CN106334540B - One kind removing endotoxic adsorbent and preparation method thereof for blood or plasma perfusion - Google Patents
One kind removing endotoxic adsorbent and preparation method thereof for blood or plasma perfusion Download PDFInfo
- Publication number
- CN106334540B CN106334540B CN201610879594.7A CN201610879594A CN106334540B CN 106334540 B CN106334540 B CN 106334540B CN 201610879594 A CN201610879594 A CN 201610879594A CN 106334540 B CN106334540 B CN 106334540B
- Authority
- CN
- China
- Prior art keywords
- carrier
- adsorbent
- carbon nano
- nano tube
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/765—Polymers containing oxygen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/44—Elemental carbon, e.g. charcoal, carbon black
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- External Artificial Organs (AREA)
Abstract
The present invention relates to the adsorbents and preparation method thereof for blood or plasma perfusion removal endotoxin (lipopolysaccharides).The adsorbent is a kind of nano composite structure adsorbent, it is using large aperture polyvinyl alcohol as carrier, with amine (ammonium) base carbon nano tube (single wall or multi wall) for aglucon, with epoxychloropropane or glutaraldehyde etc. for crosslinking agent, aglucon is made to be made with carrier microballoons covalent coupling.The adsorbent is prepared simply, and induced by endotoxin absorption property is good.It is suitable for removing the excessive endotoxin of patient's body for blood or plasma perfusion.
Description
Technical field：
The invention belongs to biomedicine technical fields.Be related to for blood perfusion removal blood in endotoxic adsorbent and
Preparation method.
Technical background：
Endotoxin (ET) is a kind of pyrogenic substances that toxicity is extremely strong, usually by cell wall institute after gram-negative bacteria death
The lipopolysaccharides (LPS) of release, lipopolysaccharides form endotoxemia after entering blood.Endotoxemia is that a kind of clinic is common
One of fatal disease, the death rate are up to 40%-90%.The U.S., Europe and Japan have nearly 4,000,000 people to suffer from endotoxin blood every year
Disease, because of the excessive use of antibiotic, annual endotoxemia patient is also up to millions of people, and there is no at present effective in China
Treatment means.
Blood perfusion technique can effectively remove the total toxin and morbid substance of blood, and be widely used in a variety of diseases
Treatment.In Europe, the United States, Deng states, wherein being successfully applied to face by the cellulose spherical adsorbent of aglucon of polymyxin B
Bed, to remove the endotoxin of too high levels in blood, domestic and foreign scholars also have more research to report the product, but because mostly viscous
Rhzomorph B aglucons fall off and toxicity problem, and Countries food and medicine Surveillance Authority FDA has been alerted uses the product with caution.
And there are no the clinical applications of such product so far in China.
Many effort have also been made in domestic scholars or industrial circle, applied many patents such as 200810028948.2,
ZL03144383.4,200510046452.4 etc. are respectively using cellulose, chitosan, Ago-Gel as carrier, with endotoxin parent
Adsorbent is made for aglucon with molecule, though good vitro Adsorption effect is achieved, because support strength is poor, ligand cou amount is small
The problems such as to practical application bring obstacle.In order to improve the intensity of adsorbent, patent 200180040297.9,
201310161110.1 wait using styrene-divinylbenzene as skeleton, and covalent modification small molecule aglucon prepares endotoxin absorbent, but
Because such adsorbent average aperture is smaller (5-10nm or so), and LPS molecular weight is generally more than 100,000 dalton, molecule
Size is larger, cannot fully be efficiently entering adsorbent endoporus, simultaneously because the hydrophobic effect of such carrier is stronger, lacks to blood
The adsorptive selectivity of middle beneficial proteins.201110113987.4 then patent is connect again using grafting molecules cluster on agarose carrier
Branch lysine or glycine betaine are made endotoxin absorbent, molecular cluster as a macromolecular due to space steric effect, in carrier
On supported quantity it is limited, and complex manufacturing process is expensive.Using polymyxin B as the adsorbent of endotoxin affinity ligand
There are more research, but the potential kidney of polymyxin B and neurotoxicity, it is made to increase all multi-risk Systems, the U.S. in clinical application
FDA has issued warning to the application of the product.Therefore, it is good to develop a kind of biocompatibility, it can selective absorption endogenous toxic material
Element, and beneficial proteins in less absorption blood, and endotoxin absorbent product simple for process are that Present clinical is badly in need of, have
The product of Important Economic and social value.
