CN102827900B - A kind of biological process produces the production technique of γ-cyclodextrin - Google Patents
A kind of biological process produces the production technique of γ-cyclodextrin Download PDFInfo
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Abstract
The present invention relates to the production technique that a kind of biological process produces γ-cyclodextrin, belong to cyclodextrin production technical field.Technical problem solved by the invention there is provided the technique that a kind of biological process produces γ-cyclodextrin, reduce the production cost of γ-cyclodextrin, technical scheme is: adopt the γ-cyclodextrin glucanotransferase deriving from bacillus alcalophilus to produce γ-cyclodextrin; Concentration according to 10% is carried out starch and is sized mixing, under 60-90 DEG C of condition, stir 5-15 minute; Design temperature 40-60 DEG C, after adjusting about pH10.0, adds γ-cyclodextrin glucanotransferase according to the amount of every gram of starch 1-10 unit, after adding the organic solvent of 2-5% (w/v), and fully reaction 8-10 hour; Reclaim organic solvent, adopt crystallization method to obtain γ-cyclodextrin.
Description
Technical field
The present invention relates to the production technique that a kind of biological process produces γ-cyclodextrin, belong to cyclodextrin production technical field.
Background technology
Cyclodextrin (Cyclodextrins, usually referred to as CD), a class by starch or polysaccharide generate under cyclomaltodextrin glucanotransferase effect by D-glucopyranose units by α-1, the general name of the end to end ring compound of 4-glycosidic link, common are the molecule of 6,7 and 8 glucose units, be called α-, β-and γ-cyclodextrin.Cyclodextrin is due to the singularity of its structure, many organism and mineral compound can be embedded, as the carrier and sorbent material etc. of quality improver, stablizer, medicine, so it all has a wide range of applications in food, medicine, chemistry, analytical chemistry, agricultural environmental protection, textile technology and biotechnology field.In three kinds of conventional cyclodextrin, beta-cyclodextrin water solubility is minimum, method easily through fractional crystallization obtains, therefore beta-cyclodextrin is prepared and widespread use at present aborning in a large number, but beta-cyclodextrin makes it be restricted the application in medicine clathration because solubleness is little, current scientific worker is just being devoted to the solubleness improving beta-cyclodextrin.Although the demand of alpha-cylodextrin is very large, application prospect is had an optimistic view of, but due to low conversion rate during existing CGTase production alpha-cylodextrin, product specificities is poor, and the solubleness of alpha-cylodextrin is relatively high, be not easy out, therefore to cause production cost too high by method separation and purification from reaction solution that is concentrated, crystallization, greatly limit the application of its industrial-scale.
Compared to α-and beta-cyclodextrin, γ-cyclodextrin, owing to having higher solubleness and larger cavity, can wrap and connect the larger compound of molecular weight thus the solubleness increasing compound, improve the emulsifying property etc. of compound, and toxicity is minimum, pungency is also very little, and security is high.Huge advantage has been demonstrated in food, medicine and other fields.Although market is large to γ-cyclodextrin product consumption, because γ-cyclodextrin transformation efficiency is low, causes γ-cyclodextrin expensive, greatly limit its application.Also only have several companies such as Wacker and Cyclolab to produce γ-cyclodextrin at present abroad, and output is very limited.
Produce γ-cyclodextrin method and only have biological process at present, concerns about bio legal system is more for the report of α-and beta-cyclodextrin, but the report producing γ-cyclodextrin about biological process is less, Cao Xinzhi etc. are when preparing γ-cyclodextrin, wide, the low-cost sweet potato starch in source is selected to be substrate, the starch fluid of preparation 5% (w/v), the output of γ-cyclodextrin is measured after adding the γ-CGTase crude enzyme liquid deriving from Bacillus alcalophilus in right amount, found that the transformation efficiency of sweet potato starch is the highest and be about 30%, but later separation is very difficult.(Cao Xinzhi. cyclomaltodextrin glucanotransferase and the biosynthetic research of γ-cyclodextrin [D]. Wuxi, Southern Yangtze University, 2005).Under the organic solvent condition of interpolation, foreign literature report peak rate of conversion is also only about 40%.The subject matter that current biological process produces γ-cyclodextrin is: one, lack good properties and have high enzyme γ-cyclodextrin glucanotransferase (γ-CGTase) alive; Two, lack the corresponding production technique of γ-cyclodextrin, for the problem that γ-cyclodextrin solubleness in water is higher, need the separating and extracting method formulating a set of economical and efficient.
