CN114478222B - Method for preparing curcumin compound monomer crystal and application thereof - Google Patents
Method for preparing curcumin compound monomer crystal and application thereof Download PDFInfo
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- CN114478222B CN114478222B CN202210237146.2A CN202210237146A CN114478222B CN 114478222 B CN114478222 B CN 114478222B CN 202210237146 A CN202210237146 A CN 202210237146A CN 114478222 B CN114478222 B CN 114478222B
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- bisdemethoxycurcumin
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- VFLDPWHFBUODDF-FCXRPNKRSA-N Curcumin Natural products C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 title claims abstract description 89
- 239000013078 crystal Substances 0.000 title claims abstract description 66
- 229940109262 curcumin Drugs 0.000 title claims abstract description 46
- 235000012754 curcumin Nutrition 0.000 title claims abstract description 46
- 239000004148 curcumin Substances 0.000 title claims abstract description 46
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 title claims abstract description 32
- -1 curcumin compound Chemical class 0.000 title abstract description 6
- JYTVKRNTTALBBZ-UHFFFAOYSA-N bis demethoxycurcumin Natural products C1=CC(O)=CC=C1C=CC(=O)CC(=O)C=CC1=CC=CC(O)=C1 JYTVKRNTTALBBZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- PREBVFJICNPEKM-YDWXAUTNSA-N bisdemethoxycurcumin Chemical compound C1=CC(O)=CC=C1\C=C\C(=O)CC(=O)\C=C\C1=CC=C(O)C=C1 PREBVFJICNPEKM-YDWXAUTNSA-N 0.000 claims abstract description 68
- YXAKCQIIROBKOP-UHFFFAOYSA-N di-p-hydroxycinnamoylmethane Natural products C=1C=C(O)C=CC=1C=CC(=O)C=C(O)C=CC1=CC=C(O)C=C1 YXAKCQIIROBKOP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000001704 evaporation Methods 0.000 claims abstract description 28
- UEPVWRDHSPMIAZ-IZTHOABVSA-N (1e,4z,6e)-5-hydroxy-7-(4-hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)hepta-1,4,6-trien-3-one Chemical compound C1=C(O)C(OC)=CC(\C=C\C(\O)=C\C(=O)\C=C\C=2C=CC(O)=CC=2)=C1 UEPVWRDHSPMIAZ-IZTHOABVSA-N 0.000 claims abstract description 24
- HJTVQHVGMGKONQ-LUZURFALSA-N Curcumin II Natural products C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=CC(O)=CC=2)=C1 HJTVQHVGMGKONQ-LUZURFALSA-N 0.000 claims abstract description 24
- NMRUIRRIQNAQEB-UHFFFAOYSA-N demethoxycurcumin Natural products OC(=CC(C=CC1=CC(=C(C=C1)O)OC)=O)C=CC1=CC=C(C=C1)O NMRUIRRIQNAQEB-UHFFFAOYSA-N 0.000 claims abstract description 24
- UEPVWRDHSPMIAZ-UHFFFAOYSA-N p-hydroxycinnamoyl feruloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(O)=CC(=O)C=CC=2C=CC(O)=CC=2)=C1 UEPVWRDHSPMIAZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
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- 238000002360 preparation method Methods 0.000 description 13
- 244000163122 Curcuma domestica Species 0.000 description 9
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- 235000003392 Curcuma domestica Nutrition 0.000 description 5
- 235000003373 curcuma longa Nutrition 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 235000014375 Curcuma Nutrition 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
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- 239000012141 concentrate Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SRMGQBFDRIIXAH-UHFFFAOYSA-N 1-phenylhept-1-enylbenzene Chemical class C=1C=CC=CC=1C(=CCCCCC)C1=CC=CC=C1 SRMGQBFDRIIXAH-UHFFFAOYSA-N 0.000 description 1
- NCDMQHRPDYHDKA-UHFFFAOYSA-N 1-phenylpent-1-enylbenzene Chemical class C=1C=CC=CC=1C(=CCCC)C1=CC=CC=C1 NCDMQHRPDYHDKA-UHFFFAOYSA-N 0.000 description 1
- 241000234299 Zingiberaceae Species 0.000 description 1
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- 206010003246 arthritis Diseases 0.000 description 1
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- 125000005594 diketone group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000000324 neuroprotective effect Effects 0.000 description 1
