Mineral delivery

Abstract

A mineral supplement or fortified food ingredient product comprising nutritional minerals and unheated protein-carbohydrate carriers or Maillard Reaction Products (MRP) produced by heating aqueous protein-carbohydrate mixtures. The components in the formulation comprise protein, carbohydrates, mineral(s) iron salts / chelates and pH modifying agents. The product may also be a mixture of complexed iron compounds that is stable to heating. The protein complexed with iron may exist as soluble colloidal dispersion of iron-protein entities. A dried formulation of the nutritional mineral supplement may be obtained by dehydration of the aqueous mixture. The wet or dried product may be used in supplements or added to foods to obtain mineral-fortified foods.

Description

[0001] MINERAL DELIVERY

[0002] TECHNICAL FIELD - MINERAL FORTIFIED INGREDIENTS

[0003] The present invention relates to processes for producing iron or other mineral supplements or food-grade mineral fortificants in the wet or dry form and products produced therefrom. The preferred formulations contain iron.

[0004] BACKGROUND TO THE INVENTION

[0005] Micronutrient deficiency, which is a lack of essential minerals (e.g., Fe, Zn, Ca), iodine and vitamins (e.g., Vit A, B and C), is an important global health issue. Micronutrient deficiencies result in poor health and losses in productivity and potential. (Micronutrient Deficiency - Our World in Data). There are WHO / FAO guidelines for food fortification with micronutrients (1).

[0006] Anaemia is a major health problem. The global prevalence of anaemia across all ages is estimated at 1 .92 billion, with the leading cause of anaemia (66.2%) being due to dietary deficiency (2). The use of nutritional supplements (Concentrated micronutrients in pills, powders, or liquid formats) and fortification of food with micronutrients are the most common strategies used to address iron and other micronutrient deficiencies. There are many iron sources that may be used and there is data on the relative bioavailability of various iron sources (e.g., ferrous sulphate, ferric ammonium citrate, ferric chloride, ferric choline citrate, ferric citrate, ferric EDTA, ferric glycerophosphate, ferric orthophosphate, ferric oxide, ferric phytate, ferric polyphosphate, ferric pyrophosphate, ferric sulphate, ferrous ammonium sulphate, ferrous carbonate,, sodium iron pyrophosphate ferrous chloride, ferrous EDTA, ferrous fumarate, ferrous gluconate, ferrous sulphate, ferrous tartrate, iron methionine, iron proteinate, reduced iron) in various animals have been published (3). The bioavailability of iron salts is influenced by other components in a formulation or food matrix. This is because of interactions of iron salts / iron chelates with other components which change the form of the iron and its reactivity and bioavailability. Ascorbic acid is an enhancer of iron absorption whereas phytates reduce iron bioavailability (4, 5). In addition, various iron sources can affect the sensory quality of the food and promote lipid oxidation. For example, iron complexes such as ferrous bisglycinate having a greater tendency to promote oxidation due to its high redox potential (6). Chelated minerals have better bioavailability compared to non-chelated minerals when added to food (7). Also chelating agents can improve the quality and stability of food through the formation of chelate complexes (8). This is because both the food vehicle (e.g., food, beverage) and the iron fortificant have reactive functional groups. Examples of chelates used in food include EDTA, orthophosphate, pyrophosphate and polyphosphates and citrate.

[0007] Amino acid, protein hydrolysates and proteins act as chelates and have been used as carriers for iron and other minerals. Milk proteins and milk protein products and peptides from milk protein form complexes that can be used to carry iron and may be used to fortify food products (9, 10). Sugars and polysaccharides are able to bind to iron and have been proposed as supplements. Examples include Fe(lll) bindingto monosaccharides (11 ), disaccharides, sugar alcohols, lactobionic acid, gluconic acid and other sugar type ligands (12-16), polymaltose (17, 18), oligosaccharides (19), glycopeptides and amino sugars(20), soluble soy bean polysaccharides (21 ), pectin (22, 23), alginate (24), and guar gum (25).

[0008] While both proteins and sugars / carbohyd rates are able to bind iron, the products of the chemical reaction between amino acids / protein and reducing sugars / carbohydrates (CHO) with reducing sugar groups (referred to as Maillard Reaction Products, MRP) are alternative carriers to unheated mixtures of proteins and carbohydrates. MRP have been found to bind minerals (26). Iron(ll)-MRP complexes have been identified as Maillard reaction intermediates in alanine / glucose / FeCl2model systems (27). Iron(lll) forms a complex with an Amadori compound derived from L-tyrosine (28). Iron binds to melanoidins from food and model systems (29), ferrous ion can be incorporated into a heated lactose-glycine system (30), and the solubility of Fe complexes in a heated glycine-glucose system increases (31).

[0009] The major components in cow’s milk are water (-87-88%), lactose (-4.8%), proteins (-3.3%) and fat (-3.7%). Cow’s milk also contains -0.7% ash. The major milk proteins in cow’s milk are caseins (2.6%) and whey proteins (0.6%). Caseins are present primarily as colloidal supramolecular entities (casein micelles with diameters between 150-300 nm). The casein micelles are hydrated aggregates of different casein polymorphs (as1-, as2-, -, and K-caseins) containing minerals (mainly calcium and phosphate, and some citrate). The milk salts (including the citrates, phosphates and chlorides of H+, K+, Na+, Mg2+and Ca2+, whether as ions in solution or as colloidal species complexed with the casein micelle) are critically important for the technological properties of milk, casein micelle stability and buffering roles, and also the stability of the proteins during processing (32). Typically bovine milk contains 30.1 mM Ca, 5.1 mM Mg, 25.5 mM Na, 36.8 mM K, 20.9 mM inorganic phosphate, 9.8 mM citrate and 30.3 mM chloride (33, 34). In milk, there is partitioning of minerals between the colloidal and serum phases of milk. For example, 20.3 mM Ca, 1 .9 mM Mg, 1 .0 mM citrate, 9.5 mM inorganic phosphate and also small amounts of Na and K are partitioned into the colloidal phase of skim milk (33). The site for calcium in the colloidal phase of milk may also be occupied by other cations. Caseins with different cations have been made by dispersing a phosphocaseinate powder in a milk ultrafiltrate. The order of association of cations with casein micelles was Fe3+>Zn2+>Ca2+>Cu2>Mg2+(35). Both oxidative states of iron (Fe2+or Fe3+) bind to casein (36, 37) .

[0010] It is known that reconstituted casein micelles can be made from isolated bovine milk caseins as mixtures of asi-, p- and K-casein and calcium, magnesium, phosphate and citrate solutions (38). A published method uses sodium caseinate in water (71 g / L), addition of salts solutions (CaCl2, and MgCl2adjusted to pH 7, and KH2PO4, Na2HPO4and citric acid adjusted to pH 6.7) to obtain casein (25.6 g / L) in 30 mM calcium, 22 mM phosphate, 9 mM citrate, and 5 mM magnesium to obtain artificial casein micelles (39). Fe- loaded casein micelles have been made by exposing milk at chilled temperatures to a high concentration of soluble iron (up to 20 mmol kg-1ferrous and ferric chloride) with or without acidification with injection of carbon dioxide under pressure (40, 41 ). Soluble iron- protein complexes have been formed in high-calcium depleted milk (-70% calcium depletion using cation-exchange resin) with 20 mmol kg-1iron (42).

[0011] There is prior art relating to mineral fortified / adjusted milk proteins. US 2003 / 0165597 A1 is a calcium and / or nutritional mineral fortified milk or milk powder that utilizes phosphates. W02009150183A1 describes micellar casein and milk protein concentrate powders, with different calcium-to-casein ratios and buffering capacity. US 11 ,224,246 B2 describes a non-micellar mineral-protein complex including an added mineral and a protein, where the mineral protein complex is soluble in a solution at a physiological pH between 6.6 to 6.9 and the complex includes the use of phosphates. The iron-casein complex has bioavailability similar to that of ferrous sulphate (43). The iron may also be stabilised and protected from the environment during processing and storage and delivered in the body. This may be achieved by applying principles of colloid chemistry, chelation and redox modulation, or by reducing the redox potential at high pH to prevent oxidation of ferrous to ferric state where ferrous salts are added (44). A desirable property of the mineral fortified ingredients is the ability of the ingredient formulation to be pasteurised. Heat treatment of ingredients is a common method used in the processing of food ingredients and manufacture of formulated foods. However, many mineral fortified formulations based on proteins are prone to coagulation or precipitation of proteins, renderingthem unsuitable for liquid applications (45-47). The heat stability of milk protein and soy-based beverages may be improved by the addition of sequestering agents (e.g., phosphates, citrates) (45, 48, 49). The distribution of Fe between the colloidal protein phase and serum phase of the Fe- casein micelle formulation is modulated by the use of a combination of citrate and phosphate with pH control to avoid precipitation of protein and improve heat stability of the preparation.

[0012] It is the objective of this invention to provide iron and / or mineral fortified ingredients comprising unheated mixtures of proteins and carbohydrates or preheated protein- carbohydrate mixtures. This invention also describes the formation of colloidal casein entities where iron instead of Ca is used for formation of mineral-protein complexes. The colloidal Fe-casein entity will have different physico-chemical and functional properties compared to a calcium-casein micelle. Other work has shown that nutraceuticals are more effectively incorporated into casein micelles compared to residual soluble caseins (50). Further objectives are to provide iron and / or mineral fortified ingredients or nutritional supplements with improved solubility and that are stable to heat processing.

[0013] BRIEF DESCRIPTION OF THE INVENTION

[0014] In its broadest aspect, the present invention relates to a method of manufacturing a soluble formulation for mineral delivery including dispersing a protein in water, adding reducing sugar / carbohydrate to the protein dispersion and adding a soluble mineral salt. Improved solubility and / or stability of the formulation is achieved by modifying at least one of the following: heating the protein-carbohydrate mixture, adjusting the pH of the protein- carbohydrate mixture, heating the protein-carbohydrate mixture without pH adjustment, adjusting the pH without heating the protein-carbohydrate mixture or using Maillard Reaction products (hereafter called MRP). The adjustment of pH may employ alkalizing agents (e.g., sodium hydroxide, sodium bicarbonate) or buffering agents (e.g., phosphate, citrate) which possess iron binding properties.

[0015] Advantageously, the invention uses unheated protein-carbohydrate mixtures (hereafter called Non MRP) or MRP in formulations forthe delivery of nutritional minerals. The formation of soluble complexes is the target for delivery of Fe and other nutritional minerals. The binding of ligands to simple iron and mineral salts increases their solubility. The use of protein-carbohydrate mixtures for carrying Fe and nutritional minerals capitalises on the binding properties of both the protein and carbohydrate component and products produced during the Maillard Reaction. Maillard Reaction Products are alternative mineral carriers to the available based on protein or sugar / carbohyd rates.

[0016] One aspect of the invention uses pH-adjusted mixture of proteins and carbohydrates as mineral carriers. Unlike other inventions where Fe carriers comprise (i) unheated whole proteins / hydrolysates without added sugars, or (ii) sugars / carbohyd rates without added proteins, this invention combines the use of proteins and sugars (with and without heating) with judicious pH adjustment at various stages during the preparation process. In unheated mixtures, the proteins and carbohydrates bind minerals (e.g., Fe, Mg, Zn), each in their own right, depending on the relative equilibrium constants for complex formation with each entity in the mixture and the pH. Another aspect of the present invention relates to provision of a mixture of mineral complexes formed by the interaction of iron / minerals with components in a wet-heated mixture of protein and reducing carbohydrates. In heated aqueous protein-carbohydrate mixtures (MRP) there will be (i) a mixture of polypeptides including intact protein and hydrolysed protein of different molecular weights, (ii) sugars and carbohydrates and heat- induced breakdown products of sugar and carbohydrates and (liii) protein / peptide- sugar / carbohydrate conjugates and (iv) other Maillard Reaction products. Many of the components in the heated protein-carbohydrate mixture have the ability to behave as anions and chelate with iron to form Fe-complexes.

[0017] The iron is in a milieu of components will bind to various components depending on the stability constant of the iron complex, pKa of the chelate and the pH of the solution. Therefore, it is important to choose the fortificant to use in various systems and to consider the interaction of the iron with the components in the formulation as well as the ability of the chelate to bind Fe. The several types of components in the heated protein- carbohydrate milieu also have the capacity to bind Fe and other minerals, depending on the relative equilibrium constants for complex formation with each entity in the mixture and pH. Altering the pH at the time of heating protein-carbohydrate mixtures changes the kinetics of the Maillard reaction and pathways, as well as the degradation reaction of proteins and carbohydrates, leading to a different composition of the final mixture. An advantage of using MRP is the range of desirable flavours that may be produced as a consequence of the Maillard reaction, which can mask undesirable taste. Also, buffering salts (e.g., bicarbonate / phosphates / citrates) which act as complexing agents and also modulate pH, may be employed to improve the properties of ingredients.

[0018] In another aspect, in place of a protein (casein, caseinate), calcium-depleted casein micelles in milk may also be used as a starting material for making colloidal enriched in iron. W02009150183A1 describes micellar casein and milk protein concentrate powders, with different calcium-to-casein ratios and buffering capacity to prepare micellar casein preparations. This invention is differentiated W02009150183A1 in that there is an intervening step in the process, calcium-depleted casein micelles may be loaded with different amount of iron to obtain Fe-rich casein micelles with judicious use of an iron salt with citrate and phosphate . The Fe-casein entities may be further combined with carbohydrates and optionally heated to form Maillard Reaction Products.

[0019] Another feature of this invention includes the use of the concept for the co-delivery of other nutrients that are synergistic with the delivery of iron / minerals in one formulation, where the synergistic nutrient can function as the carbohydrate participating in the formation of the Maillard Reaction Product or be the unreacted nutrient (e.g., prebiotics, oligosaccharide). Prebiotics increase iron absorption and reduce the adverse reaction of iron on gut microflora (51 ). Other water soluble bioactives (e.g., water-soluble vitamins such as Vit B and Vit C, and various mineral salts such as Mg, Zn) may also be incorporated into the aqueous phase. Where there is an intent to incorporate nutritional lipids or fat soluble bioactives, the protein-carbohydrate mixtures may be used to prepare oil-in-water emulsions, and wherein the oil phase may contain lipid soluble bioactives (e.g., carotenoids, vitamin D). The iron-protein entities may further be combined with oils to form an emulsion. When Fe is bound to caseins, lipid oxidation is inhibited compared to when Fe is in the free state (9, 52).

[0020] Various protein, polypeptides and hydrolysates may be used including proteins from animal, vegetable, algal or microbial sources. Preferable sources of protein include sodium caseinate, potassium caseinate, ammonium caseinate, lactic casein, whey protein isolate, and micellar milk protein. The proteins used may also be recombinant proteins produced by precision fermentation. Any reducing carbohydrate may be used in combination with any protein for formation of MRP. Examples of reducing carbohydrates include glucose, fructose, lactose, galactose, oligosaccharide, maltodextrin, starch and dried glucose syrup. The heat treatment can be carried out at various times / temperatures (e.g., 60°C for 60 mins, 80-100°C for 15 -60 min, or retorting), and pH’s. The oligosaccharides / prebiotic fibres used may also be recombinant carbohydrates produced by precision fermentation Phosphates / citrates and the Fe / mineral salt may be added prior to or after the heat treatment. These components have a dual function -that of complexing with the mineral salt and also providing buffering capacity. The addition of complexing agents reduces the activity of the mineral ion which improves heat stability, as cation mediated protein-protein interactions that lead to precipitation are decreased. Also, the addition of buffering salts (e.g., citrates / phosphates) counters the decrease in pH caused when mineral salts bind to a protein-sugar carrier. Many proteins (e.g., milk and soy proteins) are more prone to precipitation as the pH is lowered and the isoelectric point of the proteins is approached.

