CN107973750A - A kind of fat-soluble gardenia blue pigment and preparation method thereof - Google Patents
A kind of fat-soluble gardenia blue pigment and preparation method thereof Download PDFInfo
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- CN107973750A CN107973750A CN201711259763.8A CN201711259763A CN107973750A CN 107973750 A CN107973750 A CN 107973750A CN 201711259763 A CN201711259763 A CN 201711259763A CN 107973750 A CN107973750 A CN 107973750A
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- Prior art keywords
- fat
- blue pigment
- gardenia blue
- soluble
- soluble gardenia
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- 239000001055 blue pigment Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 240000001972 Gardenia jasminoides Species 0.000 title description 3
- 241000157835 Gardenia Species 0.000 claims abstract description 114
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- IBFYXTRXDNAPMM-BVTMAQQCSA-N Geniposide Chemical compound O([C@@H]1OC=C([C@@H]2[C@H]1C(=CC2)CO)C(=O)OC)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O IBFYXTRXDNAPMM-BVTMAQQCSA-N 0.000 claims abstract description 16
- IBFYXTRXDNAPMM-FZEIBHLUSA-N Geniposide Natural products COC(=O)C1=CO[C@@H](O[C@H]2O[C@@H](CO)[C@H](O)[C@@H](O)[C@@H]2O)[C@H]2[C@@H]1CC=C2CO IBFYXTRXDNAPMM-FZEIBHLUSA-N 0.000 claims abstract description 16
- VGLLGNISLBPZNL-RBUKDIBWSA-N arborescoside Natural products O=C(OC)C=1[C@@H]2C([C@H](O[C@H]3[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O3)OC=1)=C(CO)CC2 VGLLGNISLBPZNL-RBUKDIBWSA-N 0.000 claims abstract description 16
- 150000001413 amino acids Chemical class 0.000 claims abstract description 14
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000009514 concussion Effects 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 239000012141 concentrate Substances 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- 239000000049 pigment Substances 0.000 claims description 25
- 238000010898 silica gel chromatography Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- SWVMLNPDTIFDDY-FVGYRXGTSA-N methyl (2s)-2-amino-3-phenylpropanoate;hydrochloride Chemical compound Cl.COC(=O)[C@@H](N)CC1=CC=CC=C1 SWVMLNPDTIFDDY-FVGYRXGTSA-N 0.000 claims description 9
- -1 Ester hydrochloride Chemical class 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- COQRGFWWJBEXRC-UHFFFAOYSA-N hydron;methyl 2-aminoacetate;chloride Chemical compound Cl.COC(=O)CN COQRGFWWJBEXRC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 4
- VXYFARNRGZWHTJ-FVGYRXGTSA-N methyl (2s)-2-amino-3-(4-hydroxyphenyl)propanoate;hydrochloride Chemical compound Cl.COC(=O)[C@@H](N)CC1=CC=C(O)C=C1 VXYFARNRGZWHTJ-FVGYRXGTSA-N 0.000 claims description 4
- MEVUPUNLVKELNV-JEDNCBNOSA-N methyl (2s)-2-amino-4-methylsulfanylbutanoate;hydrochloride Chemical compound Cl.COC(=O)[C@@H](N)CCSC MEVUPUNLVKELNV-JEDNCBNOSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 235000001014 amino acid Nutrition 0.000 claims 5
- 238000010828 elution Methods 0.000 claims 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims 1
- 235000003704 aspartic acid Nutrition 0.000 claims 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 3
- 239000012798 spherical particle Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 23
- 229940024606 amino acid Drugs 0.000 description 11
- 235000018958 Gardenia augusta Nutrition 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 244000111489 Gardenia augusta Species 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000004885 tandem mass spectrometry Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000004075 alteration Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000432824 Asparagus densiflorus Species 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- SCGWHMHVOQPGLS-DFWYDOINSA-N (3s)-3-amino-4-methoxy-4-oxobutanoic acid;hydrochloride Chemical compound Cl.COC(=O)[C@@H](N)CC(O)=O SCGWHMHVOQPGLS-DFWYDOINSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- MAGKCHLCIBUANK-FJXQXJEOSA-N Cl.COC([C@@H](NCCC)CCO)=O Chemical compound Cl.COC([C@@H](NCCC)CCO)=O MAGKCHLCIBUANK-FJXQXJEOSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 241000123069 Ocyurus chrysurus Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/40—Colouring or decolouring of foods
- A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
- A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/22—Heterocyclic compounds, e.g. ascorbic acid, tocopherol or pyrrolidones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Nutrition Science (AREA)
- Birds (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to a kind of fat-soluble gardenia blue pigment and preparation method thereof, the preparation method includes the following steps：(1) Geniposide and amino acid methyl ester hydrochloride are weighed, is dissolved in ethanol, fully dissolving concussion is uniform；(2) it is placed in 40 DEG C~70 DEG C shaking baths, the synthesis under normal pressure under 150~220rpm, oxygen existence condition；(3) revolving removes ethanol and obtains fat-soluble gardenia blue pigment crude product after reaction；(4) concentrate, purify fat-soluble gardenia blue pigment crude product, obtain fat-soluble gardenia blue pigment sterling.The fat-soluble gardenia blue pigment is mixture, in the form of fat-soluble gardenia blue pigment is based on spherical particle, particle size about 100nm.Illumination and temperature stability are all higher than water-soluble gardenia blue pigment.