- 239000008601 oleoresin Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 239000010681 turmeric oil Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/24—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
- C07C49/245—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
- C07C49/248—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings having unsaturation outside the aromatic rings
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- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
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Abstract
The invention relates to the technical field of separation and purification of substances, and particularly discloses a method for preparing curcumin compound monomer crystals and application thereof. In the method for preparing the curcumin compound monomer crystal, the curcumin compound monomer crystal is a double demethoxycurcumin crystal, and the method comprises the steps of extracting raw materials, evaporating and crystallizing and cooling and crystallizing; the raw materials are a mixture of curcumin monomers, demethoxycurcumin and bisdemethoxycurcumin, and the extraction does not adopt a chromatographic process. The content of the bisdemethoxycurcumin in the bisdemethoxycurcumin crystal obtained by the method is not less than 90%, the appearance of the product is orange red, the crystal habit is spherulites or spheroids, and the granularity is uniform; the process is simple, the operation is convenient, the method is suitable for industrial production, and the product yield can reach more than 60%.
Description
Technical Field
The invention relates to the technical field of separation and purification of substances, in particular to a method for preparing curcumin compound monomer crystals and application thereof.
Background
Turmeric (Curcuma longa l.) belongs to the genus Curcuma, commonly used as a flavoring and dye, is the dried rhizome of Curcuma longa l. Of Curcuma genus of the family zingiberaceae, grown from india to australia, south to north east asia to Zhejiang, and used in asia for thousands of years. The active ingredients of turmeric can be curcumin (3.5% -5%) and turmeric oil (about 5%), and the curcumin has various biological activities such as anti-tumor, antiviral, alzheimer inhibiting, anti-arthritis and the like after being researched for more than 30 years.
Curcumin compounds are the most important components in turmeric, are the generic name of diphenyl heptenes contained in turmeric, and also refer to diphenyl pentenes similar in structure. The curcumin monomer, demethoxycurcumin and bisdemethoxycurcumin are three compounds with the highest content in the compounds. The structure is shown in figure 1, which is very rare diketone substance in nature, two benzene rings are positioned at two ends of the molecule, and the chain beta-diketone is clamped between the two benzene rings and forms a conjugated system with the chain beta-diketone to form a special dumbbell.
Due to the difference of three monomer structures, there is also a difference in some pharmacological activities, and in some researches, aiming at specific action targets for inhibiting or killing tumor cells, it is shown that the bisdemethoxycurcumin is superior to other two monomers in part of neuroprotective action mechanisms and certain antibacterial action mechanisms. According to structural analysis of three monomers, after two methoxy groups are removed from the bisdemethoxycurcumin, the bisdemethoxycurcumin is superior to curcumin monomers and demethoxycurcumin in stability and biological utilization rate, and has good application prospect.
Along with research on different pharmacological activities of curcumin, demethoxycurcumin and bisdemethoxycurcumin monomer compounds, the separation of the monomer compounds has very important significance. However, since the three monomers are very similar in structure and very similar in properties, it is difficult to separate the three monomers using conventional resins or screening crystallization solvents.