[0021] DETAILED DESCRIPTION OF THE INVENTION

[0022] There are various options that may be used for preparing the mineral complexes with combinations of protein and sugar / carbohydrate. Refer to Tables 1-3 Figures 1-18 and the specific examples of Fe below.

[0023] 1 . Fe-Non MRP (Without pH adjustment): Unheated protein-carbohydrate mixtures (Without any pH adjustment prior to addition of Fe)

[0024] 2. Fe-Non MRP (With pH adjustment): Unheated protein-carbohydrate mixtures with pH adjustment prior to Fe addition.

[0025] 3. Fe-MRP (Without pH adjustment): Heated protein-carbohydrate mixtures (Natural pH prior to heating) to form MRP and Without pH adjustment priorto Fe addition.

[0026] 4. Fe-MRP (pH adjustment after heating protein-CHO): Heated protein-carbohydrate mixtures (Natural pH prior to heating) to form MRP and with pH adjustment prior to Fe addition.

[0027] 5. Fe-MRP (pH adjustment prior to heating protein-CHO): Heated protein- carbohydrate mixtures (With pH adjustment priorto heating) to form MRP and Without any pH adjustment priorto addition of Fe.

[0028] 6. Fe-MRP (pH adjustment prior to heating protein-CHO + after heat treatment): Heated protein-carbohydrate mixtures (With pH adjustment prior to heating) to form MRP and with pH adjustment prior to addition of Fe.

[0029] Various options may be used for preparingthe colloidal Fe-casein entities includingthe following:

[0030] 1 . Colloidal Fe-casein entity made by reconstituting sodium caseinate and adding phosphate, citrate and an iron salt

[0031] 2. Colloidal Fe-casein entity made by reconstituting sodium caseinate and adding phosphate, citrate and an iron salt and combining this mixture with a carbohydrate

[0032] 3. Colloidal Fe-casein entity made by reconstituting sodium caseinate and adding phosphate, citrate and an iron salt and combiningthis mixture with a reducing carbohydrate and heating to form Maillard Reaction Products (where the heating may be done without pH adjustment of the mixture, with pH adjustment of the mixture prior to heating or after heating) 4. Colloidal Fe-casein entity formed by Fe addition to pre-formed Maillard Reaction Products formed by heating a mixture of caseinate-citrate- phosphate-carbohydrate (without pH adjustment prior to heating)

[0033] 5. Colloidal Fe-enriched casein entity made with Ca-depleted colloidal calcium phosphate casein micelles. The Fe-casein micelle may be made by addition of an iron salt to a Ca-depleted casein micelle preparation, with the option adjusting the formulation with added carbohydrates or adding reducing carbohydrates and heating the mixture to form Maillard Reaction Products.

[0034] The liquid formulations may be concentrated and dried to produce Fe-fortified and other mineral-fortified powders for supplements and food applications

[0035] MATERIALS FOR EXAMPLES

[0036] Ingredients: The proteins used were sodium caseinate (NaCas) from a local supplier and hydrolysed whey protein isolate (HWPI) was Pure Product™, Australia (Composition HWPI per 100g was given as 90g protein, 1 .3g fat and 4.1g carbohydrate). The carbohydrates (CHO) were glucose (glc), (dextrose monohydrate, Lotus Brand), maltodextrin DE 17 (MD17) from Dextrose Delight and Fibersol-2 (DE 8-12.5%) from ADM. The moisture content of the protein and maltodextrins powders was taken as 5%. The ferrous salt was ferrous sulphate heptahydrate (FeSO4.7H2O, MW 278.1 ). The citrate salt (Cit) was sodium citrate (MW 258.1), the phosphate salt was trisodium phosphate (M.W. 163.94). and the base for pH adjustment was sodium bicarbonate or NaOH. Food ingredients and products were: skim milk powder (Coles, 33% protein, 55% lactose), coconut milk powder (Maggi, containing 78% coconut milk powder, maltodextrin, and sodium phosphate stabiliser; 8% protein 63.4% fat, 25 % carbohydrate), organic oat milk powder (Honest to Goodness, 14.1 g protein, 7.2g fat, 66.8g carbohydrate per 100g), full cream milk (Woolworths, 3.5 g protein, 3.4 g fat, 117 mg Ca per 100 ml), soy milk(Yenson’s, 4.2g protein, 1 .9g fat, 0.9g CHO per 100 ml)., UHT whole goat milk (3.5 g protein, 3.8 g fat, 4.5 g sugars, Ca122 mg per 100ml), Spring water, soda water (Schweppes), and ginger cordial (Buderim gingerwhich contains cane sugar, ginger juice, Natural flavours, Citric acid, xanthan gum))

[0037] Preparation of protein dispersions: NaCas and HWPI dispersions were prepared by dispersingthe protein in water to obtain an aqueous dispersion at the required total solids (TS). The protein powders were dispersed by mixing the protein powder into water at ~60°C with stirring. The protein dispersion was left to hydrate for a few hours or overnight.

[0038] Preparation of unheated protein-carbohydrate mixtures (Non MRP): Unheated protein- carbohydrate mixtures with various % TS were generally made by mixing the appropriate weights of 10 or 15% TS NaCas or HWPI with the carbohydrate solutions, or by addition of the required weight of carbohydrate ingredients into the aqueous protein dispersion. Where pH adjustment was required, the unheated protein-carbohydrate mixtures were adjusted with either 1 M NaHCO3or 1 M NaOH. In some cases, sodium citrate or trisodium phosphate was added into the protein-CHO dispersion for pH-buffering action and complexation of Fe. The colloidal casein formulations were based on a published method (50) with some modifications. In place of the calcium salt as the mineral salt, ferrous sulphate was used. Briefly, trisodium phosphate and citrate were added prior to the addition of the ferrous salt. In some formulations, the citrate salt was omitted. The pH was adjusted with sodium bicarbonate or NaOH.

[0039] Preparation of heated protein-carbohydrate mixtures (MRP): For the preparation of MRP mixtures, the unheated protein-CHO mixtures were used as is (i.e., at the natural pH) or pH-adjusted prior to being heated in a kitchen steamer equipped with a boiling water bath. Preparation of Ferrous sulphate solutions: The required amount of ferrous sulphate was dissolved in water.

[0040] Preparation of Fe-citrate solutions: Sodium citrate was added into the ferrous sulphate solution to obtain the Fe-citrate complex.

[0041] Observations: Photographs were taken of each sample, and visual assessments were recorded. In describing the embodiments of the invention the term “clear” refers to optical transparency, that is, samples through which light could pass with minimal scattering. A sample described as “clear” may nonetheless exhibit colour, depending on the dissolved species present. The term “cloudy” refers to samples that scatter incident light, typically due to the presence of dispersed, aggregated, or precipitated particulate material.

[0042] First Embodiment of the Invention

[0043] EXAMPLES OF Fe-COMPLEXES WITH NaCASEINATE AS THE PROTEIN SOURCE

[0044] EXAMPLE 1

[0045] Fe-MRP (2.2NaCas:1Glc:1.05MD17) (5.5% MRP, 5.1 mM Fe)

[0046] MRP solution was adjusted to pH 7.65 prior to addition of Fe

[0047] (MRP adjusted with 1 M sodium bicarbonate prior to Fe addition)

[0048] Heated mixture

[0049] (MRP NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (2.2:1 .0:1 .05)]

[0050] A protein-CHO mixture (12.9%TS, Ratio 2.2NaCas:1 .0Glc:1 .05MD17), pH 6.7 was heated for ~ 1 hr in steamer to form MRP. The solution browned on heat treatment, which is evidence of the Maillard Reaction occurring. Fig. 1 a shows protein-CHO (2.2NaCas:1 glucose:1 .05 maltodextrin DE17) (12.9%TS: 6.7% NaCas, 3.0 %Glc, 3.2% MD17) without Fe (Left: pH 6.7, before heat, clear; Right: pH 6.5, after heat, clear). The heated mixture (pH 6.5) was then adjusted to pH 7.65 with 1 M NaHCO3. The pH adjusted MRP mixture was added slowly into the ferrous sulphate solution. The resultant MRP-Fe mixture had 5.5% MRP in 5.1 mM Fe. On addition of ferrous sulphate the colour was darker but there was no precipitate. Fig. 1 b shows Fe-MRP with 5.5%MRP (2.86%NaCas:1 .30% glc: 1 .36% maltodextrin DE17) in 5.1 mM Fe

[0051] EXAMPLE 2

[0052] Fe-Non MRP (2.2NaCas:1Glc:1.05MD17) (5.7% protein-carbohydrate in 5.4-21.3 mM Fe)

[0053] Final Fe-Non MRP pH 7.6-7.8

[0054] (Non MRP was adjusted with 1M sodium bicarbonate prior to addition of Fe)

[0055] Unheated mixture

[0056] (NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (2.2:1 .0:1 .05)]

[0057] A protein-CHO mixture (12.9%TS; Ratio 2.2NaCas:1 Glc:1 .05MD17), was prepared (Non MRP). The mixture (pH 6.5) was adjusted to -pH 7.5 with NaHCO3. The pH adjusted Non MRP mixture was added into the ferrous sulphate solution. The resultant Fe-Non MRP mixture had 5.7% Non MRP in 5.4 - 21 .3 mM Fe. Addition of the ferrous salt resulted in the development of brown colour, with increasing iron concentration resulting in darker colours, with clarity depending on the level of Fe. Fig. 2 shows Fe-Non MRP complexes with Fe (Left: Fe-MRP with 5.7% MRP in 5.4 mM Fe, clear; Middle: Fe-MRP with 5.7% Fe-MRP in10.6 mM Fe, clear; Right: Fe-MRP with 5.7% MRP in 21.3 mM Fe, cloudy).

[0058] EXAMPLE 3

[0059] Fe-MRP (2.2NaCas:1Glc:1.05MD17) (6.65%MRP, 6.2-24.8 mM Fe) Final Fe-MRP pH 7.5-7.8 (MRP formed after heat treatment was adjusted with 1 M sodium bicarbonate prior to Fe addition)

[0060] Heated mixture

[0061] (MRP NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (2.2:1 .0:1 .05)]

[0062] A protein-CHO mixture (12.9%TS, Ratio 2.2NaCas:1 .0Glc:1 .05MD17), pH 6.6 was prepared. MRP was formed by heat treatment of protein-CHO mixture (without pH adjustment prior to heating in a steamer for ~60 min). The MRP mixture (~pH 6.4) was pH adjusted with NaHCO3either before or after addition of ferrous. Ferrous sulphate solution was mixed with the MRP mixture (without pH adjustment) or to the pH-adjusted MRP mixture (pH7.65). The resultant MRP-Fe mixture had 6.65% MRP in varying concentrations of Fe. Addition of the ferrous salt resulted in the development of brown colour, with increasing iron concentration resulting in darker colours. Fig. 3 shows Fe-MRP complexes containing 6.65% MRP in varying concentrations of Fe (Left: Fe-MRP in 6.2mM Fe (pH- adjusted MRP (pH~7.6) and added into Fe solution), Solution was clear; Middle: Fe-MRP in 12.4mM Fe (MRP (without pH adjustment, pH —6.4) was added into Fe solution. The pH on addition of Fe reduced pH to 5.77 (with formation of protein precipitate) and then base was added to raise pH to 7.6 (precipitate re-dissolved on mild heat and standing to form a final clear solution; Right: Fe-MRP in 24.8mM Fe (pH-adjusted MRP(pH —7.6) was added into Fe solution, resultin in milky mixture with precipitate).

[0063] EXAMPLE 4

[0064] Fe-MRP (1.1 NaCas:1Glc:1.05MD17 ) (6.13% MRP, 5.1-20.6 mM Fe)

[0065] Final Fe-MRP Solution pH 7.7-8.2

[0066] (Protein-CHO adjusted with 1 M sodium bicarbonate prior to heating)

[0067] Heated mixture

[0068] (MRP NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (1 .1 :1 .0:1 .05)]

[0069] A protein-CHO mixture (14.3% TS; Ratiol .1 NaCas:1 .0Glc:1 .05MD17), pH 6.6, was prepared and pH-adjusted with NaHCO3to obtain a pH-adjusted mixture(pH 7.5) which had 10.72%TS. The pH-adjusted mixture was heated in a steamer for 60 min for formation of MRP. The pH after heating increased to pH 8.7. The MRP mixture was added slowly into the ferrous sulphate solutions of various concentrations for preparation of Fe-MRP complexes. The resultant Fe-MRP mixture contained 6.13% MRP in varying concentrations of Fe (5.1 mM, 10.3mM, 15.4mM and 20.6mM). Addition of the Fe solution resulted in the development of brown-black colour, with increasing iron concentration resulting in darker colours. The MRP processed in this way may be used for preparation of soluble Fe-MRP complexes in 5.1 mM Fe and 10.3 mM Fe. . At higher levels of added Fe, the solutions were slightly cloudy to cloudy, due to protein aggregation. Fig. 4 shows Fe-MRP complexes with varying Fe concentrations (Left - Fe-MRP in 5.1 mM Fe. Final pH 8.2 after addition of Fe, clear; Middle Left: Fe-MRP in 10.3 mM Fe. Final pH 8.0 after addition of Fe, clear; Middle Right: Fe-MRP in 15.4mM Fe. Final pH 7.7 after addition of Fe, slightly cloudy; Extreme Right: Fe-MRP in 20.6mM Fe. Final pH 7.7 after addition of Fe, slightly cloudy).

[0070] EXAMPLE 5

[0071] Fe-Non MRP (1.05NaCas:2.87Glc:1.0MD17) (7.2% protein-carbohydrate in 14.4 mM Fe)

[0072] Final Fe-Non MRP Solution pH 6.1-7.4

[0073] (Non MRP adjusted with 1 M sodium bicarbonate)

[0074] Unheated mixture

[0075] (NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (1.05:2.87:1.0)] A protein-CHO mixture (18% TS; Ratio 1 .05NaCas:2.87Glc:1 .0MD17), pH 6.7 was prepared (Non MRP). The unheated protein-CHO mixture was adjusted to various pH (7.8, 8.3 and 8.4) and then added into ferrous sulphate solution (36 mM Fe). The final Fe-Non MRP mixture had 7.2% protein-carbohydrate in 14.4 mM Fe. The control was unheated protein- CHO mixture was not pH-adjusted prior to addition of Fe. Without pH adjustment, addition of Fe resulted in a decrease in pH to pH~5.0 and visible precipitation in the mixture (Final Fe=14.4 mM). With pH adjustment prior to addition of Fe, the resultant Fe-Non MRP mixtures had final pH (7.1-8.6) with Fe (14.1 mM). Addition of the ferrous salt resulted in the development of brown colour, with increasing iron concentration resulting in darker colours. When unheated protein-CHO mixtures (Non MRP) (pH adjustment) are used for preparation of Fe-Non MRP complexes in mixtures containing 14.4 mM Fe, the solutions were cloudy, with cloudiness decreasing as the pH was raised. Fig. 5a shows Fe-Non MRP mixtures (Extreme Left: Fe-Non MRP, Final pH 5.9 after addition of Fe, fluffy precipitate; Second from Left: Fe-Non MRP, Final pH 7.1 after addition of Fe, slightly cloudy; Third from Left: Fe-Non MRP, Final pH 7.5 after addition of Fe, slightly cloudy; Extreme Right: Fe-Non MRP, Final pH 7.7 after addition of Fe, slightly cloudy) & Fig. 5b (Left: Fe-Non MRP, Final pH 7.5 after addition of Fe, cloudy; Middle: Fe-Non MRP, Final pH 7.8 after addition of Fe, slightly cloudy; Right: Fe-Non MRP, Final pH 8.6 after addition of Fe, slightly cloudy).

