CN116376076A - Copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film, preparation and application - Google Patents
Copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film, preparation and application Download PDFInfo
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- CN116376076A CN116376076A CN202310307469.9A CN202310307469A CN116376076A CN 116376076 A CN116376076 A CN 116376076A CN 202310307469 A CN202310307469 A CN 202310307469A CN 116376076 A CN116376076 A CN 116376076A
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- Prior art keywords
- bacterial cellulose
- copper
- silver
- film
- nano
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- 229920002749 Bacterial cellulose Polymers 0.000 title claims abstract description 161
- 239000005016 bacterial cellulose Substances 0.000 title claims abstract description 161
- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 75
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 68
- 239000010949 copper Substances 0.000 title claims abstract description 68
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 49
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 49
- 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 title claims abstract description 47
- 229940072056 alginate Drugs 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 68
- 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 abstract description 48
- 239000000661 sodium alginate Substances 0.000 claims abstract description 48
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 48
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 48
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 37
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 230000002980 postoperative effect Effects 0.000 claims abstract description 3
- 230000008467 tissue growth Effects 0.000 claims abstract description 3
- 230000037314 wound repair Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 41
- 210000004379 membrane Anatomy 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001879 copper Chemical class 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 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 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 210000002747 omentum Anatomy 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 20
- 230000035699 permeability Effects 0.000 abstract description 7
- 229910052709 silver Inorganic materials 0.000 abstract description 7
- 239000004332 silver Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- -1 silver ions Chemical class 0.000 abstract description 5
- 238000009423 ventilation Methods 0.000 abstract description 4
- 210000001124 body fluid Anatomy 0.000 abstract description 3
- 239000010839 body fluid Substances 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000151 deposition Methods 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000265 homogenisation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000005538 encapsulation Methods 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 206010052428 Wound Diseases 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 206010016807 Fluid retention Diseases 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000589220 Acetobacter Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 230000029663 wound healing Effects 0.000 description 2
- KHHAWJABJREPLJ-MBMOQRBOSA-N (3s,4s,5s,6r)-6-(hydroxymethyl)oxane-2,2,3,4,5-pentol Chemical compound OC[C@H]1OC(O)(O)[C@@H](O)[C@@H](O)[C@@H]1O KHHAWJABJREPLJ-MBMOQRBOSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000193996 Streptococcus pyogenes Species 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- SDUJOOJUQMRDAX-UHFFFAOYSA-N ethanol;thiourea Chemical compound CCO.NC(N)=S SDUJOOJUQMRDAX-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 230000002045 lasting effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 239000008104 plant cellulose Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/38—Silver; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
- A61K47/38—Cellulose; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7007—Drug-containing films, membranes or sheets
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
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- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2305/04—Alginic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Bioinformatics & Cheminformatics (AREA)
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- Manufacturing & Machinery (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Materials Engineering (AREA)
- Dermatology (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film, a preparation method and an application thereof, wherein silver nano particles are synthesized on the prepared bacterial cellulose film to obtain the bacterial cellulose/nano silver composite film; drying the bacterial cellulose/nano silver composite film, immersing the dried bacterial cellulose/nano silver composite film into sodium alginate aqueous solution to obtain a sodium alginate-immersed composite film, and performing sodium alginate crosslinking on the composite film to obtain a bacterial cellulose/nano silver/copper alginate composite film; and (3) vulcanizing to obtain a composite film with a copper sulfide layer deposited on the surface, and cleaning and drying to obtain the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film. The composite antibacterial film has good ventilation and oxygen permeability, and realizes free exchange of antibacterial copper and silver ions and electrolyte in body fluid. The composite film has controllable preparation process, high and durable antibacterial effect, and electrothermal and photothermal dual response characteristics, and has wide application prospect in the aspects of tissue growth and postoperative wound repair treatment as a medical dressing.
Description
Technical Field
The invention belongs to the field of medical composite materials, and particularly relates to a copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film with a thermal response characteristic and a preparation method thereof.
Background
The skin is used as a first defense line of an immune system, can protect internal organs of a human body, and is used as a physical and chemical barrier to prevent invasion of pathogens and prevent the human body from being influenced by dehydration. However, the process from breakage to repair of the skin is short for days and long for weeks, and during periods of no skin protection, the wound is extremely susceptible to infection by bacteria. Therefore, the development of wound dressings is an extremely important area of research in order to promote wound healing and reduce scar formation.
