New and Emerging Technologies: Redefining Natural Colour Reformulation and Applications

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1 New and Emerging Technologies: Redefining Natural Colour Reformulation and Applications Dr Jim Bullock - iformulate Ltd Food Matters Live London, November 2014 jim@iformulate.biz

But First, a Little About Us iformulate: founded by two experienced industry professionals Diverse experiences, knowledge and network: polymers, materials science, chemistry, imaging, dyes, pigments,

2 But First, a Little About Us iformulate: founded by two experienced industry professionals Diverse experiences, knowledge and network: polymers, materials science, chemistry, imaging, dyes, pigments, emulsion polymerisation, biocides, anticounterfeiting, environmental, formulation, consultancy, marketing, business development, strategy, regulatory, training, events, R&D, innovation Clients large and small across different industries which use formulation technology, providing/developing new ideas, helping commercialise technologies, project building, consultancy, workshops, contacts and training. pharma, food, cosmetics, detergents and cleaners, coatings, inks, agrochemicals, disinfection etc Benefit from translation opportunities from one industry to another Open Innovation Roadshows Supporting major UK initiatives in formulation science and technology info@iformulate.biz Dr Jim Bullock E: jim@iformulate.biz M: +44 (0) Dr David Calvert E: david@iformulate.biz M: +44 (0)

everything: Temperature, light, ph, oxygen Are difficult to characterise, purify and process Are not designed may be

3 Natural Colours: How Do They Compare to Synthetic Colours? Natural Colours Are less brilliant Have lower colour strength Have narrower colour gamut Are less stable to everything: Temperature, light, ph, oxygen Are difficult to characterise, purify and process Are not designed may be obtained sustainably from waste streams in F&B Synthetic Colours Have precisely designed physical and colouristic properties have an image problem and are candidates for substitution

4 Know Your Colour: What Have You Got? Understanding the chemical features of natural colours that cause instability Warning: These slides may feature some chemistry!

How can Colour be Destroyed, Changed or Degraded?

Light Photocatalysis: Photons of light may have a

OH- ions (high ph) may accelerate reactions such

reducing agents may attack certain chemical bonds

impurities, metals Physical interactions

5 How can Colour be Destroyed, Changed or Degraded? Heat Heat accelerates most chemical reactions Light Photocatalysis: Photons of light may have a catalytic effect ph Excess of H+ ions (low ph) or OH- ions (high ph) may accelerate reactions such as hydrolysis Oxidation or reduction Oxidising or reducing agents may attack certain chemical bonds Chemical interactions Catalysis by e.g. impurities, metals Physical interactions Aggregation of particles, solubilisation, precipitation of molecules

Know Your Colour: Anthocyanins Glycosated (sugar) derivatives of

plants Shade changes with OH /-OCH3 substitution (auxochromic

Production of Anthocyanins in Grape Cell Cultures in The

6 Know Your Colour: Anthocyanins Glycosated (sugar) derivatives of anthocyanidin 6 anthocyanidins and 400 anthocyanins identified in plants Shade changes with OH /-OCH3 substitution (auxochromic effect) Significant effect of ph on colour Images: Ananga et al 2013 Production of Anthocyanins in Grape Cell Cultures in The Mediterranean Genetic Code - Grapevine and Olive (Sladonja (Ed.) at

7 Know Your Colour: Carotenes and other Carotenoids Terpenoid long polyene conjugated chain which is the chromophore Subtle changes to shade via substituents on terminal rings (auxochromic effects) Chain may degrade oxidatively in heat or light, and be unstable in acids Hydrocarbon water insoluble, fat soluble Beta-carotene Alpha-carotene Lutein (a xanthophyll) Zeaxanthin (a xanthophyll) Lycopene

Central metal ion affects shade (auxochromic effect) Cu/Na chlorphyllin: Cu replaces Mg in ring and Na salts of carboxyl

8 Know Your Colour: Chlorophyll Porphyrin (chlorin) ring provides conjugated system (chromophore) with similar structures seen elsewhere in nature (haemoglobin) and in synthetic colorants (phthalocyanines). Central metal ion affects shade (auxochromic effect) Cu/Na chlorphyllin: Cu replaces Mg in ring and Na salts of carboxyl groups. Acid instability: Removes Mg ion and hydrolyses ester chain Alkali instability: Hydrolysis of ester chain. Heat accelerates this decomposition Chlorophyll a Chlorophyll b

Alkali breakdown products: Know Your Colour: Curcumin Diarylheptaniod: Two aromatic rings joined by π conjugated carbon chain Shade affected by: tautomeric forms (enol is more stable) minor

9 Alkali breakdown products: Know Your Colour: Curcumin Diarylheptaniod: Two aromatic rings joined by π conjugated carbon chain Shade affected by: tautomeric forms (enol is more stable) minor components: derivatives with one or both OCH3 groups missing Unstable to light, alkali Stable to heat Insoluble in water (acid-neutral), soluble in alkali Slightly soluble in vegetable oil pk a = 7.8 pk a = 8.5 pk a = 9.0 FAO Chemical and Technical Assessment 2004 Keto Enol tautomerism

10 Know Your Colour: What Have You Got? Natural colours are not just clean single molecules: Mixtures of colour, other noncoloured material Full of impurities with closely related structures (analogues) Generally poorly characterised

11 Stability: Some Approaches from F&B

Case Study: Curcumin Stabilisation: Complex with divalent

with metal salts, extraction with water/glycerol mix they

12 Case Study: Curcumin Stabilisation: Complex with divalent metal ions B.Zebib et al Bioinorganic Chemistry and Applications Vol 2010, Article ID Mechanical mixing of curcumin with metal salts, extraction with water/glycerol mix they are able to protect curcumin against chemical degradation in neutral and basic media for along period of time

.co.uk Colours extracted from natural plant materials, extraction and

13 Case Study: Anthocyanin Lakes Keracol: Colours extracted from natural plant materials, extraction and purification Claiming lake pigment formed using novel biomimicry process Marketed for cosmetics, naturally derived hair dyes and other areas products-available

Case Study: Anthocyanin Lakes Nestec/Nestle: World Patent Application 2014/023712 Example 1: Preparation of a spray-dried blue colouring

Red cabbage extract diluted into water and cooled, sodium acetate added and ph adjusted to 5.