[0076] EXAMPLE 6

[0077] Fe-MRP (1.05NaCas:2.87Glc:1.0MD17) (7.2% MRP, 14.4 mM Fe)

[0078] Final Solution pH 7-8.2

[0079] (Protein-CHO heated and then MRP adjusted with 1 M sodium bicarbonate after heat treatment)

[0080] Heated mixture

[0081] (MRP NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (1 .05:2.87:1 .0)]

[0082] A protein-CHO mixture (18% TS; Ratio 1 .05NaCas:2.87Glc:1 .0MD17) was prepared. MRP was formed by heating the protein-CHO mixture in a kitchen steamer for ~60 min to obtain a light brown solution (Fig. 6a. MRP (without Fe), Left: 18.0%TS MRP, clear; Right: 7.4% TS MRP obtained by dilution of 18%TS MRP with water, clear).

[0083] The heated protein-CHO mixture (MRP) was used without pH adjustment (Control) or adjusted to various pH and added into ferrous sulphate solution (36 mM). The resultant MRP-Fe mixtures contained Fe (14.4mM Fe) with a final pH after Fe addition of pH 6.2-8.2. Addition of the Fe salt resulted in the development of brown colour, with increasing iron concentration resulting in darker colours and improved clarity with increasing pH. Fig 6b shows Fe-MRP at various pH containing 7.2% MRP (1 .54% NaCas: 4.2% glucose: 1 .48% MD17) in 14.4mM Fe at different pH (Adjusted after MRP and prior to addition of Fe). (Extreme Left: Fe-MRP (without pH adjustment), Final pH after addition of Fe, 6.2, cloudy; Second Left: Fe-MRP (pH 7.3 prior to addition of Fe), Final pH after addition of Fe, 7.06, cloudy; Middle: Fe-MRP (pH 7.8 prior to addition of Fe), Final pH after addition of Fe, 7.35, slightly cloudy; Fourth from Left: Fe-MRP (pH 8 prior to add Fe), Final pH 7.65 after addition of Fe, quite clear; Extreme Right: Fe-MRP (pH 8.2 prior to add Fe), Final pH 7.70 after addition of Fe, quite clear). Fig. 6c shows Fe-MRP containing 7.2%MRP (1 .54% NaCas: 4.2% glucose: 1 .48% MD17) in 14.4mM Fe, (Adjusted after MRP and prior to addition of Fe). (Left: Fe-MRP; Final pH 7.6, slightly cloudy; Middle: Fe-MRP, Final pH7.96, very slightly cloudy; Right: Fe-MRP, Final pH 8.2, clear).

[0084] EXAMPLE 7

[0085] Fe-MRP (1.05NaCas:2.87Glc:1.0MD17) (7.2% MRP, 14.4 mM Fe) Fe-MRP pH 6.6-12 was pH-adjusted with 1M NaOH

[0086] Heated mixture (MRP NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (1.05:2.87:1.0)1

[0087] A protein-CHO mixture (18% TS; Ratio 1 .05NaCas:2.87Glc:1 .0MD17). MRP was formed by heating the protein-CHO mixture in a kitchen steamer for ~60 min to obtain a light brown solution. The heated protein-CHO mixture (MRP) was adjusted to various pH with different amounts of NaOH and then added into ferrous sulphate solution (36 mM), which resulted in Fe-MRP at various pH, depending on the amount of NaOH added. The resultant Fe-MRP mixtures contained 7.2% MRP (1 .54% NaCas: 4.2% glucose: 1 .48% MD17 ) in 14.4mM Fe.

[0088] The MRP solution was clear. Addition of the Fe salt resulted in the development of dark green to brown colours. All solutions were slightly cloudy, with different colours depending on pH. (Fig. 7a - Extreme Left: MRP with no added Fe (pH 6.3.), clear; Second from Left: Fe- MRP, Final pH 10.34, slightly cloudy; Middle: Fe-MRP, Final pH 11 .37, slightly cloudy; Fourth from Left: Fe-MRP, Final pH 11 .81 , slightly cloudy; Right: Fe-MRP 4, Final pH 12.08 , slightly cloudy; & Fig. 6b - Left: Fe-MRP, Final pH 6.6, cloudy; Middle: Fe-MRP, Final pH 7.7, slightly cloudy; Right: Fe-MRP, Final pH 9.2, slightly cloudy).

[0089] EXAMPLE 8

[0090] Fe-MRP (1.05NaCas:2.87Glc:1.0MD17) (6.4-8.1% MRP, 9-18 mM Fe)

[0091] Final Fe-MRP, pH 8-8.4 (Protein-CHO adjusted with 1M sodium bicarbonate prior to heating)

[0092] Heated mixture (MRP NasCas-glc-MD17) [NaCas:glucose:Maltodextrin DE 17 (1.05:2.87:1.0)1

[0093] MRP was formed by heat treatment of pH-adjusted 12.86%TS or 15%TS (Ratio 1 .05NaCas:2.87Glc:1 .0MD17) that were adjusted to pH 7.6 prior to heating in a kitchen steamer for 60 min, and then used for preparation of Fe-MRP complexes, which dark brown in colour but clear. The MRP was added slowly into the ferrous sulphate solution. The resultant Fe-MRP mixture contained 6.4-8.1% MRP solids and varying amounts of iron (9 - 18 mM Fe). Addition of the ferrous salt resulted in the development of brown to blackish colour, with increasing iron concentration resulting in darker colours. All Fe-MRP mixtures were clear without signs of precipitation.

[0094] Fig 8a shows MRP (12.86%) without Fe and Fe-MRP containing 6.43%MRP (1 .37% NaCas, 3.75% glc, 1 .31 % MD17) and various amounts of Fe (Left: 12.86% TS MRP (no added Fe), Final pH 8.9, clear, no precipitate, Middle: Fe-MRP in 9mMFe , Final pH 8.43 after addition of Fe, no precipitate; Right: Fe-MRP in 18mM Fe, Final pH 8.3 after addition of Fe, no precipitate); & Fig. 8b shows MRP (15%TS) without Fe and Fe-MRP containing 6.89% MRP and various amounts of Fe. (pH-adjusted prior to heating for formation of MRP, Fe added after MRP formation) (Left: MRP 15%TS (no added Fe) - Final pH 8.8, no precipitate; Middle: Fe-MRP in 9.7 mM Fe, Final pH 8.8 after addition of Fe, clear, no precipitate, Right: Fe-MRP 7.19% TS in19.5 mM Fe, Final pH 8.05 after addition of Fe, clear, no precipitate).

[0095] Second Embodiment of the Invention

[0096] EXAMPLES OF Fe-COMPLEXES WITH HYDROLYSED WHEY PROTEIN ISOLATE AS THE PROTEIN SOURCE

[0097] EXAMPLE 9

[0098] Fe-Non MRP (1.1 HWPI:1.0Glc:1.05MD17) (3.8% protein-carbohydrate, 9 mM Fe )

[0099] Final Fe Non-MRP Solution pH 6.2-7.7 ( adjusted with 1M NaHCO3) Unheated mixture (HWPI-glc-MD17) [HWPI:glucose:Maltodextrin DE 17 (1.1 HWPI:1.0Glc:1.05MD17)1

[0100] A mixture with 9.53% TS protein-CHO (Ratio 1 .1 NaCas:1 Glc:1 .05MD17) ) was prepared. The unheated protein-CHO mixture (Non MRP) was diluted with water to obtain 7.64%TS mixture (unadjusted pH ~7) or adjusted to obtain 7.64% TS mixtures with various pH (pH 7- 8). Equal volumes of the 7.64% TS Non MRP mixtures were mixed with ferrous sulphate (18 mM). The resultant Fe-Non MRP mixtures contained 3.81% Non MRP solids

[0101] (1 .33%HWPI:1 .21 %glc: 1 .27%MD17) and 9 mM Fe . Addition of the Fe salt resulted in the development of brown colour, but samples remained largely transparent when this level of Fe was added. Fig. 9a shows Non MRP without Fe and Fe-Non MRP atvarious pH (pH- adjusted prior to addition of Fe). (Extreme Left: Non MRP (without added Fe and without pH adjustment), pH 6.8; Second from Left: Fe-Non MRP, pH7.6 priorto Fe addition, pH 7.2 after Fe, clear; Middle: Fe-Non MRP, pH7.7 prior to Fe addition, pH 7.3 after Fe, clear; Fourth from Left: Fe-Non MRP, pH7.87 prior to Fe addition, pH pH7.4 after Fe, clear; Extreme Right: Fe-Non MRP, pH 7.9 prior to Fe addition, pH 7.5 after Fe, clear).

[0102] Assessment of heat stability: Heating of Fe-Non MRP mixtures leads to cloudiness when heated over steam until temperature reaches ~72°C. On heating signs of protein aggregation and various colours were observed (brown to green) as pH increases. Fig. 9b shows Non-MRP and Fe-Non-MRP mixtures after heating (Extreme Left: Non MRP (without added Fe and without pH adjustment), pH 6.8 before heat, pH 6.25 after heat, cloudy; Second from Left: Fe-Non MRP, pH 7.2 before heat, pH 6.82 after heat, cloudy; Middle: Fe- Non MRP, pH 7.3 before heat, pH 7.19 after heat, cloudy; Fourth from Left: Fe-Non MRP, pH7.4 before heat, pH 7.45 after heat, cloudy; Extreme Right: Fe-Non MRP, pH 7.5 before heat, pH 7.7 after heat, cloudy).

[0103] EXAMPLE 10

[0104] Fe-MRP (1.1HWPI:1Glc:1.05MD17), (4.23% MRP, 6.6 mM Fe or 26 mM Fe)

[0105] Final Fe-MRP Solution pH (~7.7) Protein-CHO adjusted with 1 M sodium bicarbonate prior to heating)

[0106] Heated mixture (MRP HWPI-glc-MD17) [HWPI:glucose:Maltodextrin DE 17 (1 .1 :1 :1 .051

[0107] MRP was formed by heat treatment of 7.64%TS pH-adjusted HWPI:glucose:maltodextrin DE17 (Ratio 1 .1 protein:1 .0 glc: 1 .05 maltodextrin) mixtures, where pH was adjusted to ~pH8.2 prior to heating. The pH adjusted protein-CHO mixture was heated for 30 min or 60 min in a kitchen steamer. After heating the pH increased to for both mixtures. The mixture heated at 30 min and 60 min respectively had pH of 8.8 and 8.5 post-heating. Fig. 10a shows MRP without Fe (Left: Heated for 30 min; Right: Heated for 60 min). This may be due to the counteracting effects of the Maillard reaction (which reduces pH) and deamidation of proteins which occurs at high pH results (which increases pH) and other reactions.

[0108] The MRP mixtures were used for preparation of Fe-MRP complexes containing 4.23% MRP (1 .48%HWP, 1 .35%glc, 1 .41 %MD17) in 6.6 mM or 26 mM Fe. Fig.10b shows Fe-MRP (Extreme Left: Fe-MRP in 6.6 mM Fe made with MRP formed by heating in a steam for ~30 min prior to Fe addition, pH after Fe addition was pH 7.8, clear; Middle Left: Fe-MRP in 26.2 mM Fe made with MRP formed by heating in a steam for ~30 min prior to Fe addition, pH after Fe addition was pH 7.6, clear; Middle Right: Fe-MRP in 6.6 mM Fe made with MRP formed by heating in a steam for ~60 min prior to Fe addition, pH after Fe addition was pH 7.7, clear; Extreme Right: Fe-MRP in 26.2 mM Fe made with MRP formed by heating in a steam for~60min prior to Fe addition, Final pH after Fe addition, pH7.6, clear). Third Embodiment of the Invention

[0109] HEAT STABILITY - EXAMPLES WITH NaCASEINATE AS THE PROTEIN SOURCE SHOWING EFFECT OF CITRATE

[0110] EXAMPLE 11

[0111] Fe-Cit-Non MRP and Fe-MRP (2.2NaCas:1Glc:1.05MD17) (7.1-8.8%TS, 5.5% protein- carbohydrate, 1.6-2.6% Fe, d.b.)

[0112] Non MRP and MRP solutions added to Fe-Cit complex in solution prior to assessment of heat stability

[0113] Unheated (Non MRP) and heated mixture MRP - [NaCas:glucose:Maltodextrin DE 17 (2.2 protein:1 .0 glc: 1 .05 maltodextrin)

[0114] An unheated mixture (Non MRP) of 12.86% TS protein-CHO (pH6.6) and a heated mixture (MRP) formed by heating 12.86% TS protein-CHO (without pH adjustment) was heated in a kitchen steamer for ~ 1 hr for preparation of MRP. The heated mixture was brown and had reduced pH (6.3), which is evidence of the Maillard Reaction occurring. The Non MRP (pH6.6) or MRP mixture (pH6.3) was combined with an aqueous mixture of ferrous sulphate and trisodium citrate (molar ratio ~1 Fe:2.5citrate) to obtain Fe-Non MRP and Fe-MRP in 21 mM Fe (1 .6% Fe, d.b.) or 41 mM Fe, (2.6% Fe, d.b.). Addition of Fe-citrate (Fe-Cit) to all samples led to formation of an olive to brown colour and all were transparent without precipitates.

[0115] Fig. 11 a shows mixtures prior to heating (Extreme Left: 7.1 %TS Fe-Non MRP in 20.6 mM Fe (1 .6% Fe d.b.) and 51 .2 mM citrate, pH6.39, clear; Middle Left: 8.8%TS Fe-Non MRP in 41 .1 mM Fe (2.6% Fe d.b.) and 102.4 mM citrate, pH6.31 , clear; Middle Right: 7.1 %TS Fe-MRP in 20.6 mM Fe (1 .6% Fe d.b.) and 51 .2 mM citrate, pH6.33, clear; Extreme Right: 8.8%TS Fe- MRP in 41 .1 mM Fe (2.6% Fe d.b.) and 102.4 mM citrate, pH6.24, clear).

[0116] Assessment of heat stability; Heat stability was tested by heatin the samples in a kitchen steamer for 15 min. Samples darkened on heating. There were no signs of precipitation. All samples were heat stable. Fig. 11 b shows mixtures after heating (Extreme Left: 7.1 %TS Fe-Non MRP in 20.6 mM Fe (1 .6% Fe d.b.) and 51 .2 mM citrate, pH 6.39 before heat, pH 6.22 after heat, dark but clear after heat; Middle Left: Fe-Non MRP (8.8%%TS) in

[0117] 41 .1 mM Fe (2.6% Fe d.b.) and 102.4 mM citrate, pH 6.31 before heat, pH 6.08 after heat, dark but clear after heat; Middle Right: Fe-MRP (7.1 %TS) in 20.6 mM Fe (1 .6% Fe d.b.) and

[0118] 51 .2 mM citrate, pH 6.33 before heat, pH 6.28 after heat, dark but clear after heat; Extreme Right: Fe-MRP (8.8%%TS) in 41 .1 mM Fe (2.6% Fe d.b.) and 102.4 mM citrate, pH6.24 before heat, pH 6.23 after heat, dark but clear).

[0119] This experiment provides an example of where MRP may be formed on heating previously unheated Fe-citrate-protein-CHO mixtures or additional MRP may be formed by heating MRP in the presence of Fe and citrate.

[0120] EXAMPLE 12

[0121] Fe-Non MRP (2.2NaCas:1.0Glc:1.05MD17) (5.5% protein-carbohydrate, 10-41 mMolal Fe)

[0122] Comparison of Fe-Non MRP made with and without added citrate, where citrate was added to protein-CHO prior to addition ferrous sulphate, followed by assessment of heat stability Unheated mixtures of 12.86% TS protein-CHO (Ratio 2.2NaCas:1 Glc:1 .05MD17) with initial pH 6.6 and pH-adjusted unheated mixtures of protein-CHO (Non MRP) adjusted to pH between 7.4 to 8.2 were prepared. Where pH adjustment was carried out, this was done with NaHCO3or NaHCO3 / NaCitrate and then the mixture added into 96 mMolal ferrous sulphate solution. The unadjusted and pH-adjusted unheated mixtures of ferrous sulphate- protein-CHO were used directly for heat stability assessment.

