Novel Formulations and Process for Development of...
Transcript of Novel Formulations and Process for Development of...
Novel Formulations and Process for Development of Microencapsulated Krill Oil
CSIRO ANIMAL, FOOD AND HEALTH SCIENCES
L Sanguansri*, Z Shen, S Bhail, LJ Cheng, DY Ying and MA Augustin
AAOCS Omega 3 symposium - Omega-3 Hot Topics: Science, Supply and Sources6-8 November 2013, Newcastle, NSW, Australia
Why Krill Oil
Krill oil (KO) is a premium source of marine omega-3 fatty acids
KO has a unique combination of omega-3 phospholipids and
astaxanthin
KO has inherent emulsifying power due to its phospholipids
Long chain omega-3 fatty acids in KO is susceptible to oxidation
KO has strong flavour and odour-might be unpleasant to some people
(challenge)
Market for KO is expected to be the fastest growing segment in the
global omega-3 ingredient market
Luz Sanguansri3 | *Frost & Sullivan, June 2011
Previous experience with different ω-3 oils - using standard emulsion preparation procedure- using heated protein-CHO as encapsulant
Luz Sanguansri4 |
Powder with different oil
TG PL Emulsion size
(D, 0.5) µm
Powder IP (hr)
@ 80°C
Omega-3 (DHA/ EPA)(g/100 g oil)
Total fat(g/100 g powder)
Surface fat(g/100 g powder)
P1 0.35 23.2 42 (15/27) 50 0.37
P2 0.12 11.8 55 (22/33) 50 0.31
P3 1.20 ~1.4 30 (10/20) 50 16.12
P4 0.45 60.5 30 (25/5) 50 0.62
Oil rich in PL has larger emulsion particle size and higher powder surface fat than triglyceride oils using the same formulation and process conditions
Typical major lipid components of krill oil, algal oil and fish oil
Luz Sanguansri5 |
Krill Oil Algal Oil Fish Oil
Triacylglycerol 40% 94.0% 99%
Diacylglycerol 1.2% 3.0%
Monoacylglycerol <1% <1%
Free fatty acids 4.2% <1% <1%
Total neutral lipids 46.8% 97.0% 99.0%
Phosphatidylcholin 35%
Lyso-phosphatidylcholin 3.1%
Phosphatidyletanolamin 2.1%
Total polar lipids 40.0%
Astaxanthin >200 ppm
KO has ≤40% TAG and ≤40% phospholipids compared to other marine oils (algal oils and fish oils) with >90% TAG
EPA
DHA
Phospholipid Triacylglycerol
Our strategy
Capitalise on the inherent emulsifying properties of krill oil phospholipids
Capitalise on the anti-oxidative properties of heated protein-carbohydrates as encapsulant
Apply chemistry and emulsion/material science capabilities to design the oil-water interface and microcapsule properties
Luz Sanguansri6 |
CSIRO’s Krill Oil Microencapsulation Technology- Emulsification and Spray Drying Process
Luz Sanguansri7 | CSIRO’s Patented Technology
Protein + carbohydrate solution
Krill oil-in-water Emulsion
Adjust pH as required
± Heat Treatment
Add krill oil and homogenise
Spray dry at 180/80°CInlet/outlet temperature
Spray dried Powder:Krill Oil embedded in Protein-
carbohydrate Matrix
Strategy 2Krill Oil
Spray dried Powder:Krill Oil embedded in Protein-
carbohydrate Matrix
Mix water and Krill Oil using high shear mixer
Add protein-carbohydrate solution (60°C) into emulsion
Adjust pH as required
Mix until homogeneous
Spray dry at 180/80°CInlet/outlet temperature
Krill Oil-in-water Emulsion
Neat Krill Oil-in-water Emulsion
Strategy 1
Preparation of phospholipid rich interface
Standard emulsion preparation steps
Particle size distribution and zeta-potential of KO in H2O emulsions (Strategy 1)
Luz Sanguansri8 |
Zeta-potential (mV)
KO emulsions (pH 8) pH 8.0
10% KO neat -50.40±3.3
10% KO in 1% Protein1 -25.9±1.0
10% KO in 2.5% Protein1 -19.3±0.6
10% KO in 3% Heated Protein2-CHO -49.6±3.03
For comparison:10% fish oil in 3% Heated Protein2-CHO -36.5±1.0
• Emulsion stabilised by Protein1 has weaker charge of the oil-water interface
• Emulsion stabilised by Heated protein2 -CHO (MRP) as encapsulant maintained the strong charge of the oil-water interface
10% KO emulsion: neat or in 1% Protein, 2.5% Protein or 3% Heated Protein-CHO
0
2
4
6
8
10
12
14
16
0.01 0.1 1 10 100
Volu
me (
%)
Particle size (µm)
1Isolectric Point = 7-9 (almost no charge at pH8)2Isoelectric Point = 4-5 (negative charge at pH8)
Stability of Krill Oil emulsions during accelerated storage at 40°C
Luz Sanguansri9 |
• pH has no significant effect on oxidation of neat KO in water emulsion during storage
• Encapsulation significantly improved the stability of krill oil-in-water emulsions during storage
• Heated protein-CHO (MRP) encapsulant provided the best protection from oxidation
