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Home , Monoglyceride

Fat structuring with partial : effect on solid profiles

Jeroen Vereecken1 Imogen Foubert1 Wouter Meeussen2 Ans Lesaffer2 Koen Dewettinck1

1Ghent University, Ghent, Belgium 2Vandemoortele N.V., Izegem, Belgium

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Introduction and background

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Importance of the solid fat content

• SFC-profile: guideline in judging the suitability of an /fat blend for a particular application • Importance for chocolate: - hardness - fast melting and flavor release - mouth feel at higher temperatures • Importance for /spreads: - spreadability at 5°C - oil exudation - thickness and mouth feel • Wassell and Young (2007): Use of SFC to select TFA-substitutes • Several studies: link between SFC and macroscopic properties => Fat structure based on SFC

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Alternatives to crystalline fat

• In the past: fat structuring based on providing solid fat by regular vegetable and , especially palm oil fractions • New trend: structuring of edible oils by alternatives to crystalline fat (Pernetti et al., 2007) • Examples: - fatty alcohols - waxes - lecithin - sorbitan tristearate (STS) - phytosterols => totally different structure from regular in fats and oils

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be as solid fat providers

• One on backbone Ï amphiphilic neutral molecule • Generally known as emulsifiers in food products • Other applications: - bread improver - antimicrobial agent - stabilization of foams - use in cosmetics

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Monoglycerides as solid fat providers

• Some similarities between monoglycerides and triglycerides: Ï typical crystallisation and melting range Ï formation of a crystal network under certain conditions Ï characterized by a certain polymorphic behaviour Ï fysical properties governed by the fatty acid profile

• Monoglycerides could be used as solid fat providers

• Less difference with triglycerides than other alternatives to crystalline fat

• Important property: higher melting point compared to triglycerides

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Monoglycerides as solid fat providers • Monoglycerides: high melting point compared to triglycerides 90 1-P 80 1,3-PP PPP 70 P Palmitic (1 en 1,3) 2-P Palmitic (2 -en 1,2) 60 Palmitic and oleic 1,2-PP Oleic (1 en 1,3) 50 Oleic (2 en 1,2) 1-O 40 1,3-PO POP PPO 30 1,3-OO Melting point point (°C) Melting 20 O POO 2-O 10 1,2-OO OOO 0 fatty acid

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Objective of the research

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Objective of the research • Study of the feasibility of monoglycerides as solid fat providers • Investigation of the solid fat profile of different monoglyceride blends ‹ Influence of the amount of saturated fatty acids ‹ Influence of the ratio of saturated fatty acids: palmitic/stearic, palmitic/behenic, stearic/ ‹ Influence of the ratio oleic/linoleic acid ‹ Influence of the amount of • Selection of the right monoglyceride mixture to provide solid fat to triglyceride systems • Investigation of the influence of the addition of water

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Experimental setup

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Investigated samples

• Use of commercial monoglycerides: produced by of vegetable oils and distillation to raise monoglyceride content (> 90%)

• SM90FHPos: based on fully hydrogenated palm (saturated)

• SM90FHRso: based on fully hydrogenated rapeseed oil (saturated)

• SM90FHHer: based on fully hydrogenated high eruca rapeseed oil (saturated)

• UM90RRso: based on refined rapeseed oil (unsaturated)

• UM90RSfo: based on refined sunflower oil (unsaturated)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Investigated samples

• UM50HOSf: non distilled sample to study the effect of the amount of diglycerides ‹ Based on high-oleic sunflower oil ‹ Contains around 30% DGL ‹ FA-profile: 81.20% oleic acid, 8.50% linoleic acid

• UM90HOSf: based on refined high oleic sunflower oil (unsaturated) ‹ To study the effect of the addition of water

• Palm oil, palm stearin and rapeseed oil used as triglyceride providers

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Performed analyses and methods

• Chemical analysis of commercial monoglycerides using: – FAME GC: Fatty acid profile – Carbon Number GC: content • Differential scanning calorimetry: reduction of the melting point of saturated monoglycerides in liquid oil • pNMR: evolution of the solid fat content as a function of temperature ‹ Determination of the solid fat profile • Pulsed field gradient NMR: determination of the complete relaxation curve ‹ Study of the influence of the addition of water

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Results and discussion

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Dilution of saturated monoglycerides with rapeseed oil