Description
Technical field
The invention belongs to biochemical field, in particular to a kind of fat-soluble gardenia blue pigment and preparation method thereof.
Background technology
Gardenia blue pigment is a kind of natural blue pigment that the approval of 1989 Nian Qi China uses, it is with madder wort cape jasmine fruit
Actually raw material undergoes microbial fermentation or the biotransformation of enzyme changes into Geniposide, or is directly sent out by Geniposide and amino acid
It is made after raw a series of polymerization, rearrangement reaction, can be widely applied to food, medicine and cosmetics.
The stability study of gardenia blue pigment finds that its is soluble easily in water, and dyeability is good, to soda acid, high temperature and a variety of
Common food additive etc. all has higher stability.But since the pigment cannot be dissolved in absolute ethyl alcohol, ethyl acetate, third
The organic solvents such as ketone, petroleum ether and grease, so as to greatly limit its application range in food industry；Meanwhile the pigment pair
Illumination is more sensitive, easily fades, and influences organoleptic quality of the product in production, storage and sales process, serious to restrict
The application of gardenia blue pigment.
Existing part research report, can be by adding pigment color protection additive, beta-cyclodextrin embedding and chemical modification
Method improve gardenia blue pigment stability.Wherein, chemic modified method is to be directed to the existing functional group's useization of natural pigment
The method increase group for learning reaction changes the structure and property of pigment, with the stability, molten for obtaining new tone or improving pigment
Xie Xing, tinting strength, tinting power, there is very big application value.
By patent retrieval, granted patent " a kind of method for preparing alcohol-soluble gardenia blue pigment derivatives " is with water-soluble Cape jasmine
Sub- cyanine and acetic anhydride are raw material, and a kind of alcohol-soluble gardenia blueness that can be dissolved in absolute ethyl alcohol is prepared for by esterification
Element, but the pigment still cannot be dissolved in the organic solvents such as ethyl acetate, acetone, petroleum ether, its light durability is not carried
Height, and the pigment composition and structure of the derivative are unclear.
In order to further widen the soluble end of gardenia blue pigment and improve its light durability, based on chemical modification method
The preparation method of fat-soluble gardenia blue pigment is explored, new way can be provided for the production and application of gardenia blue pigment.
The content of the invention
Present invention firstly provides a kind of fat-soluble gardenia blue pigment and preparation method thereof, it includes the following steps：
(1) Geniposide and amino acid methyl ester hydrochloride are weighed, is dissolved in ethanol, fully dissolving concussion is uniform；
(2) it is placed in 40~70 DEG C of shaking baths, the synthesis under normal pressure under 150~220rpm, oxygen existence condition；
(3) revolving removes ethanol and obtains fat-soluble gardenia blue pigment crude product after reaction；
(4) concentrate, purify fat-soluble gardenia blue pigment crude product, obtain fat-soluble gardenia blue pigment sterling.
The usage ratio of Geniposide and amino acid methyl ester hydrochloride described in step (1) is 1：0.8~1.4 (molar ratio)；
Ethanol described in step (1) is the ethanol that pH to 7.0 is adjusted with sodium hydroxide-ethanol solution；
The amino acid methyl ester hydrochloride is：Methionine methyl ester hydrochloride, phenylalanine methyl ester hydrochloride, asparagus fern ammonia
Acid methyl ester hydrochloride salt, glycine methyl ester hydrochloride, tyrosine methyl ester hydrochloride；Preferably phenylalanine methyl ester hydrochloride.
