CN101982469B - Method for removing bacterial endotoxins in cephalosporin antibiotics by utilizing macroporous adsorption resins - Google Patents
Method for removing bacterial endotoxins in cephalosporin antibiotics by utilizing macroporous adsorption resins Download PDFInfo
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- CN101982469B CN101982469B CN2010105175023A CN201010517502A CN101982469B CN 101982469 B CN101982469 B CN 101982469B CN 2010105175023 A CN2010105175023 A CN 2010105175023A CN 201010517502 A CN201010517502 A CN 201010517502A CN 101982469 B CN101982469 B CN 101982469B
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Abstract
The invention discloses a method for removing bacterial endotoxins in cephalosporin antibiotics by utilizing macroporous adsorption resins, comprising the following steps: firstly filtering the cephalosporin antibiotics solution containing the bacterial endotoxins and removing solid insoluble matters; then utilizing the pretreated macroporous adsorption resins to carry out static adsorption or dynamic adsorption on the cephalosporin antibiotics solution; and finally crystallizing, drying and grinding the solution after adsorption treatment, thus obtaining the product with bacterial endotoxins in accordance with the quality standard. The method has the advantages of high bacterial endotoxins removal rate, good selectivity, easy desorption, repeated use, low fluid resistance and easy magnification.
Description
Technical field
The invention belongs to separation technology field, be specifically related to the method that a kind of macroporous adsorbent resin is removed bacterial endotoxin in the cephalosporins.
Background technology
Bacterial endotoxin is the peculiar structure on the gram-negative bacteria cell wall adventitia, and its essence is LPS, on chemical structure, mainly is made up of the two parts, i.e. polysaccharide and lipoid A.Lipoid A is the active site of LPS, mainly is made up of the length fatty acids of GS, phosphatase 11 0～18 carbon, under cynnematin salts solution condition, has hydrophobicity and electronegativity.The intracellular toxin of denier gets into human body will cause high heat, diarrhoea, vasodilation, even faintness or dead.
Because cephalosporins upstream raw material producer adopts enzyme method technique production one after another, make that the bacterial endotoxin index of upstream raw material and corresponding midbody is extremely unstable, and then have influence on the quality product of cephalosporins.Simultaneously because the influence of production environment, production unit and production operation also possibly brought a certain amount of bacterial endotoxin into.In order to obtain the cephalosporins product of constant product quality, safety, study that a kind of production cost is low, to remove the method for bacterial endotoxin efficiently more and more important.
Removal bacterial endotoxin method commonly used has activated carbon method, ion-exchange-resin process, soda acid method of chemical treatment, ultrafiltration process.Wherein ion-exchange-resin process and soda acid method of chemical treatment are not suitable for cephalosporins removal bacterial endotoxin.Activated carbon method is widely used in the removal of bacterial endotoxin at present aborning.But because its absorption to material is not optionally, thereby other materials in the adsorbent solution inevitably.Because activated carbon adsorptive capacity is strong, be difficult for desorb simultaneously, can not reuse.Used ultra-filtration membrane cleans difficulty in the ultrafiltration process, replacement charge is high, resistance to flow is very big, should not handle thick liquid, so the use of ultrafiltration process limits to some extent.
Removing intracellular toxin based on the affinity adsorption of affinity media, have clearance height, advantage that selectivity is high, be the focus of research at present, but it is high to the affinity media material requirements, is not suitable for industrialized production.
Macroporous adsorbent resin is generally white granular, and mostly granularity is the 20-60 order, is one type of novel non-ionic macromolecule compound; Physico-chemical property is stable; Be insoluble in acid, alkali and the organic solvent, good to the organism selectivity, do not receive the influence of inorganic salt plasma and low molecular compound.Macroporous adsorbent resin is not also having report aspect the microbiotic removal bacterial endotoxin.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect of prior art; The advantage that the method that provides a kind of macroporous resin to remove bacterial endotoxin in the cephalosporins, this method have bacterial endotoxin clearance height, selectivity is good, desorb is easy, can use repeatedly, fluid resistance is little, be easy to amplify.
The object of the invention can reach through following measure:
A kind of method that adopts macroporous adsorbent resin to remove bacterial endotoxin in the cephalosporins comprises the steps:
The cephalosporins solution that (1) will contain bacterial endotoxin filters, and removes solid insoluble;
(2) with pretreated macroporous adsorbent resin the cephalosporins antibiotic solution is carried out Static Adsorption processing or dynamic adsorption processing;
(3) solution after the adsorption treatment is carried out crystallization, drying is pulverized.After the pulverizing promptly to bacterial endotoxin meets the cephalosporin antibiotics of industry or enterprise-quality standard, particularly meet the cephalosporin antibiotics of 2010 editions standards of pharmacopoeia.
Cephalosporins solution described in the step (1) is for obtaining the cephalosporins solution of pH value 4～10 through chemical method or biological process reaction.
Generally (bacteria endotoxin content of raw material is as greater than 10EU/mg greater than 0.3EU/mg and less than the raw material of 10EU/mg by bacteria endotoxin content for this cephalosporins solution; Particularly then belonging to defective raw material greater than 15EU/mg need handle in advance); Obtain through chemical method or biological process reaction; If wherein contained cephalosporins is without macroporous resin treatment, and its bacterial endotoxin of the product of gained is greater than standards of pharmacopoeia or company standard behind crystallizing and drying.The bacteria endotoxin content of the cephalosporins solution that general preceding method obtains is greater than 0.05EU/mg.
Present method is very low to the requirement of antibiotic concentration in the solution, and scope is wider, can be 10～300g/L, and this concentration depends primarily on difference, producer not equal of preparation feedback technology, product.
Cephalosporins among the present invention can be all injections type cephalosporins compounds, and corresponding intermediates, or its salt or acid, and it comprises a generation, two generations, three generations, the related prods in four generations.Salt wherein can be any one in sodium salt, sylvite, ammonium salt, the organic amine salt; Described organic amine salt can be triethylamine salt, Tri-n-Propylamine salt, tri-n-butylamine salt, diethylamine, l-arginine, Methionin, any one in the thanomin.
Above-mentioned cephalosporins further can be selected ceftezole, Cephazolin, cephalofruxin, cefotiam, ceftriaxone, cefotaxime, cefoperazone, ceftazime, cefonicid, cefoxitin, cefminox, cefepime or cefpirome; Or its midbody, or its salt or acid.
Cephalosporin antibiotics solution can adopt the mixing solutions of the aqueous solution or water and organic solvent, and it is mainly determined by the preparation process of cephalosporin antibiotics.
Macroporous adsorbent resin need carry out pre-treatment earlier before use, and this pretreatment process is to adopt acetone treatment earlier, is washed till neutrality, adopts sodium-hydroxide treatment again, is washed till neutrality, adopts the salt s.t. at last, is washed till neutrality.Wherein the consumption of acetone is generally 1～3 times of resin volume; Sodium hydroxide can adopt 2～10% the sodium hydroxide solution of 1～3BV, and hydrochloric acid can adopt 2～10% the hydrochloric acid soln of 1～3BV.When regenerating, can adopt back two steps of pretreatment process, promptly adopt sodium-hydroxide treatment earlier, be washed till neutrality, adopt the salt s.t. again, be washed till neutrality adsorbing saturated macroporous adsorbent resin.
Described in the step (2) in the weight in wet base of macroporous adsorbent resin and the cephalosporins solution mass ratio of cephalosporins be 1: 1～1: 10, be preferably 1: 2～1: 5, further preferred 1: 2～1: 4.
Above-mentioned Static Adsorption is treated to pretreated macroporous adsorbent resin with after cephalosporins solution mixes whip attachment, filters, and obtains the solution after the adsorption treatment.
Above-mentioned dynamic adsorption is treated to packs pretreated macroporous adsorbent resin in the packed column into, under 1～5 normal atmosphere, cephalosporins solution is adsorbed through packed column, obtains the solution after the adsorption treatment.
It is the nonpolar adsorption resin of skeleton that macroporous adsorbent resin of the present invention adopts with vinylbenzene, preferred DM1180 resin or DM825 resin.
Solution after the adsorption treatment is carried out the crystalline process can be handled by existing method, as transfers to suitable pH value, adding crystallization reagent etc.
In intermittent type adsorption treatment step, after the employing macroporous adsorbent resin was handled the cephalosporins antibiotic solution, also water or water and organic solvent mixed solvent simply cleaned the remaining small volume of solution of resin again.If the continous way adsorption treatment, this step can not adopt yet.
The present invention makes full use of on the basis of macroporous adsorbent resin characteristic; Macroporous resin is applied to the removal of bacterial endotoxin in the cephalosporins; Substitute existing bacterial endotoxin removal method, thereby obtain the cephalosporins that bacterial endotoxin meets 2010 editions standards of pharmacopoeia.
The present invention has that the bacterial endotoxin clearance is high, selectivity is good, to cephalosporins absorption less, desorb easily, can use repeatedly, fluid resistance is little, the advantage that is easy to amplify.
Embodiment
Come further to explain content of the present invention through following examples, but the embodiment that is provided should not be understood that protection domain of the present invention is constituted restriction.
The macroporous adsorbent resin that uses is available from the DM1180 and the DM825 of Shandong Lukang Record Pharmaceuticals Co., Ltd..The cephalosporins that exists bacterial endotoxin to represent in the preparation process to use bacterial endotoxin to obtain in the solution greater than the raw material reaction of 0.3EU/mg; Without macroporous resin treatment; Its bacterial endotoxin of the product of gained is greater than standards of pharmacopoeia or company standard behind crystallizing and drying, and promptly this index of product is defective.
Macroporous resin passes through pre-treatment before use earlier, and method is following:
(1) with DM1180 or the DM825 resin dress post of packing into,, be washed till tasteless then with pure water with the acetone treatment of 2 times of resin volumes (BV);
(2) sodium hydroxide solution with 2BV5% advances post, and flow velocity 2BV/h finishes the back and soaked 2 hours, is washed till neutrality with pure water;
(3) hydrochloric acid soln with 2BV5% advances post, and flow velocity 2BV/h finishes the back and soaked 2 hours, is washed till neutrality with pure water, can use.
The regeneration of macroporous resin only needs to adopt step (2) and (3) two steps in the pretreatment process to get final product.
Embodiment 1
Obtain the cefotaxime triethylamine salt solution of 1200L bacterial endotoxin through reaction greater than 0.05EU/mg; PH value 8.0, the packed column that band presses (2 normal atmosphere) entering to contain 100kg (weight in wet base) DM1180 macroporous adsorbent resin behind plate-and-frame filter press solids removed by filtration insolubles are carried out dynamic adsorption and are handled.Can also further use water washing resin after disposing.Filtrating through plastic resin treatment is regulated pH to 3.5 with hydrochloric acid, and crystallization obtains cefotaxime acid, obtains the cefotaxime acid of 240kg bacterial endotoxin less than 0.05EU/mg after drying, the pulverizing, and the rate of loss of cefotaxime acid is lower than 0.5%.
Embodiment 2
Obtain the cefotaxime triethylamine salt solution of 40L bacterial endotoxin through reaction greater than 0.05EU/mg; PH8.0; Behind plate-and-frame filter press solids removed by filtration insolubles, normal pressure gets into the packed column that contains 3.5kg (weight in wet base) DM1180 macroporous adsorbent resin down and carries out the dynamic adsorption processing.Filtrating through plastic resin treatment is regulated pH to 3.5 with hydrochloric acid, and crystallization obtains cefotaxime acid, obtains 8kg after drying, the pulverizing, and bacterial endotoxin is less than the cefotaxime acid of 0.05EU/mg, and the rate of loss of cefotaxime acid is lower than 1%.
Embodiment 3
Obtain the ceftriaxone triethylamine salt solution of 100L bacterial endotoxin through reaction greater than 0.15EU/mg; PH8.0, the packed column that band presses (2 normal atmosphere) entering to contain 3.5Kg (weight in wet base) DM1180 macroporous adsorbent resin behind plate-and-frame filter press solids removed by filtration insolubles carry out dynamic adsorption to be handled.The mixing solutions washing resin of water and organic solvent after disposing.Filtrating is added sodium acetate soln, and adds acetone, and crystallization obtains ceftriaxone sodium, obtains 15kg after drying, the pulverizing, and bacterial endotoxin is less than the ceftriaxone sodium of 0.15EU/mg, and the rate of loss of ceftriaxone sodium is lower than 1%.
Embodiment 4
Obtain the ceftezole triethylamine salt solution of 150mL bacterial endotoxin greater than 0.075EU/mg through reaction, organic phase is removed in layering, and water pH7.2 filters, and filtrating adds 8g (weight in wet base) DM825 macroporous adsorbent resin and stirs 30min.Filter, filtrating is regulated pH to 2.0 with hydrochloric acid, and crystallization obtains cefotaxime acid, obtains 25g after drying, the pulverizing, and bacterial endotoxin is less than the ceftezole acid of 0.075EU/mg, and the rate of loss of ceftezole acid is lower than 1%.
Embodiment 5
Obtain the ceftazime triethylamine salt solution of 150mL bacterial endotoxin greater than 0.1EU/mg, pH8.0, solids removed by filtration insolubles through reaction.Filtrating adds 10g (weight in wet base) DM1180 macroporous adsorbent resin and stirs 30min.Filter, filtrating obtains the ceftazime dihydrochloride with acid crystal, obtains 25g after drying, the pulverizing, and bacterial endotoxin is less than the ceftazime acid dihydrochloride of 0.1EU/mg, and the rate of loss of ceftazime acid dihydrochloride is lower than 1%.
Embodiment 6
Obtain the cephalofruxin acid solution through reaction, use NaHCO
3Regulate pH to 6.5, remove organic phase, obtain the cephalofruxin sodium solution of 3L bacterial endotoxin, the solids removed by filtration insolubles greater than 0.1EU/mg.Filtrating pressurization entering contains 80g (weight in wet base) DM825 macroporous absorption tree packed column and carries out the dynamic adsorption processing.Filtrating through plastic resin treatment is regulated pH to 2.0 with hydrochloric acid, and crystallization obtains cefuroxime acid, obtains the cefuroxime acid of 300g bacterial endotoxin less than 0.1EU/mg after drying, the pulverizing.
Embodiment 7
The cefoperazone acid crude of bacterial endotoxin greater than 0.05EU/mg added in the mixture of entry and solvent, add the sodium hydrogencarbonate dissolving again, pH7.5, solids removed by filtration insolubles.Add 20g (weight in wet base) DM1180 macroporous adsorbent resin in the filtrating and stir 30min.Filter, filtrating is regulated pH to 2.0 with hydrochloric acid, and crystallization obtains cefoperazone acid, obtains the cefoperazone acid of 50g bacterial endotoxin less than 0.05EU/mg after drying, the pulverizing.
Embodiment 8
Obtain the cefoxitin acid solution through reaction, use NaHCO
3Regulate pH to 7, remove organic phase, obtain the cefoxitin sodium solution of 500mL bacterial endotoxin, the solids removed by filtration insolubles greater than 0.1EU/mg.Add 5g (weight in wet base) DM825 macroporous adsorbent resin in the filtrating and stir 30min.Filter, filtrating is regulated pH2.5 with hydrochloric acid, and crystallization obtains cefoxitin acid, obtains the cefoxitin acid of 20g bacterial endotoxin less than 0.1EU/mg after drying, the pulverizing.
Embodiment 9
Obtain the cefotiam triethylamine salt solution of 400mL bacterial endotoxin greater than 0.1EU/mg, pH8.0, solids removed by filtration insolubles through reaction.Add 15g (weight in wet base) DM1180 macroporous adsorbent resin in the filtrating and stir 30min.Filter.Add hydrochloric acid and methylene dichloride, stir, remove organic phase.Filtrating is regulated pH to 1.0 with hydrochloric acid, and adds acetone, and crystallization obtains the cefotiam dihydrochloride, obtains the cefotiam dihydrochloride of 50g bacterial endotoxin less than 0.1EU/mg after drying, the pulverizing.
Claims (10)
1. a method that adopts macroporous adsorbent resin to remove bacterial endotoxin in the cephalosporins is characterized in that comprising the steps:
The cephalosporins solution that (1) will contain bacterial endotoxin filters, and removes solid insoluble;
(2) with pretreated macroporous adsorbent resin the cephalosporins antibiotic solution is carried out Static Adsorption processing or dynamic adsorption processing; The pretreatment process of said macroporous adsorbent resin is to adopt acetone treatment earlier, is washed till neutrality, adopts sodium-hydroxide treatment again, is washed till neutrality, adopts the salt s.t. at last, is washed till neutrality;
(3) solution after the adsorption treatment is carried out crystallization, drying is pulverized.
2. method according to claim 1 is characterized in that cephalosporins solution described in the step (1) is for obtaining the cephalosporins solution of pH value 4～10 through chemical method or biological process reaction.
3. method according to claim 1, the bacteria endotoxin content that it is characterized in that cephalosporins solution described in the step (1) is greater than 0.05EU/mg.
4. method according to claim 1, the content that it is characterized in that cephalosporins in the said cephalosporins solution is 10～300g/L.
5. according to arbitrary described method in the claim 1～4; It is characterized in that said cephalosporins is ceftezole, Cephazolin, cephalofruxin, cefotiam, ceftriaxone, cefotaxime, cefoperazone, ceftazime, cefonicid, cefoxitin, cefminox, cefepime or cefpirome, or its salt.
6. method according to claim 1 is characterized in that the mass ratio of cephalosporins in weight in wet base and the cephalosporins solution of macroporous adsorbent resin described in the step (2) is 1: 1～1: 10.
7. method according to claim 1 is characterized in that said Static Adsorption is treated to pretreated macroporous adsorbent resin with after cephalosporins solution mixes whip attachment, filters, and obtains the solution after the adsorption treatment.
8. method according to claim 1; It is characterized in that said dynamic adsorption is treated to packs pretreated macroporous adsorbent resin in the packed column into; Conventional or be forced under 1～5 normal atmosphere cephalosporins solution is adsorbed through packed column, obtain the solution after the adsorption treatment.
9. method according to claim 1 is characterized in that said macroporous adsorbent resin is for being the nonpolar adsorption resin of skeleton with vinylbenzene.
10. method according to claim 9 is characterized in that said macroporous adsorbent resin is DM1180 resin or DM825 resin.
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| CN102295654B (en) * | 2011-08-10 | 2012-07-04 | 江西新先锋医药有限公司 | Cefoxitin compound and composition thereof |
| CN102617605B (en) * | 2012-02-29 | 2014-11-05 | 石药集团中诺药业（石家庄）有限公司 | Ceftriaxone sodium compound and preparation method thereof |
| CN104437339B (en) * | 2014-12-30 | 2017-07-04 | 赖世权 | A kind of macroporous absorbent resin elutes the preprocess method of plant stain |
| CN104667892A (en) * | 2015-02-11 | 2015-06-03 | 北海和思科技有限公司 | Macroporous resin pretreatment method |
| CN104610282B (en) * | 2015-02-14 | 2017-03-15 | 石药集团中诺药业（石家庄）有限公司 | A kind of method of purification of cefazolin |
| CN114601805A (en) * | 2022-01-13 | 2022-06-10 | 南昌立健药业有限公司 | Cefminox sodium powder for injection and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1970780A (en) * | 2006-12-06 | 2007-05-30 | 云南沃森生物技术有限公司 | Process for removing endotoxin in bacteria polysaccharide by using macroporous resin |
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| US7531308B2 (en) * | 2004-04-23 | 2009-05-12 | Sigma-Aldrich Co. | Process for the reduction of endotoxins in a plasmid preparation using a carbohydrate non-ionic detergent with silica chromatography |
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| CN1970780A (en) * | 2006-12-06 | 2007-05-30 | 云南沃森生物技术有限公司 | Process for removing endotoxin in bacteria polysaccharide by using macroporous resin |
Non-Patent Citations (1)
| Title |
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| Rishard H. Chen, et al.Factors affecting endotoxin removal from recombinant therapeutic proteins by anion exchange chromatography.《Protein Expression and Purification》.2008,第64卷76-81. * |
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