Colorant compounds derived from genipin or genipin containing materials
The present disclosure provides colorant compounds and methods of isolation of the colorant compounds derived from a reaction of genipin and an amine. The colorant compositions comprise purified compounds (e.g., a purified polymer or a purified dimer) obtained from multiple fractioning by chromatography of the reaction resulting material. The purified polymer or dimer can be used as a colorant by itself or in combination with another colorant for imparting color to a food, a drug, a cosmetic, a medical device, and textile products.
1. A colorant composition comprising a polymer of formula 4:
a geometric isomer thereof, a tautomer thereof, or a salt thereof,
wherein n is an integer from 2 to 20;
wherein each A is independently selected from the group consisting of formula 5′A, formula 5′B, formula 5′C, a geometric isomer thereof, a tautomer thereof, a salt thereof, and a combination thereof:
wherein:
R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl;
and wherein T 1 is hydrogen or a methyl group; and T 2 is hydrogen or A-T 1 , wherein A and T 1 are defined above;
wherein the colorant composition is substantially free of a first additional compound selected from the group consisting of formula 2′, formula 3′A, formula 3′B, a geometric isomer thereof, a tautomer thereof, and a salt thereof:
2. The colorant composition of claim 1 , wherein the colorant composition is substantially free of a second additional compound selected from the group consisting of formula 1A, formula 1B, a geometric isomer thereof, a tautomer thereof, and a salt thereof:
3. A substantially purified polymer of formula 4:
a geometric isomer thereof, a tautomer thereof, or a salt thereof,
wherein n is an integer from 2 to 20;
wherein each A is of formula 5′A (Me), a geometric isomer thereof, a tautomer thereof, or a salt thereof:
wherein T 1 is hydrogen or a methyl group; and T 2 is hydrogen or A-T 1 , wherein A and T 1 are defined above.
4. The polymer of claim 3 having a number average molecular weight (M n ) of about 6,000.
5. The polymer of claim 3 characterized by an IR spectrum having the following peaks (±5 cm −1 ): 3393, 2949, 1726, 1630, and 1540 cm −1 .
6. A method of imparting blue color to a substrate comprising contacting the substrate with the polymer of claim 3 .
7. A product comprising (a) the polymer of claim 3 and (b) a food item, a drug or nutraceutical product, or cosmetic product.
8. A medical device colored by the polymer of claim 3 .
9. A colorant composition comprising a polymer of Formula 4:
a geometric isomer thereof, a tautomer thereof, or a salt thereof,
wherein n is an integer from 2 to 20;
wherein each A is independently selected from the group consisting of formula 5A, formula 5B, formula 5C, a geometric isomer thereof, a tautomer thereof, a salt thereof, and a combination thereof:
wherein:
R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl;
R 2 and R′ 2 are independently hydrogen, or C 1-10 alkyl;
R 3 is hydrogen or COOH;
and wherein T 1 is hydrogen or a methyl group; and T 2 is hydrogen or A-T 1 , wherein A and T 1 are defined above;
wherein the colorant composition is substantially free of a first additional compound selected from the group consisting of formula 6, formula 7, formula 8, a geometric isomer thereof, a tautomer thereof, and a salt thereof:
10. The colorant composition of claim 9 , wherein
represents an amino acid residue, wherein R 3 is COOH and R 2 and/or R′ 2 represents side chain(s) of the amino acid, and wherein the amino acid is selected from the group consisting of Glycine, Alanine, Leucine, Isoleucine, Serine, Cysteine, Threonine, Methionine, Phenylalanine, Tyrosine, Tryptophan, Histidine, Lysine, Arginine, Aspartate, Glutamate, Asparagine, Glutamine, taurine, ornithine, and citrulline, wherein the amino acid can be in a D or L configuration.
11. The colorant composition of claim 10 , wherein the colorant composition is substantially free of carbohydrates.
12. The colorant composition of claim 11 , wherein the colorant composition is at least 80% free of fatty acids, fat, and proteins.
13. A colorant composition comprising the polymer of claim 3 , wherein the colorant composition is at least 80% free of sugars and spray dried without a starch.
14. A method of preparing of a colorant composition of claim 10 comprising
(a) mixing Genipa americana juice and an amino acid selected from the group consisting of glycine, valine, lysine, methionine, tyrosine, and tryptophan;
(b) removing sugar from the mixture of (a); and
(c) isolating a colorant composition from the sugar-free product of (b),
wherein the intensity of the colorant composition obtained by the method is greater than the intensity of a colorant composition obtained from the mixture of steps (a) without removing sugar.
15. The method of claim 14 , wherein the sugar is removed in step (b) by fermentation, column chromatography, HPLC, size exclusion chromatography, reverse osmosis filtration, ultrafiltration, microfiltration, dialysis, XAD4 resin mediated separation, XAD7 resin mediated separation, or any combination thereof.
16. The method of claim 14 , wherein removing sugar from the mixture of (a) comprises
(i) sterilizing the mixture of step (a);
(ii) inoculating the sterilized mixture of step (i) with a yeast or a bacteria;
(iii) incubating the inoculated mixture of step (ii) under fermentation conditions to produce a fermentation product; and
(iv) isolating a colorant composition from the fermentation product of claim (iii).
17. The method of claim 14 , wherein the colorant composition is blue, blue green, black, green, or purple.
18. The method of claim 14 , wherein the colorant composition has improved resistance to microbial contamination compared to the colorant composition obtained from the mixture of step (a) without removing sugar.
19. The colorant composition of claim 11 , wherein the amino acid is glycine.
20. A food product comprising a food item and a colorant composition of claim 10 .
21. A drug or nutraceutical product comprising a drug or nutraceutical and a colorant composition of claim 10 .
22. A cosmetic product comprising a colorant composition of claim 10 .
23. A medical device colored by a colorant composition of claim 10 .
24. A colorant composition comprising a purified polymer of
a geometric isomer thereof, a tautomer thereof, or a salt thereof, wherein the polymer of Formula 4 is formed by reaction of
wherein n is an integer from 2 to 20;
wherein each A is independently selected from the group consisting of formula 5A, formula 5B, formula 5C, a geometric isomer thereof, a tautomer thereof, a salt thereof, and a combination thereof:
wherein R 1 is methyl; and
represents a primary alkyl amine or
represents an amino acid residue, wherein R 3 is COOH and R 2 and/or R′ 2 represents side chain(s) of the amino acid, and wherein the amino acid is selected from the group consisting of Glycine, Alanine, Valine, Leucine, Isoleucine, Serine, Cysteine, Threonine, Methionine, Phenylalanine, Tyrosine, Tryptophan, Histidine, Lysine, Arginine, Aspartate, Glutamate, Asparagine, Glutamine, taurine, ornithine, and citrulline, wherein the amino acid can be in a D or L configuration;
and wherein T 1 is hydrogen or a methyl group; and T 2 is hydrogen or A-T 1 , wherein A and T 1 are defined above.