CN109794172B - Preparation method of antibacterial hollow fiber membrane for blood purification - Google Patents
Preparation method of antibacterial hollow fiber membrane for blood purification Download PDFInfo
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- CN109794172B CN109794172B CN201910071151.9A CN201910071151A CN109794172B CN 109794172 B CN109794172 B CN 109794172B CN 201910071151 A CN201910071151 A CN 201910071151A CN 109794172 B CN109794172 B CN 109794172B
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- hollow fiber
- fiber membrane
- mesoporous silicon
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 89
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000008280 blood Substances 0.000 title claims abstract description 26
- 210000004369 blood Anatomy 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 108
- 239000010703 silicon Substances 0.000 claims abstract description 108
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229940072056 alginate Drugs 0.000 claims abstract description 64
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 64
- 229920000615 alginic acid Polymers 0.000 claims abstract description 64
- 238000005266 casting Methods 0.000 claims abstract description 33
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 239000004332 silver Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 81
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 76
- 239000007864 aqueous solution Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- OEZQCMMAFSEXQW-UHFFFAOYSA-N calcium silver Chemical compound [Ca].[Ag] OEZQCMMAFSEXQW-UHFFFAOYSA-N 0.000 claims description 45
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 38
- 239000004695 Polyether sulfone Substances 0.000 claims description 37
- 229920006393 polyether sulfone Polymers 0.000 claims description 37
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 27
- 239000000661 sodium alginate Substances 0.000 claims description 27
- 235000010413 sodium alginate Nutrition 0.000 claims description 27
- 229940005550 sodium alginate Drugs 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 27
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- 159000000007 calcium salts Chemical class 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000002166 wet spinning Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000001631 haemodialysis Methods 0.000 abstract description 12
- 230000000322 hemodialysis Effects 0.000 abstract description 12
- 239000003053 toxin Substances 0.000 abstract description 11
- 231100000765 toxin Toxicity 0.000 abstract description 11
- 108700012359 toxins Proteins 0.000 abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- -1 silver ions Chemical class 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 95
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 13
- 238000002791 soaking Methods 0.000 description 13
- 238000004108 freeze drying Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- 239000007863 gel particle Substances 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229930003779 Vitamin B12 Natural products 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 9
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 9
- 229940109239 creatinine Drugs 0.000 description 9
- 229940045136 urea Drugs 0.000 description 9
- 239000011715 vitamin B12 Substances 0.000 description 9
- 235000019163 vitamin B12 Nutrition 0.000 description 9
- 208000037157 Azotemia Diseases 0.000 description 8
- 208000009852 uremia Diseases 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002441 uremic toxin Substances 0.000 description 7
- 230000008081 blood perfusion Effects 0.000 description 5
- 230000001951 hemoperfusion Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 208000020832 chronic kidney disease Diseases 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 208000022831 chronic renal failure syndrome Diseases 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 208000024172 Cardiovascular disease Diseases 0.000 description 2
- 208000026106 cerebrovascular disease Diseases 0.000 description 2
- 208000035850 clinical syndrome Diseases 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000002526 effect on cardiovascular system Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 208000017169 kidney disease Diseases 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000003715 nutritional status Nutrition 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 208000001889 Acid-Base Imbalance Diseases 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 206010061666 Autonomic neuropathy Diseases 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 206010014418 Electrolyte imbalance Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- 238000009098 adjuvant therapy Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000028208 end stage renal disease Diseases 0.000 description 1
- 201000000523 end stage renal failure Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Analytical Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Manufacturing & Machinery (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of an antibacterial hollow fiber membrane for blood purification. The preparation method of the antibacterial hollow fiber membrane comprises the following steps: 1) loading silver and calcium ions in the mesoporous silicon; 2) preparing alginate wrapping the ion-loaded mesoporous silicon; 3) preparing a membrane casting solution; 4) and (3) spinning by a dry-jet wet method to prepare the antibacterial hollow fiber membrane. The prepared antibacterial hollow fiber membrane is an antibacterial hollow fiber membrane which can be used for blood purification. The hollow fiber membrane prepared by the invention has the advantages of high safety, simple preparation operation, low cost and the like, and can be applied to hemodialysis. The open porous structure of the hollow fiber membrane prepared by the invention can enable toxins to pass through smoothly, and selectively adsorb small molecular and medium molecular toxins, thereby achieving the effect of effectively removing the toxins. Meanwhile, the silver and calcium-loaded mesoporous silicon can release trace silver ions into blood and dialysate, so that the antibacterial effect is achieved.
