CN114835826B - Zwitterionic cellulose and preparation method and application thereof - Google Patents
Zwitterionic cellulose and preparation method and application thereof Download PDFInfo
- Publication number
- CN114835826B CN114835826B CN202210426246.XA CN202210426246A CN114835826B CN 114835826 B CN114835826 B CN 114835826B CN 202210426246 A CN202210426246 A CN 202210426246A CN 114835826 B CN114835826 B CN 114835826B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- zwitterionic
- acid
- carbon
- inner salt
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses zwitterionic cellulose and a preparation method and application thereof. The preparation method comprises the following steps: s1, a sulfhydryl acid compound and sulfamic acid inner salt containing carbon-carbon double bond are subjected to Michael addition reaction of sulfhydryl and carbon-carbon double bond to obtain a zwitterionic intermediate; s2, grafting the zwitterionic intermediate prepared by the operation on cellulose in a homogeneous system to obtain the zwitterionic cellulose. The zwitterionic cellulose is prepared by grafting the zwitterion on the cellulose in homogeneous phase, and has the characteristic of good grafting effect.
Description
Technical Field
The invention belongs to the technical field of zwitterionic materials, and particularly relates to zwitterionic cellulose and a preparation method and application thereof.
Background
Cellulose is a renewable resource with the widest distribution and the largest yield in the nature, and has the characteristics of biodegradability, biocompatibility, derivatization and the like. However, the high crystallinity of cellulose macromolecules results in indissolvable and infusible properties, which limit the development and utilization of cellulose macromolecules as a basic raw material. Therefore, the derivatization of cellulose improves the water solubility and the oil solubility of the cellulose, and can better develop abundant cellulose resources. Wherein zwitterionic cellulose is a derivative of cellulose and is capable of chemically linking the zwitterionic cellulose to hydroxyl groups on the cellulose. The zwitterionic cellulose keeps the original excellent properties of cellulose, and as the zwitterionic cellulose has the same number of positive and negative charges, the whole zwitterionic cellulose is electrically neutral, and a large number of water molecules are strongly adsorbed around the positive and negative ions, so that a hydration layer is formed. The hydration layer can prevent the adsorption of proteins, bacteria and the like on the surface of the natural cellulose, so that the zwitterionic cellulose has superior biocompatibility compared with the natural cellulose. However, at present, most of the preparation methods of zwitterionic cellulose are cellulose surface modification grafting zwitterionic, and the grafting effect is poor.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of zwitterionic cellulose, which grafts the zwitter ion on the cellulose in homogeneous phase to prepare the zwitterionic cellulose, and has the characteristic of good grafting effect.
The invention also provides a preparation method of the zwitterionic cellulose.
The invention also provides the zwitterionic cellulose prepared by the preparation method.
The invention also provides a cellulose gel.
The invention also provides a biological material.
The invention also provides application of the zwitterionic cellulose.
In a first aspect of the present invention, a method for preparing zwitterionic cellulose is provided, comprising the steps of:
s1, a sulfhydryl acid compound and sulfamic acid inner salt containing carbon-carbon double bond are subjected to Michael addition reaction of sulfhydryl and carbon-carbon double bond to obtain a zwitterionic intermediate;
s2, grafting the zwitterionic intermediate prepared by the operation on cellulose in a homogeneous system to obtain the zwitterionic cellulose.
The preparation method of the zwitterionic cellulose has at least the following beneficial effects: the prepared zwitterionic cellulose is prepared by grafting a zwitterionic intermediate on cellulose in a homogeneous system, and is different from the traditional cellulose surface modified grafting zwitterionic, and the zwitterionic cellulose has better zwitterionic grafting effect, and the prepared zwitterionic cellulose has better performance, such as biocompatibility, protein adhesion resistance and the like.
The invention adopts a simple and efficient two-step reaction, has high reaction activity, simple reaction condition and low cost, wherein the reaction of sulfhydryl and carbon-carbon double bond belongs to the Michael addition reaction type in click reaction, and is characterized by high efficiency, atom economy and mild condition. In the invention, cellulose is grafted in homogeneous phase, the selected solvent system is matched with a cellulose dissolution system, the reaction phenomenon is obvious, the obtained zwitterionic cellulose is precipitated and separated out, and the reaction condition can be judged without complicated detection means. The prepared zwitterionic cellulose has more various application modes than surface modification, can be used as an anti-adhesion coating, and can be compounded with other natural biomedical materials to prepare cellulose gel.
In some embodiments of the invention, the process for the preparation is carried out by subjecting the starting material to a dehydration treatment and then to use.
In some embodiments of the invention, the homogeneous system comprises a solvent system or an ionic liquid system comprising dimethylacetamide.
Dimethylacetamide, abbreviated DMAc.
In some preferred embodiments of the invention, the ionic liquid comprises BMIMCl, BMIMBr or BMIM-BF 4 At least one of them.
BMIMCl: 1-butyl-3-methylimidazole chloride; BMIMBr: 1-butyl-3-methylimidazole bromide; BMIM-BF 4 : 1-butyl-3-methylimidazole tetrafluoroborate.
In some embodiments of the invention, the degree of substitution of the resulting zwitterionic cellulose is from 0.6 to 0.9.
In some embodiments of the invention, the cellulose comprises at least one of lyocell, purified cotton, modal, cuprammonium, or viscose.
In some preferred embodiments of the invention, the cellulose comprises lyocell.
Through the above embodiments, the cellulose is lyocell. When dissolved, the solution of the lyocell fiber is more uniform, and the solution is clear and transparent; and further provides a uniform reaction environment for the next reaction, and the reaction effect is better.
In some embodiments of the invention, the thiol-based compound comprises at least one of a thiol fatty acid and a thiol aromatic acid.