[0123] Ferrous sulphate addition (Without citrate)

[0124] On addition of ferrous sulphate solution to the protein-CHO mixture (Ratio 2.2 Cas:1 .0glc:1 .05MD) without pH adjustment, the Fe-Non MRP with 20 mMolal Fe coagulated prior to heating. With pH-adjustment with NaHCO3prior to the addition of ferrous sulphate, the Fe-Non MRP with 10 mMolal Fe samples were clear. All Fe-Non MRP mixtures had 5.5% protein-CHO solids (2.85% NaCas,1 .30% glc, 1 .36% MD17). Fig. 12a shows Fe-Non MRP without citrate (prior to heat treatment) (Left: Fe-Non MRP (5.5% protein-carbohydrate in 20 mMolal Fe), pH 6.78 after Fe addition, cloudy; Middle: Fe-Non MRP (5.5% protein-carbohydrate in 10 mMolal Fe), pH 7.7 before Fe addition, pH 7.56 after Fe addition, clear; Right: Fe-Non MRP (5.5% protein-carbohydrate in 10 mMolal Fe), pH 8.2 before Fe addition, pH 8.0 after Fe addition, clear).

[0125] Assessment of heat stability (Without citrate): All Fe-Non MRP mixtures without citrate were precipitated or cloudy when heated in a kitchen steamer for 15 min. All Fe-Non MRP mixtures had 5.5% protein-CHO solids (2.85% NaCas:1 .30% glc: 1 .36% MD17). Figure 12b shows Fe-Non MRP without citrate after heat treatment in steam for 15 min (Left: Fe-Non MRP in (5.5% protein-carbohydrate in 20 mMolal Fe), pH 6.78 after Fe addition prior to heat, Final after heat pH 5.6, cloudy; Middle: Fe-Non MRP (5.5% protein-carbohydrate in 10 mMolal Fe), pH 7.56 after Fe addition prior to heat, Final after heat pH 8.4, cloudy; Right: Fe-Non MRP (5.5% protein-carbohydrate i n 10 mMolal Fe), pH 8.2 after Fe addition prior to heat, Final after heat pH 8.2, cloudy). While soluble Fe-complexes can be formed in 10 mMolal Fe at pH>7.5 prior to heating, they are not heat stable.

[0126] Ferrous sulphate addition to citrated protein-CHO mixture

[0127] Solid sodium citrate was added into Non MRP (Ratio 2.2 Cas:1 .0Glc:1 .05MD17) (with prior pH adjustment with NaHCO3). Ferrous sulphate was added to the citrated protein-CHO mixtures. All Fe-Non MRP mixtures had 5.5% protein-CHO solids (2.85% NaCas,1 .30% glc, 1 .36% MD17. All Fe-Non MRP in 21-41 mMolal Fe samples were clear priorto heat treatment. Fig. 12c shows Fe-citrated Non MRP prior to heat treatment (with NaHCO3 / citrate added to Non MRP prior to addition of Fe) (Left: Fe-Cit-Non MRP (5.5% protein-carbohydrate in 51 mMolal citrate and 41 mMolal Fe, pH 7.85 before citrate addition, After citrate and Fe pH7.66, clear; Middle: Fe-Cit-Non MRP (5.5% protein- carbohydrate in 103 mMolal citrate, 21 mMolal Fe, pH 7.43 before citrate addition, After citrate and Fe pH7.92, clear; Right: Fe-Non MRP (5.5% protein-carbohydrate in 103 mMolal citrate, 40 mMolal Fe, pH 8.2 before citrate addition. After citrate and Fe pH7.12, clear).

[0128] Assessment of heat stability (With citrate): The final mixtures (ferrous sulphate added to citrated protein-CHO mixture) were heated in a kitchen steamer with for 15 min. All Fe-Non MRP mixtures had 5.5% protein-CHO solids (2.85% NaCas:1 .30% glc: 1 .36% MD17). All samples darkened but remained clear after the heat treatment. This shows that soluble Fe- complexes are maintained in the presence of citrate and high pH. The darkening may be due to further Maillard reactions. Fig. 12d shows Fe-citrated Non MRP after heat treatment (with NaHCO3 / citrate added to Non MRP prior to addition of Fe) (Left: Fe-Cit-Non MRP (5.5% protein-carbohydrate in 51 mMolal citrate and 41 mMolal Fe) , After Citrate and Fe before heat pH 7.66, Final pH after heat pH 8.38, clear; Middle: Fe-Cit-Non MRP (5.5% protein-carbohydrate in 103 mMolal citrate and 21 mMolal Fe, After Citrate and Fe before heat pH 7.92, Final pH after heat pH 8.38, clear; Right: Fe-Non MRP (5.5% protein- carbohydrate in 103 mMolal citrate and 40 mMolal , After Citrate and Fe before heat 7.12, Final pH after heat pH 7.52, clear).

[0129] Fourth Embodiment of the Invention

[0130] HEAT STABILITY - EXAMPLES WITH NaCASEINATE AS THE PROTEIN SOURCE WITH ADDITION OF FIBERSOL SHOWING EFFECT OF CITRATE

[0131] EXAMPLE 13a

[0132] Fe-Cit-MRP (2.2NaCas:1Glc:1.05MD17:1.05Fibersol & 2.2NaCas:1 Glc:1.05MD17:2.09Fibersol), (11.1-12.2%TS), (2.44-2.73%Fe, d.b.)

[0133] Addition ofFibersoi in NaCas-giu-MD17 mixture prior to heat treatment for MRP formation, followed by addition offerrous-citrate complex prior to assessment of heat stability

[0134] Fibersol was added into the unheated mixtures of protein-glc-Maltodextrin DE17 to obtain 15.7%TS (Ratio 2.2NaCas: 1 Glc:1 .05MD17:1 ,05Fibersol ) and 18.5% TS (2.2NaCas:1 Glc:1.05MD17:2.09Fibersol) mixtures, which had a natural unadjusted pH of pH6.5. The mixtures were heated for 60 min in a kitchen steamer to form MRP. The pH of the MRP mixture was pH 6.3. The MRP was added into a ferrous-citrate mixture (96 mMolal ferrous sulphate: 240 mMolal citrate). Both the Fe-Cit-MRP mixtures were clear. Fig. 13a shows Fe-citrate-MRP prior to heat treatment (Left: 11 .07%TS Fe-Cit-MRP comprising 6.77% MRP (2.81 % NaCas, 1 .28% glc, 1 .34% MD17, 1 .34% fibersol) in 135 mMolal cit, 54 mMolal Fe, (2.73% Fe, d.b.), pH 6.50 before Fe-Cit, pH 6.12 after Fe-Cit, clear; Right: 12.24%TS Fe-Cit-MRP comprising 8% MRP (2.77% NaCas, 1 .32% glc, 1.32% MD17, 2.64% fibersol) in 133 mMolal cit, 54 mMolal Fe, (2.44% Fe, d.b.), pH 6.50 before Fe-Cit, pH 6.12 after Fe-Cit, clear).

[0135] Assessment of heat stability: The Fe-Cit-MRP mixture was heated again in a kitchen steamer for 15 min for assessment of heat stability. All Fe-Cit-MRP complexes were heat stable. Fig. 13b shows Fe-citrate-MRP after heat treatment. (Left: 11 .07%TS Fe-Cit-MRP comprising 6.77% MRP (2.81 % NaCas, 1 .28% glc, 1 .34% maltodextrin DE17, 1 .34% fibersol) in 135 mMolal cit, 54 mMolal Fe,(2.73% Fe, d.b.), pH 6.50 before Fe-Cit, pH 6.12 after Fe-Cit, pH 5.83 after heat, clear; Right: 12.24%TS Fe-Cit-MRP comprising 8% MRP (2.77% NaCas, 1 .32% glc, 1 .32% maltodextrin DE17, 2.64% fibersol) in 133 mMolal cit, 54 mMolal Fe, (2.44% Fe, d.b.), pH 6.50 before Fe-Cit, pH 6.12 after Fe-Cit, pH 5.83 after heat, clear).

[0136] EXAMPLE 13b

[0137] Fe-Cit-MRP (2.22NaCas:1Glc:1.06MD17:3.96Fibersol) (14.4%TS), (3.74%Fe, d.b.)

[0138] Addition ofFibersoi in NaCas-glu-MD17 mixture prior to heat treatment for MRP formation, followed by addition offerrous-citrate complex prior to assessment of heat stability

[0139] Fibersol was added into the unheated mixtures of protein-glc-Maltodextrin DE17 to obtain 10.73%TS mixture (Ratio 2.22NaCas:1 Glc:1 .06MD17:3.96Fibersol), which had a natural unadjusted pH of pH 6.5). The mixtures were heated for 60 min in a kitchen steamer to form MRP. The pH of the MRP mixture was pH 6.13. The MRP was added into a ferrous- citrate mixture (101 mMolal ferrous sulphate: 192 mMolal citrate) solution. The Fe-Cit-MRP mixture was clear before heating. The samples maintained clarity after heating for 15 min in steam, showing that they was heat stable. (Fig. 13c (Left) - 10.73% TS MRP (without Fe), pH 6.13, clear MRP (without Fe); Fig. 13c (Middle) - Fe-citrate-MRP before heating (14.3%TS Fe-Cit-MRP compromising 7.9% MRP (2.13% NaCas, 0.96% glc, 1 .02% MD17, 3.80% fibersol) in 192 mMolal cit and101 mMolal Fe (3.74% Fe, d.b.), pH 6.50 before Fe-Cit, pH 6.13 after Fe-Cit before heat, clear; Fig. 13c (Right) - 14.3%TS Fe-Cit-MRP compromising 7.9% MRP (2.13% NaCas, 0.96% glc, 1 .02% MD17, 3.80% fibersol) in 192 mMolal cit and101 mMolal Fe (3.74% Fe, d.b.), pH 6.13 after Fe-Cit before heat, pH 5.55 after heat stability assessment, clear).

[0140] EXAMPLE 13c

[0141] Fe-Cit-Non MRP (comprising various ratios of NaCas, Glc, Maltodextrin DE17 and Fibersol) and Fe (2.73-3.43%Fe, d.b.)

[0142] Addition ofFibersoi in NaCas-giu-MD17 mixture prior to heat treatment for MRP formation, followed by addition offerrous-citrate complex prior to assessment of heat stability

[0143] Fibersol was added into the unheated mixtures of protein-glc-Maltodextrin DE17 (natural unadjusted pH —6.5) and varying amounts of Fe-Cit to obtain mixtures with (i) 11 .07%TS with 6.77% protein-CHO (Ratio 2.2NaCas, 1 .0Glc,1 .05MD17, 1 .05Fibersol ), (ii) 12.24% TS with 8.00 % protein-CHO (Ratio 2.2NaCas, 1 .OGlc, 1 .05 MD17, 2.09Fibersol) and (Hi) 13.23 %TS with (2.2NaCas, 1 .OGlc, 1 .05MD17, 1 .05Fibersol). All the Fe-Cit-Non MRP mixtures were clear before heating and also after heat stability assessment in steam for 15 min.

[0144] Fig. 13d shows Fe-citrate-Non MRP prior to heat treatment (Left: 11 .07%TS Fe-cit-Non MRP with 6.77% protein-CHO (2.81 % NaCas, 1 .28% glc, 1 .34% Maltodextrin DE17 and 1 .34% fibersol) in 13 mMolal citrate and 54 mMolal Fe (2.73% Fe, d.b.), pH 6.46 before Fe-Cit, pH 6.15 after Fe-Cit before heat, clear; Middle: 12.24%TS Fe-Cit-Non MRP compromising 8% MRP (2.77% NaCas, 1 .26% glc, 1 .32% MD17, 2.64% fibersol) in 133 mMolal cit and 54 mMolal Fe (2.44% Fe, d.b.), pH 6.45 before Fe-Cit, pH 6.10 after Fe-Cit before heat, clear; Right: 13.23%TS Fe-Cit-Non MRP compromising 6.77% MRP (2.81% NaCas, 1.28% glc, 1 .34% MD17, 1 .34% fibersol) in 202 mMolal cit and 81 mMolal Fe (3.43% Fe, d.b.), pH 6.06 after Fe-Cit before heat, clear).

[0145] Fig. 13e shows Fe-citrate-Non MRP after heat stability assessment (Left: 11 .07%TS Fe-cit- Non MRP with 6.77% protein-CHO (2.81 % NaCas, 1 .28% glc, 1 .34% Maltodextrin DE17 and 1 .34% fibersol) in 133 mMolal citrate and 54 mMolal Fe (2.73% Fe, d.b.), pH 6.15 after Fe- Cit before heat, pH 5.9 after heat, clear; Middle: 12.24%TS Fe-Cit-Non MRP compromising 8% MRP (2.77% NaCas, 1 .26% glc, 1 .32% MD17, 2.64% fibersol) in 133 mMolal cit and 54 mMolal Fe (2.44% Fe, d.b.), pH 6.10 after Fe-Cit before heat, pH 5.8 after heat, clear; Right: 13.23%TS Fe-Cit-Non MRP compromising 6.77% MRP (2.81 % NaCas, 1 .28% glc, 1 .34% MD17, 1 .34% fibersol) in 202 mMolal cit and 81 mMolal Fe (3.43% Fe, d.b.), pH 6.06 after Fe-Cit before heat, pH 5.73 after heat, clear).

[0146] Fifth Embodiment of the Invention

[0147] HEAT STABILITY - EXAMPLES WITH HYDROLYSED WHEY PROTEIN ISOLATE AS THE

[0148] PROTEIN SOURCE SHOWING EFFECT OF CITRATE

[0149] EXAMPLE 14

[0150] Fe-Cit-Non MRP & Fe-Cit-MRP (1.1 HWPI:1.0Glc:1.05MD17)

[0151] MRP solutions added to Fe-Cit complex in solution prior to assessment of heat stability

[0152] Heated mixture (HWPI-glc-MD17) [HWPI:glucose:Maltodextrin DE 17 (1.1 HWPI:1.0Glc:1.05MD17)1

[0153] A mixture 9.53% TS protein-CHO (Ratio 1 .1 HWPI:1 .0Glc:1 .05MD17) was prepared. The unheated protein-CHO mixture (Non MRP) was diluted with water to obtain a 7.14% protein-carbohydrate mixture (~pH 6.9) or water / 1 mM NaHCO3to obtain a 7.14% protein- carbohydrate TS mixture (pH 7.98) or water / 1 M NaOH) to obtain a 7.14%% protein- carbohydrate mixture (pH 10.2). The unadjusted and pH adjusted protein-CHO mixtures were heated in a kitchen steamer for 60 min. The pH of the heated protein-CHO (MRP) was pH 6.65 for the non-pH unadjusted mixture, while they were pH 8.43 and pH 7.93 for the mixtures adjusted with NaHCO3and NaOH respectively. All solutions browned on heating, with more browning as pH increased. Heat treatment of the protein-CHO mixture without pH-adjustment resulted in a cloudy solution, while the base adjusted protein-CHO mixtures were clear. Fig. 14a shows unheated Non MRP and MRP mixtures (7.14% protein(HWPI)-carbohydrate) without Fe (Left: Non MRP without Fe (pH6.9), translucent; Middle Left: MRP (pH 6.9 before heat, after heat pH 6.65), cloudy; Middle Right: MRP (pH 7.98 before heat, after heat pH 8.43), pH adjustment with NaHCO3prior to heating for MRP formation, clear; Right: MRP (pH 10.2 before heat, after heat pH 7.93) - pH adjustment with NaOH prior to heating for MRP formation, clear).

