CN105901476B - The method for releasing gingko toxicity based on physics and enzymatic integrated processes - Google Patents

The method for releasing gingko toxicity based on physics and enzymatic integrated processes Download PDF

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CN105901476B
CN105901476B CN201610272890.0A CN201610272890A CN105901476B CN 105901476 B CN105901476 B CN 105901476B CN 201610272890 A CN201610272890 A CN 201610272890A CN 105901476 B CN105901476 B CN 105901476B
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gingko
enzymatic
physics
releasing
water content
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CN105901476A (en
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段金廒
钱大玮
郭盛
鲁学军
宿树兰
钱怡云
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Nanjing University of Chinese Medicine
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/16Ginkgophyta, e.g. Ginkgoaceae (Ginkgo family)

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Abstract

The invention discloses the methods for releasing gingko toxicity based on physics and enzymatic integrated processes, the present invention is screened by many experiments, bioconversion is realized using the toxic component degrading enzyme that gingko itself contains under the conditions of optimal temperature and moisturizing, efficiently 4~O of toxic component~methyl pyridoxine and cyanogen methods of glycosides that removal gingko contains, the high-temperature process then carried out makes allergic protein deactivation in gingko, and remove the volatilization of cyanogen glycosides ingredient degradation product, and remove toxic component ginkgoic acid, then the distribution according to ginkgoic acid in gingko, the moisture of gingko is reduced to a certain degree, then the highest plumule position of composition containing ginkgo acid is removed by either manually or mechanically method.The entire technological design of the present invention is reasonable, and detoxification is high-efficient, Environmental Safety, and no solvent residue is easy to operate, low in cost, and many deficiencies of the prior art can be overcome, it can be achieved that industrialized production.