Cooled and spray dried to a powder. Retains blue colour at ph < 7, unlike non-stabilized extract.

14 Case Study: Anthocyanin Lakes Nestec/Nestle: World Patent Application 2014/ Example 1: Preparation of a spray-dried blue colouring composition with red cabbage extract and tannic acid. Red cabbage extract diluted into water and cooled, sodium acetate added and ph adjusted to 5.5 Ferrous sulphate heptahydrate added, tannic acid added Maltodextrin dissolved into mixture and pasteurized. Cooled and spray dried to a powder. Retains blue colour at ph < 7, unlike non-stabilized extract. Simulated daylight exposure shows better light fastness Other examples using e.g. aluminium sulphate, other anthocyanin extracts, freeze drying The resulting SMARTIES sweets had an attractive blue colour which did not fade perceptibly during several months' storage in daylight The colouring composition can therefore be used to colour foods

15 Why Encapsulate? Stability Challenges Industry Solutions: Encapsulation: Stability (chemical, heat, light ) Formulation compatibility Controlled release Taste masking Encapsulation can be Molecular Cyclodextrins, Calixarenes, Zeolites, Metal organic frameworks etc Nano Micro Macro Photo: Idea go / freedigitalphotos.net

16 Case Study: Curcumin and Bixin Interaction of Curcumin and Bixin with β-cyclodextrin: Complexation Methods, Stability, and Applications in Food Marcolino et al, J. Agric. Food Chem.2011, 59, Curcumin: 1:2 Complex Bixin: 1:1 Complex Complexation of colorants with β-cd promoted an intensification of color and increased water solubility; however, stabilization in the presence of light occurred only for bixin

microemulsion Examples of microemulsions to solubilise colours in aqueous systems and reduce sensitivity to

17 Case Study: Microemulsions Unlike conventional emulsions, microemulsions are thermodynamically stable Particle size 10-50nm, Swollen micelle structure with surfactant close-packing Careful surfactant choice to optimise microemulsion Examples of microemulsions to solubilise colours in aqueous systems and reduce sensitivity to light Internal oil phase Surfactant Co-surfactant Mohamed Awad Saad Abd El Galeel, PhD Thesis, University of Bonn, 2002

18 Stability: Some Approaches from outside F&B

Nanoencapsulation with Lipsomes: Use in Cosmetics and Drug Delivery

permit stability during oral delivery - low ph in GI tract would

19 Nanoencapsulation with Lipsomes: Use in Cosmetics and Drug Delivery Phospholipids (synthetic or natural) - hydrophilic (phosphate group) and fatty hydrocarbon tail. Self-association in solution bilayers, micelles and liposomes. Used e.g. for. encapsulation and stabilisation of sensitive drug molecules to permit stability during oral delivery - low ph in GI tract would normally degrade peptide active ingredients Image : Sætern, Parenteral Liposome and Cyclodextrin Formulations of Camptothecin, PhD thesis University of Tromsø

Molecular Scale Encapsulation: Example - Zeolites Indigo@Silicalite: a New Organic Inorganic Hybrid Pigment In the search for

silicalite, the MFI zeolite. The resulting pigment presents high color durability against most external agents (e.g., light, temperature).

influenced by formation conditions such as the initial indigo concentration and the thermal treatment. Image: www.intechopen.

20 Molecular Scale Encapsulation: Example - Zeolites Indigo@Silicalite: a New Organic Inorganic Hybrid Pigment In the search for stable and enduring organic colors, we have combined indigo, a historical and industrially important chromophore, with silicalite, the MFI zeolite. The resulting pigment presents high color durability against most external agents (e.g., light, temperature). This stability and its physical properties are explained by the association of indigo with an inert mineral, which is also influenced by formation conditions such as the initial indigo concentration and the thermal treatment. Image: Dejoie et al, ACS Appl. Mater. Interfaces, 2010, 2 (8), pp and Applied Spectroscopy 64, 10 (2010)

Molecular Scale Encapsulation - 1200 Years Ago Maya Blue

21 Molecular Scale Encapsulation Years Ago Maya Blue (800AD): Indigo Sepiolite or Palygorskite Giustetto et al J. Phys. Chem. C2011, 115, De Bonampak al Templo Mayor by Constantino Reyes-Valerio from

22 Summary Natural colours as is have severe drawbacks in F&B applications Know your colour: Understanding chemical and physical mechanisms of instability is first step Protection mechanisms such as lake pigments and encapsulation (molecular, nano, micro ) can provide stability benefits to natural colours Look at protection solutions from outside F&B info@iformulate.biz Dr Jim Bullock E: jim@iformulate.biz M: +44 (0)

Exploring how new formulation technologies could improve the properties of natural colours

Natural Colour Summit 2013 Exploring how new formulation technologies could improve the properties of natural colours Dr Jim Bullock iformulate Ltd jim@iformulate.biz +44 7450 436515 A new company (2012)