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TRANSCRIPT
Novel Strategies for
Nanostructuring Liquid Oils
into Functional Fats
Alejandro G. Marangoni
University of Guelph
Novel strategies for structuring liquid oils
Structured
Oil
Fat crystal networks of stearic
acid rich fats in high oleic oils Structuring agent > 40% Polycrystalline fibrillar and
particle organogels Structuring agent 1-8%
Structured emulsions Structuring agent 3-6%
Polymer organogels
Structuring agent 3-10%
Target for “Fats” of the Future….
• Structured emulsions: decreased lipid content
(30-50% water), O/W and W/O emulsions
• Structured oils (oleogels): polymers, self-
assembled amphiphylic small molecules,
structuring fats. Minimum amounts of saturated
fatty acids for functionality
• Ultimate challenge: sustainable and non-
hydrogenated? = no palm oil and no fully
hydrogenated stocks.
Structuring Strategies
Building blocks can be of three types:
• Crystalline Particles and Fibers • monoacylglycerols
• fat crystals (triacylglycerols)
• plant waxes
• high melting emulsifiers
• ceramides
• Crystalline nanofibers • phytosterols + oryzanol
• 12-hydroxystearic acid
• Polymers • physical gels
• chemical gels
Organogels
Definition of a gel
A substance is a gel if it has a
continuous structure with macroscopic
dimensions that is permanent on the time
scale of an analytical experiment and is
solid-like in its rheological properties.
Flory, 1974
A gel is an organogel if
The immobilized solvent phase is an
organic liquid (vs. hydrogel)
Proposed SAFIN Organogel Definition
Self-standing, thermoreversible,
anhydrous, viscoelastic
materials structured by a three-
dimensional supramolecular
network of self-assembled small
molecules in an organic liquid at
concentrations no greater than
their percolation threshold,
usually 2% (w/w).
Cholesteryl 4-(2anthryloxy) butanoate in 2-octanol
Twisted fiber cross-section is 26.3 nm by 8.2 nm
Terech and Weiss, 1997
SAFIN microstructure: a polymer
network with an average mesh size
Terech and Weiss, 1997
Percolation and fractal theory scaling laws are obeyed
Reported organogelators relevant to food
applications (true and untrue)
• Lecithin + Sorbitan Tristearate
• Sorbitan monostearate
• Long-chain alcohols + fatty acids (18 carbon
long optimal)
• Glycerol Monostearate
• Phytosterols + Oryzanol
• Long chain, hydroxy fatty acids (12-
hydroxystearic acid or ricinelaidic acid)
• Waxes
• Ceramides
12-hydroxystearic acid (HSA)
Ricinelaidic Acid
H
O H
O
O
OH
O
OH
Directional Crystallization
• Directional Crystallization & SAFiN
Formation
13
Source: Kuwahara and others. 1996. Chemistry Letters. p 435-436.
Source: Terech and others. 1994. Langmuir. p 3406-3418
Fiber structure
Terech and Weiss, 1994
Kuwahara,1996
30µm thick sample of 2.5%HSA stored at 30oC for 24 hours, with slices taken every 3µm and
stacked using a maximum pixel intensity procedure. 100m magnification bar.
17
12-HSA
-10 0 10 20 30 40 500
1
2
3
4
5
Temperature (C)
RE
A (
%)
Fat-like
Translucent-
Opaque Gel
Clear Gel Liquid
REA
Solvent effects
-10 0 10 20 30 40 500
1
2
3
4
5
Temperature (C)
RE
A (
%)
-10 0 10 20 30 40 500
1
2
3
4
5
Temperature (C)
RE
A (
%)
CANOLA
OIL
DAG
OIL
SESAME
OIL
Liquid
Clear-gel
Translucent-opaque gel
Fat-like
Thick Liquid
-10 0 10 20 30 40 500
1
2
3
4
5
Temperature (C)
RE
A (
%)
Effect of setting temperature
on gel properties
30oC 5oC
Temperature Effects on HSA SAFIN structure
5oC
30oC
Bound oil detected by pNMR using
CMPG decay profiles
0 100 200 300 400 5000
25
50
75
100
125
1%
2%
3%
A
5%
Time (Seconds)
Am
pli
tud
e (
a.u
.)
