CN112755967A - Chitin nano fiber porous composite microsphere blood ammonia adsorbent, preparation method and application thereof - Google Patents
Chitin nano fiber porous composite microsphere blood ammonia adsorbent, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of natural polymer biomedical materials, and particularly relates to a chitin nanofiber porous composite microsphere blood ammonia adsorbent, and a preparation method and application thereof. The adsorbent is a porous network microsphere compounded by chitin nano fibers and zeolite, the zeolite is wrapped in the porous network microsphere of the chitin nano fibers, the particle size of the composite microsphere blood ammonia adsorbent is 0.1-1 mm, the pore size distribution is 2-40 nm, and the most probable pore size distribution is 5E15nm and a specific surface area of 100 to 500m2The chitin nano-fibers have the diameter of 10-50 nm, the particle size of zeolite is 0.01-50 mu m, and the content of zeolite is 1% -50%. The adsorbent provided by the invention has a multi-scale and multi-level nanofiber net structure and rich through hole channels suitable for free diffusion of blood ammonia, has good biocompatibility and blood compatibility, and has a good adsorption effect on blood ammonia.
Description
Technical Field
The invention belongs to the field of natural polymer biomedical materials, and particularly relates to a chitin nanofiber porous composite microsphere blood ammonia adsorbent, and a preparation method and application thereof.
Background
Hepatic Encephalopathy (HE) is a central nervous system dysfunction syndrome caused by dysfunction or disorder of various substances in vivo caused by dysfunction or disorder of liver function in patients with severe acute and chronic liver failure, is highlighted by neurological and psychiatric symptoms such as behavioral abnormality, character change, consciousness disorder, coma and the like, is an important cause of common complications and death of patients with severe acute and chronic liver diseases, and currently, specific treatment is lacked, so that HE prognosis is poor, and death rate is high. Current research indicates that the pathogenesis of HE is the result of a multifactorial complex, involving metabolic abnormalities in a variety of substances, with ammonia poisoning being an important factor in the pathogenesis of HE.
The blood perfusion is characterized in that the extracorporeal adsorption system is used for directly removing toxins and pathogenic factors in blood, the illness state can be quickly and effectively relieved, and the extracorporeal adsorption system has the characteristics of convenience in operation, high safety, good effect and relatively low price. The key point of the technology lies in selecting and designing adsorbent materials with strong selective adsorption capacity, high adsorption efficiency, good biocompatibility and blood compatibility, and the technology is still a technical problem to be solved urgently. In the current stage of research on blood perfusion materials, no effective adsorption material for blood ammonia exists, an adsorption material which can efficiently and selectively adsorb the blood ammonia and has good biocompatibility and blood compatibility is developed, and the adsorption material has important clinical significance for assisting in treating severe acute and chronic liver failure, removing excessive blood ammonia in blood of a patient, relieving the illness state of HE and reducing the occurrence of HE.
Natural zeolite is a framework-structured water-containing porous aluminosilicate mineral which mainly contains Na, Ca and a small number of metal ions such as Sr, Ba, K, Mg and the like. The chemical composition of a zeolite is generally expressed as: (Na, K)x(Mg,Ca,Sr,Ba)y{Al(x+2y)Si[n-(x+2y)]O2n}·mH2And O. The basic unit of the crystal structure is silicon-oxygen tetrahedron which is arranged by taking silicon as the center and four oxygen ions around the center, wherein part of Si4+Is Al3+Since substitution causes an excessive negative charge, there are ions such as alkali metals (or alkaline earth metals) that balance the charge in the structure. Meanwhile, the zeolite framework is provided with a cavity and a pore canal with certain pore diameters, so that the zeolite framework has the properties of adsorption, ion exchange and the like, and the ion exchange selectivity sequence is as follows: cs+>Rb+>K+>NH4 +>Ba2+>Sr2+>Na+>Ca2+>Fe3+>Al3+>Mg2+>Li+. Therefore, the zeolite has strong selective adsorption capacity on ammonia nitrogen, and is often used for treating ammonia nitrogen in wastewater.
The zeolite has porosity, sieving property, ion exchange property, acid resistance and strong binding property to water, although the zeolite has strong selective adsorption capacity to ammonia nitrogen, the biocompatibility and blood compatibility of the zeolite need to be improved to be applied to blood perfusion, and the powdery or granular zeolite can efficiently remove the ammonia nitrogen, but the zeolite has poor operability and is easy to leak in the using process to cause blockage, so that an efficient, simple and practical modification method capable of improving the maneuverability and stability of the zeolite is urgently needed to be found, so that the zeolite can be applied to blood perfusion to remove the ammonia.