In some preferred embodiments of the present invention, the mercaptoacid compound comprises at least one of mercaptopropionic acid, mercaptobutyric acid, mercaptovaleric acid, mercaptohexanoic acid, mercaptobenzoic acid, mercaptophenylacetic acid, or mercaptophenylpropionic acid.
In some more preferred embodiments of the present invention, the mercaptoacid compound comprises at least one of mercaptopropionic acid, mercaptobutyric acid, mercaptovaleric acid, or mercaptohexanoic acid.
In some more preferred embodiments of the present invention, the mercaptoacid compound comprises at least one of 3-mercaptopropionic acid, 2-mercaptopropionic acid, 4-mercaptobutyric acid, 3-mercaptobutyric acid, or 2-mercaptobutyric acid.
Wherein, 3-mercaptopropionic acid is abbreviated as 3-MPA; o-mercaptobenzoic acid, also known as thiosalicylic acid, abbreviated TSA.
In some embodiments of the invention, the carbon-carbon double bond-containing sulfamic acid inner salt is located at the end of the sulfamic acid inner salt.
In some preferred embodiments of the present invention, the sulfamic acid inner salt containing a carbon-carbon double bond further comprises a carbonyl group, the carbon-carbon double bond being conjugated to the carbonyl group.
In some preferred embodiments of the invention, the carbon-carbon double bond is located in the sulfamate at the end of the sulfamate remote from the sulfobetaine group.
In some preferred embodiments of the invention, the sulfobetaine group comprises
In some preferred embodiments of the present invention, the carbon-carbon double bond containing sulfamic acid inner salt comprises at least one of carbon-carbon double bond containing aminopropanesulfonic acid inner salt, carbon-carbon double bond containing aminobutanesulfonic acid inner salt, or carbon-carbon double bond containing aminopentanesulfonic acid inner salt.
In some preferred embodiments of the present invention, the carbon-carbon double bond containing inner salt of aminopropanesulfonic acid comprises at least one of inner salt of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid or inner salt of N, N-dimethyl (methacryloyloxypropyl) aminopropanesulfonic acid.
Wherein, N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt is abbreviated as DMAPS.
In some embodiments of the invention, the molar ratio of the mercaptoacid compound to the inner salt of aminopropanesulfonic acid having carbon-carbon double bonds is 1: (1-1.2).
In some embodiments of the invention, the molar ratio of the cellulose anhydroglucose units to the mercaptoacid compound is 1: (3-15).
In some embodiments of the invention, the molar ratio of the cellulose anhydroglucose units to the mercaptoacid compound is about 1:8.
in some embodiments of the invention, step S1 comprises the steps of: DBU is added into the mixed solution of the mercapto acid compound and the sulfamic acid inner salt containing carbon-carbon double bond, and the mixture reacts in a protective atmosphere in a dark place to obtain a zwitterionic intermediate, wherein the zwitterionic intermediate is a zwitterionic carboxylic acid intermediate.
Abbreviated DBU:1, 8-diazabicyclo [5.4.0] undec-7-ene.
In some preferred embodiments of the invention, the molar ratio of the DBU to the mercaptoacid compound is (4-6): 100.
in some preferred embodiments of the present invention, in step S1, the solvent in the mixed solution of the mercapto acid compound and the sulfamic acid inner salt containing a carbon-carbon double bond is formulated to include dimethylacetamide.
Before use, dimethylacetamide was dried over 4A molecular sieves for at least 12 hours.
In some more preferred embodiments of the present invention, in step S1, the solvent in the mixed solution of the mercapto acid compound and the sulfamic acid inner salt containing a carbon-carbon double bond is formulated further including at least one of N, N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.
N, N-dimethylformamide, abbreviated DMF; dimethyl sulfoxide, abbreviated as DMSO.
In some more preferred embodiments of the present invention, in step S1, DBU is added to a mixture of 3-mercaptopropionic acid and N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt, and reacted in an inert gas atmosphere at 40-50℃for 24 hours in the absence of light to obtain a zwitterionic carboxylic acid intermediate.
In some embodiments of the invention, in step S2, the zwitterionic intermediate is grafted to the cellulose by an esterification reaction between the carboxyl groups on the zwitterionic intermediate and the hydroxyl groups on the cellulose.
Wherein the carboxyl group is derived from the mercapto acid compound.
In some preferred embodiments of the invention, the zwitterionic intermediate is a zwitterionic carboxylic acid intermediate.
In some more preferred embodiments of the present invention, in step S2, after the zwitterionic carboxylic acid intermediate is subjected to a carboxyl activation treatment, the carboxyl groups on the zwitterionic carboxylic acid intermediate are esterified with the hydroxyl groups on the cellulose, thereby grafting the zwitterionic intermediate to the cellulose.
In some more preferred embodiments of the present invention, the carboxyl activating agent employed in the carboxyl activating treatment comprises N, N' -carbonyldiimidazole.
N, N' -carbonyldiimidazole, abbreviated CDI.
In some more preferred embodiments of the present invention, in step S2, the zwitterionic carboxylic acid intermediate is mixed with a cellulose solution after carboxyl activation treatment, and heated in a protective atmosphere to react to obtain the zwitterionic cellulose.
In some more preferred embodiments of the present invention, in step S2, a zwitterionic carboxylic acid intermediate and a cellulose solution are mixed, heated to 50-60 ℃ in an inert gas atmosphere, reacted for 12-24 hours, and separated and purified to obtain the zwitterionic cellulose.
In some more preferred embodiments of the present invention, in step S2, the separation and purification step includes: after the mixed reaction of the zwitterionic carboxylic acid intermediate and the cellulose solution is finished, centrifuging the reaction solution, removing supernatant to obtain solid, washing the solid with ethanol, dialyzing, and freeze-drying.
