SOFT MATTERS IN FOOD
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1 SOFT MATTERS IN FOOD Martin E. LESER Product Technology Center Marysville, OH, USA Nestle Research Center Lausanne, Switzerland Neutrons & Food Jan 29 - Feb p. 1
2 Agenda Current Consumer Trends R&D Challenges in Food Industry Conclusions, questions to be answered p. 2
3 Food Industry Transformation Consumer Good Industry Delivering Nutrition, Health and Wellness
4 Consumer Benefits meeting Trends 3 trends shaping consumer attitudes and behaviours Fresh & natural Preventive Personalized Health & well-being Pleasure «for me» Indulgence Premiumization Luxury Convenience Easy to handle On the Go Delivery of solutions
5 Consumer Trends Demand Food as an Integral Delivery System for Nutrition, Health & Wellness
6 The Value Chain in Food The Basis for R&D on Food and Nutrition From the farm to the table 6
7 Food Safety Focus Change in Food Research Product-centered / Commodity-driven Product matches expectations Cost Cost Cost Cost Sensory Nutrition Raw Material Ingredients Preparation Processing PRODUCT Packaging Storage Distribution Home Preparation Eating Delight Body Effects Health Performance Value Value Value Value Quality & Safety Value Soft Refining Bio-inspired Processing **p.o.c. Production Individualization **p.o.c. = point of consumption Consumer-centered / Benefit-driven Product delivers benefits 7
8 Food Structure in the center Product Benefits builds controls Use to create delivery systems Food Structure integrates Functional Ingredients Evidence exists that shows that food structure has an influence on digestion dynamics and nutrient extraction yield
9 Soft Matters in Food! Using Soft Condensed Matter physics concepts allows Food Scientists to significantly better understand the main structural elements building up food materials 9
10 Soft Condensed Matter Through the Eyes of a Food Colloid Scientist What is Soft Condensed Matter? Materials which are easily deformable by external stresses, electric or magnetic fields or thermal fluctuations T.A. Witten in Rev. of Modern Physics 1998 Soft matter occupies a middle ground between two extremes: the fluid state and the ideal solid state. It emerges because the thermal fuctuations that dominate the fluid state coexist with the stringent constraints characteristic of the solid state. P.G. de Gennes in his 1991 Nobel Physics Prize speech Behaviour of soft matter is dominated by one simple fact: they contain mesoscopic structures with sizes between that of a small molecule (H 2 O ~ 0.3 nm) and the beaker containing the material 10
11 R&D Challenges in Food Industry ISFRS Zürich 2009 June 15, 2009 p. 11
12 Food Products are Colloidal Systems, i.e. Soft Condensed Matter Air Bubble in Ice cream Casein micelle network in Yogurt 20 mm Oil droplet Coffee 100 nm Casein micelle in Milk Emulsion droplet in Milk Stabilized by Protein Cubosome as is formed during fat digestion 12
13 Milk - A Hierarchically Designed Natural Product Fat droplet (~ 3-5mm) Casein micelle (~ 0.2mm) Whey proteins (~ 0.015mm). Lactose (~ 0.001mm) Fat droplet membrane lipo-protein - bilayer structures Protein oligomers Tetramer aggregation Supramolecular aggregate Peptide aggregates & Ca phosphate clusters Lactose molecules Increase co-solubility of proteins 13
14 Evolution used hierachical and integrated structures to control digestive dynamics To digest fat droplets, the membrane has to be firstly digested by phospholipases liberating not only the fuel but also membrane building blocks, enzymes, bioactive peptides and nutrients. Transmission Electron microscopy Raw cow milk Complex bio-membrane around fat globule
15 Homogenized & Pasteurized Milk Transmission Electron microscopy M.-L. Dillmann, Nestlé Research Center
16 Structure evolution as function of the lipophilicity of oily ingredients Oil droplet Cubic Phase Vesicle Micelle 100 nm 75 nm 100 nm 50 nm Increase hydrophilicity of lipophilic molecules Making oil molecules more hydrophilic and amphiphilic self-assembly structures are formed (surfactants) Zoo of self-assembly structures can be formed by changing nature of the hydrophilic/lipophilic balance (HLB) of surfactants Are these structures also formed during Digestion of oil dropletys by lipases p. 16
