Patent Application
20150201659
The present invention relates to water-dispersible formulations comprising carotenoids, in particular β-carotene, and the use of said formulations to color food and beverage products.
Carotenoids are well known as food coloring agents, and have hues varying between yellow and red. The hue of β-carotene, a carotenoid that is widely used as a colorant, is typically between yellow and orange.
One factor that determines the hue of a β-carotene-containing medium is the physical state of the β-carotene in its oil or aqueous carrier phase Thus, the hue of such a medium may vary greatly, depending on the physical compartmentalization of the β-carotene in the continuous phase of the medium in which it is present.
The carotenoids, as a class, have relatively low chemical stability, and this causes a two-fold problem when they are used in food processing: the difficulty to achieve a certain desired hue and the difficulty to reproduce these results.
A further major problem encountered when using carotenoids as coloring agents in the food industry is, that once a desired hue is achieved, said hue may often change when the carotenoid or food colored with carotenoids is processed, for example, by means of pasteurization.
Various strategies for dealing with these problems have been suggested in the prior art.
U.S. Pat. No. 5,364,563 discloses a novel process for producing powdered carotenoid preparations, in which a suspension of a carotenoid in a high-boiling oil is brought into contact with superheated steam during a maximum period of 30 seconds, and subsequently emulsified the liquefied solution of said carotenoid in oil produced by said contact with superheated steam in an aqueous solution of a colloid and then spraying and drying said emulsion to a powder.
U.S. Pat. No. 4,844,934 discloses that water-dispersible carotenoid formulations are prepared by dissolving the carotenoid in a carrier oil at elevated temperatures until saturation is achieved, rapidly emulsifying the solution with an aqueous protective colloid and then removing the water, by a process in which the protective colloid used is a mixture of an ester of a long-chain fatty acid with ascorbic acid and a starch product which is soluble in cold water. The product can be used for coloring foods and is stable to creaming
U.S. Pat. No. 5,968,251 discloses that carotenoid preparations in the form of cold water-dispersible powders are produced by a) preparing a molecular-disperse solution of a carotenoid, with or without an emulsifier and/or an edible oil, in a volatile, water-miscible, organic solvent at elevated temperature and adding therein an aqueous solution of a protective colloid, whereupon the hydrophilic solvent component is transferred into the aqueous phase, and the hydrophobic phase of the carotenoid results as nanodisperse phase, b) heating the resulting hydrosol at from 40° C. to 90° C., with or without cooling of the hydrosol to from 0° C. to 30° C. beforehand, and c) removing the solvent and the water from the heated hydrosol, and converting it into a water-dispersible dry powder.
U.S. Pat. No. 5,976,575 discloses a dry powder that contains carotenoids produced by grinding a mixture of carotenoids and oil to reduce the carotenoid particle size, emulsifying the mixture with an encapsulating mixture, and drying the emulsion. The encapsulating mixture includes a starch encapsulating agent, a sugar, and an anti-oxidant. The resulting water-dispersible powder contains a high concentration of carotenoids, yet is protected from oxidation.
It is to be noted that all of the systems described in aforementioned US patents use oil as a carrier or as a solvent for the carotenoid during the manufacture process. As stated in U.S. Pat. No. 5,976,575, the carotenoids are often supplied in oil dispersions rather than in crystalline form in order to stabilize them.
However, none of these prior art publications disclosing and teaching oil dispersions has provided solutions to all of the three problems discussed hereinabove, namely readily achieving a desired hue, reproducing the desired hue from batch to batch, and preserving said hue when the food or beverage product is subjected to harsh treatment regimens such as pasteurization.
In view of the above the need remains for a new process for preparing a 3-carotene formulation that overcomes the above-mentioned problems.
It is the aim of the present invention to provide such a process and formulation.
A further aim of the present invention is to provide a formulation that, in addition to possessing the above-mentioned advantages, also permits the use of lower concentrations of β-carotene for any given hue than has been possible with the formulations and processes of the prior art.
