CN107296802B - Hydrophobic porous silicon curcumin micro-gel with antioxidant activity and preparation method thereof - Google Patents
Hydrophobic porous silicon curcumin micro-gel with antioxidant activity and preparation method thereof Download PDFInfo
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- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound 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 217
- 239000004148 curcumin Substances 0.000 title claims abstract description 108
- 229940109262 curcumin Drugs 0.000 title claims abstract description 108
- 235000012754 curcumin Nutrition 0.000 title claims abstract description 108
- 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 108
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 100
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 21
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- 239000012452 mother liquor Substances 0.000 claims abstract description 11
- 239000012154 double-distilled water Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
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- 238000005530 etching Methods 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 21
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- 239000000377 silicon dioxide Substances 0.000 claims description 17
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- 238000010438 heat treatment Methods 0.000 claims description 10
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- 230000004048 modification Effects 0.000 claims description 10
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
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- 238000002791 soaking Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000003094 microcapsule Substances 0.000 abstract description 37
- -1 DPPH free radical Chemical class 0.000 abstract description 15
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
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- 239000003814 drug Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 5
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 2
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- 238000012377 drug delivery Methods 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
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- 235000019192 riboflavin Nutrition 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
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- 229920001661 Chitosan Polymers 0.000 description 1
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- 206010061598 Immunodeficiency Diseases 0.000 description 1
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- 206010061218 Inflammation Diseases 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
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000234299 Zingiberaceae Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019654 spicy taste Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
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- 210000004881 tumor cell Anatomy 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 210000003708 urethra Anatomy 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/501—Inorganic compounds
-
- 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
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/30—Encapsulation of particles, e.g. foodstuff additives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/12—Ketones
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- 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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Abstract
The invention discloses a hydrophobic porous silicon curcumin microcapsule with antioxidant activity and a preparation method thereof, wherein the microcapsule is prepared from hydrophobic porous silicon, curcumin mother liquor and double distilled water according to the mass-volume ratio of 10: 1-1.5: 1-1.5 (mg/ml/ml). The hydrophobic porous silicon curcumin microcapsule can effectively improve the water solubility and stability of curcumin so as to be hydrophobicThe modified hydrophobic porous silicon has high loading rate to curcumin, and the curcumin release rate reaches 94.54% when the curcumin is released for 8 hours in a medium with pH of 8.5; for DPPH free radical and superoxide anion O2High clearance. Meanwhile, the preparation method is simple and convenient, wide in raw material source and low in cost, and the bioavailability of the compound is improved.
Description
Technical Field
The invention relates to curcumin micro-gel preparation, and particularly relates to hydrophobic porous silica curcumin micro-gel with antioxidant activity and a preparation method thereof.
Background
Curcumin (curcumin) is a natural phenolic pigment extracted from Curcuma rhizome of Zingiberaceae. Research shows that curcumin as a medicine has good biological activity in the aspects of anti-inflammation, bacteriostasis, antioxidation, anti-human immunodeficiency virus, liver and kidney protection, fibrosis resistance, tumor cell proliferation inhibition and rheumatoid treatment. Although curcumin shows good biological activity and application prospect in experimental research, some characteristics of curcumin per se hinder the development of curcumin in practical application, such as low water solubility, poor bioavailability, easy oxidation, spicy taste and difficult entrance, and the like. At present, the greatest challenge of curcumin in the development of functional foods and clinical treatment is low water solubility, and how to improve the water solubility of curcumin becomes