CN116284506B - Gamma-cyclodextrin-geraniol derivative and preparation method and application thereof - Google Patents
Gamma-cyclodextrin-geraniol derivative and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 48
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 37
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-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)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 GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000005792 Geraniol Substances 0.000 claims description 30
- 229940113087 geraniol Drugs 0.000 claims description 30
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 29
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- JSCUZAYKVZXKQE-JXMROGBWSA-N (2e)-1-bromo-3,7-dimethylocta-2,6-diene Chemical compound CC(C)=CCC\C(C)=C\CBr JSCUZAYKVZXKQE-JXMROGBWSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 abstract description 21
- 235000013305 food Nutrition 0.000 abstract description 10
- 238000007385 chemical modification Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000341 volatile oil Substances 0.000 abstract description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- 230000001404 mediated effect Effects 0.000 abstract description 3
- 239000012264 purified product Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000003385 bacteriostatic effect Effects 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- 241000191967 Staphylococcus aureus Species 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- -1 acyclic monoterpene compound Chemical class 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 3
- 230000003113 alkalizing effect Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000012880 LB liquid culture medium Substances 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 241000234280 Liliaceae Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930003651 acyclic monoterpene Natural products 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 208000010643 digestive system disease Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The application discloses a gamma-cyclodextrin-geraniol derivative and a preparation method and application thereof, wherein grafting of alcohol essential oil molecules on cyclodextrin molecules is realized for the first time through a bromide-mediated mode, so that the water-soluble gamma-cyclodextrin-geraniol derivative is obtained, functionalization of cyclodextrin is successfully realized through chemical modification, compared with unmodified cyclodextrin molecules, the gamma-cyclodextrin-geraniol derivative can realize antibacterial application without forming inclusion compound with guest molecules, has higher stability compared with inclusion compound, has the advantages of simple preparation method, low-cost and easily obtained raw materials, easily purified products, and expands the application range of cyclodextrin, so that the gamma-cyclodextrin-geraniol derivative has better application prospect in multiple fields such as foods, biological medicines and the like.
Description
Technical Field
The application belongs to the technical field of modification of bioactive substances, and particularly relates to a gamma-cyclodextrin-geraniol derivative, and a preparation method and application thereof.
Background
With the rapid development of the food industry, the preservation and fresh-keeping of foods has become one of the major problems in the food safety field. According to statistics, 20% -30% of food resources are lost due to spoilage every year in China on average. Microbial growth and reproduction are one of the main causes of food spoilage, and food-borne pathogenic bacteria are important sources for causing a plurality of food safety problems, and food-borne diseases have become the most prominent health problems in the world today. Most of the traditional chemical preservatives are synthesized artificially, and long-term intake of part of the chemical preservatives can increase the risks of cancers and digestive diseases, so that natural and green food additives are gradually favored by people.
Geraniol is an acyclic monoterpene compound that can be extracted from the stems or leaves of many types of plants, such as cruciferous, liliaceae, and camphoraceae. Due to their unique fragrance and high safety, geraniol and its ester derivatives are often used as fragrances, perfumes and flavors, which make it widely used in the fields of foods and cosmetics. In addition, geraniol has good pharmacological actions such as antibacterial, anticancer and anti-inflammatory. Thus, geraniol is also widely used in pharmaceutical, medical and other fields. However, geraniol is insoluble in water, volatile and easily oxidized in air, which severely limits its use in these fields.
Cyclodextrins are a generic term for a series of cyclic oligosaccharides produced by enzymatic hydrolysis of starch, the cyclic structure of which consists of a hydrophobic cavity and a hydrophilic periphery. Due to its unique molecular composition, cyclodextrin can increase the solubility and stability of hydrophobic molecules by forming inclusion complexes with hydrophobic molecules, and the effect of the entrapped molecules can be exerted by slow release. However, cyclodextrin inclusion compounds are unstable to light and heat and often introduce unnecessary odors, which severely limit their use. Thus, new functional groups can be bonded to the hydroxyl groups of the cyclodextrin by chemical modification, thereby imparting new properties thereto.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
It is therefore an object of the present application to overcome the deficiencies of the prior art and to provide a gamma-cyclodextrin-geraniol derivative.
In order to solve the technical problems, the application provides the following technical scheme:
the chemical structural formula of the gamma-cyclodextrin-geraniol derivative is shown as a formula A;
wherein R is H or geranyl, and the structural formula of the geranyl is shown as formula B:
wherein, when R is geranyl, the R is connected with the formula A through an oxygen atom at the X of the formula B.