The present inventors have now unexpectedly found that a mixture of a β-carotene-containing liquid-in-liquid dispersion with a solid-in-liquid dispersion of β-carotene produced a highly stable colorant formulation. It was also found that this formulation can be added in liquid form to a foodstuff or beverage product, thereby yielding product whose color properties could be pre-determined by means of controlling the ratio of the liquid-in-liquid dispersion to the solid-in-liquid dispersion in the colorant formulation. Furthermore, when compared with prior art formulations, significantly less β-carotene was needed to achieve a product having the same color properties. Finally, this formulation (in both liquid and dry powder form) was unexpectedly found to be stable upon pasteurization without alteration in the hue or other color properties.
Thus, the present invention is primarily directed to a water-dispersible colorant formulation comprising a mixture of (a) a solid-in-liquid dispersion of β-carotene with (b) a liquid-in-liquid dispersion of β-carotene, wherein the average particle size in said solid-in-liquid dispersion is less than about 600 nm and wherein the average droplet size of the liquid-in-liquid dispersion is less than about 200 nm. It is to be noted that in most embodiments of the colorant formulation of the present invention, the β-carotene (or other carotenoid, such as lutein) is in an unencapsulated form. This lack of encapsulation in hydrocolloid (or other) materials has functional significance for the presently-disclosed formulation, as will be explained hereinbelow.
In one preferred embodiment of the above-disclosed formulation, the average particle size of the solid-in-liquid dispersion is less than 400 nm. In a still further preferred embodiment, the average droplet size of the liquid-in-liquid suspension is less than about 120 nm.
In another preferred embodiment, of this aspect of the invention, one or both of the solid-in-liquid dispersion and the liquid-in-liquid dispersion may contain lutein or a lutein ester in addition to β-carotene, or instead of (that is, in the absence of) β-carotene.
The β-carotene, lutein and lutein esters used in the formulations, methods and processes of the present invention may be any suitable crystalline form thereof and may either obtained from a natural source or may be produced synthetically.
In one preferred embodiment, the colorant formulation is in a liquid form. In another preferred embodiment, the colorant formulation is in a dry powder form.
In one preferred embodiment of the colorant formulation, the solid in liquid dispersion comprises carotenoid crystals in an aqueous medium, and wherein said aqueous medium may optionally further comprise one or more surfactants.
In a preferred embodiment of the colorant formulation, the liquid in liquid dispersion comprises a carotenoid mixed in an oil, dispersed in an aqueous solution comprising one or more of a sugar ester, a saponin, a fatty polyglycerol ester and a polyol.
In another aspect, the present invention provides a process for preparing a colorant formulation, wherein the hue of said formulation may be controlled, comprising the steps of:
According to a further aspect, the present invention provides a water-dispersible β-carotene formulation prepared according to said process.
In another aspect, the present invention is directed to the use of the water-dispersible β-carotene formulation according to the present invention, as a colorant. In one preferred embodiment of this aspect, the β-carotene formulation obtained from the above-disclosed process may be used in a liquid form. In another preferred embodiment, the water may be removed from the liquid formulation, thereby yielding a dry powder form of said formulation. Preferably, the formulation of the present invention is used to color food products and/or beverages. In other embodiments, however, the formulation may also be used to color other products, including pharmaceutical formulations such as capsules and tablets.
In another aspect, the present invention also provides a kit for use in preparing a water-dispersible β-carotene formulation of a desired hue comprising:
In a still further aspect, the present invention is also directed to a food or beverage product comprising a water-dispersible β-carotene formulation of the present invention.