Description

The method for releasing gingko toxicity based on physics and enzymatic integrated processes
Technical field
The invention belongs to agriculture and forestry product and drug processing technique fields, are combined based on physics with enzymatic more particularly to one kind The processing method of method releasing gingko toxicity.
Background technique
Gingko is the mature seed of Ginkgoaceae plant Ginkgo biloba (Ginkgo bilobaL.).As medicinal first recorded in " Shaoxing wood Grass ", it is sweet in flavor, bitter, puckery, it is mild-natured;Return lung, kidney channel have the effect of astringing lung for relieving asthma, stop-band reducing urination, are mainly used for abundant expectoration and breath with cough, Leukorrhagia gonorrhoea, the diseases such as enuresis frequent micturition, and have the function of certain resolving sputum concurrently, the key medicine of cough and phlegm is treated for tcm clinical practice.Gingko Starch, protein, fat, vitamin and calcium rich in, phosphorus, potassium, selenium and other trace elements.Therefore be also the product of integration of drinking and medicinal herbs, Book on Chinese herbal medicine, which records it, has " tonifying Qi nourishing heart, the function of kidney-nourishing enriching yin " (" book on Chinese herbal medicine is new again "), and edible health effect is definite.
Book on Chinese herbal medicine records " gingko is toxic ", and in long-term practice, has proven to it with certain toxicity, safe handling It is restricted, constrains value dimension and the industrialized development of this valuable food and medicament dual-purpose resource of China.To prevent adverse events Generation, can only passively select limitation edible in daily use gingko.It is this passively edible with " estimator ", not only not It is able to satisfy the consumption and eating requirements of people, also brings great security risk to gingko product, causes a large amount of gingkoes unsalable, no Great economic loss only is brought to orchard worker, also seriously hinders the sustainable health development of ginkgo industry.
In recent years, domestic and foreign scholars study the material base of gingko toxicity.Traditionally the master in gingko Toxicant basis is wanted to be broadly divided into two classes: 1. using amarogentin and its homologue as the cyanogen glycoside substance of representative, in vivo Hydrolyzable generates the extremely toxic substances such as hydrogen cyanide, to generate toxic reaction;2. with ginkgoic acid, bilobol, bilobol etc. for generation Separating Ginkgo phenolic acids (induced by alkyl hydroxybenzene) substance of table can inhibit related enzyme systems activity in body and show that certain toxicity is anti- It answers.
In addition, another two substance that some scholars propose that gingko toxicity may also contain with it in recent years is closely related.One Class contains relatively high with content of glutamic acid for it, and molecular weight is in the sensitization glycoprotein substance of 20~50kDa, such Substance can lead to animal subject and allergic reaction occur, to show certain toxic effect;It is another kind of for its contain with 4~ O~methyl pyridoxine (4~O~methylpyridoxine, MPN) is the pyridoxol class compound of representative.
The poison-removing method research report of gingko is numerous, current main poison-removing method: first is that the cyanogen glycoside contained for it Substance such as impregnates fresh gingko seed with certain density sodium carbonate liquor is repeated multiple times using chemical agent.Second is that being directed to it The ginkgolic acid constituents contained, using the methods of organic solvent extraction, physical removal.The above two classes poison-removing method, although energy The toxic component in gingko is enough removed, but is primarily present environmental pollution, activity and nutrient component damages, the problems such as process is cumbersome. Activity and nutrient component damages due to solvent extraction and caused by impregnating, by decline the effect of causing gingko.
Summary of the invention
Goal of the invention: it is an object of the invention to overcome shortcoming and deficiency existing in the prior art, provides based on physics The method for releasing gingko toxicity with enzymatic integrated processes, this method can give full play to nutrition and the healthcare function of gingko, into one Step development and utilization gingko product.
Technical solution: in order to achieve the goal above, the technical scheme adopted by the invention is as follows:
A kind of gingko after detoxification, it is prepared by the following method to obtain:
(1) gingko is taken, is heated to 45 DEG C~80 DEG C, in the case where its water content is not less than 50%, continues isothermal holding 2 Hour or more;
(2) gingko after taking step (1) isothermal holding, is heated to 90 DEG C~105 DEG C, in its water content not less than 50% In the case of, heat treatment 1 hour or more;
(3) gingko after taking step (2) to heat, is dried at a temperature of being heated to 60 DEG C~100 DEG C, makes gingko Water content is down to 30%~40%;
(4) it takes step (3) water content to be down to 30%~40% gingko, after shelling, removes the plumule in gingko;
(5) it takes except the gingko after degerming in step (4), dry, the gingko after obtaining detoxification.
The method provided by the invention for releasing gingko toxicity based on physics and enzymatic integrated processes, specific steps include:
(1) gingko is taken, is heated to 45 DEG C~80 DEG C, in the case where its water content is not less than 50%, continues isothermal holding 2 Hour or more;
(2) gingko after taking step (1) isothermal holding, is heated to 90 DEG C~105 DEG C, in its water content not less than 50% In the case of, heat treatment 1 hour or more;
(3) take step (2) heat after gingko, 60 DEG C~100 DEG C at a temperature of be dried, keep gingko aqueous Amount is down to 30%~40%.
(4) it takes step (3) water content to be down to 30%~40% gingko, after heat treatment, removes the plumule in gingko.
(5) it takes except the gingko after degerming in step (4), dry, the gingko after obtaining detoxification.
Gingko described in step (1) of the present invention is that fresh gingko or process working process water content are white not less than 50% Fruit.
Preferably, the above-described method for releasing gingko toxicity based on physics and enzymatic integrated processes, step (1) in, 50 DEG C~70 DEG C are heated to, in the case where keeping water content 50%~70%, persistently keeps the temperature 2~5 hours.
Preferably, the above-described method for releasing gingko toxicity based on physics and enzymatic integrated processes, step (2) in, 90 DEG C~100 DEG C are heated to, in the case where its water content is not less than 50%, is heated 2~6 hours.
Heating method described in step (1) of the present invention, step (2) and step (3) can be modern all kinds of heating means, Such as: heat radiation heating, infrared heating or microwave heating.
It is the humidity keeping method for keeping gingko water content to be carried out in step (1) of the present invention, step (2) and step (3), It can be the combination of any one or more methods below, such as: it humidifies, is closed.
The method that plumule is removed described in step (4) of the present invention can be removal by hand or the removal of mechanical stamping formula.
The neutraceutical active ingredients abundant that gingko of the present invention after detoxification treatment contains can be applied to preparation and protect Health food and drug.
The present invention is on the basis of carrying out numerous studies to gingko toxic component and physicochemical property, according to its toxic component Distribution characteristics and physicochemical property, using different poison-removing methods, be conducive to ginkgo poisoning ingredient effectively remove with nutrition at That divides is effectively retained.
The first step of the invention is the MPN degrading enzyme itself contained using fresh gingko and cyanogen glycosides catabolic enzyme by contained 4 ~O~methyl pyridoxine (4~O~methylpyridoxine, MPN) and cyanogen methods of glycosides are largely degraded, the key of this step It is that enzyme is made to play stronger vigor, suitable temperature and humidity must be controlled, and kept for the regular hour enzyme is allowed to give full play to work With.The present invention is compared by lot of experiments, and the assay of ginkgoic acid and MPN use HPLC method, and comparison result is shown in Table 1.As a result, it has been found that control temperature is between 45 DEG C~80 DEG C, water content is not less than under the conditions of 50%, processing 2 hours or more.It is special Between 50 DEG C~70 DEG C, water content is handled 2~5 hours not preferably control temperature under the conditions of 50%~70%.By this One step, the MPN degradable 90% or more in gingko.MPN in gingko, content is all in gingko edible plumule and endosperm It is higher, even if the endosperm after edible removal plumule, remain to take in more MPN, therefore detoxification the step for progress is extremely important.
