solid – liquid equilibrium (SLE)– Minimizing the gibbs free energy G
• A very complex mixture pb• Veg. Oils blends
m’ Veg. Oils> 95% of n’ TAGs
combination of 3 FA– Each scale give rise to phase
diagrams, SFC, DSC
• Polymorphism affects the SLE
- The final model must bepredictive to help oil blenddesign
SFC Polymorphism
CompositionFA TAGs Veg.Oil / Fat
8
Liq.
SolidsTAG SLE
The SLE model
- Model INPUT:• Veg. Oil considered as a mixture of n’ TAGs
• Getting TAGs composition?• (rare) from TAGs analysis• (frequent) from FA distribution
– from which we generate a probable TAGs distribution…
- Model OUTPUT:• The TAGs distribution among the phases liquid and solids vs
temperature• Enable to compute SFC and DSC curves
Journées Chevreul 2012 : chimie du végétal et lipochi mie
α β’’
β
α
LIQUID
α β’’
β
α
LIQUID
+ …….
+
+
α β’’
β
α
LIQUID
+
9
The SLE model
- Polymorphic solid(s) – liquid equilibrium
Journées Chevreul 2012 : chimie du végétal et lipoch imie10
)ln( liquidi
nc
i
liquidi
liquid xxRTg ∑=
=1
( )
+
−
∆= ∑
=
)()()(
,
)(,)()( ln jsolid
ijsolid
ijsolidim
jsolidim
nc
i
jsolidi
jsolid xTTR
HxRTg γ11
1
Predicted for each phase Function of TAGs composition),,(& positionFAtypeFApolymorhicfTH mm =∆
∑∑= = ∂
∂∆+
∂∂+=
np
j
nc
i
ijj
i
E
papp
p T
nHm
T
GCC
1 1
∑∑= =
=nc
i
np
j
ji
ji ngnnGwithnG
1 1
)()()(min
- Results:• Solid Fat Content obtained
directly from n TAGphase j
• (equilibrium) DSC curves from:
SLE Results: PPP/OOO vs PPP/CCC
- Molecular size greatly affects crystal lattice and the SLE!
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10
10
20
30
40
50
60
70
Molar fraction (OOO)
Te
mpe
ratu
re (
ºC)
0 10 20 30 40 50 60 700
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Temperature (ºC)
solid
mo
lar
fra
ctio
n
0 10 20 30 40 50 60 700
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Temperature (ºC)
solid
mol
ar fr
actio
n
PPP (C16:0)
OOO (C18:1)
PPP (C16:0)
CCC (C10:0)
SFC
SFC
Phase diagram
-40 -20 0 20 40 60 800
10
20
30
40
50
60
Temperature (ºC)
Cp
[kJ/
mol
.K]
PPP
OOO
PPP + CCCDSC Curve
11
Journées Chevreul 2012 : chimie du végétal et lipochi mie
P: palmitic acid (C16:0) / C: capric acid (C10:0) / O: oleic acid (C18:1)
25% OOO 25% CCC 25% PPP 25% SSS mixture
- Capturing the complexity of TAG behavior in mixture
• OOO and CCC melt together over the same T range • PPP and SSS melt as pure compounds
P: palmitic acid (C16:0) / S: estearic acid (C18:0 ) / C: capric acid (C10:0) / O: oleic acid (C18:1)
12
Journées Chevreul 2012 : chimie du végétal et lipochi mie
-20 0 20 40 60 800
0.2
0.4
0.6
0.8
1
Temperature (ºC)
SF
C (
mas
s)
-20 0 20 40 60 800
500
1000
1500
Temperature (ºC)
Cp
(kJ/
K)
-20 0 20 40 60 800
0.05
0.1
0.15
0.2
0.25
Temperature (ºC)mol
s on
sol
id s
tate
/tota
l of m
ols
-20 0 20 40 60 800
0.05
0.1
0.15
0.2
0.25
Temperature (ºC)mol
s on
liqu
id s
tate
/tota
l of m
ols
PPPSSSCCCOOO
PPPSSSCCCOOO
OOO + CCC PPP SSSSFC DSC Curve
Veg. Oil: Palm oil
- Palm oil: 17 TAGs.