It is to be noted that the same colorant effect, having the same advantages as set out above and described in more detail hereinbelow (with regard to the mixture of two dispersions), may also be obtained if the two different dispersions (i.e. the liquid-in-liquid dispersion and the solid-in-liquid dispersion) are added separately to the food or beverage to be colored. Consequently, the present invention also provides a method for coloring a food or beverage product, where the hue of said product may be controlled, wherein said method comprises the steps of:
The present invention provides novel water-dispersible β-carotene formulations which, as explained hereinabove, have several advantages in relation to prior art formulations. In particular, the use of two separate dispersions in the preparation of the formulation permits the accurate control of the color and hue properties of both said formulation and of the final food or beverage product to which it is added. Furthermore, the use of a liquid formulation of the present invention in order to prepare a colored food or beverage product permits the use of significantly lower levels of β-carotene to achieve the desired hue, than are required to attain that hue when using formulations and methodologies of the prior art. In this regard, it has been surprisingly found that the hue and the strength of liquid formulations of the present invention are generally higher by 30-300% when compared with the same amount of a conventional prior formulation, such as the cold water soluble (CWS) β-carotene formulation produced by DSM. Finally, the color properties (e.g. hue and color strength) of the formulation of the present invention—whether used as a liquid or as a dry preparation—are stable when the products to which said formulation has been added are subjected to pasteurization and/or homogenization. Taken either separately or together, the aforementioned properties of the present invention are of great benefit to the food and beverage industry, since they permit the preparation of products with accurately-defined and stable color properties, at a potentially lower financial cost, in view of the reduced amount of carotenoid needed to achieve the desired hue.
According to one embodiment the use of the water-dispersible carotenoid formulation of the present invention is as an edible colorant for use in food products and in beverages.
According to another embodiment the water-dispersible β-Carotene of the present invention may be used as a pharmaceutically acceptable colorant in the manufacture of medicinal products.
As explained hereinabove, the β-carotene-containing colorant formulation of the present invention is prepared by combining two different components: (1) a β-carotene containing liquid-in-liquid dispersion, and (2) a β-carotene-containing solid-in-liquid dispersion.
The liquid in liquid dispersion of the present invention may be prepared as follows: β-carotene is mixed in an oil such as a medium chain triglyceride (MCT) oil, sunflower oil, or any other vegetable oil and/or with enzyme-modified lecithin, lysolecithin from Soy, Sunflower or Rapeseed oils with mixed tocopherols or tocopheryl acetate (TA) or D-L-tocopherol. The mixture obtained is then heated to a temperature in the range of about 140° C. to 155° C., preferably about 150° C. to obtain a solution of β-carotene in oil. Said oil solution is added to an aqueous solution containing a sugar ester, and/or saponins, and/or polyglycerol esters of fatty acids and gum Arabic, gum Senegal and structurally-similar hydrocolloids and sucrose or glucose or maltitose and glycerol and/or other polyols, which is at a temperature in the range of 80° C. to 100° C., preferably about 90° C. The combined homogenous mixture and aqueous solution are homogenized to obtain a stable carotenoid-containing liquid in liquid dispersion. The average droplet size of this dispersion was below 200 nm.
The solid in liquid dispersion of the present invention may be prepared as follows: β-carotene crystals were micronized to below 1 micron, preferred 200-400 nm in a glycerol-water medium together with one or more surfactants. The surfactant(s) used may be of any suitable type, including, but not limited to, different types of sucrose esters, polyglycerol esters of fatty acids and de-oiled lecithins from, for example, soy, sunflower, canola or rapeseed.
It was found by the present inventors that the encapsulation of the carotenoid particles (in the solid-in-liquid dispersion) by hydrocolloids such as starches, milk protein, vegetable and legume proteins, polypeptides and the like, leads to a reduced color intensity in the final colorant formulation. For example, the encapsulation of β-carotene by modified starch and subsequent drying was found to substantially reduce color intensity:
As will be seen from the above results, encapsulation led to a decrease in the ‘a’ and ‘b’ color parameters. Without wishing to be bound by theory, it is believe that this disadvantageous change is due to a reduction in transparency of the solid particles, i.e. masking by the hydrocolloid capsule.
In view of the foregoing, it may be seen that the lack of hydrocolloid encapsulation of the solid particles in the solid-in-liquid formulation is a very important feature of the present invention
Another key feature of the present invention is the very small particle and droplet sizes of the solid-in-liquid and liquid-in-solid dispersions, respectively. This reduction in particle and droplet size (with respect to prior art formulations) leads to a greatly increased color intensity, thereby permitting a large saving in the amount of β-carotene used (in the order of 30-300%). In part, the very small droplet size achieved in the present invention is a consequence of the surfactants used in the preparation of the formulation.