The reaction time of reaction described in step (2) is 16~32h, it is preferred that is 24h；
It is 60 DEG C that the bath temperature of reaction described in step (2), which is preferably,；
The reactions steps of reaction described in step (2) are：
1) Geniposide and amino acid methyl ester are attached reaction, and reaction equation is following formula (a) or (b)：
(a)
(b)
R is the side-chain radical of arbitrary amino acid in formula
2) ester occurs with-COOCH3 the groups on the-CH2OH groups and another product molecule on the latter product molecule to hand over
Change-CH2OH the groups in reaction, or a product molecule and dehydration occurs with-the CH2OH on another product molecule.
Described in step (4) concentration purification the step of be：Extracted first by organic solvent and rotate removing organic solvent,
Then purified using silica gel column chromatography；
Described the step of being extracted using organic solvent is：The fat-soluble gardenia blue pigment prepared is dried, then
The inorganic salts and impurity in the fat-soluble gardenia blue pigment crude product of a large amount of water dissolvings are added, fat-soluble gardenia blue pigment is extracted with chloroform
3 times；
Described the step of being purified using silica gel column chromatography is：Cleaned and eluted with silica gel column chromatography after concentrated by rotary evaporation, obtained
Pure fat-soluble gardenia blue pigment is obtained, eluant, eluent is chloroform and the mixed liquor of ethanol, and the proportioning of different gradient eluents is chloroform：
Ethanol=50~15：1, it is preferably chloroform：Ethanol=49：1,29：1,19：1 three gradients.
The invention further relates to the fat-soluble gardenia blue pigment prepared by the method, fat-soluble cape jasmine blueness
In the form of element is based on spherical particle, particle size about 100nm.Preferably, the fat-soluble gardenia blue pigment is mixture, its
Include compound of the structure as described in following formula (Z-1), formula (Z-2), formula (Z-3)：
The invention further relates to the fat-soluble gardenia blue pigment that the method prepares to prepare food, medicine or makeup
Application in product.
The invention further relates to application of the fat-soluble gardenia blue pigment in pigment is produced.
Answering the invention further relates to the compound described in formula (Z-1), formula (Z-2), formula (Z-3) and its in pigment is prepared
With.
The invention has the advantages that, there is provided a kind of fat-soluble gardenia blue pigment and preparation method thereof, with Geniposide, amino acid first
The gardenia blue pigment for being dissolved in water and being dissolved in a variety of fat-soluble organic solvents that ester hydrochloride prepares for reactant.By using
Amino acid methyl ester hydrochloride is reactant, avoids amino acid from introducing hydrophilic radical-COOH, and the use of ethanol is reaction medium, from
And obtain the weaker fat-soluble gardenia blue pigment of polarity.
Fat-soluble gardenia blue pigment prepared by the present invention is smooth spherical, a length of 607nm of maximum absorption wave, main functional group
There are O-C=O ,-C=O ,-C-N- ,-C=C- ,-OH and phenyl ring etc., mainly by 5 kinds of different molecular weights and the pigment group of chemical constitution
Into wherein 3 kinds of colour component molecular weight are：690.3Da, 720.3Da and 708.3Da.
Brief description of the drawings
The microscopic pattern figure of the fat-soluble gardenia blue pigments of Fig. 1.