Summary of the invention
Technical problem solved by the invention there is provided the technique that a kind of biological process produces γ-cyclodextrin, reduces the production cost of γ-cyclodextrin.For solving the problem, technical solution of the present invention is:
The γ-cyclodextrin glucanotransferase deriving from bacillus alcalophilus is adopted to produce γ-cyclodextrin; Carry out starch according to the concentration of 10-15% to size mixing, under 60-90 DEG C of condition, stir 5-15 minute; Design temperature 40-60 DEG C, after adjusting about pH10.0, adds γ-cyclodextrin glucanotransferase according to the amount of every gram of starch 1-10 unit, after adding the organic solvent of 2-5% (w/v), and fully reaction 8-10 hour; Reclaim organic solvent, adopt crystallization method to obtain γ-cyclodextrin.
The method that described fermentable produces γ-CGTase is, under certain culture condition, with E.coliBL21 (DE3)/pET20b (+)-γ-CGTase (Ji Liping, Wu Dan, Wu Jing, Chen Jian. the shake flask fermentation that recombination bacillus coli produces γ-cyclodextrin glucanotransferase optimizes Chinese biological engineering magazine, 2011,31 (10): 50-56) ferment certain hour, obtain the fermented liquid containing γ-CGTase, through high speed centrifugation, remove thalline, supernatant is crude enzyme liquid.
Describedly under 60-90 DEG C of condition, stir object that 5-15 minute starch sizes mixing to be to make starch granules fully swelling.
The optimal reactive temperature of described γ-CGTase is about 40-50 DEG C, and temperature by affecting the catalytic efficiency of enzyme to substrate, thus affects the vigor of enzyme, the action effect that all can affect enzyme too high or too low for temperature.Consider from reduction production cost, the temperature of production technique should be not too high or too low, to reduce the enzyme amount added, thus reduces production cost.
The optimal pH scope of described γ-CGTase is that the vigor of 10.5-11.0, γ-CGTase affects comparatively large by pH, considers and reduces costs, the pH of production technique should be selected near enzyme optimal reaction pH.
The mensuration of described γ-CGTase vigor adopts tetrabromo-mcresolsulfonphthalein (BCG) spectrophotometry: in acid condition, tetrabromo-mcresolsulfonphthalein presents multiple different absorption peak, when adding γ-cyclodextrin, tetrabromo-mcresolsulfonphthalein solution presents hyperchromic effect, and maximum hyperchromic wavelength is 630nm.At wavelength 630nm, within the scope of finite concentration, between the increase absorption photometric value (Δ A) of tetrabromo-mcresolsulfonphthalein and γ-CGT concentration, there is linear relationship.The fermented supernatant fluid suitably diluted is added in the test tube of 1% (w/v) Zulkovsky starch solution using 50mmol/L Gly-NaOH damping fluid (pH10.0) to prepare in advance, react 10min at 40 DEG C after, add the hydrochloric acid termination reaction of 50 μ L 1.0mol/L, add the tetrabromo-mcresolsulfonphthalein of 2mL0.2mol/L citrate buffer solution (pH4.2) and 80 μ L5mmol/L again, room temperature leaves standstill about 20min, under wavelength 630nm, measure absorbancy.One Ge Meihuo unit (U) is defined as the enzyme amount needed for γ-cyclodextrin that per minute under these conditions generates 1 μm of ol.
Described α-, the analysis of β-and γ-cyclodextrin adopts high performance liquid chromatography.Chromatographic condition: Waters 600 HPLC chromatographic instrument, Waters automatic sampler, chromatographic column ZORBAX NH
2(4.6mm × 150mm), Waters2410 Composition distribution; Moving phase (v/v) is 75% acetonitrile solution, flow velocity 1.0mL/min; Column temperature 40 DEG C.During processing sample, the centrifugal 15min of 8000r/min, abandons precipitation, adds 0.1mL α-amylase liquid effect 1h, get machine analysis on 10 μ L after 0.45 μm of ultrafiltration membrance filter in supernatant liquor.
Described organic solvent is cyclododecanone.Cyclododecanone can not only precipitate with γ-cyclodextrin specific formation inclusion complex thus improve the total transformation efficiency of starch, and cyclododecanone price is relatively low, and boiling point is low, almost all can be removed by wet distillation, seldom remains in final product.