a research hotspot of scholars at home and abroad. In order to solve the above problems, some researchers use degradable biological materials such as liposome, chitosan, starch and high molecular copolymer as carriers to improve the bioavailability of curcumin. Although the biological materials have certain advantages and characteristics in the aspects of improving the water solubility of the curcumin and slowly releasing the medicine, the biological materials also have a series of disadvantages of poor stability, poor mechanical strength, easy leakage and the like. The mesoporous material is a porous material with the pore diameter of 2-50nm, and has the characteristics of extremely high specific surface area, regular and ordered pore channel structure, narrow pore size distribution, continuously adjustable pore size and the like, so that the mesoporous material is widely applied to a drug delivery system. Since porous silicon, which is a silicon material having a spongy loose structure and first reported by Canhan in 1990, can emit high-efficiency visible light at room temperature, porous silicon materials have been regarded and studied by researchers and widely used in various fields. The porous silicon has the characteristics of adjustable pore size, easy surface modification, biocompatibility, biodegradability and the like, so that the porous silicon is applied to a drug delivery and sustained release system. Research shows that the porous silicon can be degraded into nontoxic silicic acid in vivo, and is easy to be absorbed by gastrointestinal tract and discharged from body through kidney and urethra. When the pore diameter is between 10 and 50nm, the encapsulated drug can not be crystallized in the pore canal and mostly keeps amorphous state, which greatly increases the solubility and dissolution speed of the encapsulated drug. The research on the porous silicon as the drug carrier is really numerous, and no research on loading curcumin by using hydrophobic porous silicon as the carrier is found at present.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a hydrophobic porous silicon curcumin microcapsule; the microcapsule takes hydrophobic porous silicon as a novel carrier to load curcumin, and the hydrophobic porous silicon can effectively improve the water solubility and stability of curcumin and simultaneously improve the biology thereofUtilization rate; the modified hydrophobic porous silicon has high curcumin loading rate (the amount of curcumin loaded per milligram of porous silicon) and large curcumin loading amount per milligram of porous silicon, and can effectively eliminate DPPH free radicals and superoxide anion O2-·。
The invention also provides a preparation method of the hydrophobic porous silicon curcumin microcapsule.
The technical scheme is as follows: in order to achieve the above object, the hydrophobic porous silica curcumin microcapsule with antioxidant activity according to the present invention is characterized in that the microcapsule is prepared by mixing hydrophobic porous silica, curcumin mother liquor and double distilled water in a mass-to-volume ratio of 10: 1-1.5: 1-1.5 (mg/ml/ml). The preferred ratio is 10: 1:1 (mg/ml/ml).
The hydrophobic porous silicon is obtained by forming a porous silicon film on a monocrystalline silicon wafer through electrochemical etching, preparing micron-sized porous silicon particles, and finally adding octadecylsilane to modify.
The concentration of the curcumin mother liquor is 1-1.5mg/ml, and the solvent is preferably absolute ethyl alcohol.
The preparation method of the hydrophobic porous silicon curcumin microcapsule comprises the following steps:
(1) treating a monocrystalline silicon wafer under ultrasonic waves, and then placing the monocrystalline silicon wafer in NH4OH、H2O2And H2Heating in O mixed solution, soaking in HCl and H2O2And H2Heating in the O mixed solution, and soaking the silicon wafer in ethanol for later use after washing;
(2) etching the spare silicon wafer in the step (1) by using etching liquid in a dark environment to obtain a porous silicon film;
(3) stripping the etched porous silicon film by using stripping liquid, and performing ultrasonic treatment in an ethanol solution to prepare micron-sized porous silicon particles;
(4) centrifuging the micron-sized porous silicon particles, removing a clear solution, drying the residual ethanol solution on the surfaces of the micron-sized porous silicon particles, adding toluene and octadecylsilane, uniformly mixing, heating and modifying; centrifuging after modification, removing modification liquid, respectively washing the porous silicon particles with toluene and ethanol, and drying under a vacuum condition to obtain hydrophobic porous silicon;
(5) adding curcumin mother liquor and double distilled water into the hydrophobic porous silicon obtained in the step (4) to carry out curcumin loading; obtaining the hydrophobic porous silicon curcumin microcapsule.
Wherein the monocrystalline silicon wafer in the step (1) is doped with P-type boron, and the resistance is 0.0008-0.0012 omega.
The etching solution in the step (2) is hydrofluoric acid aqueous solution absolute ethyl alcohol containing 48% of volume fraction in a volume ratio of 1: 1-1.2; the preferred ratio is 1:1.
Etching current of 30-60mA/cm for etching in the step (2)2Etching time 600- & gt 650 seconds.
The stripping solution in the step (3) is hydrofluoric acid aqueous solution and absolute ethyl alcohol with volume fraction of 48% and volume ratio of 1: 28-30; preferably in a volume ratio of 1: 29.