In many preferred embodiments of the invention, the oil phase of the liquid-in-liquid formulation is present, at a concentration of more than 30% (w/w) of said formulation.
While the means for modifying the hue of water-dispersible carotenoid formulations according to the prior art, are by chemical processes such as modifying the isomer ratio, the present invention provides means for modifying the hue by simply changing the ratio of the liquid in liquid dispersion to the solid in liquid dispersion in the mixture. Furthermore, the present invention provides a process for obtaining water-dispersible β-carotene formulations of a certain particle size mixed with liquid in liquid dispersion of Lutein or Lutein ester at the recommended particle size using various ratios to provide the required hues.
Thus, the methods, processes, compositions and uses thereof described herein with reference to β-carotene also apply to mixtures of said β-carotene with lutein and/or a lutein ester, and also to lutein and/or lutein ester alone (i.e. in place of the β-carotene), which are therefore within the scope of the present invention. Thus a liquid in liquid dispersion of one carotenoid (e.g. β-carotene) may be mixed with a solid in liquid dispersion of a second carotenoid (e.g. lutein), followed by water removal, to obtain a water-dispersible carotenoid formulation. The hue of such a liquid formulation, as a powder may be controlled by the ratio between the liquid-in-liquid dispersion to the solid-in-liquid dispersion.
It should be understood that during processing such as pasteurization the color strength of conventional powder formulations (such as DSM 10% of β-carotene such as CWS and CWD) decreases, This does not happen in the case of the liquid dispersion of liquid in liquid and dispersion of solid in liquid combination formulations prepared according to this invention. Thus a large saving in the amount of β-carotene used (30-300%.) may be achieved with use of the formulation of the present invention.
Equipment for color test:
1 kg of crystalline β-carotene, 1 kg of decaglycerol monooleate, 2 kg sugar ester type PS750 100 g of vitamin C and 20 kg water were mixed thoroughly to give a homogeneous mixture following grinding in a ball-mill. The particle size of ground β-carotene was 0.3-0.6 μm.
1 kg of crystalline β-carotene, 1 kg of medium chain triglyceride (MCT) oil, 1 kg of decaglycerol monooleate and 0.7 kg of D-alpha-tocopherol were heated with constant stirring to 150° C., until a transparent solution was obtained.
2 kg sugar ester and 3 kg of gum Arabic were dissolved in 15 kg of hot water (70-80° C.).
The β-carotene transparent solution was added without cooling to the sugar ester —gum Arabic solution with vigorous mixing and the resulting mixture was immediately homogenized in a High Pressure Homogenizer. Average droplet size was below 500 nm.
Color parameters were tested for water solution 10 mg of b-carotene in 1 liter
L*=72.3 a*=10.7 b*=38.5
1 kg of crystalline β-carotene, 1.5 kg of de-oiled soy lecithin, 2 kg sugar ester, 100 g of vitamin C and 20 kg water mixed thoroughly to give a homogeneous mixture following grinding in a ball-mill. The particle size of the ground β-carotene was 0.2-0.6 μm.
Color parameters were tested for water solution 10 mg of b-carotene in 1 liter
L*=43.2 a*=40.4 b*=33.5
1 kg of crystalline β-carotene, 2.4 kg of MCT oil, 1.4 kg of enzyme-modified lecithin and 0.3 kg of tocopherol mix were heated while constantly stirring to 150° C. until a transparent solution was obtained.
0.6 kg sugar ester were dissolved in 6 kg of hot water (70-80° C.), add 10 kg sucrose and 7 kg glycerol.
β-carotene transparent solution was added without cooling to the water phase while using high shear mixer and the resulting solution was immediately homogenized in High Pressure Homogenizer. Average droplet size was below 200 nm.