Described recovery organic solvent, the concrete grammar being obtained γ-cyclodextrin by crystallization means is:
After question response terminates, by reaction solution direct filtration, filter cake distilled water cleaning 2-3 time, collection filter cake, comprising the complex compound sediment that unreacted starch and organic solvent and γ-cyclodextrin are formed; Filter cake use water is redissolved, then by method Separation of Organic and the γ-cyclodextrin of wet distillation.After distillation terminates, filter distillate to remove unreacted starch, the aqueous solution of γ-cyclodextrin can be obtained.Finally, concentrated by aqueous solution rotary evaporation, low temperature places the crystallization obtaining γ-cyclodextrin.
Know-why of the present invention is as follows:
γ-CGTase is except producing except γ-cyclodextrin with starch generation cyclization, and coupling, disproportionation and hydrolysis reaction can also occur, and coupled reaction is the reversed reaction of cyclization, and this reaction is the ring opening cyclodextrin, then transfers on linear oligosacchardides.Under the existence condition of the small molecular sugars such as finite concentration malto-oligosaccharide or glucose, the cyclization of γ-CGTase is suppressed, and affects ultimate yield.The present invention directly adopts the starch of gelatinization to produce cyclodextrin, and under the condition that middle temperature stirs, starch granules is fully swelling, relieves the suppression of small molecular sugar to cyclization, improves the transformation efficiency of γ-CGTase.Because γ-cyclodextrin can form water-fast inclusion complex with organism, add a certain proportion of organic solvent and can remove cyclodextrin continuously from reactive system, reaction is constantly carried out towards the generation direction of cyclodextrin, be conducive to cyclodextrin to produce, relieve the product inhibition of γ-cyclodextrin to γ-CGTase simultaneously.
The present invention is the technique of producing γ-cyclodextrin according to the feature of γ-CGTase and product γ-cyclodextrin, relative to prior art, has the following advantages:
1) production method of the γ-cyclodextrin of a kind of high conversion, low cost is provided, has filled up the blank in this technical field, for biological process scale operation γ-cyclodextrin lays the foundation;
2) this reaction time of reacting total is short, only needs 8-10 hour;
3) temperature of enzyme reaction is lower, does not need to carry out violent temperature variation, less energy-consumption, is applicable to suitability for industrialized production;
4) directly utilize ative starch as substrate, relieve the restraining effect of the small molecular sugar such as glucose, maltose to the generation of γ-cyclodextrin; Add a certain proportion of organic solvent, from reactive system, remove γ-cyclodextrin continuously, make it constantly carry out to the direction generating γ-cyclodextrin, improve the transformation efficiency that γ-ring is stuck with paste, total conversion rate can reach about 60%, and wherein the ratio of γ-cyclodextrin and beta-cyclodextrin is about 9: 1.
5) organic solvent removes process approach simply, and the product purity obtained is high, and impurity is few, and can reach about 90%, Determination of Residual Organic Solvents can be used for pharmaceutical industries etc.
Generally speaking, the present invention has the advantages such as with short production cycle, feed stock conversion is high, product purity is high, technical process is simple, production cost is low.
Embodiment
Embodiment 1:
Raw materials pretreatment:
Concentration according to 10% is carried out yam starch and is sized mixing, and stirs 10 minutes, make the abundant water absorption and swelling of starch granules under 65 DEG C of conditions;
Enzymatic production process:
After pre-treatment, temperature is set as 50 DEG C, after adjusting pH10.0, adds γ-CGTase according to the ratio of every gram of starch 6 units, after then adding the cyclododecanone of 5% (w/v), fully react 9h;
The extraction process of γ-cyclodextrin:
Boiling water bath goes out after enzyme, and by reacting liquid filtering, filter cake distilled water cleaning 2-3 time, collects filter cake, the precipitation formed comprising cyclododecanone and γ-cyclodextrin and unreacted starch; Filter cake is redissolved with water again, then adopts wet distillation removing cyclododecanone, after end to be distilled, filter distillate and remove responseless starch, the aqueous solution of γ-cyclodextrin can be obtained; Concentrated by aqueous solution evaporate, low temperature places the crystallization that can obtain γ-cyclodextrin.