The chitin is derived from shells of shrimps and crabs, is an important marine natural polymer resource, is rich in content, has good biocompatibility, bioactivity and biodegradability, and is preliminarily shown to be an important biomedical material. And it has no side effect on blood components, has good scavenging effect on bilirubin, lactate, bile acid, cholesterol, uric acid, creatinine, etc., and can be used as blood perfusion adsorbent. Millions of tons of shrimp and crab shell wastes exist in the world every year, so that serious burden is caused to the economy and ecology of the world, and important ocean resources such as chitin and the like are extracted from the wastes, so that huge economic benefit can be brought.
Disclosure of Invention
One of the objectives of the present invention is to provide a chitosan nanofiber porous composite microsphere blood ammonia adsorbent, which has a multi-scale and multi-layer chitosan nanofiber mesh structure, and rich through-hole channels suitable for free diffusion of blood ammonia, and is rich in zeolite with high selective adsorption ability for blood ammonia, and has a good selective adsorption effect on blood ammonia, and good compatibility with blood.
The second purpose of the invention is to provide a preparation method of the chitin nano-fiber porous composite microsphere blood ammonia adsorbent, which adopts a low-temperature green physical dissolution method, avoids the damage to the structures of chitin and zeolite, maintains the good biocompatibility and blood compatibility of the chitin and the stronger blood ammonia selective adsorption capacity of the zeolite, and has excellent comprehensive performance.
The third purpose of the invention is to provide the application of the chitin nano-fiber porous composite microsphere blood ammonia adsorbent.
The scheme adopted by the invention for realizing one of the purposes is as follows: the chitin nanofiber porous composite microsphere blood ammonia adsorbent is a porous network microsphere compounded by chitin nanofibers and zeolite, wherein the zeolite is wrapped in the chitin nanofiber porous network microsphere, the particle size of the composite microsphere blood ammonia adsorbent is 0.1-1 mm, the pore size distribution is 2-40 nm, the most probable pore size distribution is 5-15 nm, and the specific surface area is 100-500 m2The chitin nano-fibers have the diameter of 10-50 nm, the particle size of zeolite is 0.01-50 mu m, and the content of zeolite is 1% -50%.
The second scheme adopted by the invention for achieving the purpose is as follows: a preparation method of the chitin nano fiber porous composite microsphere blood ammonia adsorbent comprises the following steps:
(1) pulverizing zeolite into 0.01-50 μm particles;
(2) dispersing a certain amount of chitin powder in a solvent consisting of alkali, urea and deionized water, freezing and unfreezing for multiple cycles, stirring at 0-5 ℃, centrifuging and defoaming, and removing undissolved impurities to obtain a uniform chitin solution, and storing at 0-5 ℃ for later use;
(3) adding a certain amount of zeolite particles obtained in the step (1) into the chitin solution obtained in the step (2), uniformly stirring at 0-5 ℃ to obtain a chitin/zeolite composite solution, and storing at 0-5 ℃ for later use;
(4) adding a certain amount of dispersant into the organic phase and stirring uniformly at 0-5 ℃;
(5) pouring the solution prepared in the step (3) into the solution obtained in the step (4), and stirring at 0-5 ℃ until uniform small balls are formed;
(6) heating the system obtained in the step (5) to 60-100 ℃, and reacting;
(7) and (3) dropwise adding the solidified dispersion liquid into the reaction system obtained in the step (6) for continuous reaction, cooling to room temperature after the reaction is finished, standing for layering, standing and solidifying the lower chitin/zeolite nanofiber porous composite microspheres at 0-40 ℃, and washing to remove the residual dispersing agent and organic phase to obtain the chitin nanofiber porous composite microsphere blood ammonia adsorbent.
Preferably, in the step (2), the alkali is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the adding amount of the alkali is 2-30% of the total mass of the solvent, and the adding amount of the urea is 1-10% of the total mass of the solvent.
Preferably, in the step (2), the chitin is an initial product or a purified product thereof, the molecular weight of the chitin is 10000-500000, and the addition amount of the chitin is 2% -10% of the total mass of the solvent.
Preferably, in the step (1), the zeolite is natural zeolite or artificial zeolite, and in the step (3), the mass ratio of the chitin to the zeolite is 1: 0.5-2.
Preferably, in the step (4), the dispersant is tween, oleic acid or span, and the addition volume of the dispersant is 0.5-20% of the volume of the organic phase.
Preferably, in the step (4), the organic phase is liquid paraffin or isooctane, and the ratio of the volume of the organic phase to the volume of the chitin/zeolite composite solution is 0.2-3: 1.
Preferably, in the step (7), the coagulating dispersion liquid is Na2SO4、NaCl、(NH4)2SO4、NH4Any one of Cl aqueous solution with the concentration of 1 wt% -30 wt%.