Description
Technical Field
The invention relates to a fiber membrane, in particular to a preparation method of an antibacterial hollow fiber membrane for blood purification.
Background
Chronic renal failure refers to a clinical syndrome consisting of a series of symptoms and metabolic disorders that lead to progressive irreversible decline in kidney function, through loss of function, from various renal diseases. The end-stage chronic renal failure is uremia, refers to clinical syndromes shared by various end-stage renal diseases, is a syndrome formed by a series of clinical manifestations when the chronic renal failure enters the end stage, and is closely related to retention of various uremic toxins in the body. Renal failure can accelerate atherosclerosis, and once arterial blockage develops, various diseases such as cardiovascular and cerebrovascular diseases, kidney diseases, liver diseases and the like can be caused. Among them, cardiovascular and cerebrovascular diseases are the leading cause of death in uremia patients. According to the world health organization, about 1700 thousands of people die of the chronic disease annually, accounting for about 30% of the total death worldwide. The uremia seriously threatens the health of human beings, and along with the continuous development of urbanization and industrialization in China, the social and economic pressure is increased, and the uremia patient population in China is further expanded. Moreover, with the development of economy and science and technology, the requirements of people on the quality of life are higher and higher, and the attention on health is up to the unprecedented level. The development of uremia blood purification therapy with adjuvant therapy effect has huge market demand and very broad prospect.
Currently, the literature reports the blood purification therapy of uremia, and the curative effect of hemodialysis or the combination of hemodialysis and hemoperfusion is more concerned. Although compared with the traditional blood purification treatment such as hemodialysis, the blood perfusion has improved capability of removing uremic toxins. However, the following problems are present: 1) blood perfusion cannot solve the problem of electrolyte and acid-base imbalance caused in the blood purification process. Therefore, blood perfusion is generally combined with hemodialysis, so that the toxin is efficiently removed, and the electrolyte and acid-base balance is kept; 2) meanwhile, after the blood perfusion is combined with the hemodialysis, the cost is greatly improved, and the patients and families have higher economic pressure; 3) when the blood adsorbent lacks specificity for adsorbing uremic toxins, the removal effect is not ideal.
In the prior published literature, CN104258829A discloses a blood phosphorus adsorbent, a preparation method thereof, and an adsorption column for blood perfusion; CN102335465A discloses a hemoperfusion apparatus for treating uremia; CN101307149A discloses a preparation method of a medical adsorbent carrier; the comparison of the effects of high-throughput dialysis, hemodiafiltration, hemodialysis and hemoperfusion on the removal of uremic toxins is disclosed in the patent of Guilian et al (observation and care of curative effect of various blood purification combined treatments for uremic complications, Anhui medicine, 2013,17, 43-345); zhangmin and the like (evaluation of curative effect of different blood purification modes on uremia toxin removal and autonomic neuropathy, Guangdong medicine 2010,22, 2943-; in Shang Sheng Dong (the influence of different hemodialysis methods on the clearance effect and the nutritional status of uremic toxins in maintenance dialysis patients, journal of practical clinical medicine 2015,19,26-29) the influence of hemodialysis, hemodiafiltration, and hemodialysis combined hemoperfusion on the clearance effect and the nutritional status of uremic toxins is studied. However, most of the above blood purification methods are blood adsorption or combined use of hemodialysis and hemoperfusion, which is difficult to solve the problems of pH and electrolyzed alkali balance, or has high treatment cost.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention aims to provide a preparation method of an antibacterial hollow fiber membrane for blood purification.
