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HAL Id: hal-02097220

https://hal.archives-ouvertes.fr/hal-02097220

Submitted on 5 Jun 2020

HAL is a multi-disciplinary open access archive for the deposit and dissemination of sci- entific research documents, whether they are pub- lished or not. The documents may come from teaching and research institutions in France or

L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires

Protein Interactions / assemblies and subsequent properties

Thomas Croguennec, Marie-Hélène Famelart

To cite this version:

Thomas Croguennec, Marie-Hélène Famelart. Protein Interactions / assemblies and subsequent prop- erties. STLOpendays, Institut National de Recherche Agronomique (INRA). UMR UMR INRA / AgroCampus Rennes : Science et Technologie du Lait et de l’?uf (1253)., Mar 2019, Rennes, France.

�hal-02097220�

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Marie-Hélène FAMELART / Thomas CROGUENNEC Interactions - Structures - Functionalities

STLOpen Days 19-21 March 2019

Protein Interactions / assemblies

and subsequent properties

(3)

• New trends in Europe driven by consumer’s expectations

More natural and healthier food products

100% milk products

(without non-dairy additives)

Innovative products

(new uses and consumption habits)

General introduction

• Additives are currently used to control dairy product quality (texture, heat stability, phase separation,…)

• Milk proteins are customizable into different assemblies

that exhibit different properties (water holding capacity, heat

stability,…) than native proteins → could be used to replace

partly or totality food additives in dairy products

(4)

Dairy manufacturers:

add value to dairy compounds (e.g. aggregated whey proteins)

MILK

CHEESE

(20 millions tonnes)

WHEY

♦ 10% of the milk volume

♦ >80% of the milk proteins (caseins)

♦ 90% of the milk volume

♦ <20% of the milk proteins (whey proteins)

Whey proteins : Large amount available around the world

General Introduction

From waste stream to value-added,

« gutter-to-gold »

Smithers, 2008

- Exceptional biological value (amino acid composition) - Ligand carriers (vitamins, minerals, fatty acids)

- Bioactive proteins and peptides

Excellent for

human nutrition

(5)

1. Whey protein aggregates for controlling emulsion heat stability and texture

2. Whey protein aggregates as texturizing ingredients

Topics of this presentation

(6)

Introduction: Whey protein aggregates for controlling emulsion heat-stability and texture

• Whey proteins : - natural emulsifiers (adsorb to oil/water interface)

- heat-sensitive proteins (heat treatments are required to extent food product shelf life)

→ heat sensitive emulsions

→ texturized (gelled) emulsions

Heat stability of whey protein emulsions (pH 7)

Stable/fluid

Fluid emulsions: Protein amount too low to build

a continuous network Oil droplet

Denatured whey proteins

Unstable/Gelled

Oil droplet Non-adsorbed whey proteins Adsorbed whey proteins Gelled emulsions : Network of proteins entrapping oil droplets

Gelled emulsions obtained by using non-dairy gelling agents

fluid emulsions obtained by using non-dairy stabilizing agents

Dairy industries

(7)

• To design whey protein emulsions at high protein concentration (>4%) that are fluid after heating?

• To design texturized (gelled) emulsions at low whey protein concentrations (<3%)?

Research Questions

How to control the texture of whey protein emulsions in a large

range of protein concentrations without non-dairy additives?

(8)

How to design whey protein emulsions at high protein concentrations that are fluid after heating in the absence of non-dairy additives?

Strategy

Stability of

the continuous phase

(replace native whey proteins by aggregated

whey proteins)

1

Stability of the oil droplets (replace native whey proteins by caseins)

2

Competition for the oil droplet surface

3

Adsorbed proteins (caseins)

Protein in the continuous phase (dense and large whey protein

aggregates)

(9)

Thermal Stability of the emulsions

Caseins (%)

W h e y p ro te in a g g re g a te s (% )

Caseins Whey proteins

How to design whey protein emulsions at high protein concentrations that are fluid after heating in the absence of non-dairy additives?

Results

Critical casein concentration

Observation at:

Oil droplet scale

Interface scale (after 1 min of

heating at 120°C)

(after 30 min of heating at 120°C)

3 4 5 6 7 8 9

0.0 0.2 0.4 0.6 0.8 1.0

Marie Chevallier, PhD thesis

(10)

Casein Oil droplet

How to design whey protein emulsions at high protein concentrations that are fluid after heating in the absence of non-dairy additives?