The UV-visible absorption spectrum of the fat-soluble gardenia blue pigments of Fig. 2
The FTIR spectrum figure of the fat-soluble gardenia blue pigments of Fig. 3
The X-ray photoelectron of the fat-soluble gardenia blue pigments of Fig. 4 can be composed entirely
The X-ray photoelectron energy Cs1 spectrums of the fat-soluble gardenia blue pigments of Fig. 5
The X-ray photoelectron energy Os1 spectrums of the fat-soluble gardenia blue pigments of Fig. 6
The X-ray photoelectron energy Ns1 spectrums of the fat-soluble gardenia blue pigments of Fig. 7
The MS figures of the fat-soluble gardenia blue pigment compound Z-1 of Fig. 8
The MS/MS figures of the fat-soluble gardenia blue pigment compound Z-1 of Fig. 9
The structural simulation figure of the fat-soluble gardenia blue pigment compound Z-1 of Figure 10
The MS figures of the fat-soluble gardenia blue pigment compound Z-2 of Figure 11
The MS/MS figures of the fat-soluble gardenia blue pigment compound Z-2 of Figure 12
The structural simulation figure of the fat-soluble gardenia blue pigment compound Z-2 of Figure 13
The MS figures of the fat-soluble gardenia blue pigment compound Z-3 of Figure 14
The MS/MS figures of the fat-soluble gardenia blue pigment compound Z-3 of Figure 15
The structural simulation figure of the fat-soluble gardenia blue pigment compound Z-3 of Figure 16
The MS figures of the fat-soluble gardenia blue pigment compound Z-4 of Figure 17
The MS/MS figures of the fat-soluble gardenia blue pigment compound Z-4 of Figure 18
The MS figures of the fat-soluble gardenia blue pigment compound Z-5 of Figure 19
The MS/MS figures of the fat-soluble gardenia blue pigment compound Z-5 of Figure 20
The light durability of fat-soluble, the water-soluble gardenia blue pigments of Figure 21：Pigment residue rate comparison diagram
The temperature stability of fat-soluble, the water-soluble gardenia blue pigments of Figure 22：Pigment residue rate comparison diagram
Embodiment
Embodiment 1-10 is used for the preparation method for illustrating fat-soluble gardenia blue pigment provided by the present invention, in this 10 realities
The amino acid methyl ester hydrochloride that is used in case is applied as methionine methyl ester hydrochloride, phenylalanine methyl ester hydrochloride, asparagus fern
Propylhomoserin methyl ester hydrochloride, glycine methyl ester hydrochloride, tyrosine methyl ester hydrochloride etc., it is preferred that be phenyalanine methyl ester hydrochloric acid
Salt.
The reaction raw materials for preparing fat-soluble gardenia blue pigment are accurately weighed according to the amount listed by table 1, it is anti-according to what is listed
Temperature and reaction time is answered to be reacted.
The preparation condition of 1 fat-soluble gardenia blue pigment of table
The preparation of embodiment 1, fat-soluble gardenia blue pigment
It is formulated according to table 1 Suo Shi, following reactions steps, prepare fat-soluble gardenia blue pigment：
Using Geniposide and phenylalanine methyl ester hydrochloride, fat-soluble gardenia blue pigment is prepared：
(1) 2mmol Geniposides and 2.6mmol phenylalanine methyl ester hydrochlorides accurately are weighed, be dissolved in 40mL ethanol；
(2) fully after dissolving concussion uniformly, it is placed in 50 DEG C of shaking baths, the normal pressure under 180rpm, oxygen existence condition
React 24h；
(3) revolving removes ethanol after reaction, and the fat-soluble gardenia blue pigment prepared is dried, and then adds big
Measure water and dissolve inorganic salts and impurity therein, extracted 3 times with chloroform；
(4) cleaned after concentrated by rotary evaporation with silica gel column chromatography, select suitable silica gel column chromatography removal of impurities with thin-layered chromatography and wash
De- agent, suitable silica gel column chromatography gradient separations eluant, eluent is chloroform：The ratio of ethanol is respectively 49：1,29：1,19：1.
The preparation of embodiment 2, fat-soluble gardenia blue pigment
It is formulated according to table 1 Suo Shi, following reactions steps, prepare fat-soluble gardenia blue pigment：
2.1st, fat-soluble gardenia blue pigment is prepared using Geniposide and methionine methyl ester hydrochloride
(1) 2mmol Geniposides are accurately weighed and 2.2mmol methionine methyl esters hydrochloride (provides several specific salt
Alternative, word description), it is dissolved in 40mL ethanol；
(2) fully after dissolving concussion uniformly, it is placed in 60 DEG C of shaking baths, the normal pressure under 180rpm, oxygen existence condition
React 24h；
(3) revolving removes ethanol after reaction, and the fat-soluble gardenia blue pigment prepared is dried, and then adds big
Measure water and dissolve inorganic salts and impurity therein, extracted 3 times with chloroform；
(4) cleaned after concentrated by rotary evaporation with silica gel column chromatography, select suitable silica gel column chromatography removal of impurities with thin-layered chromatography and wash
De- agent.