• Melting Point correctly calculated• Good SFC agreement, considering that we used two incoherent
data sources• Exp. Data: TAG composition from Sambanthamurthi R et al. (2000)• Exp. Data: mean SFC from Lin, S.W. (2002)
Journées Chevreul 2012 : chimie du végétal et lipochi mie13
-20 -10 0 10 20 30 40 500
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Temperature (ºC)
SF
C (
mas
s fr
actio
n)
SFC Vs Temperature
-20 -10 0 10 20 30 40 500
1
2
3
4
5
6
Temperature (ºC)
Cp
[kJ/
mol
.K]
Simulated DSC
Veg. Oil: Palm oil
Journées Chevreul 2012 : chimie du végétal et lipoch imie14
- DSC: temperature profile and main phase transitions • We solve S- L Equilibrium = we get equilibrium DSC
• = DSC with infinitely slow heating rate
-20 -10 0 10 20 30 40 500
0.01
0.02
0.03
0.04
0.05
0.06
Temperature ºC
Simulated
Experimental(10 ºC/min)
Experimental(5 ºC/min)
PamPamPam
1 °C/minT7 = 41,51 °C
Oil blends and interesterified blends
- Canola Oil (30%) – Fully Hydrogenated Palm Oil Stearin (70%)
• No reaction: • 96 TAGs
• After interesterification: • 162 TAGs
- Analysis:
• Both physical & interesterifiedblends predictions agree with experimental data
• Predicts the trend at lower temperature
• Reaction makes peaks different and broader
-30 -20 -10 0 10 20 30 40 50 600
2
4
6
8
10
12
14
Temperature (ºC)
Cp
[kJ/
mol
.K]
-30 -20 -10 0 10 20 30 40 50 600
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Temperature (ºC)
SF
C (
mas
s fr
actio
n)
Before reactionAfter reaction
15
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Ternary Veg. Oil blend
- Influence of interesterification• SFC is higher when SFO fraction is low• Interesterification greatly reduces the SFC
Journées Chevreul 2012 : chimie du végétal et lipoch imie16
Not interesterified Interesterified
Solid Fat Content Solid Fat Content
T = 10 ºCPREDICTED in 2 hrs
Palm Oil (PO) Sunflower Oil (SFO)
Palm Kernel Oil (PKO)
(SFO)
(PO) (PKO)
(SFO)
(PO) (PKO)
Structured Lipids Application
- Designing functional foods to get nutraceutical benefits• ex. DHA enhanced products
Journées Chevreul 2012 : chimie du végétal et lipoch imie17
TAG1 TAG2 TAG3 TAG4
sn1 caprylic caprylic caprylic caprylic
sn2 EPA DHA γ-LINOLEIC AA
sn3 caprylic caprylic caprylic caprylic
EPA C20:5
Arachidonic Acid C20:4
γγγγ-linoleic C18:3
Omega-3 Omega-6 Omega-6Omega-3
Medium FA
Medium FA
PUFA
sn2
DHA C22:6
Structured Lipids Application
- High melting SL affects palm oil initial melting T
-20 -10 0 10 20 30 40 50 600
0.2
0.4
0.6
0.8
1
Temperature (ºC)
SF
C (
mas
s fr
actio
n)
pure palm oil
palm oil +SL01 (30%): C8-EPA-C8
palm oil +SL02 (30%): C8-DHA-C8
palm oil +SL03 (30%): C8-g-linolênico-C8
palm oil +SL04 (30%): C8-AA-C8
Teles dos Santos, Gerbaud, Le Roux. Phase Equilibrium and Optimization Tools: Application forEnhanced Structured Lipids for Foods. J Am Oil Chem Soc (2011) 88:223–233.
18
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Structured Lipids Application
- The effect on SFC depends on the T range• Palm oil + (Caprylic – EPA – Caprylic)
-20 -10 0 10 20 30 40 50 600
0.2
0.4
0.6
0.8
1
Temperature (ºC)
SF
C (
mas
s fr
actio
n)pure palm oil
palm oil + SL01 5%
palm oil + SL01 10%
palm oil + SL01 20%
palm oil + SL01 30%
palm oil + SL01 40%
palm oil + SL01 50%
Teles dos Santos, Gerbaud, Le Roux. Phase Equilibrium and Optimization Tools: Application forEnhanced Structured Lipids for Foods. J Am Oil Chem Soc (2011) 88:223–233.
19
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Conclusions
- A knowledge-based predictive model• Solid (multi) – liquid equilibrium based model• Uses FA distribution or TAGs composition data
• FULLY PREDICTIVE model for SFC & equilibrium DSC curves
• Accuracy is good– We need coherent TAG & SFC data to prove that it could be even
better…
• Valid for any TAG mixture: • binary, ternary, vegetable oil, oil blend, interesterified oils
blend
• Not valid for binary FA mixture
Journées Chevreul 2012 : chimie du végétal et lipochi mie20
Teles dos Santos, Gerbaud, Le Roux. Phase Equilibrium and Optimization Tools:Application for Enhanced Structured Lipids for Foods. J Am Oil Chem Soc (2011)88:223–233.