Invention content：
It is an object of the invention to overcome deficiencies of the prior art, provides and a kind of novel can be used for blood perfusion
Remove endotoxic adsorbent and preparation method thereof in blood or blood plasma.
It is a kind of nano composite structure to remove endotoxic adsorbent provided by the present invention for blood or plasma perfusion
Adsorbent, be using porosity large aperture polyvinyl alcohol as carrier, using single wall or multi wall amine (ammonium) base carbon nano tube as aglucon, with
Epoxychloropropane or glutaraldehyde as cross linker make aglucon and carrier covalent coupling and manufactured new selective Endotoxin adsorption
Agent, the load capacity of aglucon is in 10-50mg/mL on carrier.
The PVA Carrier is spherical shape, and granularity is between 100-500um, and hydroxy radical content is in 100- on carrier bracket
Between 900umol/ml；Carrier material is porous structure, and pore-size distribution is between 50-500nm, between preferably 50-100nm.
The adsorbent aglucon is amine (ammonium) base carbon nano tube (single wall or multi wall), amine (ammonium) base content on nanotube
Between 0.1%-1%, length of carbon nanotube is between 0.5-5 microns, between carbon nanotube diameter 0.5-100nm.Carbon nanometer
Amine (ammonium) base can be covalently bonded by being crosslinked arm and carrier on pipe.
The preparation method that endotoxic adsorbent is removed provided by the present invention for blood or plasma perfusion includes following step
Suddenly：
1, macromolecule carrier (polyvinyl alcohol-triallyl isocyanate copolymer) microballoon synthesizes；
1.1 polymerization：Monomer vinyl acetate, crosslinking agent Triallyl isocyanurate, pore-foaming agent ethyl acetate and positive heptan
The mixture of alkane mixes in proportion, and appropriate (generally taking 0.5%-2%) initiator azodiisobutyronitrile is added, adds after dissolving
Enter in the aqueous solution containing polyvinyl alcohol and sodium chloride, adjustment mixing speed is evenly dispersed to drop, and heating causes polymerization, solidification.
After completion of the reaction, go out ball, ethyl alcohol dries after fully washing, and secure satisfactory grades subcarrier microballoon.
1.2 alcoholysis：Above-mentioned polymer microballoon is added in sodium hydrate methanol solution and carries out ester exchange reaction, reaction finishes
It is fully washed, is dried with methanol afterwards, the subcarrier that secures satisfactory grades (polyvinyl alcohol-triallyl isocyanate copolymer) microballoon.
2, support-activated
Carrier is activated with known reagent and method, such as epoxychloropropane and glutaraldehyde, but is not limited to these,
Washes clean after activation.
3, aglucon is fixed
Carrier microballoons and 0.1-2 times of amount (weight ratio) amine (ammonium) base carbon nano tube (single wall or multi wall) after activation are super
It is reacted at sound effect is 20-50 DEG C lower, after completion of the reaction abundant washes clean.
The concrete operations of first step macromolecule carrier microballoon of the present invention synthesis are：
In monomer vinyl acetate and crosslinking agent Triallyl isocyanurate with weight ratio 0.5-5:1 mixed system
In, (mass ratio of pore-foaming agent ethyl acetate and normal heptane is 0.5-2 to the pore-foaming agent of 0.5-5 times of mixed system of addition (volume ratio):
1) initiator azodiisobutyronitrile for accounting for mixed system weight 0.1%-2%, is added in mass ratio, is warming up to after stirring and dissolving
30-50 DEG C, it is then added to the sodium-chloride water solution of the polyvinyl alcohol containing 0.5%-2% and 0.5%-10% of 1-10 times of volume
In, stirring is allowed to be uniformly dispersed, and is warming up to 60-85 DEG C and polymerize 2-6 hours, then be warming up to 85-95 DEG C, polymerize 1-5 hours, reaction
After, filtering is fully washed with water, ethyl alcohol successively, is added in sodium hydroxide-methanol solution after dry and is carried out alcoholysis, instead
It is fully washed with methanol after answering, is dry to get macromolecule carrier polymer microballoon.
