CN114917351B - Drug carrier based on lignin nanotubes and preparation method thereof - Google Patents
Drug carrier based on lignin nanotubes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a drug carrier based on lignin nanotubes and a preparation method thereof. The drug carrier comprises lignin nanotubes and a coating layer coated on the surface of the lignin nanotubes; the coating layer comprises functional molecules crosslinked with lignin nanotubes and a phase change material for capping. The invention constructs the drug carrier based on the lignin nanotube, the constructed drug carrier has excellent loading activity and slow release function, and simultaneously, the invention also provides a process for preparing the lignin nanotube with high efficiency and low cost. The morphology of the lignin nanotubes is regulated and controlled by regulating and controlling the cosolvent, the electrolyte and the dialysis parameters, and the lignin nanotubes can be prepared in a large scale and stably stored, more importantly, the prepared lignin nanotubes are lignin nanotubes with new morphology, have a branching structure and a blocking structure, and have important influence on drug loading.
Description
Technical Field
The invention relates to the technical field of drug carriers, in particular to a drug carrier based on lignin nanotubes and a preparation method thereof.
Background
Lignin is the only renewable natural aromatic polymer in nature, and has wide sources, and accounts for 15-30% of various agriculture and forestry biomass resources, and besides, the pulping and papermaking industry can generate a large amount of lignin wastes, and most of the lignin wastes are consumed as low-value fuel or filler, so that the resource waste is caused. Lignin has the functions of antibiosis, antioxidation, ultraviolet absorption and the like, contains a large number of phenolic hydroxyl functional groups, and can be assembled into a stable nano structure by means of pi-pi interaction and hydrogen bond interaction of benzene rings. However, few researches on lignin nanotubes are reported at present, the preparation of pure lignin nanotubes takes foamed aluminum or a nano-pore aluminum mould as a template, lignin is deposited on the inner wall of the porous template through a complex chemical activation process, and the lignin nanotubes can be prepared by controlling the deposited lignin and further lignin monomer compound dehydrogenation polymerization deposition thickness, but various chemical reagents and consumables are used in the preparation process, the process is complex, the yield is low, the cost is high, and the prepared nano lignin morphology is completely limited by the microscopic morphology of the template.
With the development of nano technology, the nano material, in particular to nano particles which are used for in-vivo transportation of traditional medicines, can improve the targeting property and the utilization rate of the medicines, reduce the toxic and side effects of the medicines and have a slow release function, is a breakthrough point for the development of modern medicines. When the nano particles are used as drug carriers, part of the nano particles have a certain slow release function, such as Prussian blue nano particles; in addition, the degradable slow release layer can be added to play a slow release role, such as in vivo degradable biological materials, temperature-sensitive phase change materials and the like. When using phase change materials, there is often a problem of phase separation between each phase component in the multi-element composite phase change material, thereby causing the slow release function of the composite phase change material to be affected. Therefore, the development of the drug carrier with the functions of slow release, high efficiency and the like based on the lignin nanotubes has wide medical prospect.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a drug carrier based on lignin nanotubes and a preparation method thereof, which can effectively solve the problems of low efficiency and poor slow release effect of the existing drug carrier system.
The technical scheme for solving the technical problems is as follows:
a drug carrier based on lignin nanotubes comprises lignin nanotubes and a coating layer coated on the surface of the lignin nanotubes; the coating layer comprises functional molecules crosslinked with lignin nanotubes and a phase change material for capping.
Further, lignin nanotubes have branched structures and end capping structures such as spherical end capping structures.
The beneficial effects of the invention are as follows: the invention constructs a drug carrier by taking lignin nanotubes as a matrix, wherein the lignin nanotubes can have a branch structure and a blocking structure such as a spherical blocking structure. The branching structure can increase the surface area of the tube, and the end-capping structure can make the lignin nanotube play a good role of a carrier in the drug loading process and the like.
Meanwhile, the surface of the acidified lignin nanotube contains a large number of carboxyl groups, and can be connected with functional molecules through amide reaction. And after the lignin nanotube is modified by the functional molecules, the lignin nanotube has good dispersibility and stability.
The phase change material can enable the drug-carrying system constructed based on the lignin nanotubes to have a slow release function. Meanwhile, the research shows that the functional molecules can also effectively inhibit the phase separation problem of each component in the multi-element composite phase change material, and avoid the influence of the phase separation on the slow release function of the drug carrier.
Further, the preparation method of the lignin nanotube comprises the following steps:
adding lignin into water, then adding cosolvent, finally adding electrolyte, uniformly mixing, and dialyzing to obtain lignin nanotube; or uniformly mixing a cosolvent with water to form a cosolvent aqueous solution, then adding lignin into the cosolvent aqueous solution, finally adding electrolyte, uniformly mixing, and dialyzing to obtain lignin nanotubes;
wherein the electrolyte is a substance formed by the following anions and cations:
the cation is H + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ And Ag + Any one of them;
the anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- 、HPO 3 2- 、OH - 、CO 3 2- And HCO 3 - Any one of the following.
The beneficial effects of the invention are as follows: the lignin is added into water, and then the cosolvent is added, so that the dissolution speed of the lignin in the water can be increased, the lignin is uniformly dispersed in the water, then the electrolyte is added, the lignin nanotube can be promoted to be formed after the lignin is fully dissolved, and the lignin can be self-assembled to form the lignin nanotube in the dialysis process. The electrolyte used for forming the lignin nanotubes is the substance formed by the anions and cations, and the electrolyte is an electrolyte with weak complexing ability, and the inventor speculates that the electrolyte is likely to form the lignin nanotubes because particularly cations in the electrolyte can be complexed with the lignin, and can promote the formation of the lignin nanotubes. In the process of preparing the lignin nanotube, the size can be influenced by electrolyte, cosolvent and dialysis factors, and the diameter and the length-diameter ratio of the lignin nanotube can be regulated and controlled by regulating the parameters.
The preparation method is simple, lignin is only required to be added into water, then cosolvent is added, electrolyte is added and dissolved, and the lignin nanotube can be formed by self-assembly through dialysis, the process does not need to adopt a high-temperature environment, various reagents and consumables are not required to be used, the morphology of the obtained nano lignin is not limited by the microscopic morphology of a template, and the preparation method is an efficient and low-cost lignin nanotube preparation method, and can be used for mass preparation and stable storage.
Further, lignin nanotubes are acidified and then connected with functional molecules through an amide reaction.
Further, the functional molecule is tyrosine, histidine or cysteine.
Further, the phase change material is a single phase change material or a multi-element composite phase change material.
Further, the phase change material is tetradecanol, lauric acid or stearic acid.
Further, the phase change material includes at least two of lauric acid, stearic acid, myristic acid, palmitic acid, and behenic acid.
Further, the phase change material includes lauric acid and palmitic acid.
Further, the phase change material includes lauric acid and behenic acid.
Based on the technical scheme, the invention can also be improved as follows:
further, lignin is a pure lignin reagent such as dealkalized lignin, sodium lignin sulfonate and the like.
Further, the mass concentration of lignin in the cosolvent aqueous solution is 1-20%, that is, the lignin is added into water, and then the cosolvent is added, and the mass concentration of lignin in the reaction system reaches 1-20%.
The beneficial effects of adopting the further technical scheme are as follows: adding lignin into water, adding cosolvent to promote dissolution, wherein the lignin mass concentration is 1-20%, and under the condition of cosolvent, the lignin can be quickly dissolved and combined with electrolyte to form relatively pure lignin nanotubes, and if the lignin concentration is too high, the dissolution, the combination condition with the electrolyte and the final lignin nanotube formation rate and purity can be influenced.
Further, the cosolvent is an alcohol, an aprotic solvent, a protic solvent, a deep eutectic solvent, or an ionic liquid.
The beneficial effects of adopting the further technical scheme are as follows: the cosolvent can accelerate the dissolution rate of lignin in water, and can effectively promote the formation of lignin nanotubes after being matched with electrolyte.
Further, the alcohol is methanol, ethanol or ethylene glycol; the aprotic solvent is tetrahydrofuran or dioxane; the proton solvent is N, N-dimethylformamide; the deep eutectic solvent is choline chloride/citric acid, choline chloride/acetic acid; the ionic liquid is [ ami ] Cl, [ Bmim ] Cl, DMSO/TBAH.
The beneficial effects of adopting the further technical scheme are as follows: the cosolvent can be a pure substance or an aqueous solution of the substance, can quickly dissolve lignin in water, is combined with electrolyte, and promotes the formation of lignin nanotubes. The above-mentioned only partial cosolvent, for example, the alcohol as the cosolvent may be not only methanol, ethanol or ethylene glycol as the cosolvent in the technical solution, but also other alcohols as long as the same cosolvent can be achieved, and this is not necessarily exemplified herein.
Further, after the cosolvent is added, the volume concentration of the cosolvent in the reaction system is 10-90%.
The beneficial effects of adopting the further technical scheme are as follows: the effect of the cosolvent not only affects the dissolution rate of lignin in water, but also the added cosolvent content can affect the diameter of the formed lignin nanotubes, namely, under the condition that the lignin is completely dissolved, the diameter of the lignin nanotubes is increased along with the increase of the cosolvent content.
Further, the concentration of the electrolyte in the reaction system is made to be 0.01 to 1mol/L after the electrolyte is added.
The beneficial effects of adopting the further technical scheme are as follows: the electrolyte can be effectively combined with lignin to form lignin nanotubes only when the concentration of the electrolyte in the reaction system is 0.01-1mol/L, and if the electrolyte is more than the concentration, the electrolyte can not be well combined with lignin, so that the purity and the yield of the lignin nanotubes can be influenced, and if the electrolyte is less than the concentration, the yield of the lignin nanotubes can be influenced.
Further, the dialysis temperature is 20-60 ℃, and the dialysis time is 2-4 days.
The beneficial effects of adopting the further technical scheme are as follows: lignin can be self-assembled to form lignin nanotubes in the dialysis process, and the dialysis temperature can influence the length-diameter ratio of the nanotubes, and in the dialysis temperature range, the dialysis temperature is increased, and the length-diameter ratio of the nanotubes is reduced.
The preparation method of the drug carrier comprises the following steps:
acidifying lignin nanotubes, adding functional molecules, connecting the lignin nanotubes with the acidified lignin nanotubes through amide reaction, adding phase change materials, and blocking the lignin nanotubes.
Further, the acid treatment is carried out with concentrated nitric acid and/or concentrated sulfuric acid.
Further, the concentration of the functional molecule is 0.01 to 2mol/L.
Further, the volume ratio of the phase change material to the functional molecule is 0.5-1:2-5.
The invention has the following beneficial effects:
the invention constructs a drug carrier based on the lignin nanotube, and the constructed drug carrier has excellent loading activity and slow release function, and simultaneously provides a process for preparing the lignin nanotube with high efficiency and low cost. The morphology of the lignin nanotubes is regulated and controlled by regulating and controlling the cosolvent, the electrolyte and the dialysis parameters, and the lignin nanotubes can be prepared in a large scale and stably stored, more importantly, the prepared lignin nanotubes are lignin nanotubes with new morphology, have a branching structure and a blocking structure, and have important influence on drug loading.
Drawings
FIG. 1 is an SEM morphology of lignin nanotubes obtained in example 1 using sodium chloride as electrolyte;
FIG. 2 is an SEM morphology of lignin nanotubes obtained in example 2 using sodium bromide as electrolyte;
FIG. 3 is an SEM morphology of lignin nanotubes obtained in example 3 using sodium sulfate as electrolyte;
FIG. 4 is an SEM morphology of lignin nanotubes obtained in example 4 using sodium nitrate as electrolyte;
FIG. 5 is an SEM morphology of lignin nanotubes obtained in example 5 using copper chloride as electrolyte;
FIG. 6 is an SEM morphology of lignin nanotubes obtained in example 7 using ferric chloride as electrolyte;
FIG. 7 is an SEM topography of lignin feedstock and lignin nanotubes;
FIG. 8 is a perspective view of lignin nanotubes prepared in example 1 using sodium chloride as the electrolyte;
fig. 9 is another perspective view of lignin nanotubes prepared in example 1 using sodium chloride as the electrolyte.
Detailed Description
The examples given below are only intended to illustrate the invention and are not intended to limit the scope thereof. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding ethanol solution, wherein the mass concentration of lignin in the system is 1%, the volume concentration of ethanol is 20%, then adding sodium chloride to make the concentration of lignin be 0.1mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium chloride are fully dissolved to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 10g of lignin nanotubes in 45mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 1:2, carrying out ultrasonic treatment for 4h, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 5mL of tyrosine solution with the concentration of 0.5mol/L, stirring and reacting for 2h, adding a phase change material solution formed by compounding lauric acid and docosanoic acid, uniformly stirring, and standing for 1.5 h; the volume concentration of lauric acid and behenic acid in the phase change material solution is 20%, and the volume ratio of the phase change material solution to the tyrosine solution is 0.5:2.
Example 2:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of lignin in the system is 1%, the volume concentration of tetrahydrofuran is 20%, then adding sodium bromide to make the concentration of lignin be 0.05mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium bromide are fully dissolved, so as to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 8g of lignin nanotubes in 35mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:2, performing ultrasonic treatment for 4 hours, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 20mL of tyrosine solution with the concentration of 0.1mol/L, stirring and reacting for 2h, adding a phase change material solution formed by compounding lauric acid and stearic acid, uniformly stirring, and standing for 1.5 h; the volume concentration of lauric acid and stearic acid in the phase change material solution is 20%, and the volume ratio of the phase change material solution to the tyrosine solution is 1:3.
Example 3:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of lignin in the system is 1%, the volume concentration of tetrahydrofuran is 20%, then adding sodium sulfate to make the concentration of lignin be 0.05mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium sulfate are fully dissolved, so as to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 10g of lignin nanotubes in 30mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 1:2, carrying out ultrasonic treatment for 4h, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 20mL of tyrosine solution with the concentration of 0.1mol/L, stirring and reacting for 2h, adding a phase change material solution formed by compounding lauric acid and tetradecyl alcohol, uniformly stirring, and standing for 1.5 h; the volume concentration of lauric acid and tetradecyl alcohol in the phase change material solution is 20%, and the volume ratio of the phase change material solution to the tyrosine solution is 0.5:2.
Example 4:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of lignin in the system is 1%, the volume concentration of tetrahydrofuran is 20%, then adding sodium nitrate to make the concentration of lignin be 0.05mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium nitrate are fully dissolved, so as to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 10g of lignin nanotubes in 40mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:2, performing ultrasonic treatment for 4 hours, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 3mL of tyrosine solution with the concentration of 1mol/L, stirring and reacting for 2h, adding a phase change material solution formed by lauric acid, uniformly stirring, and standing for 1.5 h; the volume concentration of lauric acid in the phase change material solution is 60%, and the volume ratio of the phase change material solution to the tyrosine solution is 0.5:3.
Example 5:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of lignin in the system is 1%, the volume concentration of tetrahydrofuran is 20%, then adding cupric chloride to make the concentration of lignin be 0.05mol/L, and dialyzing at 30 ℃ for 48h after the lignin and cupric chloride are fully dissolved, so as to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 10g of lignin nanotubes in 35mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:2, performing ultrasonic treatment for 4 hours, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 8mL of tyrosine solution with the concentration of 0.5mol/L, stirring and reacting for 2h, adding a phase change material solution formed by docosanoic acid, uniformly stirring, and standing for 1.5 h; the volume concentration of the docosanoic acid in the phase-change material solution is 40%, and the volume ratio of the phase-change material solution to the tyrosine solution is 1:3.
Example 6:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of lignin in the system is 1%, the volume concentration of tetrahydrofuran is 20%, then adding ferrous chloride to make the concentration of lignin be 0.05mol/L, and dialyzing at 30 ℃ for 48h after the lignin and ferrous chloride are fully dissolved, so as to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 10g of lignin nanotubes in 30mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 1:2, carrying out ultrasonic treatment for 4h, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 5mL of tyrosine solution with the concentration of 0.5mol/L, stirring and reacting for 2h, adding a phase change material solution formed by compounding lauric acid and docosanoic acid, uniformly stirring, and standing for 1.5 h; the volume concentration of lauric acid and behenic acid in the phase change material solution is 10%, and the volume ratio of the phase change material solution to the tyrosine solution is 1:1.
Example 7:
a drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding Tetrahydrofuran (THF), wherein the mass concentration of lignin in the system is 1%, the volume concentration of tetrahydrofuran is 50%, then adding ferric chloride to make the concentration of lignin be 0.05mol/L, and dialyzing at 30 ℃ for 48 hours after the lignin and the ferric chloride are fully dissolved, so as to obtain the lignin nanotube.
(2) Lignin nanotube acidification
Placing 10g of lignin nanotubes in 45mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 1:2, carrying out ultrasonic treatment for 4h, cooling and precipitating, removing acid liquor, washing for multiple times by using distilled water, and drying at 120 ℃;
(3) Functional molecule and phase change material modification
Placing the acidified lignin nanotube into 10mL of tyrosine solution with the concentration of 0.5mol/L, stirring and reacting for 2h, adding a phase change material solution formed by compounding lauric acid and docosanoic acid, uniformly stirring, and standing for 1.5 h; the volume concentration of lauric acid and behenic acid in the phase change material solution is 20%, and the volume ratio of the phase change material solution to the tyrosine solution is 1:1.
SEM morphology graphs of lignin nanotubes prepared in examples 1-5 and 7 are specifically shown in FIGS. 1-6, and perspective views of lignin nanotubes prepared in example 1 are shown in FIGS. 8 and 9.
As can be seen from fig. 1-6 and fig. 8 and 9, the lignin nanotube morphology has both branched and capped structures.
In the experimental process, when ferrous chloride is used as an electrolyte, lignin nanotubes can be formed, but when ferric chloride is used as the electrolyte, lignin nanotubes can be well formed only when the concentration is not more than 0.05mol/L, and if the concentration is too high, more morphology in the formed nano material is lignin nanowires.
In addition, the invention also compares the lignin raw material and the morphology of the prepared lignin nanotubes, and particularly, the lignin nanotube is shown in fig. 7.
In fig. 7, fig. a-a "is an SEM morphology of the dealkalized lignin of the lignin feedstock, and fig. b-b" is an SEM morphology of the lignin nanotubes (example 1). As is clear from FIG. 7, the dealkalized lignin is aggregated into large particles, and the nano-sized lignin nanotubes with a length of about 500 μm and a diameter of about 500nm are obtained.
Example 8
A drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding ethanol solution, wherein the mass concentration of lignin in the system is 1%, the volume concentration of ethanol is 20%, then adding sodium chloride to make the concentration of lignin be 0.1mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium chloride are fully dissolved to obtain the lignin nanotube.
(2) Modification of phase change materials
Placing the lignin nanotube into a phase change material solution formed by compounding lauric acid and docosanoic acid, uniformly stirring, and standing for 1.5 h; the volume concentrations of lauric acid and behenic acid in the phase change material solution were 20%.
Example 9
A drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding ethanol solution, wherein the mass concentration of lignin in the system is 1%, the volume concentration of ethanol is 20%, then adding sodium chloride to make the concentration of lignin be 0.1mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium chloride are fully dissolved to obtain the lignin nanotube.
