CN108160043A - A kind of preparation method of antibiont support type collagen fiber adsorption material - Google Patents

A kind of preparation method of antibiont support type collagen fiber adsorption material Download PDF

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CN108160043A
CN108160043A CN201711363771.7A CN201711363771A CN108160043A CN 108160043 A CN108160043 A CN 108160043A CN 201711363771 A CN201711363771 A CN 201711363771A CN 108160043 A CN108160043 A CN 108160043A
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dry
antibiont
collagenous fibres
mass ratio
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谷友宝
蒋益
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28059Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078Pore diameter
    • B01J20/28085Pore diameter being more than 50 nm, i.e. macropores
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to a kind of preparation methods of antibiont support type collagen fiber adsorption material, belong to sorbing material technical field.The present invention to Chinese prickly ash albumen by carrying out enzymolysis processing, extract antibacterial peptide, it is coated by antibacterial peptide to collagenous fibres surface, by antibacterial peptide under potassium peroxydisulfate hydrolysis, cross-linked graft and coating modification, load of the bacterium on collagenous fibres surface is effectively prevent by antibacterial peptide, improves the antibiont load performance of collagenous fibres;And the present invention hydrolyzed by potassium peroxydisulfate after form sulfonic acid group, collagenous fiber material surface is modified, enhance modified collagenous fibres degree of scatter, improve adsorption capacity of the sorbing material to adsorbate simultaneously, and make to form cross-linked network inside collagenous fibres, the absorption property of material is effectively improved by the cross-linked structure of formation, so as to effectively improve the absorption property of collagen-based materials.