2.2nd, fat-soluble gardenia blue pigment is prepared using Geniposide and phenylalanine methyl ester hydrochloride
(1) 2mmol Geniposides and 2.2mmol phenylalanine methyl ester hydrochlorides accurately are weighed, be dissolved in 40mL ethanol；
(2) fully after dissolving concussion uniformly, it is placed in 40 DEG C of shaking baths, the normal pressure under 180rpm, oxygen existence condition
React 24h；
(3) revolving removes ethanol after reaction, and the fat-soluble gardenia blue pigment prepared is dried, and then adds big
Measure water and dissolve inorganic salts and impurity therein, extracted 3 times with chloroform；
(4) cleaned after concentrated by rotary evaporation with silica gel column chromatography, select suitable silica gel column chromatography removal of impurities with thin-layered chromatography and wash
De- agent.
2.3rd, fat-soluble gardenia blue pigment is prepared using Geniposide and aspartate methylester hydrochloride
(1) 2mmol Geniposides are accurately weighed and 2.2mmol aspartate methylesters hydrochloride (provides several specific salt
Alternative, word description), it is dissolved in 40mL ethanol；
(2) fully after dissolving concussion uniformly, it is placed in 70 DEG C of shaking baths, the normal pressure under 180rpm, oxygen existence condition
React 24h；
(3) revolving removes ethanol after reaction, and the fat-soluble gardenia blue pigment prepared is dried, and then adds big
Measure water and dissolve inorganic salts and impurity therein, extracted 3 times with chloroform；
(4) cleaned after concentrated by rotary evaporation with silica gel column chromatography, select suitable silica gel column chromatography removal of impurities with thin-layered chromatography and wash
De- agent.
2.3rd, fat-soluble gardenia blue pigment is prepared using Geniposide and glycine methyl ester hydrochloride
(1) 2mmol Geniposides are accurately weighed and 2.2mmol glycine methyl ester hydrochlorides (provide replacing for several specific salt
Change example, word description), it is dissolved in 40mL ethanol；
(2) fully after dissolving concussion uniformly, it is placed in 50 DEG C of shaking baths, the normal pressure under 180rpm, oxygen existence condition
React 24h；
(3) revolving removes ethanol after reaction, and the fat-soluble gardenia blue pigment prepared is dried, and then adds big
Measure water and dissolve inorganic salts and impurity therein, extracted 3 times with chloroform；
(4) cleaned after concentrated by rotary evaporation with silica gel column chromatography, select suitable silica gel column chromatography removal of impurities with thin-layered chromatography and wash
De- agent.
2.3rd, fat-soluble gardenia blue pigment is prepared using Geniposide and tyrosine methyl ester hydrochloride
(1) 2mmol Geniposides are accurately weighed and 1.8mmol tyrosine methyl ester hydrochlorides (provide replacing for several specific salt
Change example, word description), it is dissolved in 40mL ethanol；
(2) fully after dissolving concussion uniformly, it is placed in 50 DEG C of shaking baths, the normal pressure under 180rpm, oxygen existence condition
React 24h；
(3) revolving removes ethanol after reaction, and the fat-soluble gardenia blue pigment prepared is dried, and then adds big
Measure water and dissolve inorganic salts and impurity therein, extracted 3 times with chloroform；
(4) cleaned after concentrated by rotary evaporation with silica gel column chromatography, select suitable silica gel column chromatography removal of impurities with thin-layered chromatography and wash
De- agent.
In addition to above-mentioned instantiation, reaction condition and formula according to table 1, replace different amino acid methyl ester hydrochloric acid
Salt and corresponding response parameter, can complete to react, prepare fat-soluble gardenia blue pigment.
Embodiment 3, fat-soluble gardenia blue pigment structural characterization
3.1st, using the fat-soluble gardenia blue pigment for preparing of scanning electron microscope (SEM) observation embodiment 1,2
Microscopic pattern, in the form of the result is shown in Figure 1, the fat-soluble gardenia blue pigment prepared are based on spherical particle, particle size is about
100nm。
3.2nd, weigh the fat-soluble gardenia blue pigment that 0.1g embodiments 1 prepare to be dissolved in ethanol, dilute suitable multiple,
Reference is done with ethanol, using the purple in ultraviolet-visible spectrophotometer (UV-Vis) measure 400~700nm of pigment solution sections
Outside-visible absorption spectra, as shown in Figure 2.
