CN117960123A - Composite microsphere adsorbent of halloysite nanotube and cellulose derived carbon, and preparation method and application thereof - Google Patents
Composite microsphere adsorbent of halloysite nanotube and cellulose derived carbon, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a halloysite nanotube and cellulose derived carbon composite microsphere adsorbent, and a preparation method and application thereof. The composite microsphere adsorbent comprises a surface layer and an inner part, wherein the surface layer covers the inner part; the thickness of the surface layer is 10-500 mu m, and the diameter of the inner part is 5-500 mu m; the surface layer is provided with a spongy pore canal structure, and the aperture of the spongy pore canal structure is 0.1-20 mu m; the inside is provided with a radial pore canal structure, and the pore diameter of the radial pore canal structure is 1-50 mu m; the halloysite nanotubes are coated in the cellulose-derived carbon. According to the invention, the halloysite nanotube is coated in the cellulose-derived carbon, so that the blood compatibility of the halloysite nanotube is improved, and the risk caused by the sharp morphology of the halloysite nanotube is reduced. The surface layer of the microsphere adsorbent has a spongy pore structure, and the inside of the microsphere adsorbent has a radial pore structure, so that the adsorption efficiency of the adsorbent is improved.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a halloysite nanotube and cellulose derived carbon composite microsphere adsorbent, and a preparation method and application thereof.
Background
Hyperlipidemia is a high-frequency disorder closely associated with cardiovascular and cerebrovascular diseases, and is mainly manifested by overproof triglycerides, cholesterol, low-density lipoprotein cholesterol and lipoprotein (a) in blood. At present, there is a lack of specific drugs for lipoprotein (a) clinically, and there are also problems of insufficient patient tolerance, a large number of side effects in vivo, etc. of drugs for lowering the cholesterol level of low density lipoprotein. In comparison, blood lipid purification therapy based on blood perfusion technology has higher efficiency and safety. In addition, the obvious structural commonality between the low-density lipoprotein cholesterol and the lipoprotein (a) is that the surfaces are provided with apolipoprotein ApoB-100 positive micro-regions, and the characteristic provides a theoretical basis for the design of the blood perfusion adsorbent based on physical adsorption.
Blood perfusion is an extracorporeal circulation type life support technology, and has been used clinically for treating various diseases such as poisoning (medicines, pesticides, heavy metals, biotoxins, drugs, etc.), uremia, liver diseases, hyperlipidemia, septicemia, autoimmune diseases, etc. The principle of blood perfusion is that the blood of a patient is led out of the body and passes through a purification device, so that toxins in the blood are purified and removed, and the purified blood is returned to the body of the patient, thereby replacing the detoxification system of the patient to realize toxin removal.
The heart of hemodiafiltration is the hemodynamic adsorbent. In general, the hemoperfusion therapy requires that the adsorbent has high adsorption capacity, adsorption efficiency and adsorption selectivity, and also has good blood compatibility. However, for the treatment of hyperlipidemia by hemoperfusion therapy, there is currently a lack of materials capable of meeting the above requirements.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a halloysite nanotube and cellulose derived carbon composite microsphere adsorbent, and a preparation method and application thereof. The spongy pore canal structure is formed on the surface layer of the composite microsphere adsorbent, and rich radial pore structures are formed inside, so that the composite microsphere adsorbent has good adsorption selectivity, blood compatibility and high adsorption efficiency.
In order to achieve the above object, the present invention provides a composite microsphere adsorbent of halloysite nanotubes and cellulose-derived carbon, wherein the composite microsphere adsorbent comprises a surface layer and an interior, the surface layer coating the interior; the thickness of the surface layer is 10-500 mu m, and the diameter of the inner part is 5-500 mu m; the surface layer is provided with a spongy pore canal structure, and the aperture of the spongy pore canal structure is 0.1-20 mu m; the inside is provided with a radial pore canal structure, and the pore diameter of the radial pore canal structure is 1-50 mu m; the halloysite nanotubes are coated in the cellulose-derived carbon.
Halloysite is a 1:1 aluminosilicate mineral with a layered structure, is a hydrated polytype mineral of kaolinite, is usually produced in the shape of a nanotube, and has the characteristics of abundant reserves, low cost, easy obtainment, good environmental compatibility, large specific surface area, abundant surface groups, high adsorption efficiency and the like. However, the present inventors have found that if halloysite nanotubes are used in the blood lipid adsorption field, the halloysite nanotubes themselves have sharp microscopic morphology and are prone to flaking particles, which may result in poor compatibility with blood and cannot be directly applied to blood perfusion adsorbents.