Description

A kind of preparation method of antibiont support type collagen fiber adsorption material
Technical field
The present invention relates to a kind of preparation methods of antibiont support type collagen fiber adsorption material, belong to sorbing material technology Field.
Background technology
Collagenous fibres are the linear chain structure albumen of a kind of appearance white, transparent natural fiber, are largely present in lactation The skin histology of class animal is tied in hoof tissue and bone tissue, and content accounts for about 25%~33% left side of animal vivo protein total amount The right side is the most protein of animal in-vivo content, has very important effect to protection body, support organ.According to collagen Fiber to the difference of animal body concrete function, can generally be classified as basement membrane collagen, non-dimension collagen, anchoring collagen, cross-film collagen, Fento collagen, the netted collagen in six sides and collagenous fibres with other special roles etc..In α-peptide chain of collagenous fibres molecule Containing a large amount of acid and alkaline amino acid residue, all there are carboxyl and amino in every peptide chain both ends, therefore collagenous fibres have Certain isoelectric point is a kind of amphiprotic substance.In addition, also containing a large amount of-COOH ,-NH in collagenous fibres molecular side chain2、- NH-CO- ,-OH isoreactivity group have very high chemism in aqueous solution, can be combined with water molecules hydrogen bond, hydrophilic insoluble Yu Shui, in water in solvent swelling state, therefore the water absorbing capacity of collagenous fibres is very strong.In addition, peptide is existed simultaneously between collagenous fibres Ionic bond, hydrogen bond, Van der Waals force, hydrophobic bond and intermolecular Aldehyde-ammonia Condensation, aldol condensation and aldehyde alcohol histidine between chain The effects that power so that being completely embedded between tropocollagen molecule, the comprehensive strength for leading to collagenous fibres are higher.These knots of collagenous fibres Structure feature determines the good characteristics such as its good mechanical strength and stronger biocompatibility, increasingly causes researcher's Extensive concern.
Collagenous fibres are emerging with the research that its unique structure and biology performance increasingly cause absorption both at home and abroad to learn expert Interest, and its application in Industrial Wastewater Treatment is also increasingly extensive, cannot be only used for the metal ions waste water such as Cr, Cu, Fe Adsorption treatment, it may also be used for the substances such as the removing of tannin and Wastewater Dyes, enzyme, microorganism and protein in Chinese medicine preparation Removal.In addition, pretreatment, chemistry are passed it through containing a large amount of collagenous fibres in the solid waste generated in leather making process Industrial wastewater is handled as sorbing material after the processes such as modified, efficiently using for Leather Solid Waste can be not only realized, subtract Few environmental pollution, and the processing cost of industrial wastewater can be also reduced, enhance economic benefit, there is higher researching value.But Be existing collagenous fibres sorbent material due to being collagen-based materials, easily by microorganism and bacterial load, block absorption hole, lead Sorbent material absorption property is caused to lower, absorption is invalid, so prepare a kind of sorbent material of effective antibiont load has very much It is necessary.
Invention content
The technical problems to be solved by the invention:For Heat Conduction Material in use, long-time heat conduction processing makes it The problem of changing with volume stability easily is expanded, provides a kind of preparation side of low expansion high heat conduction carbon composite Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
(1)It takes fresh Chinese prickly ash seed and crushes, dry Chinese prickly ash seed powder, in mass ratio 1:25, by Chinese prickly ash seed powder It is stirred, is heated to reflux with ethylene glycol, standing is cooled to room temperature, and filters to obtain filter cake, in mass ratio 1:10, by filter cake and quality A concentration of 10% hydrochloric acid solution is stirred, and is centrifuged and is collected lower sediment, washing, dry desiccation protein;
(2)In mass ratio 1:5, desiccation protein and deionized water are stirred, pH to 6.0~6.5 is adjusted, obtains mixed liquor, it will Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid;
(3)It takes pig bone and crushes, vacuum freeze drying must dry skeletal grain, in mass ratio 1:10, by dry skeletal grain and in mass ratio 1:10, dry skeletal grain is added in glacial acetic acid, heating water bath, after being rinsed 3~5 times with deionized water, vacuum freeze drying is simultaneously Collagenous fibres must be dried;
(4)It counts in parts by weight, weighs 45~50 parts of enzymolysis liquids, 15~20 parts of dry collagenous fibres, 6~8 parts of persulfuric acid respectively Potassium and 2~3 parts of glyoxalic acids are placed in three-necked flask, adjust pH to 7.0, and heating water bath, standing is cooled to room temperature and filter residue, Washing, drying can be prepared into a kind of antibiont support type collagen fiber adsorption material.
Step(1)The temperature that is heated to reflux is 55~60 DEG C.
Step(2)The pepsin additive amount is 50U/g.
Step(4)The adjusting pH is using 5% sodium hydroxide of mass fraction.
Compared with other methods, advantageous effects are the present invention:
(1)The present invention extracts antibacterial peptide, is coated by antibacterial peptide to collagenous fibres table by carrying out enzymolysis processing to Chinese prickly ash albumen Face, by antibacterial peptide under potassium peroxydisulfate hydrolysis, cross-linked graft and coating modification effectively prevent bacterium to exist by antibacterial peptide The load on collagenous fibres surface improves the antibiont load performance of collagenous fibres;
(2)The present invention forms sulfonic acid group after being hydrolyzed by potassium peroxydisulfate, and collagenous fiber material surface is modified, makes modification Collagenous fibres degree of scatter enhances afterwards, while improves adsorption capacity of the sorbing material to adsorbate, and makes shape inside collagenous fibres Cross-linked structure is reticulated, the absorption property of material is effectively improved by the cross-linked structure of formation, so as to effectively improve collagen-based materials Absorption property.
Specific embodiment
It takes fresh Chinese prickly ash seed and crushes, dry Chinese prickly ash seed powder, then in mass ratio 1:25, by Chinese prickly ash seed Powder is stirred with ethylene glycol, and 4~5h is heated to reflux at 55~60 DEG C, and standing is cooled to room temperature, and filter cake is filtered to obtain, by matter Measure ratio 1:10, filter cake is stirred, then the centrifugation point under 1200~1300r/min with mass concentration for 10% hydrochloric acid solution From and collect lower sediment, be washed with distilled water 3~5 times, be dried in vacuo to obtain desiccation protein, then in mass ratio 1:5, by dry egg It is stirred in vain with deionized water, with the salt acid for adjusting pH that mass concentration is 10% to 6.0~6.5, obtains mixed liquor, then press stomach egg White enzyme additive amount 50U/g, pepsin is added in mixed liquor, and 3~5h of heat preservation enzymolysis, heats and boil 10 at 30~35 DEG C ~15min, standing are cooled to room temperature, and obtain enzymolysis liquid;It takes pig bone and crushes, vacuum freeze drying must dry skeletal grain, in mass ratio 1:10, by dry skeletal grain and in mass ratio 1:10, dry skeletal grain is added in glacial acetic acid, the heating water bath 2 at 45~50 DEG C After~3h, and with after deionized water flushing 3~5 times, vacuum freeze drying simultaneously must dry collagenous fibres and count in parts by weight, point It also known as measures 45~50 parts of enzymolysis liquids, 15~20 parts of dry collagenous fibres, 6~8 parts of potassium peroxydisulfates and 2~3 parts of glyoxalic acids and is placed in three In mouth flask, pH to 7.0,2~3h of heating water bath at 75~80 DEG C are adjusted with 5% sodium hydroxide of mass fraction, stands cooling To room temperature and filter residue, after being rinsed 3~5 times with deionized water, vacuum freeze drying can be prepared into a kind of antibiont load Type collagen fiber sorbing material.
Example 1
It takes fresh Chinese prickly ash seed and crushes, dry Chinese prickly ash seed powder, then in mass ratio 1:25, by Chinese prickly ash seed powder It is stirred with ethylene glycol, 4h is heated to reflux at 55 DEG C, standing is cooled to room temperature, and filters to obtain filter cake, in mass ratio 1:10, it will Filter cake is stirred, then centrifuged under 1200r/min and collect lower sediment with the hydrochloric acid solution that mass concentration is 10%, It is washed with distilled water 3 times, is dried in vacuo to obtain desiccation protein, then in mass ratio 1:5, desiccation protein and deionized water are stirred mixed It closes, with the salt acid for adjusting pH that mass concentration is 10% to 6.0, mixed liquor is obtained, then by pepsin additive amount 50U/g, by stomach cardia Enzyme is added in mixed liquor, and heat preservation enzymolysis 3h, heats and boil 10min, standing is cooled to room temperature, and obtains enzymolysis liquid at 30 DEG C;It takes Pig bone simultaneously crushes, and vacuum freeze drying must dry skeletal grain, in mass ratio 1:10, by dry skeletal grain and in mass ratio 1:10, it will be dry Dry skeletal grain be added to glacial acetic acid in, at 45 DEG C after heating water bath 2h, and with deionized water rinse 3 times after, vacuum freeze drying And collagenous fibres must be dried and counted in parts by weight, 45 parts of enzymolysis liquids, 15 parts of dry collagenous fibres, 6 parts of persulfuric acid are weighed respectively Potassium and 2 parts of glyoxalic acids are placed in three-necked flask, and pH to 7.0, the heating water bath at 75 DEG C are adjusted with 5% sodium hydroxide of mass fraction 2h, standing is cooled to room temperature and filter residue, and after being rinsed 3 times with deionized water, vacuum freeze drying can be prepared into a kind of anti- Biological load type collagen fiber sorbing material.
Example 2
It takes fresh Chinese prickly ash seed and crushes, dry Chinese prickly ash seed powder, then in mass ratio 1:25, by Chinese prickly ash seed powder It is stirred with ethylene glycol, 4h is heated to reflux at 57 DEG C, standing is cooled to room temperature, and filters to obtain filter cake, in mass ratio 1:10, it will Filter cake is stirred, then centrifuged under 1250r/min and collect lower sediment with the hydrochloric acid solution that mass concentration is 10%, It is washed with distilled water 4 times, is dried in vacuo to obtain desiccation protein, then in mass ratio 1:5, desiccation protein and deionized water are stirred mixed It closes, with the salt acid for adjusting pH that mass concentration is 10% to 6.2, mixed liquor is obtained, then by pepsin additive amount 50U/g, by stomach cardia Enzyme is added in mixed liquor, and heat preservation enzymolysis 4h, heats and boil 12min, standing is cooled to room temperature, and obtains enzymolysis liquid at 32 DEG C;It takes Pig bone simultaneously crushes, and vacuum freeze drying must dry skeletal grain, in mass ratio 1:10, by dry skeletal grain and in mass ratio 1:10, it will be dry Dry skeletal grain be added to glacial acetic acid in, at 47 DEG C after heating water bath 2h, and with deionized water rinse 4 times after, vacuum freeze drying And collagenous fibres must be dried and counted in parts by weight, 47 parts of enzymolysis liquids, 17 parts of dry collagenous fibres, 7 parts of persulfuric acid are weighed respectively Potassium and 2 parts of glyoxalic acids are placed in three-necked flask, and pH to 7.0, the heating water bath at 77 DEG C are adjusted with 5% sodium hydroxide of mass fraction 2h, standing is cooled to room temperature and filter residue, and after being rinsed 4 times with deionized water, vacuum freeze drying can be prepared into a kind of anti- Biological load type collagen fiber sorbing material.
Example 3
It takes fresh Chinese prickly ash seed and crushes, dry Chinese prickly ash seed powder, then in mass ratio 1:25, by Chinese prickly ash seed powder It is stirred with ethylene glycol, 5h is heated to reflux at 60 DEG C, standing is cooled to room temperature, and filters to obtain filter cake, in mass ratio 1:10, it will Filter cake is stirred, then centrifuged under 1300r/min and collect lower sediment with the hydrochloric acid solution that mass concentration is 10%, It is washed with distilled water 5 times, is dried in vacuo to obtain desiccation protein, then in mass ratio 1:5, desiccation protein and deionized water are stirred mixed It closes, with the salt acid for adjusting pH that mass concentration is 10% to 6.5, mixed liquor is obtained, then by pepsin additive amount 50U/g, by stomach cardia Enzyme is added in mixed liquor, and heat preservation enzymolysis 5h, heats and boil 12min, standing is cooled to room temperature, and obtains enzymolysis liquid at 35 DEG C;It takes Pig bone simultaneously crushes, and vacuum freeze drying must dry skeletal grain, in mass ratio 1:10, by dry skeletal grain and in mass ratio 1:10, it will be dry Dry skeletal grain be added to glacial acetic acid in, at 50 DEG C after heating water bath 3h, and with deionized water rinse 5 times after, vacuum freeze drying And collagenous fibres must be dried and counted in parts by weight, 50 parts of enzymolysis liquids, 20 parts of dry collagenous fibres, 8 parts of persulfuric acid are weighed respectively Potassium and 3 parts of glyoxalic acids are placed in three-necked flask, and pH to 7.0, the heating water bath at 80 DEG C are adjusted with 5% sodium hydroxide of mass fraction 3h, standing is cooled to room temperature and filter residue, and after being rinsed 5 times with deionized water, vacuum freeze drying can be prepared into a kind of anti- Biological load type collagen fiber sorbing material.
Example 1,2,3 prepared by the present invention is tested for the property, minimal inhibitory concentration≤4mgAg/L.Simultaneously For the present invention by repeated using still having higher antibacterial activity after 5 times to this sorbing material, specific surface area is reachable 5.6398m2/ g, average adsorption aperture position 152.

Claims (4)

1. a kind of preparation method of antibiont support type collagen fiber adsorption material, it is characterised in that specifically preparation process is:
(1)It takes fresh Chinese prickly ash seed and crushes, dry Chinese prickly ash seed powder, in mass ratio 1:25, by Chinese prickly ash seed powder It is stirred, is heated to reflux with ethylene glycol, standing is cooled to room temperature, and filters to obtain filter cake, in mass ratio 1:10, by filter cake and quality A concentration of 10% hydrochloric acid solution is stirred, and is centrifuged and is collected lower sediment, washing, dry desiccation protein;
(2)In mass ratio 1:5, desiccation protein and deionized water are stirred, pH to 6.0~6.5 is adjusted, obtains mixed liquor, it will Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid;
(3)It takes pig bone and crushes, vacuum freeze drying must dry skeletal grain, in mass ratio 1:10, by dry skeletal grain and in mass ratio 1:10, dry skeletal grain is added in glacial acetic acid, heating water bath, after being rinsed 3~5 times with deionized water, vacuum freeze drying is simultaneously Collagenous fibres must be dried;
(4)It counts in parts by weight, weighs 45~50 parts of enzymolysis liquids, 15~20 parts of dry collagenous fibres, 6~8 parts of persulfuric acid respectively Potassium and 2~3 parts of glyoxalic acids are placed in three-necked flask, adjust pH to 7.0, and heating water bath, standing is cooled to room temperature and filter residue, Washing, drying can be prepared into a kind of antibiont support type collagen fiber adsorption material.
2. a kind of preparation method of antibiont support type collagen fiber adsorption material according to claim 1, feature exist In:Step(1)The temperature that is heated to reflux is 55~60 DEG C.
3. a kind of preparation method of antibiont support type collagen fiber adsorption material according to claim 1, feature exist In:Step(2)The pepsin additive amount is 50U/g.
4. a kind of preparation method of antibiont support type collagen fiber adsorption material according to claim 1, feature exist In:Step(4)The adjusting pH is using 5% sodium hydroxide of mass fraction.
CN201711363771.7A 2017-12-18 2017-12-18 A kind of preparation method of antibiont support type collagen fiber adsorption material Pending CN108160043A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110820331A (en) * 2019-11-25 2020-02-21 张威劲 Preparation method of high-strength anti-wrinkle finishing agent material for natural fiber fabric
CN115336620A (en) * 2022-08-22 2022-11-15 山东海奥斯生物科技股份有限公司 Process for preparing casing by utilizing collagen fibers recovered from waste water

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JP2009240889A (en) * 2008-03-31 2009-10-22 Nara Prefecture Gas adsorbent and gas adsorbing filter using the same
CN102744043A (en) * 2012-07-02 2012-10-24 陕西科技大学 Synthesis method of carboxylation modified collagen fiber adsorbent
CN105132506A (en) * 2015-09-28 2015-12-09 昆明理工大学 Preparation method of chili seed antibacterial peptide
CN105594758A (en) * 2015-12-28 2016-05-25 常州思宇环保材料科技有限公司 Preparation method of silver-loaded protein controlled-release disinfectant for animals
CN107138137A (en) * 2017-06-08 2017-09-08 四川大学 A kind of antibiotic property amidoxime group extraction of uranium from seawater adsorbent and preparation method thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110820331A (en) * 2019-11-25 2020-02-21 张威劲 Preparation method of high-strength anti-wrinkle finishing agent material for natural fiber fabric
CN115336620A (en) * 2022-08-22 2022-11-15 山东海奥斯生物科技股份有限公司 Process for preparing casing by utilizing collagen fibers recovered from waste water

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