[0154] Non MRP and MRP mixtures were mixed with Fe-citrate solution. The resultant Fe-Cit-MRP mixtures (6.26 & 8.44%TS) contained 4.08% MRP solids 1 .43% HWPI, 1 .30%glc, 1 .36% MD1 7) and Fe (27 or 55 mMolal). Addition of the Fe-citrate solution to Non-MRP and MRP resulted in the development of brown colour. Fe-cit-Non MRP were transparent before heating. Fe-cit-MRP made from MRP formed by heating at the unadjusted pH were cloudy, whereas Fe-cit-MRP made from MRP formed by heating at the high pH to form MRP prior to Fe-cit addition were clear Fe-Cit-Non MRP and Fe-Cit-MRP. All samples had 4.08% protein- CHO solids (1 .43% HWPI:1 ,30%glc:1 ,36%MD17).

[0155] Fig 14 b shows samples before heating (Extreme Left: Fe-Cit-Non MRP in and 68 mMolal cit and 27mMolal Fe, pH 6.34 after addition of Fe-cit, clear; Second from Left: Fe-Cit-Non MRP in 137 mMolal cit and 55 mMolal Fe, pH 6.18 after addition of Fe-cit, clear; Third from Left: Fe-Cit-MRP in 68 mMolal cit and 27mMolal, MRP formed by heat treatment of non-pH- adjusted protein-CHO (natural pH - pH 6.9), pH 6.36 after addition of Fe-cit, cloudy; Fourth from Left: Fe-Cit-MRP in 137 mMolal cit and 55 mMolal Fe, MRP formed by heat treatment of non-pH adjusted protein-CHO (natural pH - pH 6.9), pH 6.21 after addition of Fe-cit, cloudy; Fourth from Right: Fe-Cit-MRP in 68 mMolal cit and 27mMolal Fe , MRP formed by heat treatment of protein-CHO (pH adjusted to pH 8 with NaHCO3 prior to heating), pH 6.97 after addition of Fe-cit, clear; Third from Right: Fe-Cit-MRP in 137 mMolal cit and 55 mMolal Fe,MRP formed by heat treatment of protein-CHO (pH adjusted to pH 8 with NaHCO3 prior to heating), pH 6.68 after addition of Fe-cit, clear; Second from Right: Fe- Cit-Non MRP in 68 mMolal cit and 27mMolal Fe, MRP formed by heat treatment of protein- CHO (pH adjusted to 10.2 with NaOH prior to heating), pH 6.35 after addition of Fe-cit, clear; Extreme Right: Fe-Cit-Non MRP in 137 mMolal cit and 55 mMolal Fe (3.62% Fe, d.b.), MRP formed by heat treatment of protein-CHO (pH adjusted to 10.2 with NaOH prior to heating), pH 6.36 after addition of Fe-cit, clear).

[0156] Assessment of heat stability: The Fe-Cit-Non MRP and Fe-Cit-MRP mixtures were heated again in a kitchen steamer for 15 min for assessment of heat stability. All Fe-Cit-Non MRP complexes containing 27 mMolal Fe or 55 molal Fe were not heat stable, with cloudy precipitates and pH after heat treatment reduced to 6.34 and 6.18 respectively. After heat treatment of Fe-Cit-MRP for ~15 min, some samples were cloudy while others were transparent. The Fe-Cit-MRP samples made from MRP formed by heat treatment of non- pH-adjusted protein-CHO were not heat stable. However, Fe-Cit-MRP samples made from MRP formed by heat treatment of pH-adjusted protein-CHO (adjusted to pH 8 with NaHCO3or pH10.2 with NaOH prior to heating) were heat stable. Fig. 14c shows the samples after heat treatment of Fe-Cit-Non MRP and Fe-Cit-MRP containing 4.08% protein-CHO solids (1 .43% HWPI:1 .30%glc:1 .36%MD17). (Extreme Left: Fe-Cit-Non MRP in and 68 mMolal cit and 27mMolal Fe, pH 6.34 after addition of Fe-cit, pH 6.26 after heat, cloudy; Second from Left: Fe-Cit-Non MRP in 137 mMolal cit and 55 mMolal Fe, pH 6.18 after addition of Fe-cit, pH 6.05 after heat, aggregation, cloudy; Third from Left: Fe-Cit-MRP in 68 mMolal cit and 27mMolal Fe, MRP formed by heat treatment of non-pH-adjusted protein-CHO (natural pH - pH 6.9), pH 6.36 after addition of Fe-cit, pH 6.13 after heat, cloudy; Fourth from Left: Fe- Cit-MRP in 137 mMolal cit and 55 mMolal Fe, MRP formed by heat treatment of non-pH adjusted protein-CHO (natural pH - pH 6.9), pH 6.21 after addition of Fe-cit, pH 5.95 after heat, cloudy; Fourth from Right: Fe-Cit-MRP in 68 mMolal cit and 27mMolal Fe, MRP formed by heat treatment of protein-CHO (pH adjusted to pH 8 with NaHCO3 prior to heating), pH 6.97 after addition of Fe-cit, pH 6.95 after heat, clear; Third from Right: Fe-Cit- MRP in 137 mMolal cit and 55 mMolal Fe, pH 6.68 after addition of Fe-cit pH 6.55 after heat, clear; Second from Right: Fe-Cit-MRP in 68 mMolal cit and 27mMolal Fe, MRP formed by heat treatment of protein-CHO (pH adjusted to 10.2 with NaOH prior to heating), pH 6.65 after addition of Fe-cit, pH 6.09 after heat, clear; Extreme Right: Fe-Cit-Non MRP in 137 mMolal cit and 55 mMolal Fe, MRP formed by heat treatment of protein-CHO (pH adjusted to 10.2 with NaOH prior to heating), pH 6.36 after addition of Fe-cit, pH 5.87 after heat, clear).

[0157] Sixth Embodiment of the Invention

[0158] HEAT STABILITY - EXAMPLES WITH NaCASEINATE AS THE PROTEIN SOURCE WITH VARYING RATIOS OF PROTEIN:CATBOHYDRATE SHOWING EFFECT OF CITRATE

[0159] EXAMPLE 15

[0160] Fe-Cit-MRP (Various Protein:CHO ratios), Various Fe (2.7-4.8% d.b.)

[0161] MRP solutions comprising various ratios of proteimCHO added to Fe-Cit complex in solution prior to assessment of heat stability

[0162] MRP was made by heat treatment (60 min in kitchen steamer) of various protein-CHO mixtures [8-16% protein-CHO solids, varying proteimCHO ratios (4:96 to 21 : 1 )] at the natural pH (—6.5) . After heat treatment there was slight browning and a slight decrease in pH (Fig. 15a&d). The MRP was added to a Fe-Cit mixture to obtain final formulations with mixtures with 8-13% TS (with 3.6-6.9% protein-CHO solids), depending on the formulation (Fig. 15b&d). The Fe-Cit-MRP formulations were heated in a kitchen steamer for 15 min to test for heat stability. Except for the formulation with 4.8% Fe (d.b.) which was slightly cloudy for the heat stability assessment, all formulations with 92.7-3.9% Fe, d.b. were heat stable (Fig. 15c&f).

[0163] Fig. 15 a shows MRP mixtures, pH ~6.5 (without Fe), with various proteimCHO (4.5:95.5 to 1 :1 ) ratios. (Extreme Left : (Ratio proteimCHO = 4.5:95.5); 16%TS MRP (0.67% protein, 0.67% MD17, 14.67% glc), pH 6.35, translucent; Second from Left: (Ratio protein:CHO=10:90); 15.9%TS MRP (1 .33% protein, 1 .33% MD17, 13.2% glc), pH 6.33, clear; Third from Left: (Ratio protein:CHO=16.7:83.3); 10.7%TS MRP (1.67% protein, 1.67% MD17, 7.33% glc), pH 6.37, clear; Third from Right: (Ratio protein:CHO=33.33:66.6); 10.3%TS MRP (3.33% protein, 3.33% MD17, 3.67% glc), pH 6.36, clear; Second from Right: (Ratio protein:CHO=50:50); 10%TS MRP (5.0% protein, 5.0% MD17), pH6.38, clear; Extreme Right: (Ratio protein:CHO=50:50); 10%TS MRP (5.0% protein, 5.0% MD17), pH 6.36, clear)

[0164] Fig. 15 b shows samples before heating of Fe-Cit- MRP mixtures with various protein: CHO (4.5:95.5 to 1 :1 ) ratios. (Extreme Left: (Ratio protein:CHO= 4.5:95); 11 .22%TS Fe-Cit-MRP (0.29% protein, 0.29% MD17, 6.29% glc) in 137 mMolal citrate and 55 mMolal Fe (2.74%, d.b.), pH 6.04, clear; Second from Left: (Ratio proteimCHO =10:90); 11 .16%TS Fe-Cit-MRP (0.57% protein, 0.57% MD17, 5.66% glc) in 137 mMolal citrate and 55 mMolal Fe (2.75%, d.b.), pH 6.03, clear; Third from Left: (Ratio protein:CHO=16.7:83.3); 8.94%TS Fe-Cit-MRP (0.71% protein, 0.71 % MD17, 3.14% glc) in 137 mMolal citrate and 55 mMolal Fe (3.44%, d.b.), pH 6.05, clear; Third from Right: (Ratio protein:CHO=33.3:66.6); 8.79%TS Fe-Cit-MRP (1 .43% protein, 1 .43% MD17, 1 .57% glc) in in 137 mMolal citrate and 55 mMolal Fe (3.49%, d.b.), pH 6.06, clear; Second from Right: (Ratio protein:CHO=50:50); 8.65%TS Fe-Cit-MRP (2.14% protein, 2.14% MD17) in in 137 mMolal citrate and 55 mMolal Fe (3.55%, d.b.), pH 6.08, clear; Extreme Right: (Ratio protein:CHC=50:50): 12.87% TS Fe-Cit-MRP (2.14% protein, 2.14% MD17) in 267 mMolal citrate and 110 mMolal Fe (4.77%, d.b.), pH 5.85, slightly cloudy).

[0165] Fig. 15c shows heated Fe-Cit- MRP mixtures, with various protein: CHO (4.5:95 to 1 :1 ) ratios. (Extreme from Left: (Ratio protei CHO = 4.5:95); 11 .22%TS Fe-Cit-MRP (0.29% protein, 0.29% MD17, 6.29% glc) in 137 mMolal citrate and 55 mMolal Fe (2.74%, d.b.), pH 6.04 before heat, pH 6.04 after heat, clear; Second from Left:(Ratio proteimCHO =10:90); 11 .16%TS Fe-Cit-MRP (0.57% protein, 0.57% MD17, 5.66% glc) in 137 mMolal citrate and 55 mMolal Fe (2.75%, d.b.), pH 6.03 before heat, pH after heat, clear; Third from Left: (Ratio protein:CHO=16.7:83.3); 8.94%TS Fe-Cit-MRP (0.71% protein, 0.71 % MD17, 3.14% glc) in 137 mMolal citrate and 55 mMolal Fe (3.44%, d.b.), pH 6.50 before heat, pH after heat, clear; Third from Right: (Ratio protein:CHO=33.3:66.6); 8.79%TS Fe-Cit-MRP (1 .43% protein, 1 .43% MD17, 1 .57% glc) in in 137 mMolal citrate and 55 mMolal Fe (3.49%, d.b.), pH 6.06 before heat, pH 6.03 after heat, clear; Second from Right: (Ratio protein:CHC=50:50); 8.65%TS Fe-Cit-MRP (2.14% protein, 2.14% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.55%, d.b.), pH 6.08 before heat, pH 6.04 after heat, clear; Extreme Right: (Ratio protein:CHC=50:50); 12.87% TS Fe-Cit-MRP (2.14% protein, 2.14% MD17) in 267 mMolal citrate and 110 mMolal Fe (4.77%, d.b.), pH 5.85 before heat, pH 5.87 after heat, slightly cloudy)

[0166] Figure 15 d shows MRP mixtures, pH ~6.5 (without Fe), with various proteimCHO (95.5:4.5 to 1 :1 ) ratios. (Extreme Left: (Ratio proteimCHO = 95.5:4.5); 14.67%TS MRP (14.0% protein, 0.67% MD17), pH 6.35, translucent; Second from Left: (Ratio proteimCHO = 89.5:10.5); 12.67%TS MRP (11 .33% protein, 1 .33% MD17), pH 6.21 , translucent; Middle: (Ratio protein:CHO= 85.7:14.3); 9.33%TS MRP (8.0% protein, 1.33% MD17), pH 6.26, translucent; Second from Right: (Ratio protein:CHO=83.3:16.7); 10.0%TS MRP (8.33% protein, 1 .67% MD17), pH 6.28, translucent; Extreme Right: (Ratio protein:CHO=60:40); 8.33%TS MRP (5.0% protein, 3.33% MD17), pH 6.30, translucent).

[0167] Fig. 15e shows Fe-Cit- MRP mixtures before heat, with various protein: CHO 95.5:4.5 to 1 :1 ) ratios. (Extreme Left: (Ratio proteimCHO = 95.5:4.5) 10.65%TS Fe-Cit-MRP (6.0% protein, 0.29% MD17) in 137 mMolal citrate and 55 mMolal Fe (2.88%, d.b.), pH 6.12, clear; Second from Left: (Ratio proteimCHO = 89.5:10.5); 9.79%TS Fe-Cit-MRP (4.86% protein, 0.57% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.14%, d.b.), pH 6.02, clear; Middle: (Ratio protein:CHO= 85.7:14.3); 9.33%TS Fe-Cit-MRP (3.43% protein, 0.57% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.67%, d.b.), pH 6.04, clear; Second from Right: (Ratio protein:CHO=83.3:16.7); 8.65%TS Fe-Cit-MRP (3.57% protein, 0.71 % MD17) in 137 mMolal citrate and 55 mMolal Fe (3.55%, d.b.), pH 6.04, clear; Extreme Right: (Ratio protein:CHO=60:40); 7.94%TS MRP (2.14% protein, 1 .43% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.87%, d.b.), pH 6.06, clear).

[0168] Fig. 15 f. shows heated Fe-Cit- MRP mixtures, with various protein: CHO (95.5:4.5 to 1 :1 ) ratios. (Extreme Left: (Ratio proteimCHO = 95.5:4.5); 10.65%TS Fe-Cit-MRP (6.0% protein, 0.29% MD17) in 137 mMolal citrate and 55 mMolal Fe (2.88%, d.b.), pH 6.12 before heat, pH 6.04 after heat, clear; Second from Left: (Ratio proteimCHO = 89.5:10.5); 9.79%TS Fe- Cit-MRP (4.86% protein, 0.57% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.14%, d.b.), pH 6.02 before heat, pH 6.02 after heat, clear; Middle (Ratio protein:CHO= 85.7:14.3); 9.33%TS Fe-Cit-MRP (3.43% protein, 0.57% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.67%, d.b.), pH 6.04 before heat, clear; Second from Right: (Ratio protein:CHO=83.3:16.7): 8.65%TS Fe-Cit-MRP (3.57% protein, 0.71 % MD17) in 137 mMolal citrate and 55 mMolal Fe (3.55%, d.b.), pH 6.04 before heat, pH 6.04 after heat, clear; Extreme Right: (Ratio protein:CHO=60:40); 7.94%TS MRP (2.14% protein, 1 .43% MD17) in 137 mMolal citrate and 55 mMolal Fe (3.87%, d.b.), pH 6.06 before heat, pH 6.04 after heat, clear).

