CN106578835A - Alpha-cyclodextrin-benzoic acid inclusion compound and preparation method thereof - Google Patents

Alpha-cyclodextrin-benzoic acid inclusion compound and preparation method thereof Download PDF

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Publication number
CN106578835A
CN106578835A CN201710021939.XA CN201710021939A CN106578835A CN 106578835 A CN106578835 A CN 106578835A CN 201710021939 A CN201710021939 A CN 201710021939A CN 106578835 A CN106578835 A CN 106578835A
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cyclodextrin
benzoic acid
alpha
preparation
inclusion compound
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王建辉
宁静恒
黄寿恩
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Changsha University of Science and Technology
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Changsha University of Science and Technology
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Priority to CN201710021939.XA priority Critical patent/CN106578835A/en
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    • 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
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154—Organic compounds; Microorganisms; Enzymes
    • 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
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/42—Preservation of non-alcoholic beverages
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/12—Carboxylic acids; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/40—Cyclodextrins; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/738—Cyclodextrins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Birds (AREA)
  • Microbiology (AREA)
  • Nutrition Science (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dermatology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses an alpha-cyclodextrin-benzoic acid inclusion compound and a preparation method thereof. The alpha-cyclodextrin-benzoic acid inclusion compound comprises alpha-cyclodextrin and benzoic acid in a proportion of 1: 1. The preparation method comprises (1) feeding alpha-cyclodextrin and benzoic acid according to a mole ratio of alpha-cyclodextrin to benzoic acid of 1: 2.2 and respectively dissolving the materials through deionized water and anhydrous ethanol, (2) mixing and heating the two solutions and carrying out ultrasonic treatment so that the reaction is complete, and (3) placing the reaction solution in a cool place, and volatilizing the solvent in a natural state to obtain alpha-cyclodextrin-benzoic acid inclusion compound crystals. Benzoic acid is a water insoluble weak acidic bacteriostatic agent and is easy to lose antibacterial activity in an alkaline environment. Alpha-cyclodextrin is easy to form an inclusion, is often used to improve the physical and chemical properties of the inclusion molecules and is stable in an alkaline environment. The benzoic acid is encapsulated in the cyclodextrin cavity so that the stable alpha-cyclodextrin-benzoic acid inclusion compound is formed. The alpha-cyclodextrin-benzoic acid inclusion compound improves the chemical stability of the benzoic acid and water solubility and has a wide application prospect as a bacteriostatic agent.