The volume mass ratio of the toluene to the octadecylsilane to the blow-dried micron-sized porous silicon particles in the step (4) is 1.5-1.6: 0.4-0.5: 50 (ml/ml/mg); the preferred ratio is 1.6: 0.4: 50 (ml/ml/mg).
And (5) loading curcumin for 2-24 hours at the temperature of 25-65 ℃ by water bath standing, magnetic stirring or shaking table shaking.
The principle of the invention is shown in figure 1, the hydrophobic porous silicon curcumin microcapsule takes the unique advantages of huge specific surface area and volume, controllable size and nano-pore channel, easiness in modification and the like of hydrophobic porous silicon as a curcumin carrier, and curcumin with hydrophobicity is adsorbed on the surface of the porous silicon. When the porous silicon-curcumin microcapsule is conveyed to a certain place, the porous silicon is degraded, and the curcumin is released.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the hydrophobic porous silicon curcumin microcapsule can effectively improve the water solubility and stability of curcumin, the hydrophobic porous silicon is used as a novel carrier to load curcumin, the loading capacity of modified hydrophobic porous silicon to curcumin can reach the maximum value of 22.3 percent, the loading capacity of curcumin to porous silicon per milligram is 22.3 mu g, and the curcumin is loaded at pH7.4 and 5In the medium, the release rates of curcumin are 85.29% and 81.61% respectively, and both have a tendency of continuously rising, and in the medium with the pH of 8.5, the release rate of curcumin reaches the maximum value which is 94.54% when the curcumin is released for 8 hours; can effectively remove DPPH free radical and superoxide radical anion O2-. 47.54% of DPPH radical scavenging rate, superoxide anion O2The clearance of-is 63.64%. Meanwhile, the preparation method is simple and convenient, wide in raw material source and low in cost, and the bioavailability of the compound is improved.
According to the invention, the hydrophobic porous silicon is used as a novel carrier to load curcumin, the novel hydrophobic porous silicon curcumin microcapsule is prepared, and relevant information is provided for the application of curcumin in the fields of food and medicine through the research on the loading rate and the sustained release characteristic of the microcapsule.
Drawings
FIG. 1 is a schematic diagram of curcumin loading and slow release based on hydrophobic porous silicon;
FIG. 2 is a schematic structural representation of hydrophobic porous silicon particles prepared in example 1 of the present invention;
FIG. 3 is a schematic representation of the characterization of hydrophobic porous silicon-curcumin microcapsules prepared in example 1 of the present invention;
FIG. 4 is a graph of the release profile of hydrophobic porous silicon-curcumin microcapsules in different pH media;
FIG. 5 is a graph showing the scavenging effect of the hydrophobic porous silicon-curcumin microcapsule release liquid on DPPH free radicals;
FIG. 6 shows the release liquid of hydrophobic porous silicon-curcumin microcapsule to superoxide anion O2Graph of the clearance effect of.
Detailed Description
The invention is further illustrated by the following figures and examples.
The anhydrous ethanol used in the invention is purchased from national medicine group chemical reagent limited company, the hydrofluoric acid is purchased from Aladdin company, the curcumin (chromatographic grade > 98%) is purchased from Shanghai Yuanye Biotech limited company, the ammonia (NH4OH), the methanol and the hydrogen peroxide (H2O2) are purchased from Nanjing chemical reagent limited company, the octadecylsilane is purchased from Bailingwei technology, and the silicon wafer (0.0008-0.0012 omega-cm, (100) and boron doped) is purchased from Siltronix company.