Preferably, in the step (7), the concrete operation of standing and solidifying the lower layer chitin/zeolite nanofiber porous composite microspheres at 0-40 ℃ is as follows: pouring the chitin/zeolite nanofiber porous composite microspheres at the lower layer into a coagulating bath for standing, wherein the coagulating bath comprises water, 20-100 wt% of ethanol, a ketone solution, an ester solution and 1-20 wt% of Na2SO41 to 20 wt% (NH)4)2SO4The solidification time is 0.5-8 h, and the solidification temperature is 0-40 ℃.
The scheme adopted by the invention for realizing the third purpose is as follows: an application of the porous composite microsphere blood ammonia adsorbent of chitin nano-fiber in adsorbing blood ammonia or treating water and purifying and extracting.
The invention adopts the chitin modified zeolite material, not only retains the strong selective adsorption capacity of the zeolite to ammonia nitrogen, but also can improve the biocompatibility, blood compatibility and processability of the zeolite, and obtains the chitin/zeolite composite adsorbent with structure and performance suitable for blood perfusion, which is used for removing blood ammonia, makes up the blank that no effective adsorption material for the blood ammonia exists in the prior art, and has practical feasibility and clinical application prospect.
The preparation method aims to combine the chitin with good biocompatibility, blood compatibility and processability with the zeolite with strong selective ammonia nitrogen adsorption capacity, and obtain the chitin/zeolite nanofiber porous composite microsphere ammonia adsorbent which is uniformly distributed in size, has excellent ammonia nitrogen adsorption capacity, good biocompatibility and blood compatibility and is prepared by emulsifying and thermally-induced self-assembly processes. The material can be directly contacted with blood in use, and has good blood compatibility. The liver function failure can be effectively treated by the synergistic effect of the liver function failure treatment agent and bilirubin and inflammatory factor adsorbents developed in the same series, the lives of severe patients can be saved, the life quality of the patients can be improved, and the liver function failure treatment agent has important social value and economic value. In addition, the application of the chitin/zeolite nanofiber porous composite microsphere blood ammonia adsorbent is not limited to toxin adsorption of blood purification, and the chitin/zeolite nanofiber porous composite microsphere blood ammonia adsorbent can also be used for water treatment, purification extraction and other applications.
The invention has the following advantages and beneficial effects:
(1) the chitin nano fiber porous composite microsphere blood ammonia adsorbent provided by the invention has a multi-scale and multi-level chitin nano fiber mesh structure, is rich in through hole channels suitable for free diffusion of blood ammonia, is rich in zeolite with high selective blood ammonia adsorption capacity, and has a good adsorption effect on blood ammonia. The basic carrier of the microsphere is chitin, so that the microsphere has good biocompatibility and blood compatibility, small adsorption quantity to albumin and platelets, no hemolysis phenomenon, good compatibility with erythrocytes, no toxicity to human hepatocytes and no influence on a blood coagulation system and an electrolyte system in blood.
(2) The preparation method adopts a low-temperature green physical dissolution method to dissolve the chitin in the alkali/urea aqueous solution, combines the chitin with the zeolite to be uniformly dispersed in the solution, and forms the chitin/zeolite nanofiber porous composite microspheres of the chitin nanofiber-coated zeolite in the emulsion method and the thermal-induced self-assembly process, thereby avoiding the damage to the structures of the chitin and the zeolite in the process, maintaining the good biocompatibility and blood compatibility of the chitin and the stronger selective adsorption capacity of the zeolite, and having excellent comprehensive performance.
(3) The chitin nano fiber porous composite microsphere blood ammonia adsorbent fills up the blank of related products at home and abroad, and the adopted raw materials are cheap and easily available and are rich renewable resources; the size and the aperture of the microsphere can be adjusted, the preparation process is simple and controllable, the cost is low, and the microsphere is non-toxic and pollution-free and can be produced on a large scale; the adsorbent has high adsorption efficiency on blood ammonia, strong selectivity and easy popularization and application; the adsorbent has good biocompatibility and blood compatibility, no risk of coagulation and electrolyte disorder, no influence on blood components, can be used for removing blood ammonia through plasma perfusion and relieving the illness state of patients with hepatic encephalopathy, is a good medical blood purification and adsorption material, and can also be used for water treatment, purification, extraction and other purposes, so the adsorbent has wide application prospect.