17 Phase diagram: Oleic acid-monoglyceride (in PBS buffer with bile acids) SAXS Experiments Oleic acid and mononoglycerides can form a variety of different self-assembly structures Influence of ph is due to Oleic acid deprotonation Final digestion of oil is expected to produce a ratio 2:1 oleic acidmonoglyceride reversed microemulsion (EME), reversed micellar cubic phase (Fd3m),reversed hexagonal phase (H2), vesicles. PhD S. Salentinig University of Graz, Austria p. 17
18 Experimental design: Digestion of Oil followed by Small Angle X-ray Scattering or light scattering Online investigation of Triolein digestion using Time resolved SAXS. Influence of lipase, ph and bile salts on formed structures during digestion and kinetics can be measured. PhD S. Salentinig University of Graz, Austria p. 18
19 Self-Assembly Structures are formed inside the Oil Droplets During Lipase Digestion Online investigation of Triolein droplet digestion using Time resolved SAXS. Fd3m vesicle EME EMulsion H2 Fd3m Salentinig Phd, Graz university Various self-assembled structures are formed during digestion, i.e, not only vesicles and micelles Self-assembly structures (i.e., interface) are formed inside oil droplets; water and hydrophilic components (e.g. bile salts, lipase) are transported inside the oil droplets enabling digestion of triglycerides inside the oil droplets. PhD S. Salentinig University of Graz, Austria p. 19
20 Casein Micelles - Adhesive Colloids Casein micelles: Self assembled particles with ph-dependent charge density but mainly sterically stabilized Dual binding model of casein micelles D.S. Horne, Int. Dairy J. 8 (1998) 171 D.J. McMahon, W.R. McManus J. Dairy Sci. 81, 2985 (1998) Hairy layer of -casein (extended brush)
21 ph Acid-induced Casein Micelle Aggregation: The yoghurt making process Reducing steric casein stabilisation Ph.D P. Aichinger, Nestlé Research
22 Influence of Milk Processing G' [Pa] Ph.D P. Aichinger, Nestlé Research Heat-treatment 90 C/10min 5 4 Onset of gelation 3 heated unheated 2 1 ph 5.35 ph 4.95 Paar Physica MCR 500, CC27, 0.1Hz, 0.04% strain Time [min] Gelation conditions: 40 C, 3% GDL
23 Multi-angle 3D time resolved static and dynamic LS Mass size I(0), R H 6, RG I(0), R H, R G Decrease in size and mass C. Moitzi R g 1+99 diluted 1+99 I(0) R H 6 R G ph ph Increase in mass Size is still decreasing R R G G /R H,q= R G /R H,q=0 I(0) ph ph Interpretation: Casein micelles are getting smaller and more homogeneous with a higher average density
24 Emulsion resistance to acid-induced Precipitation No DS Mixed emulsions : No DS : 0.1%DS : 0.5%DS : 1% DS 0.1%DS d 43 (mm) 1.0 1% DS ph Static LS Malvern Mastersizer Ph.D L. Jourdain Adsorbed CN-DS complexes protect the emulsion from acid-induced precipitation when 1%DS
25 Whey Protein aggregation, Microgels E.v.d. Linden, P.Venema, COCIS (2007) Schmitt et al. Soft Matter 2010 Negative-staining TEM micrograph from a freshly prepared 4 wt% WPM dispersion. Scale bar is 0.5 µm. Protein structures formed by heat-denatured whey proteins as a function of the ionic strength and difference between the iso-electric point (IEP) of the protein and the ph of the solution. p. 25
26 Some Concluding Remarks Soft Condensed Matter Physics concepts help to understand behaviour of Food Raw Materials and their corresponding processed end products Knowing equilibrium conditions and kinetics of structure (de-structure) formation is essential Future functional food colloids will be developed in the context of Foods as an integral delivery system Using Scattering Methods will significantly help to investigate the multi-structural principles (on different length scales using mixtures of different molecules)
27 Acknowledgements M. Michel, A. Syrbe, J. B, Bezelgues, S. Serieye, L. Sagalowicz, H. J. Watzke, M.L.- Dillmann, M. Rouvet, P. Frossard, S. Acquistapace, C. Appolonia-Nouzille, C. Schmitt, P. Reis, L. Jourdain, H.J. Watzke, E. Kolodziejczyk, E. Hughes, S. Acquistapace, V. Clément, C. Tedeschi, C. Milo R. Miller (Max Planck Institute, Golm, Germany) K. Holmberg (Chalmers University, Gothenburg, Sweden) E. Dickinson, B. Murray (University of Leeds, UK) S. Salentinig, O. Glatter (University of Graz, Austria) C. Moitzi, A, Stradner P. Schurtenberger et al. (University of Fribourg, CH) 27
28 What to do now with my new inventions? 28
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