Color parameters were tested for water solution 10 mg of b-carotene in 1 liter
L*=83.5 a*=4.5 b*=45.8
1 kg of crystalline β-carotene, 1.5 kg of de-oiled sunflower lecithin, 2 kg sugar ester, 100 g of vitamin C and 20 kg water mixed thoroughly to give a homogeneous mixture following grinding in a ball-mill. The particle size of the ground β-carotene was 0.2-0.6 μm.
Color parameters were tested for water solution 10 mg of b-carotene in 1 liter
L*=45.5 a*=41.2 b*=37.5
1 kg of crystalline β-carotene, 2.1 kg of MCT oil, 1 kg of enzyme-modified lecithin and 0.3 kg of tocopherol mix were heated while constantly stirring to 150° C. until a transparent solution was obtained.
1 kg Q-Naturele 200 (saponin extract) was mixed in 4 kg of hot water (70-80° C.), and 4 kg sucrose and 5 kg glycerol were added.
β-carotene transparent solution was added without cooling to the water phase while using a high shear mixer and the resulting solution was immediately homogenized in a High Pressure Homogenizer. The average droplet size was below 200 nm.
Color parameters were tested for water solution 10 mg of b-carotene in 1 liter
L*=82.5 a*=11.5 b*=51.2
1 kg of crystalline β-carotene, 1.5 kg of de-oiled sunflower lecithin, 2 kg sugar ester, 100 g of vitamin C and 20 kg water were mixed thoroughly to give a homogeneous mixture following grinding in a ball-mill. The particle size of the ground β-carotene was 0.2-0.6 μm.
The color parameters were tested in a solution of 10 mg of b-carotene in 1 liter of water.
L*=45.5 a*=41.2 b*=37.5
1 kg of marigold oleoresin, 1 kg of MCT oil and 0.3 kg of tocopherol mix were heated with constant stirring to 150° C. until a transparent solution was obtained.
1.1 kg Q-Naturele 200 (saponin extract) was mixed in 4.5 kg of hot water (70-80° C.); add 4.5 kg sucrose and 5 kg glycerol.
β-carotene transparent solution was added without cooling to the water phase using a high shear mixer and the resulting solution was immediately homogenized in a High Pressure Homogenizer. The average droplet size was below 200 nm.
Color parameters were tested for a solution of 10 mg of beta-carotene in 1 liter in water.
L*=58.8 a*=8.6 b*=50.8
5% orange juice beverage was chosen as a model:
a) A compound that consists of orange juice concentrate, sugar syrup, orange flavor oil and the following β-carotene formulation was prepared.
a.1) β-carotene formulations:
a.1.1) Conventional powder form β-Carotene Cold Water Soluble (CWS) prepared with starch as a stabilizer (such as the cold water soluble (CWS) 10% β-carotene formulation produced by DSM) was used to color the finished beverage with, 3, 5 and 10 ppm β-Carotene.
a.1.2) liquid form of a mix of β-Carotene dispersion of liquid in liquid and β-carotene dispersion of solid in liquid in chosen combination (1-99%) was used to color the finished beverage with 2, 3, 5 and 10 ppm β-Carotene.
b) The colored compound was homogenized in a two stage pressure homogenizer: first stage at 200 bars and second stage at 50 bars.
c) Bottling syrup was prepared, using the homogenized colored compound, sugar syrup, organic acid, ascorbic acid (200 ppm in finished product) and pectin added as a stabilizer.
d) The bottling syrup was diluted with water to provide the desired finished beverage.
e) The beverage was pasteurized to 85° C. in a hot bath.
f) 500 ml PET bottles were quickly filled and sealed.
g) The sealed bottles were immediately cooled in an ice bath to less than 25° C.
h) The bottles were stored in a day light cabinet
i) A series of the following analyses were conducted
I1) L.a.b scale by colorimeter (Hunter Lab)
I2) color Hue value by colorimeter (Hunter Lab)
I3) color strength value by colorimeter (Hunter Lab)
I4) color strength value by spectrophotometer (E 1:1 method)
Mixing a liquid-in-liquid dispersion with a solid-in-liquid dispersion (both from Example 1) at a ratio of 60:40 yielded a formulation that gave the same hue at 10 ppm compared to 10 ppm β-carotene from 10% CWS (obtained from DSM). Following pasteurization of the beverage the hue of the DSM powder changed significantly, while the mixture of the liquid-in-liquid dispersion and the solid-in-liquid dispersion maintained a stable hue.