0 100 200 300 400 5000
25
50
75
100
1255C
15C
20C
30C
B
Time (Seconds)
Am
pli
tud
e (
a.u
.)
At 5oC there is a very large amount of highly confined oil and at 30oC there is far
less This supports a highly branched network at 5oC and a more annealed network
at 30oC
Crystallization of Trapped Oil
-50 -45 -40 -350.0
0.1
0.2
0.3
0.4
0.5
0.6
5oC
30oC
Temperature (oC)
Heat
Flo
w (
W/g
)
Enthalpy
Peak
Temp.
Onset
temp.
End
Temp.
Peak
width
J/g oC oC oC oC
5oC 40.77 -43.13 -38.51 -48.40* 9.89*
30oC 40.01 -43.10 -38.92 -49.99* 11.07*
Effect of Storage Temperature on G’
5oC 15
oC 20
oC 30
oC 40
oC
100
1000
10000
100000
1000000
10000000
100000000A
Storage Temperature (oC)
G' (
Pa)
5oC 15
oC 20
oC 30
oC 40
oC
100
1000
10000
100000
1000000
10000000
100000000B
Storage Temperature (oC)
G' (
Pa)
5oC 15
oC 20
oC 30
oC 40
oC
100
1000
10000
100000
1000000
10000000
100000000C
Storage Temperature (oC)
G'(
Pa)
5oC 15
oC 20
oC 30
oC 40
oC
100
1000
10000
100000
1000000
10000000
100000000D
Storage Temperature (oC)
G' (
Pa)
A) 1%HSA, B) 2%HSA, C) 3%HSA, D) 5%HSA
Shear Effects - Static
Edmund Co, M.Sc.
Shear Effects - 400 s-1
Edmund Co, M.Sc.
1 °C per Minute ↑ Slow Cooling Rate Fibrillar Microstructures
Spherulitic Microstructures Fast Cooling Rate
30 °C per Minute ↓
Cooling Rate and
Microstructure
30
Source: XY Liu and PD Sawant. 2002. Advanced Materials 14(6).
Cooling Rate and Mechanical
Properties
31
Oscillatory Shear Strain and Microstructure
Increasing Oscillatory Strain During Crystallization
Low Cooling Rate (1 °C / min)
32
Thickness: 4 μm
20 μm
32 μm
Oscillatory Shear Strain and Microstructure
Increasing Oscillatory Strain & Frequency During Crystallization
High Cooling Rate (30 °C / min)
33
Oscillatory Shear Strain and
Mechanical Properties
34
Oscillatory Shear Strain and
Mechanical Properties
35
Oscillatory Shear Strain and Oil-Binding Capacity
36
Gelation and Crystallization
37
Oscillatory Shear Stress and Mechanical
Properties
38
Oscillatory Shear Stress and Oil-
Binding Capacity
39
Ceramide Organogelator
Sphingolipids, ceramides, glycolipids
C2 Ceramide
C2 Fiber Morphology
2% C-2 ceramide in canola oil or 5% C-24 ceramde in oil
Sphingolipids
Fatty acid content
Fatty acid Egg SM Milk SM
mol%
14:0 ND 3.4
16:0 86.6 23.4
18:0 5.9 2.6
20:0 1.5 0.6
20:4 ND 1.5
22:0 3.0 18.2
23:0 ND 30.0
24:0 3.0 17.7
24:1 ND 2.6
Milk Sphingomyelin treated with
sphinomyelinase
7% sphingomyelin in canola oil
𝛽-sitosterol + 𝛾-oryzanol
Bot and Agterof (2006)
CH3
OH
CH3
CH3
R
CH3
CH3
CH3
O
OOH
O
CH3
beta-sitosterol
R=H campestryl ferulateR=CH3 sitosteryl ferulate- double bond = campestanyl, sitostanyl ferulate
ferulic acid
47
Plant Waxes
Effective at low concentrations (1-4%)
Derived from natural (plant) sources
Commercially/widely available
– Rice Bran Wax (RBX)
– Sunflower Wax (SFX)
– Candelilla Wax (CLX)
– Carnauba Wax (CRX)
48
Critical Concentration (C*)+
Material RBX SFX CLX CRX
Ester Content (%) 92-97 97-100 27-35 84-85
Free Fatty Acid (%) 0-2 0-1 7-10 3-3.5
Free Fatty Alcohol (%) - - 10-15 2-3
Hydrocarbons (%) - - 50-65 1.5-3
Resins/Others(%) 3-8 0-3 - 6.5-10
Melting Point (C) 78-82 74-77 60-73 80-85
Data provided by Koster Keunan Inc.