The apparatus used in the invention mainly comprises:
NJ320 pulse etching apparatus, Xiamen Najing Analyzer Co., Ltd
OTL1200 type tube furnace, Nanjing university Instrument plant
KQ-300DE ultrasonic cleaner, Kunshan ultrasonic Instrument Co., Ltd
Molresearch 1005a analytical ultrapure water machine, Shanghai Mohler Biotech Ltd
Self-made polytetrafluoroethylene etching groove laboratory
SZ-2 automatic double-water distiller, Shanghai West Analyzer Co., Ltd
UV6100A ultraviolet spectrophotometer, Shanghai Meta analysis Instrument Co., Ltd
Model AM-3250B magnetic stirrer, Tianjin Orthon instruments ltd
PHS-3C precision pH meter, Shanghai three-letter instrument factory
TDZ5-WS desk type low speed automatic balance centrifuge, Changshan intelligent centrifuge Instrument Co., Ltd
SHIMADZU AUY220 analytical balance, Shimadzu, Japan
Eppendorf 5415 model refrigerated centrifuge, Ebende China Co., Ltd
Hitachi, S-3400N scanning Electron microscope, Hitachi, Japan
Dong electronic DG5033A type microplate reader, Nanjing electronic group medical equipment Limited liability company
ZQTY-70 Table-type full-temperature oscillation full-temperature incubator, Shanghai Zhichu instruments Co., Ltd
HH-S2 digital display constant temperature water bath, medical instrument factory of gold jar city.
Example 1
(1) Selecting a P-type boron-doped monocrystalline silicon wafer with the resistance of 0.0008-0.0012 omega, cutting into a standby silicon wafer of 3 multiplied by 3cm, and respectively treating with acetone, methanol and deionized water under ultrasonic waves for 15 min. Then put into NH4OH：H2O2：H2O is 1:1: 75 in 5(v/v/v) Mixed solutionHeating in water bath at the temperature of 15min, and soaking in HCl: h2O2：H2Heating in a mixed solution of O1: 1:5(v/v/v) in a water bath at 75 ℃ for 15min, and finally washing with deionized water and ethanol in sequence; the processed silicon wafer is soaked in ethanol before use, so that secondary pollution is prevented;
(2) and (2) adopting hydrofluoric acid aqueous solution (HF) containing 48% of volume fraction for the spare silicon chip in the step (1): absolute ethyl alcohol (C)2H5Etching with etching solution with OH (1: 1) (v/v) in dark environment at 30-60mA/cm2Etching time is 600-;
(3) with 3.3% stripping solution (HF: C)2H5OH, 1:29, v/v) stripping the etched porous silicon film, and performing ultrasonic treatment in an ethanol solution for 30min to prepare micron-sized porous silicon particles;
(4) centrifuging the prepared micron-sized porous silicon particles in a centrifuge at 1914 Xg for 10min, discarding the clear solution, and drying the residual ethanol solution on the surfaces of the wet micron-sized porous silicon particles by using nitrogen to obtain 50mg of the micron-sized porous silicon particles until no liquid flows; then, 1.6mL of toluene and 0.4mL of octadecylsilane were added, and the mixture was uniformly mixed and heated in a water bath at 80 ℃ for 24 hours. Centrifuging at 1914 Xg for 10min in a centrifuge after finishing modification, discarding modification liquid, washing the obtained porous silicon particles once with toluene and three times with ethanol, and drying the wet porous silicon particles in a tube furnace at 60 ℃ for 2h under vacuum condition to obtain hydrophobic porous silicon;
(5) 10mg of hydrophobic porous silicon was added to 1mL of curcumin mother liquor (1mg/mL) and 1mL of double distilled water, allowed to stand by a water bath, and loaded at 65 ℃ for 24 hours.
The structure of the hydrophobic porous silicon prepared in this example is characterized as shown in fig. 2; and observing the appearance of the prepared and dried porous silicon particles, and placing a small amount of the particles under a high-resolution thermal field emission scanning electron microscope to observe the overall appearance and the pore size of the sample. Wherein A is the cross section electron microscope picture of the porous silicon water, B is the horizontal electron microscope picture of the porous silicon, C is the electron microscope picture of the porous silicon particles, and D is the electron microscope picture of the side surface of the porous silicon. As can be seen from fig. 2, the hydrophobic porous silicon particles have a porous structure, a large specific surface area, a high loading rate, and a mesoporous pore size, so that curcumin loaded into the particles can exist in an amorphous state.
The characterization of the hydrophobic porous silica curcumin microcapsule prepared in the embodiment is shown in fig. 3; a small amount of dried porous silicon carrying curcumin is observed under a high-resolution thermal field emission scanning electron microscope for the surface morphology, the pore size and the overall morphology of the porous silicon particles, and a common camera is used for photographing to observe the appearance morphology color of the porous silicon particles. Wherein A is a front electron microscope picture of the porous silicon-curcumin microcapsule, B is a cross section electron microscope picture of the porous silicon-curcumin microcapsule, C is an electron microscope picture of the porous silicon-curcumin microcapsule particle, and D is a color picture of the porous silicon-curcumin microcapsule. It can be seen from fig. 3 that curcumin is indeed loaded into hydrophobic porous silicon.
Example 2
The etching solution is basically the same as the steps (1) to (5) of the embodiment 1, except that the etching solution in the step (2) is absolute ethyl alcohol containing 48 percent of hydrofluoric acid aqueous solution by volume fraction in a volume ratio of 1: 1.2; step (3) stripping solution (HF: C)2H5OH, 1:28, v/v); step (4) adding 1.5mL of toluene and 0.5mL of octadecylsilane into 50mg of micron-sized porous silicon particles, and step (5) adding 1.5mL of curcumin mother liquor (1.5mg/mL) and 1.5mL of double distilled water into 10mg of hydrophobic porous silicon, and loading for 2h at the temperature of 45 ℃ by magnetic stirring.
Example 3
Substantially the same as in steps (1) to (5) of example 1 except that the stripping solution (HF: C) in step (3)2H5OH, 1:30, v/v); step (5), 1.2mL of curcumin mother liquor (1.2mg/mL) and 1.2mL of double distilled water are added into 10mg of hydrophobic porous silicon, and the mixture is shaken by a shaking table and loaded for 12 hours at the temperature of 25 ℃.
Example 4
The release of curcumin on the surface of the porous silicon is tested by adopting a direct drug release method, and an in-vitro release experiment is carried out.
10mg of the porous silica curcumin microcapsules prepared in example 1 were put into 10mL centrifuge tubes containing 3mL of 40% ethanol-physiological saline release media with different pH values (5, 7.4, 8.5), shaken in a constant temperature shaker (180r/min) at 37 ℃ in the dark, centrifuged for 5min at 1914 Xg for 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10h, and 0.5mL of the supernatant was taken out into 2mL centrifuge tubes, and 0.5mL of the release media was replenished. The supernatant was centrifuged at high speed (17226 Xg) for 10min, and 200. mu.L of the supernatant was applied to a 96-well plate and measured for absorbance at 405nm using a microplate reader. And (4) calculating the cumulative release amount of the curcumin.
As shown in fig. 4, the hydrophobic porous silica curcumin microcapsules prepared in example 1 release well in 40% ethanol-physiological saline at different pH (5, 7.4, 8.5), and the release rates of curcumin in the media of pH7.4 and 5 are 85.29% and 81.61% respectively at 10h release, and both of them have a tendency to continuously increase. In the medium at pH 8.5, the curcumin release rate had reached a maximum of 94.54% when released for 8 h. The release amount results of the hydrophobic porous silicocurcumin microcapsules prepared in examples 2 and 3 are similar to those of example 1.
Example 5
And (3) calculating the loading rate:
the curcumin loading rate was calculated using a difference method, i.e. the amount of curcumin loaded onto the porous silicon was equal to the amount of original curcumin minus the amount of free curcumin after loading. The method for calculating the amount of free curcumin is as follows: the loaded porous silicon suspension is placed in a centrifuge 1914 Xg for centrifugation for 10min, the supernatant is sucked out and transferred into a 10mL brown volumetric flask, the precipitated porous silicon is washed once by 40% ethanol, and is washed twice by double distilled water, the washing liquid is transferred into the 10mL brown volumetric flask, and finally the volume is determined by ethanol. Filtering curcumin solution in volumetric flask with 0.45 μm organic filter membrane, diluting filtrate with ethanol 5 times, measuring ultraviolet absorbance at 426nm, and calculating the concentration of free curcumin after loading.
Example 1 a hydrophobic porous silicon-curcumin microcapsule was prepared, the loading rate of curcumin reached 22.3%, and the loading of curcumin per mg of porous silicon was 22.3 μ g. The loading rate results for the hydrophobic porous silica curcumin microcapsules prepared in examples 2 and 3 were similar to example 1.
Example 6
In-vitro DPPH free radical scavenging test of porous silicon-curcumin microcapsule release liquid:
10mg of the dried porous silica curcumin (PSi-Cur) microcapsule prepared in example 1 is accurately weighed into a 10mL centrifuge tube, 2mL of absolute ethyl alcohol is added, the mixture is shaken for 10min under an oscillator, after the porous silica curcumin and the ethyl alcohol are fully mixed, the mixture is centrifuged for 10min under 1914 Xg, and the supernatant is the released curcumin solution. Adding 20 μ L curcumin release solution into 200 μ L reaction system in 96-well plate, adding 180 μ L60 μ M DPPH working solution, shaking, mixing, detecting at 530nm with microplate reader, detecting once every 5min, and continuously detecting for 40 min.
Curcumin in the blank control group was replaced with 20 μ L of absolute ethanol, and the rest was identical to the experimental group. All the above operations were carried out at room temperature in the absence of light. The absorbance value of the mixed solution at 530nm in the reaction system represents the content of DPPH free radicals. Taking the light absorption value of curcumin per se into consideration, adding 20 mu L of curcumin release solution and 180 mu L of absolute ethyl alcohol to be the background absorption value of curcumin. The clearance rate (%) [ a0- (Ax-Ax0) ]/a0 × 100%. Wherein A0 is the light absorption value of the blank control group, Ax is the light absorption value after adding the curcumin solution to be detected, and Ax0 is the background absorption value of the curcumin solution to be detected.
As shown in figure 5, the hydrophobic porous silicon curcumin microcapsule release solution prepared in the embodiment 1 of the invention has time dependence on the action of DPPH free radicals, and the clearance reaches 47.54 percent after 40min of action. The hydrophobic porous silica curcumin microcapsule clearance rate results prepared in examples 2 and 3 were similar to example 1.
Example 7
Porous silicon-curcumin microcapsule release liquid for superoxide anion O2In vitro clearance assay:
a10 mL centrifuge tube was charged with 0.1mL of 130mmol/L methionine solution, 0.1mL of 20. mu. mol/L riboflavin solution, 0.2mL of 750. mu. mol/L NBT solution, 3.2mL of phosphate buffer (pH7.8, 50mM), and 0.4mL of curcumin release solution obtained in example 6. The curcumin solution in the blank control group was changed to 0.4mL of absolute ethanol. Placing the reaction solution under an ultraviolet lamp at equal intervals for 2min, irradiating O2-generated by riboflavin, reducing NBT into blue products, measuring the light absorption value at the wavelength of 590nm under an ultraviolet spectrophotometer, and calculating the clearance rate of the porous silicon curcumin microcapsule on superoxide anion O2-. The clearance was calculated as (%) ═ clearance (a blank-a sample)/a blank × 100%. Meanwhile, the same conditions are adopted, and the same volume of vitamin (Vc) with different concentrations of 20mg/mL, 40mg/mL, 60mg/mL, 80mg/mL and 100mg/mL is used as a comparison to compare the scavenging capacity to superoxide anion O2-.
As shown in figure 6, the releasing liquid of the hydrophobic porous silicon curcumin microcapsule prepared in the example 1 has the capacity of eliminating superoxide anion O2- & gt by 60.08 percent, which is equivalent to the capacity of eliminating superoxide anion O2- & gt by 80mg/mL vitamin. The hydrophobic porous silica curcumin microcapsule clearance rate results prepared in examples 2 and 3 were similar to example 1.