In the prior art, a chromatography process is mainly adopted for separating three monomers, for example, CN201310531494.1 adopts polyamide resin as a chromatography filler, chloroform-methanol-glacial acetic acid is adopted as an eluent, and three monomer compounds are obtained after respectively collecting the eluent, concentrating and recrystallizing; CN201010103117.4 describes the separation and purification by macroporous resin adsorption, eluting with acetone-2% glacial acetic acid (50:50), and collecting curcumin, demethoxycurcumin and demethoxycurcumin fractions, respectively; CN200910074614.3 subjecting oleoresin to gradient elution on chromatographic separation medium, collecting eluate, concentrating to obtain curcumin, demethoxycurcumin and bisdemethoxycurcumin crystals; the separation of the monomer compounds by chromatographic separation is a conventional method, but the method has the advantages of small treatment capacity, large solvent consumption and high consumption, and can only be applied to laboratories at present. CN201711352560.3 discloses a method for obtaining bisdemethoxycurcumin from turmeric raw material through multiple times of crystallization, but the steps are more, the stability is not well ensured, and meanwhile, the product yield is low.
In view of the above, there is still a need for further research into methods for separating monomeric compounds of the curcumin type.
Disclosure of Invention
Aiming at the problems of the prior art, one of the purposes of the invention is to provide a method for efficiently producing the bisdemethoxycurcumin crystal with high purity.
In order to achieve the object, the technical scheme of the invention is as follows:
A method for preparing curcumin monomer crystals, wherein the curcumin monomer crystals are bisdemethoxycurcumin crystals, and the method comprises the steps of extracting raw materials, evaporating and crystallizing, and cooling and crystallizing; the raw materials are a mixture of curcumin monomers, demethoxycurcumin and bisdemethoxycurcumin, and the extraction does not adopt a chromatographic process.
According to the invention, after the mixture of curcumin monomer, demethoxycurcumin and bisdemethoxycurcumin is directly subjected to simple extraction, the bisdemethoxycurcumin crystal with high purity and high yield is successfully prepared by combining a two-stage crystallization process, the use of a traditional chromatography process is abandoned, and the industrial production efficiency of the crystal preparation is improved.
The conventional chromatographic process in the invention refers to a technology established by utilizing the differences of physicochemical properties of different substances. It consists of two phases: one is a stationary phase and the other is a mobile phase. When the mixture to be separated passes through the stationary phase with the mobile phase, the components are redistributed in the two phases continuously due to the difference in physicochemical properties of the components, the ability to interact (adsorb, dissolve, bind, etc.) with the two phases, the partition (content ratio) in the two phases being different and moving forward with the mobile phase. The effluent liquid is collected in a fractional manner, and each single component contained in the sample can be obtained, so that the aim of separating each component is fulfilled.
As a specific embodiment, the preparation method of the invention comprises the following steps:
Step 1: extracting: taking bisdemethoxycurcumin as a raw material, adding an extractant with a certain proportion, and extracting the curcumin to obtain an extract;
Step 2: and (3) crystallization: evaporating and crystallizing the extract liquid obtained in the step 1 under a certain condition, cooling and crystallizing, performing solid-liquid separation to obtain a crude product of the double demethoxycurcumin, and further drying to obtain the double demethoxycurcumin.
In the extraction step of the method, the extractant used is an alcohol solvent containing more than 1 hydroxyl group and 2-4C; ethanol, isopropanol or n-butanol are preferred.
More preferably, the extractant used is ethanol.
In the method of the invention, the weight-volume ratio of the raw materials to the extractant is 1 (5-30) g/mL; preferably 1 (5-10) g/mL.
Or preferably, the weight volume ratio of the raw materials to the extractant is 1 (8-12) g/mL, so that the solvent consumption can be saved, and the ideal non-target object removal effect can be realized.
The invention researches the extractant and the dosage thereof, and in the preferred scheme, the extractant can be better matched with the subsequent two-stage crystallization link to obtain better purity and yield.
In the method of the present invention, the mass percentage of the bisdemethoxycurcumin in the raw material is not less than 30%, preferably 35% or more, and more preferably 40% or more. Can further ensure high-efficiency extraction.