(2) Modification of phase change materials
Placing the lignin nanotube into lauric acid solution, stirring uniformly, and standing for 1.5 h.
Example 10
A drug carrier based on lignin nanotubes is prepared by the following steps:
(1) Preparation of lignin nanotubes
Adding dealkalized lignin into water, then adding ethanol solution, wherein the mass concentration of lignin in the system is 1%, the volume concentration of ethanol is 20%, then adding sodium chloride to make the concentration of lignin be 0.1mol/L, and dialyzing at 30 ℃ for 48h after lignin and sodium chloride are fully dissolved to obtain the lignin nanotube.
(2) Modification of phase change materials
Placing the lignin nanotube into a tetradecanol solution, uniformly stirring, and standing for 1.5 h.
Example 11
The drug carriers prepared in examples 1 to 5 and examples 8 to 10 were used for carrying drugs, namely, doxorubicin to be carried was added into the system before modification of the phase change material, and then modification was carried out by modification of the phase change material, the addition amounts of doxorubicin in each example were the same, and the encapsulation efficiency and the cumulative drug release rate of 120 hours were calculated, and the results are shown in Table 1.
TABLE 1 encapsulation efficiency and drug Release
As can be seen from the data in table 1, although examples 1 to 5 and examples 8 to 9 adopt different technical schemes, for example, the technical parameters of examples 1 to 5 are different, and examples 8 to 9 are modified directly by using a phase change material, and are not modified by using functional molecules or are not acidified, but have no significant difference in encapsulation efficiency of the drug.
For the cumulative drug release rate within 120h, the release rates of examples 1 to 3 were 40%, 50% and 50%, while examples 4 and 5 reached 76% and 78%, and according to the technical solutions of examples 1 to 5, the acid treatment and the functional molecule modification can affect the drug release rate of the multi-component composite phase change material.
The same phase change materials are used in example 8 and example 1, which are all multi-element composite phase change materials, but the process of acid treatment and functional molecule modification is absent in example 8, the drug release rate in 120h reaches 72%, and the release rate is almost the same as that of the single phase change materials used in example 4, example 5, example 9 and example 10, but is significantly higher than that of examples 1, example 2 and example 3. Therefore, in the regulation and control process of the functional molecules on the multi-element composite phase change material, the phase separation which can occur in the multi-element composite phase change material is possibly inhibited, so that the slow release function of the carrier is effectively regulated and controlled.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (3)
1. The preparation method of the drug carrier based on the lignin nanotubes is characterized in that the lignin nanotubes are acidified, then functional molecules are added to enable the lignin nanotubes to be connected with the acidified lignin nanotubes through amide reaction, and then phase change materials are added to obtain the drug carrier;
the acidification is to carry out acid treatment by adopting a mixed solution of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 1:2; the functional molecule is tyrosine; the phase change material is selected from any one of multi-element composite phase change materials of lauric acid and docosanoic acid, lauric acid and stearic acid, lauric acid and tetradecyl alcohol.
2. The method of claim 1, wherein the lignin nanotubes are prepared by the following method:
adding lignin into water, then adding cosolvent, finally adding electrolyte, uniformly mixing, and dialyzing to obtain lignin nanotube; or uniformly mixing a cosolvent with water to form a cosolvent aqueous solution, then adding lignin into the cosolvent aqueous solution, finally adding electrolyte, uniformly mixing, and dialyzing to obtain lignin nanotubes;
wherein the electrolyte is a substance formed by the following anions and cations:
the cation is H + 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ And Ag + Any one of them;
the anion being Cl - 、Br - 、I - 、NO 3 - 、SO 4 2- 、HSO 4 - 、PO 4 3- 、HPO 4 2- 、HPO 3 2- 、OH - 、CO 3 2- And HCO 3 - Any one of the following.
3. The drug carrier prepared by the method of claim 1 or 2, which is characterized by comprising lignin nanotubes and a coating layer coated on the surface of the lignin nanotubes; the coating layer comprises functional molecules crosslinked with lignin nanotubes, and a phase change material.
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