The coupling of macromolecule carrier microballoon and aglucon of the present invention is carried out occasionally by method known to document and reaction condition
Connection, can be by first activated carrier microballoon, then immobilized ligands；Also can directly come coupling carrier and be matched with bifunctional coupling agents
Base.
When being prepared the present invention relates to macromolecule carrier microballoon, the weight ratio of reaction monomers and crosslinking agent is preferably 0.5-5：1, it is excellent
Select 1-4:1.
Aglucon of the present invention【Amine (ammonium) base carbon nano tube (single wall or multi wall)】Fixed amount is 20-120mg/ml,
It is preferred that 40-100mg/ml.
The adsorbent that the present invention designs has higher mechanical strength and physical and chemical stability, and conventional method can be used such as
Damp and hot and ray sterilizing etc..
Adsorbent provided by the invention can be used for blood plasma or whole blood perfusion is used to remove the endotoxin in blood samples of patients, be used for
Treat the relevant disease of endotoxemia.
The advantages of the present invention
The present invention designs according to endotoxic molecular size and surface chemical property is combined and has synthesized large aperture polyvinyl alcohol
Microballoon, then grafting carries amine (ammonium) base carbon nano tube with endotoxin surface opposite charges inside or outside microballoon aperture
(single wall or multi wall), prepares the adsorbent with nano composite structure, which has larger aperture,
Endotoxin molecule can be freely accessible to absorbent interior, while carbon nanotube hydrophobic effect and nano effect (small-size effect etc.)
It is cooperateed with the electrostatic force of amine/ammonium in carbon nanotube, greatly improves the adsorption capacity of adsorbent induced by endotoxin.Absorption is real
It tests and shows that endotoxin absorbent of the invention has excellent adsorption capacity to the endotoxin in blood, can be used for treating endogenous toxic material
Plain mass formed by blood stasis.
Specific implementation mode
Embodiment 1
(1) prepared by carrier microballoons
Respectively by 15g vinyl acetates, 30g triallyl second cyanurates, 15ml ethyl acetate and 30ml normal heptanes add
Enter to tri- mouthfuls of 2000ml it is flat in, be warming up to 30 DEG C, be stirring evenly and then adding into 0.9g azo-bis-isobutyl cyanides, 1500ml is added after dissolving
Aqueous solution (sodium chloride containing 0.5% polyvinyl alcohol and 10%), adjustment mixing speed make drop to suitable size and disperse
Uniformly, 65 DEG C are warming up to, heat preservation polymerization 2 hours then heats to 85 DEG C in heat preservation 2 hours, filters to obtain white sphere polymers.
White sphere polymers water, ethyl alcohol fully clean successively, dry.The above-mentioned white sphere polymers dried are added to 2%
NaOH methanol solutions in, in 40 DEG C of alcoholysis reactions 12 hours, after completion of the reaction, filter, methanol fully washs, dry to get
Required carrier microballoons.Carrier microballoons grain size 150-450um, average pore size 100nm, hydroxy radical content is that 120umol/ml carriers are micro-
Ball.
(2) carrier microballoons activate
150ml dimethyl sulfoxide (DMSO)s, 100ml epoxychloropropane, with the hydrogen of 3mol/L is added in the carrier microballoons for taking 15g to dry
Sodium oxide molybdena adjusts pH10-11, and 40 DEG C are reacted 3 hours, distillation water wash to neutrality, and survey epoxide number is 80umol/ml carrier microballoons.
(3) amido carbon nanotube aglucon is fixed
Carrier microballoons 10ml after activating is weighed, be added to the advance ultrasonic disperses of 50ml contains 1% aminated multi-wall carbon nano-tube
In pipe aqueous solution, under ultrasonication, 45 DEG C of concussion reactions 3 hours are fully rinsed after completion of the reaction with distilled water to get to fixation
There are the nano composite structure adsorbent (adsorbent 1) of amido multi-walled carbon nano-tube, content of carbon nanotubes to be adsorbed for 40mg/ml
Agent.