In the method, evaporation is carried out at the rate of 50 ml/h-200 ml/h during the evaporation and crystallization, so that the total solid content of the solution obtained after the evaporation and crystallization is 10% -30%; the temperature of the evaporative crystallization is 60-80 ℃, the pressure is-0.03-0.06 MPa, and the stirring rotating speed is 10-60 r/min;
and/or, when the temperature is reduced and crystallized, the temperature is reduced at a speed of 2-10 ℃/h until the end point temperature is 25-35 ℃.
Preferably, in the evaporation crystallization, the evaporation is carried out at a rate of 50ml/h to 100ml/h, so that the total solid content of the solution obtained after the evaporation crystallization is finished is 15% -20%; and when the temperature is reduced and crystallized, the temperature is reduced at a cooling rate of 4-7 ℃/h until the end temperature is 25-30 ℃.
The invention carries out a great deal of research on the control of the crystallization process, and finally combines the selection of the extractant and the two-stage crystallization condition to obtain the double demethoxycurcumin product with high purity and high yield.
The invention also provides a bisdemethoxycurcumin crystal, which is prepared by the method; preferably, the content of the bisdemethoxycurcumin in the bisdemethoxycurcumin crystal is not less than 90%, the crystal appearance is orange red, the crystal habit is spherulites or spheroids, the granularity is uniform, and the crystallinity is good.
The invention also provides an application of the method, or the bisdemethoxycurcumin crystal in preparing health-care products or medicines.
The invention has the advantages that:
The method can obtain the double demethoxycurcumin crystal with the orange crystal habit of spherocrystal or spheroid, and the product has good granularity and high crystallinity, and the content of the double demethoxycurcumin is not less than 90 percent. The preparation method is simple and convenient, is suitable for industrial production, and the product yield can reach more than 60%.
Drawings
FIG. 1 is a block diagram of curcumin monomers, demethoxycurcumin and bisdemethoxycurcumin.
FIG. 2 is a photograph of a crystal habit of the bisdemethoxycurcumin crystal obtained in example 1 of the present invention, which is observed under a polarizing microscope.
FIG. 3 is an XRD pattern of the bisdemethoxycurcumin crystals obtained in example 1 of the present invention.
FIG. 4 is an SEM image of the bisdemethoxycurcumin crystals obtained in example 1 of the present invention.
Fig. 5 is a liquid phase detection profile of a curcumin standard.
FIG. 6 is a liquid phase detection chart of the bisdemethoxycurcumin crystal product prepared in example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents and the like used in the examples below, unless otherwise indicated, are all those available commercially or may be prepared by methods conventional in the art.
In the invention, the curcumin raw material (the mixture containing curcumin monomer, demethoxycurcumin and bisdemethoxycurcumin) and the content of the curcumin monomer, demethoxycurcumin and bisdemethoxycurcumin are measured according to the detection method of T/CCCMHPIE < 1.48-2019 > plant extract curcumin.
The habit and particle size of the crystals were observed and measured by a microscope.
The total solid content calculation formula is: total solids content = weight of non-volatile matter in solution/weight of total solution.
The curcumin materials used in the examples below were all commercially available from morning light Biotechnology group Co., ltd.
Example 1
The embodiment provides a preparation method of a bisdemethoxycurcumin crystal, which specifically comprises the following steps:
Extraction: curcumin with 29.2 percent of curcumin monomer, 17.3 percent of single demethoxycurcumin and 50 percent of bisdemethoxycurcumin is taken as a raw material, 10 times of ethanol (10 times of volume (mL) of ethanol is added based on the weight (g) of the curcumin) is added for extracting the curcumin, and an ethanol extract is obtained by filtering;
and (3) evaporating and crystallizing: evaporating the ethanol extract obtained above at 65 deg.C, pressure of-0.04 MPa and stirring rotation speed of 40r/min at evaporation rate of 100ml/h to obtain concentrated solution with total solid content of 20%;
cooling and crystallizing: cooling the concentrated solution to 25 ℃ at a cooling rate of 5 ℃/h under the condition of 65 ℃ and preserving heat for 5 hours to grow crystals, carrying out solid-liquid separation on the obtained crystals to obtain a crude product of the bisdemethoxycurcumin crystals, and drying the crude product at 105 ℃ for 2 hours to obtain the bisdemethoxycurcumin crystals.