A liquid form of a mix of a β-Carotene liquid-in-liquid dispersion with a β-carotene solid-in-liquid dispersion (of Example 2) at a ratio of 60:40 was used to color the finished beverage with 3, 5 and 10 ppm β-Carotene.
Unpasteurized vs. pasteurized orange juice colored with β-carotene:
1. The results indicate that the intensity of the color (L value) of the CWS formulation decreased significantly at all levels (L value increased) following pasteurization while the color intensity of the Liquid dispersion mixture did not change significantly.
2. The results indicate that the red tone (‘a’ value) of CWS formulation decreased significantly at all levels (‘a’ values decreased) following pasteurization while the red tone of the liquid dispersion mixture did not change significantly.
3. The result indicate that the yellow tone (‘b’ value) of the CWS formulation increased significantly at all levels (‘b’ values increased) following pasteurization while the yellow tone of the liquid mixture did not change significantly.
L.a.b, and Hue value and E1:1 measurements of pasteurized orange juice beverage colored with 5 and 10 ppm of β-carotene from powder DSM 10% CWS/S Vs. liquid form of a 50:50 mixture of a liquid-in-liquid dispersion and a solid-in-liquid dispersion:
1. The results indicate that the Hue value of 5% orange juice colored with 5 ppm β-carotene using liquid-in-liquid dispersion and solid-in-liquid dispersion mixture (natural and synthetic) is close to the Hue of juice colored with 10 ppm β-carotene from DSM 10% CWS/S (synthetic).
2. The results indicate that the E1:1 value of orange juice colored with 5 ppm β-carotene prepared from a liquid-in-liquid and solid-in-liquid dispersion mixture (natural and synthetic) is 38-72% higher than the E1:1 value of 5% orange juice colored with the same amount of β-carotene from DSM 10% CWS/S (synthetic)
3. The results indicate that the E1:1 value of orange juice colored with 10 ppm β-carotene prepared from a liquid-in-liquid dispersion and solid-in-liquid dispersion mixture (natural and synthetic) is 66-107% higher than the E1:1 value of 5% orange juice colored with the same amount of β-carotene from DSM 10% CWS/S (synthetic)
4. These result indicate that the hue and strength of 5% juice colored with β-carotene from a liquid form of a mixture of a liquid-in-liquid dispersion and a solid-in-liquid dispersion is significantly higher than the hue and strength of 5% juice colored with β-carotene from DSM 10% CWS/S.
5. These results confirm the organoleptic observation of the hue and strength of 5% orange juice colored with a liquid-in-liquid dispersion and solid-in-liquid dispersion mixture compared with the same juice colored with DSM 10% CWS/S.
6. The results indicate that at least a 30% cost saving of β-carotene can be achieved by the use of a liquid β-carotene liquid-in-liquid dispersion and solid-in-liquid dispersion formulation mixture, compared to the use of DSM 10% CWS/S.
7. The results indicate that the synthetic and the natural formulation of liquid β-carotene liquid-in-liquid dispersion and solid-in-liquid dispersion formulation mixture behave the same.
300 g a solid-in-liquid dispersion and 700 g of a liquid-in-liquid dispersion were mixed and 100 g of modified starch was added while stirring vigorously. The mixture was then immediately spray dried to obtain a cold water soluble stable powder. The spray drying operation was conducted in a conventional spray dryer.
While embodiments of the invention have been described by way of description, it will be apparent that the invention may be carried out with many modifications, variations and adaptations, without departing from its spirit or exceeding the scope of the claims.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IL2013/000066 | 8/26/2013 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61693291 | Aug 2012 | US |