Embodiment 2
(1) prepared by carrier microballoons
20g vinyl acetates, 5g triallyl second cyanurates, 20ml ethyl acetate and 20ml normal heptanes are added respectively
To tri- mouthfuls of 1500ml it is flat in, be warming up to 45 DEG C, be stirring evenly and then adding into 0.5g azo-bis-isobutyl cyanides, 1000ml water is added after dissolving
Solution (sodium chloride containing 1.0% polyvinyl alcohol and 5%), adjustment mixing speed make drop to suitable size and disperse equal
It is even, 75 DEG C are warming up to, heat preservation polymerization 4 hours then heats to 90 DEG C in heat preservation 3 hours, the white sphere polymers of filtering.In vain
Chromosphere shaped polymer water, ethyl alcohol fully clean successively, dry.By it is above-mentioned dry white it is spherical be added to 2% NaOH first
In alcoholic solution, in 45 DEG C of alcoholysis reactions 24 hours, after completion of the reaction, filter, methanol is fully washed, dried to get required carrier
Microballoon.Carrier microballoons grain size 200-400um, average pore size 120nm, hydroxy radical content is 200umol/ml carrier microballoons.
(2) carrier microballoons activate
150ml dimethyl sulfoxide (DMSO)s, 100ml epoxychloropropane, with the hydrogen of 3mol/L is added in the carrier microballoons for taking 15g to dry
Sodium oxide molybdena adjusts pH10-11, and 45 DEG C are reacted 5 hours, distillation water wash to neutrality, and survey epoxide number is 62umol/ml carrier microballoons.
(3) amido carbon nanotube aglucon
Carrier microballoons 10ml after activating is weighed, 1% aminated single-walled carbon nanotube of the advance ultrasonic disperses of 50ml is added to
In aqueous solution, under ultrasonication, 37 DEG C of concussion reactions 5 hours are fully rinsed after completion of the reaction with distilled water to get to being fixed with
The nano composite structure adsorbent (adsorbent 2) of aminated single-walled carbon nanotube, content of carbon nanotubes are 50mg/ml adsorbents.
Embodiment 3
(1) prepared by carrier microballoons
Respectively by 15g vinyl acetates, 15g triallyl second cyanurates, 25ml ethyl acetate and 10ml normal heptanes add
Enter to tri- mouthfuls of 1500ml it is flat in, be warming up to 40 DEG C, be stirring evenly and then adding into 0.3g azo-bis-isobutyl cyanides, 1000ml is added after dissolving
Aqueous solution (sodium chloride containing 1.5% polyvinyl alcohol and 3%), adjustment mixing speed make drop to suitable size and disperse equal
It is even, 65 DEG C are warming up to, heat preservation polymerization 6 hours then heats to 95 DEG C in heat preservation 4 hours, the white sphere polymers of filtering.In vain
Chromosphere shaped polymer water, ethyl alcohol fully clean successively, dry.By it is above-mentioned dry white it is spherical be added to 2% NaOH first
In alcoholic solution, in 40 DEG C of alcoholysis reactions 6 hours, after completion of the reaction, filter, methanol is fully washed, dried micro- to get required carrier
Ball.Carrier microballoons grain size 250-350um, average pore size 80nm, hydroxy radical content is 150umol/ml carrier microballoons.
(2) carrier microballoons activate
80ml dimethyl sulfoxide (DMSO)s, 80ml epoxychloropropane, with the hydrogen-oxygen of 3mol/L is added in the carrier microballoons for taking 10g to dry
Change sodium and adjust pH10-11,40 DEG C are reacted 6 hours, distillation water wash to neutrality, and survey epoxide number is 51umol/ml carrier microballoons.
(3) ammonium carbon nanotube aglucon
Carrier microballoons 10ml after activating is weighed, 0.5% ammonium multi-wall carbon nano-tube of the advance ultrasonic disperses of 50ml is added to
In pipe aqueous solution, under ultrasonication, 30 DEG C of concussion reactions 5 hours are fully rinsed after completion of the reaction with distilled water to get to fixation
It is 30mg/ml adsorbents to have the nano composite structure adsorbent (adsorbent 3) of ammonium multi-walled carbon nanotube, content of carbon nanotubes.