The preparation method comprises the steps of firstly loading silver ions and calcium ions on mesoporous silicon, then primarily wrapping the mesoporous silicon by using alginate, and simultaneously dispersing the silver-and calcium-loaded mesoporous silicon in a high molecular solution to form a casting solution; and (3) carrying out solidification molding in a sodium alginate aqueous solution and a calcium ion solution by a dry-jet wet spinning technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an antibacterial hollow fiber membrane comprises the following steps:
1) loading silver and calcium ions in the mesoporous silicon: dispersing mesoporous silicon in a solution of silver salt and calcium salt, and drying the obtained suspension to obtain silver-calcium-loaded mesoporous silicon;
2) preparing alginate wrapping the ion-loaded mesoporous silicon: dispersing silver-and calcium-loaded mesoporous silicon in an alginate solution to obtain gel-like particles, and sieving to obtain alginate wrapping the ion-loaded mesoporous silicon;
3) preparing a casting solution: mixing polyether sulfone, alginate wrapping the ion-loaded mesoporous silicon, a pore-forming agent and a solvent, and defoaming to obtain a membrane casting solution;
4) preparing the antibacterial hollow fiber membrane by dry-jet wet spinning: and (3) spraying the membrane casting solution through a spinning nozzle, and sequentially adding the membrane casting solution into an alginate solution and a calcium salt solution for forming under the conditions of certain core solution flow rate and air section distance to obtain the antibacterial hollow fiber membrane.
Preferably, in step 1) of the preparation method of the antibacterial hollow fiber membrane, the dosage ratio of the mesoporous silicon to the solution of the silver salt and the calcium salt is 1 g: (60-100) mL.
Preferably, in step 1) of the preparation method of the antibacterial hollow fiber membrane, the solution of silver salt and calcium salt is an aqueous solution containing silver nitrate and calcium nitrate; wherein, the mass concentration of the silver nitrate is 2.5-5 percent, and the mass concentration of the calcium nitrate is 2.5-5 percent.
Preferably, in the step 1) of the preparation method of the antibacterial hollow fiber membrane, the mesoporous silicon is ultrasonically dispersed in silver nitrate and calcium nitrate aqueous solution under normal pressure, the solution is oscillated on a shaking table to obtain suspension, and the suspension is vacuumized and repeated for 3-5 times.
Preferably, in step 1) of the preparation method of the antibacterial hollow fiber membrane, the suspension is dried by freeze drying.
Preferably, in step 2) of the preparation method of the antibacterial hollow fiber membrane, the dosage ratio of the silver and calcium-loaded mesoporous silicon to the alginate solution is 1 g: (80-200) mL.
Preferably, in the step 2) of the preparation method of the antibacterial hollow fiber membrane, the alginate solution is a sodium alginate aqueous solution with the mass concentration of 2.5-5%.
Preferably, in the step 2) of the preparation method of the antibacterial hollow fiber membrane, the antibacterial hollow fiber membrane is sieved to be a molecular sieve with 800-1200 meshes; further preferably, the sieve is a 1000 mesh sieve. And 2) after sieving, collecting particles under the sieve, namely the alginate wrapping the ion-loaded mesoporous silicon.
Preferably, in step 3) of the preparation method of the antibacterial hollow fiber membrane, the use amount ratio of the polyether sulfone, the alginate wrapping the ion-loaded mesoporous silicon, the pore-forming agent and the solvent is 1 g: (0.01-0.05) g: (0.04-0.08) g: (0.5-1.5) mL.
Preferably, in step 3) of the preparation method of the antibacterial hollow fiber membrane, the pore-forming agent is at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol and diethylene glycol; further preferably, the pore-foaming agent is at least one of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol; still further preferably, the pore-forming agent is polyvinylpyrrolidone; in some preferred embodiments of the present invention, the polyvinylpyrrolidone is selected from the group consisting of polyvinylpyrrolidone type K30.
Preferably, in step 3) of the preparation method of the antibacterial hollow fiber membrane, the solvent is at least one of dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylacetamide; further preferably, the solvent is dimethylacetamide or dimethylformamide.
Preferably, in step 3) of the preparation method of the antibacterial hollow fiber membrane, the defoaming mode is standing defoaming; more preferably, the standing time for standing and defoaming is 8 to 12 hours, and the standing temperature is 10 to 35 ℃.