Analysis of remaining EPA during storage Analysis of remaining DHA during storage Propanal Headspace Analysis during storage
0
50000
100000
150000
200000
250000
300000
GC
are
a o
f p
rop
anal
(x1
0-4
)
Day 11
Day 18
Day 25
50
60
70
80
90
100
% R
em
ain
ing
of
EPA
Day 11
Day 18
Day 25
50
60
70
80
90
100
% R
em
ain
ing
of
DH
A
Day 11
Day 18
Day 25
KO emulsion 17.5 months at 4°C
CSIRO’s Krill Oil Microencapsulation Technology- Strategy 1 vs. Strategy 2
Luz Sanguansri10 | CSIRO’s Patented Technology
Protein + carbohydrate solution
Krill oil-in-water Emulsion
Adjust pH as required
± Heat Treatment
Add krill oil and homogenise
Spray dry at 180/80°CInlet/outlet temperature
Spray dried Powder:Krill Oil embedded in Protein-
carbohydrate Matrix
Strategy 2Krill Oil
Spray dried Powder:Krill Oil embedded in Protein-
carbohydrate Matrix
Mix water and Krill Oil using high shear mixer
Add protein-carbohydrate solution (60°C) into emulsion
Adjust pH as required
Mix until homogeneous
Spray dry at 180/80°CInlet/outlet temperature
Krill Oil-in-water Emulsion
Neat Krill Oil-in-water Emulsion
Strategy 1
Same formulation,Different process
Different in zeta potential (different oil-water interface)
Stability of Krill oil powder during storage at 40°C
Luz Sanguansri11 |
P1 10% KO neat + maltodextrin (Strategy 1)P2 10% KO in 1% protein + maltodextrin (Strategy 1)P3 10% KO in 3% heated protein-carbohydrates + maltodextrin (Strategy 1)P4 10% KO in 3% heated protein-carbohydrates + maltodextrin (Strategy 2)
50
60
70
80
90
100
EPA DHA EPA DHA EPA DHA
Day 0 day 17 Day 28Pe
rce
nta
ge r
em
ain
ing
of
LC-n
-3 P
UFA
s
50% KO P1 50% KO P2 50% KO P3 50% KO P4
0
2
4
6
8
10
12
14
16
50% KO P1 50% KO P2 50% KO P3 50% KO P4
Pro
pan
al G
C a
rea
(x1
0-4
)
Day 0 Day 17 Day 28
Heated protein-CHO (MRP) encapsulant provided the best protection from oxidation during storage
CSIRO’s Microencapsulation Technology- Embedding and Extrusion process
Luz Sanguansri12 |
Add into protein-carbohydrate
High temperature &
high shear Mixing
Extrude through a die
Dry
Apply secondary coating (optional)
Extruded Pellet: Krill Oil embedded in Protein-
carbohydrate Matrix
Krill Oil
Neat Krill Oil-in-water Emulsion
Spray dried Powder:Krill Oil embedded in Protein-
carbohydrate Matrix
Mix water and Krill Oil using high shear mixer
Add protein-carbohydrate solution (60°C) into emulsion
Adjust pH as required
Mix until homogeneous
Spray dry at 180/80°CInlet/outlet temperature
Krill Oil-in-water Emulsion ± additives
CSIRO’s Patented Technology
Extruded samples with Krill Oil (non-expanded)
Luz Sanguansri13 |
KO emulsion embedded in different matrices
KO Content(% dry basis)
Ratio of DHA/EPA
LF1: KO in water emulsion(protein-CHO blend matrix)
8.82 0.51
LF1: KO in water emulsion (heated protein-CHO matrix)
14.14 0.52
LF1: KO in water emulsion (protein matrix)
15.16 0.52
LF1: KO in water emulsion(carbohydrate matrix)
11.88 0.50
LF2: KO in MRP emulsion + PP(carbohydrate matrix)
9.73 0.50
LF3: KO in MRP emulsion (carbohydrate matrix)
7.10 0.50
Up to 15% krill oil was embedded in protein matrix Krill oil emulsions were stable during high temperature & high shear extrusion
Extruded snacks with Krill Oil (expanded)
Luz Sanguansri14 |
KO emulsion embedded in a snack formulation
KO Content(% dry basis)
Ratio of DHA/EPA
KO in water emulsion 7.76 0.51
KO in MRP emulsion + PP 8.53 0.51
KO in MRP emulsion 3.92 0.50
Up to 8.5% krill oil was embedded in extruded expanded snacksKrill oil emulsions were stable during extrusion of expanded snacks
Summary
Microencapsulation enhanced the oxidative stability of krill oil emulsions and spray dried KO powder during storage
The encapsulant formulation and order of processing affect the oil-water interface and stability during storage
Protein or protein-carbohydrate encapsulants enhanced the oxidative stability of KO during storage
Heated protein-carbohydrate encapsulant provided the best protection from oxidation in emulsion and powder
Stabilised KO emulsions are stable to high temperature and high shear extrusion
Luz Sanguansri15 |
CSIRO ANIMAL, FOOD AND HEALTH SCIENCES | PREVENTATIVE HEALTH FLAGSHIP
Thank you
Luz Sanguansri | Research Team Leader, Food Systems EngineeringTel: +61 3 9731 3228 | Email: [email protected]: www.csiro.au
Acknowledgement
Keith Pitts – for the production of extruded samples
Michael Mazzonetto – for production of krill oil powders