+ All concentrations recorded as (w/w).
CLX – 2%
CRX – 4%
RBX – 1%
SFX – 1%
49
Brightfield Microscopy at C*
Sample RBX SFX CLX CRX
% Wax (w/w)
1 1 2 4
Avg. Length (um)
16.2 20.4 3.9 19.2
Standard Deviation
+ 4.63 + 6.27 + 0.97 + 7.02
SFX
CLX CRX
RBX
50
X-Ray Diffraction – Neat Waxes
51
Differential Scanning Calorimetry - Tm
30
40
50
60
70
80
90
0 20 40 60 80 100 120
Wax Concentration (w/w)
Tm
(°C
)
RBX
SFX
CLX
CRX
52
Differential Scanning Calorimetry - Tc
30
40
50
60
70
80
90
0 20 40 60 80 100 120
Wax Concentration (w/w)
Tc (
°C)
RBX
SFX
CLX
CRX
53
Differential Scanning Calorimetry – ΔHm (J/g)
0
50
100
150
200
250
0 20 40 60 80 100 120
Wax Concentration (w/w)
En
tha
lpy o
f M
eltin
g (
J/g
)
RBX
SFX
CLX
CRX
54
Differential Scanning Calorimetry – ΔHc (J/g)
0
50
100
150
200
250
0 20 40 60 80 100 120
Wax Concentration (w/w)
En
tha
lpy o
f C
rysta
lliza
tion
(J/g
)
RBX
SFX
CLX
CRX
55
RBX SFX CLX CRX
Concentration 1% Neat 1% Neat 2% Neat 4% Neat
ΔHm (J/g) 1.7 211 5.89 194 1.36 155 5.56 195
ΔSm (mJ/g/K) 4.78 595 16.9 557 25.3 464 15.8 552
SFC 0.95 93.7 1.98 97.8 2.97 99.1 3.43 98.7
Differential Scanning Calorimetry
Sato et al.
56
Controlled Stress Small Deformation Rheology
1.0E+01
1.0E+02
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1 10 100 1000 10000
Osc. Stress (Pa)
G' (P
a)
1% RBX
1% SFX
1% CLX
2% CLX
4% CRX
57
Small deformation rheology: G’ vs.
SFC for 5-10% Gels:
RBX SFX CLX CRX %
Wax SFC
(%)
G’ (Pa) Std. Dev.
(Pa)
SFC
(%)
G’ (Pa) Std. Dev.
(Pa)
SFC
(%)
G’ (Pa) Std.
Dev.
(Pa)
SFC
(%)
G’ (Pa) Std.
Dev.