[0169] Seventh Embodiment of the Invention

[0170] HEAT STABILITY - EXAMPLES WITH NaCASEINATE AS THE PROTEIN SOURCE SHOWING EFFECT OF PHOSPHATE

[0171] EXAMPLE 16

[0172] Fe-phosphate-Non MRP and Fe-phosphate-MRP (I.ONaCas: 1.0MD17) (5.5%TS, 2.8% Fe, d.b.), and Fe-phosphate-MRP (I.ONaCas: 1.0MD17, 1.7% Fe, d.b.) -without addition of base

[0173] Sodium phosphate was added to Non MRP and MRP solutions prior to addition of ferrous sulphate and assessment of heat stability

[0174] Unheated (Non MRP) and heated mixture MRP - [NaCas: Maltodextrin DE 17 (1 .0:1 .0)]

[0175] An unheated mixture (Non MRP) of 10% TS protein-CHO (pH~ 6.6) and a heated mixture (MRP) formed by heating 10% TS protein-CHO (without pH adjustment) in a kitchen steamer for - 1 hr for preparation of MRP. The heated mixture was brown and had reduced pH -6.4, which is evidence of the Maillard Reaction occurring. A sodium phosphate solution was added into the Non MRP (pH 6.6) and MRP mixture (pH6.3), followed by the addition of a ferrous sulphate solution. The final Fe-phosphate-Non MRP and Fe- phosphate-MRP (5.5% TS with 4.3% protein-CHO solids, 2.8% fe d.b.). Both of the final mixtures (pH 7.5 for Fe-Non MRP and pH 6.7 for Fe-MRP) had precipitates and were not subjected to further heat stability assessment. The mixture with MRP had less visible precipitate that that with non-MRP. A Fe-MRP formulation with lower levels of Fe (4.9% TS with 4.3% protein-CHO solids, 1 .7% Fe d.b.) with pH 9.3 prior to heating, was heat stable after heat treatment in steam for 15 min. The pH of Fe-MRP after heating was 8.6 with no obvious visual precipitation.

[0176] Fig. 16 shows Fe-phosphate-Non MRP and Fe-phosphate-MRP. (Left: 5.5%TS Fe- phosphate-Non MRP (with 2.14% NaCas, 2.14% MD17) in 50 mMolal phosphate and 27.5 mMolal Fe (2.8% d.b.), final pH 6.7, heavy precipitate; Middle: 5.5%TS Fe-phosphate-MRP (with 2.14% NaCas, 2.14% MD17) in 50 mMolal phosphate and 27.5 mMolal Fe (2.8% d.b.), final pH 7.5, precipitate; Right: 4.9%TS Fe-phosphate-MRP (with 2.14% NaCas, 2.14% MD17) in 28 mMolal phosphate and 15 mMolal Fe (1 .7% d.b.), final pH 8.59, clear).

[0177] Eight Embodiment of the Invention

[0178] APPLICATIONS IN FOOD - EXAMPLES WITH NaCASEINATE AS THE PROTEIN SOURCE WITH VARIOUS FORMULATIONS AND ORDER OF PROCESSING

[0179] EXAMPLE 17

[0180] Fe-MRP (I.ONaCas: 1.0MD17) (6.86% MRP, 12.3 mM Fe) - Additions to food products

[0181] MRP formed by heating pH-adjusted 12% protein-carbohydrate mixture prior to addition of ferrous sulphate and Fe-additive added to fortify food. Refer to Table 2

[0182] Fe-additive formulation

[0183] A NaCaseinate-Maltodextrin DE17 mixture (20% TS) was pH-adjusted with 0.75 M NaHCO3.to obtain a pH adjusted 12% protein-carbohydrate mixture (pH 7.4). This mixture was heated in a kitchen steamer for ~1 h to obtain MRP (pH~8.6), termed MRP dj. The MRP solution was mixed with a solution of ferrous sulphate to obtain the Fe-MRP additive containing 6.86% MRP and 12.3 mMolal Fe (pH ~8.1 ).

[0184] Heat stability of Fe-additive

[0185] Heat treatment of the Fe-MRPAdj additive containing 6.86% MRP in 12.3 mMolal Fe (pH ~8.1) in steam for 15 min did not result in precipitation, showing that the Fe-MRPAdj additive was heat stable. Fig. 17a shows MRP and Fe-MRP samples. (Left: MRPAdj formed on heating pH- adjusted mixture [12% protein-carbohydrate (1 Caseinate:1 Maltodextrin MD 17)], pH before heating ~7.4, pH after heating ~8.6; Middle: Fe-MRPAdj(6.86% MRP in 12.33 mMolal Fe), pH ~8.1 ; Right: Fe-MRPAdj (6.86% MRP in 12.33 mMolal Fe) after heat treatment in steam for 15 min, pH after heating ~8.3, no precipitate).

[0186] Fe-fortified reconstituted skim milk

[0187] The Fe-MRPdj additive was added to a reconstituted skim milk solution, which was made by reconstituting instant skim milk powder in water. The Fe-fortified skim milk was comprised of 10% milk skim solids and 8.6-68.7 mg / 250 ml serve). Addition of Fe-MRP resulted in milks which a fawn to light chocolate colour, with increasing brownness as the Fe concentration was increased. All samples were stable to heating in steam for ~20 min. Fig. 17b Fe-fortified reconstituted skim milk made by addition of Fe-MRPAdj(6.86% MRP in 12.33 mMolal Fe) to reconstituted skim milk. (Top: Before heat treatment; Bottom: After heat treatment in steam for ~20 min. Extreme Left: 10% skim milk solids - No Fe; Before heat pH 6.5; Second from Left: 10% skim milk solids, 8.6 mg Fe / 250 ml serve, Before heat pH 6.6; Middle: 10% skim milk solids, 17.2 mg Fe / 250 ml serve; Before heat pH 6.6; Second from Right: 10% skim milk solids, 34.3 mg Fe / 250 ml serve, Before heat pH 6.7; Extreme Right: 10% skim milk solids, 68.7 mg Fe / 250 ml serve, Before heat pH 6.8).

[0188] Fe additive used for fortification of spring water

[0189] The Fe-MRPdj was added to lime flavoured spring water to obtain Fe-fortified spring water with 8.6 mg / 250 ml serve or 17.1 mg.250 ml serve. The samples darkened on heating in steam but were heat stable, indicating that the Fe-fortified spring water could be pasteurised. Fig. 17c shows Fe-fortified Spring water made by addition of Fe-MRPAdj(6.86% MRP in 12.33 mMolal Fe) to lime flavoured spring water. (Top: Before heat treatment; Bottom: After heat treatment in steam. Extreme Left: Spring water - No Fe; Before heat pH 4.4; Middle: Fe-fortified Spring water (8.6 mg Fe / 250 ml serve), Before heat pH ~5.4; Right: Fe-fortified Spring water (17.1 mg Fe / 250 ml serve), Before heat pH 6.8).

[0190] Fe-fortified reconstituted coconut milk

[0191] The Fe-MRPdjadditive was added to a coconut milk dispersion containing a coconut milk powder mix. The Fe-fortified coconut milk was comprised of 20% coconut milk ingredient solids and 8.6-68.7 mg / 250 ml serve. Samples were off-white to light brown, with samples containing increasing levels of Fe being darker brown. All samples were stable to heating in steam. Fig. 17d shows Fe-fortified coconut milk made by addition of Fe-MRPAdj(6.86% MRP in 12.33 mMolal Fe) to reconstituted coconut milk after heat treatment in a steamer for ~15 min. (Extreme Left: 20% coconut milk solids - No Fe; Before heat pH 6.5; Second from Left: 20% coconut milk solids, 8.6 mg Fe / 250 ml serve; Before heat pH 6.9; Middle: 20% coconut milk solids, 17.2 mg Fe / 250 ml serve; Before heat pH 7.1 ; Second from Right: 20% coconut milk solids, 34.3 mg Fe / 250 ml serve; Before heat pH 7.3; Extreme Right: 20% coconut milk solids, 68.7 mg Fe / 250 ml serve, Before heat pH 7.5).

[0192] Fe-fortified water-in-oil emulsions

[0193] An emulsion was made by mixing 70 g Fe-MRP (6.86% MRP, 12.3 mM Fe, pH 8.5) with 5 g oil in a blender to form a homogenous mixture containing -6.7% oil (-50% oil, dry basis). A stable water-in-oil emulsion was formed (Fig. 17e).

[0194] EXAMPLE 18

[0195] Fe-MRP (2.0NaCas: 1.0glucose:1MD17) (6.86% MRP, 12.3 mM Fe) additions to food products

[0196] Fe-MRP formed employing different order of processing: (a) heating a protein-carbohydrate mixture, followed by pH adjustment prior to addition of ferrous sulphate (Fe-MRPNat) or (b) pH-adjusting the protein-carbohydrate mixture before heating and addition of ferrous sulphate after heating (Fe-MRPAdj). Refer to Table 3. The Fe-MRP was then used to fortify a range of food products

[0197] Fe-additive formulation

[0198] MRP was made using two different orders of processing. For one, a Nacaseinate-glucose- Maltodextrin DE17 mixture (20% TS, pH 6.44) was heated in a kitchen steamer for -1 h to obtain MRP (pH~6.3) and then diluted with 0.75 M NaHCO3.to obtain 12% protein- carbohydrate mixture (pH 7.7). This MRP solution, termed (MRPNat) was mixed with a solution of ferrous sulphate to obtain the Fe-additive containing 6.86% MRP and 12.3 mMolal Fe (pH 7.6). The Fe-MRPNat additive was soluble.

[0199] For the other, a Nacaseinate-glucose-Maltodextrin DE17 mixture (20% TS) was pH- adjusted with 0.75 M NaHCO3to obtain a pH adjusted 12% protein-carbohydrate mixture (pH 7.45). This mixture was heated in a kitchen steamer for -1 h to obtain MRP (pH~8.4). The MRP solution , termed (MRPAdj) was mixed with a solution of ferrous sulphate to obtain the Fe-MRP additive containing 6.86% MRP and 12.3 mMolal Fe (pH 8.1 ). The Fe-MRPAdjadditive was soluble. The Fe-MRPAdjadditive a very dark brown compared to the Fe-MRPNat additive.

[0200] Heat stability of Fe-additive

[0201] Heat treatment of the Fe-MRPNat containing 6.86% MRP & 12.3 mMolal Fe (pH 7.6) resulted in darkening of the mixture. The Fe-MRPNat additive had a very fine precipitate when heated in steam for 10 min. The Fe-MRPAdjcontaining 6.86% MRP and 12.3 mMolal Fe (pH 8.1 ) was heat stable when subject to heat treatment in a steamer for 10 min. Fig. 18a shows MRP and Fe-MRP (6.86% MRP in 12.33 mMolal Fe) made using different order of processing.. MRP made by heating a protein-carbohydrate mixtures at different pH with before heat and after heat comparisons. (Extreme Left: MRPNat formed at natural pH (20%TS; 2Caseinate:1 MD17: 1 glucose), pH before heating was 6.56, pH after heating was 6.33; Second from Left:.Fe-MRPNat (pH7.6) before heating; MRPNat was adjusted to 7.66 prior to add Fe; Second from Right: Fe-MRPNat after heating in steam for 10 min (Fe addition to MRP formed on heating protein-carbohydrate mixture at the natural pH, followed by addition of base and then ferrous sulphate); Extreme Right: Fe-MRPAdjafter heating in steam for 10 min (Fe addition to MRPAdjformed on heating pH-adjusted protein-carbohydrate mixture prior to addition of ferrous sulphate, pH 8.1 was before heating).

[0202] Fe -fortified full-cream cow milk The Fe-MRP additives (Fe-MRPNat and Fe-MRP dj) were added to full-cream milk reconstituted from full-cream milk powder to obtain fortified milks with 5-60 mg Fe / 250 serve. The final formulations were half the strength of the original milk. Fe fortified halfstrength full cream milks were browner, with higher Fe levels having darker colour. With equivalent levels of Fe, darker colours were obtained with Fe-MRPAdjthan with Fe-MRPNat. At 40 mg or 60 mg Fe / serve milks fortified with Fe-MRPAdjwere not heat stable whereas halfstrength milk fortified with Fe-MRPNatat 60 mg / serve were heat stable when subject to heat treatment in a kitchen steamer for 15 min. Half strength full-cream milk formulations fortified with ferrous sulphate at levels of addition of 10, 30 and 60 mg Fe / 250 ml serve were also heat stable. Fig.18b shows Half-strength full cream milk and Fe-fortified halfstrength full cream milk made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe) to full-cream milk. MRP was made by heating protein-carbohydrate mixtures (1 NaCaseinate:glucose:1 Maltodextrin MD 17) at different pH. Top - Before heat and Bottom - after heat. Extreme Top-before heat; Bottom - after heating in a steamer for 15 min. Extreme Left: Half-strength full cream milk - no Fe; Before heat pH 6.7; Second from Left: Fe-fortified half-strength full cream milk containing 10 mg Fe / 250 ml serve fortified with Fe- MRPNat, Before heat pH 7.0; Middle: Fe-fortified half-strength full cream milk containing 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.3; Second from Right: Fe- fortified half-strength full cream milk containing 10 mg Fe / 250 ml serve fortified with Fe- MRPdj, Before heat pH 7.0; Extreme Right: Fe-fortified half-strength full cream milk containing 60 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 7.4).

[0203] Fe -fortified soy milk

[0204] The Fe-MRP additives (Fe-MRPNat and Fe-MRPAdj) were added to fresh soy milk. The final formulations were half the strength of the original soy milk with 10 or 60 mg / 250 ml serve. Fe foritified half strength soy milks were more brown, with higher Fe levels having darker colour. With equivalent Fe, darker colour was obtained with Fe-MRPAdjthan with Fe-MRPNat. All half strength soy milks fortified with Fe-MRP at 10 or 60 mg / 250 ml serve were heat stable.when subject to heat treatment in a kitchen steamer for 15 min. Fig 18 c shows Halfstrength soy milk and Fe-fortified half-strength soy milk made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe) to soy milk. MRP was made by heating protein- carbohydrate mixtures (1 NaCaseinate:glucose:1 Maltodextrin MD 17) at different pH, Top- before heat; Bottom - after heating in a steamer for 15 min. (Extreme Left: Half-strength soy milk - no Fe; Before heat pH 6.75; Second from Left: Fe-fortified half-strength soy milk containing 10 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.1 ; Middle: Fe- fortified half-strength soy milk containing 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.5; Second from Right: Fe-fortified half-strength soy milk containing 10 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 7.1 ; Extreme Right: Fe-fortified half-strength soy milk containing 60 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 7.7).

[0205] Fe-fortified soda water

[0206] The Fe-MRP additives (Fe-MRPNat and Fe-MRPAdj) were added to soda water (Schweppes) to obtain Fe fortified soda water at levels of 10 mg Fe / 250 ml serve or 60 mg Fe / 250 ml serve. The pH of the Fe -fortified soda water was increased with increasing levels of addition of Fe-MRP. The large increase in pH on addition of Fe-MRP was due to the pH of the Fe-MRP - as the soda water has no buffering capacity. Control of pH may help clarity.

[0207] Fe fortified soda water were browner, with higher Fe levels having darker colour. With equivalent Fe, darker colour was obtained with Fe-MRPAdjthan with Fe-MRPNat, this was especially obvious at the lower Fe fortification level (10mg / 250 ml serve). All half-strength soda water fortified with Fe-MRP at 10 mg or 60 mg / serve were heat stable when subject to heat treatment in a kitchen steamer for 15 min. Fig. 18d shows Half strength soda water and Fe-fortified half-strength soda water made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe) to soda water. MRP was made by heating protein-carbohydrate mixtures (1 NaCaseinate:glucose:1 Maltodextrin MD 17) at different pH, Top-before heat, Bottom - after heating in a steamer for 15 min. (Extreme Left: Half-strength soda water - no Fe, Before heat pH 4.2; Second from Left: Fe-fortified half-strength soda water containing 10 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 5.7; Middle: Fe-fortified halfstrength soda water containing 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 6.6; Second from Right: Fe-fortified half-strength soda water containing 10 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 5.6; Extreme Right: Fe-fortified halfstrength soda water containing 60 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 6.5).

[0208] Fe-fortified ginger cordial drink

[0209] The Fe MRP additives (Fe-MRPNat and Fe-MRPAdj) were added to ginger cordial which had been diluted in water (1 part ginger cordial:3 parts water). The Fe-fortified ginger drink Fe foritifed ginger drink were more brown, with higher Fe levels having darker colour. With equivalent Fe, darker colour was obtained with Fe-MRPAdjthan with Fe-MRPNat, this was especially obvious at the lower Fe fortification level (10mg / 250 ml serve). Ginger drink fortified with Fe-MRPNat at 60 mg / 250 ml serve were heat stable when subject to heat treatment in a kitchen steamer for 15 min., whereas slight signs of flocculation were found at 10mg / 250 ml serve before and after heating. Ginger drink fortified with Fe-MRPAdjat 10 or 60 mg / 250 ml serve all had slight flocks before and after heating. Control of pH may help clarity. Fig. 18e shows ginger drink and Fe-fortified ginger drink made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe) to ginger drink made by addition to water to ginger cordial. MRP was made by heating protein-carbohydrate mixtures

[0210] (1 NaCaseinate:glucose:1 Maltodextrin MD 17) at different pH, Before heat and after heat comparisons, Top-before heat; Bottom - after heating in a steamer for 15 min. Extreme Left: Ginger drink - no Fe, Before heat pH 3.4, Second from Left: Fe-fortified ginger drink containing 10 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 5.5; Middle: Fe- fortified ginger drink containing 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 6.9 (Slight flocculation in unheated and heated samples); Second from Right: Fe- fortified half-strength ginger drink containing 10 mg Fe / 250 ml serve fortified with Fe- MRPdj, Before heat pH 5.5; Extreme Right: Fe-fortified ginger drink containing 60 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 7.1 (Slight flocculation in unheated and heated samples);

[0211] Fe-fortified reconstituted skim milk powder

[0212] The Fe-MRP additive additives (Fe-MRPNat and Fe-MRPAdj) were added to a 20% TS reconstituted skim milk solution and diluted with water to obtain Fe-fortified skim milk (11 .2-12.5%TS comprising 10% milk solids and 30-60 mg / 250 ml serve). Reconstituted milks formulations (10% milk solids) fortified with ferrous sulphate were also made. Samples fortified with Fe-MRP were more brown, with higher levels being more brown. Fe- milks fortified with of FeSO4or Fe- MRP (Ratio 2NaCas:1 glucose:1 maltrodextrin) MRPNat up to 60 mg Fe / serve were stable to heating (30 min in steam). However, Fe-milks fortified with Fe-MRPAdjgelled on heating. Fig.18f shows reconstituted skim milk and Fe-fortified reconstituted milk made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe) to fullcream milk. MRP was made by heating protein-carbohydrate mixtures (1 NaCaseinate:glucose:1 Maltodextrin MD 17) at different pH, Top-before heat; Bottom - after heating in a steamer for 30 min. (Extreme Left: Reconstituted skim milk, 10% skim milk solids, - no Fe; Before heat pH 6.6; Second from Left: Fe-fortified reconstituted skim milk, 10% skim milk solids, 30 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.0; Middle: Fe-fortified reconstituted milk, 10% skim milk solids, 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.2; Second from Right: Fe-fortified reconstituted milk, 10% skim milk solids, 30 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 7.1 ; Extreme Right: Fe-fortified reconstituted skim milk, 10% skim milk solids, 60 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 7.2).

[0213] Fe-fortified goat milk

[0214] The Fe-MRP additives (Fe-MRPNat and Fe-MRPAdj) were added to whole goat milk to obtain fortified half-strength milks with 5-60 mg Fe / 250 serve. The final formulations were half the strength of the original whole goat milk. Fe fortified half-strength whole goat milks were browner, with higher Fe levels having darker colour. With equivalent levels of Fe, darker colours were obtained with Fe-MRPAdjthan with Fe-MRPNat. All Fe-fortified half strength goat milk (5-60 mg Fe / serve) were heat stable to heating in a home steamer for 30 min. Half strength goat milk formulations fortified with ferrous sulphate at levels of addition of 10, 30 and 60 mg Fe / 250 ml serve were also heat stable. Fig. 18g shows Half-strength whole goat milk and Fe-fortified half-strength whole goat milk made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe) to UHT whole goat milk. MRP was made by heating protein- carbohydrate mixtures (1 NaCaseinate:glucose:1 Maltodextrin MD 17) at different pH. Before heat and after heat comparisons, Top-before heat; Bottom - after heating in a steamer for 30 min. Extreme Left: Half-strength whole goat milk - no Fe; Before heat pH 6.5; Second from Left: Fe-fortified half-strength whole goat milk containing 10 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 6.8; Third from Left: Fe-fortified halfstrength whole goat milk containing 30 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.1 ; Middle: Fe-fortified half-strength whole goat milk containing 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.3; Third from Right: Fe-fortified halfstrength whole goat milk containing 10 mg Fe / 250 ml serve fortified with Fe-MRPAdj, Before heat pH 6.8; Second from Right: Fe-fortified half-strength whole goat milk containing 30 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.1 ; Extreme Right: Fe-fortified half-strength whole goat milk containing 60 mg Fe / 250 ml serve fortified with Fe-MRPNat, Before heat pH 7.2).

[0215] Fe-fortified reconstituted coconut milk

[0216] The Fe-MRP additive (Fe-MRPNat) was added to a coconut milk dispersion containing a coconut milk powder mix. The Fe-fortified coconut milk was comprised of 20% coconut milk ingredient solids and 8.6-69 mg / 250 ml serve. Samples were off-white to light brown, with samples containing increasing levels of Fe being darker brown. Samples containing 8.6-34 mg Fe / 250 ml serve were stable to heating in steam for 10-15 min. The sample containing ~69 mg Fe / 250 ml serve showed signs of precipitation when heated in steam for 10-15 min. Fig. 18h shows Heated reconstituted coconut milk and Fe-fortified coconut milk made by addition of Fe-MRP (6.86% MRP in 12.33 mMolal Fe), MRP formed by heating a 20%TS protein-carbohydrate mixture (2 Caseinate: 1 glucose:1 Maltodextrin DE17) at the natural pH (without pH adjustment prior to heating) followed by pH-adjustment and dilution to 12%TS protein-CHO MRP formed by dilution of heated (MRPNat), Top-before heat, Bottom - after heating in a steamer for 15 min. (Extreme Left: Reconstituted coconut milk, 20% coconut milk solids - No Fe, Before heat pH 6.5; Second from Left: Fe-fortified coconut milk, 20% coconut milk solids, 8.6 mg Fe / 250 ml serve; Before heat pH 6.7; Middle: Fe-fortified reconstituted coconut milk 20% coconut milk solids, 17.2 mg Fe / 250 ml serve; Before heat pH 7.0; Second from Right: Fe-fortified reconstituted coconut milk, 20% coconut milk solids, 34.3 mg Fe / 250 ml serve; Before heat pH 7.1 ; Extreme Right: Fe- fortified reconstituted coconut milk, 20% coconut milk solids, 68.7 mg Fe / 250 ml serve; Before heat pH 7.2).

[0217] Fe-fortified oat milk

[0218] The Fe-MRP Natadditive was added to an oat milk dispersion containing made by reconstituting oat milk powder in water. The Fe-fortified oat milk was comprised of 10% oat milk solids and 8.6-68.7 mg / 250 ml serve. Samples were beige to brown, with samples containing increasing levels of Fe being darker brown. All samples were stable to heating in steam. Fig.18i shows Fe-fortified reconstituted oat milk made by addition of Fe-MRPNat (6.86% MRP in 12.33 mMolal Fe) to reconstituted skim milk MRP formed by heating a 20%TS protein-carbohydrate mixture (2 Caseinate: 1 glucose:1 Maltodextrin DE17) at the natural pH (without pH adjustment prior to heating) followed by pH-adjustment and dilution to 12%TS protein-CHO MRP formed by dilution of heated (MRPNat). (Extreme Left: 10% oat milk solids - No Fe; Before heat pH 6.1 ; Second from Left: 10% oat milk solids, 8.6 mg Fe / 250 ml serve, Before heat pH 7.0; Middle: 10% oat milk solids, 17.2 mg Fe / 250 ml serve, Before heat pH 7.2; Second from Right: 10% oat milk solids, 34.3 mg Fe / 250 ml serve, Before heat pH 7.6; Extreme Right: 10% oat milk solids, 68.7 mg Fe / 250 ml serve; Before heat pH 7.8)

[0219] Ninth Embodiment of the Invention

[0220] EXAMPLES OF COLLOIDAL Fe-CASEIN ENTITIES WITH NaCASEINATE AS THE PROTEIN SOURCE WITH VARIOUS FORMULATIONS CONTAINING PHOSPHATE AND CITRATE AND ORDER OF PROCESSING

[0221] EXAMPLE 19

[0222] Colloidal Fe-casein entities with caseinate-citrate-phosphate-30 mMolal Fe (pH adjusted): A 5% sodium caseinate dispersion was made and to this was added citrate and phosphate to make a caseinate-citrate-phosphate mixture. Ferrous sulphate solution was then added to the caseinate-citrate-phosphate dispersion with pH 6.1 . While there were localised flocks formed on the addition of the iron salt to the caseinate-citrate-phosphate mixture, the focus largely dissolved on standing for 1 hr and addition of NaOH. The final formulation was a pH adjusted colloidal Fe-casein entities formulation (pH 7.5, 3.6% total solids) comprising a caseinate-citrate-phosphate-Fe mixture (2.5% casein:10 mMolal citrate: 22 mMolal phosphate: 30 mMolal Fe). On heating, there was further dissolution of the precipitate. There were no obvious large protein focus on heating in steam for ~1 h but a very fine precipitate formed, suggesting that the Fe-casein entities with citrate and phosphate were largely stable to heat-induced protein precipitation. The mixture was a dark bluish green. Fig. 19a (Left) shows heated Fe-casein micelle formulation. pH prior to heating was 7.5; pH after heating was ~6.9.

[0223] Colloidal Fe-casein entities with caseinate-phosphate-30 mMolal Fe (pH adjusted) : A 5% sodium caseinate dispersion was made and to this was added phosphate to make a caseinate-phosphate mixture. Ferrous sulphate solution was then added to the caseinate- citrate-phosphate dispersion with a pH of 6.3. The pH was adjusted with NaOH. The final formulation was a pH adjusted colloidal Fe-casein entities formulation (pH 8.1 , 3.3% total solids) comprising a caseinate-citrate-phosphate-Fe mixture (2.4% casein:10 mMolal citrate: 31 mMolal phosphate: 30 mMolal Fe). There were heavy precipitates formed on the addition of the iron salt to the caseinate-phosphate. These precipitates did not dissolve on standing. Heating of the final mixture in steam for ~1 h resulted showed that the mixture was not heat stable. There were significant presence of whitish precipitates in the heated mixture, which had green-blue hue. Fig. 19b (Right) shows heated Fe-casein micelle formulation (2.5% casein, 31 mMolal phosphate, 30 mMolal Fe). pH prior to heating was 8.1 ; pH after heating was ~7.3. This formulation with phosphate alone in the colloidal Fe- casein entities mixture has inferior physical properties compared to the formulation which had a mixture of citrate and phosphate, showing the role of citrate in modulating functionality.

[0224] Colloidal Fe-casein entities formulation with caseinate-citrate-phosphate and various Fe content (without pH adjustment): Fe-casein-citrate-phosphate formulations with various levels of Fe were prepared without pH adjustment. The formulations were made by combining a caseinate-trisodium citrate-trisodium phosphate dispersion (4% caseinate solids in 16 mMolal Citrate and 35.3 mMolal Phosphate) with various amounts of 0.2 Molal ferrous sulphate to obtain mixtures with a final Fe concentration of 7 - 31 mM. There were no visible focus in the dispersion containing 7 mMolal Fe. On heating in a home steamer (1 h), there was no precipitate in dispersions containing 7-22 mMolal Fe but a slight precipitate in the dispersion containing 31 mM Fe. Fig. 19 b shows Fe-casein micelle formulations without added carbohydrates (without pH adjustment). Top - Unheated samples & Bottom - Heated samples. (Extreme left: Fe-casein micelle in 7 mMolal Fe (5.1 % total solids; 4% casein, 16 mMolal citrate, 34 mMolal phosphate), pH before heating 8.0, pH after heating 7.9; Second from left: Fe-casein micelle in 12 mMolal Fe (5.1% total solids; 4% casein, 15 mMolal citrate, 33 mMolal phosphate), pH before heating 7.6, pH after heating 7.5; Second from right: Fe-casein micelle in 22 mMolal Fe (5.1 % total solids; 4% casein, 14 mMolal citrate, 31 mMolal phosphate), pH before heating 6.9, pH after heating 6.8; Extreme right: Fe-casein micelle in 31 mMolal Fe (5.2% total solids; 4% casein, 14 mMolal citrate, 30 mMolal phosphate), pH before heating 6.6, pH after heating 6.3).

[0225] EXAMPLE 20

[0226] Colloidal Fe-casein entities formulation (caseinate-citrate-phosphate-30 mMolal Fe) with glucose and maltodextrin DE 17 (pH adjusted): A 5% sodium caseinate dispersion was made and to this was added citrate, phosphate, glucose and maltodextrin DE 17 (MD17) to make a caseinate-citrate-phosphate-glucose-MD17 mixture. The ratio of glucose solids: MD 17 solids was 1 :1 .04. Ferrous sulphate was added. The pH of the caseinate- citrate-phosphate-glucose-MD17-Fe mixture was 6.4. NaOH was then added. The final formulation was a pH adjusted colloidal Fe-casein entities formulation (pH 8.5, 8.2% total solids) comprising a caseinate-citrate-phosphate-Fe-carbohydrate mixture (2.5% casein:10 mMolal citrate: 22 mMolal phosphate: 30 mMolal Fe : 4.65% carbohydrate). While there were localised flocs formed on the addition of the iron salt, the flocks largely dissolved on standing. There was no precipitation on heatingthe final formulation in steam for ~1 h, suggesting that the colloidal Fe-casein entities were heat stable. The mixture was a dark bluish green. Avisual comparison between the sample with glucose / MD 17 and those without carbohydrate showed that the addition of carbohydrate increased the clarity of the sample. Fig 20 shows heated Fe-casein micelle formulation with glucose and MD17 (2.5% casein, 4.65% carbohydrate, 10 mMolal citrate, 22 mMolal phosphate, 30 mMolal Fe). The carbohydrate was a mixture of glucose:MD17 (1 :1.04). The pH prior to heating was 8.5; pH decreased to 7.3 on heating.

[0227] EXAMPLE 21

[0228] Colloidal Fe-casein entities formulation (caseinate-citrate-phosphate-30 mMolal Fe) with glucose (pH adjusted): A 5% sodium caseinate dispersion was made and to this was added citrate, phosphate and glucose to make a caseinate-citrate-phosphate-glucose mixture. NaOH was added, followed by ferrous sulphate. The final formulation was a pH adjusted Colloidal Fe-casein entities formulation (pH 8.7, 8.1 % total solids) comprising a caseinate-citrate-phosphate-Fe- mixture (2.5% casein:10 mMolal citrate: 22 mMolal phosphate: 30 mMolal Fe : 4.55% glucose). While there were localised flocs formed on the addition of the iron salt, the flocs largely dissolved on standing. There was no precipitates after heating the final formulation in steam for ~1 / 2 h, suggesting that the Colloidal Fe- casein entities was heat stable. The mixture was a dark bluish green prior to heating and darkened / browned on heating. A visual comparison between the sample with glucose and those without carbohydrate showed that the addition of carbohydrate increased the clarity of the sample. Fig. 21 shows Fe-casein micelle formulation with glucose (2.5% casein, 4.55% glucose, 10 mMolal citrate, 22 mMolal phosphate: 30 mMolal Fe). Left - Prior to heating (pH —8.7); Right- After heating (pH —7.8).

[0229] EXAMPLE 22

[0230] Colloidal Fe-casein entities formulation (caseinate-citrate-phosphate-30 mMolal Fe) with maltodextrin DE17 (pH adjusted): A 5% sodium caseinate dispersion was made and to this was added citrate, phosphate and glucose to make a caseinate-citrate-phosphate- glucose mixture. NaOH was added, followed by ferrous sulphate. The final formulation was a pH adjusted colloidal Fe-casein entities formulation (pH ~8.4, 8.3% total solids) comprising a caseinate-citrate-phosphate-Fe-MD17 mixture (2.5% casein:10 mMolal citrate: 22 mMolal phosphate: 30 mMolal Fe : 4.75% MD17). While there were localised flocs formed on the addition of the iron salt, most of the flocs dissolved on standing. There was no precipitates after heating the final formulation in steam for ~1 / 2 h, suggesting that the colloidal Fe-casein entities was heat stable. The mixture was a dark bluish green prior to heating and darkened / browned on heating. Avisual comparison between the sample with MD17 and those without carbohydrate showed that the addition of carbohydrate increased the clarity of the sample. Fig. 22 shows Fe-casein micelle formulation with MD17 (2.5% casein, 4.75% MD17,10 mMolal citrate: 22 mMolal phosphate: 30 mMolal Fe). Left: Prior to heating (pH —8.4); Right- After heating (pH —7.9).

[0231] EXAMPE 23

[0232] Colloidal Fe-casein entities formulation (caseinate-citrate-phosphate-30 mMolal Fe) with Fibersol DE12 (pH adjusted): A 5% sodium caseinate dispersion was made and to this was added citrate, phosphate and glucose to make a caseinate-citrate-phosphate- glucose mixture. NaOH was added, followed by ferrous sulphate. The final formulation was a pH adjusted colloidal Fe-casein entities formulation (pH ~8.5, 8.3% total solids) comprising a caseinate-citrate-phosphate-Fe-Fibersol mixture (2.5% casein:10 mMolal citrate: 22 mMolal phosphate: 30 mMolal Fe : 4.75% Fibersol). While there were localised flocs formed on the addition of the iron salt, the flocs dissolved on standing. A visual comparison between the sample with Fibersol and those other carbohydrates (glucose / MD 17, glucose only, or MD17 only) showed that the addition of carbohydrate increased the clarity of the sample. Fig. 23 shows Fe-casein micelle formulation with Fibersol (2.5% casein, 4.75% Fibersol, 10 mMolal citrate, 22 mMolal phosphate, 30 mMolal Fe). Left: - Prior to heating (pH —8.5); Right - After heating (pH — 7.9) .

[0233] There was no precipitates after heating the final formulation in steam for —1 / 2 h, suggesting that the colloidal Fe-casein entities was heat stable. The mixture was a dark bluish green priorto heating and darkened / browned on heating.

[0234] EXAMPLE 24 Colloidal Fe-casein entities Maillard Reaction Products with ~30 mMolal Fe - Effects of order of processing

[0235] A caseinate dispersion (5% solids) was mixed with trisodium citrate solution trisodium phosphate solution to form a dispersion (5% total solids; 4% casein, 16 mMolal citrate, 35 mMolal phosphate; pH 9.4). Colloidal Fe-casein entities Maillard Reaction Products (MRP) were formed using different order of processing.

[0236] Fe addition to pre-formed MRP obtained by heating: The pre-formed MRP mixture was made by heating the caseinate-citrate-phosphate-glucose dispersion (3.03% casein, 2.8% glucose, 12.1 mMolal citrate, 26.7 mMolal phosphate) or caseinate-citrate-phosphate- MD17 dispersion (3.03% casein, 2.9% MD17, 12.1 mMolal citrate, 26.7 mMolal phosphate) in a steamer for 1 h. The dispersion containing glucose or maltodextrin was reduced from 9.4 (before heat pH) to pH 7.5 and pH 7.7 pH respectively after heating. The ferrous solution was then added to the pre-formed MRP mixture to obtain the Colloidal Fe-casein entities MRP dispersions (2.56% casein, 10.3 mMolal citrate, 22.6 mMolal phosphate containing either 2.33% glucose or 2.56% MD17). The addition of Fe resulted in a cloudy mixture with a decreased pH (pH~6). However, addition of base (~0.5 ml of 1 M NaOH) resulted in clearing of the cloudy precipitates and made the solutions stable to protein precipitation on heating in steam for 1 h. Fig. 24a shows Fe-casein micelle MRP dispersions with carbohydrate made by addition of Fe to preformed MRP, followed by additional heating of Fe-containing dispersion for 1 h in a steamer, and subsequent pH- adjustment to pH 7.5-7.7. Left - Formulation with glucose; Right - Formulation with MD17.

[0237] Fe addition to casein-citrate-phosphate-carbohydrate mixture (without pH adjustment prior to heating): Mixtures of Fe-casein-citrate-phosphate-glucose (2.56% casein, 2.33% glucose, 10.3 mMolal citrate, 22.6 mMolal phosphate, 31 mMolal Fe; pH 6.3) or Fe-casein- citrate-phosphate-MD17 (2.56% casein, 2.46% MD17, 10.3 mMolal citrate, 22.6 mMolal phosphate, 31 mMolal Fe; pH 6.4) were prepared. The unheated Fe-containing mixtures were bluish green. The addition of ferrous sulphate to the unheated casein-citrate- phosphate-carbohydrate mixture resulted in cloudiness. Heating of the mixtures in steam for 1 h resulted in some cloudiness, which still remained after pH adjustment of the heated mixtures to -pH 6.6-6.7 (Fig. 24b shows Fe-casein micelle- glucose mixtures. Left - Unheated dispersion (2.56% casein, 2.33% glucose, 10.3 mMolal citrate, 22.6 mMolal phosphate, 31 mMolal Fe) at pH 6.3, slightly cloudy; Right - Dispersion after pH adjustment to pH 6.6 with addition of NaOH, cloudy. Fig. 24c shows Fe-casein micelle- MD17 mixtures. Left: Unheated dispersion (2.56% casein, 2.46% MD17, 10.3 mMolal citrate, 22.6 mMolal phosphate, 31 mMolal Fe) at pH 6.4, slightly cloudy; Right: Dispersion after pH adjustment to pH 6.6 with addition of NaOH, cloudy.

[0238] Fe addition to casein-citrate-phosphate-carbohydrate mixture (pH adjustment prior to heating): Mixtures of Fe-casein-citrate-phosphate-glucose (2.53% casein, 2.30% glucose, 10.1 mMolal citrate, 22.2 mMolal phosphate, 30.3 mMolal Fe; pH 7.4) or Fe-casein-citrate- phosphate-MD17 (2.53% casein, 2.43% glucose, 10.1 mMolal citrate, 22.2 mMolal phosphate, 30.3 mMolal Fe; pH 7.6) were prepared. The unheated Fe-containing mixtures were dark brown. The addition of ferrous sulphate to the unheated casein-citrate- phosphate-carbohydrate mixture resulted in cloudiness, which most cleared on standing. Heating of the mixtures in steam for 1 h reduced the pH to -6.9 and 7.1 for mixtures with glucose and MD17 respectively. The mixtures darkened and there were no visible signs of precipitation. Fig. 24d shows Fe-casein micelle-glucose mixtures (2.53% casein, 2.30% glucose, 10.1 mMolal citrate, 22.2 mMolal phosphate, 30.3 mMolal Fe). Left - Unheated dispersion that was adjusted to pH 7.4; Right - Dispersion after heating (pH reduced to 6.9). Figure 24e shows Fe-casein micelle- MD17 mixtures (2.53% casein, 2.43% MD17, 10.1 mMolal citrate, 22.2 mMolal phosphate, 30.3 mMolal Fe). Left: Unheated dispersion that was adjusted to pH 7.6 Right: Dispersion after heating (pH reduced to 7.1).

[0239] Summary of Methods and Effects

[0240] The major levers that can be used in isolation or in combination in order to develop soluble and heat stable Fe-protein-CHO complexes are: i Adjustment of pH ii Addition of citrate or a combination of citrate and phosphate iii Heat treatment of protein-CHO mixtures to form MRP iv Adjustment of pH prior to heat treatment to form MRP v Conjugation with high molecular weight sugars / maltodextrin

[0241] Effects of heat treatment of protein-sugar mixtures:

[0242] • Heat treatment of protein-sugar mixtures (unadjusted pH prior to heating, pH ~7) results in decrease in pH due to the Maillard reaction

[0243] • Higher pH during heat treatment increases brown pigment formation which is expected as Maillard is increased with higher pH. There is also a contribution of the caramelisation reaction so sugar to brown pigment formation

[0244] • Longer treatment time at same pH results in more browning with increased time, which is expected due to increasing extent of the Maillard reaction

[0245] • Heat treatment at pH <7.5 results in a decrease in pH on heating, which is due to the Maillard reaction

[0246] • Heat treatment at pH > 7.5 to 8 results in increase in pH. There are other reactions occurring, includingthe deamidation of proteins which results in the formation of ammonia which raises the pH.

[0247] Fe-Non MRP and Fe-MRP formulations

[0248] • Addition of Fe reduces pH, due to shifts in equilibria and release of H+on binding; increasing Fe causes larger decrease in pH

[0249] • Fe-Non MRP and Fe-MRP complexes may be cloudy or transparent depending on the formulation and pH and conditions for formation of the MRP prior to formation of the Fe-MRP complexes: o Increasing Fe results in increasing cloudiness of Fe-protein-CHO mixtures o Increasing pH improves solubility of Fe complexes, which is to be expected due to reduced electrostatic interactions (increasing charge on protein with increasing pH) o Heat treatment of the same protein-CHO mixture for longer times improves the solubility of Fe-MRP complexes formed

[0250] • At the same pH and concentration of protein-CHO, more soluble Fe-complexes are formed with MRP than with Non MRP

[0251] Heat stability of Fe-caseinate and Fe-HWPI

[0252] • Where soluble Fe-MRP and Fe-Non MRP were heated, there was less flocculation in caseinate samples then in HWPI samples • Heat stability of Fe-MRP and Fe-Non MRP mixtures may be achieved by judicious adjustment of pH and use of buffering salts (e.g., citrate). This has the effect of reducing the Fe activity (mineral ion activity) and reducing the sensitivity of proteins to heat-induced aggregation

[0253] • Adjustment of pH prior to heating to high pH prior to heating (before addition of Fe) results in Fe-MRP and Fe-Cit-MRP mixtures that were more stable to subsequent heating

[0254] Various strategies can be used to improve the solubility and heat stability of Fe-protein- CHO mixtures. As shown in the examples, one is to increase the pH of the protein-CHO mixture prior to the formation of MRP and Fe addition. Furthermore, heat stability can be further improved by use of buffering salts (e.g., citrate)

[0255] References

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[0306] Table 3 : Process for preparation of (Fe-MRPNat) and (Fe-MRPAdj) for fortification of food products

[0307] (Example 18)

Claims

CLAIMS1 . A method of manufacturing a soluble formulation for mineral delivery including:(a) Dispersing a protein in water(b) Adding reducing sugar / carbohydrate to the protein dispersion(c) Adding a soluble mineral salt wherein solubility or stability of the formulation is modified by at least one of the following:(i) Using Maillard Reaction products(ii) Heating the protein-carbohydrate mixture(iii) Adjusting the pH of the protein-carbohydrate mixture(iv) Heating the protein-carbohydrate mixture without pH adjustment(v) Adjusting the pH without heating the protein-carbohydrate mixture wherein the modification of the formulation leads to mineral delivery suitable for food supplements, nutrition, additives, fortified foods, beverages or powders.

2. The method as claimed in claim 1 , wherein the mineral includes Iron.

3. The method as claimed in claim 1 , wherein the mixture is dried.

4. The method as claimed in claim 1 , wherein the protein is casein, whey protein, protein hydrolysates, or vegetable and other food proteins.

5. The method as claimed in claim 1 , wherein protein is from non-animal sources, including recombinant proteins made by precision fermentation.

6. The method as claimed in claim 1 , wherein the sugar / carbohydrate includes a reducing sugar group (glucose, fructose, lactose, oligosaccharide, maltodextrin, dried glucose syrup, hydrolysed starch, fibre).

7. The method as claimed in claim 6, wherein the carbohydrate / fibre is prebiotic.

8. The method as claimed in claim 1 , wherein the range for ratio for protein to carbohydrate is between 95:5 and 5:95, preferably the range is between 1 :4 and 4:1 .

9. The method as claimed in claim 1 , wherein the heat treatment is high temperature for longer duration times.

10. The method as claimed in claim 1 , wherein the heat treatment has shorter times for higher temperatures when the pH is in the range 6.5-12.11 . The method as claimed in claim 1 , wherein where the mineral salt (sodium / potassium / ammonium) or iron / mineral phosphate or citrate, and where the phosphate salt is orthophosphate, hexametaphosphate, pyrophosphate or polyphosphate.

12. The method as claimed in claim 1 , wherein the mineral salt is added prior to heating the protein-carbohydrate mixture.

13. The method as claimed in claim 11 , wherein phosphates / citrates are added to adjust pH and complex iron / minerals, preferably to increase pH.

14. The method as claimed in claim 1 , wherein the salt is added to the protein- carbohydrate mixture after heating.

15. The method as claimed in claim 1 , wherein oil is incorporated into the formulation for the preparation of oil-in-water emulsions16. The method as claimed in claim 14, wherein nutritional bioactives are loaded into the water and / or oil phase.

17. A mineral supplement containing Maillard Reaction products wherein the nutritional mineral is selected from one or more soluble compounds of magnesium, calcium, zinc and manganese18. A mineral fortified protein-carbohydrate mixture containing Maillard Reaction products.

19. A method of manufacturing a soluble formulation including:(a) Dispersing a protein in water(b) Adding reducing sugar / carbohydrate to the protein dispersion wherein solubility or stability of the formulation is achieved by heating the protein- carbohydrate mixture with or without prior pH adjustment to form Maillard Reaction Products, wherein the resulting formulation exhibits improved stability during storage and is suitable for incorporation into food or supplement products20. A method of manufacturing a mineral powder with Maillard Reaction Products includingthe steps of:(a) Dispersing a protein in water(b) Adding reducing sugar / carbohydrate to the protein dispersion(c) Heating the protein-carbohydrate mixture with or without prior pH adjustment to form Maillard Reaction Products wherein the mineral powder is obtained by(i) Adding a mineral salt to the Maillard Reaction Products which could be a liquid dispersion or a dispersion reconstituted from a dried Maillard Reaction Products powder.(ii) Dehydration step21 . A method of manufacturing a Fe-casein micelle for delivery of iron including(a) Dispersing a casein ingredient in water(b) Adding a mixture of citrate and phosphate to the protein dispersion(c) Adding a soluble iron salt wherein the properties of the Fe-casein micelle formulation may optionally be modified by one or more of the following steps: (i) Adjusting the pH of the mixture, (ii) Adding carbohydrate to the mixture, (iii) H eating the mixture, wherein the formulations enable iron delivery suitable for food supplements, nutrition, additives, fortified foods, beverages or powders.

22. A method of manufacturing a Fe-casein micelle formulation containing pre-formed Maillard Reaction Products which comprises the following steps(a) Dispersing a casein ingredient in water with a carbohydrate(b) Adding a mixture of citrate and phosphate to the caseinate-carbohydrate dispersion,(c) Heating to form Maillard Reaction Products(d) Adding a soluble iron salt wherein the properties of the Fe-casein micelle formulation may be modified by one or more of the following steps: (i) Adjusting the pH of the casein-carbohydrate dispersion prior to heating, (ii) Adjusting the pH of the Fe-containing formulation, wherein the formulations enable iron delivery suitable for food supplements, nutrition, additives, fortified foods, beverages or powders.

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