Drawings
FIGS. 1-2 are SEM images of the porous composite microsphere of chitin/zeolite nanofiber prepared in example 1;
FIG. 3 is a TEM image of the ultrathin section of the porous composite microsphere of chitin/zeolite nanofibers prepared in example 1;
FIG. 4 is toxicity test of the control group, chitin nanofiber microspheres, chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite ═ 2: 1; 1: 1; 1:2) and zeolite on human normal hepatocytes (L-02) in example 6;
fig. 5 is a fluorescence micrograph of the control, chitin nanofiber microspheres, and chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite: 2:1) cultured on human normal hepatocytes (L-02) in example 7;
FIGS. 6 to 7 show the effect of the hollow white control group, the chitin nanofiber microspheres, the chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite: 2: 1; 1:1) and zeolite on the blood coagulation system in example 8;
FIG. 8 is the effect of the control blank, chitin nanofibrous microspheres, chitin/zeolite nanofibrous porous composite microspheres (chitin: zeolite: 2: 1; 1:1) and zeolite on the protein in plasma of the animal model with high blood ammonia in example 9;
FIG. 9 shows the adsorption effect of the hollow white control group, the chitosan nanofiber microspheres, the chitosan/zeolite nanofiber porous composite microspheres (chitin: zeolite: 2: 1; 1:1) and zeolite on blood ammonia in plasma of a high blood ammonia animal model in example 9;
fig. 10 shows the effect of the chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite: 1) in example 10 on the removal of blood ammonia from plasma at different initial blood ammonia concentrations;
note:
a chitin: chitin nano-fiber porous composite microspheres;
CZ 1: chitin/zeolite nanofiber porous composite microspheres, chitin: zeolite 2: 1;
CZ 2: chitin/zeolite nanofiber porous composite microspheres, chitin: zeolite 1: 1;
CZ 3: chitin/zeolite nanofiber porous composite microspheres; chitin: zeolite 1: 2;
zeolite: zeolite
PT: prothrombin time
APTT: partial thromboplastin activation time
TP: total protein.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
EXAMPLE 1 preparation of chitin/zeolite nanofiber porous composite microspheres
The preparation method of chitin/NaOH/urea aqueous solution is the prior art and is used according to the method disclosed in ZL 200310111566.3. 5g of chitin powder was dispersed in 95g of an aqueous solution of NaOH/urea, stirred for 10min (NaOH: urea: 11:4), frozen at-35 ℃ for 4 hours, and then thawed with stirring in an ice bath. Freezing/thawing for 3 cycles to obtain clear and transparent chitin solution with weight percentage concentration of 5%, centrifuging the chitin solution at 4 deg.C and 7000rad/min for 10min, defoaming and removing undissolved impurities to obtain chitin solution with mass percentage of 5%, and keeping at 0 deg.C. Pulverizing natural zeolite with high speed pulverizer or high speed ball mill, and sieving with 100 mesh sieve. 2.5g of sieved zeolite is added into 100g of chitin solution, and the mixture is stirred in ice bath to obtain chitin/zeolite composite solution for later use at 0 ℃. Adding 10mL of span 85 into 100mL of isooctane, stirring for 1h at the temperature of 0 ℃ at 500rad/min, adding a chitin/zeolite composite solution, continuously stirring for 2h, removing the ice bath, raising the temperature of a water bath kettle to 80 ℃, continuously stirring for 10-20 min, dropwise adding a 30% sodium chloride solution, stirring for 20 min, standing, dividing a mixture system into two layers, pouring out the upper organic phase isooctane and redundant emulsifiers, pouring the lower chitin/zeolite nanofiber porous composite microspheres into low-speed stirring absolute ethyl alcohol, solidifying and dispersing for 1h, standing, removing the upper absolute ethyl alcohol, soaking for 24h with clean absolute ethyl alcohol, rinsing with distilled water for multiple times to obtain regenerated chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite: 2:1), preserving in a 75% ethanol solution at the temperature of 0-5 ℃, or repeatedly replacing water in the microspheres with tert-butyl alcohol, quenching with liquid nitrogen, and freeze drying for storage. Observing through a scanning electron microscope, the average particle size of the prepared chitin/zeolite nanofiber porous composite microspheres is about 200 mu m, and the surfaces of the microspheres present a chitin/zeolite nanofiber porous fiber network structure of chitin nanofiber and chitin nanofiber-coated zeolite, as shown in figures 1-2; the microspheres are embedded and ultra-thinly sliced and then observed by a transmission electron microscope, and the zeolite in the prepared chitin/zeolite nanofiber porous composite microspheres is dispersed in a chitin nanofiber mesh structure, is combined with chitin nanofibers and is wrapped in the nanofiber microspheres, as shown in fig. 3.