(Pa)
5 3.64 1.64 x104a
4.912x103
- - - 4.1 4.77x105a
1.04x105
4.47 1.84x105a
1.55x105
6 4.36 2.18x104a
8.2x103
4.87 1.51x105a
5.642x104
4.83 6.19x105a
3.62x105
5.51 1.90x105a
1.49x105
7 5.04 4.88x105abc
2.169x105
5.56 2.08x105a
1.193x105
5.8 9.78x105a
4.08x105
6.44 1.70x105a
4.21x105
8 5.44 1.19x106bd
6.653x105
6.54 2.06x105a
9.855x104
6.66 3.19x105a
6.2x105
7.47 2.65x106b
4.50x105
9 6.01 8.3x105acd
4.387x105
7.34 3.75x105a
1.916x105
7.52 4.04x106bc
4.58x106
8.35 3.09x106b
1.14x106
10 6.91 5.05x105acd
6.018x104
8.33 2.71x105a
2.157x105
8.36 1.68x106ac
8.56x105
9.18 9.51x105a
6.88x105
58
Brightfield Microscopy – 10% Gels
RBX SFX
CLX CRX
59
Brightfield Microscopy – Image Analysis
Sample RBX SFX CLX CRX
% Wax (w/w)
1 10 1 10 1 10 1 10
Avg. Length (um)
16.2 21.1 20.4 37.5 3.9 5.9 19.2 31.3
Standard Deviation
+ 4.63 + 5.95 + 6.27 + 13.63 + 0.97 + 1.48 + 7.02 + 9.53
Needles?
Oil Binding
0 5 10 15 20 25 300
20
40
60
80
0
5
10
15
1%RBX
1%SFX
4%CRX
1%CLX
2%CLX
liquid oil
Time (hrs)
Oil
Lo
st (%
)
Oil Binding
0 5 10 15 20 25 300
20
40
60
80
0
5
10
15
1%RBX
1%SFX
4%CRX
1%CLX
2%CLX
liquid oil
Time (hrs)
Oil
Lo
st (%
)
r2>0.999
Two-step kinetics
PLATEAU (%) 25.98 59.34 50.04 11.72 31.36 9.993
Y0 = 0.0 = 0.0 = 0.0 = 0.0 = 0.0 = 0.0
% FAST 92.28 33.70 46.37 91.32 22.53 46.58
kFAST (h-1)
0.1665 0.3294 0.3053 0.1040 0.3006 9.663
kSLOW (h-1) 3.095 2.872 2.670 1.349 3.017 173.0
Fast half-life (h) 4.164 2.104 2.271 6.663 2.306 0.07173
Slow half-life (h) 0.2239 0.2414 0.2596 0.5139 0.2297 0.004007
1%CLX 1%RBX 1%SFX 2%CLX 4%CRX Free oil
0 1 2(1 ) (1 )FAST SLOWk t k tY Y Y e Y e
64
Oil Binding Mechanism – Porosity
Sample kFAST
[h-1] Fractal
Dimension (Db)
SFC (%)
% Fill
1% RBX 0.330 1.62 0.95 19.3
1% SFX 0.305 1.55 0.97 13.5
2% CLX 0.104 1.75 1.97 29.3
4% CRX 0.301 1.40 3.94 8.41
Oil Binding Mechanism – Porosity and crystal size
Sample kFAST
[h-1] Maximum Leakage
(%)
Fractal Dimension
(Db)
SFC (%)
Porosity (1-fill)
Crystal length (um)
1% RBX
0.330 59.3 1.62 0.95
0.807 16.2
1% SFX
0.305 50.0 1.55 0.97
0.865 20.4
1% CLX
0.166 26.0 1.75 1.97
0.707 3.9
4% CRX
0.301 31.4 1.40 3.94
0.916 19.2
Potential Applications of Edible Oil Organogels
1) Inhibition of oil migration
2) Controlled release of bio-actives
3) Healthy structuring of food lipids
4) Stabilization of w/o emulsions
β-Carotene
β-Carotene, a lipophilic phyto-nutrient
with antioxidant properties, has been
associated with a decreased risk for a
number of chronic diseases.
β-Carotene
Bioavailability of β-C: 10-30%
The presence of dietary fats in the
digestive tract increases the
bioavailability of β-C.