- by adding sufficient amount of caseins to cover oil droplet surface (control of the size and stability of the oil droplets)

→ estimated value: mass of oil (g) × specific surface (m

2

/g of oil) × protein interfacial load (g/m

2

) (protein interfacial load ∼ 2mg/m

2

for caseins)

Main findings

Casein

Whey proteins aggregates in the continuous phase of the emulsions Oil droplet

- By selecting large and dense whey protein aggregates (small number, low

interfacial adsorption rate and low reactivity on heating)

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How to obtain texturized (gelled) emulsions at low whey protein concentrations without non-dairy additives ?

Strategy

Connect oil droplets with whey proteins aggregates (low density)

1

Control inter-droplet distance (oil content/

homogenization pressure)

2

Homogenizationpressure

Caseins for stabilizing oil droplets interface

0.01 0.10 1.00 10.00 100.00

0 10 20 30 40 50

Inter-dropletdistance (µm)

Oil content (%)

Whey protein aggregates used as connectors

(low density/elongated aggregatesfactal aggregates)

Size of the whey protein aggregates

inter-droplet distance

(12)

Results

How to obtain texturized (gelled) emulsions at low whey protein concentrations without non-dairy additives ?

0 0.5 1 1.5 2

0 1 2 3

Casein (%)

W h e y p ro te in a g g re g a te s (% )

Unstable

Fluid

Gel Viscous

Emulsion texture changes with the oil droplet surface composition

Observations at:

Emulsion scale Interface scale

Thibault Loiseleux, PhD thesis

(13)

How to obtain texturized (gelled) emulsions at low whey protein concentrations without non-dairy additives ?

- Select aggregates of low density (fractal aggregates of whey proteins)

- Use whey protein aggregates as « connector » at the surface of the oil droplets (size of the aggregates ∼ distance between oil droplets)

- In combination with the homogenization pressure, use caseins as emulsifiers to control the size of the oil droplets (distance between oil droplets)

« connected » oil droplets

Whey protein aggregates (= connecting agent)

Caseins (with the homogenizing

pressure, they control the oil droplet size and the distance between oil droplets)

The number of « connectors » defines the texture of the emulsions (gel, viscous, fluid)

Main findings

(14)

Introduction: whey proteins as texturizing ingredients

Whey proteins: • Heat-induced aggregates produced by heating treatments in solution for increased functional properties

• Dry heating or heating a protein powder: process used for white egg powders for increasing foaming,

emulsifying and gelling properties (Kato et al. 1989),

• Dry heating of dairy powders: less studied and not used

• Dry heating: a way to produce other changes of whey proteins

 Limited diffusion of solutes = less aggregation

 Traces or addition of lactose, degradation products of Maillard intermediates such as dicarbonyl

 crosslinks

(15)

How to custom protein assemblies with targeted sizes?

How to custom their functional properties such as their ability to entrap large amounts of water and deliver high viscosities?

• to replace food texturizing additives

Research Questions

(16)

How to custom protein assemblies with targeted sizes?

pH 9.5

Drying Dry heating Suspension

100 ° C

200 µm 30 µm

Powder Dry-heated

powder in suspension Whey

proteins

Elise Schong, PhD thesis

(17)

pH 9.5

Drying

100 µm 50 µm

Whey proteins

Powder

• Dry heating  powder no longer soluble

• Crosslinks between proteins

• Microparticles have a size and shape related to the size of the powder before dry heating

Dry heating Suspension

100 ° C

Dry-heated powder in suspension

How to custom protein assemblies with targeted sizes?

(18)

How to custom their functional properties such as their ability to entrap large amounts of water and deliver high viscosities?

• Yield of transfer of whey proteins in microparticles with:

 time of dry heating

 addition of lactose (0.2, 0.3 and 0.5 g/10 g protein)

• 1 g of powder can lead to 0.9 g of microparticles

• 1 g of powder leads to around 15 g of wet particles

• The water content is around 95% of the wet weigh of microparticles

• Due to the porous structure of powders

0.0 0.2 0.4 0.6 0.8 1.0

0 5 10

D ry yi e ld ( g d ry m ic ro p a rt ic le s/ g p o w d e r)

Time of dry heating (h)

Lac 0.2 Lac 0.3 Lac 0.5

0 5 10 15 20 25

0 5 10

W e t yi e ld ( g w e t m ic ro p a rt ic le s/ g p o w d e r)

Time of dry heating (h)

Lac=0.2

Lac=0.3

Lac=0.5

(19)

How to custom their functional properties such as their ability to entrap large amounts of water and deliver high viscosities?