- Computer aided design of oil blends • Finding the blend that matches targeted SFC and DSC • Objective: to anticipate the most promising lab experiments
We are open to
SLE Results: 4 TAGs mixture
- Composition in each phase• Solid phase is gradually enriched with SSS; • OOO fraction gradually decreases in liquid phase
-20 0 20 40 60 800
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Temperature (ºC)
mols
on sol
id/to
tal o
f mols
on s
olid
-20 0 20 40 60 800
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Temperature (ºC)
mols
on liqu
id/to
tal o
f mols on
liqu
id
PPPSSSCCCOOO
PPPSSSCCCOOO
-20 0 20 40 60 80Temperature (ºC)
-20 0 20 40 60 80Temperature (ºC)
-20 0 20 40 60 800
0.05
0.1
0.15
0.2
0.25
Temperature (ºC)mol
s on
sol
id s
tate
/tota
l of m
ols
-20 0 20 40 60 800
0.05
0.1
0.15
0.2
0.25
Temperature (ºC)mol
s on
liqu
id s
tate
/tota
l of m
ols
PPPSSSCCCOOO
PPPSSSCCCOOO
21
Journées Chevreul 2012 : chimie du végétal et lipochi mie
eq - DSC theoretical prediction Vs Experimental Data
1 °C/minT7 = 41,51 °C
C.P. Tan, Y.B. Che Man.Differential scanning calorimetric analysis of palm oil, palm oilbased products and coconut oil: effects of scanning rate variation .Food Chemistry 76 (2002) 89–102
� Palm Oil
22
Journées Chevreul 2012 : chimie du végétal et lipochi mie
A FA-based model could not capture that
Transition Temperatures (ºC)1 2 3 4 5
Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc.
Peanut Oil -51,7 nc* -29,7 -28 -14,57 -11 0,83 2 8,26 7
Grapeseed Oil -39,32 -40 -31,62 -30 -22,82 -21 -15,12 -15 - -
eq - DSC theoretical prediction Vs Experimental Data
Exp Data .: C.P. Tan and Y.B. Che Man . Differential Scanning CalorimetricAnalysis of Edible Oils: Comparison of Thermal Properties and ChemicalComposition. JAOCS, Vol. 77, no. 2 (2000)
Calc .: calculated by VODesign
*nc : no convergence
23
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Single VO: Cocoa Butter
- Cocoa butter: 12 TAGs.• High accuracy for lower temperatures• Shorter melting range corrected detected
• time elapsed: 26s
10 20 30 40 500
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Temperature (ºC)
SF
C (
mas
s fr
actio
n)
SFC Vs Temperature
10 20 30 40 500
1
2
3
4
5
6
7
8
9
10
Temperature (ºC)
Cp
[kJ/
mol
.K]
Simulated DSC
Exp. Data: WON, K. W. THERMODYNAMIC MODEL OF LIQUID-SOLID EQUILIBRIA FOR NATURAL FATS AND OILS. Fluid Phase Equilibria [S.I.], v. 82, p. 261-273, 1993.
PREDICTEDPREDICTED
24
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Unconventional oils
- Milkfat – corn oil (80-20) interesterified : 145 TAGs• Simulated and experimental results in agreement (T > 20 ºC)• Time: 15 min 37 s
0 10 20 30 400
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
(a) Temperature (ºC)
SF
C (
mas
s fr
actio
n)
0 10 20 30 400
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
(b) Temperature (ºC)
Cp
[kJ/
mol
.K]
Exp. Data: RODRIGUES, J. N.; GIOIELLI, L. A. Food Research International, v. 36, n. 2, p. 149-159, 2003.MilkCorn_8020.txt 25
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Unconventional oils
- Theoretical prediction for value-added vegetable oil• Grapeseed Oil: 10 TAGs
-40 -30 -20 -10 00
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
(a) Temperature (ºC)
SF
C (
mas
s fr
actio
n)
-40 -30 -20 -10 00
1
2
3
4
5
6
(b) Temperature (ºC)
Cp
[kJ/
mol
.K]
26
Journées Chevreul 2012 : chimie du végétal et lipochi mie
Influence of Temperature: ternary blend not interesterified
Journées Chevreul 2012 : chimie du végétal et lipoch imie27
PO–SFO–PKO
0 °C 10 °C
15 °C 25 °C
30 °C 35 °C
0.80 0.45
0.35 0.20
0.14 0.09
PREDICTED
Influence of Temperature: ternary blend interesterified
Journées Chevreul 2012 : chimie du végétal et lipoch imie28
PO–SFO–PKO 0 °C 10 °C
15 °C25 °C
30 °C 35 °C
0.90
0.35
0.12
0.50
0.18
0.06
PREDICTED