Claims (10)
1. A hydrophobic porous silica curcumin particle with antioxidant activity is characterized in that the hydrophobic porous silica, curcumin mother liquor and double distilled water are mixed according to the mass-volume ratio of mg/mL/mL of 10: 1-1.5: 1-1.5;
the preparation method of the hydrophobic porous silicocurcumin particles comprises the following steps:
(1) treating a monocrystalline silicon wafer under ultrasonic waves, and then placing the monocrystalline silicon wafer in NH4OH、H2O2And H2Heating in O mixed solution, soaking in HCl and H2O2And H2Heating in the O mixed solution, and soaking the silicon wafer in ethanol for later use after washing;
(2) etching the spare silicon wafer in the step (1) by using etching liquid in a dark environment to obtain a porous silicon film;
(3) stripping the etched porous silicon film by using stripping liquid, and performing ultrasonic treatment in an ethanol solution to prepare micron-sized porous silicon particles;
(4) centrifuging the micron-sized porous silicon particles, removing a clear solution, drying the residual ethanol solution on the surfaces of the micron-sized porous silicon particles, adding toluene and octadecylsilane, uniformly mixing, heating and modifying; centrifuging after modification, removing modification liquid, respectively washing the porous silicon particles with toluene and ethanol, and drying under a vacuum condition to obtain hydrophobic porous silicon;
(5) adding curcumin mother liquor and double distilled water into the hydrophobic porous silicon obtained in the step (4) to carry out curcumin loading; obtaining the hydrophobic porous silica curcumin particles.
2. The hydrophobic porous silicon curcumin particles as claimed in claim 1, wherein the hydrophobic porous silicon is prepared by forming a porous silicon film from a monocrystalline silicon wafer through electrochemical etching, preparing the porous silicon film into micron-sized porous silicon particles, and finally adding octadecylsilane to modify the micron-sized porous silicon particles.
3. The hydrophobic porous silica curcumin particulate of claim 1, the concentration of the curcumin mother liquor being 1-1.5 mg/ml.
4. A method for preparing hydrophobic porous silica curcumin particles as claimed in claim 1, comprising the steps of:
(1) treating a monocrystalline silicon wafer under ultrasonic waves, and then placing the monocrystalline silicon wafer in NH4OH、H2O2And H2Heating in O mixed solution, soaking in HCl and H2O2And H2Heating in the O mixed solution, and soaking the silicon wafer in ethanol for later use after washing;
(2) etching the spare silicon wafer in the step (1) by using etching liquid in a dark environment to obtain a porous silicon film;
(3) stripping the etched porous silicon film by using stripping liquid, and performing ultrasonic treatment in an ethanol solution to prepare micron-sized porous silicon particles;
(4) centrifuging the micron-sized porous silicon particles, removing a clear solution, drying the residual ethanol solution on the surfaces of the micron-sized porous silicon particles, adding toluene and octadecylsilane, uniformly mixing, heating and modifying; centrifuging after modification, removing modification liquid, respectively washing the porous silicon particles with toluene and ethanol, and drying under a vacuum condition to obtain hydrophobic porous silicon;
(5) adding curcumin mother liquor and double distilled water into the hydrophobic porous silicon obtained in the step (4) to carry out curcumin loading; obtaining the hydrophobic porous silica curcumin particles.
5. The method according to claim 4, wherein the single crystal silicon wafer of step (1) is doped with P-type boron and has a resistance of 0.0008-0.0012 Ω.
6. The preparation method according to claim 4, wherein the etching solution in the step (2) is a hydrofluoric acid aqueous solution containing 48% of volume fraction and absolute ethyl alcohol in a volume ratio of 1: 1-1.2.
7. The method according to claim 4, wherein the etching current of the etching in the step (2) is 30-60mA/cm2Etching time 600- & gt 650 seconds.
8. The preparation method according to claim 4, characterized in that the stripping solution in step (3) is hydrofluoric acid aqueous solution containing 3.3% volume fraction and absolute ethyl alcohol in a volume ratio of 1: 28-30.
9. The preparation method according to claim 4, wherein the volume-to-mass ratio mL/mL/mg of the toluene, the octadecylsilane and the blow-dried micron-sized porous silicon particles in the step (4) is 1.5-1.6: 0.4-0.5: 50.
10. the preparation method according to claim 4, wherein the curcumin is loaded in the step (5) for 2 to 24 hours at a temperature of 25 to 65 ℃ by water bath standing, magnetic stirring or shaking table shaking.
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