The special pore canal structure of the composite microsphere adsorbent can realize the rapid diffusion and flow of plasma fluid containing substances to be adsorbed. Wherein, the halloysite nanotube is coated in the cellulose derivative carbon in a form of full coating and half coating; full cladding means that halloysite nanotubes are fully embedded into cellulose-derived carbon; the semi-coating means that one part of the halloysite nanotube is coated by the cellulose-derived carbon, and the other part of the halloysite nanotube is partially exposed on the surface of the cellulose-derived carbon or is attached to the surface of the cellulose-derived carbon.
According to a specific embodiment of the present invention, preferably, the radial duct structure is formed by arranging lamellar tissues; the lamellar structure is a structure formed by arranging cellulose derived carbon coated with halloysite nanotubes according to radial orientation. The thin layer structure of the cellulose-derived carbon is helpful for diffusing fluid and penetrating substances to be adsorbed, and the coating structure formed by the cellulose-derived carbon and the halloysite nanotubes is helpful for reducing the risk of hemolysis and coagulation possibly caused by the sharp morphology of the halloysite nanotubes.
According to a specific embodiment of the present invention, it is preferable that the particle size of the composite microsphere adsorbent is 200 to 5000. Mu.m, more preferably 500 to 2000. Mu.m. Too large particle size can hinder the diffusion of fluid inside the microsphere, while too small particle size can increase the head needed to achieve circulation during perfusion. The size of the particle size can be realized by controlling the solid content of the slurry and the diameter of an outlet when the slurry is dripped into liquid nitrogen.
According to a specific embodiment of the present invention, the specific surface area of the composite microsphere adsorbent is preferably 5 to 2000 m 2·g-1, more preferably 300 to 1500 m 2·g-1.
According to a specific embodiment of the present invention, it is preferable that the halloysite nanotube has a length of 0.5 to 30 μm, an inner diameter of 10 to 40 nm, and an outer diameter of 40 to 70 nm.
According to a specific embodiment of the present invention, preferably, the cellulose-derived carbon has a nano-scale pore structure having a pore size of 1 to 100 nm a.
According to a specific embodiment of the present invention, preferably, the cellulose-derived carbon is obtained from cellulose after carbonization. The cellulose surface has rich oxygen-containing functional groups, and has good hydrophilicity, dispersibility and biocompatibility. In addition, the cellulose derivative carbon obtained after carbonizing the cellulose has rich pore structure, so that the cellulose derivative carbon can be better applied to the field of adsorption separation.
According to a specific embodiment of the present invention, preferably, the cellulose includes one or a combination of two or more of microcrystalline cellulose, nanocellulose, hydroxymethyl cellulose, cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc., more preferably microcrystalline cellulose, carboxymethyl cellulose.
The invention also provides a preparation method of the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent, wherein the preparation method comprises the following steps:
(1) According to the solubilizer: cellulose: dispersing agent: halloysite nanotubes: solvent= (3-10): (3-10): (0.1-1): (1-5): (15-20), dispersing the solubilizer, the cellulose, the dispersing agent and the halloysite nanotubes in a solvent, and heating to dissolve the cellulose to obtain slurry;
(2) Dropping the slurry into liquid nitrogen, and pre-freezing to form first precursor microspheres of the ice-containing template;
(3) Lyophilizing the first precursor microsphere, and removing the ice template to obtain a second precursor microsphere;
(4) Carbonizing the second precursor microsphere in inert gas to obtain the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent.
According to a specific embodiment of the present invention, preferably, the solubilizing agent includes one or a combination of two or more of N-methylmorpholine-N-oxide, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate and the like, more preferably N-methylmorpholine-N-oxide.
According to a specific embodiment of the present invention, preferably, the dispersant includes one or a combination of two or more of polyethylene glycol, polysorbate, polyethylene glycol octylphenyl ether, and the like.
According to a specific embodiment of the present invention, preferably, the solvent includes one or a combination of two or more of water, ethanol, methanol, dimethylsulfoxide, and the like.
According to a specific embodiment of the present invention, preferably, the heating temperature is 40-90 ℃.
According to a specific embodiment of the present invention, the pre-freezing is preferably performed for a time of 1 to 30min, more preferably 5 to 10 min.
According to a specific embodiment of the present invention, preferably, the lyophilization temperature is from 0 ℃ to-90 ℃, more preferably from-50 to-70 ℃; the lyophilization time is 12-120 h, more preferably 24-48 h.
In the pre-freezing and freeze-drying process, the spongy pore canal structure is formed because the slurry has extremely high supercooling degree when in contact with liquid nitrogen, so that the rate of grain formation is far higher than that of dendrite formation and growth, and the solvent template is more prone to forming fine crystals without growth directions, therefore, after the solvent and the ice template are removed by freeze-drying, cellulose loaded with halloysite nanotubes on the surface layer retains the spongy structure formed when the fine crystal template exists, and the structure is favorable for enabling substances to be adsorbed on the surface of the composite microsphere rapidly when the composite microsphere is in primary contact with plasma or whole blood, and improving the adsorption and removal efficiency. Meanwhile, in the process of pre-freezing the precursor slurry, the radial pore structure is obtained after the solvent is quickly solidified and grows in a dendrite form to form an ice template. After lyophilization to remove solvent and ice templates, the cellulose loaded with halloysite nanotubes inside retains the radial structure formed in the presence of dendrite templates. The structure is favorable for the adsorbate to diffuse from the surface of the composite microsphere to the inside, and improves the utilization rate of the adsorbent in unit volume.
According to a specific embodiment of the present invention, preferably, in step (2), the slurry is slowly dropped dropwise into liquid nitrogen; the dropping rate is 1-2 drops/s. If the dropping speed is too high, the last dropped slurry microsphere may not be completely frozen, which may cause adhesion of two microspheres, resulting in a decrease in uniformity of particle size in the preparation of the composite microsphere.
According to a specific embodiment of the present invention, preferably, the carbonization temperature is 300-1500 ℃, more preferably 500-800 ℃; the carbonization time is 1-10 h, more preferably 2-5 h.
According to a specific embodiment of the present invention, preferably, the inert gas is argon and/or nitrogen, etc., more preferably argon.
The invention also provides a blood perfusion device, wherein the blood perfusion device comprises the composite microsphere adsorbent of the halloysite nanotube and cellulose derived carbon.
The invention also provides application of the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent in the field of blood fat adsorption, wherein the composite microsphere adsorbent is used for removing lipoprotein a, low-density lipoprotein cholesterol, triglyceride and the like. The lipoprotein a may also be referred to as lipoprotein (a), abbreviated lp (a).
Compared with the prior art, the invention has the beneficial effects that:
(1) The surface layer of the composite microsphere adsorbent provided by the invention has a spongy pore structure, and the inside of the composite microsphere adsorbent is provided with a radial macroporous pore structure, so that the diffusion and the flow of plasma or whole blood in the composite microsphere adsorbent are facilitated, and the adsorption efficiency of the composite microsphere is further improved.
(2) According to the invention, the halloysite nanotube and the cellulose derivative carbon are mixed and modified, so that the halloysite nanotube is coated in the cellulose derivative carbon, the blood compatibility of the halloysite nanotube is improved, the possible hemolysis and coagulation risk caused by the sharp morphology of the halloysite nanotube can be reduced, and the halloysite nanotube can be better applied to the blood fat adsorption field.
(3) The composite microsphere adsorbent prepared by the invention can be applied to the fields of blood fat adsorption and blood perfusion, has large adsorption capacity and good adsorption selectivity for low-density lipoprotein cholesterol, lipoprotein (a), cholesterol, triglyceride and the like, has good blood compatibility and low beneficial protein adsorption capacity, and has good biological safety.
Drawings
FIG. 1 is an optical image of a halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent prepared in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the sphere surface of a halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent prepared in example 1 of the present invention.
FIG. 3 is a magnified SEM image of the sphere surface of a halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent prepared in example 1 of the present invention.
FIG. 4 is an SEM image of a spherical section of a composite microsphere adsorbent of halloysite nanotubes and cellulose-derived carbon prepared in example 1 of the present invention.
FIG. 5 is a magnified SEM image of a spherical section of a composite microsphere adsorbent of halloysite nanotubes and cellulose-derived carbon prepared in example 1 of the present invention.
FIG. 6 is a magnified SEM image of the lamellar structure inside the sphere of the composite microsphere adsorbent of halloysite nanotubes and cellulose-derived carbon prepared in example 1 of the present invention.
FIG. 7 is an X-ray diffraction (XRD) pattern of a halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent prepared in example 1 of the present invention.
FIG. 8 is a pore size distribution diagram of the nano-scale intrinsic pore structure obtained by carbonization in example 1 of the present invention.
FIG. 9 is an SEM image of a spherical section of a composite microsphere adsorbent prepared according to comparative example 2.
FIG. 10 shows the clearance of the different adsorbents in test example 1 after adsorption in the plasma of a real hyperlipidemic patient for 2 hours.
FIG. 11 shows the clearance of the different adsorbents in test example 2 after adsorption in the plasma of a real hyperlipidemic patient for 2 hours.
FIG. 12 shows the clearance of the different adsorbents in test example 3 after adsorption in plasma of a real hyperlipidemic patient for 2 hours.
FIG. 13 is a graph showing the adsorption kinetics of different adsorbents in the plasma of a real hyperlipidemia patient in test example 4.
FIG. 14 shows the adsorption of beneficial proteins by different adsorbents in the plasma of a real hyperlipidemic patient in test example 5.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a halloysite nanotube and cellulose derived carbon composite microsphere adsorbent, which is prepared by the following steps:
(1) Fully mixing 5.0 g microcrystalline cellulose, 1.0 g halloysite nanotube, 0.1 g polyethylene glycol and 3.0 g N-methylmorpholine-N-oxide in 15.0 g water, and uniformly stirring at 70 ℃ to form uniform slurry;
(2) Slowly dripping the slurry in the step (1) into liquid nitrogen dropwise at a rate of 1-2 drops/s to pre-freeze 5min so as to form first precursor microspheres with a particle size in a range of 300-800 mu m;
(3) Rapidly transferring the first precursor microspheres in the step (2) from liquid nitrogen to a freeze dryer at the temperature of minus 90 ℃, freeze-drying 72 h and taking out to obtain second precursor microspheres with the particle size of 300-800 mu m;
(4) Carbonizing the second precursor microsphere in the step (3) in an argon atmosphere at the carbonizing temperature of 700 ℃ and carbonizing time of 5h to obtain the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent with the particle size of 300-800 mu m.
The optical image of the composite microsphere adsorbent prepared in this example was taken, and the result is shown in fig. 1, and it can be seen that the prepared composite microsphere adsorbent has uniform particle size and morphology.
SEM characterization was performed on the surface and the tangential plane of the composite microsphere adsorbent prepared in this example, and the results are shown in fig. 2,3, 4,5 and 6. As can be seen from fig. 2 and 3, the surface of the composite microsphere adsorbent has a pore structure. As can be seen in fig. 4, the composite microsphere adsorbent has a typical outer sponge-like pore structure and an inner radial pore structure. As can be seen from fig. 5, the lamellar structure inside the composite microsphere adsorbent is in an oriented arrangement. As can be seen from fig. 6, the lamellar structure constituting the internal radial pore structure is cellulose-derived carbon loaded with halloysite nanotubes, both of which form a coating structure.
XRD characterization is carried out on the composite microsphere adsorbent prepared in the embodiment, and the result is shown in figure 7, so that the composite microsphere adsorbent mainly consists of two phases of halloysite nanotubes and cellulose-derived carbon, and other impurity phases are not generated in the preparation process.
The thickness of the surface layer of the composite microsphere adsorbent is about 200 mu m, and the diameter of the inner part is 400 mu m; the pore diameter of the spongy pore structure of the surface layer is about 5 mu m, and the pore diameter of the radial pore structure of the inner layer is about 10 mu m; the specific surface area is 1032.4 m 2·g-1; the pore size distribution of the carbonized nano-scale intrinsic pore structure is shown in figure 8.
Example 2
The embodiment provides another halloysite nanotube and cellulose derived carbon composite microsphere adsorbent by changing raw materials and part of experimental parameters, and the preparation process is as follows:
(1) Fully mixing and dispersing 3.5 g carboxymethyl cellulose, 1.0 g halloysite nanotube, 0.1 g polyethylene glycol and 3.0 g N-methylmorpholine-N-oxide in 15.0 g water, and uniformly stirring at 70 ℃ to form uniform slurry;
(2) Slowly dripping the slurry in the step (1) into liquid nitrogen dropwise at a rate of 1-2 drops/s to pre-freeze 5min to form first precursor microspheres with a particle size in the range of 200-500 mu m;
(3) Rapidly transferring the first precursor microspheres in the step (2) from liquid nitrogen to a freeze dryer at the temperature of minus 90 ℃, freeze-drying 72 h, and taking out to obtain second precursor microspheres with the particle size of 200-500 mu m;
(4) Carbonizing the second precursor microsphere in the step (3) in an argon atmosphere at the carbonizing temperature of 500 ℃ and carbonizing time of 5 h to obtain the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent with the particle size of 200-500 mu m.
The thickness of the surface layer of the composite microsphere adsorbent is about 150 mu m, and the diameter of the inner part is 350 mu m; the pore diameter of the spongy pore structure of the surface layer is about 5 mu m, and the pore diameter of the radial pore structure of the inner layer is about 15 mu m; the specific surface area is 742.9 m 2·g-1.
Example 3
The embodiment provides another halloysite nanotube and cellulose derived carbon composite microsphere adsorbent by changing raw materials and part of experimental parameters, and the preparation process is as follows:
(1) Fully mixing and dispersing 5.0 g microcrystalline cellulose, 1.0 g halloysite nanotube, 0.3 g polysorbate and 3.0 g N-methylmorpholine-N-oxide in 20.0 g water, and uniformly stirring at 70 ℃ to form uniform slurry;
(2) Slowly dripping the slurry in the step (1) into liquid nitrogen dropwise at a rate of 1-2 drops/s to pre-freeze 5min to form first precursor microspheres with a particle size in a range of 300-600 mu m;
(3) Rapidly transferring the first precursor microspheres in the step (2) from liquid nitrogen to a freeze dryer at the temperature of minus 90 ℃, freeze-drying 72 h, and taking out to obtain second precursor microspheres with the particle size of 300-600 mu m;
(4) Carbonizing the second precursor microsphere in the step (3) in an argon atmosphere at the carbonizing temperature of 500 ℃ and carbonizing time of 5h to obtain the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent with the particle size of 300-600 mu m.
The thickness of the surface layer of the composite microsphere adsorbent is about 200 mu m, and the diameter of the inner part is 400 mu m; the pore diameter of the spongy pore structure of the surface layer is about 5 mu m, and the pore diameter of the radial pore structure of the inner layer is about 10 mu m; the specific surface area is 911.7 m 2·g-1.
The thickness of the surface layer of the composite microsphere adsorbent is about 200 mu m, and the diameter of the inner part is 400 mu m; the pore diameter of the spongy pore structure of the surface layer is about 5 mu m, and the pore diameter of the radial pore structure of the inner layer is about 10 mu m; the specific surface area was 911.7 m 2·g-1.
Comparative example 1
This comparative example provides a cellulose derivative carbon microsphere adsorbent, which is prepared in a similar manner to example 1, except that halloysite nanotubes are not added during the slurry preparation process, and finally the cellulose derivative carbon microsphere adsorbent is obtained.
Comparative example 2
The comparative example provides a composite microsphere adsorbent, which is prepared by the following steps: according to the raw material ratio and the process parameters of the step (1) in the example 1, slurry is prepared, then slurry feeding is completed at the speed of 3 m.s -1 at the inlet air temperature of 185 ℃ and the outlet air temperature of 85 ℃ by a spray drying granulation method, spray drying granulation is completed by using a nozzle with the caliber of 0.7 mm, and as shown in fig. 9, the composite microsphere adsorbent with a loose structure and no specific pore structure is obtained, and the particle size of the composite microsphere adsorbent is about 300 mu m.
Comparative example 3
This comparative example provides a composite microsphere adsorbent, which is prepared in a similar manner to example 1, except that the carbonization step is not performed, and the non-carbonized second composite microsphere precursor obtained in step (3) is directly used as the composite microsphere adsorbent.
The following experiments on lipid absorption were performed using the plasma of hyperlipidemia from a truly hyperlipidemic patient for examples 1-3 and comparative examples 1-3, wherein the initial content of lipoprotein (a) was 110.95 mg.dL -1, the initial content of cholesterol was 10. mmol.L -1, the initial content of triglyceride was 2. mmol.L -1, and the initial content of low-density lipoprotein cholesterol was 5.66 mmol.L -1; the method for calculating the clearance rate comprises the following steps: (pre-adsorption content-post-adsorption content)/pre-adsorption content.
The specific test process is as follows:
test example 1
The composite microsphere adsorbents of halloysite nanotubes and cellulose-derived charcoal prepared in example 1, example 2 and example 3 and the cellulose-derived charcoal microsphere adsorbent prepared in comparative example 1 were 10 mg each, and were thoroughly mixed with 5. 5 mL hyperlipidemia plasma obtained from a real hyperlipidemia patient, and incubated 2h at a rate of 120 rpm in a thermostatic water bath shaker at 37 ℃. The specific test process is as follows:
(1) The composite microsphere adsorbent of example 1 and the microsphere adsorbent of comparative example 1 after cultivation were separated from hyperlipidemia plasma, respectively, the hyperlipidemia plasma before and after cultivation was taken and the level of lipoprotein (a) therein was tested by immunonephelometry in sequence, and clearance (%) of lipoprotein (a) was calculated, respectively. The clearance of lipoprotein (a) by the adsorbents prepared in example 1, example 2, example 3 and comparative example 1 was 71.62%, 70.47%, 66.43% and 37.70%, respectively.
(2) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, respectively testing the level of low density lipoprotein cholesterol therein by direct method, and respectively calculating clearance (%) of low density lipoprotein cholesterol. The adsorbents prepared in example 1, example 2, example 3 and comparative example 1 had the clearance rates of 59.16%, 57.12%, 56.23% and 53.71% of low density lipoprotein cholesterol, respectively.
(3) The above-mentioned incubation steps were repeated, and the levels of triglycerides in hyperlipidemia plasma before and after incubation were tested by GPO-PAP method, respectively, and the clearance (%) of triglycerides was calculated, respectively. The adsorbents prepared in example 1, example 2, example 3 and comparative example 1 had the removal rates of 59.02%, 60.12%, 59.83% and 55.72% of triglyceride, respectively.
(4) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, testing cholesterol level by cholesterol oxidase method, and calculating the clearance (%) of microsphere to cholesterol. The adsorbents prepared in example 1, example 2, example 3 and comparative example 1 had cholesterol removal rates of 82.23%, 76.43%, 71.64% and 55.35%, respectively.
Fig. 10 summarizes the results of the clearance of lipoprotein (a), low density lipoprotein cholesterol, triglyceride and cholesterol from the composite microsphere adsorbents prepared in examples 1-3 and the microsphere adsorbent prepared in comparative example 1, and it can be seen from the graph that the composite microsphere of halloysite nanotube and cellulose-derived carbon has better clearance effect on the above hyperlipidemia markers and realizes better adsorption clearance effect, indicating that the halloysite nanotube has important effect on the improvement of adsorption performance compared with the cellulose-derived carbon microsphere without halloysite nanotube.
Test example 2
The composite microsphere adsorbents prepared in example 1 and comparative example 2 were 10 mg each, and mixed thoroughly with 5 mL hyperlipidemia plasma from a real hyperlipidemia patient, and incubated 2h at a rate of 120 rpm in a thermostatic water bath shaker at 37 ℃. The specific test process is as follows:
(1) Separating the cultured composite microsphere adsorbent from hyperlipidemia blood plasma, sequentially testing the level of lipoprotein (a) in the hyperlipidemia blood plasma before and after culturing by using an immunoturbidimetry, and calculating the clearance (%) of lipoprotein (a) respectively. The clearance of lipoprotein (a) by the adsorbents prepared in example 1 and comparative example 2 was 71.62% and 41.43%, respectively.
(2) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, respectively testing the level of low density lipoprotein cholesterol therein by direct method, and respectively calculating clearance (%) of low density lipoprotein cholesterol. The clearance of the adsorbents prepared in example 1 and comparative example 2 to low density lipoprotein cholesterol was 59.16% and 50.01%, respectively.
(3) The above-mentioned incubation steps were repeated, and the levels of triglycerides in hyperlipidemia plasma before and after incubation were tested by GPO-PAP method, respectively, and the clearance (%) of triglycerides was calculated, respectively. The removal rates of the adsorbents prepared in example 1 and comparative example 2 were 59.02% and 45.14%, respectively.
(4) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, testing cholesterol level by cholesterol oxidase method, and calculating the clearance (%) of microsphere to cholesterol. The clearance of cholesterol by the adsorbents prepared in example 1 and comparative example 2 was 82.23% and 63.12%, respectively.
Fig. 11 summarizes the results of the clearance of lipoprotein (a), low density lipoprotein cholesterol, triglyceride and cholesterol by the composite microsphere adsorbent prepared in the above example 1 and comparative example 2, and it can be seen from the graph that the composite microsphere adsorbent having a specific pore structure obtained by the pre-freezing-freeze-drying method has a better clearance effect on the above several hyperlipidemia markers than the composite microsphere adsorbent having no specific pore structure, and a better adsorption clearance effect is achieved, indicating that the design of the pore structure of the composite microsphere adsorbent has an important effect on the improvement of adsorption performance.
Test example 3
The composite microsphere adsorbents prepared in example 1 and comparative example 3 were 10 mg each, and mixed thoroughly with 5. 5 mL hyperlipidemia plasma obtained from a real hyperlipidemia patient, and incubated in a thermostatic water bath shaker at 37℃at a rate of 120 rpm for 2. 2 h. The specific test process is as follows:
(1) Separating the cultured composite microsphere adsorbent, the second composite microsphere precursor and the hyperlipidemia plasma, taking the hyperlipidemia plasma before and after the culture, testing the level of the lipoprotein (a) by an immunoturbidimetry, and respectively calculating the clearance (%) of the lipoprotein (a). The clearance of lipoprotein (a) by the adsorbents prepared in example 1 and comparative example 3 was 71.62% and 11.93%, respectively.
(2) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, respectively testing the level of low density lipoprotein cholesterol therein by direct method, and respectively calculating clearance (%) of low density lipoprotein cholesterol. The clearance of the adsorbents prepared in example 1 and comparative example 3 to the low density lipoprotein cholesterol was 59.16% and 17.30%, respectively.
(3) The above-mentioned incubation steps were repeated, and the levels of triglycerides in hyperlipidemia plasma before and after incubation were tested by GPO-PAP method, respectively, and the clearance (%) of triglycerides was calculated, respectively. The removal rates of the adsorbents prepared in example 1 and comparative example 3 were 59.02% and 33.38% respectively.
(4) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, testing cholesterol level by cholesterol oxidase method, and calculating the clearance (%) of microsphere to cholesterol. The clearance of cholesterol by the adsorbents prepared in example 1 and comparative example 3 was 82.23% and 29.45%, respectively.
Fig. 12 summarizes the results of the composite microsphere adsorbents prepared in the above examples 1 and 3 on the clearance of lipoprotein (a), low density lipoprotein cholesterol, triglyceride and cholesterol, and it can be seen from the graph that the composite microsphere adsorbent (example 1) obtained after carbonization has better clearance effect on the above hyperlipidemia markers than the non-carbonized second composite microsphere precursor (comparative example 3), and realizes better adsorption clearance effect, indicating that the intrinsic pore structure obtained after carbonization of cellulose has important effect on the improvement of adsorption performance.
Test example 4
The samples prepared in examples 1 to 3 and comparative example 1 were tested for their clearance of lipoprotein (a), cholesterol, triglyceride, and low density lipoprotein cholesterol, respectively, at different incubation times, so as to compare the adsorption efficiencies between the different samples, and the specific test procedure was as follows:
The halloysite nanotube and cellulose-derived carbon composite microsphere adsorbents prepared in example 1, example 2 and example 3 and the cellulose-derived carbon microsphere adsorbent prepared in comparative example 1 were 10 mg each, and were thoroughly mixed with 5. 5mL hyperlipidemia plasma obtained from a real hyperlipidemia patient, and incubated at a rate of 120 rpm in a constant temperature water bath shaker at 37 ℃.
5 Parallel test samples were prepared for each example or comparative example according to the above experimental conditions, and clearance (%) of lipoprotein (a), cholesterol, triglyceride, and low-density lipoprotein cholesterol was measured when incubated with 0min, 30min, 60 min, 90min, and 120 min, respectively. The experiment was repeated 3 times to obtain an error bar of the adsorption kinetics curve.
FIG. 13 is a graph summarizing adsorption kinetics curves of the composite microsphere adsorbents prepared in examples 1 to 3 and the microsphere adsorbent prepared in comparative example 1 on lipoprotein (a), cholesterol, triglyceride, and low density lipoprotein cholesterol. As can be seen from the graph, the composite microsphere adsorbents prepared in example 1, example 2 and example 3 all show higher removal efficiency for lipid components, and the composite microsphere adsorbent prepared in example 1 shows higher removal efficiency under the same incubation time compared with comparative example 1, which indicates that the specific pore channel structure prepared by the pre-freezing-lyophilization method has a faster adsorption speed, and can significantly improve the adsorption efficiency of the composite microsphere adsorbent.
Test example 5
Serum albumin content in the hyperlipidemia plasma used in the test example was 40. g.L -1, and immunoglobulin content was 23. g.L -1. The specific test process is as follows:
(1) The halloysite nanotube and cellulose-derived carbon composite microsphere adsorbents prepared in example 1, example 2 and example 3 were taken and each 10 mg was thoroughly mixed with 5 mL hyperlipidemia plasma from a real hyperlipidemia patient, and incubated 2 h in a 37 ℃ constant temperature water bath shaker at a rate of 120 rpm.
(2) Separating the cultured composite microsphere adsorbent from hyperlipidemia blood plasma, sequentially testing serum albumin levels of the hyperlipidemia blood plasma before and after culturing by using a differential heat reducing reagent method, and calculating clearance (%) of serum albumin respectively. The clearance of the adsorbents prepared in example 1, example 2 and example 3 to serum albumin was 4.12%, 3.11% and 6.35%, respectively.
(3) Repeating the above cultivation steps, taking hyperlipidemia blood plasma before and after cultivation, respectively testing the immunoglobulin level by immunoelectrophoresis, and respectively calculating clearance (%) of immunoglobulin. The clearance of the adsorbents prepared in example 1, example 2 and example 3 to immunoglobulin was 0.93%, 6.58% and 3.24%, respectively.
Fig. 14 summarizes the results of the clearance rate of serum albumin and immunoglobulin from the composite microsphere adsorbents prepared in example 1, example 2 and example 3, and it can be seen from the graph that the clearance rate of serum albumin, immunoglobulin and other beneficial protein components in plasma of the composite microsphere adsorbent is extremely low, and the composite microsphere adsorbent shows excellent biocompatibility and biosafety.
Claims (14)
1. A composite microsphere adsorbent of halloysite nanotubes and cellulose-derived carbon, wherein the composite microsphere adsorbent comprises a surface layer and an interior, the surface layer coating the interior; the thickness of the surface layer is 10-500 mu m, and the diameter of the inner part is 5-500 mu m;
the surface layer is provided with a spongy pore canal structure, and the aperture of the spongy pore canal structure is 0.1-20 mu m;
the inside is provided with a radial pore canal structure, and the pore diameter of the radial pore canal structure is 1-50 mu m;
the halloysite nanotubes are coated in the cellulose-derived carbon.
2. The composite microsphere adsorbent of claim 1, wherein the radial channel structure is formed by an arrangement of lamellar tissues;
The lamellar structure is cellulose derived carbon coated with halloysite nanotubes.
3. The composite microsphere adsorbent of claim 1, wherein the composite microsphere adsorbent has a particle size of 200-5000 μm.
4. The composite microsphere adsorbent of claim 1, wherein the composite microsphere adsorbent has a specific surface area of 5-2000 m 2·g-1.
5. The composite microsphere adsorbent of claim 1, wherein the cellulose derived carbon has a nanoscale pore structure with a pore size of 1-100 nm.
6. The composite microsphere adsorbent of claim 5, wherein the cellulose-derived carbon is obtained from cellulose after carbonization;
The cellulose comprises one or more of microcrystalline cellulose, nanocellulose, hydroxymethyl cellulose, cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose.
7. The method for preparing a halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent according to any one of claims 1 to 6, wherein the preparation method comprises the following steps:
(1) According to the solubilizer: cellulose: dispersing agent: halloysite nanotubes: solvent= (3-10): (3-10): (0.1-1): (1-5): (15-20), dispersing the solubilizer, the cellulose, the dispersing agent and the halloysite nanotubes in a solvent, and heating to dissolve the cellulose to obtain slurry;
(2) Dropping the slurry into liquid nitrogen, and pre-freezing to form first precursor microspheres of the ice-containing template;
(3) Lyophilizing the first precursor microsphere, and removing the ice template to obtain a second precursor microsphere;
(4) Carbonizing the second precursor microsphere in inert gas to obtain the halloysite nanotube and cellulose derived carbon composite microsphere adsorbent.
8. The preparation method according to claim 7, wherein the solubilizing agent comprises one or a combination of two or more of N-methylmorpholine-N-oxide, 1-butyl-3-methylimidazole chloride and 1-ethyl-3-methylimidazole acetate.
9. The preparation method of claim 7, wherein the dispersing agent comprises one or a combination of more than two of polyethylene glycol, polysorbate and polyethylene glycol octyl phenyl ether.
10. The method of claim 7, wherein the pre-freezing is performed for a period of time ranging from 1 to 30min.
11. The method according to claim 7, wherein the lyophilization temperature is 0-90 ℃ and the lyophilization time is 12-120 h.
12. The process according to claim 7, wherein the carbonization temperature is 300 to 1500 ℃ and the carbonization time is 1 to 10 h.
13. A hemodiafiltration device, wherein the hemodiafiltration device comprises the halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent of any one of claims 1-6.
14. Use of the halloysite nanotube and cellulose-derived carbon composite microsphere adsorbent according to any one of claims 1-6 in the field of lipid adsorption, wherein the composite microsphere adsorbent is used for removing lipoprotein a, low density lipoprotein cholesterol, cholesterol and triglyceride.
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