Described α-, the analysis of β-and γ-cyclodextrin adopts high performance liquid chromatography.Chromatographic condition: Waters 600 HPLC chromatographic instrument, Waters automatic sampler, chromatographic column ZORBAX NH
2(4.6mm × 150mm), Waters2410 Composition distribution; Moving phase (v/v) is 75% acetonitrile solution, flow velocity 1.0mL/min; Column temperature 40 DEG C.During processing sample, the centrifugal 15min of 8000r/min, abandons precipitation, adds 0.1mL α-amylase liquid effect 1h, get machine analysis on 10 μ L after 0.45 μm of ultrafiltration membrance filter in supernatant liquor.The results are shown in Table 1, starch total conversion rate can reach 60%, and in product, γ-CGT proportion is that 55.4%, β-CGT accounts for 4.6%,
The condition of production of γ-CGT under the different embodiment of table 1
(ND＝not dected)
Embodiment 2
Raw materials pretreatment:
With embodiment 1
Enzymatic production process:
After pre-treatment, temperature is set as 40 DEG C, after adjusting pH10.0, adds γ-CGTase according to the ratio of every gram of starch 3 units, after then adding the cyclododecanone of reaction system 4% (w/v), fully reaction 10 hours;
The extraction process of γ-cyclodextrin and detection method:
With embodiment 1
The results are shown in Table 1, the total conversion rate of starch is up to 55%, and in product, γ-cyclodextrin proportion is 50%, and beta-cyclodextrin accounts for 5%.
Embodiment 3
Raw materials pretreatment:
With embodiment 1
Enzymatic production process:
After pre-treatment, temperature is set as 60 DEG C, after adjusting pH10.0, adds γ-CGTase according to the ratio of every gram of starch 10 units, after then adding the cyclododecanone of 2.6% (w/v), fully reaction 8 hours;
The extraction process of γ-cyclodextrin and detection method:
With embodiment 1
The results are shown in Table 1, the total conversion rate of starch is up to 52%, and in product, γ-cyclodextrin proportion is 48%, and beta-cyclodextrin accounts for 4%.
Claims (1)
1. biological process produces a production technique for γ-cyclodextrin, it is characterized in that, adopts the γ-cyclodextrin glucanotransferase deriving from bacillus alcalophilus Alkalophilic Bacillusclarkii 7364 to produce γ-cyclodextrin; Concentration according to 10% is carried out starch and is sized mixing, under 60-90 DEG C of condition, stir 5-15 minute; Design temperature 40-60 DEG C, after adjusting pH10.0, adds γ-cyclodextrin glucanotransferase according to the amount of every gram of starch 1-10 unit, after adding the organic solvent of 2-5%w/v, and fully reaction 8-10 hour; Reclaim organic solvent, adopt crystallization method to obtain γ-cyclodextrin; Described recovery organic solvent, crystallization method are: by reaction solution direct filtration, and filter cake distilled water cleaning 2-3 time, collects filter cake, the complex compound sediment formed comprising organic solvent and γ-cyclodextrin and responseless starch; Filter cake is redissolved again, then adopts wet distillation removing organic solvent, after end to be distilled, filter distillate and remove responseless starch, namely obtain the aqueous solution of γ-cyclodextrin; Concentrated by aqueous solution evaporate, low temperature places the crystallization namely obtaining γ-cyclodextrin; Described organic solvent is cyclododecanone.
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| CN110615860A (en) * | 2018-06-20 | 2019-12-27 | 江苏恒瑞医药股份有限公司 | Method for purifying sugammadex sodium |
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| CN104630305A (en) * | 2013-11-07 | 2015-05-20 | 南通康威尔生物化工有限公司 | Production method of gamma-cyclodextrin |
| CN109400760B (en) * | 2018-11-02 | 2020-12-15 | 江南大学 | Method for purifying gamma-cyclodextrin by using cyclodextrin hydrolase |
| CN110846360B (en) * | 2019-11-29 | 2022-03-15 | 江南大学 | Method for inhibiting starch retrogradation |
| CN111394407B (en) * | 2020-04-03 | 2022-06-14 | 淄博千汇生物科技有限公司 | Preparation method of gamma-cyclodextrin |
| CN111394406B (en) * | 2020-04-03 | 2022-05-31 | 淄博千汇生物科技有限公司 | Preparation method of gamma-cyclodextrin |
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