Another object of the present application is to overcome the deficiencies of the prior art and to provide a process for the preparation of gamma-cyclodextrin-geraniol derivatives.
In order to solve the technical problems, the application provides the following technical scheme:
comprises the steps of dissolving geranyl bromide in an organic solvent to obtain a first solution;
dissolving gamma-cyclodextrin in a water-organic solvent mixed system, adding alkaline water and stirring to obtain a second solution;
the first solution is dripped into the second solution, stirred at room temperature for reaction, the pH value of the system is regulated to be neutral after the reaction, and the gamma-cyclodextrin-geraniol derivative is obtained through dialysis, filtration, freezing and drying.
As a preferred embodiment of the method for producing a gamma-cyclodextrin-geraniol derivative of the present application, wherein: the molar ratio of the gamma-cyclodextrin to the geranyl bromide is 2:1 to 1:2.
as a preferred embodiment of the method for producing a gamma-cyclodextrin-geraniol derivative of the present application, wherein: the organic solvent is acetonitrile.
As a preferred embodiment of the method for producing a gamma-cyclodextrin-geraniol derivative of the present application, wherein: and adding alkaline water and stirring, wherein the alkaline water is sodium hydroxide solution, and the stirring time is 30min.
As a preferred embodiment of the method for producing a gamma-cyclodextrin-geraniol derivative of the present application, wherein: the preparation method of the geranyl bromide comprises the steps of,
dissolving geraniol and pyridine in anhydrous diethyl ether, stirring under ice water bath, and cooling to obtain solution A;
dissolving phosphorus tribromide in anhydrous diethyl ether to obtain a solution B, dripping the solution B into the solution A, and stirring and mixing;
and (3) transferring the mixed solution to a separating funnel, taking the supernatant, washing, removing water, filtering and rotary evaporating to obtain the geranyl bromide.
As a preferred embodiment of the method for producing a gamma-cyclodextrin-geraniol derivative of the present application, wherein: the washing is to wash the supernatant three times with 5% sodium bicarbonate solution, deionized water and saturated sodium chloride solution, respectively.
It is a further object of the present application to overcome the deficiencies of the prior art and to provide the use of a gamma-cyclodextrin-geraniol derivative.
As a preferred embodiment of the use of the gamma-cyclodextrin-geraniol derivative of the present application, wherein: the derivative is a water-soluble material, wherein geraniol essential oil molecules are grafted on cyclodextrin molecules.
As a preferred embodiment of the use of the gamma-cyclodextrin-geraniol derivative of the present application, wherein: the gamma-cyclodextrin-geraniol derivative can realize antibacterial application without forming inclusion compound with a guest molecule.
As a preferred embodiment of the use of the gamma-cyclodextrin-geraniol derivative of the present application, wherein: the gamma-cyclodextrin-geraniol derivatives have higher stability relative to the inclusion compound.
The application has the beneficial effects that:
(1) The application provides a gamma-cyclodextrin-geraniol derivative, which realizes the grafting of alcohol essential oil molecules (geraniol) on cyclodextrin molecules for the first time in a bromide-mediated mode, and obtains a water-soluble material.
(2) The application successfully realizes the functionalization of cyclodextrin by chemical modification, compared with unmodified cyclodextrin molecules, the gamma-cyclodextrin-geraniol derivative can realize antibacterial application without forming inclusion compound with guest molecules, and has higher stability compared with the inclusion compound.
(3) The preparation method is simple, the raw materials are cheap and easy to obtain, and the product is easy to purify, so that the application range of the cyclodextrin is widened, and the cyclodextrin has better application prospects in various fields such as foods, biological medicines and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a synthetic scheme of a gamma-cyclodextrin-geraniol derivative of the present application.
FIG. 2 is an infrared spectrum of a gamma-cyclodextrin prepared in example 1 of the present application and a gamma-cyclodextrin-geraniol derivative prepared in accordance with the present application.
FIG. 3 is a diagram showing nuclear magnetic resonance hydrogen spectra of gamma-cyclodextrin-geraniol derivatives prepared in examples 1 to 3 of the present application.
FIG. 4 is a graph showing the bacteriostatic effect of gamma-cyclodextrin-geraniol derivatives prepared according to the application on E.coli.