Maximum β-C micellarisation was reached by 30 min for oil; but not until 75 min for gel.
β-Carotene release was significantly delayed by the immobilization of oil within the 12-HSA network.
Healthy Oil Structuring
TAGs : 12-HSA Organogel < Butter and Margarine (p<0.05)
Emulsion Stabilization 0 15 30 120 d1 d2 d4 d7 d14 d21
80:20 +
12-HSA
The addition of 12-HSA to
w/o emulsions
significantly increases
their stability.
Time at 23°C:
80:20
Day 1
Day 7
Day 14
Day 21
80:20:2
Structured emulsions:
Monoglyceride Gels
O C
O
CH3
CH2OH
CH2OH
H
Monoglyceride Monostearin (GMS)
Amphiphillic Molecule
Forms lyotropic liquid crystals in water
+ ionic co-surfactant
MAG + stearic acid in alkaline water
0.00 0.05 0.10 1.4 1.5 1.6
4.18134
89.2
67.2
54.3
194
97.0 64.7
70oC (L)
45oC (L)
268
q (Å-1)
Inte
nsity
Zetzl et al., 2009
Critical Packing Parameter
(Israelachvili, Mitchell, Ninham, 1976)
VS
a l
V= molecular volume
a= hydrated cross sectional area of polar head group
l= molecular length
Sagalowicz, Leser, Watzke and Michel, TIFS 17: 204-214 (2006)
Patented technology - U.S. Patent 7357597
Any oil Hydrogen bonding
between vesicles
Multi-layer monoglyceride
walls interspersed
with water
Any oil
Vesicle Vesicle
Patent Priority date: May 7, 2004
Oil-soluble nutraceuticals and
pharmaceuticals in core
Water-soluble nutraceuticals
and pharmaceuticals in walls
Delivery of Functional Ingredients
Monglyceride multilayers
surrounding oil droplets
0.03 0.08 0.13 0.18 0.23 0.28 0.33
MAG gel
MAGcrystal
d00150Å
A
q (Å-1)
Inte
nsity
1.1 1.3 1.5 1.7 1.9
MAG gel
MAG crystal
MAG in water
q (Å-1)
O
O
O
O
O
O
O
O
O
O
O
O
OH OHOH OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
OH OHOH OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
OH OHOH OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
OH OHOH OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
Presence of liquid crystalline phases of
monoglycerides are necessary for
structure formation
L
Data 1
10
50
100
150
O
O
O
O
O
O
O
O
O
O
O
O
OH O HOH OHOH OHOH OHO H OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
OH OHO H OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
OH OHOH OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
OH OHOH OHOH OHOH OHOH OHOH OH
O
O
O
O
O
O
O
O
O
O
O
O
OHOH OHOH OHOH OHOH OHOH OHOH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHOHOHOH OHOH OHOH OHOH OHOH OHO H O HOH
OHOHO HOH OHOH OH OH OH OH OH OH OH OH OH O H
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHOHOHOH OHOH OHOH OHOH O HOH OHOH OHOH
OHOHOHOH OHOH OH OH OH OH
OH O H O H OH OH OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHO HOHOH OHOH OHOH OHOH OHOH OHOH OHOH
OHO HO HOH OHOH OH OH OH OH OH OH OH OH OH OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHO HO HOH OHOH OHOH OHOH OHOH OHOH O HOH
OHO HO HOH OHOH OH OH OH OH OH OH OH OH OH O H
O
O
OHO H
O
O
OHOH
O
O
OHOH
O
O
OHO H
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
O HOH
O
O
OHOH
O
O
OHO H
O
O
OHOH
O
O
OHOH
O
O
O
O
OH
O
O
OH
O
OHO H
O
OH
O
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHO H
O
O
O HOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
OO O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHO
O
O
O
OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OOH
O
O
OO
O
O
O
O
O
O
O
O
O
O
OH
O
O
OH
O
O
OHOH
O
O
OHOH
O
O
OHO H
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHO H
O
O
O HOH
O
O
OHOH
O
O
OHOH
O
O
O HOH
O
O
OHOH
O
O
OHOH
O
O
O H OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
O H OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
O
O
OH
O
O
OH
O
OH
O
OHO H
O
O
OH
O
OHOH
O
OH
O
O
O
OH
O
O
OHO H
O
O
OHOH
O
O
OHOH
O
O
O HOH
O
O
OHOH
O
O
OHOH
O
O
OHO H
O
O
O HOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
OHOH
O
O
O HOH
O
O
OH OH
O
O
OH O H
O
O
O H OH
O
O
OH O H
O
O
OH O H
O
O
OH OH
O
O
O H OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
OH OH
O
O
O H OH
L L (-gel)-gel
(coagel)
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O HOHOHOH OHO H OHOH OHOH OHOH OHOH OHOH
O HOHOHOH OHO H OH OH OH OH OH OH OH OH OH OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHOHOHOH OHOH OHO H OHOH OHO H OHOH OHOH
OHOHOHOH OHOH OH OH OH OH O H OH OH OH OH OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHOHOHOH OHOH O HOH OHO H OHOH OHOH OHOH
OHOHOHOH OHOH OH O H O H OH OH OH OH OH OH OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OHOHOHOH OHOH OHOH OHOH OHOH O HOH OHO H
OHOHOHO H OHOH OH OH OH OH OH OH OH O H O H OH
-gel coagel
Fluorescence microscopy
Coumarin 6
87
Fresh gel 25°C, 2 weeks 45°C, 2 weeks
100 μm 100 μm 100 μm
Wang and Marangoni, RSC Advances 2014,
Fresh gel
morphology
88
100 μm 100 μm
100 μm
-gel stabilization
• Low-temperature (5oC)
• Specific co-surfactants (SSL)
• Surfactant : Co-surfactant ratio (1:9-1:19)
• Absence of shear
• Slow cooling (hot fill!)
More complete view of phase behavior
Wang and Marangoni, RSC Advances 2014,
So, does it work as a
shortening?
GLUTEN PEAK TESTER
Paddle
Sample Cup
Paddle
SAMPLE GPT CURVE
0
5
10
15
20
25
30
35
40
45
50
0 2 4 6 8 10 12
To
rqu
e (
BE
)
Time (min)
Max Torque (BE)
Peak Max Time (min)
Lift Off Time (min)
Time required for gluten to
aggregate and exhibit maximum
torque on the spindle, before
breaking down
Peak max time with lipid addition
0
1
2
3
4
5
6
0 6 12 18 24 0 6 12 18 24
Tim
e (m
in)
Lipid content (% of flour on equivalent lipid basis)
MAG Gel
Mixture
IE Soy
Oil
Hard Wheat Flour Soft Wheat Flour
The proof is in the danish…
Chocolate Chip Cookie – 50%
Reduction in Sat Fats
101
Structure influences physiological response!
www.coasun.com
Polymer Oleogels
Ethylcellulose
Degree of substitution ↔ Solubility
MAX 3 substitutions
per glucose
W. Koch. J. Indust. Eng. Chem., 1937
5 10 15 20 25 30 35 40 45 50 55
% Ethoxy
Num
ber
of
ethox
y
gro
ups
per
glu
cose
3.0
2.0
1.0
0
Commercial EC ~ 48% C2H5O 2.4 -2.5 DS
Properties are dependent upon the degree of etherification
or substitution (DS)
Polar & non-polar organic solvents
Water
Basic aqueous solution
EC Varieties
• Different varieties – Expressed as a cP value – 10 cP, 45 cP, etc…
• Measured by making a 5% solution – EC in 80% toluene and 20% ethanol
– Measured in a rotational viscometer @ 25 oC
• Extrapolating from the work of Rowe (1985) – 10 cP – 24 kDa
– 45 cP – 57 kDa
– 100 cP – 74 kDa
R. C. Rowe, Int. J. Pharm., 1986, 29, 37–41.
106
Viscosity-MW
viscosity ↔ length of the polymer molecule
(i.e. degree of polymerization)
Indirect measurement of the molar weight of the polymer
Molar weight = k (happ)n
Molar weight ↔ Mechanical properties of the gel
Commercial EC: 4, 10, 22, 45, 100, 300, … [cP]
SEC HPLC
108
EC MW
109
EC Type
Peak Elution
Time (min)
Estimated Mp
(kDa)
4 cP 33.04 11.1
10 cP 32.79 13.0
20 cP 32.26 18.1
45 cP 31.48 29.4
100 cP 31.03 39.0
300 cP 30.10 69.6
Thermal Properties
110
Gel Formation
• Crystalline ethylcellulose added to an oil
• Heated to above the glass transition temperature
– ~ 140oC
• Gels below the gelation
temperature when cooled
• Stable for a year or more t
111
112
140oC
Ethylcellulose Powder
Oleogel Preparation
> Tg
10% 90%
< 30
mins
112
+ surfactant
1:3 w/w
113
Need to go above Tg
Tg
TM
Gel formation now possible
113
Cryo-TEM of EC oleogel after extensive
isobutanol deoiling
EC Oleogels: Oven method
115
Roles of each component
• Polymer strands provide the back-bone for cross-linked
network
• Surfactant acts as a “plasticizer” in gelation process
(different from its well-known ‘micellar solubilization effect’)
• Gelation is a swelling-driven process - Oil acts like a
medium
+ oil
heating
&
stirring
clear
solution
cooling
gel !
Plasticization
• Plasticizer interacts with gel sites, causing the polymer chains to fall apart in certain places
• Causing
• Reduction in Tm (due to reduced
friction and entanglement)
• Reduction in Tg (due to decrease in H-bonding and increase in free volume)
• Increase in permeability
• Advantages are
• lower thermal processing
temperature
• improved thermal stability of composites
• better toughness and flexibility
Gel mechanical properties - methods
• Texture Profile Analysis (Texture Analyzer)
– Samples – 15 mm x 15 mm x 10 mm
– 50 % Compression
– Duplicate batches of 15 samples each
• Back extrusion (Texture Analyzer)
– 30 mm penetration into the sample
– (Approxmately 30 mL in a 50 mL centrifuge tube)
– Duplicate batches of 6 samples each
118
Back Extrusion
119
30 mm
0
20
40
60
80
100
120
0 5 10 15 20 25 30
Fo
rce (
N)
Penetration Distance (mm)
Back extrusion profile
Fmax
Texture Profile Analysis
• TPA:
– Compress sample to 50% of
original height (x2)
– Provides a variety of parameters
• Hardness, chewiness, springiness..
TA-XT2 Texture Analyzer
121
Oil Type
> 60% 18:1
> 53% 18:2
> 55% 18:3
122
123
Viscosity / MW Effect • Canola Oil Oleogels with 10% EC
123
124
Oil x MW Effect 124
FORCE @ 1 MM PENETRATION
125
125
126
Power-law scaling
4%
6%
8%
10%
126
10%
8%
6%
127
SCANNING ELECTRON MICROSCOPY
• Modification of previously utilized techniques by Laredo et al. (2011)
and Dey et al.(2011)
• 3 Different Oil types
– Canola Oil, Soybean Oil, Flaxseed Oil
– Posses a wide range in fatty acid composition
• 2 different EC molecular weights
– 45 cP (10-14%)
– 100 cP (10%)
• Wash the sample surface with a solvent
to expose the oleogel matrix
– Isobutanol
– No fracturing of the sample!!
127
128
SAMPLE PREPARATION
• EC added to oil and heated above glass transition temperature
• Poured onto glass slide during cooling
• After 24 h, various amounts of isobutanol dropped on the gel to
remove surface oil
• Samples were glued to a copper holder, frozen in a liquid nitrogen
slush, sublimated for 30 minutes, and coated with 30 nm of gold
Oleogel Sample
128
129
129
Partial Oil Removal
130
EC Oleogel Microstructure Ref: Zetzl et al., Food Funct., 2012, 3, 327-337.
130
131
Canola Oil
14% 45 cP EC
3.1 mL Isobutanol
131
132
Cryo-scanning electron micrographs of canola oil oleogels (oil partially removed)
132
133 Above oleogels made using:
10 % Ethylcellulose, 45 cP
Washed with 2.4 mL Isobutanol
133
Oil type – microstructure –
mechanical strength
134
Concentration-microstructure-
mechanical strength
Canola Oil Organogels (45 cP) With Varying
Ethylcellulose Concentrations
Above oleogels made using:
Canola Oil, 45 cP Ethylcellulose
Washed with 2.4 mL Isobutanol
y = -0.3804x + 8.1692
R2 = 0.994
134
9%
11%
13%
15%
135
MW-microstructure-mechanical strength
Above oleogels made using:
10 % Ethylcellulose, 45 cP and 100 cP
Washed with 2.4 mL Isobutanol
135
136
Oleogel Use In Frankfurters
• Comminuted (finely ground) meat product
– Very similar to a hot dog
– Typical composition: trimmed meat, added fat,
water/ice, salt, phosphate
136
Sample Preparation
• Frankfurter batters were made using a typical
formulation and processing conditions used in industry
– 25% Fat and 12% protein
• 35 g of prepared batter added to 50 mL centrifuge
tubes
• Cooked to 72 oC in 1.5 hr using a water bath
137
HARDNESS OF
FRANKFURTERS
138
138
CHEWINESS OF
FRANKFURTERS
139
139
140
Canola Oil
Canola Oleogel
Beef Fat
100% replacement of added fat
Fat Globules
140
141
141
Canola Oil Product
- No globules greater than 23 µm
Median Fat Globule Size
- Beef Fat Control: 25 µm
- Canola Oil Oleogel: 7 µm
- Canola Oil Control: 3 µm
142
Advantages of Using Oleogels
• Little to no process modifications required
• Produces products that are texturally similar to animal fat control products
• Clean Label (few ingredients)
– Meat, Salt, Ethylcellulose, Vegetable Oil
• Provides health benefits of mono and polyunsaturated fatty acids
• Added potential for nutraceutical delivery / encapsulation
– Lipid soluble molecules such as lycopene, β-carotene, Vitamin E
142
143
References
• The top 10 causes of death, WHO, 2013
http://who.int/mediacentre/factsheets/fs310/en/index2.html
• R. P.Mensink, P. L. Zock, A. D. M. Kester and M. B. Katan, Am. J. Clin. Nutr., 2003, 77, 1146–1155.
• Mozaffarian D, Clarke R (2009). Quantitative effects on cardiovascular risk factors and coronary heart disease risk of replacing partially hydrogenated vegetable oils with other fats and oils. Eur J Clin Nutr 63(Suppl 2):S22–S33
• EC Structure image from ETHOCEL Handbook, Dow Cellulosics
• R. C. Rowe, Int. J. Pharm., 1986, 29, 37–41.
• T. Laredo, S. Barbut and A. G. Marangoni, Soft Matter, 2011, 7, 2734–2743.
• Dey T, Kim DA, Marangoni AG (2011) Ethylcellulose Oleogels. In: Marangoni AG, Garti N (eds) Edible Oleogels. AOCS Press, Urbana, pp 295-312
• Zetzl et al., Food Funct., 2012, 3, 327-337.
Acknowledgements
Natural Sciences and Engineering Research Council
Canada Research Chairs Program
Ontario Ministry of Agriculture and Food
Coasun Inc.
THANK YOU!
Questions?
?