• Very high melting point of saturated monoglycerides compared to other glycerides • Dilution of monoglycerides with rapeseed oil • Analysis of the dilutions by DSC to derive the melting point of the system • Ideal phase behaviour governed by the Hildebrand equation: ∆H ≈ 1 1 ’ )xln( = ∆ − ÷ with x = mole fraction of the solid component in liquid oil R « Tm T ◊ H = melting enthalpy of the solid component R = universal gas constant = 8.314 J/mol.K

Tm = melting point of the non diluted solid component T = melting point of the diluted solid component LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Dilution of commercial monoglycerides with rapeseed oil

SM90FHRso: distilled monoglycerides based on fully hydrogenated rapeseed oil 78

73

68

63 Melting point (°C) point Melting

58

53 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Mass fraction of SM90FHRso in rapeseed oil Ï Ideal phase behaviour following the Hildebrandt equation

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Fatty acid composition of the investigated samples

Fatty acid SM90FHPos SM90FHRso SM90FHHer UM90RRso UM90RSfo

Palmitic (C16:0) 58.64 6.93 0.97 6.01 7.60 Stearic (C18:0) 39.03 90.21 4.17 1.71 4.71 Behenic (C22:0) 0.05 0.49 84.54 0.14 0.49 Oleic (C18:1) 0.00 0.06 0.06 63.27 22.41 Linoleic (C18:2) 0.00 0.06 0.00 17.79 64.01 SFA 99.79 99.67 97.98 8.80 13.18 => Study of different effects, e.g. ratio P/S, by creating specific mixtures

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of SFA-content on solid fat profile • Variation of SFA by mixing UM90RRso, SM90FHRso and SM90FHPos (ratio palmitic/stearic = 1) 100 15% SFA Different regions: 90 95% SFA 20% SFA 25% SFA ‹ 80 30% SFA below 15°C: small difference 35% SFA between different SFA-levels 70 40% SFA 45% SFA 60 50% SFA ‹ between 15°C and 25°C: huge 50 55% SFA 60% SFA reduction of SFC for low SFA 40 65% SFA levels ( < 40%) 70% SFA 30 75% SFA 80% SFA ‹ above 25°C: gradual reduction 20 Solid (%) content fat Solid 15% SFA 85% SFA of SFC for higher SFA levels 10 90% SFA 95% SFA 0 5 15 25 35 45 55 65 75 For further experiments: 30% SFA Temperature (°C) (level used by health organizations)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of palmitic (P)/stearic (S) ratio on solid fat profile • Variation of palmitic/stearic ratio by mixing UM90RRso, SM90FHRso and SM90FHPos (SFA-content = 30%) 90 80 0.3 P/S Effect at higher temperatures: 0.4 P/S 70 0.5 P/S 0.6 P/S ‹ lower SFC for higher ratios 60 0.7 P/S 0.8 P/S ‹ explanation: higher melting 50 0.9 P/S 1.0 P/S point of compared 40 1.1 P/S P/S = 0.3 1.2 P/S to 30 1.3 P/S 1.4 P/S 20 1.5 P/S Solid (%) Solid fatcontent P/S = 1.7 1.6 P/S 10 1.7 P/S 0 5 15 25 35 45 55 65 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of palmitic (P)/behenic (B) ratio on solid fat profile • Variation of palmitic/behenic ratio by mixing UM90RRso, SM90FHRso, SM90FHPos and SM90FHHer (P/S = 1 and SFA-content = 30%) 90 0.3 P/B 80 0.4 P/B 0.5 P/B 70 0.6 P/B 0.7 P/B Same effect as for ratio P/S 60 0.8 P/B 0.9 P/B 50 1 P/B 1.5 P/B 40 2 P/B P/B = 0.3 3 P/B 30 4 P/B 5 P/B 20 10 P/B Solid fat content (%) fat content Solid P/B = 90 20 P/B 10 50 P/B 90 P/B 0 5 15 25 35 45 55 65 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of stearic (P)/behenic (B) ratio on solid fat profile • Variation of stearic/behenic ratio by mixing UM90RRso, SM90FHRso, SM90FHPos and SM90FHHer (P/S = 1 and SFA-content = 30%) 100 0.3 S/B 0.4 S/B 90 0.5 S/B 80 0.6 S/B 0.7 S/B Same effect as for 70 0.8 S/B ratio P/S and P/B 60 0.9 S/B 1 S/B 50 1.5 S/B 40 2 S/B 3 S/B 30 S/B = 0.3 4 S/B 5 S/B