• Porous structure of powders  Microparticles entrap a large amount of water

• Ability of microparticles to swell in the water phase: by a factor around 4

Time after water addition

(20)

How to custom their functional properties such as their ability to entrap large amounts of water and deliver high viscosities?

D ry h e a tin g = cr o ss- lin ks

DH powder

Proteins

+ aqueous phase

swelling

Repulsions between

proteins in the microparticle

(21)

How to custom their functional properties such as their ability to entrap large amounts of water and deliver high viscosities?

Spray dried powder: 23 g macroparticles/kg suspension

0.0001 0.001 0.01 0.1 1 10 100 1000

0.01 0.1 1 10 100 1000

V is co si ty (P a .s )

Shear rate (s

-1

)

Simplesse100

24h DH

72h DH 48h DH

36h DH

• Very high viscosity as compared to micro-particulated whey proteins (d[4,3]~10 µm)

• Viscosity decreases with increased dry heating duration

 reduced d[4,3]

 reduced water content

(22)

• Mechanism of formation and nature of the protein crosslinks is still speculative

• We can form microparticles only at pH > 8.0

• The longer the whey protein solution is stored at pH 9.5, the higher the amount of microparticles

• Role of:

 alkaline pH  protein denaturation? Increased exposure of lysine residues?

 lactose  Degradation via Maillard reactions? or degradation products of lactose at high temperature?

Is still under study.

Conclusions

pH 9.5

Whey proteins

(23)

• Whey protein aggregates: high diversity of structures  High diversity of functionalities

 Large and dense aggregates (microgels) → heat-stability (solutions/emulsions)

 Low density aggregates (fractal) → functionality dependent on the size o Small fractal aggregates : cold-gelation (CaCl

2

or acidic pH), limited

syneresis

o Medium fractal aggregates : connectivity between droplets, texture o Large fractal aggregates : increase viscosity

 Very large porous aggregates (microparticles) → water entrapment, texture

• Whey protein aggregates can be produced at the industrial scale (poster N°4 - Domitille de Guibert: “ Designing innovative technological routes for the production and stabilization by drying of protein fractal assemblies ”).

General conclusions

(24)

• Chevallier, M., Riaublanc, A., Cauty, C., Hamon, F., Rousseau, F., Thevenot, J., Lopez, C., Croguennec, T., 2019, The repartition of whey protein microgels and caseins between fat droplet surface and the continuous phase governs the heat stability of emulsions. Colloids and surface A, 563, 217-225.

• Schong, E., Famelart M.H., 2019, Influence of lactose on the formation of whey protein microparticles obtained by dry heating at alkaline pH. Food Hydrocolloids, 87, 477-486.

• Chevallier, M., Riaublanc, A., Lopez, C., Hamon, P., Rousseau, F., Thevenot, J., Croguennec, T., 2018, Increasing the heat-stability of whey protein-rich emulsions by combining the functional role of WPM and caseins. Food hydrocolloids, 76, 164-172.

• Kharlamova, A., 2017, texture des matrices laitières avec des agrégats de proteins laitières. PhD thesis, Université du Maine, France.

• Loiseleux, T., Rolland-Sabate, A., Garnier, C., Guilois, S., Croguennec, T., Anton, M., Riaublanc, A., 2018,

Determination of hydro-colloidal characteristics of milk protein aggregates using Asymmetrical Flow Field-Flow Fractionation coupled with Multiangle Laser Light Scattering and Differential Refractometer (AF4-MALLS-DRi).

Food hydrocolloids, 74, 197-206

• Schong, E., Famelart M.H., 2018, Dry heating of whey proteins leads to formation of microspheres with useful functional properties. Food Research International, 113, 210-220.

• Schong, E., Famelart, M.H., 2017, Dry heating of whey proteins. Food Research International, 100, 31-44.

• Famelart, M.H., Schong, E., Croguennec T., 2018, Dry heating a freeze-dried whey protein powder: Formation of microparticles at pH 9.5. J. Food Eng., 224, 112-120.

• Chevallier, M., Riaublanc, A., Lopez, C., Hamon, P., Rousseau, F., Croguennec, T., 2016, Aggregated whey proteins and trace of caseins synergistically improve the heat stability of whey protein-rich emulsions. Food hydrocolloids, 61, 487-495.

• Patent WO2018185192 (A1) - 2018-10-11 - « Stabilized protein aggregate particules and process for the preparation of said particles », M. H. Famelart, T. Croguennec, P. Schuck, E. Schong, T. Sevrin.

Publications in relation to the study

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THANK YOU FOR YOUR ATTENTION

MERCI

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