In some more preferred embodiments of the invention, in step S2, the dialysis time is at least 3 days.
In some more preferred embodiments of the invention, the cellulose comprises lyocell fibers and the step of formulating the cellulose solution comprises: heating and soaking the mixture of the lyocell fibers and the dimethylacetamide in a protective atmosphere, adding lithium chloride, stirring, cooling, and dissolving the lyocell fibers to obtain a lyocell fiber solution.
The lithium chloride was dried in a vacuum oven at 120℃for 2h before use. Before use, dimethylacetamide was dried over 4A molecular sieve for 12h.
In some more preferred embodiments of the invention, the step of formulating the cellulose solution comprises: heating a mixture of 0.83-1.75g of lyocell fibers and 80mL of dimethylacetamide in an inert gas atmosphere to 115-125 ℃, stirring and soaking for 60-120min, cooling to 105-110 ℃, adding 8g of lithium chloride, stirring for 50-90min, cooling, and dissolving the lyocell fibers to obtain a lyocell fiber solution.
Wherein the obtained lyocell fiber solution is in the form of pale yellow transparent liquid.
The lyocell fibers were dried in a vacuum oven at 110 c for 12 hours.
In some more preferred embodiments of the invention, the mass percentage of cellulose in the cellulose solution is 1-2%.
In some more preferred embodiments of the invention, the mass percentage of cellulose in the cellulose solution is 1.5%.
In some embodiments of the invention, the method of preparation comprises the steps of:
s1, a mixed solution I of a sulfhydryl acid compound and sulfamic acid inner salt containing carbon-carbon double bonds is subjected to Michael addition reaction of sulfhydryl groups and carbon-carbon double bonds to obtain a mixed solution II containing a zwitterionic intermediate;
s2-1, mixing the mixed solution II with a carboxyl activating agent, and performing carboxyl activating treatment on the zwitterionic intermediate to obtain a mixed solution III;
s2-2, mixing the mixed solution III with a cellulose solution to obtain a homogeneous system, and grafting the zwitterionic intermediate subjected to carboxyl activation treatment on the cellulose in the homogeneous system to obtain the zwitterionic cellulose.
In some preferred embodiments of the present invention, in step S2-1, N' -carbonyldiimidazole is added to the mixture ii and reacted in a protective atmosphere to obtain an activated zwitterionic intermediate, which is a zwitterionic carboxylic acid intermediate.
In some more preferred embodiments of the present invention, in step S2-1, the molar ratio of N, N' -carbonyldiimidazole to the mercaptoacid compound is 1:1.
in some more preferred embodiments of the present invention, in step S2-1, N' -carbonyldiimidazole is added to the mixture II, and the mixture is reacted at 40-50℃for 1-3 hours in an inert gas atmosphere to obtain an activated zwitterionic carboxylic acid intermediate.
In some preferred embodiments of the invention, the solvent in the mixed liquor i comprises a solvent i, the solvent of the cellulose solution comprises a solvent ii, and both the solvent i and the solvent ii comprise dimethylacetamide.
In some preferred embodiments of the present invention, the solvent I further comprises at least one of N, N-dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone.
In a second aspect of the invention, a zwitterionic cellulose is provided, the zwitterionic cellulose being produced by the above-described process.
In a third aspect of the present invention, a zwitterionic cellulose is provided, the zwitterionic cellulose having the structural formula (1):
the R is 1 、R 2 And R is 3 Independently selected from H, Wherein m is not less than 1,4 is not less than 1, and 4 is not less than 1.
In a fourth aspect of the present invention, a cellulose gel is provided, wherein the raw materials for preparing the cellulose gel comprise the zwitterionic cellulose.
In a fifth aspect of the present invention, a biological material is provided, wherein the biological material is prepared from the zwitterionic cellulose or the biological material comprises the zwitterionic cellulose.
In a sixth aspect of the invention, the use of the zwitterionic cellulose as described above in the manufacture of a biomaterial or medical product is presented.
In some embodiments of the invention, the medical product comprises at least one of a medical device or a medicament.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic diagram of the preparation principle of zwitterionic cellulose in example 1 of the present invention;
FIG. 2 is a chart showing the nuclear magnetic resonance hydrogen spectrum of zwitterionic cellulose in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of zwitterionic cellulose in example 1 of the present invention;
FIG. 4 is a graph showing the cytotoxicity test results of zwitterionic cellulose in example 1 of the present invention;
FIG. 5 is a graph showing the results of the BSA adsorption test of the cellulose hydrogel microspheres of example 1 of the present invention;
FIG. 6 is a photograph showing a cellulose hydrogel microsphere (mass ratio of sodium alginate to zwitterionic cellulose 9:1) in example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment discloses a zwitterionic cellulose, which comprises the following preparation processes:
pretreatment of materials:
the raw materials used are dehydrated: the materials used comprise lithium chloride, dimethylacetamide and lyocell fibers. The lithium chloride is dehydrated, namely dried for 2 hours in a vacuum box at 120 ℃, dimethylacetamide is dried for 12 hours by using a 4A molecular sieve, and lyocell fiber is dried for 12 hours at 110 ℃ in the vacuum box;
dissolution of lyocell: 1.74g of lyocell fiber was taken and fed into a reaction vessel; 80mL of dimethylacetamide is measured and added into a reaction vessel, the gas in the reaction vessel is replaced by inert gas, the temperature is raised to 120 ℃, and stirring and soaking are carried out for 1h; then cooling to 110 ℃, adding 8g of lithium chloride, and continuously stirring for 1h; then the heating device is closed, the temperature is naturally reduced to the room temperature, and in the process of reducing the temperature, the lyocell is completely dissolved, and the solution is in a pale yellow transparent liquid shape;
(II) according to a molar ratio of 1:1 weighing 0.27g (2.5 mmol) of 3-MPA and 0.70g (2.5 mmol) of DMAPS, and dissolving 3-MPA with 3mL of DMAc to obtain 3-MPA solution; because the solubility of DMAPS in DMAc is low, adding 4mL of DMAc and 1mL of DMSO helps to dissolve, and a DMAPS solution is obtained;
(III) transferring the 3-MPA solution and the DMAPS solution prepared in the step (II) into a round bottom flask in sequence, adding 19mg of DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), replacing inert gas, and carrying out light-shielding and 45 ℃ reaction for 24 hours to obtain an intermediate product;
(IV) without purifying the intermediate, 0.41g CDI (2.5 mmol) was added, inert gas was replaced, and the reaction was carried out at 45℃for 3 hours;
(V) according to the cellulose anhydroglucose unit AGU: the molar ratio of 3-MPA is 1:3, adding 6.75g of cellulose solution with the concentration of 2% W/W, replacing inert gas, heating to 52 ℃, and reacting for 24 hours;
directly centrifuging the reaction solution obtained in the step (V), pouring out supernatant to obtain white solid, and dissolving precipitate by using DMSO (dimethyl sulfoxide), wherein the precipitate can be completely dissolved, which indicates that the lyocell fiber is successfully modified (cellulose cannot be dissolved if not successfully modified);
washing the solid with absolute ethanol for 3 times, dissolving with water, dialyzing for 3 days, filtering, and freeze-drying the filtrate to obtain the product with the yield of 53.7%.