EXAMPLE 2 preparation of chitin/zeolite nanofiber porous composite microspheres
The preparation method of chitin/NaOH/urea aqueous solution is the prior art and is used according to the method disclosed in ZL 200310111566.3. 5g of chitin powder was dispersed in 95g of an aqueous solution of NaOH/urea, stirred for 10min (NaOH: urea: 11:4), frozen at-35 ℃ for 4 hours, and then thawed with stirring in an ice bath. Freezing/thawing for 3 cycles to obtain clear and transparent chitin solution with weight percentage concentration of 5%, centrifuging the chitin solution at 4 deg.C and 7000rad/min for 10min, defoaming and removing undissolved impurities to obtain 5% chitin solution, and keeping at 0 deg.C. Pulverizing natural zeolite with high speed pulverizer or high speed ball mill, and sieving with 100 mesh sieve. Adding 5g of sieved zeolite into 100g of chitin solution, stirring in ice bath to obtain chitin/zeolite composite solution, and keeping at 0 ℃ for later use. Adding 10mL of span 85 into 100mL of isooctane, stirring for 1h at the temperature of 0 ℃ at 500rad/min, adding a chitin/zeolite composite solution, continuously stirring for 2h, removing the ice bath, raising the temperature of a water bath kettle to 80 ℃, continuously stirring for 10-20 min, dropwise adding a 30% sodium chloride solution, stirring for 20 min, standing, dividing a mixture system into two layers, pouring out the upper organic phase isooctane and redundant emulsifiers, pouring the lower chitin/zeolite nanofiber porous composite microspheres into low-speed stirring absolute ethyl alcohol, solidifying and dispersing for 1h, standing, removing the upper absolute ethyl alcohol, soaking for 24h with clean absolute ethyl alcohol, rinsing with distilled water for multiple times to obtain regenerated chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite 1:1), preserving in a 75% ethanol solution at the temperature of 0-5 ℃, or repeatedly replacing the water in the microspheres with tert-butyl alcohol, quenching with liquid nitrogen, and freeze drying for storage.
EXAMPLE 3 preparation of chitin/zeolite nanofiber porous composite microspheres
The preparation method of chitin/NaOH/urea aqueous solution is the prior art and is used according to the method disclosed in ZL 200310111566.3. 5g of chitin powder was dispersed in 95g of an aqueous solution of NaOH/urea, stirred for 10min (NaOH: urea: 11:4), frozen at-35 ℃ for 4 hours, and then thawed with stirring in an ice bath. Freezing/thawing for 3 cycles to obtain clear and transparent chitin solution with weight percentage concentration of 5%, centrifuging the chitin solution at 4 deg.C and 7000rad/min for 10min, defoaming and removing undissolved impurities to obtain chitin solution with mass percentage of 5%, and keeping at 0 deg.C. Pulverizing natural zeolite with high speed pulverizer or high speed ball mill, and sieving with 100 mesh sieve. Adding 7.5g of sieved zeolite into 100g of chitin solution, stirring in ice bath to obtain chitin/zeolite composite solution, and keeping at 0 ℃ for later use. Adding 10mL of span 85 into 100mL of isooctane, stirring for 1h at the temperature of 0 ℃ at 500rad/min, adding a chitin/zeolite composite solution, continuously stirring for 2h, removing the ice bath, raising the temperature of a water bath kettle to 80 ℃, continuously stirring for 10-20 min, dropwise adding a 30% sodium chloride solution, stirring for 20 min, standing, dividing a mixture system into two layers, pouring out the upper organic phase isooctane and redundant emulsifiers, pouring the lower chitin/zeolite nanofiber porous composite microspheres into low-speed stirring absolute ethyl alcohol, solidifying and dispersing for 1h, standing, removing the upper absolute ethyl alcohol, soaking for 24h with clean absolute ethyl alcohol, rinsing with distilled water for multiple times to obtain regenerated chitin/zeolite nanofiber porous composite microspheres (chitin: zeolite 1:2), preserving in a 75% ethanol solution at the temperature of 0-5 ℃, or repeatedly replacing the water in the microspheres with tert-butyl alcohol, quenching with liquid nitrogen, and freeze drying for storage.
EXAMPLE 4 preparation of chitin/zeolite nanofiber porous composite microspheres
The preparation method of chitin/NaOH/urea aqueous solution is the prior art and is used according to the method disclosed in ZL 200310111566.3. 5g of chitin powder was dispersed in 95g of an aqueous solution of NaOH/urea, stirred for 10min (NaOH: urea: 11:4), frozen at-35 ℃ for 4 hours, and then thawed with stirring in an ice bath. Freezing/thawing for 3 cycles to obtain clear and transparent chitin solution with weight percentage concentration of 5%, centrifuging the chitin solution at 4 deg.C and 7000rad/min for 10min, defoaming and removing undissolved impurities to obtain chitin solution with mass percentage of 5%, and keeping at 4 deg.C. Pulverizing natural zeolite with high speed pulverizer or high speed ball mill, and sieving with 100 mesh sieve. Adding 5g of sieved zeolite into 100g of chitin solution, stirring in ice bath to obtain chitin/zeolite composite solution, and keeping at 4 ℃ for later use. Adding 0.5mL of Tween into 100mL of liquid paraffin, stirring for 1h at 4 ℃ at 500rad/min, adding a chitin/zeolite composite solution, continuously stirring for 2h, removing the ice bath, raising the temperature of a water bath kettle to 60 ℃, continuously stirring for 10-20 min, dropwise adding 20% of sodium sulfate, stirring for 10-20 min, standing, dividing a mixture system into two layers, pouring out the upper organic phase liquid paraffin and the redundant emulsifier, pouring the lower chitin/zeolite nanofiber porous composite microspheres into acetone stirred at a low speed, solidifying and dispersing for 1h, standing, removing the upper acetone, soaking for 24h with clean acetone, rinsing with distilled water for multiple times to obtain regenerated chitin/zeolite nanofiber porous composite microspheres, and (3) storing the microspheres in a 75% ethanol solution at 0-5 ℃, or repeatedly replacing water in the microspheres with tert-butyl alcohol, quenching the microspheres with liquid nitrogen, and freeze-drying the microspheres for storage.
EXAMPLE 5 preparation of chitin/zeolite nanofiber porous composite microspheres
The preparation method of chitin/NaOH/urea aqueous solution is the prior art and is used according to the method disclosed in ZL 200310111566.3. 5g of chitin powder was dispersed in 95g of an aqueous solution of NaOH/urea, stirred for 10min (NaOH: urea: 11:4), frozen at-35 ℃ for 4 hours, and then thawed with stirring in an ice bath. Freezing/thawing for 3 cycles to obtain clear and transparent chitin solution with weight percentage concentration of 5%, centrifuging the chitin solution at 4 deg.C and 7000rad/min for 10min, defoaming and removing undissolved impurities to obtain chitin solution with mass percentage of 5%, and keeping at 5 deg.C. Pulverizing natural zeolite with high speed pulverizer or high speed ball mill, and sieving with 100 mesh sieve. Adding 7.5g of sieved zeolite into 100g of chitin solution, stirring in ice bath to obtain chitin/zeolite composite solution, and keeping at 5 ℃ for later use. Adding 20mL of span 85 into 100mL of isooctane, stirring for 1h at the temperature of 5 ℃ at 500rad/min, adding 100mL of chitin/zeolite composite solution, continuously stirring for 2h, removing the ice bath, raising the temperature of a water bath kettle to 100 ℃, continuously stirring for 10-20 min, dropwise adding 30% sodium chloride, stirring for 10-20 min, standing, dividing the mixture system into two layers, pouring out the upper organic isooctane and redundant emulsifiers, pouring the lower chitin/zeolite nanofiber porous composite microspheres into low-speed stirring absolute ethyl alcohol, curing and dispersing for 1h, standing, removing the upper absolute ethyl alcohol, soaking for 24h with clean absolute ethyl alcohol, rinsing with distilled water for multiple times to obtain regenerated chitin/zeolite nanofiber porous composite microspheres, storing in 75% ethanol solution at the temperature of 0-5 ℃, or repeatedly replacing the water in the microspheres with tert-butyl alcohol, quenching with liquid nitrogen, and freeze drying for storage.
Example 6 cytotoxicity assay
The freeze-dried microspheres were replaced with sterile PBS several times to prepare a 5mg/mL mixture, which was autoclaved for future use. 200 μ L of human normal hepatocytes (L-02) were added to a 96-well plate at 2000 cells/well, and then placed at 37 ℃ in 5% CO2Culturing in DMEM high-sugar medium containing 10% fetal calf serum and 1% penicillin/streptomycin dual-antibody for 12h under the environment, replacing fresh medium, adding the mixture of chitin/zeolite nanofiber porous composite microspheres and the mixture of chitin nanofiber microspheres (20 μ L/pore or 40 μ L/pore) prepared in examples 1-3,the control group was also prepared by adding the same amount of PBS. After 48h of cell culture, the medium was discarded, and 200. mu.L of a CCK8 working solution (CCK 8: medium 1:10) was added to each well with a blank well without cells as a background group, and then placed in an incubator under the same conditions for 4 h. mu.L of supernatant per well was taken in a new 96-well plate and the absorbance value A was measured at a wavelength of 450 nm. The cell viability (cell viability) can be calculated according to the following formula:
Cell viability(％)＝(Atest–Abackground)/(Acontrol-ABackground)×100％
(Atest、AcontrolAnd ABackgroundAbsorbance values for test, control and background groups, respectively).
Cell toxicity experiments show that the chitin nanofiber microspheres and the chitin/zeolite nanofiber porous composite microspheres both have good biocompatibility, and after the material is cultured with cells, the survival rate of the cells is close to 100%, which shows that the material has no toxicity, as shown in figure 4.
Example 7 cell culture experiments
The chitin nanofiber microspheres and the freeze-dried microspheres prepared in example 1 were replaced with sterile PBS for several times, and mixed into a mixed solution with a concentration of 5mg/mL, and autoclaved for later use. 50 μ L of the microsphere PBS mixture was transferred to a 24-well plate. 1mL of a suspension of human normal hepatocytes (L-02) (cell density of 50000 cells/mL) was added to each sample, which was then placed at 37 ℃ and 5% CO2Culturing for 48h in DMEM high-sugar medium containing 10% fetal calf serum and 1% penicillin/streptomycin double antibody under the environment. Cells were stained for live/dead cells using Calcein-AM/PI dye: the medium was aspirated off and washed twice with PBS, 300. mu.L of encein-AM/PI dye was added to each well and stained in a 37 ℃ dark incubator for 15-30 min, and the fluorescently stained microspheres and cells were observed and photographed under a fluorescent microscope, as shown in FIG. 5. And dehydrating the fixed cells by using gradient tert-butyl alcohol, quenching by using liquid nitrogen, freeze-drying, spraying gold, and observing the shapes of the microspheres and the cells by using a scanning electron microscope.
Example 8 coagulation assay
Fresh rabbit blood from normal rabbits was drawn as per blood: sodium citrate 9:1 anticoagulated for later use. The chitin nanofiber microspheres, zeolite, and the freeze-dried chitin/zeolite nanofiber porous composite microspheres prepared in examples 1 and 2 (chitin: zeolite ═ 2:1) were replaced with sterile PBS for several times, and the mixture was subjected to suction filtration for use. Weighing 0.5g of sample, adding 2ml of blood sample, slowly inverting at constant speed for several times, incubating for 4h at 37 ℃ in a shaking table, centrifuging to obtain supernatant, and detecting Prothrombin Time (PT), Activated Partial Thromboplastin Time (APTT), Thrombin Time (TT), Fibrinogen (FIB) and activated whole blood coagulation time (ACT) by using a coagulometer. PT values and APTT values of various adsorbing materials are shown in figures 6-7. The data show that the blood compatibility of the zeolite is poor, but the chitin is modified greatly, the blood coagulation time of the chitin/zeolite nanofiber porous composite microspheres is close to that of a control group, and the chitin/zeolite nanofiber porous composite microspheres have good blood compatibility.
Example 9 static adsorption experiment of protein and blood ammonia in plasma of blood ammonia animal model
Fresh rabbit blood from a blood ammonia animal model was drawn according to blood: sodium citrate 9:1 anticoagulation, centrifuging the blood sample at 2000r/min for 10min, collecting supernatant to obtain high blood ammonia plasma, subpackaging and storing in a refrigerator at-20 deg.C for plasma adsorption test. 20mg of chitin nanofiber microspheres, the chitin/zeolite nanofiber porous composite microspheres prepared in examples 1 and 2 (chitin: zeolite: 2: 1; 1:1) and zeolite samples were weighed respectively, 2mL of plasma with different initial blood ammonia concentrations was added respectively, after adsorption for 4h at 37 ℃, the supernatant was taken and put on an automatic biochemical analyzer to detect the content of protein and blood ammonia in the plasma. Total Protein (TP); albumin (ALB); globulin (GLB); creatinine (Creatinine); blood Ammonia (AMON). The results of protein adsorption in plasma are shown in fig. 8, and the results of blood ammonia adsorption are shown in fig. 9. The results show that the adsorbent sample has no adsorption effect on the protein; the chitin/zeolite nanofiber porous composite microspheres have high capacity of removing blood ammonia, and the adsorption capacity is increased along with the increase of the content of zeolite. Therefore, the chitin/zeolite nanofiber porous composite microspheres have selective adsorption capacity on the blood ammonia.
Example 10 static adsorption experiment of blood ammonia in plasma of blood ammonia animal model
Fresh rabbit blood from a blood ammonia animal model was drawn as blood: sodium citrate 9:1 anticoagulation, centrifuging the blood sample at 2000r/min for 10min, collecting supernatant to obtain high blood ammonia plasma, subpackaging and storing in a refrigerator at-20 deg.C for plasma adsorption test. Weighing 40mg of a dried chitin/zeolite nanofiber porous composite microsphere (chitin: zeolite 1:1) prepared in example 2, adding 2mL of plasma with different initial blood ammonia concentrations, adsorbing at 37 ℃ for 2h, 4h, 6h, 8h and 10h, taking supernatant, detecting the blood ammonia content in the plasma on an automatic biochemical analyzer, wherein the initial concentration is 246.3 mu mol/L, and reducing the initial concentration to 85.3 mu mol/L after adsorption, as shown in fig. 10; the initial concentration is 307.8 mu mol/L, and the concentration is reduced to 169.1 mu mol/L after adsorption; the initial concentration was 424.8. mu. mol/L, and the concentration decreased to 297.9. mu. mol/L after adsorption, all showing efficient adsorption of blood ammonia.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A chitin nano fiber porous composite microsphere blood ammonia adsorbent is characterized in that: the adsorbent is a porous network microsphere compounded by chitin nano fibers and zeolite, the zeolite is wrapped in the porous network microsphere of the chitin nano fibers, the particle size of the composite microsphere blood ammonia adsorbent is 0.1-1 mm, the pore size distribution is 2-40 nm, the most probable pore size distribution is 5-15 nm, and the specific surface area is 100-500 m2The chitin nano-fibers have the diameter of 10-50 nm, the particle size of zeolite is 0.01-50 mu m, and the content of zeolite is 1% -50%.
2. The preparation method of the chitin nano fiber porous composite microsphere blood ammonia adsorbent as claimed in claim 1, characterized by comprising the following steps:
(1) pulverizing zeolite into 0.01-50 μm particles;
(2) dispersing a certain amount of chitin powder in a solvent consisting of alkali, urea and deionized water, freezing and unfreezing for multiple cycles, stirring at 0-5 ℃, centrifuging and defoaming, and removing undissolved impurities to obtain a uniform chitin solution, and storing at 0-5 ℃ for later use;
(3) adding a certain amount of zeolite particles obtained in the step (1) into the chitin solution obtained in the step (2), uniformly stirring at 0-5 ℃ to obtain a chitin/zeolite composite solution, and storing at 0-5 ℃ for later use;
(4) adding a certain amount of dispersant into the organic phase and stirring uniformly at 0-5 ℃;
(5) pouring the solution prepared in the step (3) into the solution obtained in the step (4), and stirring at 0-5 ℃ until uniform small balls are formed;
(6) heating the system obtained in the step (5) to 60-100 ℃, and reacting;
(7) and (3) dropwise adding the solidified dispersion liquid into the reaction system obtained in the step (6) for continuous reaction, cooling to room temperature after the reaction is finished, standing for layering, standing and solidifying the lower chitin/zeolite nanofiber porous composite microspheres at 0-40 ℃, and washing to remove the residual dispersing agent and organic phase to obtain the chitin nanofiber porous composite microsphere blood ammonia adsorbent.
3. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (2), the alkali is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the adding amount of the alkali is 2-30% of the total mass of the solvent, and the adding amount of the urea is 1-10% of the total mass of the solvent.
4. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (2), the chitin is an initial product or a purified product thereof, the molecular weight of the chitin is 10000-500000, and the addition amount of the chitin is 2% -10% of the total mass of the solvent.
5. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (1), the zeolite is natural zeolite or artificial zeolite, and in the step (3), the mass ratio of the chitin to the zeolite is 1: 0.5-2.
6. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (4), the dispersant is tween, oleic acid or span, and the adding volume of the dispersant is 0.5-20% of the volume of the organic phase.
7. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (4), the organic phase is liquid paraffin or isooctane, and the ratio of the volume of the organic phase to the volume of the chitin/zeolite composite solution is 0.2-3: 1.
8. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (7), the coagulating dispersion liquid is Na2SO4、NaCl、(NH4)2SO4、NH4Any one of Cl aqueous solution with the concentration of 1 wt% -30 wt%.
9. The method for preparing the chitin nano-fiber porous composite microsphere ammonia adsorbent according to claim 2, wherein the method comprises the following steps: in the step (7), the concrete operation of standing and solidifying the lower layer chitin/zeolite nanofiber porous composite microspheres at 0-40 ℃ is as follows: pouring the chitin/zeolite nanofiber porous composite microspheres at the lower layer into a coagulating bath for standing, wherein the coagulating bath comprises water, 20-100 wt% of ethanol, a ketone solution, an ester solution and 1-20 wt% of Na2SO41 to 20 wt% (NH)4)2SO4The solidification time is 0.5-8 h, and the solidification temperature is 0-40 ℃.
10. An application of the porous composite microsphere blood ammonia adsorbent of chitin nano-fiber in adsorbing blood ammonia or treating water and purifying and extracting.
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