CN102286044B - Preparation method of natamycin laminar crystal - Google Patents
Preparation method of natamycin laminar crystal Download PDFInfo
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- CN102286044B CN102286044B CN201110242485.1A CN201110242485A CN102286044B CN 102286044 B CN102286044 B CN 102286044B CN 201110242485 A CN201110242485 A CN 201110242485A CN 102286044 B CN102286044 B CN 102286044B
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Abstract
The invention relates to a preparation method of a natamycin laminar crystal, and the preparation method comprises the following steps: (1) adding natamycin mycelium into a methanol and water mixed liquid, wherein the volume ratio of methanol to water is (60-90):(40-10); (2) adjusting the pH value to 10-12 with a basic substance; (3) carrying out liquid-solid separation and collecting filtrate to obtain a natamycin extract; (4) concentrating the extract until the content of natamycin is 18-26 mg/mL, and flocculating to remove insoluble substances to obtain a natamycin fine extract; (5) acidifying the natamycin fine extract by two stages: firstly dripping acid slowly until the pH value decreases to 8-9, then stirring for more than 1 hour, then slowly dripping the acid until the pH value decreases to 6-7, and then stirring for more than 3 hours to obtain a crystallization liquid of the laminar natamycin crystal; and (6) carrying out liquid-solid separation and drying in vacuum to obtain the laminar natamycin crystal. By adoption of the preparation method provided by the invention, the uniform natamycin laminar crystal can be prepared, the subsequent crystal washing and drying difficulties are reduced, and the crystal filtering and drying time is shortened.
Description
Technical field
The present invention relates to a kind of method of preparing tennecetin tabular crystal from mycelium.
Background technology
Tennecetin (Natamycin) claims that again pimaricin (Pimaricin) is a kind of polyene macrolide antibiotics, and it can suppress the growth of yeast and mould, and does not act on the normal microflora in human intestinal.Follow-up study and the evaluation of application aspect just tennecetin have been carried out from the 1996 foodstuff additive councils of Nian Qi China, the national standard of formally putting into effect tennecetin in 2011, the course of processing as antimildew agent for food for food such as cheese, cake, meat intestines.
Tennecetin molecular formula is C33H47NO13; Molecular weight is 665.75 dalton; Be amphoteric substance, iso-electric point is 6.5.
Tennecetin is produced by streptomycete fermentation, and fermented liquid, after liquid-solid separation, is collected mycelium, by adding the method for organic solvent and adjusting pH, finally can obtain the crystal of tennecetin.The crystalline substance of tennecetin is practised two kinds of sheet and needle-likes, and they all belong to α-tennecetin crystallographic system.
In the separation and purification process of tennecetin, the not isomorphous of tennecetin is practised filtration velocity and the time of drying that can affect tennecetin crystal.Needle-like is brilliant to be practised and is easy to coalescent agglomeratingly, is easy to again wrap up impurity and affects purity when coalescent, increases filtration, washing and dry difficulty simultaneously.The tennecetin crystal that the extracting method that adopts Chinese patent CN101062934A to announce makes is hour hand shape or unbodied, is unfavorable for the filtration of tennecetin crystal and is dried, and filtration and time of drying are all longer.
Summary of the invention
The object of this invention is to provide a kind of preparation method of tennecetin tabular crystal, it can make the tennecetin tabular crystal of homogeneous, washs and dry difficulty thereby reduce follow-up crystal, shortens filtration and the time of drying of crystal.
Technical solution of the present invention is to form like this: a kind of preparation method of tennecetin tabular crystal, is characterized in that: it comprises the following steps:
A, get in the mixed solution that tennecetin mycelium adds methyl alcohol and water; In described methyl alcohol and the mixed solution of water, the volume ratio of methyl alcohol and water is 60-90: 40-10; The mixed solution of every 1L methyl alcohol and water adds 90-110g tennecetin mycelium;
B, the pH value of solution that obtains with alkaline matter uniform stirring regulating step a, to 10-12, are dissolved in mixing solutions tennecetin;
C, the solution that step b is obtained carry out liquid-solid separation, and collection filtrate obtains the extracting solution of tennecetin;
The extracting solution of tennecetin that d, enrichment step c obtain is to tennecetin content between 18～26mg/ml, and flocculation removes the insolubles of separating out in this process, obtains tennecetin essence extracting solution;
E, the tennecetin essence extracting solution that acidification step d obtains in two stages:
First stage stirs tennecetin essence extracting solution while slowly drips acid, makes the pH value of tennecetin essence extracting solution progressively be reduced to 8-9, in the situation that pH value is no longer gone up, then stirs more than 1 hour;
Subordinate phase continues to stir tennecetin essence extracting solution while slowly drips acid, make the pH value of tennecetin essence extracting solution progressively be reduced to 6-7, in the situation that pH value is no longer gone up, then stir more than 3 hours, obtain the crystal solution of the tennecetin crystal of sheet;
F, the crystal solution of tennecetin crystal that step e is obtained are carried out liquid-solid separation, and then vacuum-drying obtains sheet tennecetin crystal.