Preferably, in step 4) of the method for producing an antibacterial hollow fiber membrane, the driving pressure for ejection is 0.08 to 0.5 MPa.
Preferably, in the step 4) of the preparation method of the antibacterial hollow fiber membrane, the flow rate of the core liquid is 10mL/min to 50 mL/min.
Preferably, in the step 4) of the preparation method of the antibacterial hollow fiber membrane, the distance of the air section is 0-20 cm.
Preferably, in step 4) of the method for preparing the antibacterial hollow fiber membrane, the core liquid is water.
In the step 4) of the preparation method of the antibacterial hollow fiber membrane, the alginate solution is a first solidification solution; preferably, the alginate solution is sodium alginate aqueous solution with the temperature of 50-80 ℃ and the mass concentration of 5-10%.
In the step 4) of the preparation method of the antibacterial hollow fiber membrane, the calcium salt solution is a second solidification solution; preferably, the calcium salt solution is a calcium nitrate aqueous solution with the temperature of 30-70 ℃ and the mass concentration of 1-4.5%.
Preferably, in step 4), the antibacterial hollow fiber membrane is prepared by soaking and air-drying the formed membrane material.
Preferably, in the step 4) of the preparation method of the antibacterial hollow fiber membrane, the membrane material is soaked and cleaned for 24 to 72 hours by water with the temperature of 70 to 90 ℃.
Preferably, in step 4), the air-drying is air-drying.
An antibacterial hollow fiber membrane for purifying blood is prepared by the preparation method.
The invention has the beneficial effects that:
the hollow fiber membrane prepared by the invention has the advantages of high safety, simple preparation operation, low cost and the like, and can be applied to hemodialysis. The open porous structure of the hollow fiber membrane prepared by the invention can enable toxins to pass through smoothly, and selectively adsorb small molecular and medium molecular toxins, thereby achieving the effect of effectively removing the toxins. Meanwhile, the silver and calcium-loaded mesoporous silicon can release trace silver ions into blood and dialysate, so that the antibacterial effect is achieved.
In particular, the advantages of the invention are as follows:
1) the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane prepared by the method has a finger-shaped pore structure and a sponge porous structure which are formed by polymers, and is high in permeability and fast in mass transfer dynamics.
2) The prepared mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane has a microporous structure formed by mesoporous silicon, can adsorb micromolecular and mesomolecular toxins diffused to the dialysate side in time, and improves the clearance rate of the toxins.
3) The mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane prepared by the method contains silver-and calcium-loaded mesoporous silicon, and calcium ions released in the preparation process of the hollow fiber membrane can assist in enhancing the mechanical strength of alginate in a membrane matrix material.
4) The mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane prepared by the method contains silver-and calcium-loaded mesoporous silicon, and can release silver ions in time to achieve an antibacterial effect.
5) The matrix of the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane prepared by the invention is polyether sulfone, alginate and mesoporous silicon, and the blood compatibility is good.
6) The mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane prepared by the method has good removal performance on urea, creatinine and vitamin B12, the removal rate on urea can reach 95.2%, the removal rate on creatinine can reach 93.4%, and the removal rate on vitamin B12 can reach 57.4%.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 2.5% silver nitrate and 3.5% calcium nitrate water solution. Ultrasonically dispersing 4.0g of mesoporous silicon in 400mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 4 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 3.5g of silver-and calcium-loaded mesoporous silicon in 350mL of 3.0% sodium alginate aqueous solution, stirring at normal temperature for 4h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
40g of polyether sulfone, 0.57g of alginate wrapping silver-calcium-loaded mesoporous silicon and 1.6g K30-polyvinylpyrrolidone are dissolved/dispersed in 20mL of dimethylacetamide, and then are kept stand at 10 ℃ for 9h to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.2MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 55 ℃ and the concentration of 5.0 percent and a calcium nitrate aqueous solution with the temperature of 30 ℃ and the concentration of 3.5 percent under the conditions of 10mL/min core solution (water) and 20cm air section distance for forming. And (3) soaking and cleaning the solid hollow fiber membrane in water at 75 ℃ for 54h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 2
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 2.5% silver nitrate and 5.0% calcium nitrate water solution. Ultrasonically dispersing 5.0g of mesoporous silicon in 300mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 5 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 4.5g of silver-and calcium-loaded mesoporous silicon in 675mL of 2.5% sodium alginate aqueous solution, stirring at normal temperature for 4h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
Dissolving/dispersing 60g of polyether sulfone, 1.0g of alginate wrapping silver-calcium-loaded mesoporous silicon and 3.6g K30-polyvinylpyrrolidone in 30mL of dimethylacetamide, and standing at 20 ℃ for 8h to obtain a casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.08MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 50 ℃ and the concentration of 8.0 percent and a calcium nitrate aqueous solution with the temperature of 40 ℃ and the concentration of 1.0 percent under the conditions of a core solution (water) with the concentration of 40mL/min and an air section distance of 0cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane by water at 70 ℃ for 48h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 3
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 3.5% silver nitrate and 2.5% calcium nitrate water solution. Ultrasonically dispersing 6.0g of mesoporous silicon in 360mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 3 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 5.0g of silver-and calcium-loaded mesoporous silicon in 750mL of 5.0% sodium alginate aqueous solution, stirring at normal temperature for 3h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
50g of polyether sulfone, 2.5g of alginate wrapping silver-calcium-loaded mesoporous silicon and 4.0g K30-polyvinylpyrrolidone are dissolved/dispersed in 75mL of dimethylacetamide, and then are kept stand for 9 hours at 35 ℃ to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.5MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 80 ℃ and the concentration of 10.0 percent and a calcium nitrate aqueous solution with the temperature of 50 ℃ and the concentration of 1.0 percent under the conditions of a core solution (water) with the concentration of 30mL/min and an air section distance of 15cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane in water at 70 ℃ for 24h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 4
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 4.0% silver nitrate and 3.0% calcium nitrate water solution. Ultrasonically dispersing 6.0g of mesoporous silicon in 480mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 3 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 5.0g of silver-and calcium-loaded mesoporous silicon in 500mL of 4.5% sodium alginate aqueous solution, stirring at normal temperature for 3h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
40g of polyether sulfone, 1.5g of alginate wrapping silver-calcium-loaded mesoporous silicon and 3.2g K30-polyvinylpyrrolidone are dissolved/dispersed in 60mL of dimethylacetamide, and then are kept stand for 11h at 25 ℃ to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.25MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 65 ℃ and the concentration of 7.0 percent and a calcium nitrate aqueous solution with the temperature of 35 ℃ and the concentration of 1.5 percent under the conditions of a core solution (water) with the concentration of 50mL/min and an air section distance of 10cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane by water at 90 ℃ for 72h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 5
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 3.0% silver nitrate and 3.0% calcium nitrate water solution. Ultrasonically dispersing 6.0g of mesoporous silicon in 480mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 3 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 5.0g of silver-and calcium-loaded mesoporous silicon in 400mL of 3.5% sodium alginate aqueous solution, stirring at normal temperature for 5h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
Dissolving/dispersing 60g of polyether sulfone, 2.25g of alginate wrapping silver-calcium-loaded mesoporous silicon and 4.8g K30-polyvinylpyrrolidone in 90mL of dimethylacetamide, and standing at 20 ℃ for 10 hours to obtain a casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.1MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 60 ℃ and the concentration of 10.0 percent and a calcium nitrate aqueous solution with the temperature of 55 ℃ and the concentration of 2.5 percent under the conditions of a core solution (water) with the concentration of 15mL/min and an air section distance of 15cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane by water at the temperature of 80 ℃ for 36 hours, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 6
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 3.0% silver nitrate and 2.5% calcium nitrate water solution. Ultrasonically dispersing 5.0g of mesoporous silicon in 500mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 3 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 4.5g of silver-and calcium-loaded mesoporous silicon in 675mL of 2.5% sodium alginate aqueous solution, stirring at normal temperature for 3h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
50g of polyether sulfone, 1.43g of alginate wrapping silver-calcium-loaded mesoporous silicon and 2.0g K30-polyvinylpyrrolidone are dissolved/dispersed in 50mL of dimethylacetamide, and then are kept stand at 35 ℃ for 12 hours to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.4MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 75 ℃ and the concentration of 7.0 percent and a calcium nitrate aqueous solution with the temperature of 55 ℃ and the concentration of 1.5 percent under the conditions of a core solution (water) with the concentration of 20mL/min and an air section distance of 15cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane by water at 90 ℃ for 42h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 7
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 5.0% silver nitrate and 4.5% calcium nitrate water solution. Ultrasonically dispersing 6.0g of mesoporous silicon in 600mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 5 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 5.0g of silver-calcium-loaded mesoporous silicon in 1000mL of 3.0% sodium alginate aqueous solution, stirring at normal temperature for 4h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-calcium-loaded mesoporous silicon-coated alginate.
Dissolving/dispersing 60g of polyether sulfone, 2.0g of alginate wrapping silver-calcium-loaded mesoporous silicon and 2.4g K30-polyvinylpyrrolidone in 60mL of dimethylacetamide, and standing at 15 ℃ for 10 hours to obtain a casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.15MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 80 ℃ and the concentration of 6.0 percent and a calcium nitrate aqueous solution with the temperature of 60 ℃ and the concentration of 4.5 percent under the conditions of a core solution (water) with the concentration of 25mL/min and an air section distance of 10cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane by water at the temperature of 80 ℃ for 60 hours, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 8
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 5.0% silver nitrate and 4.5% calcium nitrate water solution. Ultrasonically dispersing 6.0g of mesoporous silicon in 600mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 4 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 3.5g of silver-and calcium-loaded mesoporous silicon in 700mL of 4.0% sodium alginate aqueous solution, stirring at normal temperature for 5h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
50g of polyether sulfone, 0.71g of alginate wrapping silver-calcium-loaded mesoporous silicon and 3.0g K30-polyvinylpyrrolidone are dissolved/dispersed in 25mL of dimethylacetamide, and then are kept stand at 30 ℃ for 12 hours to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.45MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 70 ℃ and the concentration of 8.0 percent and a calcium nitrate aqueous solution with the temperature of 70 ℃ and the concentration of 2.0 percent under the conditions of a core solution (water) with the concentration of 45mL/min and an air section distance of 5cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane in water at 85 ℃ for 42h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Example 9
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 4.5% silver nitrate and 5.0% calcium nitrate water solution. Ultrasonically dispersing 5.0g of mesoporous silicon in 400mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 5 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
Dispersing 4.5g of silver-and calcium-loaded mesoporous silicon in 900mL of 3.5% sodium alginate aqueous solution, stirring at normal temperature for 5h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles under the sieve to obtain the silver-and calcium-loaded mesoporous silicon-coated alginate.
40g of polyether sulfone, 1.0g of alginate wrapping silver-calcium-loaded mesoporous silicon and 2.4g K30-polyvinylpyrrolidone are dissolved/dispersed in 40mL of dimethylacetamide, and then are kept stand for 8h at 25 ℃ to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.2MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 60 ℃ and the concentration of 9.0 percent and a calcium nitrate aqueous solution with the temperature of 65 ℃ and the concentration of 4.0 percent under the conditions of a core solution (water) with the concentration of 35mL/min and an air section distance of 0cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane in water at the temperature of 80 ℃ for 66h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane.
Comparative example 1
Dissolving silver nitrate in deionized water to obtain 4.5% silver nitrate water solution. Ultrasonically dispersing 5.0g of mesoporous silicon in 400mL of silver nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 5 times; and freeze-drying the suspension to obtain the silver-loaded mesoporous silicon.
Dispersing 4.5g of silver-loaded mesoporous silicon in 900mL of 3.5% sodium alginate aqueous solution, stirring at normal temperature for 5h to obtain gel particles, screening by using a 1000-mesh molecular sieve, and collecting particles below the sieve to obtain alginate wrapping the silver-loaded mesoporous silicon.
40g of polyether sulfone, 1.0g of alginate wrapping the silver-loaded mesoporous silicon and 2.4g K30-polyvinylpyrrolidone are dissolved/dispersed in 40mL of dimethylacetamide, and then are kept stand for 8 hours at 25 ℃ to obtain the casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.2MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 60 ℃ and the concentration of 9.0 percent and a calcium nitrate aqueous solution with the temperature of 65 ℃ and the concentration of 4.0 percent under the conditions of a core solution (water) with the concentration of 35mL/min and an air section distance of 0cm for forming. Soaking and cleaning the solid hollow fiber membrane in water at the temperature of 80 ℃ for 66h, and then airing in the air to obtain the mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane wrapping the mesoporous silicon in a pre-crosslinked manner without sodium alginate.
Comparative example 2
40g of polyethersulfone and 2.4g K30-polyvinylpyrrolidone were dissolved/dispersed in 40mL of dimethylacetamide, followed by standing at 25 ℃ for 8 hours to obtain a casting solution.
The casting solution is sprayed out through a spinning nozzle under the drive of 0.2MPa, and sequentially enters a sodium alginate aqueous solution with the temperature of 60 ℃ and the concentration of 9.0 percent and a calcium nitrate aqueous solution with the temperature of 65 ℃ and the concentration of 4.0 percent under the conditions of a core solution (water) with the concentration of 35mL/min and an air section distance of 0cm for forming. And (3) soaking and cleaning the solid hollow fiber membrane in water at the temperature of 80 ℃ for 66h, and then airing in the air to obtain the alginate/polyether sulfone antibacterial hollow fiber membrane.
Comparative example 3
Dissolving silver nitrate and calcium nitrate in deionized water to obtain 4.5% silver nitrate and 5.0% calcium nitrate water solution. Ultrasonically dispersing 5.0g of mesoporous silicon in 400mL of silver nitrate and calcium nitrate aqueous solution under normal pressure, oscillating on a shaking table to obtain suspension, vacuumizing, and repeating for 5 times; and (3) freeze-drying the suspension to obtain the silver-calcium-loaded mesoporous silicon.
40g of polyethersulfone, 1.0g of silver-calcium-loaded mesoporous silicon and 2.4g K30-polyvinylpyrrolidone were dissolved/dispersed in 40mL of dimethylacetamide, followed by standing at 25 ℃ for 8 hours to obtain a casting solution.
The casting solution is driven by 0.2MPa to be sprayed out through a spinning nozzle and enters 65 ℃ aqueous solution for forming under the conditions of 35mL/min of core solution (water) and 0cm of air section distance. And (3) soaking and cleaning the solid hollow fiber membrane by water at the temperature of 80 ℃ for 66h, and then airing in the air to obtain the mesoporous silicon/polyether sulfone antibacterial hollow fiber membrane.
Application testing
The antibacterial hollow fiber membrane prepared by the method is applied to blood purification, and the specific method comprises the following steps:
the antibacterial hollow fiber membranes prepared in examples 1 to 9 and comparative examples 1 to 3 were processed to prepare hollow fiber membrane hemodialyzers, each of which contained about 4200 hollow fiber membranes, the effective length of which was 190mm and the effective area of which was 0.6m2. The blood is sodium citrate anticoagulated pig blood, and urea, creatinine and vitamin B12 are added to make the concentration of urea about 450ppm, creatinine about 28ppm and vitamin B12 about 678 ppm. Three replicates were set up for each example. The inlet flow rate is controlled to be 200mL/min, the medium is filtered by the dialyzer and returns to the medium bottle without any treatment, a circulation system is formed, and sampling is carried out periodically for detection. After the time point, each sample was sampled, prepared and tested using the kit and the concentration and clearance of urea, creatinine and vitamin B12 were calculated. The test results are shown in table 1 below.
TABLE 1 clearance of antibacterial hollow fiber membranes for urea, creatinine, and vitamin B12
The test results showed that the antibacterial hollow fiber membranes prepared in examples 1 to 9 had good clearance of urea, creatinine and vitamin B12. And the cleaning performance of the hollow fiber membranes is better for urea, creatinine and vitamin B12 compared with the hollow fiber membranes of comparative example 1 (the mesoporous silicon is not pre-loaded with calcium), comparative example 2 (the mesoporous silicon does not contain silver and calcium), and comparative example 3 (the mesoporous silicon does not contain alginate).
The hollow fiber membrane with better antibacterial and toxin adsorption functions and hydrophilicity is prepared by the method, and the preparation method is simple to operate. The obtained mesoporous silicon/alginate/polyether sulfone antibacterial hollow fiber membrane has an open nano-micron hierarchical pore structure, is good in hydrophilicity, can release silver ions for antibiosis, can adsorb and remove uremic toxin at the same time, is high in removal rate of urea, creatinine and vitamin B12, and is particularly suitable for blood purification treatment of uremic patients. And the matrix material of the hollow fiber membrane is polyether sulfone and alginate, so that the hollow fiber membrane has biological safety.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention. Various changes and modifications can be made by one skilled in the art, and any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of an antibacterial hollow fiber membrane is characterized by comprising the following steps: the method comprises the following steps:
1) loading silver and calcium ions in the mesoporous silicon: dispersing mesoporous silicon in a solution of silver salt and calcium salt, and drying the obtained suspension to obtain silver-calcium-loaded mesoporous silicon;
2) preparing alginate wrapping silver and calcium-loaded mesoporous silicon: dispersing silver-and calcium-loaded mesoporous silicon in an alginate solution to obtain gel-like particles, and sieving to obtain alginate wrapping the ion-loaded mesoporous silicon;
3) preparing a casting solution: mixing polyether sulfone, alginate wrapping the ion-loaded mesoporous silicon, a pore-forming agent and a solvent, and defoaming to obtain a membrane casting solution;
4) preparing the antibacterial hollow fiber membrane by dry-jet wet spinning: spraying the membrane casting solution through a spinning nozzle, and sequentially entering an alginate solution and a calcium salt solution for forming under the conditions of certain core solution flow rate and air section distance to obtain an antibacterial hollow fiber membrane;
in the step 1), the dosage ratio of the mesoporous silicon to the solution of silver salt and calcium salt is 1 g: (60-100) mL;
in the step 2), the dosage ratio of the silver and calcium-loaded mesoporous silicon to the alginate solution is 1 g: (80-200) mL;
in the step 3), the dosage ratio of the polyether sulfone, the alginate wrapping the ion-loaded mesoporous silicon, the pore-forming agent and the solvent is 1 g:
(0.01～0.05)g：(0.04～0.08)g：(0.5～1.5)mL；
in the step 4), the ejected driving pressure is 0.08MPa to 0.5 MPa; the flow rate of the core liquid is 10mL/min to 50mL/min, and the air section distance is 0cm to 20 cm; the core liquid is water;
the antibacterial hollow fiber membrane is used for blood purification.
2. The method for preparing an antibacterial hollow fiber membrane according to claim 1, characterized in that: in the step 1), the solution of silver salt and calcium salt is an aqueous solution containing silver nitrate and calcium nitrate; wherein, the mass concentration of the silver nitrate is 2.5-5 percent, and the mass concentration of the calcium nitrate is 2.5-5 percent.
3. The method for preparing an antibacterial hollow fiber membrane according to claim 1, characterized in that: in the step 2), the alginate solution is sodium alginate water solution with the mass concentration of 2.5-5%.
4. The method for preparing an antibacterial hollow fiber membrane according to claim 1, characterized in that: in the step 3), the pore-foaming agent is at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol and diethylene glycol; the solvent is at least one of dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylacetamide.
5. The method for preparing an antibacterial hollow fiber membrane according to claim 1, characterized in that: in the step 4), the alginate solution is a sodium alginate aqueous solution with the temperature of 50-80 ℃ and the mass concentration of 5-10%; the calcium salt solution is calcium nitrate water solution with the temperature of 30-70 ℃ and the mass concentration of 1-4.5%.
6. An antibacterial hollow fiber membrane for blood purification, characterized in that: is prepared by the preparation method of any one of claims 1 to 5.
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