CN112457432A - Method for preparing oxidized chitosan and derivatives thereof by electrolytic method - Google Patents
Method for preparing oxidized chitosan and derivatives thereof by electrolytic method Download PDFInfo
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention discloses a method for preparing oxidized chitosan and derivatives thereof by an electrolytic method. The invention selectively oxidizes the chitosan and the derivatives thereof in an electrolytic cell by adopting a small amount of sodium iodate under the condition of keeping out of the sun, and obtains the oxidized chitosan and the derivatives thereof containing aldehyde groups with high chemical reaction activity after dialysis separation. Compared with the traditional method, the method has the advantages of less using amount of the oxidant, controllable degree of oxidation and environmental protection, and is a novel environmental-friendly preparation method of the oxidized chitosan and the derivatives thereof.
Description
Technical Field
The invention relates to a method for preparing oxidized chitosan and derivatives thereof by an electrolytic method, which is applied to the field of biomedical materials.
Background
Biomaterials often require the use of cross-linking agents to reduce immunogenicity, improve physical and mechanical properties, and increase resistance to degradation. At present, oxidized polysaccharide is applied to the cross-linking of biological materials, sodium periodate is usually adopted as an oxidant for the preparation of the oxidized polysaccharide, polysaccharide containing an o-dihydroxy structure is selectively oxidized to generate aldehyde groups with strong reaction activity, and the molar ratio of the sodium periodate to the polysaccharide is controlled to control the degree of oxidation, so that the oxidized polysaccharide with different aldehyde group contents is obtained. Bennshu uses sodium periodate to oxidize cellulose, prepares oxidized cellulose, and studies the adsorption effect of the oxidized cellulose on urea (Bennshu. synthesis of cellulose derivative and research on adsorption performance [ D ]. Tianjin: doctor paper of Tianjin university, 2005.).
However, sodium periodate is expensive and the production cost is high. In order to reduce the production cost, the modern process adopts an electrolysis method to prepare the sodium gluconateIodate, and then periodate was used to oxidize the starch. Chennina adopts Pb- (BrO 3-/Br-) system, electrooxidizes starch to synthesize dialdehyde starch, and obtains the optimal reaction conditions by studying the reaction conditions of temperature, current, sulfuric acid concentration and the like, namely, at 35 ℃, the sulfuric acid concentration is 0.05mol/L, and the current density is 15mA/cm2Starch concentration is 10%, and current efficiency can reach 50% (Chennina, Chenyan, Zhengxi, etc.. with Pb- (BrO)3 --／Br-) Indirect electric oxidation synthesis of dialdehyde starch [ J ] by using medium]Electrochemical, 2009, 15 (4): 458-461). But the operation flow is complicated, the equipment is complex, and the large-scale production is difficult.
At present, in the preparation of biological materials, a sodium periodate method direct oxidation method is generally adopted, and a large amount of sodium periodate is utilized to obtain enough oxidation degree, so that oxidized polysaccharide is prepared. Because sodium periodate has a large molecular weight, according to the reaction molar ratio of 1:1, a large amount of expensive sodium periodate is consumed, and finally, the reduced sodium iodate byproduct needs to be removed from the product and causes environmental pollution.
Chitosan is the only basic amino-oligosaccharide existing in large amount in natural sugar, has the functions of antioxidation, antibacterial activity, anti-inflammation/wound healing promotion, anticancer/antitumor function, antivirus function and the like, and is widely applied to the preparation of biological materials. Because the chitosan structure does not contain ortho-dihydroxy, and contains two adjacent hydroxy and amino groups. The current research shows that sodium periodate can still selectively oxidize adjacent hydroxyl and amino to prepare the oxidized chitosan. In fact, sodium periodate can also oxidize chitosan derivatives, such as chitosan oligosaccharide, hydroxymethyl chitosan, chitosan quaternary ammonium salt, and the like. In the aspect of an electrolytic method, the method is only applied to oxidizing starch at present, and no report about the preparation of oxidized chitosan and derivatives thereof by the electrolytic method is provided.
Therefore, how to synthesize the oxidized chitosan and the derivatives thereof with reduced cost and environmental friendliness is a technical problem to be solved.
The present invention relates to the following reactions:
(1) at the cathode, H+Obtain electronsTo become hydrogen;
(2) at the anode, first, sodium iodate is oxidized to become sodium periodate; then, sodium periodate reacts with chitosan and its derivatives, and adjacent hydroxyl and amino (or imino) are oxidized into dialdehyde structure, so as to obtain oxidized chitosan and its derivatives, and at the same time, sodium periodate is reduced into sodium iodate; finally, the sodium iodate is electro-oxidized into sodium periodate at the anode; "oxidation-reduction-oxidation" is repeated in such a way that chitosan and derivatives thereof are continuously oxidized into oxidized chitosan and derivatives thereof in the process until the required degree of oxidation is achieved.