The fresh gingko of table 1 ginkgoic acid and MPN content under different in moisture different temperatures
Second step of the invention makes gingko holding high temperature 1 hour or more after enzymatic hydrolysis, makees to the further decomposition of ginkgoic acid With fairly obvious, the present invention passes through lot of experiments, the results are shown in Table 2.Gingko is heated to 90 DEG C~100 DEG C of high temperature, is protected Water content is held under the conditions of 50%~70%, is handled 2~6 hours, ginkgo acid content can be made to reduce 30%~40%, while this is high Warm step can also be such that the volatilization of cyanogen glycosides ingredient degradation product removes, and can also make allergic protein deactivation therein.
Gingko ginkgoic acid and the MPN content under 60% moisture condition of different temperatures after digesting of table 2
It is of the invention step 3: gingko after taking step (2) to heat, 60 DEG C~100 DEG C at a temperature of done It is dry, so that gingko water content is down to 30%~40%.The purpose of this step is the convenience in order to subsequent except degerming operation, improves work Efficiency.Moisture is excessively high, and gingko pulp is in semisolid, and not easily molded, plumule difficulty removes;Moisture is small, and pulp is hard, easy fragmentation, embryo Bud is also difficult to remove.
4th step of the invention is primarily directed to another kind of toxic component phenolic acid~ginkgoic acid contained in gingko The processing of progress.The substance is the derivative of a kind of salicylic acid structure, and the side chain carbon number on 6 can be 13~17, Pendant double bonds number can be 0~3, have higher fat-soluble, currently used poison-removing method is solvent extraction.Present invention process pair Gingko sample is separated into mesosperm, 4 part of endotesta, endosperm and plumule, respectively by the measurement of ginkgo acid content in each position of gingko Partial weight ratio is as follows based on dry product: mesosperm 19.69%, endotesta 1.36%, endosperm 76.72%, plumule 2.23%.In edible part: endosperm 97.18%, plumule 2.82%.It is analyzed using HPLC method, each position based on dry product Middle toxic component content is shown in Table 3.
Each position ginkgoic acid of 3 gingko of table and ginkgotoxin content
The plumule of gingko is the highest position of composition containing ginkgo sour component, and Germ wt accounts for the 2.82% of edible part total weight, But the ginkgoic acid contained accounts for the 60%~70% of edible part.Although still thering is more ginkgoic acid to protect by the processing of preceding 2 step It staying wherein, the present invention is removed the plumule of high composition containing ginkgo acid by physical removal methods, so pass through the gingko of two-step pretreatment, Ginkgoic acid can remove 80%~90%.Meanwhile by removal plumule operation, it can make to form cavity in the middle part of gingko, be used in hot biography It leads, is conducive to its subsequent drying and crushing and processing.
The utility model has the advantages that gingko Compound Machining poison-removing method provided by the invention has the advantage that
The ginkgo detoxicating method reported at present is mostly handled using solvent extraction or other chemical reagent soaked for detoxification, this On the one hand a little methods easily cause considerable damage and the loss of effective component and nutritional ingredient, influence the nutrition and health care function of gingko product Effect;On the other hand, dissolvent residual is easily caused by the way that solvent extraction is added.Gingko Compound Machining poison-removing method master provided by the invention To merge physical removal methods by the heating method stage by stage of control temperature and humidity, can retain as far as possible to the maximum extent white The effective components such as flavones contained in fruit, lactone, amino acid, vitamin and minerals and nutritional ingredient, without influencing gingko The performance of effect.In addition, the composite toxicity method for being released fresh gingko based on physics and enzymatic integrated processes that the present invention uses, is not had It is useful to arrive any organic solvent and chemical reagent, it also not will cause the pollution of organic solvent and reagent to environment, there is processing It is low in cost, it can be achieved that large-scale production, economic results in society with higher.
Specific embodiment
The present invention is furture elucidated combined with specific embodiments below, it should be understood that these embodiments be merely to illustrate the present invention and It is not used in and limits the scope of the invention, after the present invention has been read, those skilled in the art are to various shapes of equal value of the invention The modification of formula falls within the application range as defined in the appended claims.
A kind of gingko toxicity Compound Machining poison-removing method of embodiment 1
(1) take the gingko of fresh removal exosper makes gingko water content be kept above 60% in temperature 60 C environment, Duration 5 hours.
(2) gingko is heated to 100 DEG C again, heated 2 hours, change the heating method of step using temperature-controlled drying case, heating Process does not open air blast, closed, to keep certain humidity;
(3) gingko handled through upper step, the temperature using temperature control forced air drying equipment in 90 DEG C are dried, and make gingko water Divide and drop to 30%, gingko is shelled using manual, removed endotesta and plumule;
(3) gingko after degerming further utilizes method described in (2) and temperature dry, makes moisture up to 10%.
Related composition detection;Through treated the gingko of embodiment 1, the 15% of degradable to the former content of ginkgoic acid therein, 4 ~O~methyl pyridoxine (MPN) is down to the 5% of former content, can get the gingko of low toxicity, as the original for processing all kinds of gingko products Material.
A kind of gingko toxicity Compound Machining poison-removing method of embodiment 2
(1) gingko after removing exosper and drying of learning from else's experience is kept above gingko water content in temperature 50 C environment 50%, the duration 4 hours.
(2) gingko is heated to 90 DEG C again, heated 6 hours.The heating method of the step uses infrared temperature-controlled drying equipment, Heating process moderately humidifies, closed, to keep certain humidity;
(3) gingko handled through upper step, it is dry crude dry in 100 DEG C of temperature progress using temperature control microwave dryer, make white Fruit moisture drops to 35%, and gingko is shelled using the manual method combined with machinery, removes endotesta and plumule;
(4) gingko after degerming is directly used in the exploitation of related gingko product.
Related composition detection;Through treated the gingko of embodiment 2, the 17% of degradable to the former content of ginkgoic acid therein, 4 ~O~methyl pyridoxine (MPN) is down to the 4% of former content, can get the gingko of low toxicity, as the original for processing all kinds of gingko products Material.
A kind of gingko toxicity Compound Machining poison-removing method of embodiment 3
(1) gingko is taken, in temperature 70 C environment, gingko water content is made to be kept above 60%, the duration 2 hours.
(2) gingko is heated to 100 DEG C again, heated 2 hours.This step heating method uses microwave temperature-controlled drying equipment, Heating process moderately humidifies, closed, to keep certain humidity;
(3) gingko handled through upper step, it is dry crude dry in 100 DEG C of temperature progress using temperature control microwave dryer, make white Fruit moisture drops to 35%, and gingko is shelled using mechanical pressing method, and mechanical shock method removes plumule;
(4) gingko after degerming, it is further dry using infra-red drying equipment, make moisture up to 20%, reaches further The humidity needed is processed, can be used as the exploitation raw material of all kinds of gingko products.
Related composition detection;Through treated the gingko of embodiment 3, the 16% of degradable to the former content of ginkgoic acid therein, 4 ~O~methyl pyridoxine (MPN) is down to the 5% of former content, can get the gingko of low toxicity, as the original for processing all kinds of gingko products Material.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (4)

1. a kind of method for releasing gingko toxicity based on physics and enzymatic integrated processes, which comprises the following steps:
(1) gingko is taken, in the case where being heated to 50 DEG C~70 DEG C holding water content 50%~70%, it is small persistently to keep the temperature 2~5 When;
(2) gingko after taking step (1) isothermal holding, is heated to 90 DEG C~100 DEG C, the case where its water content is not less than 50% Under, it heats 2~6 hours;
(3) gingko after taking step (2) to heat, is dried at a temperature of being heated to 60 DEG C~100 DEG C, keeps gingko aqueous Amount is down to 30%~40%;
(4) it takes step (3) water content to be down to 30%~40% gingko, after shelling, removes the plumule in gingko;
(5) it takes except the gingko after degerming in step (4), dry, the gingko after obtaining detoxification.
2. the method according to claim 1 for releasing gingko toxicity based on physics and enzymatic integrated processes, which is characterized in that Step (1), step (2) and step (3) heating method are heat radiation heating, infrared heating or microwave heating.
3. the method according to claim 1 for releasing gingko toxicity based on physics and enzymatic integrated processes, which is characterized in that In step (1), step (2) and step (3), gingko water content keeping method be humidification and/or it is closed.
4. the method according to claim 1 for releasing gingko toxicity based on physics and enzymatic integrated processes, which is characterized in that The method that gingko plumule is removed described in step (4) is removal by hand or the removal of mechanical stamping formula.
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CN106578848B (en) * 2016-12-05 2020-07-07 江南大学 Method for efficiently reducing ginkgolic acid content in ginkgo nuts
CN106666336A (en) * 2017-01-13 2017-05-17 江南大学 Method for reducing toxic substances in ginkgo biloba
CN107212095B (en) * 2017-05-18 2019-12-31 镇江市智农食品有限公司 Ginkgo high-calcium milk beverage and preparation method thereof
CN108208539B (en) * 2017-12-01 2021-09-10 江苏大学 Method and device for processing low-toxicity ginkgo kernels
CN108094836A (en) * 2017-12-27 2018-06-01 江南大学 A kind of method for reducing hydrogen cyanide content in ginkgo and its product
CN108743632B (en) * 2018-04-27 2021-07-27 浙江工业大学 Method for removing ginkgolic acid in ginkgo by ultrasonic assistance
CN109222087A (en) * 2018-09-26 2019-01-18 合肥工业大学 A kind of instant brewed powder of gingko functional and preparation method thereof

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