Embodiment 4
(1) prepared by carrier microballoons
Respectively by 10g vinyl acetates, 15g triallyl second cyanurates, 20ml ethyl acetate and 10ml normal heptanes add
Enter to tri- mouthfuls of 1500ml it is flat in, be warming up to 40 DEG C, be stirring evenly and then adding into 0.25g azo-bis-isobutyl cyanides, be added after dissolving
1000ml aqueous solutions (sodium chloride containing 2.0% polyvinyl alcohol and 0.5%), adjustment mixing speed make drop to suitable size
And be uniformly dispersed, 65 DEG C are warming up to, polyase 13 hour is kept the temperature, then heats to 90 DEG C in heat preservation 4 hours, the white of filtering is spherical
Polymer.White sphere polymers water, ethyl alcohol fully clean successively, dry.The above-mentioned white dried spherical is added to 2%
NaOH methanol solutions in, in 45 DEG C of alcoholysis reactions 4 hours, after completion of the reaction, filter, methanol is fully washed, dried to get institute
Need carrier microballoons.Carrier microballoons grain size 200-500um, average pore size 50nm, hydroxy radical content is 120umol/ml carrier microballoons.
(2) carrier microballoons activate
The carrier microballoons for taking 10g to dry, are added the HCl solution of 10% glutaraldehyde water solution 50ml, 0.15mol/L
10ml, 40 DEG C are reacted 6 hours, distillation water wash to neutrality, and survey aldehyde group content value is 105umol/ml carrier microballoons.
(3) amido carbon nanotube aglucon
Carrier microballoons 10ml after activating is weighed, 1.5% aminated multi-wall carbon nano-tube of the advance ultrasonic disperses of 50ml is added to
In pipe aqueous solution, under ultrasonication, 45 DEG C of concussion reactions 5 hours are fully rinsed after completion of the reaction with distilled water to get to fixation
It is 75mg/ml adsorbents to have the nano composite structure adsorbent (adsorbent 4) of amido multi-walled carbon nanotube, content of carbon nanotubes.
Embodiment 5：Contrast test
Be to compare using foreign countries' commercialization endotoxin absorbent (polymyxin B is aglucon), respectively takes above-mentioned 4 kinds of adsorbents and right
It is appropriate according to adsorbent, it is fully eluted totally with sodium chloride injection after moist heat sterilization, accurately weighs 1ml and remove depyrogenation in 25ml
In conical flask, 10ml is added and contains endotoxic blood or blood plasma (endotoxin concns 15EU/ml), after sealing, 37 DEG C in shaking table
In 120 beats/min of concussion absorption 3 hours, then use endogenous toxic material in the front and back blood of chromogenic substrate limulus reagent test detection absorption or blood plasma
The concentration of element calculates adsorption rate, as a result as shown in Table 1, the results showed that, with amine (ammonium) base (single wall or multi wall) carbon nanotube
For the nano composite structure adsorbent of aglucon, compares, have to endotoxin in blood or blood plasma higher with external identical product
Adsorption efficiency.
One adsorbent of table is to endotoxic absorption property in blood plasma and blood
Claims (6)
1. one kind removing endotoxic adsorbent for blood or plasma perfusion, it is characterised in that the adsorbent is that a kind of nanometer is multiple
The adsorbent of structure is closed, the adsorbent is using large aperture polyvinyl alcohol based microballoon as carrier, with single wall amido carbon nano tube, multi wall
Amido carbon nano tube, single wall ammonium carbon nano tube or multi wall ammonium carbon nano tube are aglucon, with epoxychloropropane or penta
Dialdehyde is crosslinking agent, and aglucon and carrier covalent coupling, obtained nano composite structure adsorbent is made to prepare simple, induced by endotoxin
With good absorption property：
The adsorbent is prepared with the following method：
1st step, high-molecular polyivnyl alcohol-triallyl isocyanate copolymerization carrier microballoon synthesis；
1.1st step, polymerization：Monomer vinyl acetate, crosslinking agent Triallyl isocyanurate, pore-foaming agent ethyl acetate and positive heptan
The mixture of alkane is uniformly mixed, and 0.5%-2% initiator azodiisobutyronitriles are added, and is added after dissolving and is contained polyvinyl alcohol and chlorination
In the aqueous solution of sodium, adjustment mixing speed is evenly dispersed to drop, and heating causes polymerization, solidification；After completion of the reaction, go out ball, second
Alcohol dries after fully washing, and obtains polymer microballoon；
1.2nd step, alcoholysis：Above-mentioned polymer microballoon is added in sodium hydrate methanol solution and carries out ester exchange reaction, has been reacted
It is fully washed, is dried, the sub- polyvinyl alcohol that secures satisfactory grades-triallyl isocyanate copolymerization carrier microballoon with methanol after finishing；
It is 2nd step, support-activated
Carrier is activated with known reagent and method, washes clean after activation；
3rd step, aglucon are fixed
Carrier microballoons after activation and by weight 0.1-2 times of the single wall amido carbon nano tube measured, the aminated carbon nanometer of multi wall
Pipe, single wall ammonium carbon nano tube or multi wall ammonium carbon nano tube react under ultrasonication at 20-50 DEG C, after completion of the reaction
Abundant washes clean.