Description

A kind of alpha-cyclodextrin-benzoic acid clathrate and preparation method thereof
Technical field
The invention belongs to food additive synthesis technical field, and in particular to a kind of new alpha-cyclodextrin-benzoic acid bag Compound, the invention also discloses the preparation method of this clathrate.
Background technology
Benzoic acid（Benzoic acid）, be one of earliest chemical antibacterial for occurring, be widely used in preserving peracidity fruit, Beverage, brined vegetable and other acid foods, while also serving as the preservative of medicine, cosmetics.Benzoic acid is active because containing in molecule Carboxyl and hydrophobicity phenyl, chemical property is more active, causes it to occur poor, poorly water-soluble of stability etc. in application process and lacks Fall into, these drawbacks limit its further applications.
Alpha-cyclodextrin molecule is slightly tapered columnar stereochemical structure, and inner chamber is in hydrophobicity, and outer wall is in hydrophobicity, is had Nontoxic, tasteless and chemical property is more stable, storage will not go bad for many years, but mineral acid hydrolyzable alpha-cyclodextrin generates Portugal The sugared and a series of non-annularity maltose of grape.Meanwhile, alpha-cyclodextrin is a kind of good dietary fiber, and water solublity is higher and energy is obvious Promote big enteral lactic acid bacteria and bifidobacterium growth.Above characteristic allows alpha-cyclodextrin fully to ensure its edible safety, It is able to be widely used as additive, function additive etc. in food industry.
In view of alpha-cyclodextrin is nontoxic, tasteless, and the special molecular structure and property with " inner chamber is hydrophobic, outer wall is hydrophilic ", Its cavity can include numerous guest molecules and form clathrate, and then cause the properties such as guest molecule physics, chemistry, biology Change.The present invention modifies benzoic acid using alpha-cyclodextrin inclusion technique, forms stable alpha-cyclodextrin-benzoic acid clathrate, Some outstanding problems that benzoic acid exists as food antibacterial can be solved.Gained clathrate is prepared by with good dissolving Degree, and can steadily in the long term store and use.Therefore, new alpha-cyclodextrin-benzoic acid clathrate that prepared by the present invention, gives it more Excellent water solublity and stability, remain the good bacteriostasis of benzoic acid, it is also possible to which playing improves abnormal smells from the patient, reduces it to people The stimulation of the organs such as body the intestines and stomach, preferably plays the performance such as benzoic antiseptic and inhibiting bacteria function, fresh-keeping, has expanded such antibacterial Range of application.
The content of the invention
The technical problem to be solved is, for benzoic acid chemical property is active, the low characteristic of dissolubility, there is provided A kind of new alpha-cyclodextrin-benzoic acid clathrate so that benzoic stability, water solublity are improved.
The present invention provides a kind of alpha-cyclodextrin-benzoic acid clathrate, includes alpha-cyclodextrin and benzoic acid, wherein Inclusion ratio For 1:1.
The present invention provides a kind of preparation method of above-mentioned alpha-cyclodextrin-benzoic acid clathrate, comprises the following steps.
（1）According to mol ratio nAlpha-cyclodextrin: nBenzoic acid=1:2.2 feed intake, and it is dissolved in respectively in deionized water and ethanol.
（2） 60oThis alcohol benzoate solution is slowly dropped in alpha-cyclodextrin aqueous solution under C ultrasound conditions, ultrasound 70 min, after the completion of question response, by reaction solution shady place are moved to, and after 72 h that volatilize naturally, separate out crystal.Sucking filtration, with a small quantity Deionized water and washes of absolute alcohol for several times, 60o3 h are vacuum dried under C, white powder clathrate is obtained.
（3）It is of the invention to be to the determination methods that Inclusion ratio is adopted, a kind of alpha-cyclodextrin-benzene based on ultraviolet visible spectrometry The Inclusion ratio criterion of formic acid clathrate.Benzoic standard concentration curve is drawn initially with ultraviolet visible spectrometry, is accurately claimed The clathrate of certain mass is taken, in certain wave strong point absorbance is measured, standard concentration curve equation is substituted into, in obtaining clathrate Benzoic content（nBenzoic acid）, while calculating the content of alpha-cyclodextrin（nAlpha-cyclodextrin）, Inclusion ratio is calculated for 1:1（Inclusion ratio= nBenzoic acid/nAlpha-cyclodextrin）.
（4）The present invention is to the determination methods that solubilizing effect is adopted, a kind of alpha-cyclodextrin based on ultraviolet visible spectrometry- The solubilizing effect criterion of benzoic acid clathrate.Benzoic standard concentration curve is drawn initially with ultraviolet visible spectrometry, will After the alpha-cyclodextrin solution of variable concentrations is sufficiently mixed with benzoic acid, obtain contained in solution according to the absorbance for measuring Benzoic acid（S）, contrast intrinsic solubility of the benzoic acid in aqueous solution under similarity condition（S0=0.028×10-5 mol/L）, so as to Calculate solubilization factor（S/S0）.
Present method invention prepares alpha-cyclodextrin-benzoic acid clathrate, and the clathrate has good dissolubility and stability, So that benzoic acid biocompatibility has certain enhancing, and improve benzoic bioavailability.
Description of the drawings
The description of the drawings of the present invention is as follows.
Fig. 1 is alpha-cyclodextrin infrared spectrogram.
Fig. 2 is benzoic acid infrared spectrogram.
Fig. 3 is alpha-cyclodextrin and benzoic acid physical mixture and alpha-cyclodextrin-benzoic acid clathrate infared spectrum.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
The preparation of 1 alpha-cyclodextrin of embodiment-benzoic acid clathrate
0.9728 g is dissolved in 40 mL deionized waters（0.001 mol）Alpha-cyclodextrin, separately dissolves in 2.0 mL dehydrated alcohol 0.2687 g（0.0022 mol）Benzoic acid, 60oThis alcohol benzoate solution is slowly dropped to into α-ring paste under C ultrasound conditions In smart aqueous solution, reaction solution after the completion of question response, is moved to shady place by ultrasonic 70 min, after 72 h that volatilize naturally, is separated out brilliant Body.Sucking filtration, 60 with a small amount of deionized water and washes of absolute alcohol for several timeso3 h are vacuum dried under C, white powder bag is obtained Compound.
The Inclusion ratio of 2 alpha-cyclodextrins of embodiment-benzoic acid clathrate is calculated
Alpha-cyclodextrin-benzoic acid clathrate that certain mass is implemented to be prepared in 1 is weighed, using ultraviolet visible spectrometry as inclusion Than the criterion for calculating.Concrete operations are as follows, and in certain wave strong point absorbance is measured, and calculated according to standard concentration curve, obtain Benzoic acid content in clathrate, and then the content of alpha-cyclodextrin in clathrate is obtained, so as to calculate alpha-cyclodextrin-benzoic acid bag The Host-guest ratio of compound is 1:1.
The solubilized effect of the alpha-cyclodextrin para Toluic Acid of embodiment 3
Precise alpha-cyclodextrin, is configured to concentration and is respectively 0,5,10,15,20 and 25 mmol/L alpha-cyclodextrin solution, takes Each 10 mL of above-mentioned solution, plus the benzoic acid of certain mass, ultrasonic 30 min dissolvings are complete, after solid-liquid reaches balance, place one In week, filter, in maximum absorption wave strong point mensuration absorbance.The results are shown in Table 1, using ultraviolet visible spectrometry determine benzoic acid α- Solubilized effect in cyclodextrin solution, with the increase of alpha-cyclodextrin concentration, the dissolubility of benzoic acid molecule increases, and illustrates α-ring Dextrin para Toluic Acid has good solubilization.
The solubilized effect of the alpha-cyclodextrin of table 1
α-CD（10-3mol/L） 0 5 10 15 20 25
S（10-5mol/L） 0.028 0.053 0.093 0.155 0.187 0.231
S/So - 1.89 3.32 5.54 6.68 8.25
S：Content of the benzoic acid in α-CD- benzoic acid clathrates；So：Saturation solubility of the benzoic acid in water, herein= 0.028×10-5 mol/L；S/So：Solubilization factor.
Knowable to infrared spectrum, alpha-cyclodextrin-benzoic acid clathrate first（Fig. 3 b）With alpha-cyclodextrin spectrogram（Fig. 1）Or Benzoic collection of illustrative plates（Fig. 2）Compare, while absworption peak increased, position also there occurs movement；Secondly its clathrate and α- Cyclodextrin and benzoic physical mixture（Fig. 3 a）Also have significantly different, illustrate method of the present invention, using not being Generation alpha-cyclodextrin and benzoic physical mixed, but benzoic acid inclusion forms stable clathrate in alpha-cyclodextrin inner chamber.

Claims (5)

1. a kind of alpha-cyclodextrin-benzoic acid clathrate, it is characterised in that containing alpha-cyclodextrin and benzoic acid, alpha-cyclodextrin and benzene The Inclusion ratio of formic acid is 1:1.
2. the preparation method of alpha-cyclodextrin as claimed in claim 1-benzoic acid clathrate, it is characterised in that including following step Suddenly：
According to mol ratio nAlpha-cyclodextrin:nBenzoic acid=1:2.2 feed intake, and it is dissolved in respectively in dehydrated alcohol and deionized water；
Blend step（1）The two kinds of solution for obtaining, carry out inclusion experiment, and inclusion process is using heating ultrasonic method；
By step（2）Mixed solution, clathrate crystal is obtained using solvent evaporation method.
3. preparation method according to claim 2, it is characterised in that step（1）Employed in organic solvent for anhydrous Ethanol.
4. preparation method according to claim 2, is characterised by, step（2）In ultrasonic method, the inclusion reaction time be 70 Min, reaction temperature is 60oC。
5. preparation method according to claim 2, it is characterised in that step（3）In solvent evaporation method refer to solvent from So volatilization, clathrate crystal is separated out.
CN201710021939.XA 2017-01-12 2017-01-12 Alpha-cyclodextrin-benzoic acid inclusion compound and preparation method thereof Pending CN106578835A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105394352A (en) * 2015-12-09 2016-03-16 广州英赛特生物技术有限公司 Application of 2-hydroxybenzoic acid-beta-cyclodextrin inclusion compound in preparation of animal feed additive

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105394352A (en) * 2015-12-09 2016-03-16 广州英赛特生物技术有限公司 Application of 2-hydroxybenzoic acid-beta-cyclodextrin inclusion compound in preparation of animal feed additive

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
方亮: "《药剂学（第3版）》", 31 March 2016 *
李学红: "环糊精在抗菌食品包装中的基础应用研究", 《中国博士学位论文全文数据库 工程科技I辑》 *

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