CN116584501A - Nanocellulose/copper sulfide composite material with sterilization performance and preparation method and application thereof - Google Patents
Nanocellulose/copper sulfide composite material with sterilization performance and preparation method and application thereof Download PDFInfo
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- CN116584501A CN116584501A CN202310441317.8A CN202310441317A CN116584501A CN 116584501 A CN116584501 A CN 116584501A CN 202310441317 A CN202310441317 A CN 202310441317A CN 116584501 A CN116584501 A CN 116584501A
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 21
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 22
- 150000001879 copper Chemical class 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000004806 packaging method and process Methods 0.000 claims abstract description 3
- 238000005260 corrosion Methods 0.000 claims abstract 2
- 230000007797 corrosion Effects 0.000 claims abstract 2
- 239000010949 copper Substances 0.000 claims description 46
- 229920002678 cellulose Polymers 0.000 claims description 36
- 239000001913 cellulose Substances 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 235000010980 cellulose Nutrition 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 241000894006 Bacteria Species 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 18
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 18
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 7
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 7
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 7
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 7
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- 239000002077 nanosphere Substances 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CGDZIZIRXNUVKL-UHFFFAOYSA-L dicopper nitrate sulfate Chemical compound [Cu+2].[Cu+2].[O-][N+]([O-])=O.[O-]S([O-])(=O)=O CGDZIZIRXNUVKL-UHFFFAOYSA-L 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000003756 stirring Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000006228 supernatant Substances 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- -1 Copper (I) Sulfides Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 210000000170 cell membrane Anatomy 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000003642 reactive oxygen metabolite Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 230000007018 DNA scission Effects 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001085 differential centrifugation Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- 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
- A01N59/20—Copper
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a nano cellulose/copper sulfide composite material with sterilization performance, and a preparation method and application thereof. The preparation method comprises the following steps: the nano cellulose and copper salt are mixed in an organic solvent to obtain a precursor solution, and then a sulfur source is added to prepare the nano cellulose/copper sulfide composite material by a sol-gel method. The composite material prepared by the invention combines the advantages of the nanocellulose and the copper sulfide, realizes the synergistic sterilization effect, and has good dispersion stability. The composite material prepared by the invention can be widely applied to the fields of corrosion resistance, mildew resistance, antibacterial biological films, food packaging, air filtration sterilization and the like.
Description
Technical Field
The invention relates to the technical field of organic/inorganic composite nano materials, in particular to a nano cellulose/copper sulfide composite material with sterilization performance, and a preparation method and application thereof.
Background
The inorganic antibacterial agent has the advantages of broad spectrum, durability, heat resistance, no bacterial drug resistance and the like due to the antibacterial effect, is a relatively popular type of antibacterial agent for research, is hopeful to solve the drug resistance generated by antibiotics, and is widely used in various sterilization fields (Ye L., cao Z., liu X., et al noble metal-based nanomaterials as antib acterial agents [ J ]. Journal of Alloys and Compounds,2022, 904:164091). However, the toxicity of inorganic bactericides and instability due to nanosize effects greatly limit the application and bactericidal effects of inorganic nano-antibacterial materials. The research shows that the inorganic antibacterial agent is compounded on the organic polymer material, so that the toxicity can be well reduced, the dispersibility of the inorganic nano material can be improved, the nano material can be kept stable in nano dimension for a long time, and finally the aim of improving the antibacterial effect is achieved. Compared with synthetic polymers, the natural polymers have the advantages of good biocompatibility, low cost and the like, and especially, the cellulose is the natural polymer material with the most abundant yield, and has great potential in the aspect of nano material carriers.
Copper-sulfur compound Cu 2-x S (wherein x has a value in the range of 0 to 1) is formed by covalent bonds rather than ionic bonds, and its structure and atomic ratio vary with the oxidation state of copper, often Cu 2 S，Cu 9 S 5 ，Cu 8 S 4 And CuS, etc. Cu (Cu) 2-x S is an excellent photoelectric material which is widely used as an electrode material and a sensor material; the catalyst can also be used as an adsorbent and a catalyst to adsorb various heavy metal ions to catalyze and degrade organic compounds so as to relieve environmental pollution; there has also been a great deal of research in recent years for biomedical applications, including as lightThe stimulating and chemocatalytic antitumor agent, contrast agent is used for medical imaging, and can be used as near infrared response bactericide for relieving symptoms such as diabetes (Zhao Y., pan H., lou Y., et al Plasmonic Cu2-xS nanocryss: opt ical and Structural Properties of Copper-Decipient Copper (I) Sulfides [ J ]].Journal of the American Chemical Society,2009,131(12):4253-4261)。Cu 2-x S itself has a bactericidal effect (Han H., yang J., li X., et al, milling light on transition metal sulfides: new choices as hig hly efficient antibacterial agents [ J ]]Nano Res,2021,14 (8): 2512-2534), especially copper-sulfur compounds containing monovalent copper, e.g. Cu 2 S and Cu 9 S 5 Has a stronger bactericidal effect than CuS of all bivalent copper (Sunada K., minoshima M., hashi moto K.Highly efficient antiviral and antibacterial activities of soli d-state cuprous compounds [ J)]J Hazard Mater,2012,235-236:265-270). At the same time, nano-sized Cu 2-x S has outstanding antibacterial effect due to large specific surface area and nano-size effect, in order to prevent nano Cu 2-x The aggregation of S realizes long-term antibacterial effect, and a carrier or a stabilizer is needed to prevent nano Cu 2-x Aggregation of S (Sun S., li P., liang S., et al, differential coupler sulfate (Cu) 2-x S)micro-/nanostructures:a co mprehensive review on synthesis,modifications and applications[J].Nanoscale,2017,9(32):11357-11404)。
Researchers have used a simple one-step hydrothermal process to prepare CuS nanoparticles on or in porous cellulose fibers that are well dispersed and stable, providing rich CuS adsorption sites for mercury ions (Guo J., tian h., he J. Integration of CuS nanoparticles and cellulose fibers towards fast, selective and ef ficient capture and separation of mercury ions J., chemical Engineer ing Journal,2021, 408:127336). The synthesis of CuS nanorods by a hydrothermal method using Cellulose Acetate (CA) as a template was also studied, and it was found that the CuS structure morphology synthesized without experimental CA as a template disappeared and was prone to agglomeration (Manikann T., padmalaaya G., mahalakshm S., et al, facility hydro thermal bio-synthesis of cellulos e acetate templated CuS nanorods like fibres: anti bacterial, cytotoxic ity effects and DNA cleavage properties against A549 lung cancer cells [ J ]. IET Nanobiotechnology,2020,14 (1): 47-52). However, the hydrothermal method has a longer reaction period and requires a solvent under certain conditions, and the cellulose used is not a nanomaterial, so that the final product after loading is not nano-sized, and therefore, a new method for preparing the nanocellulose/copper sulfide nanocomposite is necessary to be developed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a nano cellulose/copper sulfide composite material with sterilization performance, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the preparation of the nanocellulose/copper sulfide composite material with sterilization performance comprises the following steps:
(1) Acid hydrolyzing the cellulose raw material for different times, centrifuging, dialyzing and vacuum drying to obtain nanocellulose with different morphologies;
(2) Then uniformly mixing the obtained nanocellulose and copper salt in an organic solvent to obtain a precursor dispersion liquid;
(3) And finally, slowly dropwise adding a sulfur source solution under the heating condition, and reacting by a sol-gel method to obtain the nano cellulose/copper sulfide composite material.
Preferably, in step (1), the cellulose raw material is a commercial microcrystalline cellulose product, bagasse; sulfuric acid or hydrochloric acid is used for acid hydrolysis, and the acid hydrolysis time is 1-5 hours; the nanocellulose with different morphologies is Cellulose Nanofiber (CNF), cellulose Nanocrystal (CNC) or Cellulose Nanosphere (CNS).
Preferably, the aspect ratio of the nanocellulose prepared in the step (1) with different morphologies is 2.4-40.8, and the transverse diameter is 5-55nm.
Preferably, the copper salt in the step (2) is more than one of copper sulfate, copper nitrate, copper chloride or copper acetate monohydrate; the organic solvent is more than one of glycol, diglycol, glycerol or glycerin; cu in the nanocellulose and copper salt 2+ Quality of (2)The ratio is 1:0.32-1:1.28.
Preferably, the sulfur source in the step (3) is more than one of thiourea, thioacetamide, sodium sulfide or sodium thiosulfate; the molar ratio of the sulfur source to the copper salt is 1:1-1:2.
Preferably, the heating condition in the step (3) is 160-180 ℃ and the reaction time is 1-5 hours.
Preferably, the CuS nanoparticle on the nanocellulose surface in the nanocellulose/copper sulfide composite material in the step (3) is Cu 2-x S (x is between 0 and 1) and the size is 8-100 nm.
Preferably, the nanocellulose/copper sulfide composite material of step (3) is Cu 2-x S (x is between 0 and 1) is obtained by in-situ growth outside nanocellulose.
The invention provides a nano cellulose/copper sulfide composite material with sterilization performance, which is prepared by any one of the preparation methods.
Preferably, nanocellulose and Cu in the nanocellulose/copper sulfide composite material 2-x The synergistic effect of S (x is between 0 and 1) can interact with bacteria to physically sterilize, and active oxygen is generated in the slightly acidic environment in the bacteria to promote bacterial death.
The invention also provides application of the nanocellulose/copper sulfide composite material with sterilization performance in the fields of corrosion prevention, mildew prevention, antibacterial biofilm resistance, food packaging and air filtration sterilization.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) Nanocellulose and Cu 2-x S (x is between 0 and 1) has good dimensional stability after being compounded;
(2) The nano cellulose/copper sulfide composite material with stable size has the function of easily generating interaction with the surface of bacteria to damage cell membranes, so that the bacteria die;
(3) Cu on nanocellulose/copper sulfide composite material aggregated on bacterial surface 2-x S (x is between 0 and 1) may destroy bacteria by generating reactive oxygen species using the slightly acidic environment of the bacteria.
Drawings
FIG. 1 is a diagram showing the synthesis of nanocellulose/copper sulfide composites of different morphologies and the mechanism by which nanocellulose/copper sulfide composites kill bacteria by generating reactive oxygen species and copper ions to disrupt cell membranes.
FIG. 2 is an infrared spectrum of nanocellulose and nanocellulose/copper sulfide composite in examples 1-3.
FIG. 3 is an X-ray diffraction pattern of the nanocellulose/copper sulfide composite material obtained in examples 1-3.
FIG. 4 is a graph of the antimicrobial effect of examples 1-3 and comparative materials, where I is a blank, II-V is CuS, CNF/CuS, CNC/CuS and CNS/CuS at a concentration of 0.15mg/mL, and VI-IX is CuS, CNF/CuS, CNC/CuS and CNS/CuS at a concentration of 0.2 mg/mL.
FIG. 5 is a scanning electron microscope image of nanocomposite coated bacteria in an antimicrobial experiment.
Detailed Description
The aim of the invention is achieved by the following technical scheme.
The preparation of the nano cellulose/copper sulfide composite material with sterilization performance comprises the steps of dispersing nano cellulose and copper salt in an organic solvent, heating to obtain a precursor solution, and then adding a sulfur source to prepare the nano cellulose/copper sulfide composite material by a sol-gel method. The method specifically comprises the following steps:
(1) Adding cellulose raw material into deionized water, dispersing for 0.5 hours at room temperature by ultrasonic, slowly dripping concentrated sulfuric acid or concentrated hydrochloric acid into the dispersion liquid under stirring to ensure that the volume concentration of final acid is 64%, and carrying out acid hydrolysis for 1-5 hours at 45 ℃, wherein an acid hydrolysis sample is subjected to simultaneous stirring and ultrasonic reaction. And finally adding five times of deionized water to terminate the reaction, centrifugally washing four times, collecting sediment in the first two times, centrifugally washing in the last two times to collect the supernatant, and collecting the acid hydrolyzed sample through differential centrifugation. Dialyzing the supernatant to neutrality, and freeze-drying to obtain three nanocellulose (CNF, CNC and CNS) with different morphologies and length-diameter ratios.
(2) Weighing copper salt with certain amount, stirring at room temperature, dissolving in organic solvent (blue-green), and mixing with nanocellulose and copperCu in salt 2+ Weighing a certain amount of nano cellulose according to the mass ratio of 1:0.32-1:1.28, adding the nano cellulose into copper salt solution, stirring the solution at normal temperature for 2 hours, and fully adsorbing the solution to form precursor dispersion liquid.
(3) The flask containing the precursor dispersion was transferred to an oil bath and heated to 160-180 ℃. And (3) weighing a certain amount of sulfur source according to the molar ratio of the sulfur source to the copper salt of 1:1-1:2, dissolving the sulfur source in 10mL of organic solvent, dripping the solution into the precursor dispersion liquid, stirring at 320rpm for reaction for 1-5 hours, and changing the solution from blue-green to yellow firstly and then slowly to black. And cooling after the reaction is finished, centrifugally collecting the precipitate, washing with water and ethanol for three times, and drying in vacuum to obtain the nano-cellulose/copper sulfide composite material.
The following describes the technical scheme of the present invention in further detail with reference to specific embodiments and drawings, but the embodiments and the protection scope of the present invention are not limited thereto.
Example 1
(1) 2g of commercial microcrystalline cellulose product is weighed and added into 25mL of deionized water, ultrasonic dispersion is carried out for 0.5 hour at room temperature, concentrated sulfuric acid is slowly added into the dispersion liquid in a dropwise manner under stirring to ensure that the volume concentration of the final sulfuric acid is 64%, acid hydrolysis is carried out at 45 ℃ for 1 hour, 250mL of deionized water is added to terminate the reaction, centrifugal washing is carried out for four times by using the deionized water, sediment is collected in the first two times, and supernatant is collected in the last two times of centrifugal washing. Dialyzing the supernatant to neutrality, and lyophilizing to obtain cellulose nanofiber CNF, wherein TEM (transmission electron microscope jem-1400plus, voltage: 100 kv) is used for characterizing CNF with diameter of 10-55nm, length of 400-2200nm, and length-diameter ratio of 40+ -0.8.
(2) 1mmol (0.2 g) of copper acetate monohydrate was weighed out and dissolved in 40mL of ethylene glycol (blue-green) with stirring at room temperature. Then 0.1g of prepared CNF is weighed and added into copper acetate solution, and the mixture is stirred for 2 hours at normal temperature to be fully adsorbed to form precursor dispersion liquid.
(3) The flask containing the precursor dispersion was transferred to an oil bath and heated to 160 ℃. 0.5mmol of Thioacetamide (TAA) is weighed and dissolved in 10mL of ethylene glycol under stirring at normal temperature to obtain a TAA solution, the TAA solution is dripped into the precursor dispersion liquid, and the solution is stirred and reacted for 3 hours at 320rpm, and the solution turns yellow from blue-green first and then turns black slowly. After the reaction is finishedCooling to room temperature, centrifuging to collect precipitate, washing with water and ethanol for three times, vacuum drying to obtain brown cellulose nanofiber/copper sulfide composite material CNF/CuS, and characterizing Cu in CNC/CuS by XRD 2-x S (x is between 0 and 1) is Cu 9 S 5 Characterization of Cu Using TEM 2-x The size of S (x is between 0 and 1) is 90+/-10 nm.
Example 2
(1) 2g of commercial microcrystalline cellulose product is weighed and added into 25mL of deionized water, ultrasonic dispersion is carried out for 0.5 hour at room temperature, 25mL of concentrated sulfuric acid is slowly added dropwise into the dispersion liquid under stirring to ensure that the volume concentration of the final sulfuric acid is 64%, acid hydrolysis is carried out at 45 ℃ for 3 hours, 250mL of deionized water is added to terminate the reaction, centrifugal washing is carried out for four times by using the deionized water, sediment is collected in the first two times, and supernatant is collected in the last two times of centrifugal washing. Dialyzing the supernatant to neutrality, and freeze-drying to obtain cellulose nanocrystalline CNC, wherein the TEM characterizes the CNC with the diameter range of 5-24nm, the length of 50-400nm and the length-diameter ratio of 16+/-0.2.
(2) 1mmol (0.2 g) of copper acetate monohydrate was weighed out and dissolved in 40mL of ethylene glycol (blue-green) with stirring at room temperature. Then 0.1g of prepared CNC is weighed and added into copper acetate solution, and the mixture is stirred for 2 hours at normal temperature to be fully adsorbed to form precursor dispersion liquid.
(3) The flask containing the precursor dispersion was transferred to an oil bath and heated to 160 ℃. 0.5mmol of Thioacetamide (TAA) is weighed and dissolved in 10mL of ethylene glycol under stirring at normal temperature to obtain a TAA solution, the TAA solution is dripped into the precursor dispersion liquid, and the solution is stirred and reacted for 3 hours at 320rpm, and the solution turns yellow from blue-green first and then turns black slowly. Cooling to room temperature after the reaction is finished, centrifugally collecting precipitate, washing with water and ethanol for three times, and vacuum drying to obtain brown cellulose nanocrystalline/copper sulfide composite material CNC/CuS, wherein Cu in CNC/CuS is represented by XRD 2-x S (x is between 0 and 1) is Cu 9 S 5 Characterization of Cu Using TEM 2-x The S (x is between 0 and 1) has a size of 50.+ -. 8nm.
Example 3
(1) 2g of commercial microcrystalline cellulose product is weighed and added into 25mL of deionized water, ultrasonic dispersion is carried out at room temperature, 25mL of concentrated sulfuric acid is slowly added into the dispersion liquid under the simultaneous actions of stirring and ultrasonic treatment to ensure that the volume concentration of the final sulfuric acid is 64%, acid hydrolysis is carried out at 45 ℃ for 5 hours, 250mL of deionized water is added to terminate the reaction, centrifugal washing is carried out for four times by using the deionized water, sediment is collected in the first two times, and supernatant is collected in the last two times of centrifugal washing. Dialyzing the supernatant to neutrality, and freeze-drying to obtain cellulose nanosphere CNS, wherein TEM characterizes CNS with diameter ranging from 10nm to 50nm, length ranging from 20 nm to 200nm and length-diameter ratio of 3+/-0.6.
(2) 1mmol (0.2 g) of copper acetate monohydrate was weighed out and dissolved in 40mL of ethylene glycol (blue-green) with stirring at room temperature. Then 0.1g of the prepared CNS is weighed and added into copper acetate solution, and the mixture is stirred for 2 hours at normal temperature to be fully adsorbed to form precursor dispersion liquid.
(3) The flask containing the precursor dispersion was transferred to an oil bath and heated to 160 ℃. 0.5mmol of Thioacetamide (TAA) is weighed and dissolved in 10mL of ethylene glycol under stirring at normal temperature to obtain a TAA solution, the TAA solution is dripped into the precursor dispersion liquid, and the solution is stirred and reacted for 3 hours at 320rpm, and the solution turns yellow from blue-green first and then turns black slowly. Cooling to room temperature after the reaction is finished, centrifugally collecting precipitate, washing with water and ethanol for three times, and vacuum drying to obtain brown cellulose nanosphere/copper sulfide composite material CNS/CuS, wherein Cu in CNC/CuS is represented by XRD 2-x S (x is between 0 and 1) is Cu 9 S 5 Characterization of Cu Using TEM 2-x S (x is between 0 and 1) has a size of 10.+ -. 2nm.
Example 4
(1) Pretreating purchased bagasse by sodium hydroxide for 12 hours, drying, weighing 2g, adding into 25mL of deionized water, slowly dropwise adding 25mL of concentrated sulfuric acid into the dispersion liquid under stirring to ensure that the volume concentration of the final sulfuric acid is 64%, carrying out acid hydrolysis at 45 ℃ for 3 hours, adding 250mL of deionized water to terminate the reaction, centrifugally washing four times by using the deionized water, collecting the precipitate twice, and centrifugally washing twice to collect the supernatant. Dialyzing the supernatant to neutrality, and finally freeze-drying to obtain the cellulose nanocrystalline CNC.
(2) 1mmol of copper chloride was weighed out and dissolved in 40mL of diethylene glycol with stirring at room temperature. Then weighing 0.2g of CNC, adding the CNC into the copper chloride solution, stirring the mixture at normal temperature for 2 hours, and fully adsorbing the mixture to form precursor dispersion liquid.
(3) Will be loaded with precursorThe flask of the dispersion was transferred to an oil bath and heated to 180 ℃. 0.5mmol of thiourea is weighed and dissolved in 10mL of diethylene glycol under stirring at normal temperature to obtain thiourea solution, and the thiourea solution is added into the precursor dispersion liquid dropwise, and the precursor dispersion liquid is stirred at 320rpm for reaction for 5 hours. Cooling to room temperature after the reaction is finished, centrifugally collecting precipitate, washing with water and ethanol for three times, and vacuum drying to obtain cellulose nanocrystalline/copper sulfide composite material CNC/CuS, and characterizing Cu by using TEM 2-x The size of S (x is between 0 and 1) is 64+ -8 nm.
Example 5
(1) 2g of commercial microcrystalline cellulose product was weighed into 25mL of deionized water, 45mL of concentrated hydrochloric acid was slowly added dropwise to the dispersion with stirring to give a final sulfuric acid volume concentration of 64%, acid hydrolysis was carried out at 45℃for 3h, then 250mL of deionized water was added to terminate the reaction, centrifugal washing was carried out four times with deionized water, the precipitate was collected in the first two times, and the supernatant was collected in the last two centrifugal washes. Dialyzing the supernatant to neutrality, and finally freeze-drying to obtain the cellulose nanocrystalline CNC.
(2) 1mmol of copper sulfate was weighed and dissolved in 40mL of glycerol with stirring at room temperature. Then 0.05g of prepared CNC is weighed and added into the copper sulfate solution, and the mixture is stirred for 2 hours at normal temperature to be fully adsorbed to form precursor dispersion liquid.
(3) The flask containing the precursor dispersion was transferred to an oil bath and heated to 170 ℃. 0.5mmol of sodium thiosulfate is weighed and dissolved in 10mL of glycerol under stirring at normal temperature to obtain a sodium thiosulfate solution, and the sodium thiosulfate solution is dropwise added into the precursor dispersion liquid to react for 1 hour under stirring at 320 rpm. Cooling to room temperature after the reaction is finished, centrifugally collecting precipitate, washing with water and ethanol for three times, and vacuum drying to obtain cellulose nanocrystalline/copper sulfide composite material CNC/CuS, and characterizing Cu by using TEM 2-x The S (x is between 0 and 1) has a size of 55.+ -.9 nm.
Example 6
(1) 2g of commercial microcrystalline cellulose product was weighed into 25mL of deionized water, 25mL of concentrated sulfuric acid was slowly added dropwise to the dispersion with stirring to give a final sulfuric acid volume concentration of 64%, acid hydrolysis was carried out at 45℃for 3 hours, then 250mL of deionized water was added to terminate the reaction, centrifugal washing was carried out four times with deionized water, the precipitate was collected in the first two times, and the supernatant was collected in the last two centrifugal washes. Dialyzing the supernatant to neutrality, and finally freeze-drying to obtain the cellulose nanocrystalline CNC.
(2) 1mmol of copper nitrate was weighed and dissolved in 40mL of glycerin with stirring at room temperature. Then 0.1g of prepared CNC is weighed and added into the copper sulfate solution, and the mixture is stirred for 2 hours at normal temperature to be fully adsorbed to form precursor dispersion liquid.
(3) The flask containing the precursor dispersion was transferred to an oil bath and heated to 160 ℃. 1mmol of sodium sulfide is weighed and stirred at normal temperature to be dissolved in 10mL of glycerin to obtain sodium sulfide solution, and the sodium sulfide solution is dropwise added into the precursor dispersion liquid to be stirred at 320rpm for reaction for 1 hour. Cooling to room temperature after the reaction is finished, centrifugally collecting precipitate, washing with water and ethanol for three times, and vacuum drying to obtain the cellulose nanocrystalline/copper sulfide composite material CNC/CuS, wherein Cu in the CNC/CuS is represented by XRD 2-x S (x is between 0 and 1) is CuS, and Cu is characterized by TEM 2-x S (x is between 0 and 1) has a size of 73.+ -. 4nm.
Comparative example
(1) 1mmol (0.2 g) of copper acetate monohydrate was weighed out and dissolved in 40ml of ethylene glycol with stirring at room temperature. 0.5mmol (0.038 g) of Thioacetamide (TAA) was weighed out and dissolved in 10mL of ethylene glycol under stirring at room temperature to obtain a TAA solution.
(2) The flask containing copper acetate was put into an oil bath, heated to 165 ℃, and then the TAA solution was slowly added dropwise, and the reaction was stirred at 320rpm for 3 hours, and the solution turned from blue-green to yellow and then to black slowly. Cooling to room temperature after the reaction is finished, centrifugally collecting precipitate, washing with water and ethanol for three times, and vacuum drying to obtain copper sulfide CuS, and characterizing Cu in the CuS by XRD 2-x S (x is between 0 and 1) is Cu 9 S 5 Characterization of Cu Using TEM 2-x The size of S (x is between 0 and 1) is 100+/-12 nm.
1. Characterization of nanocellulose/copper sulfide composite
Infrared spectra of CNF, CNF/CuS, CNC, CNC/CuS, CNS and CNS/CuS in examples 1-3 were measured using a TENSOR 27/hyper type infrared spectrometer (FITR). The results are shown in FIG. 2, FITR maps at 3425, 2900, 1640, 1060 and 896cm -1 Is respectively attributed to stretching vibration of hydroxyl groups on nanocellulose, stretching of C-H, bending vibration of H-O-H, C-O-C in pyranose ringVibration is related to C-H vibration. 817cm -1 The characteristic absorption peak at this point is caused by the stretching vibration of S-O, possibly the sulfonic acid group obtained on nanocellulose during sulfuric acid hydrolysis, and is visible with Cu 2-x After S (x is between 0 and 1), 3425 and 817cm -1 Characteristic absorption peaks at the sites are weakened, indicating groups of nanocellulose and Cu after complexing 2-x There is an interaction between S (x is between 0 and 1).
The X-ray diffraction patterns of the composites of examples 1-3 were tested using an X-ray diffractometer (Netherlands Panalytical Empyrean), and FIG. 3 shows the X-ray diffraction patterns (XRDs) of the composites CNF/CuS, CNC/CuS and CNS/CuS of examples 1-3. Typical cellulose diffraction peaks (jcpdsno.47-1748) are shown at 2θ=14.99°, 16.49 ° and 22.78 °. Diffraction peaks at 27.77 °, 29.25 °, 32.16 °, 41.48 °, 46.17 °, 54.70 ° and 85.52 ° are well directed to Cu having a hexagonal phase structure 9 S 5 (0015), (107), (1010), (0117), (0120), (1115) and (1220) planes (JCPLS No. 47-1748).
2. Antibacterial experiments
Bacteria were cultured to have an OD600 of about 0.5, and the bacterial solution was diluted 10 times and mixed with nanocellulose/copper sulfide composite materials of different concentrations for 1 hour. Adding physiological saline for dilution 10 4 After that, 0.1mL of the plate was again aspirated therefrom, and then placed in a 37℃incubator for 16 hours, and then photographed to observe the number of bacteria. As shown in fig. 4, it is evident that there is little bactericidal effect of uncomplexed CuS, and the bactericidal effect is significantly improved after nanocellulose is compounded, especially for the CNS/CuS composite of example 3. At a concentration of 0.2mg/mL each, CNC/CuS and CNS/CuS in examples 2 and 3 completely killed the bacteria, compared to the less bactericidal effect of CNF/CuS and CuS alone. This illustrates nanocellulose and Cu 2-x S (x is between 0 and 1) exhibits synergistic antimicrobial effects after compounding.
The synthesis of nanocellulose/copper sulfide composites of different morphologies and the mechanism by which nanocellulose/copper sulfide composites kill bacteria by generating reactive oxygen species and copper ions to destroy cell membranes are shown in figure 1.
3. Scanning electron microscope characterization of composite material contact with bacteria
Bacteria co-cultured in the antibacterial experiment were diluted, centrifuged at 8000rpm for 5 minutes, the supernatant was discarded, fixed with 2.5% glutaraldehyde, soaked in ethanol solutions of different concentrations, and then added dropwise to a silicon wafer, and the bacterial morphology was observed by scanning electron microscopy (ZEISS Gemini 300, germany). As shown in FIG. 5, the nanocellulose/copper sulfide composite material is coated outside bacteria, nanocellulose and Cu 2-x S (x is between 0 and 1) has synergistic coating effect on bacterial cells after compounding, promotes contact of materials and bacteria, generates active oxygen and releases Cu through physical contact 2+ The means of (a) destroying the cellular structure causes the bacteria to die.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the nanocellulose/copper sulfide composite material with sterilization performance is characterized by comprising the following steps:
(1) Acid hydrolyzing the cellulose raw material for different times, centrifuging, dialyzing and vacuum drying to obtain nanocellulose with different morphologies;
(2) Then uniformly mixing nano cellulose and copper salt in an organic solvent to obtain precursor dispersion liquid;
(3) And finally, slowly dropwise adding a sulfur source under the heating condition, and reacting by a sol-gel method to obtain the nanocellulose/copper sulfide composite material.
2. The method for preparing the nano-cellulose/copper sulfide composite material with sterilization performance according to claim 1, wherein the cellulose raw material in the step (1) is a commercial microcrystalline cellulose product or bagasse; sulfuric acid or hydrochloric acid is used for acid hydrolysis, and the acid hydrolysis time is 1-5 hours; the nanocellulose with different morphologies is Cellulose Nanofiber (CNF), cellulose Nanocrystal (CNC) or Cellulose Nanosphere (CNS).
3. The method for preparing the nano-cellulose/copper sulfide composite material with sterilization performance according to claim 1, wherein the aspect ratio of the nano-cellulose with different morphologies in the step (1) is 2.4-40.8, and the transverse diameter is 5-55nm.
4. The method for preparing the nanocellulose/copper sulfide composite material with sterilization performance according to claim 1, wherein the copper salt in the step (2) is one or more of copper sulfate copper nitrate, copper chloride or copper acetate monohydrate; the organic solvent is one or more of ethylene glycol, diethylene glycol, glycerol or glycerin; cu in the nanocellulose and copper salt 2+ The mass ratio of (2) is 1:0.32-1:1.28.
5. The method for preparing the nanocellulose/cupric sulfide composite material with sterilization performance according to claim 1, wherein the sulfur source in the step (3) is more than one of thiourea, thioacetamide, sodium sulfide or sodium thiosulfate; the molar ratio of the sulfur source to the copper salt is 1:1-1:2; the heating condition is that the temperature is 160-180 ℃ and the reaction time is 1-5 hours.
6. The method for preparing a nano-cellulose/copper sulfide composite material with sterilization performance according to claim 1, wherein the CuS nano-particles on the surface of the nano-cellulose in the nano-cellulose/copper sulfide composite material in the step (3) are Cu 2-x S (x is between 0 and 1) and the size is 8-100 nm.
7. The method for preparing a nano-cellulose/copper sulfide composite material with sterilization performance according to claim 1, wherein the nano-cellulose/copper sulfide composite material in the step (3) is Cu 2-x S (x is between 0 and 1) is obtained by in-situ growth outside nanocellulose.
8. A nanocellulose/copper sulfide composite material having bactericidal properties produced by the method of any one of claims 1-7.
9. The nanocellulose/cupric sulfide composite material with bactericidal properties as in claim 8 wherein nanocellulose and Cu are 2-x The synergistic effect of S (x is between 0 and 1) can interact with bacteria to kill bacteria, and active oxygen is generated in the slightly acidic environment in the bacteria to promote the death of the bacteria.
10. The use of a nanocellulose/copper sulfide composite material with bactericidal properties as claimed in claim 8 in the fields of corrosion protection, mildew resistance, antibacterial biofilm resistance, food packaging and air filtration sterilization.
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