By the preparation method of the bisdemethoxycurcumin crystal, the bisdemethoxycurcumin crystal is orange-red, the crystal habit is spherocrystal or spheroid, the content of the bisdemethoxycurcumin is 95.8%, and the yield of the bisdemethoxycurcumin is 73.6%.
The crystal habit photo observed under the polarizing microscope is shown in fig. 2, the XRD pattern of the bisdemethoxycurcumin crystal obtained in this example is shown in fig. 3, the sem pattern is shown in fig. 4, the liquid phase detection pattern of the curcumin standard product obtained in the test of bisdemethoxycurcumin content is shown in fig. 5, and the liquid phase detection pattern of the bisdemethoxycurcumin crystal product obtained in this example is shown in fig. 6.
Example 2
The embodiment provides a preparation method of a bisdemethoxycurcumin crystal, which specifically comprises the following steps:
extraction: taking curcumin with the curcumin monomer content of 47.2%, the single demethoxycurcumin content of 19.5% and the bisdemethoxycurcumin content of 30% as raw materials, adding 30 times of isopropanol (mL) based on the weight (g) of the curcumin) solvent for extracting the curcumin, and filtering to obtain isopropanol extract;
and (3) evaporating and crystallizing: evaporating the obtained isopropanol extract at the temperature of 70 ℃ and the pressure of-0.06 MPa and the stirring rotation speed of 60r/min at the evaporation rate of 200ml/h until the concentrate with the total solid content of 10% is obtained;
Cooling and crystallizing: cooling the concentrated solution to 35 ℃ at the temperature of 80 ℃ according to the cooling rate of 2 ℃/h, preserving heat for 8 hours, growing crystals, carrying out solid-liquid separation on the obtained crystals to obtain a crude product of the bisdemethoxycurcumin crystals, and drying the crude product at 105 ℃ for 2 hours to obtain the bisdemethoxycurcumin crystals.
By the preparation method of the bisdemethoxycurcumin crystal, the bisdemethoxycurcumin crystal is orange-red, the crystal habit is spherocrystal or spheroid, the content of the bisdemethoxycurcumin is 92.5%, and the yield of the bisdemethoxycurcumin is 61.3%.
Example 3
The embodiment provides a preparation method of a bisdemethoxycurcumin crystal, which specifically comprises the following steps:
Extraction: taking curcumin with 36.4 percent of curcumin monomer, 21.6 percent of single demethoxycurcumin and 40 percent of double demethoxycurcumin as raw materials, adding 20 times of n-butanol (based on the weight (g) of the curcumin, adding 20 times of n-butanol with the volume (mL) of the n-butanol) of the curcumin for extracting, and filtering to obtain n-butanol extract;
and (3) evaporating and crystallizing: evaporating the obtained n-butanol extract at 80 deg.C, pressure of-0.06 MPa and stirring rotation speed of 10r/min at an evaporation rate of 50ml/h to obtain concentrated solution with total solid content of 15%;
cooling and crystallizing: cooling the concentrated solution to 30 ℃ at the temperature of 10 ℃ per hour at the temperature of 80 ℃ and preserving heat for 10 hours to grow crystals, carrying out solid-liquid separation on the obtained crystals to obtain a crude product of the bisdemethoxycurcumin crystals, and drying the crude product of the bisdemethoxycurcumin crystals at 105 ℃ for 2 hours to obtain the bisdemethoxycurcumin crystals.
By the preparation method of the bisdemethoxycurcumin crystal, the bisdemethoxycurcumin crystal is orange-red, the crystal habit is spherocrystal or spheroid, the content of the bisdemethoxycurcumin is 90.5%, and the yield of the bisdemethoxycurcumin is 64.7%.
Example 4
The embodiment provides a preparation method of a bisdemethoxycurcumin crystal, which specifically comprises the following steps:
Extraction: curcumin with 46.1 percent of curcumin monomer, 15.2 percent of single demethoxycurcumin and 35 percent of bisdemethoxycurcumin is taken as a raw material, 5 times of ethanol (based on the weight (g) of the curcumin, 5 times of ethanol with the volume (mL) of ethanol) is added for extracting the curcumin, and an ethanol extract is obtained by filtering;
and (3) evaporating and crystallizing: evaporating the ethanol extract at the temperature of 60 ℃ and the pressure of-0.06 MPa and the stirring rotation speed of 40r/min at the evaporation rate of 100ml/h until the concentrate with the total solid content of 30% is obtained;
cooling and crystallizing: cooling the concentrated solution to 25 ℃ at the temperature of 2 ℃/h, preserving heat for 15h at the temperature of 60 ℃ to grow crystals, carrying out solid-liquid separation on the obtained crystals to obtain a crude product of the bisdemethoxycurcumin crystals, and drying at 105 ℃ for 2h to obtain the bisdemethoxycurcumin crystals.
By the preparation method of the bisdemethoxycurcumin crystal, the bisdemethoxycurcumin crystal is orange-red, the crystal habit is spherocrystal or spheroid, the content of the bisdemethoxycurcumin is 93.6%, and the yield of the bisdemethoxycurcumin is 69.3%.
Comparative experiment 1
In this comparative experiment, the preparation effects of example 1 and comparative examples 1 to 6 were compared.
The experimental parameters in comparative examples 1 to 6 were the same as those of example 1 except for the experimental condition parameter values explicitly listed in table 1. In addition, table 1 also shows the preparation performance indexes of the bisdemethoxycurcumin obtained under different experimental conditions.
TABLE 1
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (7)
1. The method for preparing the curcumin monomer crystal is characterized by comprising the steps of extracting raw materials, evaporating and crystallizing and cooling and crystallizing; the raw materials are a mixture of curcumin monomers, demethoxycurcumin and bisdemethoxycurcumin, and the mass percentage of the bisdemethoxycurcumin in the raw materials is not less than 30%; the extraction does not adopt a chromatographic process;
In the extraction step, the extractant is ethanol, isopropanol or n-butanol, and the weight volume ratio of the raw materials to the extractant is 1 (5-30) g/mL;
During the evaporation and crystallization, evaporating at a rate of 50 ml/h-200 ml/h to ensure that the total solid content of the solution obtained after the evaporation and crystallization is 10% -30%; the temperature of the evaporative crystallization is 60-80 ℃, the pressure is-0.03-0.06 MPa, and the stirring rotating speed is 10-60 r/min;
and when the temperature is reduced and crystallized, the temperature is reduced at a speed of 2-10 ℃/h until the end temperature is 25-35 ℃.
2. The method according to claim 1, wherein in the extraction step, the extractant used is ethanol.
3. The method according to claim 1, wherein the weight to volume ratio of the raw material to the extractant is 1 (5-10) g/mL.
4. A method according to claim 3, wherein the weight to volume ratio of the raw material to the extractant is 1 (8-12) g/mL.
5. The method according to claim 1, wherein the raw material contains more than 35% of bisdemethoxycurcumin by mass.
6. The method according to claim 5, wherein the raw material contains 40% or more of bisdemethoxycurcumin by mass.
7. The method according to any one of claims 1 to 6, wherein the evaporation is performed at a rate of 50ml/h to 100ml/h at the time of the evaporation crystallization, so that the total solid content of the solution obtained after the completion of the evaporation crystallization is 15% to 20%; and when the temperature is reduced and crystallized, the temperature is reduced at a cooling rate of 4-7 ℃/h until the end temperature is 25-30 ℃.
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| CN113773184A (en) * | 2020-06-10 | 2021-12-10 | 晨光生物科技集团股份有限公司 | Method for extracting curcumin compound |
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