3.3rd, embodiment 1,2 is made using Fourier infrared spectrograph (FTIR) and x-ray photoelectron spectroscopy (XPS)
The characteristic group of the standby fat-soluble gardenia blue pigment obtained is measured, as shown in Fig. 3~7 and table 2~4.
The C element relevant surfaces functional group content of 2 fat-soluble gardenia blue pigment of table
The O element relevant surfaces functional group contents of 3 fat-soluble gardenia blue pigment of table
The N element relevant surfaces functional group content of 4 fat-soluble gardenia blue pigment of table
3.4th, using quadrupole rod-flight time tandem mass spectrometer to by 5 kinds of isolated fat-soluble Cape jasmines of silica gel column chromatography
The molecular weight and concrete structure of sub- cyanine (Z-1, Z-2, Z-3, Z-4, Z-5) are analyzed, and obtain 5 kinds of fat-soluble cape jasmine bluenesss
The mass spectrogram of element, and analyze and obtain the structural formula of wherein 3 kinds fat-soluble gardenia blue pigments.The result is shown in Fig. 8~20.
Embodiment 4, fat-soluble gardenia blue pigment study on the stability
4.1st, dissolubility is investigated：
Equivalent is placed in the fat-soluble gardenia blue pigment and water-soluble gardenia blue pigment that case study on implementation 1,2 is prepared respectively
In isometric distilled water and various organic solvents, fully dissolving, examines or check dissolubility.
Table 5 is fat-soluble, dissolubility of the water-soluble gardenia blue pigment in different solvents
Note：√ is readily soluble；× insoluble
4.2nd, light durability is investigated
Fat-soluble gardenia blue under the conditions of examination sunlight, light direct projection, room scattering and dark lucifuge (control) respectively
The stability of pigment and water-soluble gardenia blue pigment.Intensity of illumination is as shown in table 6：
The intensity of illumination of 6 different illumination conditions of table
The fat-soluble gardenia blue pigment powder that case study on implementation 1,2 is prepared and water-soluble gardenia blue pigment powder difference
It is dissolved in absolute ethyl alcohol and distilled water, is 0.8 with ultraviolet specrophotometer tune solution absorbance, initial color is tested with color difference meter
Adjust, by two kinds of pigment solution packing in test tube, each illumination condition 3 is parallel, is dissipated in sunlight, light direct projection, interior
The absorbance penetrated and survey pigment solution after placement 7d under four illumination conditions of dark lucifuge with ultraviolet specrophotometer, uses color difference meter
Survey tone (the measure L of pigment solution*、a*、b*Value, L*Value represents solution colour brightness, L*Value is bigger, shows that the color of solution is bright
Degree is bigger；a*Value is to describe the variable of solution colour red green degree, a*For on the occasion of and it is bigger when, show that solution colour is redder, a*
For negative value and bigger absolute value when, show that color is greener；b*Value is to describe the variable of solution colour yellow blue degree, b*For on the occasion of and
When bigger, show that solution colour is more yellow, b*For negative value and bigger absolute value when, show that color is more blue), calculate pigment residue rate and
Aberration.The result is shown in Figure 21 and table 7, the results show that the light durability of fat-soluble gardenia blue pigment is significantly higher than water-soluble cape jasmine
Cyanine.
Light durability --- the aberration of fat-soluble, the water-soluble gardenia blue pigment of table 7
Note：Same letter represents that difference is not notable, and different letters represent significant difference (P<0.05)
4.3rd, temperature stability is investigated
Fat-soluble Cape jasmine under the conditions of 4 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C and room temperature (25 DEG C, control) is examined or check respectively
The stability of sub- cyanine and water-soluble gardenia blue pigment.
The fat-soluble gardenia blue pigment powder and water-soluble gardenia blue pigment powder point that case study on implementation 1-10 is prepared
It is not dissolved in absolute ethyl alcohol and distilled water, is 0.8 with ultraviolet specrophotometer tune solution absorbance, initial color is tested with color difference meter
Adjust, two kinds of pigment solutions are divided in 50mL spiral cover centrifuge tubes, each temperature conditionss 3 are parallel, and lucifuge is protected in water-bath
Temperature, room temperature (control) is wrapped with masking foil to be placed in lucifuge cabinet.The extinction of pigment solution is surveyed after 24h with ultraviolet specrophotometer
Degree, the tone of pigment solution is surveyed with color difference meter, calculates pigment residue rate and aberration.The result is shown in Figure 22 and table 8.
Temperature stability --- the aberration of fat-soluble, the water-soluble gardenia blue pigment of table 8
Note：Same letter represents that difference is not notable, and different letters represent significant difference (P<0.05)
Finally it should be noted that above example is used only as helping skilled in the art to understand the essence of the present invention,
Rather than the specific of protection domain is limited.
Claims (10)
1. a kind of preparation method of fat-soluble gardenia blue pigment, it is characterised in that include the following steps：
(1) Geniposide and amino acid methyl ester hydrochloride are weighed, is dissolved in ethanol, fully dissolving concussion is uniform；
(2) it is placed in 40 DEG C~70 DEG C shaking baths, the synthesis under normal pressure under 150~220rpm, oxygen existence condition；
(3) revolving removes ethanol and obtains fat-soluble gardenia blue pigment crude product after reaction；
(4) concentrate, purify fat-soluble gardenia blue pigment crude product, obtain fat-soluble gardenia blue pigment sterling.
2. according to the method described in claim 1, it is characterized in that,
The usage ratio of Geniposide and amino acid methyl ester hydrochloride described in step (1) is 1：0.8~1.4；
The ethanol that ethanol described in step (1) is pH7.0；
The amino acid methyl ester hydrochloride is：Methionine methyl ester hydrochloride, phenylalanine methyl ester hydrochloride, aspartic acid first
Ester hydrochloride, glycine methyl ester hydrochloride, tyrosine methyl ester hydrochloride；Preferably phenylalanine methyl ester hydrochloride.
3. method according to claim 1 or 2, it is characterised in that
The reaction time of reaction described in step (2) is 16~32h, is preferably 24h；
The bath temperature of reaction described in step (2) is 60 DEG C；
The reaction process of reaction described in step (2) is：
1) Geniposide and amino acid methyl ester are attached reaction, and reaction equation is following formula (a) or (b)：
(a)
(b)
R is the side-chain radical of arbitrary amino acid in formula；
2) it is anti-with the-COOCH3 groups generation ester exchange on the-CH2OH groups and another product molecule on the latter product molecule
Should obtain-CH2OH groups on fat-soluble gardenia blue pigment molecule, or a product molecule with another product molecule-
CH2OH occurs dehydration and obtains fat-soluble gardenia blue pigment molecule.
4. method according to claim 1 or 2, it is characterised in that
Described in step (4) concentration purification the step of be：Extracted first by organic solvent and rotate removing organic solvent, then
Purified using silica gel column chromatography.
5. according to the method described in claim 4, it is characterized in that,
Described the step of being extracted using organic solvent is：The fat-soluble gardenia blue pigment prepared is dried, is then added
Substantial amounts of water, dissolves inorganic salts and impurity in fat-soluble gardenia blue pigment crude product, and fat-soluble gardenia blue pigment 3 is extracted with chloroform
It is secondary；
Described the step of being purified using silica gel column chromatography is：Cleaned, obtained with silica gel column chromatography gradient elution after concentrated by rotary evaporation
Pure fat-soluble gardenia blue pigment is obtained, eluant, eluent is chloroform and the mixed liquor of ethanol, and the proportioning of different gradient elution agent is chloroform：
Ethanol=50~15：1, it is preferably chloroform：Ethanol=49：1,29：1,19：1 three gradients.
6. the fat-soluble gardenia blue pigment prepared by any the methods of claim 1-5.
7. fat-soluble gardenia blue pigment according to claim 6, it is characterised in that the fat-soluble gardenia blue pigment is
Mixture, including such as following formula (Z-1), formula (Z-2), formula (Z-3) described compound：
8. the fat-soluble gardenia blue pigment that any methods of claim 1-5 prepare is preparing food, medicine or change
Application in cosmetic.
9. application of the fat-soluble gardenia blue pigment in pigment is produced described in claim 6 or 7.
10. formula (Z-1), formula (Z-2), formula (Z-3) compound described in claim 7 and its application in pigment is produced.
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