Disclosure of Invention
1. A method for preparing oxidized chitosan and derivatives thereof by an electrolytic method, wherein the reaction is carried out in a special electrolytic cell with a low-temperature cooling device, comprises the following steps:
(1) adding 100-300 parts by weight of dilute sulfuric acid solution with the concentration of 0.15-0.3 mol/L into an anode tank of an electrolytic cell, weighing 0.3-1.5 parts by weight of sodium iodate, adding into the anode tank, and stirring to completely dissolve the sodium iodate;
(2) weighing 5-10 parts by weight of chitosan and derivatives thereof, adding into an anode tank, and stirring to completely dissolve the chitosan and the derivatives thereof;
(3) adding 200-300 parts by weight of dilute sulfuric acid with the concentration of 0.15-0.3 mol/L into a cathode tank of an electrolytic cell;
(4) turning on a direct current power supply, setting the current to be 0.2A-1.5A, controlling the temperature to be 5-60 ℃, and reacting for 0.5-5.0 hours under the condition of light shielding;
(5) pouring the reactant into a dialysis bag with the molecular weight cutoff of 500-8000 Da, putting the dialysis bag into 500-3000 parts by weight of distilled water, dialyzing for 12 hours, collecting the distilled water after the first dialysis, then putting the dialysis bag into 500-3000 parts by weight of distilled water, changing the distilled water every 12 hours, and dialyzing for 12 hours-72 hours;
(6) taking out the product in the dialysis bag, and performing vacuum drying or freeze drying to obtain oxidized chitosan and derivatives thereof;
(7) the collected distilled water after the first dialysis can be added with sulfuric acid and sodium iodate, and can be used for preparing the solution in (1).
2. The electrolytic process for the preparation of oxidized chitosan and its derivatives as claimed in claim 1, wherein the structure of the dedicated electrolytic cell with low temperature cooling means is shown in figure 1.
3. The electrolytic process for the production of oxidized chitosan and derivatives thereof as claimed in claim 1, wherein said chitosan and derivatives thereof are chitosan, chitosan oligosaccharide, carboxymethyl chitosan, mono-quaternary ammonium salt of chitosan, di-quaternary ammonium salt of chitosan.
Compared with the traditional sodium periodate oxidation method, the technology of the patent has the following advantages:
(1) replacing the higher-priced sodium periodate with the lower-priced sodium iodate: in the traditional preparation of oxidized chitosan, sodium periodate is used as an oxidizing agent, and the method uses sodium iodate as an oxidizing agent. In contrast, the sodium iodate is low in price, and particularly, the manufacturing cost can be saved during large-scale production;
(2) the using amount of the oxidant is less: in the conventional sodium periodate oxidation method, the molar ratio of the oxidant to the ortho-dihydroxy is 1:1, and because the sodium periodate has a large molecular weight (about 214), a large amount of sodium periodate is often used when a product with a higher oxidation degree or a raw material of chitosan and derivatives thereof is needed. By adopting the method, as the sodium iodate is oxidized into the sodium periodate in the electrolytic cell, once the sodium periodate is oxidized into the sodium iodate after the chitosan and the derivatives thereof are oxidized, the generated sodium iodate can be immediately oxidized into the sodium periodate in the electrolytic cell, so that the sodium iodate is continuously subjected to an oxidation-reduction-oxidation process, and the process is repeated in such a way, and the chitosan and the derivatives thereof are continuously oxidized. Therefore, only a small amount of sodium iodate is needed to obtain a large amount of chitosan and derivatives thereof with the required oxidation degree;
(3) the oxidation degree can be controlled: because a small amount of sodium iodate in the system can obtain the oxidized chitosan and the derivatives thereof with the required oxidation degree, the oxidation degree is not controlled by the using amount of sodium periodate in the traditional oxidation method, and the oxidation degree can be regulated and controlled by controlling the oxidation conditions (such as time, temperature and the like) in the actual preparation process;
(4) a very high degree of oxidation can be achieved: because the sodium iodate is recycled, theoretically, the oxidation degree of the product can reach 100 percent by controlling the oxidation condition and using a small amount of sodium iodate;
(5) green and environment-friendly: the traditional oxidation method of sodium periodate needs to use a large amount of sodium periodate, the sodium periodate is reduced to become sodium iodate which is difficult to recover, and finally, a large amount of sodium periodate is discharged into the environment to cause environmental pollution. Particularly, when the oxidation degree is high or the batch production is carried out, the pollution is particularly obvious. In the method, the sodium iodate can be recycled, so that the dosage of the oxidant can be greatly reduced, and the pollution is greatly reduced. Is particularly suitable for large-scale production;
(6) hydrogen can be recovered: a byproduct hydrogen gas is generated at the cathode, and can be recycled;
(7) the cost is proper: although the electrolysis method is high in equipment investment and the like, the added value of the biological material is high, so that the relative cost is reduced, and the large-scale production is expected to be realized.
In conclusion, the invention uses a small amount of sodium iodate with lower price as a raw material, adopts an electrolytic method to prepare the oxidized chitosan and the derivatives thereof, has the characteristics of small using amount of an oxidant, controllable degree of oxidation and environmental protection, is particularly suitable for large-scale production, can be used as a biological cross-linking agent, a chemical coupling agent, a microsphere cross-linking agent, a cross-linking agent of immobilized enzyme and the like, has high added value, and can be widely applied to the fields of medicine, food, biology, chemical industry and the like.
Drawings
Fig. 1 is a schematic view of a dedicated electrolytic cell with a cryogenic cooling means, wherein,
(1) the constant temperature system has refrigeration and heating functions, and can regulate and control the temperature in the anode tank to be 5-60 ℃ through circulating liquid in a cooling pipe connected to the anode tank;
(2) the direct current power supply can provide direct current of 0.2A-1.0A and is respectively connected to the anode tank and the cathode tank of the electrolytic cell through electric wires;
(3) adopting a titanium sheet or a platinum sheet as a cathode and adopting a platinum sheet, a gold sheet or graphite as an anode;
(4) the diaphragm membrane is cation exchange membrane, such as polyethylene heterogeneous cation exchange membrane and GCCM-S cation exchange membrane;
(5) the electrolytic cell is made of polytetrafluoroethylene;
(6) the stirring device can adopt mechanical stirring or magnetic stirring, and can dissolve or uniformly mix reactants.
Detailed Description
The present invention is described in detail below by way of examples, it being necessary here to point out that the examples are provided for the purpose of further illustration of the invention and are not to be construed as limiting the scope of protection of the invention, since numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the above teachings.
Example 1
(1) Adding 200ml of dilute sulfuric acid solution with the concentration of 0.3mol/L into an anode tank of an electrolytic cell, weighing 0.25 g of sodium iodate, adding into the anode tank, and stirring to completely dissolve the sodium iodate;
(2) weighing 4 g of chitosan, adding the chitosan into an anode tank, and stirring to completely dissolve the chitosan;
(3) 300ml of dilute sulfuric acid with the concentration of 0.15mol/L is added into a cathode tank of an electrolytic cell;
(4) turning on a direct current power supply, setting the current to be 1.0A, controlling the temperature to be 50 ℃, and reacting for 3 hours under the condition of keeping out of the sun;
(5) adding 200ml of absolute ethyl alcohol, collecting the precipitate, and collecting waste liquor;
(6) pouring the precipitate into a dialysis bag with molecular weight cutoff of 8000Da, putting the dialysis bag into 500ml of distilled water, dialyzing for 12h, and collecting the distilled water after the first dialysis;
(7) then placing the dialysis bag in 1500ml of distilled water, changing the distilled water every 12 hours, and dialyzing for 48 hours;
(8) taking out the product in the dialysis bag, and obtaining oxidized chitosan by a freeze drying method;
(9) mixing the waste liquid in the step (5) and the distilled water collected in the step (6) after the first dialysis, and taking 200ml of mixed liquid;
(10) adding 3 g of concentrated sulfuric acid, 0.1 g of sodium iodate and 4 g of chitosan, and completely dissolving the materials;
(11) then, the steps are carried out according to the step (4) and the subsequent steps;
in this example, a titanium sheet was used as a cathode and a platinum sheet was used as an anode, and a polyethylene heterogeneous cation exchange membrane was used, followed by mechanical stirring.
Example 2
(1) Adding 100ml of dilute sulfuric acid solution with the concentration of 0.2mol/L into an anode tank of an electrolytic cell, weighing 0.5 g of sodium iodate, adding into the anode tank, and stirring to completely dissolve the sodium iodate;
(2) weighing 10 g of chitosan oligosaccharide, adding the chitosan oligosaccharide into an anode tank, and stirring to completely dissolve the chitosan oligosaccharide;
(3) adding 250ml of dilute sulfuric acid with the concentration of 0.3mol/L into a cathode tank of an electrolytic cell;
(4) turning on a direct current power supply, setting the current to be 1.5A, controlling the temperature to be 16 ℃, and reacting for 2 hours under the condition of keeping out of the sun;
(5) pouring the reactant into a dialysis bag with the molecular weight cutoff of 500Da, putting the dialysis bag into 1500ml of distilled water, changing the distilled water every 12 hours, and dialyzing for 24 hours;
(6) taking out the product in the dialysis bag, and performing freeze drying to obtain oxidized chitosan oligosaccharide;
in the example, a platinum sheet is used as a cathode, graphite is used as an anode, a diaphragm membrane is a GCCM-S cation exchange membrane, and magnetic stirring is carried out.
Example 3
(1) Adding 300ml of dilute sulfuric acid solution with the concentration of 0.15mol/L into an anode tank of an electrolytic cell, weighing 1 g of sodium iodate, adding into the anode tank, and stirring to completely dissolve the sodium iodate;
(2) weighing 10 g of chitosan biquaternary ammonium salt, adding the chitosan biquaternary ammonium salt into an anode tank, and stirring to completely dissolve the chitosan biquaternary ammonium salt;
(3) 200ml of dilute sulfuric acid with the concentration of 0.2mol/L is added into a cathode tank of an electrolytic cell;
(4) turning on a direct current power supply, setting the current to be 0.6A, controlling the temperature to be 5 ℃, and reacting for 5.0 hours under the condition of keeping out of the sun;
(5) pouring the reactant into a dialysis bag with the molecular weight cutoff of 3000Da, putting the dialysis bag into 500ml of distilled water for dialysis for 12h, and collecting the dialyzed distilled water;
(6) then putting the dialysis bag into 2000ml of distilled water for dialysis for 12 hours, changing the distilled water every 12 hours, and dialyzing for 48 hours;
(7) taking out the product in the dialysis bag, and drying in vacuum to obtain oxidized chitosan biquaternary ammonium salt;
(8) taking 300ml of distilled water collected in the step (5) and subjected to first dialysis, adding 4.5 g of concentrated sulfuric acid with the concentration of 98%, uniformly stirring, adding 0.6 g of sodium iodate, adding into an anode tank, dissolving in the anode tank, and stirring to completely dissolve the sodium iodate;
(9) then, the operation of the step (2) and the subsequent steps is carried out;
in this example, a titanium sheet is used as a cathode, a gold sheet is used as an anode, a diaphragm membrane is a polyethylene heterogeneous cation exchange membrane, and magnetic stirring is performed.
Claims (3)
1. The electrolytic process of preparing oxidized chitosan and its derivative features that the reaction is performed in a special electrolytic cell with low temperature cooling unit, and includes the following steps:
(1) adding 100-300 parts by weight of dilute sulfuric acid solution with the concentration of 0.15-0.3 mol/L into an anode tank of an electrolytic cell, weighing 0.3-1.5 parts by weight of sodium iodate, adding into the anode tank, and stirring to completely dissolve the sodium iodate;
(2) weighing 5-10 parts by weight of chitosan and derivatives thereof, adding into an anode tank, and stirring to completely dissolve the chitosan and the derivatives thereof;
(3) adding 200-300 parts by weight of dilute sulfuric acid with the concentration of 0.15-0.3 mol/L into a cathode tank of an electrolytic cell;
(4) turning on a direct current power supply, setting the current to be 0.2A-1.5A, controlling the temperature to be 5-60 ℃, and reacting for 0.5-5.0 hours under the condition of light shielding;
(5) pouring the reactant into a dialysis bag with the molecular weight cutoff of 500-8000 Da, putting the dialysis bag into 500-3000 parts by weight of distilled water, dialyzing for 12 hours, collecting the distilled water after the first dialysis, then putting the dialysis bag into 500-3000 parts by weight of distilled water, changing the distilled water every 12 hours, and dialyzing for 12 hours-72 hours;
(6) taking out the product in the dialysis bag, and performing vacuum drying or freeze drying to obtain oxidized chitosan and derivatives thereof;
(7) the collected distilled water after the first dialysis can be added with sulfuric acid and sodium iodate, and can be used for preparing the solution in (1).
2. The electrolytic process for the preparation of oxidized chitosan and its derivatives as claimed in claim 1, wherein said dedicated electrolytic cell with cryogenic cooling means is characterized by the structure shown in figure 1:
(1) the constant temperature system has refrigeration and heating functions, and can regulate and control the temperature in the anode tank to be 5-60 ℃ through circulating liquid in a cooling pipe connected to the anode tank;
(2) the direct current power supply can provide direct current of 0.2A-1.0A and is respectively connected to the anode tank and the cathode tank of the electrolytic cell through electric wires;
(3) adopting a titanium sheet or a platinum sheet as a cathode and adopting a platinum sheet, a gold sheet or graphite as an anode;
(4) the diaphragm membrane is cation exchange membrane, such as polyethylene heterogeneous cation exchange membrane and GCCM-S cation exchange membrane;
(5) the electrolytic cell is made of polytetrafluoroethylene;
(6) the stirring device can adopt mechanical stirring or magnetic stirring, and can dissolve or uniformly mix reactants.
3. The electrolytic process of claim 1, wherein said chitosan and its derivatives are chitosan, chitosan oligosaccharide, carboxymethyl chitosan, chitosan mono-quaternary ammonium salt, chitosan di-quaternary ammonium salt.
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