2. adsorbent according to claim 1, it is characterised in that the PVA Carrier is spherical shape, and granularity is in 100-
Between 500um, hydroxy radical content is between 100-900umol/ml on carrier bracket；Carrier material is porous structure, pore-size distribution
Between 50-500nm.
3. adsorbent according to claim 1, it is characterised in that described to exist with amido on base carbon nanotube or ammonium content
Between 0.1%-1%, length of carbon nanotube is between 0.5-5 microns, between carbon nanotube diameter 0.5-100nm, on the carrier
The load capacity of aglucon is in 10-50mg/mL；Amido or ammonium can be covalently bonded by being crosslinked arm and carrier in carbon nanotube.
4. adsorbent according to claim 1, it is characterised in that the specific behaviour that macromolecule carrier microballoon described in the 1st step synthesizes
Make as follows：
In monomer vinyl acetate and crosslinking agent Triallyl isocyanurate with weight ratio 0.5-5:In 1 mixed system, press
0.5-5 times of pore-foaming agent is added in volume ratio, and the mass ratio of ethyl acetate and normal heptane is 0.5-2 in pore-foaming agent:1, in mass ratio
The initiator azodiisobutyronitrile of 0.1%-2% is added, is warming up to 30-50 DEG C after stirring and dissolving, is then added to 1-10 times of volume
The polyvinyl alcohol of 0.5%-2% containing mass percent and 0.5%-10% sodium-chloride water solution in, stirring be allowed to be uniformly dispersed, heat up
It polymerize 2-6 hours to 60-85 DEG C, then is warming up to 85-95 DEG C, polymerize 1-5 hours, after completion of the reaction, water, second are used in filtering successively
Alcohol fully washs, and is added in sodium hydroxide-methanol solution after dry and carries out alcoholysis, fully washed with methanol after completion of the reaction,
Drying is to get macromolecule carrier polymer microballoon.
5. adsorbent according to claim 1, it is characterised in that the aglucon single wall amido carbon nano tube, multi wall amido
The fixed amount of carbon nano tube, single wall ammonium carbon nano tube or multi wall ammonium carbon nano tube is 20-120mg/ml.