Preparation principle of the present invention is described as follows: applicant of the present invention finds that by research the content of methyl alcohol in tennecetin extracting solution has a great impact crystalline substance habit, and growing the grain technique can be improved the size distribution of tabular crystal in the crystallisation process of tennecetin, improve the purity of tennecetin crystal.According to above 2 points, the present invention adopts the mixed solution of a certain proportion of methyl alcohol and water to extract from tennecetin mycelium and purifying tennecetin, then by crystallization and growing the grain technique, acidifying tennecetin essence extracting solution stage by stage, thus prepare the higher tennecetin crystal of purity of sheet.The object of acidifying tennecetin essence extracting solution is stage by stage: in the first stage, make the pH value of tennecetin essence extracting solution slowly have the decline of control by dripping acid, slowly there is the solubleness of the reduction tennecetin of control, prevent that the phenomenon of tennecetin outburst nucleation from occurring; Now crystallization and dissolving tend to be balanced, and be beneficial to growing up of crystal, but now solubleness are larger, and the words yield of direct filtration is low, so continue steadily to regulate pH to subordinate phase, now reach the iso-electric point of tennecetin, solubleness minimum, and yield is high.If be directly transferred to iso-electric point, tennecetin rapid crystallization, the crystal size heterogeneity obtaining and parcel impurity.Subordinate phase continues slowly and controlledly to regulate the object of pH value to 6～7 to be to make the surface that mainly occurs in established nucleus of separating out of tennecetin, and the tennecetin tabular crystal particle obtaining is thus large, size-grade distribution is more even, and purity is higher.
Compared to prior art, the invention has the advantages that: the present invention is taking the mycelium of tennecetin culture as object, by controlling methyl alcohol and the ratio of water and the crystallisation process of tennecetin in extracting solution, thereby can make the tennecetin tabular crystal of homogeneous, reducing follow-up crystal filters and dry difficulty, shorten filtration and the time of drying of crystal, be convenient to industrialized production control.
Brief description of the drawings
Fig. 1 is the photomicrography crystal morphology figure of embodiment 1 gained tabular crystal.
Fig. 2 is the photomicrography crystal morphology figure of embodiment 4 gained crystal.
Fig. 3 is the photomicrography crystal morphology figure of the group 9 gained crystal organized of contrast experiment.
Embodiment
Below in conjunction with embodiment, embodiment and Figure of description, content of the present invention is elaborated:
One, embodiment:
The specific embodiment of the invention provides a kind of preparation method of tennecetin tabular crystal, it is characterized in that: it comprises the following steps:
A, get in the mixed solution that tennecetin mycelium adds methyl alcohol and water; In described methyl alcohol and the mixed solution of water, the volume ratio of methyl alcohol and water is 60-90: 40-10; The mixed solution of every 1L methyl alcohol and water adds 90-110g tennecetin mycelium;
Tennecetin mycelium described in this step is wet mycelium or the dry mycelium that natamycin fermentation liquor obtains by Technology in Solid/Liquid Separation, preferably the dry mycelium of moisture content≤5%.Certainly, also can adopt wet mycelium, if the water content of wet mycelium is higher, preferably measure in advance the moisture content of wet mycelium, ratio that like this can suitable corresponding minimizing water in the time preparing the mixed solution of methyl alcohol and water.Described methyl alcohol and the volume ratio of water are preferably 73: 27, and the mixed solution of every 1L methyl alcohol and water preferably adds 100g tennecetin mycelium.