In the process of development in the field of medical engineering, natural polymers have received extensive attention from medical biomaterial researchers. Sodium alginate is derived from natural algae and is a linear, unbranched polysaccharide consisting of 1, 4-linked beta-D-mannonic acid (M units) and alpha-L-month Gui Quansuan (G units). The high content of M chain segment of sodium alginate can produce cell factor through human monocyte, and has good effect on chronic wound healing. With its excellent properties of good biocompatibility, degradability, and structural stability, it has been proven to be a suitable candidate for the manufacture of biomaterials and nanocomposites. Sodium alginate, in the presence of divalent cations, is capable of forming a gel by ionic interactions, thus rendering it potentially of great potential in the biomedical field, but the lack of antimicrobial properties and poor mechanical properties have limited its application in the field of high performance dressings. Researchers increase the mechanical properties of sodium alginate by adding polymers such as polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like, however, the use of synthetic polymer materials can significantly reduce the histocompatibility of sodium alginate.
Bacterial cellulose is a natural polymer material biosynthesized by acetobacter, has the characteristics of high porosity and water absorption, high mechanical strength, easy molding, good biocompatibility and the like, and is considered as an excellent wound dressing substrate. The primary structure of bacterial cellulose is similar to that of plant cellulose, with unbranched polymers of beta-1, 4 chain pyranose. However, bacterial cellulose itself does not have antibacterial activity to prevent wound infection. For this reason, many researchers add functional fillers (such as magnesium oxide, zinc oxide, etc.) to bacterial cellulose to enhance the mechanical properties of the bacterial cellulose and simultaneously endow the composite material with antibacterial property, but the adsorption efficiency and stability of the antibacterial agents in the material are not high, the antibacterial duration is short and the antibacterial agents are easy to deviate, so that the material loses antibacterial property. The bacterial cellulose has a nano-porous three-dimensional network structure, has a high specific surface area, has a large number of hydroxyl bonds and ether bonds on the surface, and is a natural template matrix for in-situ deposition of nano particles. At the same time, bacterial cellulose can also be considered as the ideal hydrophilic matrix into which the nanoparticles are incorporated. How to effectively combine the antibacterial nano particles with the bacterial cellulose and realize the controllable release of the antibacterial particles at the same time is an important obstacle for developing bacterial cellulose antibacterial dressing. From this point of view, the preparation of biomedical dressings with non-toxicity, good antibacterial activity, good mechanical properties and high water retention on the basis of the introduction of antibacterial particles remains a challenging problem in scientific research and production practice.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with the thermal response characteristic and the preparation method thereof. Based on the 3D nano network of bacterial cellulose, the composite antibacterial film realizes free exchange of antibacterial copper and silver ions and electrolyte in body fluid while presenting good air permeability and oxygen permeability.
The invention is realized by the following technical scheme.
In one aspect of the invention, a preparation method of a copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film is provided, which comprises the following steps:
s1, performing alkaline boiling and purification on a bacterial cellulose omentum, mechanically crushing to obtain bacterial cellulose homogenate, and performing vacuum suction filtration to obtain a uniform bacterial cellulose film;
s2, soaking the bacterial cellulose membrane in silver ion solution, performing hydrothermal reaction, and synthesizing silver nano particles on the bacterial cellulose membrane to obtain a bacterial cellulose/nano silver composite film;
s3, drying the bacterial cellulose/nano silver composite film, immersing the dried bacterial cellulose/nano silver composite film in sodium alginate aqueous solution to obtain a composite film immersed in sodium alginate, and placing the composite film immersed in sodium alginate into copper salt solution coagulation bath to crosslink the sodium alginate; washing with deionized water to obtain a bacterial cellulose/nano silver/copper alginate composite film;
s4, immersing the bacterial cellulose/nano silver/copper alginate composite film into a sulfur source for vulcanization treatment to obtain a composite film with a copper sulfide layer deposited on the surface, cleaning and drying to obtain the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film.
Preferably, the silver ion solution includes a silver salt solution and a silver ammonia solution;
the silver salt in the silver salt solution is one or more of silver nitrate, silver chlorate and silver perchlorate;
the silver ammonia solution is AgNO 3 The solution and dilute ammonia water are prepared.
Preferably, the concentration of the silver ion solution is 0.1-1mol/L.
Preferably, the bacterial cellulose membrane is soaked in the silver ion solution for 10-30min at 120-160 ℃ in hydrothermal reaction temperature.
Preferably, the mass concentration of the sodium alginate solution is 0.5-2%; the bacterial cellulose/nano silver composite film is immersed in the sodium alginate aqueous solution for 3-5min.
Preferably, the copper salt is one or more of copper sulfate, copper nitrate, copper chloride and copper acetate; the mass concentration of copper salt in the copper salt coagulation bath is 1-5%; the coagulating bath temperature of the copper salt solution is 10-30 ℃ and the time is 10-30min.
Preferably, the sulfur source comprises one or more of thiourea, ammonium sulfide, sodium sulfide, carbon disulfide and elemental sulfur; the concentration of the sulfur source in the sulfur source solution is 0.1-1mol/L.
Preferably, the solvent of the sulfur source solution is one or a combination of more of water, ethanol and dimethyl sulfoxide.
Preferably, the vulcanization treatment is carried out for a reaction time of 30-120s and a vulcanization temperature of 20-70 ℃.
In another aspect of the invention, a copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics is provided, the composite antibacterial film has a sandwich structure, an inner layer is a bacterial cellulose porous film with hydrothermally grown nano silver particles, an intermediate layer is copper alginate crosslinked by copper ions, and an outer layer is a copper sulfide encapsulation layer which is vulcanized and deposited by depending on a copper alginate layer.
Compared with the prior art, the invention has the following beneficial effects:
the polymer matrix of the composite antibacterial film prepared by the invention is purely natural biomass high molecular sodium alginate and bacterial cellulose, the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics has a sandwich structure, the inner layer is a bacterial cellulose porous film for in-situ hydrothermal growth of nano silver, the middle layer is copper ion crosslinked sodium alginate, the outer layer is a copper sulfide functional layer formed by depending on copper alginate sulfide deposition, the prepared copper alginate encapsulated bacterial cellulose composite antibacterial film not only maintains the biocompatibility, degradability and moisture absorption and water retention of an alginic acid material and bacterial cellulose, but also endows the material with good photo-thermal and electrothermal response capability due to the introduction of the copper sulfide layer while ensuring the excellent antibacterial characteristics of the composite material.
The composite antibacterial film has good ventilation and oxygen permeability, and realizes free exchange of antibacterial copper and silver ions and electrolyte in body fluid. Through the design of the copper alginate encapsulated bacterial cellulose/nano silver deposited nano copper sulfide composite structure, the ventilation and oxygen permeability of the bacterial cellulose and the moisture absorption and water retention and ion exchange capacity of the sodium alginate can be effectively exerted. In the internal bacterial cellulose/nano silver composite membrane, nano silver can be used as antibacterial particles to transport silver ions to the surface of a dressing system through a copper alginate pipeline by osmotic pressure, and further copper alginate releases silver ions to a wound surface by ion exchange to perform antibacterial. The photothermal agent copper sulfide is used for stimulating the surface of the composite antibacterial film through illumination or electrification, so that the photothermal auxiliary antibacterial effect can be realized, the photothermal and electrothermal conversion of the surface of the film can be effectively realized, the transmission and release rate of the internal nano silver can be promoted through the thermal effect, and the intelligent controllability of the antibacterial medical film in the treatment process can be realized.
According to the preparation method of bacterial cellulose homogenate, the hydrothermal synthesis preparation method of nano silver is simple and feasible, the copper alginate material and the bacterial cellulose composite film form an interpenetrating structure, a copper sulfide layer is deposited for uniform and efficient encapsulation, and the nano porous structure of the bacterial cellulose is not damaged; meanwhile, the moisture absorption, air permeability, skin affinity and antibacterial property of the film are ensured, the preparation process is environment-friendly, the cost is low, and the film can be industrially produced. The copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film with the thermal response characteristic has wide application prospect in the aspect of tissue growth and postoperative wound repair treatment.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate and do not limit the invention, and together with the description serve to explain the principle of the invention:
FIGS. 1 (a) and (b) show the photo-thermal effects of copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response in the present invention, respectively, and FIG. 1 (a) shows the surface temperature-time curve of the composite film under 250W near infrared light; FIG. 1 (b) is an optical and infrared image of the surface of a composite film at 250W near infrared light for various times.
FIGS. 2 (a) and (b) respectively show the electrothermal effect of the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response in the invention, and FIG. 2 (a) is a graph of temperature versus time of the composite film under different voltages; fig. 2 (b) is an infrared thermal image of an electrically heated test sample and an associated composite film.
Fig. 3 shows the antibacterial effect of the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response in the present invention, wherein 1 is the composite film with thermal response, 2 is the bacterial cellulose/silver film, 3 is the bacterial cellulose/silver/copper alginate film, and 4 is the bacterial cellulose film.
Detailed Description
The present invention will now be described in detail with reference to the drawings and the specific embodiments thereof, wherein the exemplary embodiments and descriptions of the present invention are provided for illustration of the invention and are not intended to be limiting.
The invention provides a preparation method of a copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics, which comprises the following steps of;
step 1, preparing a bacterial cellulose film:
and (3) putting the bacterial cellulose omentum synthesized by the acetobacter into a sodium hydroxide solution for alkaline boiling and purification, washing to be neutral, and then further mechanically crushing by using a high-pressure homogenizer to obtain bacterial cellulose homogenate. Then, a uniform bacterial cellulose film is obtained by vacuum filtration.
taking a bacterial cellulose membrane as a template, soaking the bacterial cellulose membrane in silver ion solution with the concentration of 0.1-1mol/L, placing the silver ion solution into an autoclave for hydrothermal reaction at the temperature of 120-160 ℃ for 10-30min until the off-white bacterial cellulose membrane turns brown, and proving that silver nano particles are successfully synthesized.
Wherein the silver ion solution comprises silver salt solution or silver ammonia solution; the silver salt in the silver salt solution is one or more of silver nitrate, silver chlorate and silver perchlorate; the silver ammonia solution is AgNO 3 The solution and dilute ammonia water are prepared;
step 3, preparing a copper alginate encapsulation structure:
drying the bacterial cellulose/nano silver composite film prepared by a hydrothermal method in an oven at 40-80 ℃ to constant weight, and then immersing the bacterial cellulose/nano silver composite film in sodium alginate aqueous solution with mass concentration of 0.5-2% for 3-5min; and further placing the composite film impregnated with sodium alginate into a copper salt solution coagulation bath with the mass concentration of 1-5%, wherein the temperature is 10-30 ℃ and the time is 10-30min, so as to realize the crosslinking of the sodium alginate. After the bacterial cellulose is washed by deionized water, the copper ion crosslinked sodium alginate molecular chain enters network gaps of the bacterial cellulose, and the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial medical dressing is obtained.
Wherein the copper salt is one or more of copper sulfate, copper nitrate, copper chloride and copper acetate.
And 4, depositing a thermally-responsive copper sulfide layer:
depending on copper salt in the copper ion cross-linked sodium alginate layer, immersing the bacterial cellulose/nano silver/copper alginate composite film into a sulfur source with the concentration of 0.1-1mol/L, carrying out vulcanization reaction at the temperature of 20-70 ℃ for 30-120s, depositing in situ on the surface of the composite film to form a layer of copper sulfide, taking out, washing with deionized water, and drying to obtain the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics.
Wherein the sulfur source comprises one or more of thiourea, ammonium sulfide, sodium sulfide, carbon disulfide and elemental sulfur. The sulfur source solvent is one or a combination of more of water, ethanol and carbon disulfide.
The prepared composite antibacterial film has a sandwich structure, wherein the inner layer is a bacterial cellulose porous film for in-situ hydrothermal growth of nano silver particles, the middle layer is copper ion crosslinked sodium alginate, and the outer layer is a copper sulfide functional layer formed by copper alginate sulfide deposition.
The invention will be described in further detail by means of specific examples.
Example 1
1) Preparation of bacterial cellulose film:
putting 10g of gel-state bacterial cellulose into a sodium hydroxide solution with the pH of 13, performing alkaline boiling for 4 hours, taking out, washing with deionized water to be neutral, performing homogenization treatment in a high-pressure homogenizer for 20 minutes, setting the homogenization pressure to be 80MPa, obtaining bacterial cellulose homogenate, preparing a bacterial cellulose film through vacuum suction filtration, and drying for later use.
2) Synthesizing nano silver by an in-situ hydrothermal method:
taking a bacterial cellulose membrane as a template, soaking the bacterial cellulose membrane in 0.5mol/L silver nitrate solution, and placing the bacterial cellulose membrane in an autoclave with the reaction condition of 0.1MPa and 120 ℃ for 20min to carry out hydrothermal reaction until the off-white bacterial cellulose membrane turns brown, thereby proving that silver nano particles are successfully synthesized.
3) Preparation of copper alginate encapsulation structure:
and (3) drying the bacterial cellulose/nano silver composite film prepared by a hydrothermal method in a baking oven at 60 ℃ until the weight is constant, then immersing the bacterial cellulose/nano silver composite film in sodium alginate aqueous solution with the mass concentration of 1% for 3min, and further immersing the composite film immersed in sodium alginate in copper sulfate solution with the mass concentration of 3% at 10 ℃ for 30min to realize crosslinking of the sodium alginate. After the bacterial cellulose is washed by deionized water, the copper ion crosslinked sodium alginate molecular chain enters network gaps of the bacterial cellulose, and the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial medical dressing is obtained.
4) Deposition of a thermally responsive copper sulfide layer:
depending on copper salt in the copper sulfate solution cross-linking sodium alginate layer, immersing the bacterial cellulose/nano silver/copper alginate composite film into ammonium sulfide aqueous solution with the concentration of sulfur element of 0.5mol/L, vulcanizing at 70 ℃ for 30s, depositing a layer of copper sulfide on the surface of the composite film in situ, taking out, washing with deionized water, and drying to obtain the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics.
Example 2
1) Preparation of bacterial cellulose film:
putting 10g of gel-state bacterial cellulose into a sodium hydroxide solution with the pH of 13, performing alkaline boiling for 4 hours, taking out, washing with deionized water to be neutral, performing homogenization treatment in a high-pressure homogenizer for 20 minutes, setting the homogenization pressure to be 80MPa, obtaining bacterial cellulose homogenate, preparing a bacterial cellulose film through vacuum suction filtration, and drying for later use.
2) Synthesizing nano silver by an in-situ hydrothermal method:
taking a bacterial cellulose membrane as a template, soaking the bacterial cellulose membrane in 0.1mol/L silver ammonia solution, and placing the bacterial cellulose membrane in an autoclave with the reaction condition of 0.1MPa and 140 ℃ for 30min to carry out hydrothermal reaction until the off-white bacterial cellulose membrane turns brown, thus proving that silver nano particles are successfully synthesized.
3) Preparation of copper alginate encapsulation structure:
and (3) drying the bacterial cellulose/nano silver composite film prepared by a hydrothermal method in an oven at 80 ℃ until the weight is constant, immersing the bacterial cellulose/nano silver composite film in a sodium alginate aqueous solution with the mass concentration of 2% for 4min, and immersing the sodium alginate-immersed composite film in a copper nitrate solution with the mass concentration of 1% at 15 ℃ for 20min to realize crosslinking of the sodium alginate. After the bacterial cellulose is washed by deionized water, the copper ion crosslinked sodium alginate molecular chain enters network gaps of the bacterial cellulose, and the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial medical dressing is obtained.
4) Deposition of a thermally responsive copper sulfide layer:
copper salt in the sodium alginate layer is crosslinked by means of copper sulfate solution, the bacterial cellulose/nano silver/copper alginate composite film is immersed into carbon disulfide solution with the concentration of sulfur element of 0.1mol/L, the copper sulfide layer is vulcanized at 60 ℃ for 60 seconds, a layer of copper sulfide is deposited on the surface of the composite film in situ, deionized water is taken out, washed and dried, and the bacterial cellulose/nano silver composite antibacterial film encapsulated by the copper alginate with thermal response characteristics is obtained.
Example 3
1) Preparation of bacterial cellulose film:
putting 10g of gel-state bacterial cellulose into a sodium hydroxide solution with the pH of 13, performing alkaline boiling for 4 hours, taking out, washing with deionized water to be neutral, performing homogenization treatment in a high-pressure homogenizer for 20 minutes, setting the homogenization pressure to be 60MPa, obtaining bacterial cellulose homogenate, preparing a bacterial cellulose film through vacuum suction filtration, and drying for later use.
2) Synthesizing nano silver by a hydrothermal method:
taking a bacterial cellulose membrane as a template, soaking the bacterial cellulose membrane in 0.3mol/L silver chlorate solution, and placing the bacterial cellulose membrane in an autoclave with the reaction condition of 0.1MPa and 160 ℃ for 10min to carry out hydrothermal reaction until the off-white bacterial cellulose membrane turns brown, thus proving that silver nano particles are successfully synthesized.
3) Preparation of copper alginate encapsulation structure:
and (3) drying the bacterial cellulose/nano silver composite film prepared by a hydrothermal method in a baking oven at 60 ℃ until the weight is constant, immersing the bacterial cellulose/nano silver composite film in sodium alginate aqueous solution with the mass concentration of 1.0% for 5min, and immersing the composite film immersed in sodium alginate in copper chloride solution with the mass concentration of 5% at 25 ℃ for 10min to realize crosslinking of the sodium alginate. After the bacterial cellulose is washed by deionized water, the copper ion crosslinked sodium alginate molecular chain enters network gaps of the bacterial cellulose, and the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial medical dressing is obtained.
4) Deposition of a thermally responsive copper sulfide layer:
depending on copper salt in a copper sulfate solution cross-linking sodium alginate layer, immersing a bacterial cellulose/nano silver/copper alginate composite film into elemental sulfur and carbon disulfide solution with the concentration of sulfur element of 0.3mol/L, vulcanizing at 20 ℃ for 90 seconds, depositing a layer of copper sulfide on the surface of the composite film in situ, taking out, washing with deionized water, and drying to obtain the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics.
Example 4
1) Preparation of bacterial cellulose film:
putting 10g of gel-state bacterial cellulose into a sodium hydroxide solution with the pH of 13, performing alkaline boiling for 4 hours, taking out, washing with deionized water to be neutral, performing homogenization treatment in a high-pressure homogenizer for 20 minutes, setting the homogenization pressure to be 60MPa, obtaining bacterial cellulose homogenate, preparing a bacterial cellulose film through vacuum suction filtration, and drying for later use.
2) Synthesizing nano silver by an in-situ hydrothermal method:
taking a bacterial cellulose membrane as a template, soaking the bacterial cellulose membrane in 1mol/L silver perchlorate solution, and placing the bacterial cellulose membrane in an autoclave with the reaction condition of 0.1MPa and 160 ℃ for 10min to carry out hydrothermal reaction until the off-white bacterial cellulose membrane turns brown, so that successful synthesis of silver nanoparticles is proved.
3) Preparation of copper alginate encapsulation structure:
and (3) drying the bacterial cellulose/nano silver composite film prepared by a hydrothermal method in a baking oven at 40 ℃ until the weight is constant, immersing the bacterial cellulose/nano silver composite film in a sodium alginate aqueous solution with the mass concentration of 2% for waiting for 5min, and further immersing the composite film immersed in the sodium alginate in a copper acetate solution with the mass concentration of 5% at 30 ℃ for 10min to realize crosslinking of the sodium alginate. After the bacterial cellulose is washed by deionized water, the copper ion crosslinked sodium alginate molecular chain enters network gaps of the bacterial cellulose, and the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial medical dressing is obtained.
4) Deposition of a thermally responsive copper sulfide layer:
and (3) depending on copper salt in the copper sulfate solution cross-linking sodium alginate layer, immersing the bacterial cellulose/nano silver/copper alginate composite film into thiourea ethanol solution with the concentration of sulfur element of 1mol/L, vulcanizing for 120s at 20 ℃, depositing a layer of copper sulfide on the surface of the composite film in situ, taking out, washing with deionized water, and drying to obtain the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film with thermal response characteristics.
Comparative example 1
Adding nano silver particles into bacterial cellulose homogenate, preparing a bacterial cellulose/nano silver composite film through vacuum suction filtration, soaking in 2% sodium alginate aqueous solution for 5min after drying, taking out and crosslinking with 1% copper sulfate solution for 10min, and obtaining the copper alginate-encapsulated bacterial cellulose/nano silver composite antibacterial film.
The antibacterial medical dressings obtained in the above examples 1 to 4 and comparative examples were subjected to Co-60 gamma radiation sterilization treatment, and then subjected to relevant performance tests, the specific test contents and the material properties are shown in the following table:
the copper alginate encapsulated bacterial cellulose composite antibacterial film has good thermal response and thermal stability to light and electricity, and the highest temperature can reach about 70 ℃ as proved by the figures 1 (a) and (b) and the figures 2 (a) and (b). As can be seen from fig. 3, the copper alginate-encapsulated bacterial cellulose composite antibacterial film has excellent inhibition effect on escherichia coli and staphylococcus aureus, and has more remarkable antibacterial effect under the photothermal auxiliary antibacterial effect of CuS. By combining the above examples, table 1 and fig. 1 (a), (b), fig. 2 (a), (b) and fig. 3, it can be seen that the copper alginate-encapsulated bacterial cellulose composite antibacterial film prepared by the invention not only maintains the biocompatibility, degradability and moisture absorption and retention of the alginic acid material and bacterial cellulose, but also ensures the excellent antibacterial property of the composite material, and simultaneously gives the material good photo-thermal and electrothermal response capability, good ventilation and oxygen permeability, and high-efficiency and lasting antibacterial property. The wet tensile strength is not less than 3.1MPa, the dry tensile strength is not less than 17MPa, the water absorption is not less than 300%, the effect of inhibiting staphylococcus aureus in the composite antibacterial film is not less than 98.9%, the effect of inhibiting escherichia coli is not less than 96.5%, the effect of inhibiting streptococcus pyogenes is not less than 96.2%, and the silver ion release time is up to 7 days; and simultaneously has dual response characteristics of electric heating and photo-thermal. The composite antibacterial film prepared by the method is a polymer composite material with good processing performance.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (10)
1. The preparation method of the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film is characterized by comprising the following steps of:
(a) Performing alkaline boiling purification on a bacterial cellulose omentum, mechanically crushing to obtain bacterial cellulose homogenate, and performing vacuum suction filtration to obtain a uniform bacterial cellulose film;
(b) Soaking a bacterial cellulose membrane in a silver ion solution, performing a hydrothermal reaction, and synthesizing silver nano particles on the bacterial cellulose membrane to obtain a bacterial cellulose/nano silver composite film;
(c) Drying the bacterial cellulose/nano silver composite film, immersing the dried bacterial cellulose/nano silver composite film into sodium alginate aqueous solution to obtain a composite film immersed in sodium alginate, and placing the composite film immersed in sodium alginate into copper salt solution coagulation bath to carry out sodium alginate crosslinking; washing with deionized water to obtain a bacterial cellulose/nano silver/copper alginate composite film;
(d) Immersing the bacterial cellulose/nano silver/copper alginate composite film into a sulfur source for vulcanization treatment to obtain a composite film with a copper sulfide layer deposited on the surface, cleaning and drying to obtain the copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film.
2. The method for preparing the copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film according to claim 1, wherein the silver ion solution comprises a silver salt solution or a silver ammonia solution;
the silver salt in the silver salt solution is one or more of silver nitrate, silver chlorate and silver perchlorate;
the silver ammonia solution is AgNO 3 The solution is prepared with dilute ammonia water;
the concentration of the silver ion solution is 0.1-1mol/L.
3. The copper alginate encapsulated bacterial cellulose/nano silver composite antibacterial film and the preparation method thereof according to claim 1, wherein the bacterial cellulose film is soaked in silver ion solution and has a hydrothermal reaction temperature of 120-160 ℃ for 10-30min.
4. The copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film and the preparation method thereof according to claim 1, wherein the mass concentration of the sodium alginate solution is 0.5-2%; the bacterial cellulose/nano silver composite film is immersed in the sodium alginate aqueous solution for 3-5min.
5. The copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film and the preparation method thereof according to claim 1, wherein the copper salt is one or more of copper sulfate, copper nitrate, copper chloride and copper acetate; the mass concentration of copper salt in the copper salt coagulation bath is 1-5%; the coagulating bath temperature of the copper salt solution is 10-30 ℃ and the time is 10-30min.
6. The copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film and the preparation method thereof according to claim 1, wherein the sulfur source comprises one or more of thiourea, ammonium sulfide, sodium sulfide, carbon disulfide and elemental sulfur; the concentration of the sulfur source in the sulfur source solution is 0.1-1mol/L.
7. The copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film and the preparation method thereof according to claim 1, wherein the solvent of the sulfur source solution is one or a combination of more of water, ethanol and dimethyl sulfoxide.
8. The copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film and the preparation method thereof according to claim 1, wherein the vulcanization treatment is carried out for 30-120s at a vulcanization temperature of 20-70 ℃.
9. A copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film prepared by the method of any one of claims 1-8.
10. Use of copper alginate-encapsulated bacterial cellulose/nano-silver composite antibacterial film prepared by the method of any one of claims 1-8 for tissue growth and postoperative wound repair treatment.
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