CN112480287B - Oxidized chitosan, preparation method and application thereof - Google Patents

Oxidized chitosan, preparation method and application thereof Download PDF

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CN112480287B
CN112480287B CN202011163828.0A CN202011163828A CN112480287B CN 112480287 B CN112480287 B CN 112480287B CN 202011163828 A CN202011163828 A CN 202011163828A CN 112480287 B CN112480287 B CN 112480287B
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chitosan
ball milling
persulfate
oxidized
mixture
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CN112480287A (en
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葛亮
仇稳
维克利
黄�俊
包一翔
余刚
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Tsinghua University
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Abstract

The invention relates to a preparation method of oxidized chitosan, which comprises the following steps: mixing solid chitosan and a solid oxidant, and ball-milling the obtained solid mixture under the condition of no solvent. The invention also relates to the oxidized chitosan prepared by the preparation method of the oxidized chitosan and application thereof. The invention further relates to a medicament and a water-filtering material.

Description

Oxidized chitosan, preparation method and application thereof
Technical Field
The invention relates to the technical field of biological material preparation, in particular to oxidized chitosan and a preparation method and application thereof.
Background
Chitosan is a linear aminopolysaccharide consisting of randomly distributed β (1 → 4) D-glucosamine (deacetylation units) and N-acetyl-D-glucosamine (acetyl units). A common preparation method of chitosan is deacetylation of chitin, which is an important constituent of exoskeleton of crustaceans (such as crab and shrimp) and fungal cell walls, using excess sodium hydroxide as a reagent and water as a solvent (as shown in FIG. 1). The pKa of the chitosan amino group is about 6.5, the amino group is significantly protonated in neutral solution, with an increased degree of protonation at low pH and/or high degree of deacetylation. Therefore, chitosan is easily bound to negatively charged substances. The chitosan increases the transport of the medicine on the surface of the mucosal epithelium and has good biocompatibility and biodegradability. Chitosan has a wide range of uses, particularly in the biomedical field. In agricultural production, it can be used as seed treatment agent and biological pesticide to help plant resist fungal infection. In brewing wine, it can be used as a clarifying agent. In industry, it can be used for self-healing polyurethane coatings. As an antimicrobial agent in medicine, it is a useful bandage to achieve reduced bleeding. Chitosan has potential applications in other areas, for example, it is used for drug delivery through skin or by food consumption. The chitosan and the composite material thereof can be used as a purifying material for removing polluted water and sewage. Proper modification of chitosan will further promote its functions, such as increasing the adsorption capacity of the adsorbent, thereby increasing the adsorption capacity of the adsorbent.
In order to improve the adsorption performance of chitosan, a number of physical modification (e.g., foaming, blending, etc.) and chemical modification methods have been studied. Chemical methods produce large quantities of chitosan derivatives with a variety of good properties. Generally, chemical modification methods include crosslinking, oxidation, grafting, substitution of functional groups (particularly amino and hydroxyl groups), and the like. The oxidation method is a simple and effective method for modifying chitosan. The modified chitosan is obtained by using an oxidizing agent such as hydrogen peroxide or a reactive radical. Generally, this treatment randomly depolymerizes chitosan, thereby reducing its viscosity and increasing its biodegradability (also in vivo), and introduces hydrophilic oxygen-containing functional groups, such as carbonyl groups, carboxymethyl groups, etc., into the biopolymer to modify chitosan and introduce specific functions. The oxidation process, as well as other chemical modification processes of chitosan, are carried out by chemical reactions in solution (especially in water due to the good solubility of chitosan in polar solvents). However, this expensive and non-green method is disadvantageous for the wide application of modified chitosan due to the large amount of solvent used in the production process. Thus, simpler, less costly, and greener processes would facilitate the utilization of such materials in a variety of applications.
Disclosure of Invention
Based on this, there is a need for an oxidized chitosan which can be easily mass-produced under solvent-free conditions, and a preparation method and applications thereof.
In one aspect of the present invention, a method for preparing oxidized chitosan is provided, which comprises the following steps:
mixing solid chitosan and a solid oxidant, and ball-milling the obtained solid mixture under the condition of no solvent.
In one embodiment, the solid oxidizer is selected from one or more of persulfates, metal peroxides, percarbonates.
In one embodiment, the mass percentage of the oxidant in the mixture is 10% to 50%.
In one embodiment, the power of the ball mill is more than or equal to 1 kw/kg.
In one embodiment, the ball milling power is 1-4 kw/kg, and the ball milling time is 0.5-3 h.
In one embodiment, the oxidant is persulfate, the mass percentage of the persulfate in the mixture is 30% -40%, the ball milling power is 3-4 kw/kg, and the ball milling time is 1-2 h.
In one embodiment, the oxidizing agent is calcium peroxide, the mass percentage of the calcium peroxide in the mixture is 40% -50%, the ball milling power is 3-4 kw/kg, and the ball milling time is 1-2 h.
In one embodiment, the oxidizing agent is sodium percarbonate, the mass percentage of the sodium percarbonate in the mixture is 10-20%, the ball milling power is 3-4 kw/kg, and the ball milling time is 2-3 h.
In still another aspect of the present invention, there is provided an oxidized chitosan prepared by the method for preparing an oxidized chitosan.
In still another aspect of the present invention, there is provided the use of said oxidized chitosan as an adsorbent or a drug carrier.
In still another aspect of the present invention, there is provided a medicament comprising a negatively charged pharmaceutically active ingredient and a medicament carrier comprising the oxidized chitosan of claim 11.
In one embodiment, the negatively charged pharmaceutically active ingredient is an antibiotic.
In one embodiment, the antibiotic is penicillin.
In still another aspect of the present invention, there is provided a water filtration material comprising said oxidized chitosan.
The preparation method of the oxidized chitosan provided by the invention does not use any solvent, adopts a ball-milling mechanochemical method and utilizes an oxidant to oxidize the chitosan in a solid phase. Because no solvent is used, the production cost can be greatly reduced, and the pollution of some non-green solvents to the environment can be avoided. Therefore, the method is particularly suitable for industrial large-scale production.
The oxidized chitosan prepared by the preparation method of the oxidized chitosan provided by the invention has good adsorption capacity and adsorption performance. In the high crystallinity of native chitosan, the polymer chains are packed in parallel, tightly entangled. The inventor of the invention firstly discovers that under the action of ball milling and an oxidant, hydrogen bonds between amino and hydroxyl in the primary chitosan can be destroyed, and simultaneously-NH2The group is oxidized into-NO, the polymer chain is broken, the length of the polymer chain is reduced, the entanglement among the polymer chains is loosened, the polymer chain becomes disordered and the material is amorphous, and the material is converted from the primary chitosan with a crystal structure into the oxidized chitosan with an amorphous structure, so that the adsorbate can enter the inside of the oxidized chitosan particles more easily, and the adsorption performance of the oxidized chitosan is further improved.
Drawings
FIG. 1 is a schematic diagram of chitosan preparation by deacetylation of chitin;
FIG. 2 is a schematic view of a process for preparing oxidized chitosan according to the present invention;
FIG. 3 is a thermal analysis spectrum of oxidized chitosan by mechanochemical reaction obtained by different mass percentage of potassium persulfate and different ball milling time;
FIG. 4 is a Fourier transform infrared spectrum of chitosan oxide obtained with different mass percent potassium persulfate and different ball milling times;
FIG. 5 is a schematic diagram of a chemical reaction of ball-milling oxidized chitosan;
FIG. 6 is a schematic diagram showing morphological changes of chitosan before and after ball milling.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The embodiment of the invention provides a preparation method of oxidized chitosan, which comprises the following steps:
s10, mixing the solid chitosan with the solid oxidant, and ball-milling the obtained solid mixture under the condition of no solvent.
According to the preparation method of the oxidized chitosan provided by the embodiment of the invention, no solvent is used, a ball-milling mechanochemical method is adopted, and the chitosan is oxidized in a solid phase by using an oxidant. Because no solvent is used, the production cost can be greatly reduced, and the pollution of some non-green solvents to the environment can be avoided. Therefore, the method is particularly suitable for industrial large-scale production.
The chitosan is a biopolymer obtained by deacetylation of chitin, can have various deacetylation degrees and molecular weights, and can be prepared by any deacetylation method known to those skilled in the art.
The solid oxidant may be selected from one or more of persulfates, metal peroxides, percarbonates. The persulfate, the calcium peroxide and the sodium percarbonate are green reagents and are environment-friendly. Preferably, the solid oxidizer is a persulfate. The persulfate may be one or more of sodium persulfate, potassium persulfate, and ammonium persulfate. The metal peroxide may be calcium peroxide or sodium peroxide. The percarbonate may be sodium percarbonate and/or potassium percarbonate.
The mass percentage of the oxidizing agent in the mixture may be any value between 10% and 50%, and for example, may be 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%.
The ball milling of the present invention belongs to a mechanochemical method, and is characterized in that mechanical energy is acted on the mixture through various forces of impact, friction, shearing, compression, etc. By means of said ball milling, said mixture is susceptible to a large accumulation of mechanical energy due to the strong mechanical forces, and since said mixture is two or more solids, chemical reactions between them occur. The ball milling is used to react the solid materials directly under strong mechanical forces without the addition of solvents. And thus is more environmentally friendly than solvent processes.
In order to make the preparation method of the oxidized chitosan more economic and effective, the power of the ball mill is more than 1 kw/kg.
In a preferred embodiment, the power of the ball milling is 1-4 kw/kg, and the ball milling time is 0.5-3 h.
In one embodiment, the oxidant is persulfate, the mass percentage of the persulfate in the mixture can be 30% -40%, the ball milling power is 3 kw/kg-4 kw/kg, and the ball milling time is 1 h-2 h.
In another embodiment, the oxidizing agent is calcium peroxide, the persulfate is 40-50% by mass in the mixture, the ball milling power is 3-4 kw/kg, and the ball milling time is 1-2 hours.
In another embodiment, the oxidant is sodium percarbonate, the persulfate is contained in the mixture in an amount of 10-20% by mass, the ball milling power is 3-4 kw/kg, and the ball milling time is 2-3 h.
The ball milling may be performed by a high energy ball mill. The high-energy ball mill can be a planetary ball mill, a centrifugal ball mill (also called rolling ball mill), a vibration ball mill or a stirring ball mill.
The type of the ball mill, the diameter and weight of the grinding balls in the ball mill and the ball milling time are all parameters which influence the mechanical energy provided by the ball mill to the solid material. Different ball mill types can provide the same mechanical energy using different parameters.
The filling rate of the mixture in the high-energy ball mill can be 10-60%, and the filling rate range can enable the mixture to be more sufficiently ball-milled, so that the adsorption capacity of the oxidized chitosan can be improved, and the preferable range is 40%.
The invention also provides the oxidized chitosan prepared by the preparation method of the oxidized chitosan.
The oxidized chitosan prepared by the preparation method of the oxidized chitosan provided by the embodiment of the invention can be preparedHas good adsorption capacity and adsorption performance. In the high crystallinity of native chitosan, the polymer chains are packed in parallel, tightly entangled. The inventor of the invention firstly discovers that under the action of ball milling and an oxidant, hydrogen bonds between amino and hydroxyl in the primary chitosan can be destroyed, and simultaneously-NH2The group is oxidized into-NO, the polymer chain is broken, the length of the polymer chain is reduced, the entanglement among the polymer chains is loosened, the polymer chain becomes disordered and the material is amorphous, and the material is converted from the primary chitosan with a crystal structure into the oxidized chitosan with an amorphous structure, so that the adsorbate can enter the inside of the oxidized chitosan particles more easily, and the adsorption performance of the oxidized chitosan is further improved.
The invention further provides application of the oxidized chitosan serving as an adsorbent or a drug carrier.
The adsorbent may be a dye adsorbent.
The adsorbent may be used for purifying water.
The invention also provides a water filtering material, which comprises the oxidized chitosan.
The invention further provides a medicament, which comprises a negatively charged medicament active ingredient and a medicament carrier, wherein the medicament carrier comprises the oxidized chitosan.
In one embodiment, the negatively charged pharmaceutically active ingredient is an antibiotic.
In one embodiment, the antibiotic is penicillin.
The following are specific examples. The present invention is intended to be further described in detail to assist those skilled in the art and researchers to further understand the present invention, and the technical conditions and the like do not limit the present invention. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention. The reagents and equipment used in the following examples are as follows:
chitosan with CAS number of 9012-76-4; potassium persulfate with CAS number 7727-21-1; sodium percarbonate with CAS number 15630-89-4; calcium peroxide, CAS number 1305-79-9.
The ball mill is a planetary ball mill, and the model is QM-3SP2, Nanda instruments.
Example 1
(1) Potassium persulfate (KPS) was mixed with chitosan at different mass fractions (potassium persulfate content 0% to 50% as shown in Table 1) to give a solid mixture with a total mass of 2 g.
(2) The mixture from step (1) was placed in a milling jar containing 128g of stainless steel milling balls (diameter 5mm) with a jar fill of 40%. The planetary ball mill was operated at 225 rpm to provide 3.9kw/kg of mechanical power to the mixture. The mechanochemical reaction was carried out at different ball milling times as indicated in table 1.
FIG. 3 is a chart showing the thermogram of mechanochemical reaction obtained with different mass percent contents of potassium persulfate and different ball milling times (at N)2Obtained under protection) and the dotted line is its first derivative plot. In the figure, a curve labeled 30% PS-0h represents a thermal analysis curve or a first derivative curve of chitosan without ball milling, to which potassium persulfate was added in an amount of 30% by mass; a curve marked as 30% PS-1h represents a thermal analysis curve or a first derivative curve of chitosan added with 30% of potassium persulfate by mass percentage and ball-milled for 1 hour; the curve labeled 30% PS-3h represents the thermal analysis curve or first derivative curve of chitosan ball-milled for 3 hours with 30% by mass of potassium persulfate added.
As can be seen from fig. 3, the thermal decomposition of chitosan is divided into two mass loss stages (identified by the first derivative plot): the first (>100 ℃) is due to the evaporation of chitosan moisture; the second, most significant mass loss rate at 300 ℃, is about 60% due to thermal degradation of its polymer. An unground mixture of 30% potassium persulfate resulted in two changes: one with a smaller transition at 200 c and one with a larger transition at 260 c. Both of these transitions are attributed to the onset of polymer degradation before the thermal degradation temperature (300 ℃) where the amount of weight loss changes from 300 ℃ to 260 ℃, indicating that the chitosan is partially oxidized by potassium persulfate, thus its degradation temperature decreases, indicating that it is possible to oxidize chitosan with potassium persulfate. The 30% PS-0h total mass loss was small compared to chitosan due to the presence of non-volatile potassium persulfate and potassium sulfate in the sample. Similar trends appeared for the samples ball milled for 1 hour (30% PS-1h) and 3 hours (30% PS-3 h). The two transitions caused by potassium persulfate (occurring at 220 ℃ and 260 ℃) determine a more significant mass loss, probably due to improved contact between chitosan and potassium persulfate, as well as partial oxidation of chitosan and reduction of biopolymer chain length caused by potassium persulfate. The primary role of potassium persulfate in the thermal degradation of chitosan in ball-milled samples can be inferred by the almost insignificant mass reduction at 300 ℃ and the more significant mass loss caused by the two lower temperatures (i.e., 220 ℃ and 260 ℃).
FIG. 4 is a Fourier transform infrared spectrum of the reaction products obtained at different mass percent levels of potassium persulfate and different ball milling times. In the figure, the curve marked as 0% PS-3h represents the infrared spectrum curve of the reaction product after 3 hours of ball milling of chitosan without potassium persulfate added; a curve labeled 30% PS-0h, representing the infrared spectrum curve of the reaction product of chitosan without ball milling, to which potassium persulfate was added in an amount of 30% by mass; a curve marked as 30% PS-1h represents the infrared spectrum curve of a reaction product of chitosan added with 30% of potassium persulfate by mass percentage and ball milled for 1 hour; a curve marked as 30% PS-3h represents the infrared spectrum curve of a reaction product of chitosan added with 30% of potassium persulfate by mass percentage and ball-milled for 3 hours; a curve marked as 50% PS-1h represents the infrared spectrum curve of a reaction product of chitosan added with 50% of potassium persulfate by mass percentage and ball milled for 1 hour; the curve labeled 50% PS-3h represents the IR spectrum of the reaction product of chitosan ball milled for 3 hours with the addition of 50% by mass of potassium persulfate.
The results show that the reaction product of the chitosan without potassium persulfate after 3 hours of reaction (0% PS-3 hours) has no significant difference from the chitosan, indicating that no oxidation reaction occurs. Mixtures of unground chitosan and 30% by mass of potassium persulfate (30% PS-0h) exhibited several new absorption peaks, as they were associated with various oscillations of the S ═ O bond and other bonds of potassium persulfate.Compared with chitosan, the mixture of potassium persulfate and chitosan with the mass percentage of 30 percent shows obvious change after being ground for 1 hour (30 percent PS-1 hour), the strength of the potassium persulfate peak is obviously reduced, and the N-H vibration peak (1600 cm)-1) Almost unrecognizable vibration associated with the vibration of the amido-carbonyl group (1650 cm)-1C ═ O) can still be resolved; by-NH-co2Vibration intensity (1350--1) Is also reduced. When the spectrum obtained by grinding a mixture of potassium persulfate and chitosan at 30% by mass for 1 hour (30% PS-1h) was compared with the spectrum obtained by grinding a mixture of potassium persulfate and chitosan at 50% by mass for 1 hour (50% PS-1h), it was noted that the peak C ═ O had a lower wavenumber (1630 cm)-1) A significant displacement occurs. This indicates that the peak is formed by the superposition of two peaks: one is the peak of the original carbonyl group whose intensity is decreasing, and the other is formed by NH2Oxidation to form new N ═ O groups, which explains N-H and-NH2The reason why the peak intensity is reduced.
The spectrum of the mixture of 30% by mass of persulfate and chitosan after ball milling for 3 hours (30% PS-3h) is very obvious, and the spectrum of the mixture of 50% by mass of persulfate and chitosan after ball milling for 3 hours (50% PS-3h) is more obvious. In both cases, chemical change (i.e. NH)2Oxidation of the group to an N ═ O group) is more pronounced. The degree of deacetylation determination confirmed this: the deacetylation degree of the chitosan oxide prepared by ball milling a mixture of 30% by mass of persulfate and chitosan for 3 hours is 77.7%, and the deacetylation degree of the chitosan oxide prepared by ball milling a mixture of 30% by mass of persulfate and chitosan for 1 hour is 63.5%. The important peak in the 50% PS-3h spectral curve is 850cm-1This is due to the vibration of C-S-O. This indicates the effect of potassium persulfate: part of the mixture is activated by high-energy ball milling to form potassium persulfate free radicals (high-degree oxidizing agents) and part of the mixture forms sulfonic chitosan.
And (3) testing the adsorption performance of the oxidized chitosan prepared by potassium persulfate with different mass percent and different ball milling time by using active red 2 anionic dye (containing two sulfonic groups) as model adsorption. Mixing products (5mg) obtained after the mixture of potassium persulfate (0-50%) and chitosan with different mass percentage contents react for different ball milling time (0-3h) with 50mL of 100mg/L active red 2 aqueous solution. The mixed solution was not subjected to any pH modification, and after stirring at a rotation speed of 160 rpm at room temperature (20 ℃ C.) for 5 hours, the solution was aliquoted, filtered through a 0.22 μm filter, and subjected to quantitative analysis of active Red 2 by spectrophotometry, and the adsorption capacity (adsorption capacity: 2 mg of active Red adsorbed per gram of oxidized chitosan) of each sample was calculated, the results being shown in Table 1.
TABLE 1
Figure GDA0002893188230000091
As can be seen from the results of Table 1, chitosan had a better adsorption capacity (485.5mg/g) due to a large amount of-NH2Protonation in water to produce-NH3 +And can bind to negatively charged reactive red 2 molecules. As the ball milling time is prolonged, the specific surface area of chitosan and the exposure of-NH are reduced due to the reduction of the particle size2The amount of (a) increases, and the ability to adsorb active red 2 increases. However, when the ball milling time exceeds 1 hour, the supply of further mechanical energy starts to cause the degradation of the polymer, and the adsorption amount tends to decrease. The addition of potassium persulfate causes the chitosan to oxidize during the ball milling process, especially-NH2The group oxidizes to-NO and the polymer chain breaks. Chemical changes that may occur in the ball-milled oxidized chitosan are shown in fig. 5. although-NH2The content is slightly reduced (i.e. the degree of deacetylation), but oxidation has a favourable effect on the adsorption of activated red 2. This is due to the reduction of polymer chain length and chain entanglement (this is due to NH)2Number reduction) so that the adsorbate can reach the interior of the oxidized chitosan particle. Specifically, in the high-crystallinity raw chitosan, the polymer chains are filled in a parallel form, tightly entangled, and under the action of ball milling and an oxidizing agent, hydrogen bonds between amino groups and hydroxyl groups in the raw chitosan can be broken, so that the raw chitosan is converted from a crystal structure to an amorphous structure, the polymer chains are disordered and the material is amorphous, and the chain entanglement is reduced and loosened, as shown in fig. 6, the raw chitosan hasAmorphous fraction (a) and crystalline fraction (B), the amorphous fraction becoming less entangled (C) and the crystalline fraction becoming somewhat amorphous (D) after ball milling. Therefore, the internal functional groups of the oxidized chitosan may adsorb contaminants. The product of ball milling a 30% mass fraction mixture of potassium persulfate and chitosan for 1 hour had a maximum adsorption of 973.7mg/g (the adsorption capacity was measured at pH 6) under the optimum adsorption experimental conditions (ball milling power of 3.9kw/kg, ball milling time of 1 hour). The addition of potassium persulfate is not advantageous for non-ball milling.
Example 2
Example 2 the preparation method of oxidized chitosan was substantially the same as that of example 1 except that: calcium peroxide was used instead of potassium persulfate in example 1.
The adsorption performance of the oxidized chitosan prepared by calcium peroxide with different mass percentage and different ball milling time is tested by taking active red 2 anionic dye (containing two sulfonic groups) as model adsorption. Mixing a product (5mg) obtained after the mixture of calcium peroxide (0-50%) and chitosan with different mass percentage contents react for different ball milling time (0-3h) with 50mL of 100mg/L active red 2 aqueous solution. The mixed solution was not subjected to any pH modification, and after stirring at a rotation speed of 160 rpm at room temperature (20 ℃ C.) for 5 hours, the solution was aliquoted, filtered through a 0.22 μm filter, and subjected to quantitative analysis of active Red 2 by spectrophotometry, and the adsorption capacity (adsorption capacity: 2 mg of active Red adsorbed per gram of oxidized chitosan) of each sample was calculated, the results being shown in Table 2.
TABLE 2
Figure GDA0002893188230000101
Figure GDA0002893188230000111
The results in Table 2 show that calcium peroxide can also improve the adsorption capacity of chitosan, and oxidized chitosan can be obtained. For calcium peroxide, a 50% by weight mixture of calcium peroxide and chitosan ball milled for 1 hour had the maximum adsorption capacity (897.6mg/g, measured at pH 6).
In contrast to the results in Table 1, calcium peroxide is less reactive than potassium persulfate because it requires a higher mass concentration percentage to achieve maximum adsorption capacity, but the maximum adsorption capacity (897.6mg/g) that can be achieved by oxidizing chitosan with calcium peroxide as the oxidant product is less than the maximum adsorption capacity (973.7mg/g) that can be achieved by oxidizing chitosan with potassium persulfate as the oxidant product. However, when calcium peroxide and potassium persulfate are used as the oxidizing agents, the ball milling time for the product to oxidize chitosan to reach the maximum adsorption capacity is consistent.
Example 3
Example 3 the preparation method of oxidized chitosan was substantially the same as that of example 1 except that: sodium percarbonate was used instead of potassium persulfate in example 1.
And (3) testing the adsorption performance of the oxidized chitosan prepared by sodium percarbonate with different mass percentage contents and different ball milling time by using active red 2 anionic dye (active red 2, containing two sulfonic groups) as model adsorption. The product (5mg) of the reaction of the mixture of sodium percarbonate (0-50%) and chitosan in different mass percentages for different ball milling times (0-3h) was mixed with 50mL of 100mg/L aqueous solution of active red 2. The mixed solution was stirred at a rotation speed of 160 rpm for 5 hours at room temperature (20 ℃) without any pH modification, and the solution was aliquoted, filtered through a 0.22 μm filter, and quantitatively analyzed for active red 2 by spectrophotometry, and the adsorption capacity (adsorption capacity: 2 mg of active red adsorbed per gram of oxidized chitosan) of each sample was calculated, and the results are shown in table 3.
TABLE 3
Figure GDA0002893188230000112
The results in Table 3 show that sodium percarbonate can also increase the adsorption capacity of chitosan, i.e., oxidized chitosan is obtained. For sodium percarbonate, the product of ball milling a 20% by mass mixture of sodium percarbonate and chitosan for 3 hours had the maximum adsorption capacity (848.5mg/g, measured at pH 6).
In contrast to the results in table 1, a lower mass percentage (20%) was used for adsorption of activated red 2, using sodium percarbonate as the oxidant, but a longer ball milling time (3 hours) was required to reach the maximum adsorption capacity of the product. Thus, it is relatively less reactive than potassium persulfate, but to a large extent it also initiates other modifications of chitosan, which is detrimental to the increase of adsorption capacity.
Example 4
Example 4 the preparation method of oxidized chitosan was exactly the same as that of example 1, and the product obtained was washed with distilled water to remove the possible residual oxidizing agent potassium persulfate, dried overnight at room temperature, and using penicillin G anion as model drug. The steps of adsorbing penicillin G by using the chitosan oxide are as follows: 5mg of oxidized chitosan was placed in an Erlenmeyer flask and mixed with 50ml of 100mg/L aqueous penicillin G solution. The flask was stirred at 160 rpm for 24 hours, and then an aliquot of the solution was removed and analyzed quantitatively by LC-MS for the residual concentration of penicillin G. The penicillin G adsorption capacity (adsorption capacity: milligrams of penicillin G adsorbed per gram of oxidized chitosan) was calculated for each sample, and the results are shown in Table 4.
TABLE 4
Figure GDA0002893188230000121
The results showed that chitosan had a better penicillin G adsorption capacity (488.7mg/G) due to the high amount of-NH content2Will protonate to form NH in water3 +Capable of binding to negatively charged penicillin G molecules. As the ball milling time is prolonged, the specific surface area of the oxidized chitosan and the exposure of-NH are reduced due to the reduction of the particle size2The amount of penicillin G adsorbed by the immobilized penicillin G adsorbent increases. Thus, potassium persulfate oxidized chitosan promoted the adsorption of penicillin G. Specifically, the content of the compound is 40 percent by massThe adsorption capacity (957.5mg/G) of penicillin G by the product oxidized chitosan obtained by ball milling the mixture of potassium sulfate and chitosan for 1 hour is increased by two times compared with the adsorption capacity (488.7mg/G) of penicillin G by chitosan. As mentioned above, the ball milling and the action of potassium persulfate can cause the chitosan polymer chain to be shortened and a small amount of-NH to be generated2The oxidation is carried out to form an N ═ O group, the hydrogen bond between the amino group and the hydroxyl group of the chitosan is broken, the chitosan is oxidized to form an amorphous structure, and the polymer chain is slightly entangled. Therefore, penicillin G molecules more easily enter the inside of the oxidized chitosan particles, thereby improving the adsorption capacity thereof.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A medicine is characterized by comprising a negatively charged medicinal active ingredient and a medicinal carrier, wherein the negatively charged medicinal active ingredient is penicillin, the medicinal carrier is oxidized chitosan,
the oxidized chitosan is prepared by ball milling a mixture of solid chitosan and a solid oxidant under the solvent-free condition, wherein the solid oxidant is persulfate, the mass percentage of the persulfate in the mixture is 30% -40%, the ball milling power is 3.9kW/kg, and the ball milling time is 1 h.
2. The pharmaceutical of claim 1, wherein the persulfate salt is selected from one or more of sodium persulfate, potassium persulfate, and ammonium persulfate.
3. A water filtering material is characterized by comprising oxidized chitosan, wherein the oxidized chitosan is prepared by ball milling a mixture of solid chitosan and a solid oxidant under the condition of no solvent,
the solid oxidant is persulfate, the mass percentage of the persulfate in the mixture is 30% -40%, the ball milling power is 3.9kW/kg, and the ball milling time is 1-2 h.
4. A water filtering material according to claim 3, wherein the persulfate is selected from one or more of sodium persulfate, potassium persulfate and ammonium persulfate.
5. A water filtering material is characterized by comprising oxidized chitosan, wherein the oxidized chitosan is prepared by ball milling a mixture of solid chitosan and a solid oxidant under the condition of no solvent,
the solid oxidant is metal peroxide, the mass percentage of the metal peroxide in the mixture is 40% -50%, the ball milling power is 3.9kW/kg, and the ball milling time is 2 hours.
6. Water filtering material according to claim 5, wherein said metal peroxide is selected from calcium peroxide or sodium peroxide.
7. A water filtering material is characterized by comprising oxidized chitosan, wherein the oxidized chitosan is prepared by ball milling a mixture of solid chitosan and a solid oxidant under the condition of no solvent,
the solid oxidant is percarbonate, the mass percentage of the percarbonate in the mixture is 20%, the ball milling power is 3.9kW/kg, and the ball milling time is 3 hours.
8. A drainage material according to claim 7, wherein the percarbonate is selected from sodium percarbonate and/or potassium percarbonate.
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