Figure 5 is a graph showing the bacteriostatic effect of gamma-cyclodextrin-geraniol derivatives prepared according to the application on staphylococcus aureus.
FIG. 6 is a thermogravimetric curve of gamma-cyclodextrin-geraniol derivatives prepared according to the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials used in the application are all commonly and commercially available without special description.
The chemical formula of the pyridine used in the application is shown as formula C
Example 1:
the embodiment provides a preparation method of a gamma-cyclodextrin-geraniol derivative, which comprises the following steps:
1) Preparation of geranyl bromides
Geraniol (0.05 mol) and pyridine (0.025 mol) are dissolved in 30mL of anhydrous diethyl ether, stirred and cooled in a three-necked flask under the ice water bath condition, and phosphorus tribromide (0.025 mol) dissolved in the anhydrous diethyl ether is dropwise added into the three-necked flask by using a constant pressure dropping funnel after the system is cooled to 0 ℃, and stirring is continued for 30min after the addition;
transferring the reacted liquid into a separating funnel, respectively washing the upper layer liquid three times by using 5% sodium bicarbonate solution, deionized water and saturated sodium chloride solution, adding anhydrous magnesium sulfate for water removal, filtering, and rotary evaporating to obtain geranyl bromide.
2) Preparation of gamma-cyclodextrin-geraniol derivatives
The molar ratio of the geranyl bromide to the gamma-cyclodextrin is 1:2;
dissolving gamma-cyclodextrin (2 mmol) in a water-acetonitrile mixed system, adding sodium hydroxide (10 mmol), stirring and alkalizing for 30min, dripping geranyl bromide (1 mmol) dissolved in acetonitrile into a reaction system, stirring and reacting for 12h at room temperature after dripping, adjusting the pH of the reaction solution to be neutral after the reaction is finished, dialyzing for 72h, filtering, and freeze-drying to obtain the gamma-cyclodextrin-geraniol derivative.
FIG. 2a is an infrared spectrum of gamma-cyclodextrin, 3394 and 2928cm -1 The peak values of (2) correspond to the stretching vibration of O-H of hydroxyl group in gamma-cyclodextrin molecule and the stretching vibration of C-H in glucose skeleton. 1640. 1157 and 1027cm -1 The peaks at the positions correspond to H-O-H bending, C-O stretching vibration and C-O-C stretching vibration respectively.
FIG. 2b is an infrared spectrum of a gamma-cyclodextrin-geraniol derivative of the present example at 2928cm compared to gamma-cyclodextrin -1 The nearby peak broadens and becomes stronger and moves to 2925cm -1 This is-CH in the grafted geraniol 3 and-CH 2 And (3) a result of superposition of the peak of C-H absorption of gamma-CD. Furthermore, the derivative was found to be at 1640cm -1 The peak at this point also became stronger due to the presence of c=c in the geraniol side chain. These results indicate that geraniol was successfully grafted onto gamma-cyclodextrin.
FIG. 3a is a nuclear magnetic resonance hydrogen spectrum of gamma-cyclodextrin, wherein the peaks of the solvent corresponding to heavy water are located at about 4.74ppm,5.03, 3.59, 3.85, 3.50, 3.82 and 3.79ppm, and the peaks respectively correspond to H-1, H-2, H-3, H-4, H-5 and H-6 of gamma-cyclodextrin.
FIG. 3b is a nuclear magnetic resonance hydrogen spectrum of a gamma-cyclodextrin-geraniol derivative showing a distinct new peak between 1 and 2.5ppm in this example. These new peaks appear due to the grafting of geraniol into-CH 2 -and-CH 3 。
Example 2:
the preparation method of the gamma-cyclodextrin-geraniol derivative comprises the following steps:
1) Preparation of geranyl bromides
Geraniol (0.05 mol) and pyridine (0.025 mol) are dissolved in 30mL of anhydrous diethyl ether, stirred and cooled in a three-necked flask under the ice water bath condition, and phosphorus tribromide (0.025 mol) dissolved in the anhydrous diethyl ether is dropwise added into the three-necked flask by using a constant pressure dropping funnel after the system is cooled to 0 ℃, and stirring is continued for 30min after the addition;
transferring the reacted liquid into a separating funnel, respectively washing the upper layer liquid three times by using 5% sodium bicarbonate solution, deionized water and saturated sodium chloride solution, adding anhydrous magnesium sulfate for water removal, filtering, and rotary evaporating to obtain geranyl bromide.