Solid fat content (%) content fat Solid 20 S/B = 90 10 S/B 10 20 S/B 50 S/B 0 90 S/B 5 15 25 35 45 55 65 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of oleic (O)/linoleic (L) ratio on solid fat profile • Variation of oleic/linoleic ratio by mixing UM90RRso, UM90RSfo, SM90FHRso and SM90FHPos (P/S = 1 and SFA-content = 30%) 90 80 0.4 O/L Effect at lower temperatures: 0.5 O/L 70 0.6 O/L ‹ lower SFC for lower ratios O/L = 3.5 0.7 O/L 60 0.8 O/L 0.9 O/L ‹ explanation: higher melting 50 1 O/L 1.2 O/L point of oleic acid compared 40 1.4 O/L to linoleic acid O/L = 0.4 1.6 O/L 30 1.8 O/L 2 O/L ‹ no difference at higher 20 2.5 O/L Solid fat content (%) fat Solid content 3 O/L temperature because of same 10 3.5 O/L level and type of SFA 0 5 10 15 20 25 30 35 40 45 50 55 60 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of diglycerides (DGL) on solid fat profile

• Variation of diglyceride content by mixing UM50HOSf, UM90RRso, UM90RSfo, SM90FHRso and SM90FHPos (P/S = 1, O/L = 3 and SFA-content = 30%) 90 80 3 DGL 70 4 DGL Effect at lower temperatures: 3% DGL 5 DGL 60 6 DGL 7 DGL ‹ lower SFC for higher DGL 50 8 DGL content 40 9 DGL 10 DGL ‹ explanation: lower melting 30 12 DGL 18% DGL 14 DGL point of DGL compared to 20 16 DGL

Solid fat content (%) fat content Solid MGL 18 DGL 10 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Search for the desired SFC-profile

• Variation of SFC at high temperatures by varying P/S, P/B or S/B ratio • Variation of SFC at low temperatures by varying O/L ratio => specific SFC-profile obtained by selection of the right ratio of P/S and O/L • Investigation of 4 new mixtures of SM90FHRso, SM90FHPos, UM90RRso and UM90RSfo with SFA-content = 30% • H-L: high SFC at low temperatures, low SFC at high temperatures • L-H: low SFC at low tempertures, high SFC at high temperatures • H-H: high SFC at low temperatures, high SFC at high temperatures • L-H: low SFC at low temperatures, low SFC at high temperatures • Comparison with two triglyceride samples: – TGL sample 1: 45% palm oil, 35% palm stearin, 20% rapeseed oil – TGL sample 2: 27% palm oil, 21% palm stearin, 52% rapeseed oil

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Evolution of the SFC-profile of four extreme mixtures 100 90 80 H-L 70 L-H 60 H-H L-L 50 TGL sample 1 TGL sample 2 40 30 Aim: obtain SFC-profile

Solid fat content (%)fat content Solid 20 TGL sample 1 by adding 10 MGL-mixture to TGL 0 sample 2 5 10 15 20 25 30 35 40 45 50 55 60 65 70 Temperature (°C) LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Monoglycerides as solid fat providers

60 55 50 45 40 25% H-L Good correlation 35 33% H-L between TGL 30 50% H-L sample 1 and 50% 25 TGL sample 1 TGL sample 2 20 mixture of H-L and 15 TGL sample 2

Solid fat content (%) fat content Solid 10 5 0 5 10 15 20 25 30 35 40 45 50 55 60 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of water on solid fat profile of monoglycerides

• Addition of 2% water to a system with 20%UM90HOSf (based on high oleic sunflower oil) and 80% triglycerides (30% SFA) 40

35

30

25

UM90HOSf 20 UM90HOSf+2% water + 2% water 15

10

Solid fat content (%) Solidfat content 5

0 5 10 15 20 25 30 35 40 45 50 55 60 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of water on solid fat profile of monoglycerides

• Addition of 2% water to a system with 20% SM90FHRso and 80% triglycerides (30% SFA) 35

30

25 + 2% water 20 SM90FHRso SM90FHRso+2% water 15

10

Solid fat(%) Solid content 5

0 5 15 25 35 45 55 65 75 Temperature (°C)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Influence of water: difference between saturated (SM90FHRso) and unsaturated (UM90HOSf) monoglycerides • Further investigation by a study of the complete relaxation curve (on which an SFC-measurement is based) • Study at 4 temperatures: 5°C, 20°C, 35°C en 50°C

RF Pulse Deadtime

(E11-E70) F SFC= E11 E70 + (E11 -E70) F Solid signal SFCSTD E70 F = (100SFCSTD)(E11 -E70) Liquid signal

E70

0 20 40 60 80 100 120 140 160 180 200

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve UM90HOSf-mixture at 5°C

Sample with 20% UM90HOSf Sample with 20% UM90HOSf + 2% water 1100 After addition of 2% water: 1000 900 • Less strong solid signal 800 700 • Higher remaining liquid 600 signal 500 Ω 400 more protons in the NMR-signal 300 liquid state 200 100 0 0 10 20 30 40 50 60 70 80 90 100110120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve UM90HOSf-mixture at 20°C

Sample with 20% UM90HOSf Sample with 20% UM90HOSf + 2% water 1100 After addition of 2% water: 1000 • Less strong solid signal 900 800 • Higher remaining liquid 700 signal 600 500 Ω more protons in the 400

NMR-signal liquid state 300 200 100 0 0 10 20 30 40 50 60 70 80 90 100110120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve UM90HOSf-mixture at 35°C

Sample with 20% UM90HOSf Sample with 20% UM90HOSf + 2% water 1000 900 800 No difference after addition 700 of 2% water 600 500 400

NMR-signal 300 200 100 0 0 10 20 30 40 50 60 70 80 90 100110120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve UM90HOSf-mixture at 50°C

Sample with 20% UM90HOSf Sample with 20% UM90HOSf + 2% water 1000 900 800 700 • No difference after 600 addition of water 500 • No solid signal anymore 400

NMR-signal 300 200 100 0 0 10 20 30 40 50 60 70 80 90 100 110 120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve SM90FHRso-mixture at 5°C

Sample with 20% SM90FHRso Sample with 20% SM90FHRso + 2% water 1100 1000 900 No difference after addition 800 of 2% water 700 600 500 400 NMR-signal 300 200 100 0 0 10 20 30 40 50 60 70 80 90 100 110 120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve SM90FHRso-mixture at 20°C

Sample with 20% SM90FHRso Sample with 20% SM90FHRso + 2% water 1000 900 800 No difference after addition 700 of 2% water 600 500 400

NMR-signal 300 200 100 0 0 10 20 30 40 50 60 70 80 90 100 110 120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve SM90FHRso-mixture at 35°C

Sample with 20% SM90FHRso Sample with 20% SM90FHRso + 2% water 1000 After addition of 2% water: 900 • Relaxation length of solid 800 signal increased 700 600 • Protons in condition 500 between solid and liquid 400 state? NMR-signal 300 200 • Same liquid signal 100 0 0 10 20 30 40 50 60 70 80 90 100110120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Relaxation curve SM90FHRso-mixture at 50°C

Sample with 20% SM90FHRso Sample with 20% SM90FRso + 2% water 1000 After addition of 2% water: 900 • Relaxation length of solid 800 signal increased 700 600 • Protons in condition 500 between solid and liquid 400 state? NMR-signal 300 200 • Same liquid signal 100 • Difference smaller as for 0 35°C 0 10 20 30 40 50 60 70 80 90 100110120 Time (µs)

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Conclusions

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Conclusions

• Monoglycerides could be used as solid fat providers

• Modification of SFC-profile at high temperatures by varying ratio of saturated fatty acids, e.g. ratio P/S

• Modification of SFC-profile at low temperatures by varying ratio oleic versus linoleic acid or DGL-content

• Different signal when water is present ‹ Reduction at low temperatures for unsaturated monoglycerides ‹ Increase at high temperatures for saturated monoglycerides

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Acknowledgements

• Vandemoortele N.V. is acknowledged for their scientific and financial collaboration and for providing the samples for this research • Especially Wouter Meeussen, Ans Lesaffer and André De Laporte are acknowledged for their contribution to this research

• Palsgaard is acknowledged for providing the sample UM90RRso

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be Fat structuring with partial glycerides: effect on solid fat profiles

Jeroen Vereecken1 Imogen Foubert1 Wouter Meeussen2 Ans Lesaffer2 Koen Dewettinck1

1Ghent University, Ghent, Belgium 2Vandemoortele N.V., Izegem, Belgium

LABORATORY of FOOD TECHNOLOGY and ENGINEERING www.fte.ugent.be