B, the pH value of solution that obtains with alkaline matter uniform stirring regulating step a, to 10-12, are dissolved in mixing solutions tennecetin;
Alkaline matter described in this step is preferably sodium hydroxide or ammoniacal liquor etc., for industrial conventional regulator solution is to alkaline material.
C, the solution that step b is obtained carry out liquid-solid separation, and collection filtrate obtains the extracting solution of tennecetin;
Solid separation method described in this step can adopt solid separation method conventional in microbiotic leaching process, as centrifugal in Plate Filtration, gravity, suction filtration, cross flow filter etc., and its object is to remove bacterium slag, collects filtrate to obtain the extracting solution of tennecetin.
The extracting solution of tennecetin that d, enrichment step c obtain is to tennecetin content between 18～26mg/ml, and flocculation removes the insolubles of separating out in this process, obtains tennecetin essence extracting solution;
Concentration method described in this step can adopt conventional vacuum concentration method.
E, the tennecetin essence extracting solution that acidification step d obtains in two stages:
First stage stirs tennecetin essence extracting solution while slowly drips acid, (optimum value is determined according to the concentration of tennecetin to make the pH value of tennecetin essence extracting solution progressively be reduced to 8-9, as in the time that the concentration of tennecetin is 22mg/ml, pH value is 8.6), in the situation that pH value is no longer gone up, stir again 1 hour above (preferably 1 hour), make the nucleation and crystal growth of tennecetin reach balance;
Subordinate phase continues to stir tennecetin essence extracting solution while slowly drips acid, make the pH value of tennecetin essence extracting solution progressively be reduced to 6-7, in the situation that pH value is no longer gone up, stir again 3 hours above (preferably 3-5 hour), obtain the crystal solution of the tennecetin crystal of sheet.
The acid that the acidifying regulate process of this step is used is industrial conventional acid, example hydrochloric acid, sulfuric acid etc.In this step, stir as conventional at the uniform velocity stirring means, as magnetic agitation, mechanical stirring etc., the object stirring is to make crystal solution to mix on the one hand, avoid the too low tennecetin outburst nucleation that causes of local pH, can make on the other hand the crystal of tennecetin fully be suspended in crystal solution, avoid crystal bonding parcel impurity.
F, the crystal solution of tennecetin crystal that step e is obtained are carried out liquid-solid separation, and then vacuum-drying obtains sheet tennecetin crystal.
The solid-liquid separating method that any conventional is selected in the liquid-solid separation of the crystal solution described in this step all can, as suction filtration, centrifuging etc.The tennecetin crystal that this step obtains through liquid-solid separation, available 50% alcohol-water (V: V) solution washing 3 times, under 50 DEG C ,-0.09MPa condition, vacuum-drying, to constant weight, can obtain the micro-yellowish sheet tennecetin crystal of white, purity approximately 90%.
Two, specific embodiment
Embodiment 1
The dry mycelium 100g that gets tennecetin, wherein tennecetin content is 11.2% (w/w), adds the mixed solution (volume ratio of methyl alcohol and water is 75: 25) of 1L methyl alcohol and water, stirs mycelium is fully suspended.Regulate the rear stirring of pH value to 11.35 1 hour with the NaOH of 10mol/L.Suction filtration isolate slag, collects filtrate, obtains the tennecetin extracting solution of yellowish brown.Extracting solution to the content of tennecetin of concentrated tennecetin is 22.6mg/ml, and flocculation removes the insolubles of separating out in this process, obtains the smart extracting solution of tennecetin.Stir subsequently while the HCl of the slow 10mol/L of dropping, make the pH value of tennecetin essence extracting solution progressively be reduced to 8.65, in the situation that pH value is no longer gone up, then stir 1 hour.Then continue to stir while the HCl of the slow 10mol/L of dropping, make the pH value of tennecetin essence extracting solution progressively be reduced to 6.61, in the situation that pH value is no longer gone up, then stir 4 hours.Suction filtration crystal solution afterwards, obtain sheet tennecetin crystal, with after 50% ethanol-water solution washing crystal 3 times, under 50 DEG C ,-0.09MPa condition, vacuum-drying is to constant weight, obtain the micro-yellowish sheet tennecetin crystal 7.11g of white, purity 92.1%.Crystal is coated on wave carrier piece, obtains crystal morphology as shown in Figure 1 100 times of lower photomicrographys with Olympus VANOX-S type microscope, brilliant habit as sheet, thicker, big or small homogeneous, does not wrap up impurity.
Embodiment 2
The dry mycelium 90g that gets tennecetin, wherein tennecetin content is
12.1%(w/w), add the mixed solution (volume ratio of methyl alcohol and water is 60: 40) of 1L methyl alcohol and water, stir mycelium is fully suspended.Regulate the rear stirring of pH value to 10 1.5 hours with the NaOH of 10mol/L.Suction filtration isolate slag, collects filtrate, obtains the tennecetin extracting solution of yellowish brown.Extracting solution to the content of tennecetin of concentrated tennecetin is 18mg/ml, and flocculation removes the insolubles of separating out in this process, obtains the smart extracting solution of tennecetin.Stir subsequently while the HCl of the slow 10mol/L of dropping, make the pH value of tennecetin essence extracting solution progressively be reduced to 8, in the situation that pH value is no longer gone up, then stir 1.5 hours.Then continue to stir while the HCl of the slow 10mol/L of dropping, make the pH value of tennecetin essence extracting solution progressively be reduced to 6, in the situation that pH value is no longer gone up, then stir 3 hours.Suction filtration crystal solution afterwards, obtains sheet tennecetin crystal, and with after 50% ethanol-water solution washing crystal 3 times, under 50 DEG C ,-0.09MPa condition, vacuum-drying, to constant weight, obtains the micro-yellowish sheet tennecetin crystal of white
6.96g, purity
91.5%.Tabular crystal shape under microscopic examination is with embodiment 1.
Embodiment 3
The dry mycelium 110g that gets tennecetin, wherein tennecetin content is
10.3%(w/w), add the mixed solution (volume ratio of methyl alcohol and water is 90: 10) of 1L methyl alcohol and water, stir mycelium is fully suspended.Regulate the rear stirring of pH value to 12 1 hour with the NaOH of 10mol/L.Suction filtration isolate slag, collects filtrate, obtains the tennecetin extracting solution of yellowish brown.Extracting solution to the content of tennecetin of concentrated tennecetin is 26mg/ml, and flocculation removes the insolubles of separating out in this process, obtains the smart extracting solution of tennecetin.Stir subsequently while the HCl of the slow 10mol/L of dropping, make the pH value of tennecetin essence extracting solution progressively be reduced to 9, in the situation that pH value is no longer gone up, then stir 2 hours.Then continue to stir while the HCl of the slow 10mol/L of dropping, make the pH value of tennecetin essence extracting solution progressively be reduced to 7, in the situation that pH value is no longer gone up, then stir 5 hours.Suction filtration crystal solution afterwards, obtains sheet tennecetin crystal, and with after 50% ethanol-water solution washing crystal 3 times, under 50 DEG C ,-0.09MPa condition, vacuum-drying, to constant weight, obtains the micro-yellowish sheet tennecetin crystal of white
7.27g, purity
90.3%.Tabular crystal shape under microscopic examination is with embodiment 1.
Embodiment 4 (control group)
As the method for embodiment 1, only the step of acidifying is stage by stage changed into: the HCl that directly drips 10mol/L in tennecetin essence extracting solution regulates pH value to 6.5.Suction filtration, washing crystal final vacuum are dried to constant weight afterwards, obtain coalescent and are surrounded by the tennecetin tabular crystal 7.51g of impurity, purity 85.5%.Obtain crystal morphology as shown in Figure 2 by the method for microphotograph in embodiment 1,
crystalsize heterogeneity, coalescent and wrap up impurity, pattern is poor compared with embodiment 1.
Comparative illustration by embodiment 1-3 and embodiment 4: in the crystallisation process of tennecetin, adopt the growing the grain technique of the essence of acidifying tennecetin stage by stage extracting solution can improve the size distribution of tabular crystal, improve the purity of tennecetin crystal.
Contrast experiment's group
As embodiment 1 method, only change the ratio of methyl alcohol and water in the mixing solutions of methyl alcohol and water, the tennecetin in mycelium is extracted in grouping, and the filtration time (liquid-solid separation) of the crystal solution of the tennecetin crystal making is as shown in table 1 with time of drying:
Table 1 different ratios mixing solutions filtration time and contrast time of drying
Group 9 crystal that make obtain crystal morphology as shown in Figure 3 by photomicrography method in embodiment 1, brilliant habit as needle-like.
Result shows, the content of methyl alcohol is practised and being had a great impact crystalline substance, and the tennecetin crystal filtration time that flake crystalline is practised is all short compared with the tennecetin crystal of the brilliant habit of needle-like with time of drying, is more conducive to the solid-liquid separation in tennecetin leaching process.
Claims (3)
1. a preparation method for tennecetin tabular crystal, is characterized in that: it comprises the following steps:
A, get in the mixed solution that tennecetin mycelium adds methyl alcohol and water; In described methyl alcohol and the mixed solution of water, the volume ratio of methyl alcohol and water is 60-90: 40-10; The mixed solution of every lL methyl alcohol and water adds 90-110g tennecetin mycelium, the dry mycelium that described tennecetin mycelium is moisture content≤5%;
B, the pH value of solution that obtains with alkaline matter uniform stirring regulating step a are to 10-12;
C, the solution that step b is obtained carry out liquid-solid separation, and collection filtrate obtains the extracting solution of tennecetin;
The extracting solution of tennecetin that d, enrichment step c obtain is to tennecetin content between 18～26mg/m1, and flocculation removes the insolubles of separating out in this process, obtains tennecetin essence extracting solution;
E, the tennecetin essence extracting solution that acidification step d obtains in two stages:
First stage stirs tennecetin essence extracting solution while slowly drips acid, makes the pH value of tennecetin essence extracting solution progressively be reduced to 8-9, in the situation that pH value is no longer gone up, then stirs more than l hour;
Subordinate phase continues to stir tennecetin essence extracting solution while slowly drips acid, make the pH value of tennecetin essence extracting solution progressively be reduced to 6-7, in the situation that pH value is no longer gone up, then stir more than 3 hours, obtain the crystal solution of the tennecetin crystal of sheet;
F, the crystal solution of tennecetin crystal that step e is obtained are carried out liquid-solid separation, and then vacuum-drying obtains sheet tennecetin crystal.
2. the preparation method of tennecetin tabular crystal according to claim 1, is characterized in that: the methyl alcohol described in step a and the volume ratio of water are 73: 27, and the mixed solution of every 1L methyl alcohol and water adds 100g tennecetin mycelium.
3. the preparation method of tennecetin tabular crystal according to claim 1, is characterized in that: in step e, the first stage, in the situation that pH value is no longer gone up, then stir 1 hour; Subordinate phase, in the situation that pH value is no longer gone up, then stirs 3-5 hour.
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| CN104876989B (en) * | 2015-05-14 | 2017-10-20 | 浙江新银象生物工程有限公司 | A kind of preparation method of natamycin acicular crystal |
| CN108659075A (en) * | 2018-06-19 | 2018-10-16 | 苏州汉德瑞生物工程有限公司 | A kind of preparation method of novel polymolecularity Natamycin |
| US11591360B2 (en) * | 2018-08-16 | 2023-02-28 | Dsm Ip Assets B.V. | Epoxide polyene amphoteric macrolide and process for purifying natamycin |
| CN110790801B (en) * | 2019-11-19 | 2021-05-04 | 浙江新银象生物工程有限公司 | Preparation method of high-purity white natamycin |
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| US3892850A (en) * | 1956-03-13 | 1975-07-01 | Gist Brocades Nv | Pimaricin and process of producing same |
| US5942611A (en) * | 1995-01-19 | 1999-08-24 | Cultor Ltd. | Process for natamycin recovery |
| CN1515678A (en) * | 2003-08-25 | 2004-07-28 | 天津科技大学 | Preparation method of natamycin |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3892850A (en) * | 1956-03-13 | 1975-07-01 | Gist Brocades Nv | Pimaricin and process of producing same |
| US5942611A (en) * | 1995-01-19 | 1999-08-24 | Cultor Ltd. | Process for natamycin recovery |
| CN1515678A (en) * | 2003-08-25 | 2004-07-28 | 天津科技大学 | Preparation method of natamycin |
Non-Patent Citations (2)
| Title |
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| 殷昊等.纳他霉素分离技术的研究进展.《食品工业科技》.2007,第28卷(第07期),244-246. |
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