2) Preparation of gamma-cyclodextrin-geraniol derivatives
The molar ratio of the geranyl bromide to the gamma-cyclodextrin is 1:1, a step of;
dissolving gamma-cyclodextrin (2 mmol) in a water-acetonitrile mixed system, adding sodium hydroxide (10 mmol), stirring and alkalizing for 30min, dripping geranyl bromide (2 mmol) dissolved in acetonitrile into a reaction system, stirring and reacting for 12h at room temperature after dripping, adjusting the pH of the reaction solution to be neutral after the reaction is finished, dialyzing for 72h, filtering, and freeze-drying to obtain the gamma-cyclodextrin-geraniol derivative.
FIG. 2c is an infrared spectrum of a gamma-cyclodextrin-geraniol derivative of the present example at 2928cm compared to gamma-cyclodextrin -1 The nearby peak broadens and becomes stronger and moves to 2925cm -1 This is-CH in the grafted geraniol 2 -and-CH 3 And (2) a C-H absorption peak of gamma-cyclodextrin. Furthermore, the derivative was found to be at 1640cm -1 The peak at this point also became stronger due to the presence of c=c in the geraniol side chain. These results indicate that geraniol was successfully grafted onto gamma-cyclodextrin.
FIG. 3c is a nuclear magnetic resonance hydrogen spectrum of a gamma-cyclodextrin-geraniol derivative showing a distinct new peak between 1 and 2.5ppm in this example. These new peaks appear due to the grafting of geraniol into-CH 2 -and-CH 3 。
Example 3:
the preparation method of the gamma-cyclodextrin-geraniol derivative comprises the following steps:
1) Preparation of geranyl bromides
Geraniol (0.05 mol) and pyridine (0.025 mol) are dissolved in 30mL of anhydrous diethyl ether, stirred and cooled in a three-necked flask under the ice water bath condition, and phosphorus tribromide (0.025 mol) dissolved in the anhydrous diethyl ether is dropwise added into the three-necked flask by using a constant pressure dropping funnel after the system is cooled to 0 ℃, and stirring is continued for 30min after the addition;
transferring the reacted liquid into a separating funnel, respectively washing the upper layer liquid three times by using 5% sodium bicarbonate solution, deionized water and saturated sodium chloride solution, adding anhydrous magnesium sulfate for water removal, filtering, and rotary evaporating to obtain geranyl bromide.
2) Preparation of gamma-cyclodextrin-geraniol derivatives
The molar ratio of geranyl bromide to gamma-cyclodextrin is 2:1, a step of;
dissolving gamma-cyclodextrin (2 mmol) in a water-acetonitrile mixed system, adding sodium hydroxide (10 mmol), stirring and alkalizing for 30min, dripping geranyl bromide (4 mmol) dissolved in acetonitrile into a reaction system, stirring and reacting for 12h at room temperature after dripping, adjusting the pH of the reaction solution to be neutral after the reaction is finished, dialyzing for 72h, filtering, and freeze-drying to obtain the gamma-cyclodextrin-geraniol derivative.
FIG. 2d is an infrared spectrum of a gamma-cyclodextrin-geraniol derivative of the present example at 2928cm compared to gamma-cyclodextrin -1 The nearby peak broadens and becomes stronger and moves to 2925cm -1 This is-CH in the grafted geraniol 3 and-CH 2 And (2) a C-H absorption peak of gamma-cyclodextrin. Furthermore, the derivative was found to be at 1640cm -1 The peak at this point also became stronger due to the presence of c=c in the geraniol side chain, which indicates that geraniol was successfully grafted to γ -cyclodextrin.
FIG. 3d is a nuclear magnetic resonance hydrogen spectrum of a gamma-cyclodextrin-geraniol derivative showing a distinct new peak between 1 and 2.5ppm in this example. These new peaks appear due to the grafting of geraniol into-CH 2 -and-CH 3 。
Example 4
This example is used to determine the solubility of the prepared derivatives of the present application, and comprises:
1. solubility test in Water
Dissolving excessive gamma-cyclodextrin and gamma-cyclodextrin-geraniol derivatives in deionized water, stirring at room temperature for 12h, filtering, freeze-drying the filtrate, weighing the mass of the obtained solid, and determining the solubility in water;
mixing geraniol and water according to a volume ratio of 1:3 mixing and observing the layering condition.
The results of the solubility measurements of geraniol, γ -cyclodextrin, and γ -cyclodextrin-geraniol derivatives in examples 1, 2, and 3, respectively, are shown in Table 1 as Ger, γ -CD-Ger1, γ -CD-Ger2, and γ -CD-Ger 3.
Table 1 results of solubility determination of samples in water
2. Organic solvent solubility test
20mg of each sample was dissolved in 4mL of an organic solvent, stirred for 12 hours, and the dissolution state was observed, and the dissolution state was classified into three cases of solubility, slight solubility and insolubility, and the results are shown in Table 2.
Table 2 solubility of samples in organic solvents
Note that: +soluble; slightly dissolving; insoluble.
According to the application, the prepared derivative has solubility in water and organic solvent by grafting geraniol on cyclodextrin molecules, so that the defects that geraniol is insoluble in water and cyclodextrin is indissolvable in organic solvent in the prior art are overcome, and meanwhile, products with different solubilities can be obtained by adjusting the molar ratio of geranyl bromide to gamma-cyclodextrin, so that the application range of the material is widened.
Example 5
The antibacterial effect of the prepared derivative is measured in the embodiment, and the antibacterial effect is specifically as follows:
1. experimental strain
The experimental species selected in this example were the most common gram negative (E.coli) and gram positive (Staphylococcus aureus).
2. Operating procedure
Coli and staphylococcus aureus were streaked onto LB solid medium, respectively, and streaked plates were incubated at 37 ℃ for 24h. Picking single colony in the plate, inoculating into LB liquid culture medium, culturing in shaking table to logarithmic phase, and diluting bacterial liquid concentration to 10 5 CFU/mL was ready for use.
Liquid medium with a sample concentration of 3mg/mL was prepared in a test tube. To the test tube, 5. Mu.L of the above-mentioned bacterial liquid was added, and LB liquid medium without adding a sample was used as a blank. The test tube containing the culture solution was cultured in a shaker for 3 hours, then 100. Mu.L of the culture solution in the test tube was spread on LB solid medium, and cultured in a constant temperature incubator at 37℃for 24 hours, observed and photographed.
Fig. 4 shows the results of the bacteriostasis experiment of escherichia coli, wherein a, b, c, d, e sequentially corresponds to the blank, the gamma-cyclodextrin and the derivatives of example 1, example 2 and example 3. As can be seen from the figure, the unmodified γ -cyclodextrin did not exhibit a significant bacteriostatic effect, and the colony count of the plate corresponding to the γ -cyclodextrin-geraniol derivative was significantly reduced, and the bacteriostatic effect was also significantly improved with increasing geraniol addition ratio, relative to the blank control.
Fig. 5 shows the results of an experiment for inhibiting staphylococcus aureus, wherein a, b, c, d, e corresponds to the results of an experiment for inhibiting bacteria of a blank, gamma-cyclodextrin and the derivatives of example 1, example 2 and example 3 in sequence. It can be seen that the unmodified gamma-cyclodextrin does not exhibit a bacteriostatic effect on staphylococcus aureus, and furthermore, the gamma-cyclodextrin-geraniol derivative exhibits a stronger bacteriostatic effect on staphylococcus aureus than escherichia coli.
Example 6
The embodiment is used for exploring the antibacterial effect of the prepared derivative under different concentrations, and specifically comprises the following steps:
coli and staphylococcus aureus were streaked onto LB solid medium, respectively, and streaked plates were incubated at 37 ℃ for 24h. Picking single colony in the plate, inoculating into LB liquid culture medium, culturing in shaking table to logarithmic phase, and diluting bacterial liquid concentration to 10 5 CFU/mL was ready for use.
A liquid medium having a sample concentration of 1, 2 and 3mg/mL was prepared in a test tube, 5. Mu.L of the above-mentioned bacterial liquid was added to the test tube, LB liquid medium without the addition of sample was used as a blank, the test tube containing the culture liquid was cultured in a shaker for 3 hours, then 100. Mu.L of the culture liquid in the test tube was spread on LB solid medium and cultured in a constant temperature incubator at 37℃for 24 hours, and the results of bacteriostasis experiments at the respective concentrations were shown in tables 3 to 5 below.
TABLE 3 bacteriostatic effect of 1mg/mL sample concentration
TABLE 5 bacteriostatic effect with sample concentration of 3mg/mL
As can be seen from the experimental results, the gamma-cyclodextrin-geraniol derivatives prepared by the application have good antibacterial effect compared with cyclodextrin under different concentrations, and when the concentration of gamma-CD-Ger 3 reaches 3mg/mL, 100% antibacterial effect can be realized, and meanwhile, experiments show that if the concentration of a sample in antibacterial liquid is continuously increased, the sample is separated out due to the fact that the solubility of the derivative is exceeded, and the antibacterial effect cannot be further increased; and when the proportion of geranyl bromide in the gamma-cyclodextrin-geraniol derivative is further increased, the solubility of the derivative is reduced, and the antibacterial rate is not increased and reduced at the same concentration, so that the optimal effect can be realized by selecting 3mg/mL of gamma-CD-Ger 3 antibacterial liquid.
Example 7
This example was used to investigate the thermal stability of the prepared derivatives of the application, in particular:
the thermal stability of the derivative was determined by thermogravimetric analysis, 5-10 mg of the sample was taken and the weight change of the sample was determined in a thermogravimetric analyzer at 25-550 ℃.
The thermogravimetric analysis results are shown in fig. 6, wherein a, b, c, d corresponds to the thermogravimetric curves of γ -cyclodextrin and the derivatives of example 1, example 2, and example 3 in order. The derivatives corresponding to examples 1, 2 and 3 reach the maximum weight loss temperature at 318 ℃, 302 ℃ and 297 ℃ respectively, which shows that the thermal stability of the derivatives prepared by the application is good.
In conclusion, the application realizes the grafting of alcohol essential oil molecules (geraniol) on cyclodextrin molecules for the first time through a bromide-mediated mode, obtains the water-soluble gamma-cyclodextrin-geraniol derivative, successfully realizes the functionalization of cyclodextrin by chemical modification, can realize the antibacterial application without forming inclusion compound with guest molecules relative to unmodified cyclodextrin molecules, and has higher stability relative to the inclusion compound.
The preparation method is simple, the raw materials are cheap and easy to obtain, and the product is easy to purify, so that the application range of the cyclodextrin is widened, and the cyclodextrin has better application prospects in various fields such as foods, biological medicines and the like.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (6)
1. A method for preparing a gamma-cyclodextrin-geraniol derivative, which is characterized by comprising the following steps: comprising the steps of (a) a step of,
dissolving geranyl bromide in an organic solvent to obtain a first solution;
dissolving gamma-cyclodextrin in a water-organic solvent mixed system, adding alkaline water and stirring to obtain a second solution;
dripping the first solution into the second solution, stirring at room temperature for reaction, regulating the pH value of the system to be neutral after the reaction, dialyzing, filtering, and freeze-drying to obtain the gamma-cyclodextrin-geraniol derivative;
wherein, the mol ratio of the gamma-cyclodextrin to the geranyl bromide is 2: 1-1: 2;
the chemical structural formula of the gamma-cyclodextrin-geraniol derivative is shown as a formula A;
(A)
Wherein R is H or geranyl, and the structural formula of the geranyl is shown as formula B:
(B)
Wherein, when R is geranyl, the R is connected with the formula A through an oxygen atom at the X of the formula B.
2. A process for the preparation of a gamma-cyclodextrin-geraniol derivative according to claim 1, wherein: the organic solvent is acetonitrile.
3. A process for the preparation of a gamma-cyclodextrin-geraniol derivative according to claim 1, wherein: and adding alkaline water and stirring, wherein the alkaline water is sodium hydroxide solution, and the stirring time is 30min.
4. A process for the preparation of a gamma-cyclodextrin-geraniol derivative according to claim 1, wherein: the preparation method of the geranyl bromide comprises the steps of,
dissolving geraniol and pyridine in anhydrous diethyl ether, stirring under ice water bath, and cooling to obtain solution A;
dissolving phosphorus tribromide in anhydrous diethyl ether to obtain a solution B, dripping the solution B into the solution A, and stirring and mixing;
and (3) transferring the mixed solution to a separating funnel, taking the supernatant, washing, removing water, filtering and rotary evaporating to obtain the geranyl bromide.
5. A process for the preparation of a gamma-cyclodextrin-geraniol derivative according to claim 1, wherein: the washing is to wash the supernatant three times with 5% sodium bicarbonate solution, deionized water and saturated sodium chloride solution, respectively.
6. Use of a gamma-cyclodextrin-geraniol derivative according to claim 1, wherein: the gamma-cyclodextrin-geraniol derivative can realize antibacterial application without forming inclusion compound with a guest molecule.
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