The product obtained in this example 1 H spectrum:
1 HNMR(400MHz,DMSO-d 6 )
delta 4.46 (d, 2H), 3.69 (d, 2H), 3.5 (m, 2H), 3.10 (s, 6H), 2.33 (s, 1H), 2.12 (t, 2H), 2.02 (m, 2H), 1.15 (d, 3H); wherein several methyl characteristic peaks of the target product appear in the spectrogram. Therefore, the steps are proved to be successful in preparing the target product with the correct structural formula.
The embodiment provides a cellulose gel, in particular a cellulose gel microsphere, the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment, and the preparation process comprises the following steps:
the zwitterionic cellulose prepared in the embodiment is used as a raw material to prepare a series of sodium alginate/zwitterionic cellulose mixed solutions, wherein the sum of mass fractions of the sodium alginate and the zwitterionic cellulose in the mixed solutions is 2%, and a PBS buffer solution (0.01 mol/L, pH is 6.0) is adopted as a solvent.
The mixed solution was slowly dropped into a barium chloride aqueous solution having a mass fraction of 2% using a 5mL syringe, to obtain a series of cellulose hydrogel spheres containing zwitterionic cellulose.
Wherein, in the series of cellulose hydrogel spheres, the mass ratio of the sodium alginate to the zwitterionic cellulose is 9: 1. 8: 2. 6: 4. 5:5.
the embodiment provides a biological material, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a medicament comprising the zwitterionic cellulose prepared by the embodiment.
Example 2
The embodiment discloses a zwitterionic cellulose, which comprises the following preparation processes:
pretreatment of materials: the specific procedure is the same as in example 1;
(II) according to a molar ratio of 1:1 weighing 0.54g (5 mmol) of 3-MPA and 1.40g (5 mmol) of DMAPS, and dissolving the 3-MPA with 6mL of DMAc to obtain a 3-MPA solution; DMAPS was dissolved with 8mL of DMAc and 2mL of DMSO to give a DMAPS solution;
(III) transferring the 3-MPA solution and the DMAPS solution prepared in the step (II) into a round bottom flask in sequence, adding 38mg of DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), replacing inert gas, and carrying out light-shielding and 45 ℃ reaction for 24 hours to obtain an intermediate product;
(IV) without purifying the intermediate, 0.82g CDI (5 mmol) was added, inert gas was replaced, and the reaction was carried out at 45℃for 3 hours;
(V) according to the cellulose anhydroglucose unit AGU: the molar ratio of 3-MPA is 1:6, adding 9.0g of cellulose solution with the concentration of 1.5% W/W, replacing inert gas, heating to 60 ℃ and reacting for 24 hours;
directly centrifuging the reaction solution obtained in the step (V), pouring out supernatant to obtain white solid, and dissolving precipitate by using DMSO (dimethyl sulfoxide) to completely dissolve the precipitate;
washing the solid with absolute ethanol for 3 times, dissolving with water, dialyzing for 3 days, filtering, and freeze-drying the filtrate to obtain the product with the yield of 67.3%.
The embodiment provides a cellulose gel, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a biological material, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a medicament comprising the zwitterionic cellulose prepared by the embodiment.
Example 3
This example discloses a zwitterionic cellulose which differs from example 1 in that:
in step (v), the cellulose anhydroglucose unit AGU: the molar ratio of 3-MPA is 1:8.
the yield of the zwitterionic cellulose finally prepared in this example was 70.2%.
The embodiment provides a cellulose gel, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a biological material, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a medicament comprising the zwitterionic cellulose prepared by the embodiment.
Example 4
This example discloses a zwitterionic cellulose which differs from example 1 in that:
in step (v), the cellulose anhydroglucose unit AGU: the molar ratio of 3-MPA is 1:10.
the yield of the zwitterionic cellulose finally prepared in this example was 74.4%.
The embodiment provides a cellulose gel, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a biological material, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a medicament comprising the zwitterionic cellulose prepared by the embodiment.
Example 5
This example discloses a zwitterionic cellulose which differs from example 1 in that:
in step (v), the cellulose anhydroglucose unit AGU: the molar ratio of 3-MPA is 1:15.
the yield of the zwitterionic cellulose finally prepared in this example was 75.8%.
The embodiment provides a cellulose gel, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a biological material, and the preparation raw materials comprise the zwitterionic cellulose prepared by the embodiment.
The embodiment provides a medicament comprising the zwitterionic cellulose prepared by the embodiment.
From examples 1 to 5, it is known that, as the cellulose anhydroglucose unit AGU: the molar ratio of 3-MPA increases and the product yield increases gradually. As the yield of the product is increased firstly, then slowly, the increasing benefit is gradually reduced, but the cost is increased; in general, AGU is most preferably used: the molar ratio of 3-MPA is 1:8.
example 6
The embodiment discloses a zwitterionic cellulose, which comprises the following preparation processes:
pretreatment of materials: the specific procedure is the same as in example 1;
(II) according to a molar ratio of 1:1, weighing 0.39g (2.5 mmol) of TSA (thiosalicylic acid) and 0.70g (2.5 mmol) of DMAPS, dissolving the TSA with 3mL of DMAc to obtain a TSA solution, dissolving the DMAPS in the DMAc with low solubility, and adding 4mL of DMAc and 1mL of DMSO to dissolve the DMAPS solution;
(III) transferring the 3-MPA solution and the DMAPS solution prepared in the step (II) into a round bottom flask in sequence, adding 19mg of DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene), replacing inert gas, and carrying out light-shielding and 45 ℃ reaction for 24 hours to obtain an intermediate product;
(IV) without purifying the intermediate, 0.41g CDI (2.5 mmol) was added, inert gas was replaced, and the reaction was carried out at 45℃for 3 hours;
(V) according to the cellulose anhydroglucose unit AGU: the molar ratio of TSA is 1:6, adding 4.5g of cellulose solution with the concentration of 1.5% W/W, replacing inert gas, heating to 60 ℃ and reacting for 24 hours;
pouring the reaction solution obtained in the step (V) into 100mL of ethanol for precipitation, centrifuging, and pouring out supernatant to obtain pale yellow solid;
washing the solid with absolute ethanol for 3 times, dissolving the solid with water, dialyzing for 3 days, filtering, and freeze-drying the filtrate to obtain the product with the yield of less than 10%.
Compared with example 1, the thiol acid compound used in this example is TSA containing benzene ring, and the yield of the final zwitterionic cellulose is significantly lower than that of examples 1-5 (aliphatic thiol acid compound is used in examples 1-5). The inventors speculate that the cause is: compared to aliphatic mercapto acids, TSA containing benzene rings may be because benzene rings reduce the nucleophilicity of mercapto groups and steric hindrance also affects carboxyl esterification.
Comparative example 1
The comparative example discloses a zwitterionic cellulose, the preparation process of which comprises:
pretreatment of materials: the specific procedure is the same as in example 1;
(II) 0.54g (5 mmol) of 3-MPA was weighed, dissolved in 6mL of DMAc, and transferred to a reaction vessel; then, 0.82g (5 mmol) of CDI was weighed, dissolved in 4mL of DMAc, transferred to a reaction vessel, replaced with nitrogen, and reacted at 45℃for 3 hours;
(III) weighing 18.0g of 1.5% W/W cellulose solution, dripping into a reaction container, and then heating to 60 ℃ for continuous reaction for 12-24 hours;
this comparative example was prepared by reacting cellulose with 3-mercaptopropionic acid followed by DMAPS.
Reacting for 12 hr, sampling, adding ethanol, precipitating, centrifuging, removing supernatant, and separating precipitate with solvent DMSO, DMAc, DMF, H 2 O detects solubility, none of which is soluble; the reaction was then continued for 24 hours, at which time a gum-like substance was produced in the reaction vessel and no further reaction was allowed to proceed.
The reason for this is presumed to be: when the reaction time is insufficient, the substitution degree of OH on cellulose is too low, the hydrogen bonding effect of cellulose is strong, and the product cannot be dissolved in a common solvent; while extending the reaction time can theoretically increase the degree of substitution of OH, side reactions occur between mercapto groups on the substituents to form disulfide bonds, resulting in some degree of crosslinking, which in turn leads to insoluble gum-like materials.
In example 1, the mercapto group is reacted with the carbon-carbon double bond, and the mercapto group is reacted first, thereby avoiding the above situation. When carboxyl reacts with cellulose again, the reaction yield can be improved by prolonging the time and increasing the feeding ratio.
Test examples
The test example tests the performance of the zwitterionic cellulose obtained in the example, and specifically comprises the following steps:
(1) The substitution degree of the zwitterionic cellulose is tested, and the organic element analysis test results are shown in table 1, wherein the organic element analyzer has the instrument model as follows: eletantar Vario EL cube; test mode: CHNS mode.
TABLE 1 zwitterionic cellulose substitution test results table
| Element(s) | N(％) | C(％) | H(％) | S(％) | O(％) |
| Example 1 | 2.42 | 44.13 | 7.19 | 11.04 | / |
Degree of substitutionThe degree of substitution was about 0.76.
The literature polym.bull (2014) 71:2559-2569 authors used a cellulose surface modification scheme, specifically using click reaction of azido cellulose with terminal alkynes, to introduce sulfabetaine side chains whose elemental analysis gave an N% content of 4.1%, but since each substituent contains 4 nitrogen atoms, the number of substituents was 1/4, i.e. 1%, of the nitrogen content. The substitution degree of the zwitterionic cellulose prepared by the invention is obviously higher.
(2) In vitro cytotoxicity test:
the MTT test step comprises the following steps:
1) Log phase L929 mouse cells were collected, cell suspension concentration was adjusted, 100 μl was added to each well, and the wells were plated to give 10000 cells/well (96 well flat bottom plate, edge wells filled with sterile PBS) to be tested.
2) Transferred to a carbon dioxide cell incubator with 5% CO 2 Incubating at 37 ℃ and culturing for 18-24 hours until the cell monolayer is fully paved at the bottom of the hole, and adding medicine (the zwitterionic cellulose prepared in the example 1) after the cells are attached to the wall. 3 concentration gradients (mass fractions of zwitterionic cellulose in the mixture of zwitterionic cellulose and PBS buffer are 0.5%, 1.0% and 2.0% respectively) were set, 5 compound wells were set per 100uL well, and a positive control group (1 mol/L NaOH+ medium) and a negative control group (fresh medium of equal amount was added without drug).
3) Then continue in carbon dioxide cell incubator 5% CO 2 Incubation was carried out at 37℃for 24 hours.
4) The test samples in the well plate were removed, the wells were washed 2 times with PBS solution, 50uL of MTT solution was added to each well, incubated in an incubator for 4 hours, and then the wells were discarded.
5) 200. Mu.L of DMSO was added to each well and the mixture was shaken on a shaker for 10min at low speed to allow the crystals to dissolve well. Then incubating in an incubator for 4-6 hours; after the incubation, the solution was aspirated and added to a new 96-well plate, and the plate was put into an microplate reader, and the absorbance value of each well at an absorption wavelength of 570nm was measured.
The results of the test are shown in fig. 4, with cytotoxicity rating of 1.
(3) Bovine serum albumin BSA adsorption assay:
the series of cellulose hydrogel microspheres (abbreviated as hydrogel spheres) prepared in example 1 were subjected to BSA adsorption test, and pure alginic acid gel microspheres without zwitterionic cellulose according to the present invention were used as a control.
The method comprises the following specific steps:
weighing 20mg of dry hydrogel spheres, putting the hydrogel spheres into 10mL of PBS buffer solution (0.01M, pH 6.0) containing 1mg/mL BSA, and carrying out constant-temperature shaking soaking at 25 ℃ for 12 hours; then taking the supernatant, and measuring the absorbance of the supernatant at 277nm by using an ultraviolet spectrophotometer; drawing an ultraviolet absorption standard curve of BSA, wherein the curve has better linearity in the concentration range of 0.02-2.0mg/mL, and the regression curve is y=0.6137x+0.1044, R 2 = 0.9991; hydrogel sphere BSA adsorption was calculated from the standard curve.
The method for calculating the adsorption quantity comprises the following steps:
wherein: ρ0 and ρ1 are the mass concentration (mg/mL) of BSA in the pre-and post-adsorption solutions, respectively, V is the solution volume, and m is the hydrogel sphere mass.
The test results are shown in FIG. 5, and the measured adsorption rate is reduced by 87.5% compared with the control group.
The traditional surface modification reaction can only occur on the surface of the cellulose cluster, the occurrence site is probabilistic, and the inside of the cellulose cluster cannot be contacted with reactants, so that the grafting is uneven, the grafting rate is low, and the substitution degree is low. The invention grafts amphoteric substances on cellulose in homogeneous phase, can basically reach the degree of single molecular chain, and has equal probability of each AGU unit site when contacting with reactants, so the grafting is uniform and the substitution degree is high.
The zwitterionic celluloses prepared in examples 2-6 were all subjected to nuclear magnetic characterization, and the results indicate that the target compounds were prepared with substitution degrees of 0.6-0.9. The zwitterionic celluloses prepared in examples 2-6 were comparable to the zwitterionic celluloses prepared in example 1.
The invention adopts a simple and efficient two-step reaction, has high reaction activity, simple reaction conditions and convenient operation. Wherein, the reaction of sulfhydryl and carbon-carbon double bond belongs to the Michael addition reaction type in click reaction, and is characterized by high efficiency, atom economy and mild condition; the adopted activator CDI is an efficient acylating agent and carboxylic acid activating agent for the esterification reaction of carboxyl and hydroxyl, and has higher application value compared with DCC, EDC and the like.
The invention carries out amphoteric ion modification on cellulose under homogeneous phase condition, and one of the technical difficulties is that: if the dissolution system of cellulose is compatible with the subsequent modification reaction system, any reaction system which is incompatible with the cellulose solution system can lead to the destabilization of the cellulose solution to be separated out, and the subsequent modification reaction can not be smoothly carried out. The reaction reagent selected by the invention is skillfully selected after creative labor, can be compatible with the cellulose solution and has little influence on the stability of the cellulose solution. The final target product can be directly separated out in the system, and the post-treatment is very convenient.
It should be noted that "room temperature" herein, unless otherwise specified, is about 25 ℃; the meaning of "about" with respect to a numerical value herein is an error of 2%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (12)
1. A method for preparing zwitterionic cellulose, comprising the steps of:
s1, a sulfhydryl acid compound and sulfamic acid inner salt containing carbon-carbon double bond are subjected to Michael addition reaction of sulfhydryl and carbon-carbon double bond to obtain a zwitterionic intermediate, and the zwitterionic intermediate is not purified;
s2, grafting the zwitterionic intermediate prepared by the operation on cellulose in a homogeneous system to obtain the zwitterionic cellulose;
in step S2, grafting the zwitterionic intermediate on the cellulose through esterification reaction between carboxyl on the zwitterionic intermediate and hydroxyl on the cellulose;
the mercapto acid compound is at least one of mercapto propionic acid, mercapto butyric acid, mercapto valeric acid, mercapto caproic acid, mercapto benzoic acid, mercapto phenylacetic acid or mercapto phenylpropionic acid;
the sulfamic acid inner salt containing carbon-carbon double bond is N, N-dimethyl (methacryloxypropyl) aminopropanesulfonic acid inner salt orWherein 4 is greater than or equal to a is greater than or equal to 1.
2. The method of claim 1, wherein the homogeneous system comprises a solvent system or an ionic liquid system comprising dimethylacetamide.
3. The method of preparing a zwitterionic cellulose according to claim 1, wherein the cellulose comprises at least one of lyocell, purified cotton, modal, cuprammonium, or viscose.
4. The method for producing a zwitterionic cellulose according to claim 1, wherein the mercapto acid compound is at least one of mercaptopropionic acid, mercaptobutyric acid, mercaptovaleric acid, and mercaptohexanoic acid.
5. The method for producing a zwitterionic cellulose according to claim 1, wherein the inner salt of aminopropanesulfonic acid having a carbon-carbon double bond comprises at least one of inner salt of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid or inner salt of N, N-dimethyl (methacryloyloxypropyl) aminopropanesulfonic acid.
6. The method for preparing zwitterionic cellulose according to claim 1, characterized in that the method comprises the steps of:
s1, a mixed solution I of a sulfhydryl acid compound and sulfamic acid inner salt containing carbon-carbon double bonds is subjected to Michael addition reaction of sulfhydryl groups and carbon-carbon double bonds to obtain a mixed solution II containing a zwitterionic intermediate;
s2-1, mixing the mixed solution II with a carboxyl activating agent, and performing carboxyl activating treatment on the zwitterionic intermediate to obtain a mixed solution III;
s2-2, mixing the mixed solution III with a cellulose solution to obtain a homogeneous system, and grafting the zwitterionic intermediate subjected to carboxyl activation treatment on the cellulose in the homogeneous system to obtain the zwitterionic cellulose.
7. The method according to claim 6, wherein the solvent in the mixed solution I comprises a solvent I, the solvent of the cellulose solution comprises a solvent II, and both the solvent I and the solvent II comprise dimethylacetamide.
8. Zwitterionic cellulose, characterized in that it is produced by the process according to any one of claims 1 to 7.
9. The zwitterionic cellulose of claim 8, wherein the mercaptoacid compound is 3-mercaptopropionic acid or thiosalicylic acid and the inner salt of aminopropanesulfonic acid having a carbon-carbon double bond is an inner salt of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid.
10. A cellulose gel, characterized in that the raw material for the preparation of the cellulose gel comprises zwitterionic cellulose prepared by the method according to any one of claims 1-7.
11. A biomaterial, characterized in that the starting material for its preparation comprises a zwitterionic cellulose obtainable by the process according to any one of claims 1 to 7.
12. Use of a zwitterionic cellulose obtainable by a process according to any one of claims 1 to 7 in the manufacture of a biomaterial or medical product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210426246.XA CN114835826B (en) | 2022-04-22 | 2022-04-22 | Zwitterionic cellulose and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210426246.XA CN114835826B (en) | 2022-04-22 | 2022-04-22 | Zwitterionic cellulose and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114835826A CN114835826A (en) | 2022-08-02 |
| CN114835826B true CN114835826B (en) | 2023-08-22 |
Family
ID=82565777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210426246.XA Active CN114835826B (en) | 2022-04-22 | 2022-04-22 | Zwitterionic cellulose and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114835826B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260315B (en) * | 2022-08-12 | 2024-08-27 | 深圳华源再生医学有限公司 | Modification method of cellulose, betaine type amphoteric cellulose, and preparation method and application thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB976392A (en) * | 1960-07-18 | 1964-11-25 | Gevaert Photo Prod Nv | Improvements in or relating to the preparation of arylaminosulphonate derivatives ofnatural and synthetic polymers |
| US4664806A (en) * | 1985-01-22 | 1987-05-12 | Ciba-Geigy Corporation | Anionically modified polysaccharides chromatography agents |
| CN102277141A (en) * | 2011-04-26 | 2011-12-14 | 中国海洋石油总公司 | Guar derivative-based betaine-type amphoteric thickening agent and preparation method thereof |
| CN104028114A (en) * | 2014-05-16 | 2014-09-10 | 浙江大学 | Preparation method of nanofiltration membrane based on nano betaine type carboxymethyl cellulose |
| CN104031154A (en) * | 2014-06-20 | 2014-09-10 | 天津大学 | Zwitter-ion-containing 3-dimethylpropanesulfonic acid starch and preparation method thereof |
| CN104045771A (en) * | 2014-06-27 | 2014-09-17 | 南京林业大学 | Preparation method of homogeneous-phase synthesized betaine type amphoteric cellulose |
| CN104045846A (en) * | 2014-05-30 | 2014-09-17 | 天津工业大学 | Double ion modified cellulose membrane and making method thereof |
| CN105293478A (en) * | 2015-11-24 | 2016-02-03 | 华南理工大学 | Betaine type amphoteric ionic compound modified graphene oxide and preparation method thereof |
| CN105693935A (en) * | 2016-03-17 | 2016-06-22 | 中山大学 | Zwitterionic hydroxyethyl cellulose modified substance and preparation method and application thereof |
| CN106397674A (en) * | 2016-09-23 | 2017-02-15 | 中山大学 | Temperature-sensitive postoperative adhesion cellulose modifying material and preparation method and application thereof |
| CN106554423A (en) * | 2016-11-29 | 2017-04-05 | 东北林业大学 | A kind of amphion cellulose material and preparation method thereof |
| CN109400720A (en) * | 2018-10-22 | 2019-03-01 | 信阳师范学院 | A kind of preparation method and application of amphoteric cellulose adsorbent |
| CN110804104A (en) * | 2019-10-30 | 2020-02-18 | 暨南大学 | Cell membrane bionic surface modified bacterial cellulose and preparation method and application thereof |
| FR3085953A1 (en) * | 2018-09-18 | 2020-03-20 | Universite de Bordeaux | HYDROGEL PARTICLES OF STIMULABLE BIPHILIC POLYMERS FOR STABILIZING WATER-IN-WATER EMULSIONS |
| CN113667141A (en) * | 2021-07-09 | 2021-11-19 | 深圳华源再生医学有限公司 | Alginate hydrogel for resisting protein adhesion and preparation method and application thereof |
-
2022
- 2022-04-22 CN CN202210426246.XA patent/CN114835826B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB976392A (en) * | 1960-07-18 | 1964-11-25 | Gevaert Photo Prod Nv | Improvements in or relating to the preparation of arylaminosulphonate derivatives ofnatural and synthetic polymers |
| US4664806A (en) * | 1985-01-22 | 1987-05-12 | Ciba-Geigy Corporation | Anionically modified polysaccharides chromatography agents |
| CN102277141A (en) * | 2011-04-26 | 2011-12-14 | 中国海洋石油总公司 | Guar derivative-based betaine-type amphoteric thickening agent and preparation method thereof |
| CN104028114A (en) * | 2014-05-16 | 2014-09-10 | 浙江大学 | Preparation method of nanofiltration membrane based on nano betaine type carboxymethyl cellulose |
| CN104045846A (en) * | 2014-05-30 | 2014-09-17 | 天津工业大学 | Double ion modified cellulose membrane and making method thereof |
| CN104031154A (en) * | 2014-06-20 | 2014-09-10 | 天津大学 | Zwitter-ion-containing 3-dimethylpropanesulfonic acid starch and preparation method thereof |
| CN104045771A (en) * | 2014-06-27 | 2014-09-17 | 南京林业大学 | Preparation method of homogeneous-phase synthesized betaine type amphoteric cellulose |
| CN105293478A (en) * | 2015-11-24 | 2016-02-03 | 华南理工大学 | Betaine type amphoteric ionic compound modified graphene oxide and preparation method thereof |
| CN105693935A (en) * | 2016-03-17 | 2016-06-22 | 中山大学 | Zwitterionic hydroxyethyl cellulose modified substance and preparation method and application thereof |
| CN106397674A (en) * | 2016-09-23 | 2017-02-15 | 中山大学 | Temperature-sensitive postoperative adhesion cellulose modifying material and preparation method and application thereof |
| CN106554423A (en) * | 2016-11-29 | 2017-04-05 | 东北林业大学 | A kind of amphion cellulose material and preparation method thereof |
| FR3085953A1 (en) * | 2018-09-18 | 2020-03-20 | Universite de Bordeaux | HYDROGEL PARTICLES OF STIMULABLE BIPHILIC POLYMERS FOR STABILIZING WATER-IN-WATER EMULSIONS |
| CN109400720A (en) * | 2018-10-22 | 2019-03-01 | 信阳师范学院 | A kind of preparation method and application of amphoteric cellulose adsorbent |
| CN110804104A (en) * | 2019-10-30 | 2020-02-18 | 暨南大学 | Cell membrane bionic surface modified bacterial cellulose and preparation method and application thereof |
| CN113667141A (en) * | 2021-07-09 | 2021-11-19 | 深圳华源再生医学有限公司 | Alginate hydrogel for resisting protein adhesion and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 含巯基/二硫键聚合物生物材料;李春鸽等;《化学进展》;20130124(第01期);第126-138页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114835826A (en) | 2022-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114835826B (en) | Zwitterionic cellulose and preparation method and application thereof | |
| EP0013181B1 (en) | Chitin derivative, material comprising said derivative and process for the preparation thereof | |
| EP2137219A1 (en) | Method for making a polysaccharide dialdehyde having high purity | |
| WO2019052321A1 (en) | Water-soluble chitosan antimicrobial derivative and preparation method therefor | |
| WO2019227525A1 (en) | Application and preparation method of chitooligosaccharide-based compound | |
| CN112778537A (en) | Modified gelatin and preparation method thereof, light-curable aqueous solution and preparation method thereof | |
| CN111533827B (en) | Electronegative polysaccharide quaternary ammonium salt hemostatic material and preparation method and application thereof | |
| CN111518172B (en) | High-generation dendritic polylysine antibacterial peptide and preparation method thereof | |
| CN112321745A (en) | Norbornene derivative modified sodium alginate | |
| CN102702389A (en) | Thermo-sensitive chitosan derivative-hydroxypentyl chitosan and preparation method thereof | |
| US20130274225A1 (en) | Method for making a polysaccharide dialdehyde having high purity | |
| CN113171760A (en) | High-strength imprinted composite membrane and preparation method and application thereof | |
| CN101864138A (en) | Preparation method of chitosan temperature sensitivity stable nanometer micelle | |
| WO2019192628A2 (en) | Thiolated chitosan derivative, chitosan hydrogel, and preparation methods therefor and applications thereof | |
| CN115260315B (en) | Modification method of cellulose, betaine type amphoteric cellulose, and preparation method and application thereof | |
| JP2602535B2 (en) | Aminoethylated water-soluble polymer and its production method | |
| CN114716702A (en) | Preparation method of thiol-ene photo-click hyaluronic acid-based bio-ink | |
| CN110256605B (en) | High-antioxidant phenolic chitosan Schiff base and preparation method and application thereof | |
| CN102585034B (en) | Method for sulfonating pectin | |
| CN111974367A (en) | Preparation method of polylysine modified cellulose material for adsorbing copper ions | |
| CN111808206A (en) | Modified biomass with ultraviolet absorption function, preparation method and application | |
| CN114106215A (en) | Sulfhydryl modified hyaluronic acid (sodium) and cross-linked product thereof, and preparation method and application thereof | |
| CN111154010A (en) | Medical cationic polymer biopolymer material, preparation method and application | |
| CN113999403B (en) | Quaternized soybean protein, quaternized soybean protein-dopamine, and preparation method and application thereof | |
| CN116535540B (en) | Quaternized modified chitin, sponge thereof, preparation method of porous microsphere and application of quaternized modified chitin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |