Modulation of the thermomechanical properties of fats using surfactants

Transcription

1 Modulation of the thermomechanical properties of fats using surfactants Alejandro Marangoni 1, Nuria Acevedo 1,2 1 Department of Food Science University of Guelph 2 Department of Food Science Iowa State University

2 Representation of the different structural levels present in a fat crystal network d Tuning fork Sn-2 Sn-1 Sn-3 Molecule Acevedo and Marangoni, Crystal Growth and Design, 2010a 2

3 Can we deliver improved functionality of fat by modifying the properties of the nanoscale? 3

4 roll-in shortening 4

5 Intensity, au The shortening 0.46 nm 0.39 nm 0.37 nm

6 Fatty Acid APPS Our GMP GMS BFP shortening 14: : :1c : : :1t :1t :1t :1t :1t :1t :1t :1t :1c :1c :1c :1c :1c :2tt :2t9& :2c9t t,t :2c9-t Fatty Acid APPS Our GMP GMS BFP shortening 20: :3n :1c :3n :2tt CLA : : :5n Trans fat content

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8 Glyceryl Monostearate (GMS) Sorbitan Monostearate (SMS) Polyethylene Glycol Sorbitan Monostearate -Tween 60- (PGMS) Glyceryl Monopalmitate (GMP) Sorbitan Monopalmitate (SMP) Sodium Stearoyl Lactylate (SSL) Phosphatidylcholine (P-CHOLINE) (BFP-75) Caravan 75 BFP Mono and Di Glycerides from hydrogenated palm fat 8

9 Crystallization in a votator FULLY HIDROGENATED SOYBEAN OIL (FHSO) SOYBEAN OIL (SO) 10:90 40:60 (w/w) Votator Configurations No Emulsifier 1% and 3% Emulsifier VESSEL VOTATOR LINE PUMP UNIT A -2 o C UNIT B UNIT C 15 o C 10 o C SAMPLE AB 1. GMS (Glyceryl Monostearate) 2. SSL (Sodium Stearoyl Lactylate) 3. SMS (Sorbitan Monostearate) 4. PGMS (Polyethylene Glycol Sorbitan Monostearate) 5. P-CHOLINE (Phosphatidylcholine) 6. BFP (Mono and Di Glycerides from hydrogenated palm fat) 7. SMP (Sorbitan Monopalmitate) 8. GMP (Glyceryl Monopalmitate) A and C: scraped surface chillers B: working unit SAMPLE ACB SAMPLE ABC 75 SAMPLES CONTROL: HIGH SATURATED AND TRANS FAT ROLL- IN SHORTENING ANALYSIS 9

10 MATERIALS AND METHODS Rheological Properties Small Deformation Tests Thermal Properties Differential Scanning Calorimetry (DSC) ANALYSIS Physical Properties Solid Fat Content (SFC ) Oil Binding Capacity (OMG) Microstructure Polarized Light Microscopy (PLM) Nanostructure Powder X-ray Diffraction (SAXD, WAXD) Cryo-TEM 10

11 SFC SFC (%) SFC (%) SFC (%) SFC (%) SFC (%) :60 NO EMULSIFIER :70 NO EMULSIFIER ab abc ab abc acb Temperature ( C) Temperature ( C) 25 20:80 NO EMULSIFIER 50 CONTROL ab abc acb Temperature ( C) Temperature ( C) abc no E abc noe abc no E Temperature ( C) 11

12 SFC (%) SFC (%) 30 NO EMULSIFIER 25 1%GMS 1%SSL 20 1% PGMS 1% P-CHOLINE 15 1% BFP 1% GMP 10 1% SMP 5 1% SMS 0 30:70 ABC 1%E Temperature ( C) 30 NO EMULSIFIER 25 3%SSL 3%PGMS 3%P-CHOLINE 20 3% BFP 15 3%GMP 3%SMP 10 3%SMS :70 ABC 3%E Temperature ( C) 12

13 OIL BINDING FHSO:SO PROPORTION FAT MIXTURE 10:90 20:80 30:70 40:60 NO EMULSIFIER AB NO EMULSIFIER ABC NO EMULSIFIER ACB OIL MIGRATION (%) 1%GMS AB %GMS ABC %GMS ACB %GMS AB 7.4 3%GMS ABC %GMS ACB %SSL AB %SSL ABC %SSL ACB %SSL AB %SSL ABC %SSL ACB %SMS ABC %SMS ACB %SMS ABC %SMS ACB %PGMS ABC %PGMS ACB %PGMS ABC %PGMS ACB %P-CHOLINE ABC 7.9 1%P-CHOLINE ACB 7.1 3%P-CHOLINE ABC %P-CHOLINE ACB %BFP ABC 5.8 1%BFP ACB 6.9 3%BFP ABC %BFP ACB %SMP ABC %SMP ACB 5.6 3%SMP ABC %SMP ACB 7.8 1%GMP ABC 3.1 1%GMP ACB 3.8 3%GMP ABC %GMP ACB 7.3 SHORTENING CONTROL 2.8 % 13

14 RHEOLOGICAL PROPERTIES G' (MPa) 2.0 ABC ACB 30: % NO EMULSIFIER 1%GMS 1% SSL 3% SSL GMS P-CHOLINE BFP GMP 1% PGMS 3% PGMS 1% P-CHOLINE 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP Control 1% 1% SMS 3% SMS NO EMULSIFIER 1%GMS 1% SSL 3% SSL 1% PGMS 3% PGMS 1% P-CHOLINE P-CHOLINE BFP 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP Control Control 14

15 RHEOLOGICAL PROPERTIES * (Pa) 1500 ABC ACB 30: NO EMULSIFIER 1%GMS 1% SSL 3% SSL 1% PGMS 3% PGMS 1% P-CHOLINE 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP 1% SMS 3% SMS NO EMULSIFIER 1%GMS 1% SSL 3% SSL 1% PGMS 3% PGMS 1% P-CHOLINE 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP Control 1% GMS GMP Control BFP 1% Control GMP

16 MICROSTRUCTURE (PLM) Equivalent Diameter ( m) Control Fat blend ABC ACB 30: µm NO EMULSIFIER 1%GMS 1% SSL 3% SSL 1% PGMS 3% PGMS 1% P-CHOLINE 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP 1% SMS 3% SMS NO EMULSIFIER 1%GMS 1% SSL 3% SSL 1% PGMS 3% PGMS 1% P-CHOLINE 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP Control Control Equivalent Diameter Fat blends GMP m < Control Eq. Diam 16

17 PLM Equivalent Diameter ( m) Equivalent Diameter ( m) Equivalent Diameter ( m) Equivalent Diameter ( m) 2.5 NO EMULSIFIER :80 abc ab abc ab abc acb ab abc acb acb CONTROL NO EMULSIFIER 1%GMS 3%GMS 1% SSL 1%PGMS 1% SMS 3% SMS Control ab 1% GMS ab 1% SSL ab 3% SSL abc 1% GMS abc 3% GMS abc 1% SSL abc 3% SSL acb NO EMULSIFIER acb 1% GMS acb 3% GMS 10:90 acb 1% SSL acb 3% SSL CONTROL NO EMULSIFIER 1%GMS 3%GMS 1% SSL 3% SSL 3%PGMS 20:80 acb 1% SMS 3% SMS Control 17

18 NANOSTRUCTURE FHSO:SO SHORTENING CONTROL 18

19 NANOSTRUCTURE Domain Size (Å) Nano-equivalent Diam. (nm) :70 ABC 20: Fat blends < Control Cryo-TEM NO EMULSIFIER 1%GMS 1% SSL 1% PGMS 1% BFP 1% GMP 1% SMP 1% SMS AB NO EMULSIFIER AB 3%GMS ABC NO EMULSIFIER ACB NO EMULSIFIER ACB 1%GMS CONTROL GMS 1% PGMS BFP Eq. Diam. GMP SMS Length/With ratio Control = 4 Fat blends = :70 ABC 20:80 SAXRD Fat blends Control NO EMULSIFIER 1%GMS 1% SSL 3% SSL 1% PGMS 3% PGMS 1% P-CHOLINE 3% P-CHOLINE 1% BFP 3% BFP 1% GMP 3% GMP 1% SMP 3% SMP 1% SMS 3% SMS NO EMULSIFIER 1%GMS 3%GMS 1% SSL 3% SSL 1%PGMS 3%PGMS 1% SMS 3% SMS CONTROL 19

20 Physical Properties Rheological Properties Thermal Properties Microstructure Nanostructure OMG (%) SFC 20 C (%) G (MPa) * (Pa) T m ( C) H m (J/g) Eq.D (µm) EqD (nm) L/W ratio Polymorphic form CONTROL :60 ABC :70 AB ND ND 30:70 ABC :70 AB 1%GMS :70 ABC 1%GMS 30:70 ACB 1%GMS 30:70 ABC 1%GMP 30:70 ACB 1%GMP 30:70 ABC 1%Pchol. 30:70 ACB 1%Pchol. 30:70 ABC 1%BFP 30:70 ABC 1%BFP ND ND ND ND ND ND ND ND

21 Diffusion Coefficient, D (x m 2 /s) C name number D = 41 ms D = 61 ms D = 41 ms D = 61 ms ABC NO EMULSIFIER ABC NO EMULSIFIER AB NO EMULSIFIER ABC NO EMULSIFIER ABC 1% GMS ACB NO EMULSIFIER ABC 1% SSL ABC 1% SMS ABC 1% PGMS ABC 1% P-CHOLINE ABC 1% BFP ABC 1% SMP ABC 1% GMP REFERENCE SHORTENING 1.59 ± ±

22 Mechanism? Case 1 limited amount of emulsifiers is miscible in fat system. The small amounts of emulsifiers act as impurities and result in imperfections of fat crystals. It will promote or retard polymorphic transformation of fat crystals. Case 2 fats and emulsifiersare highly miscible. In this case, fats-emulsifiers binary phase shows miscible phase behavior or molecular compound formation. Case 3 fats and emulsifiers are totally imiscible in a soild state. In nucleation, emulsifiers may work as seeds of fat crystals under special conditions, foe example, a template film. In crystal growth, the emulsifiers are adsorbed at steps or kninks of fat crystals at crystal-liquid interfaces and inhibit crystal growth and thereby modify crystal morphology. Case 4 emulsion systems; emulsifiers may induce fat emulsifiers interaction. Acceleration of nucleation may occur at the interface of the emulsion onto which the adsorbed hydrophilic emulsifiers become templetes for heteroginious nucleation. Garti, 2002, FOOD EMULSIFIERS:STRUCTURE-REACTIVITY RELATIONSHIPS, DESIGN AND APPLICATIONS. In Physical Properties of Lipids, Marcel Dekker Inc., NY 22

23 Entropy-driven functionalization of the melting behavior of fats T m H S m m P 23

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26 Average of the 63 enthalpies of melting = 30.7 kj/mol 26

27 Temperatures normalized to 37 o C 27

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30 Entropy, not Enthalpy 30

31 Statistical Thermodynamic Proposal 31

32 Isolated System? NVT ensemble 32

33 Microcanonical Ensemble = Statistical Ensemble of Isolated Systems 33

34 Microscopic World S k lnw B n! W k!( n k )! S is the configurational entropy for mixing k imperfections into n lattice sites. W is the number of combinations of k in n, where order is not important. W S 2 1 ln 2 ln 1 ln S S SS kb WS kb WS kb W 2 S1 34

35 For a perfect (GMP) crystal without impurities, k=0 and W=1 n! W k!( n k )! and thus: WSSS 1 S S k lnw SSS impurity SSS B SSS impurity 35

36 Macroscopic World - melting S m H T m m S S S m L S S S ( S S ) ( S S ) m,1 m,2 L1 S1 L2 S 2 ( S S ) ( S S ) S 2 S1 L1 L2 36

37 Macro-micro proposal S S R lnw S S SSS GMP SSS SSS GMP m, SSS m, SSS GMP lnw SSS GMP S S m, SSS m, SSS GMP R 37

38 Can we control epitaxial stacking of lamellae using surfactants? 38

39 Can we make 2D van der Waals heterostructures? 39

40 Engineering epitaxial stacking using surfactants via modulation of surface energy 40

41 How? By control of surface nucleation H f d [001] T 38.5 mj / m T 2V f (001) 2 Compares favourably with Lifshitz model A SS M 2 2 S 3 ε 1 3hν n 1 S kt 4 εs n S SS A / 24 (0.165 nm) 35.0 mj / m SS

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43 Nice Lift! 43

44 Funding Agencies Natural Sciences and Engineering Research Council Canada Research Chairs Program Ontario Ministry of Agriculture and Food Coasun Inc.

45 Thank You! Thank You!