6. adsorbent according to claim 5, it is characterised in that the aglucon single wall amido carbon nano tube, multi wall amido
The preferred 40-100mg/ml of fixed amount of carbon nano tube, single wall ammonium carbon nano tube or multi wall ammonium carbon nano tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610879594.7A CN106334540B (en) | 2016-10-09 | 2016-10-09 | One kind removing endotoxic adsorbent and preparation method thereof for blood or plasma perfusion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610879594.7A CN106334540B (en) | 2016-10-09 | 2016-10-09 | One kind removing endotoxic adsorbent and preparation method thereof for blood or plasma perfusion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106334540A CN106334540A (en) | 2017-01-18 |
| CN106334540B true CN106334540B (en) | 2018-07-31 |
Family
ID=57838819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610879594.7A Active CN106334540B (en) | 2016-10-09 | 2016-10-09 | One kind removing endotoxic adsorbent and preparation method thereof for blood or plasma perfusion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106334540B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855003B (en) * | 2018-06-28 | 2021-01-05 | 南开大学 | Immunoadsorbent for removing inflammatory factors in blood and preparation method thereof |
| CN111632202A (en) * | 2020-06-29 | 2020-09-08 | 南开大学 | Tumor cell adhesion material and preparation method and application thereof |
| CN111686704B (en) * | 2020-07-02 | 2023-08-08 | 苏州仝康医疗科技有限公司 | Blood purification adsorbent and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828804A (en) * | 2015-03-25 | 2015-08-12 | 清华大学 | A preparing method of a porous carbon nanotube-charcoal spherical composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10064406B2 (en) * | 2011-01-06 | 2018-09-04 | Cytosorbents Corporation | Polymeric sorbent for removal of impurities from whole blood and blood products |
-
2016
- 2016-10-09 CN CN201610879594.7A patent/CN106334540B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828804A (en) * | 2015-03-25 | 2015-08-12 | 清华大学 | A preparing method of a porous carbon nanotube-charcoal spherical composite material |
Non-Patent Citations (2)
| Title |
|---|
| Novel chitosan/poly(vinyl) alcohol thin adsorptive membranes modified with amino functionalized multi-walled carbon nanotubes for Cu(II) removal from water: Preparation, characterization, adsorption kinetics and thermodynamics;E. Salehi等;《Separation and Purification Technology》;20120210;第89卷;第309-319页 * |
| 多壁碳纳米管与活性炭吸附中分子毒素的比较;李桂芬等;《生物医学工程学杂志》;20110831;第28卷(第4期);第758-762页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106334540A (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baydemir et al. | Selective removal of bilirubin from human plasma with bilirubin-imprinted particles | |
| JP4996791B2 (en) | Endotoxin adsorbent and method for removing endotoxin using the same | |
| Ma et al. | Highly carbonylated cellulose nanofibrous membranes utilizing maleic anhydride grafting for efficient lysozyme adsorption | |
| US6037458A (en) | Adsorbent for serum amyloid protein | |
| Cao et al. | Polymyxin B immobilized on cross-linked cellulose microspheres for endotoxin adsorption | |
| CN106334540B (en) | One kind removing endotoxic adsorbent and preparation method thereof for blood or plasma perfusion | |
| Denizli et al. | Heparin-immobilized polyhydroxyethylmethacrylate microbeads for cholesterol removal: a preliminary report | |
| US5216127A (en) | Adsorbent for serum amyloid protein | |
| Amaly et al. | Copper complex formed with pyridine rings grafted on cellulose nanofibrous membranes for highly efficient lysozyme adsorption | |
| CN103406111A (en) | Adsorbent for removing endotoxin by blood perfusion and preparation method thereof | |
| Esfandyari-Manesh et al. | Dipyridamole recognition and controlled release by uniformly sized molecularly imprinted nanospheres | |
| CN101817932A (en) | Polyamido-amine dendrimers -modified macroporous crosslinked chitosan microsphere and preparation method thereof | |
| KR20200010442A (en) | Polymeric Sorbents, Preparations and Uses thereof | |
| JP2023130402A (en) | Use of hemocompatible porous polymer bead sorbent for removal of endotoxemia-inducing molecules | |
| US11364480B2 (en) | Chromatography medium with bound microglobules and method for the preparation thereof | |
| CN107876031A (en) | A kind of uremia blood-purifying adsorbing agent and preparation method thereof | |
| Ju et al. | Advancement in separation materials for blood purification therapy | |
| Çorman | Poly-l-lysine modified cryogels for efficient bilirubin removal from human plasma | |
| Jung et al. | pH-sensitive cellulose/chitin nanofibrillar hydrogel for dye pollutant removal | |
| Zong et al. | Preparation of PVA/amino multi-walled carbon nanotubes nanocomposite microspheres for endotoxin adsorption | |
| Zhou et al. | Preparation of surface molecularly imprinted polymer and its application for the selective extraction of teicoplanin from water | |
| CN109277085A (en) | A kind of production method of adsorbent for bilirubin | |
| Lv et al. | Fast clean-up and selective enrichment of florfenicol in milk by restricted access media molecularly imprinted magnetic microspheres based on surface-initiated photoiniferter-mediated polymerization | |
| Sahiner et al. | Sucrose based ionic liquid colloidal microgels in separation of biomacromolecules | |
| Zhang et al. | Effects of different spacer arms on Cibacron Blue modification and protein affinity adsorption on magnetic microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |