CN113016823A - Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles - Google Patents
Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles Download PDFInfo
- Publication number
- CN113016823A CN113016823A CN202110143900.1A CN202110143900A CN113016823A CN 113016823 A CN113016823 A CN 113016823A CN 202110143900 A CN202110143900 A CN 202110143900A CN 113016823 A CN113016823 A CN 113016823A
- Authority
- CN
- China
- Prior art keywords
- infrared
- antibacterial
- bimetallic
- photo
- nanoparticles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 111
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002244 precipitate Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 12
- 239000012498 ultrapure water Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- -1 amine compound Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 10
- 239000012620 biological material Substances 0.000 abstract description 8
- 230000001954 sterilising effect Effects 0.000 abstract description 8
- 206010059866 Drug resistance Diseases 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 239000010931 gold Substances 0.000 description 25
- 229910052737 gold Inorganic materials 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 19
- 239000012488 sample solution Substances 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000009210 therapy by ultrasound Methods 0.000 description 11
- 241000191967 Staphylococcus aureus Species 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000012258 culturing Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 7
- 230000002401 inhibitory effect Effects 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000002965 ELISA Methods 0.000 description 4
- 239000012880 LB liquid culture medium Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 238000009630 liquid culture Methods 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 208000035143 Bacterial infection Diseases 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 208000022362 bacterial infectious disease Diseases 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241000192125 Firmicutes Species 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000003501 co-culture Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 108010078777 Colistin Proteins 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003346 colistin Drugs 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- JORAUNFTUVJTNG-BSTBCYLQSA-N n-[(2s)-4-amino-1-[[(2s,3r)-1-[[(2s)-4-amino-1-oxo-1-[[(3s,6s,9s,12s,15r,18s,21s)-6,9,18-tris(2-aminoethyl)-3-[(1r)-1-hydroxyethyl]-12,15-bis(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-h Chemical compound CC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@H]([C@@H](C)O)CN[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O.CCC(C)CCCCC(=O)N[C@@H](CCN)C(=O)N[C@H]([C@@H](C)O)CN[C@@H](CCN)C(=O)N[C@H]1CCNC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCN)NC(=O)[C@H](CCN)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CCN)NC1=O JORAUNFTUVJTNG-BSTBCYLQSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- XDJYMJULXQKGMM-UHFFFAOYSA-N polymyxin E1 Natural products CCC(C)CCCCC(=O)NC(CCN)C(=O)NC(C(C)O)C(=O)NC(CCN)C(=O)NC1CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C(CC(C)C)NC(=O)C(CCN)NC1=O XDJYMJULXQKGMM-UHFFFAOYSA-N 0.000 description 1
- KNIWPHSUTGNZST-UHFFFAOYSA-N polymyxin E2 Natural products CC(C)CCCCC(=O)NC(CCN)C(=O)NC(C(C)O)C(=O)NC(CCN)C(=O)NC1CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C(CC(C)C)NC(=O)C(CCN)NC1=O KNIWPHSUTGNZST-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/085—Infrared radiation
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/20—Targets to be treated
- A61L2202/24—Medical instruments, e.g. endoscopes, catheters, sharps
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/20—Targets to be treated
- A61L2202/26—Textiles, e.g. towels, beds, cloths
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles, which comprises the following steps: adding chloroauric acid, copper chloride, long-chain organic amine and a reducing agent into ultrapure water, stirring overnight, carrying out oil bath heating, cooling a reaction product, centrifuging the reaction product, dissolving the obtained precipitate into deionized water, washing the precipitate with the deionized water and ethanol for three to four times, and carrying out vacuum drying to obtain the near-infrared bimetallic nano-particle. Compared with other nanoparticles, the near-infrared bimetallic nanoparticle obtained by the invention has certain antibacterial activity, can realize photo-thermal sterilization under the irradiation of near-infrared light, shows high-efficiency antibacterial activity after the two nanoparticles are combined, can be widely applied to the aspects of biological materials, medical instruments, wound antibacterial sterilization and the like, reduces the drug resistance risk of bacteria, and has wide application prospect in the field of future antibacterial materials.
Description
Technical Field
The invention belongs to the technical field of antibacterial metal nano materials, and particularly relates to a preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles.
Background
Bacterial infections have become a major threat to human health worldwide and to address this challenge, antibiotics such as penicillin and colistin have been developed to treat bacterial infections. However, the long-term and excessive use of traditional antibiotics has contributed to the production of multidrug-resistant bacteria, while threatening public health through various routes such as food, water and livestock. To address this problem, antibacterial biomaterials gradually walked into our field of view. Antibacterial biomaterials are novel biomaterials which have a large killing function or inhibiting capability on microorganisms through physical and chemical actions, and researchers habitually divide the antibacterial biomaterials into a natural antibacterial biomaterial, an organic antibacterial material and an inorganic antibacterial material according to different effective antibacterial components in the antibacterial biomaterials. Among them, metal nano antibacterial materials are becoming hot spots for research of antibacterial biomaterials because they can maintain an effective sterilization rate for a long time and have a long service life.
Gold nanoparticles (AuNPs) are a nano material which is an early research, and are widely used in the fields of disease diagnosis and treatment, drug delivery, biological analysis and the like because of simple and uniform preparation, stable property, good biocompatibility and easy modification by biomolecules. The current research proves that the gold nanoparticles show unique antibacterial activity. Gold is multivalent, so gold nanoparticles can bind to multiple types of ligands; in addition, the ultra-large specific surface area of AuNPs provides rich binding sites with target bacteria, and the AuNPs have broad-spectrum antibacterial property, namely the AuNPs show antibacterial capability to gram-negative bacteria and gram-positive bacteria, and even show certain inhibition capability to multidrug-resistant bacteria. Compared with common antibiotics, AuNPs target molecules such as DNA, protein and the like in bacteria, so that the bacteria are difficult to establish a defense system, and the AuNPs are difficult to generate drug resistance.
However, the single gold nano-ion has larger dosage for achieving the antibacterial effect, and the nano-gold is expensive and scarce, so that the cost can be reduced, the functionality can be improved, and the dosage can be reduced by combining the nano-gold with other cheap metals. The long-chain organic amine is used as the end capping agent to influence the growth condition of the nano particles, so that the nano particles with different shapes are prepared.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of the existing metal antibacterial material, the photo-thermal antibacterial near-infrared bimetallic nanoparticle (Au @ CuO for short) is prepared, the preparation method of the near-infrared bimetallic nanoparticle prepared by the invention is simple, expensive instruments are not needed, and the technical blank and the blank of simultaneously applying a plurality of fields can be made up; the problems are solved: 1. the problem of large amount of the antibacterial agent required by a single gold nano particle; 2. the drug resistance problem occurring in the process of treating bacterial infection; 3. The conventional antibacterial materials cause a problem of side effects.
The invention also provides the bimetal nano particles which are prepared by the method and have good biocompatibility and absorption at the near infrared position, the antibacterial activity of the bimetal nano particles and the application of the bimetal nano particles in the aspects of photo-thermal antibiosis.
The technical scheme is as follows:
a preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles comprises the following steps:
step 1, adding chloroauric acid, copper chloride, long-chain organic amine and a reducing agent into ultrapure water, stirring for 12-18h, heating for reaction for 0.5-1 h, cooling to 20-30 ℃ to obtain a reactant, centrifuging the reactant, dispersing the centrifuged precipitate sequentially through deionized water and absolute ethyl alcohol, washing and centrifuging, and drying the precipitate obtained by washing and centrifuging to obtain the photothermal antibacterial near-infrared bimetallic nano-particle.
Further, in the preparation method, the ratio of the chloroauric acid, the copper chloride, the long-chain organic amine, the reducing agent and the ultrapure water is that 25-30 mL of ultrapure water is used for dissolving 0.03-0.04 g of chloroauric acid, 0.026-0.03 g of copper chloride, 0.1-0.45 g of long-chain organic amine and 0.25-0.3 g of reducing agent.
Further, in the preparation method, the long-chain organic amine is an organic amine compound with a carbon chain length in the range of C10-C18.
In the preparation method, the reducing agent is a substance for reducing chloroauric acid into Au 0.
Further, in the preparation method, the stirring speed for stirring for 12-18 hours is 500-600 r/min.
Further, in the preparation method, the reaction temperature of the heating reaction is 100-120 ℃.
Further, the preparation method comprises the step of drying in vacuum, wherein the temperature of the vacuum drying is 50-60 ℃, the vacuum degree is 0.08-0.09 MPa, and the drying time is 24-36 hours.
Further, in the preparation method, the washing centrifugation is centrifugation for 8-10 min under the condition of 9000-10000 rpm.
Further, in the preparation method, the reducing agent comprises any one of sodium borohydride, ascorbic acid, sodium citrate, glucose, hydrogen peroxide, hydroxylamine hydrochloride or amino acid.
Further, the reactant is centrifuged for 8-10 min under 9000-10000 rpm.
Further, the step of dispersing the centrifuged precipitate sequentially with deionized water and absolute ethanol is to disperse the obtained precipitate with deionized water or ethanol in a ratio of 1: 5-6, and performing ultrasonic treatment at room temperature for 10-15 min to disperse.
The photo-thermal antibacterial near-infrared bimetallic nano-particle prepared by the preparation method is applied to chemical antibacterial and photo-thermal antibacterial synergistic antibacterial.
Escherichia coli and Staphylococcus aureus were used to explore their own antibacterial activity and applications in the field of photothermal antibacterial. Compared with other nanoparticles, the nano-gold nanoparticle disclosed by the invention can solve the problem that the amount of an antibacterial agent required by a single gold nanoparticle is large, and can realize the synergistic effect of chemical antibacterial and photo-thermal antibacterial in the biomedical field.
The antibacterial activity based on single gold nanoparticles is lower, the cost is higher, and the introduction of cheap metals such as copper and copper-based compounds can improve the bactericidal activity and reduce the cost. In addition, after being combined with gold nanoparticles, the cytotoxicity of the copper-based compound is reduced, so that the copper-based compound can exert effective bactericidal performance at a lower concentration. On the other hand, the gold nanoparticles have strong photo-thermal conversion capability, and can generate local heat under near-infrared radiation, so that bacteria are killed. Therefore, the bimetallic nano-particles prepared by the invention combine the advantages of gold and copper-based nano-particles, have certain antibacterial activity and have absorption in a near-infrared region. The tip of the bimetal nano particle can damage the bacterial cell membrane, so that the content is leaked; in addition, when the laser with the wavelength of 808 nm irradiates, the near-infrared double-metal nano particles can also convert light energy into heat, so that local high temperature is caused, and finally bacteria die.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, gold and a copper-based compound are combined for the first time to prepare the bimetallic nano-particle, and the gold nano-particle has a certain antibacterial effect on gram-negative bacteria and gram-positive bacteria; secondly, copper-based compounds also have antimicrobial properties and are currently the only metals used in hospitals to reduce bioburden.
(2) The bimetallic nano-particle prepared by the invention introduces the copper-based compound on the preparation of the gold nano-particle, can be absorbed in a near infrared region without adding a photosensitizer, has simple synthesis process and low preparation cost, and can be applied and produced on a large scale.
(3) The bimetal nano particle prepared by the invention has certain antibacterial activity, and can be applied to the aspects of instrument disinfection, medical textile disinfection and the like.
(4) The bimetal nano particle prepared by the invention can realize the synergistic effect of chemical antibiosis and photo-thermal antibiosis, improve the antibacterial activity, reduce the side effect, and compared with the use of antibiotics, the bimetal nano particle can not generate risks such as bacterial drug resistance and the like.
(5) The bimetal nano particles prepared by the invention have higher photo-thermal conversion efficiency, and compared with a blank group, the bimetal nano particles have the advantages of fast temperature rise and obviously improved sterilization effect under the irradiation of near infrared light.
Drawings
FIG. 1 is a transmission electron microscope image of the near-infrared bimetallic nanoparticles of example 1 of the present invention;
FIG. 2 is a UV-Vis spectrum of the near-infrared bimetallic nanoparticles of example 1 of the present invention;
fig. 3 is an XRD spectrum of the near-infrared bimetallic nanoparticle of example 1 of the present invention;
FIG. 4 is a Zeta potential diagram of the near infrared bimetallic nanoparticles of example 1 of the present invention;
FIG. 5 is an XPS spectrum of a near-infrared bimetallic nanoparticle of example 1 of the present invention;
FIG. 6 shows that the minimum inhibitory concentration of the bi-metal nanoparticles to Escherichia coli is determined after culturing the bi-metal nanoparticles of example 1 in the absence of laser irradiation and after laser irradiation at 808 nm for 24 h, and the absorbance of the bi-metal nanoparticles is measured by an enzyme-linked immunosorbent assay at a wavelength of 600 nm; the graph shows that the absorbance of the escherichia coli is smaller in turn along with the increase of the concentration of the near-infrared bimetallic nanoparticles, and the escherichia coli has certain antibacterial activity. However, the absorbance of E.coli was decreased to a greater extent at the same concentration after the 808 nm laser irradiation, indicating that it had a more excellent antibacterial effect after the near-infrared irradiation.
FIG. 7 shows that the minimum inhibitory concentration of the near-infrared bimetallic nanoparticles to Staphylococcus aureus is determined after the near-infrared bimetallic nanoparticles of example 1 are cultured for 24 h without laser irradiation and with laser irradiation of 808 nm, and the absorbance of the nanoparticles at a wavelength of 600 nm is measured by using an enzyme-linked immunosorbent assay; the graph shows that the absorbance of staphylococcus aureus is smaller in turn along with the increase of the concentration of the near-infrared bimetallic nanoparticles, and the staphylococcus aureus has certain antibacterial activity. However, the absorbance of staphylococcus aureus is reduced to a larger extent at the same concentration after 808 nm laser irradiation, which shows that the staphylococcus aureus has more excellent antibacterial effect after near infrared light irradiation.
Fig. 8 is a colony count diagram of escherichia coli after the near-infrared bimetallic nanoparticle of example 1 of the present invention is irradiated without laser and after the near-infrared bimetallic nanoparticle is irradiated with 808 nm laser, which shows that the near-infrared bimetallic nanoparticle can better inhibit the growth of bacteria under photo-thermal conditions, and that the antibacterial performance is better at higher concentrations, which shows that the near-infrared bimetallic nanoparticle can effectively sterilize under photo-thermal conditions.
Fig. 9 is a graph of the colony number of staphylococcus aureus after the near-infrared bimetallic nanoparticle of example 1 is irradiated without laser and after being irradiated by 808 nm laser, which shows that the near-infrared bimetallic nanoparticle can better inhibit the growth of bacteria under the photo-thermal condition, and the higher the concentration is, the better the antibacterial performance is, which shows that the near-infrared bimetallic nanoparticle can effectively sterilize under the photo-thermal condition.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
A preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles comprises the following steps:
step 1, weighing 0.03 g of chloroauric acid, 0.026 g of copper chloride, 0.25 g of glucose and 0.1 g of hexadecylamine, placing the weighed materials in a 50 mL scintillation bottle, adding 25 mL of ultrapure water, and stirring at room temperature for 18h at 600 r/min.
And 2, transferring the scintillation vial into an oil bath, and reacting for 0.5 h at 100 ℃ under the stirring condition of 600 r/min.
And 3, after the reaction is finished, cooling the synthesized product to 25 ℃.
And 4, placing the obtained brown black solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, adding 25 mL of deionized water into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the precipitate.
And 5, placing the solution in a centrifuge, centrifuging for 8 min at 10000 rpm, repeating for three times, adding 25 mL of ethanol into the obtained precipitate, adding 25 mL of absolute ethanol into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the ethanol.
And 6, placing the solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, and repeating for three times.
And 7, placing the obtained precipitate in a vacuum drying oven at the temperature of 50 ℃, the vacuum degree of 0.09 MPa and the time of 36 hours to obtain the near-infrared bimetallic nanoparticle powder.
The transmission electron microscope image of the near-infrared bimetallic nanoparticle prepared in this example is shown in fig. 1, which shows that the nanoparticle is star-shaped and has a particle size of about 200 nm.
The UV-Vis spectrum of the near-infrared bimetallic nanoparticle prepared in this example is shown in FIG. 2, which shows that the near-infrared bimetallic nanoparticle has absorption at 800-1100 nm. The XRD spectrum of the near-infrared bimetallic nanoparticle prepared in this example is shown in fig. 3, in which the near-infrared bimetallic nanoparticles all show diffraction peaks corresponding to the (111), (200) and (220) crystal planes, indicating that the bimetallic was successfully doped and has a good crystal structure. The Zeta potential diagram of the near-infrared bimetallic nanoparticle prepared in this example is shown in fig. 4, which shows that the potential of the gold nanoparticle is-5.1 mV, and the potential of the near-infrared bimetallic nanoparticle is +11.6 mV. Mainly because the gold nanoparticles are terminated by sodium citrate in the preparation process, the gold nanoparticles are negatively charged; and hexadecylamine is used in the preparation process of the near-infrared bimetallic nanoparticles, and gold nanoparticles can react with the hexadecylamine to form Au-N bonds, so that the gold nanoparticles are positively charged.
The XPS spectrum of the near-infrared bimetallic nanoparticle prepared in the example is shown in FIG. 5, in which Cu2p is observed in the spectral region 953.9 eV of Cu2p1/2The absorption peak of (2) was observed at 934.2 eV, and Cu2p was observed3/2Absorption peaks of (2), Cu was observed at 962.8 eV and 943.4 eV2+Wherein the characteristic peak at 943 eV demonstrates that the predominant state of Cu in the bimetallic nanoparticle is CuO; in the figure, Au4f is observed in the Au4f spectral region at 84.2 eV and 87.8 eV respectively7/2And Au4f5/2The state of Au in the bimetallic nanoparticles was confirmed to be Au (0).
Example 2
A preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles comprises the following steps:
step 1, weighing 0.03 g of chloroauric acid, 0.026 g of copper chloride, 0.25 g of glucose and 0.45 g of hexadecylamine, placing the weighed materials in a 50 mL scintillation bottle, adding 25 mL of ultrapure water, and stirring at room temperature for 18h at 600 r/min.
And 2, transferring the scintillation vial into an oil bath, and reacting for 0.5 h at 100 ℃ under the stirring condition of 600 r/min.
And 3, after the reaction is finished, cooling the synthesized product to 25 ℃.
And 4, placing the obtained brown black solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, adding 25 mL of deionized water into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the precipitate.
And 5, placing the solution in a centrifuge, centrifuging for 8 min at 10000 rpm, repeating for three times, adding 25 mL of ethanol into the obtained precipitate, adding 25 mL of absolute ethanol into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the ethanol.
And 6, placing the solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, and repeating for three times.
And 7, placing the obtained precipitate in a vacuum drying oven at the temperature of 50 ℃, the vacuum degree of 0.09 MPa and the time of 36 hours to obtain the near-infrared bimetallic nanoparticle powder.
The near-infrared bimetallic nanoparticles prepared by the embodiment are subjected to transmission electron microscope test, and the prepared nanoparticles are in a linear reticular structure and have the particle size of about 200 nm.
Example 3
A preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles comprises the following steps:
step 1, weighing 0.03 g of chloroauric acid, 0.026 g of copper chloride, 0.25 g of glucose and 0.35 g of hexadecylamine, placing the weighed materials in a 50 mL scintillation bottle, adding 25 mL of ultrapure water, and stirring at room temperature for 18h at 600 r/min.
And 2, transferring the scintillation vial into an oil bath, and reacting for 0.5 h at 100 ℃ under the stirring condition of 600 r/min.
And 3, after the reaction is finished, cooling the synthesized product to 25 ℃.
And 4, placing the obtained brown black solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, adding 25 mL of deionized water into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the precipitate.
And 5, placing the solution in a centrifuge, centrifuging for 8 min at 10000 rpm, repeating for three times, adding 25 mL of ethanol into the obtained precipitate, adding 25 mL of absolute ethanol into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the ethanol.
And 6, placing the solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, and repeating for three times.
And 7, placing the obtained precipitate in a vacuum drying oven at the temperature of 50 ℃, the vacuum degree of 0.09 MPa and the time of 36 hours to obtain the near-infrared bimetallic nanoparticle powder.
The near-infrared bimetallic nanoparticles prepared in this example were subjected to transmission electron microscope testing, and the prepared nanoparticles were dendritic and had a particle size of about 200 nm.
Example 4
A preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles comprises the following steps:
step 1, weighing 0.03 g of chloroauric acid, 0.026 g of copper chloride, 0.25 g of glucose and 0.25 g of hexadecylamine, placing the weighed materials in a 50 mL scintillation flask, adding 25 mL of ultrapure water, and stirring at room temperature for 18h at 600 r/min.
And 2, transferring the scintillation vial into an oil bath, and reacting for 0.5 h at 100 ℃ under the stirring condition of 600 r/min.
And 3, after the reaction is finished, cooling the synthesized product to 25 ℃.
And 4, placing the obtained brown black solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, adding 25 mL of deionized water into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the precipitate.
And 5, placing the solution in a centrifuge, centrifuging for 8 min at 10000 rpm, repeating for three times, adding 25 mL of ethanol into the obtained precipitate, adding 25 mL of absolute ethanol into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the ethanol.
And 6, placing the solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, and repeating for three times.
And 7, placing the obtained precipitate in a vacuum drying oven at the temperature of 50 ℃, the vacuum degree of 0.09 MPa and the time of 36 hours to obtain the near-infrared bimetallic nanoparticle powder.
The near-infrared bimetallic nanoparticles prepared in this example were subjected to transmission electron microscopy, and the prepared nanoparticles were flower-shaped and had a particle size of about 200 nm.
Example 5
A preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles comprises the following steps:
step 1, weighing 0.03 g of chloroauric acid, 0.026 g of copper chloride, 0.25 g of glucose and 0.07 g of hexadecylamine, placing the weighed materials in a 50 mL scintillation flask, adding 25 mL of ultrapure water, and stirring at room temperature for 18h at 600 r/min.
And 2, transferring the scintillation vial into an oil bath, and reacting for 0.5 h at 100 ℃ under the stirring condition of 600 r/min.
And 3, after the reaction is finished, cooling the synthesized product to 25 ℃.
And 4, placing the obtained brown black solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, adding 25 mL of deionized water into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the precipitate.
And 5, placing the solution in a centrifuge, centrifuging for 8 min at 10000 rpm, repeating for three times, adding 25 mL of ethanol into the obtained precipitate, adding 25 mL of absolute ethanol into the obtained precipitate, and performing ultrasonic treatment at room temperature for 10 min to disperse the ethanol.
And 6, placing the solution in a centrifuge, centrifuging for 8 min at the rotating speed of 10000 rpm, and repeating for three times.
And 7, placing the obtained precipitate in a vacuum drying oven at the temperature of 50 ℃, the vacuum degree of 0.09 MPa and the time of 36 hours to obtain the near-infrared bimetallic nanoparticle powder.
The near-infrared bimetallic nanoparticles prepared in this example were tested by transmission electron microscopy, and the prepared nanoparticles were spherical and had a particle size of about 200 nm.
Example 6
Example 1 minimal inhibitory concentration test of the prepared near-infrared bimetallic nanoparticles.
The near-infrared bimetallic nanoparticles prepared in example 1 are prepared into sample solutions (0. mu.g/mL, 3.125. mu.g/mL, 6.25. mu.g/mL, 12.5. mu.g/mL and 25. mu.g/mL) with different concentrations by the following specific preparation process: taking 1.6 mg of near-infrared bimetallic nanoparticles prepared in example 1 and a 10 mL centrifuge tube, adding 4 mL of LB liquid culture solution to prepare a sample solution with the concentration of 400 mu g/mL, diluting the sample solution with the concentration of 400 mu g/mL in half to prepare sample solutions with the concentrations of 25 mu g/mL, 12.5 mu g/mL, 6.25 mu g/mL and 3.125 mu g/mL respectively, and adding 100: 1 is added after activationEscherichia coli liquid (OD)600= 0.1), blank group is LB liquid culture medium without sample addition (0. mu.g/mL), control group is mixed solution without 808 nm laser irradiation with sample addition concentration of 25. mu.g/mL, 12.5. mu.g/mL, 6.25. mu.g/mL, 3.125. mu.g/mL respectively. After co-culturing for 2 h in 37 deg.C constant temperature shaking incubator at rotation speed of 120 r/min, experimental group and blank group were cultured at 1.5 Wcm with 808 nm laser-2Irradiating for 10 min, and culturing in 37 deg.C constant temperature incubator at 120 r/min for 24 h while culturing control group in 37 deg.C constant temperature incubator at 120 r/min for 24 h without any treatment. And (3) putting 200 mu L of mixed solution after co-culture for 24 h into a 96-well plate, performing three groups of parallel experiments at each concentration, and then measuring the absorbance of the mixed solution at 600 nm by using an enzyme-linked immunosorbent assay, wherein the smaller the absorbance, the better the sterilization effect is proved.
Example 7
Example 1 minimal inhibitory concentration test of the prepared near-infrared bimetallic nanoparticles.
The near-infrared bimetallic nanoparticles prepared in example 1 are prepared into sample solutions (0. mu.g/mL, 3.125. mu.g/mL, 6.25. mu.g/mL, 12.5. mu.g/mL and 25. mu.g/mL) with different concentrations by the following specific preparation process: taking 1.6 mg of near-infrared bimetallic nanoparticles prepared in example 1 and a 10 mL centrifuge tube, adding 4 mL of LB liquid culture solution to prepare a sample solution with the concentration of 400 mu g/mL, diluting the sample solution with the concentration of 400 mu g/mL in half to prepare sample solutions with the concentrations of 25 mu g/mL, 12.5 mu g/mL, 6.25 mu g/mL and 3.125 mu g/mL respectively, and adding 100: 1, adding activated staphylococcus aureus liquid (OD)600= 0.1), blank group is LB liquid culture medium without sample addition (0. mu.g/mL), control group is mixed solution without 808 nm laser irradiation with sample addition concentration of 25. mu.g/mL, 12.5. mu.g/mL, 6.25. mu.g/mL, 3.125. mu.g/mL respectively. After co-culturing for 2 h in 37 deg.C constant temperature shaking incubator at rotation speed of 120 r/min, experimental group and blank group were cultured at 1.5 Wcm with 808 nm laser-2Irradiating for 10 min, placing in 37 deg.C constant temperature incubator at rotation speed of 120 r/min, shaking and culturing for 24 h, while the control group is cultured at 37 deg.C constant temperature without any treatmentShaking and culturing for 24 h at the rotation speed of 120 r/min in the box. And (3) putting 200 mu L of mixed solution after co-culture for 24 h into a 96-well plate, performing three groups of parallel experiments at each concentration, and then measuring the absorbance of the mixed solution at 600 nm by using an enzyme-linked immunosorbent assay, wherein the smaller the absorbance, the better the sterilization effect is proved.
Example 8
Colony count experiments for the near-infrared bimetallic nanoparticles prepared in example 1.
The near-infrared bimetallic nanoparticles prepared in example 1 are prepared into sample solutions (0. mu.g/mL, 3.125. mu.g/mL, 6.25. mu.g/mL, 12.5. mu.g/mL, 25. mu.g/mL, 50. mu.g/mL) with different concentrations by the following specific preparation process: taking 1.6 mg of near-infrared bimetallic nanoparticles prepared in example 1 and a 10 mL centrifuge tube, adding 4 mL of LB liquid culture solution to prepare a sample solution with the concentration of 400 mu g/mL, diluting the sample solution with the concentration of 400 mu g/mL in half to prepare sample solutions with the concentrations of 50 mu g/mL, 25 mu g/mL, 12.5 mu g/mL, 6.25 mu g/mL and 3.125 mu g/mL respectively, and mixing the sample solutions with different concentrations in a ratio of 100: 1 ratio of the activated Escherichia coli bacterial liquid (OD)600= 0.1), blank group is LB liquid culture medium without sample addition (0. mu.g/mL), control group is mixture solution without 808 nm laser irradiation with sample addition concentration of 50. mu.g/mL, 25. mu.g/mL, 12.5. mu.g/mL, 6.25. mu.g/mL, 3.125. mu.g/mL respectively. After co-culturing for 2 h in 37 deg.C constant temperature shaking incubator at rotation speed of 120 r/min, experimental group and blank group were cultured at 1.5 Wcm with 808 nm laser-2Irradiating for 10 min, placing in a 37 deg.C constant temperature incubator at rotation speed of 120 r/min for shaking culture for 24 h, while a control group without any treatment is subjected to shaking culture at rotation speed of 120 r/min for 24 h in a 37 deg.C constant temperature incubator, and then performing shaking culture according to the following conditions of 1: 9 proportional dilution 105And (3) doubling, respectively taking 30 mu L of the diluted liquid of the experimental group, the blank group and the control group, coating the diluted liquid on the surface of a solid culture medium, putting the solid culture medium into a constant-temperature incubator at 37 ℃ for further culture for 24 h, taking out and observing the number of colonies.
The experiment of the colony count of the near-infrared bimetallic nanoparticle for inhibiting the growth of escherichia coli is shown in fig. 8, and the total number of colonies is obviously reduced by 808 nm laser irradiation compared with that of a blank group (the blank group is also irradiated) and a control group which is not irradiated by 808 nm laser, so that the near-infrared bimetallic nanoparticle is proved to have excellent photo-thermal sterilization performance.
Example 9
Colony count experiments for the near-infrared bimetallic nanoparticles prepared in example 1.
The near-infrared bimetallic nanoparticles prepared in example 1 are prepared into sample solutions (0. mu.g/mL, 3.125. mu.g/mL, 6.25. mu.g/mL, 12.5. mu.g/mL, 25. mu.g/mL, 50. mu.g/mL) with different concentrations by the following specific preparation process: taking 1.6 mg of near-infrared bimetallic nanoparticles prepared in example 1 and a 10 mL centrifuge tube, adding 4 mL of LB liquid culture solution to prepare a sample solution with the concentration of 400 mu g/mL, diluting the sample solution with the concentration of 400 mu g/mL in half to prepare sample solutions with the concentrations of 50 mu g/mL, 25 mu g/mL, 12.5 mu g/mL, 6.25 mu g/mL and 3.125 mu g/mL respectively, and mixing the sample solutions with different concentrations in a ratio of 100: 1, adding activated staphylococcus aureus liquid (OD)600= 0.1), blank group is LB liquid culture medium without sample addition (0. mu.g/mL), control group is mixture solution without 808 nm laser irradiation with sample addition concentration of 50. mu.g/mL, 25. mu.g/mL, 12.5. mu.g/mL, 6.25. mu.g/mL, 3.125. mu.g/mL respectively. After co-culturing for 2 h in 37 deg.C constant temperature shaking incubator at rotation speed of 120 r/min, experimental group and blank group were cultured at 1.5 Wcm with 808 nm laser-2Irradiating for 10 min, placing in a 37 deg.C constant temperature incubator at rotation speed of 120 r/min for shaking culture for 24 h, while a control group without any treatment is subjected to shaking culture at rotation speed of 120 r/min for 24 h in a 37 deg.C constant temperature incubator, and then performing shaking culture according to the following conditions of 1: 9 proportional dilution 105And (3) doubling, respectively taking 30 mu L of the diluted liquid of the experimental group, the blank group and the control group, coating the diluted liquid on the surface of a solid culture medium, putting the solid culture medium into a constant-temperature incubator at 37 ℃ for further culture for 24 h, taking out and observing the number of colonies.
The experiment of the colony count of the near-infrared bimetallic nanoparticle for inhibiting the growth of staphylococcus aureus is shown in fig. 9, and the experiment shows that the total number of colonies is obviously reduced by 808 nm laser irradiation compared with a blank group (the blank group is irradiated in the same way) and a control group which is not irradiated by 808 nm laser, so that the near-infrared bimetallic nanoparticle has excellent photo-thermal sterilization performance.
Claims (9)
1. A preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles is characterized by comprising the following steps:
step 1, adding chloroauric acid, copper chloride, long-chain organic amine and a reducing agent into ultrapure water, stirring for 12-18h, heating for reaction for 0.5-1 h, cooling to 20-30 ℃ to obtain a reactant, centrifuging the reactant, dispersing the centrifuged precipitate sequentially through deionized water and absolute ethyl alcohol, washing and centrifuging, and drying the precipitate obtained by washing and centrifuging to obtain the photothermal antibacterial near-infrared bimetallic nano-particle.
2. The method according to claim 1, wherein the chloroauric acid, the copper chloride, the long-chain organic amine, the reducing agent and the ultrapure water are dissolved in a volume of 25 to 30 mL of ultrapure water, wherein the volume ratio of the chloroauric acid to the copper chloride to the reducing agent is 0.03 to 0.04 g of the chloroauric acid to 0.026 to 0.03 g of the copper chloride to 0.1 to 0.45 g of the long-chain organic amine to 0.25 to 0.3 g of the reducing agent.
3. The method according to claim 1, wherein the long-chain organic amine is an organic amine compound having a carbon chain length in the range of C10 to C18.
4. The method according to claim 1, wherein the reducing agent is a substance that reduces chloroauric acid to Au 0.
5. The preparation method according to claim 1, wherein the stirring speed for 12-18h is 500-600 r/min.
6. The method as claimed in claim 1, wherein the reaction temperature of the heating reaction is 100-120 ℃.
7. The preparation method according to claim 1, wherein the drying is vacuum drying, the vacuum drying temperature is 50-60 ℃, the vacuum degree is 0.08-0.09 MPa, and the drying time is 24-36 h.
8. The production method according to claim 4, wherein the reducing agent includes any one of sodium borohydride, ascorbic acid, sodium citrate, glucose, hydrogen peroxide, hydroxylamine hydrochloride, or an amino acid.
9. The photo-thermal antibacterial near-infrared bimetallic nano-particles prepared by the preparation method of claim 1 are applied to chemical antibacterial and photo-thermal antibacterial.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110143900.1A CN113016823B (en) | 2021-02-02 | 2021-02-02 | Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110143900.1A CN113016823B (en) | 2021-02-02 | 2021-02-02 | Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113016823A true CN113016823A (en) | 2021-06-25 |
| CN113016823B CN113016823B (en) | 2022-04-15 |
Family
ID=76459711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110143900.1A Active CN113016823B (en) | 2021-02-02 | 2021-02-02 | Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113016823B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113827613A (en) * | 2021-10-19 | 2021-12-24 | 天津大学 | Atomic precision cluster enzyme, preparation and application thereof in nervous system diseases |
| CN114451511A (en) * | 2022-01-05 | 2022-05-10 | 华南理工大学 | Antibacterial nano-particles and preparation method and application thereof |
| CN114452386A (en) * | 2022-01-14 | 2022-05-10 | 江苏大学 | Preparation method and application of gold-copper bimetallic nano-enzyme composite material |
| CN114711251A (en) * | 2022-03-25 | 2022-07-08 | 扬州大学 | Titanium carbide-manganese sulfide composite bacteriostatic material, preparation method thereof and bacteriostatic method |
| CN115300482A (en) * | 2022-08-17 | 2022-11-08 | 山东大学 | Bovine serum albumin coated chlorhexidine loaded nickel phosphide nano-capsule, preparation method and antibacterial application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02225402A (en) * | 1989-02-28 | 1990-09-07 | Kanebo Ltd | Antibacterial composition |
| US20050267233A1 (en) * | 2004-05-25 | 2005-12-01 | Joshi Ashok V | Anti-microbial handle system |
| US20060172013A1 (en) * | 2005-02-03 | 2006-08-03 | Akira Hirai | Process for preparing copper oxide-coated antibacterial material |
| CN104162657A (en) * | 2014-07-21 | 2014-11-26 | 江苏大学 | Super-long copper nanowire and preparing method thereof |
| CN106392097A (en) * | 2016-09-29 | 2017-02-15 | 武汉科技大学 | Cu-Ag bimetallic nano material, preparation method and application thereof |
| CN107518004A (en) * | 2016-06-21 | 2017-12-29 | 张家港市山牧新材料技术开发有限公司 | A kind of preparation method of Nanometer Copper antibacterial granule |
| CN108552221A (en) * | 2018-04-11 | 2018-09-21 | 石狮纳通新材料科技有限公司 | A kind of copper selenide nanometer material preparation method and antibacterial applications near infrared absorption characteristic |
| CN109819979A (en) * | 2019-03-15 | 2019-05-31 | 尚蒙科技无锡有限公司 | Nano silver copper bimetallic colloid/liquid of high anti-microbial property and preparation method thereof |
| CN110051837A (en) * | 2019-04-08 | 2019-07-26 | 南京师范大学 | A kind of CuO/ZnO/Au nanoparticle and its preparation method and application |
| KR102064464B1 (en) * | 2018-02-13 | 2020-01-10 | 포항공과대학교 산학협력단 | Method of manufacturing nanoparticles containing Au, copper core and silica shell |
| CN110854396A (en) * | 2019-11-07 | 2020-02-28 | 南京师范大学 | PtAg nanocrystalline with porous double-hollow-sphere structure and preparation method and application thereof |
| CN111909691A (en) * | 2020-06-23 | 2020-11-10 | 南京师范大学 | Preparation method of photo-thermal antibacterial near-infrared carbon quantum dots, product and application thereof |
-
2021
- 2021-02-02 CN CN202110143900.1A patent/CN113016823B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02225402A (en) * | 1989-02-28 | 1990-09-07 | Kanebo Ltd | Antibacterial composition |
| US20050267233A1 (en) * | 2004-05-25 | 2005-12-01 | Joshi Ashok V | Anti-microbial handle system |
| US20060172013A1 (en) * | 2005-02-03 | 2006-08-03 | Akira Hirai | Process for preparing copper oxide-coated antibacterial material |
| CN104162657A (en) * | 2014-07-21 | 2014-11-26 | 江苏大学 | Super-long copper nanowire and preparing method thereof |
| CN107518004A (en) * | 2016-06-21 | 2017-12-29 | 张家港市山牧新材料技术开发有限公司 | A kind of preparation method of Nanometer Copper antibacterial granule |
| CN106392097A (en) * | 2016-09-29 | 2017-02-15 | 武汉科技大学 | Cu-Ag bimetallic nano material, preparation method and application thereof |
| KR102064464B1 (en) * | 2018-02-13 | 2020-01-10 | 포항공과대학교 산학협력단 | Method of manufacturing nanoparticles containing Au, copper core and silica shell |
| CN108552221A (en) * | 2018-04-11 | 2018-09-21 | 石狮纳通新材料科技有限公司 | A kind of copper selenide nanometer material preparation method and antibacterial applications near infrared absorption characteristic |
| CN109819979A (en) * | 2019-03-15 | 2019-05-31 | 尚蒙科技无锡有限公司 | Nano silver copper bimetallic colloid/liquid of high anti-microbial property and preparation method thereof |
| CN110051837A (en) * | 2019-04-08 | 2019-07-26 | 南京师范大学 | A kind of CuO/ZnO/Au nanoparticle and its preparation method and application |
| CN110854396A (en) * | 2019-11-07 | 2020-02-28 | 南京师范大学 | PtAg nanocrystalline with porous double-hollow-sphere structure and preparation method and application thereof |
| CN111909691A (en) * | 2020-06-23 | 2020-11-10 | 南京师范大学 | Preparation method of photo-thermal antibacterial near-infrared carbon quantum dots, product and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| RENATA DOBRUCKA等: "Evaluation of biologically synthesized Au-CuO and CuO-ZnO nanoparticles against glioma cells and microorganisms", 《SAUDI PHARMACEUTICAL JOURNAL》 * |
| 何杰，薛茹君主编: "《工业催化》", 31 August 2014 * |
| 李培义等: "微波加热法所制Ag/Cu双金属纳米粒子的表征及其抗菌性能分析", 《武汉科技大学学报》 * |
| 高雷等: "金-铜纳米粒子的简易制备及其对亚硝酸盐的电化学传感性能的研究", 《江西科技师范大学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113827613A (en) * | 2021-10-19 | 2021-12-24 | 天津大学 | Atomic precision cluster enzyme, preparation and application thereof in nervous system diseases |
| CN114451511A (en) * | 2022-01-05 | 2022-05-10 | 华南理工大学 | Antibacterial nano-particles and preparation method and application thereof |
| CN114451511B (en) * | 2022-01-05 | 2023-09-26 | 华南理工大学 | Antibacterial nano-particles and preparation method and application thereof |
| CN114452386A (en) * | 2022-01-14 | 2022-05-10 | 江苏大学 | Preparation method and application of gold-copper bimetallic nano-enzyme composite material |
| CN114452386B (en) * | 2022-01-14 | 2023-10-10 | 江苏大学 | Preparation method and application of gold-copper bimetallic nano enzyme composite material |
| CN114711251A (en) * | 2022-03-25 | 2022-07-08 | 扬州大学 | Titanium carbide-manganese sulfide composite bacteriostatic material, preparation method thereof and bacteriostatic method |
| CN114711251B (en) * | 2022-03-25 | 2024-01-19 | 扬州大学 | Titanium carbide-manganese sulfide composite antibacterial material, preparation method thereof and antibacterial method |
| CN115300482A (en) * | 2022-08-17 | 2022-11-08 | 山东大学 | Bovine serum albumin coated chlorhexidine loaded nickel phosphide nano-capsule, preparation method and antibacterial application thereof |
| CN115300482B (en) * | 2022-08-17 | 2023-11-28 | 山东大学 | Bovine serum albumin coated chlorhexidine loaded nickel phosphide nanocapsule, preparation method and antibacterial application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113016823B (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113016823B (en) | Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles | |
| Hu et al. | In situ fabrication of ultrasmall gold nanoparticles/2D MOFs hybrid as nanozyme for antibacterial therapy | |
| Shan et al. | Cu2MoS4 nanozyme with NIR‐II light enhanced catalytic activity for efficient eradication of multidrug‐resistant bacteria | |
| Zhang et al. | Near-infrared-triggered antibacterial and antifungal photodynamic therapy based on lanthanide-doped upconversion nanoparticles | |
| CN114306382B (en) | Copper-based nanoenzyme as well as preparation method and application thereof | |
| Zhang et al. | Constructing a highly efficient CuS/Cu9S5 heterojunction with boosted interfacial charge transfer for near-infrared photocatalytic disinfection | |
| Padma et al. | Studies on green synthesis of copper nanoparticles using Punica granatum | |
| Naskar et al. | Black phosphorus nanomaterials as multi-potent and emerging platforms against bacterial infections | |
| JP2011514883A (en) | Silver nanoparticles having specific surface area and method for producing the same | |
| Roberson et al. | Synthesis and characterization silver, zinc oxide and hybrid silver/zinc oxide nanoparticles for antimicrobial applications | |
| CN105596367A (en) | Nano-silver antibacterial gel with chitosan-poloxamer as gel matrix and preparation method and application of nano-silver antibacterial gel | |
| CN113234436B (en) | Near-infrared carbon quantum dot/silicon dioxide composite material and preparation method and application thereof | |
| Guo et al. | A bifunctional nanoplatform based on copper manganate nanoflakes for bacterial elimination via a catalytic and photothermal synergistic effect | |
| Qie et al. | Design, synthesis, and application of carbon dots with synergistic antibacterial activity | |
| CN110051837A (en) | A kind of CuO/ZnO/Au nanoparticle and its preparation method and application | |
| Momeni et al. | Antimicrobial effect of silver nanoparticles synthesized with Bougainvillea glabra extract on staphylococcus aureus and Escherichia Coli | |
| Wang et al. | A biodegradable and near-infrared light-activatable photothermal nanoconvertor for bacterial inactivation | |
| Toiserkani | Fabrication and characterization chitosan/functionalized zinc oxide bionanocomposites and study of their antibacterial activity | |
| Uzair et al. | Targeting microbial biofilms: by Arctium lappa l. synthesised biocompatible CeO2‐NPs encapsulated in nano‐chitosan | |
| CN111066784A (en) | Ag/AgCl/cellulose composite antibacterial material and preparation method and application thereof | |
| CN112209445B (en) | Preparation method and application of molybdenum trioxide nanodot antibacterial material | |
| Delgado-Beleño et al. | Characterization of silver nanoparticles encapsulated using an ion-exchange-mediated method and their application as antimicrobial agents | |
| Hussain et al. | Green synthesis of silver nanoparticles prepared by leaves extract of Trigonila foenum-graecum and its antibacterial potential against Escherichia coli and Pseudomonas aeruginosa | |
| Mizerska et al. | Bacterial cell killing properties of silver-loaded polysiloxane microspheres | |
| CN111228488A (en) | Preparation method of LDH-Ce6-Ag nano composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |