CN109497088B - Near-infrared light response antibacterial agent and preparation method thereof - Google Patents
Near-infrared light response antibacterial agent and preparation method thereof Download PDFInfo
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- CN109497088B CN109497088B CN201811611971.4A CN201811611971A CN109497088B CN 109497088 B CN109497088 B CN 109497088B CN 201811611971 A CN201811611971 A CN 201811611971A CN 109497088 B CN109497088 B CN 109497088B
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 42
- 230000004298 light response Effects 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title description 9
- 239000010936 titanium Substances 0.000 claims abstract description 130
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 119
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 118
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002105 nanoparticle Substances 0.000 claims abstract description 72
- 239000002086 nanomaterial Substances 0.000 claims abstract description 71
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010931 gold Substances 0.000 claims abstract description 48
- 229910052737 gold Inorganic materials 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 235000013024 sodium fluoride Nutrition 0.000 claims description 12
- 239000011775 sodium fluoride Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- NBSLDXHEXGYVEP-UHFFFAOYSA-N erbium(3+) trinitrate hydrate Chemical compound O.[Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O NBSLDXHEXGYVEP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052753 mercury Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- CSMODXNYVLLZNJ-UHFFFAOYSA-N ytterbium(3+) trinitrate hydrate Chemical compound O.[Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CSMODXNYVLLZNJ-UHFFFAOYSA-N 0.000 claims description 6
- WUVRZBFIXJWTGS-UHFFFAOYSA-N yttrium(3+);trinitrate;hydrate Chemical compound O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WUVRZBFIXJWTGS-UHFFFAOYSA-N 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 244000052616 bacterial pathogen Species 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- 206010019280 Heart failures Diseases 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 206010040070 Septic Shock Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000036303 septic shock Effects 0.000 description 1
- 208000026775 severe diarrhea Diseases 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
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Abstract
A method for preparing a near-infrared light-responsive antibacterial agent comprises the following steps: step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method; step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles; 3, wrapping the trivalent titanium doped titanium oxide nano material modified by the gold nano particles by using an up-conversion material; the composite material contains the up-conversion material, the up-conversion material can convert near infrared light into visible light and ultraviolet light, the doping of trivalent titanium and the modification of gold nanoparticles can convert TiO into2The photoresponse range of the invention is expanded to a visible light region, so that visible/ultraviolet light emitted by the up-conversion material is efficiently absorbed, and the photocatalytic antibacterial effect of the invention in deep biological tissues is finally realized.
Description
Technical Field
The invention belongs to the technical field of photocatalytic antibacterial, and particularly relates to a near-infrared light response antibacterial agent and a preparation method thereof.
Background
Bacteria are important microorganisms, and some pathogenic bacteria seriously threaten the life health of people: pathogenic bacteria can invade the blood circulation of the human body through wounds, and cause systemic complications such as septic shock, heart failure and the like. Such as pathogenic escherichia coli, can enter the intestinal organs of human bodies through food and water environments and the like, cause severe diarrhea and even directly cause death.
TiO2Is a photocatalytic inorganic antibacterial agent, such as TiO2After absorbing ultraviolet light with the wavelength of less than 387nm, valence band electrons are excited to a conduction band to become electrons e with higher activity-Simultaneously, forming a band on the valence bandPositive hole h+(ii) a The highly active electrons are capable of reacting with O in solution2Formation of superoxide radical O2 -At the same time, the hole and H2O reacts to generate hydroxyl radical OH; these reactive oxygen species first destroy the cell wall of the bacteria, causing the overall structure of the bacteria to be destroyed; after the cell wall is destroyed, the active species can easily pass through the cell membrane, and the phosphodiester bond between DNA bases is cut off, so that the double helix structure of the DNA is destroyed, and the reproduction of bacteria is influenced. The photocatalytic inorganic antibacterial agent has wide antibacterial spectrum, does not generate bacterial drug resistance, and is an antibacterial agent with great potential.
At present, TiO2Photocatalytic antimicrobial agents have achieved a number of excellent results, however they still have certain limitations; for example, chinese patent CN201010609018.3 discloses an antibacterial agent with bactericidal effect under indoor conventional light source, however, the indoor conventional light source belongs to visible light, its penetration depth is limited, and it cannot realize antibacterial effect in deep biological tissue.
Disclosure of Invention
The invention provides a near-infrared light responsive antibacterial agent and a preparation method thereof, which can effectively react TiO with the antibacterial agent2The photoresponse range of the nano titanium dioxide is expanded to a near infrared region, the photocatalytic antibacterial effect of the nano titanium dioxide in deep biological tissues is realized, and the technical scheme is as follows:
the antibacterial agent is a composite material consisting of an up-conversion material and a gold nanoparticle modified trivalent titanium doped titanium oxide nano material, wherein the trivalent titanium doped titanium oxide nano material is a trivalent titanium doped titanium oxide nano particle, a gold nanoparticle is attached to the outside of the trivalent titanium doped titanium oxide nano particle to form a gold nanoparticle modified trivalent titanium doped titanium oxide nano particle, and the up-conversion particle is wrapped on the outside of the gold nanoparticle modified trivalent titanium doped titanium oxide nano particle.
The titanium in the titanium oxide nano material doped with trivalent titanium exists in the form of trivalent titanium and tetravalent titanium in TiO2In the crystal lattice, Ti is formed3+-O-Ti4+And (5) structure.
The photoresponse range of the antibacterial agent is 900-1100 nm.
The preparation method of the near-infrared light response antibacterial agent comprises the following steps:
step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method;
step 1.1, placing titanium dioxide in a hydrogen atmosphere for calcination at the temperature of 500-700 ℃ for 0.5-3 h to obtain a titanium oxide nano material doped with trivalent titanium;
step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles;
step 2.1, placing the titanium oxide nano material doped with the trivalent titanium into a chloroauric acid solution with the concentration of 0.5-5.0 mmol/L, and sufficiently stirring in a dark place to obtain a mixture A;
step 2.2, centrifuging the mixture A, removing supernatant, and dispersing in deionized water again to obtain a mixture B;
step 2.3, placing the mixture B under a mercury lamp for irradiating for 15-30 min, washing the obtained product with deionized water, and obtaining a gold nanoparticle modified titanium dioxide nano material doped with trivalent titanium;
3, wrapping the trivalent titanium doped titanium oxide nano material modified by the gold nano particles by using an up-conversion material;
step 3.1, dissolving yttrium nitrate hydrate, ytterbium nitrate hydrate, erbium nitrate hydrate and urea in water according to (0.75-0.80)% w, (0.15-0.20)% wt, (0.01-0.05)% wt and 1.5-3% wt, and stirring until the materials are fully mixed to obtain a mixture C;
step 3.2, adding the gold-modified trivalent titanium doped titanium oxide nano material into the mixture C, fully stirring, heating to react the mixture C with the gold-modified trivalent titanium doped titanium oxide nano material, wherein the reaction temperature is 70-90 ℃, the heating time is 2-3 hours, and naturally cooling to room temperature after the reaction is finished to obtain a mixture D;
3.3, cleaning the mixture D with deionized water, transferring the mixture D into an oven for drying, and then calcining the mixture D at the calcining temperature of 400-800 ℃ for 2-3 h to obtain a mixture E;
and 3.4, transferring the mixed solution of sodium fluoride, hydrofluoric acid and deionized water into a hydrothermal reaction kettle, wherein the concentration of the sodium fluoride is 0.1mol/L, the concentration of the hydrofluoric acid is 0.6-1% by weight, adding the mixture E into the hydrothermal reaction kettle, reacting for 2-4 hours at 80-100 ℃, naturally cooling a product obtained by the reaction to room temperature, and then centrifugally washing and drying to obtain the near-infrared light response antibacterial agent.
The drying temperature in the step 3.4 is 60-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the composite material contains an up-conversion material, and the up-conversion material can convert near infrared light into visible light and ultraviolet light; doping of trivalent titanium and modification of gold nanoparticles can convert TiO into2The photoresponse range of the invention is expanded to a visible light region, so that visible/ultraviolet light emitted by the up-conversion material is efficiently absorbed, and the photocatalytic antibacterial effect of the invention in deep biological tissues is finally realized.
Drawings
FIG. 1 is an X-ray diffraction pattern of a trivalent titanium doped titanium oxide nanomaterial modified with gold nanoparticles composited with an upconverting material;
fig. 2 is a transmission electron microscope image of the up-conversion material composite trivalent titanium doped titanium oxide nanomaterial modified by gold nanoparticles under different resolutions.
Detailed Description
Example 1
As shown in figures 1 and 2, the invention provides a near-infrared light response antibacterial agent, the light response range of which is 900-1100 nm; the antibacterial agent is a composite material consisting of an up-conversion material and a gold nanoparticle modified trivalent titanium doped titanium oxide nano material, wherein the trivalent titanium doped titanium oxide nano material is a trivalent titanium doped titanium oxide nano particle, a gold nanoparticle is attached to the outside of the trivalent titanium doped titanium oxide nano particle to form a gold nanoparticle modified trivalent titanium doped titanium oxide nano particle, and the up-conversion particle is wrapped on the outside of the gold nanoparticle modified trivalent titanium doped titanium oxide nano particle.
The titanium in the titanium oxide nano material doped with trivalent titanium exists in the form of trivalent titanium and tetravalent titanium in TiO2In the crystal lattice, Ti is formed3+-O-Ti4+And (5) structure.
The photoresponse range of the antibacterial agent is 900-1100 nm.
The preparation method of the near-infrared light response antibacterial agent comprises the following steps:
step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method;
step 1.1, placing titanium dioxide in a hydrogen atmosphere for calcination, wherein the calcination temperature is 600 ℃, and the calcination time is 2 hours, so as to obtain a titanium oxide nano material doped with trivalent titanium;
step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles;
step 2.1, dispersing 0.01g of trivalent titanium doped titanium oxide nano material in a chloroauric acid solution with the concentration of 2mmol/L, and sufficiently stirring for 12 hours in a dark place to obtain a mixture A;
step 2.2, centrifuging the mixture A, removing supernatant, and dispersing in 10ml of deionized water again to obtain a mixture B;
step 2.3, placing the mixture B under a mercury lamp for irradiating for 30min, washing the obtained product with deionized water, and obtaining the gold nanoparticle modified trivalent titanium doped titanium oxide nano material;
3, wrapping the trivalent titanium doped titanium oxide nano material modified by the gold nano particles by using an up-conversion material;
step 3.1, 0.75 percent of yttrium nitrate hydrate, ytterbium nitrate hydrate and erbium nitrate hydrate by weight; 0.20% wt; dissolving 0.05 wt% of urea in 100ml of deionized water, stirring until the urea is fully mixed, and adding 1.5g of urea into the solution to obtain a mixture C;
step 3.2, adding the gold-modified trivalent titanium doped titanium oxide nano material into the mixture C, fully stirring, heating to react the mixture C with the gold-modified trivalent titanium doped titanium oxide nano material at the temperature of 70 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is finished to obtain a mixture D;
3.3, cleaning the mixture D with deionized water, transferring the mixture D into an oven for drying, and then calcining the mixture D at the calcining temperature of 600 ℃ for 2 hours to obtain a mixture E;
and 3.4, transferring the mixed solution of sodium fluoride, hydrofluoric acid and deionized water into a hydrothermal reaction kettle, wherein the concentration of the sodium fluoride is 0.1mol/L, the concentration of the hydrofluoric acid is 0.6 wt%, adding the mixture E, reacting for 2 hours at 80 ℃, naturally cooling a product obtained by the reaction to room temperature, centrifugally washing, and drying at 60 ℃ to obtain the near-infrared light response antibacterial agent.
2.0mL of 1.0X 105And (3) adding the Escherichia coli liquid of CFU/mL into a quartz cup, and then adding 1.0mg of gold-modified trivalent titanium doped titanium dioxide material wrapped by the upconversion material. After stirring well, the mixture is treated with a 980nm laser (0.68W/cm)2) Samples were taken by irradiation for 60 min. 100 mu L of the diluted 100-fold bacterial liquid is dispersed on a solid culture medium and cultured for 24h at 37 ℃ to calculate the number of colonies, and then the sterilization efficiency is calculated to be more than 99.9 percent according to the number of the colonies. The experiment uses the untreated bacteria liquid as a blank, and each group of data is measured for three times on average to obtain an average value and calculate the error.
Example 2
As shown in figures 1 and 2, the invention provides a near-infrared light response antibacterial agent, the light response range of which is 900-1100 nm; the antibacterial agent is a composite material consisting of an up-conversion material and a gold nanoparticle modified trivalent titanium doped titanium oxide nano material, wherein the trivalent titanium doped titanium oxide nano material is a trivalent titanium doped titanium oxide nano particle, a gold nanoparticle is attached to the outside of the trivalent titanium doped titanium oxide nano particle to form a gold nanoparticle modified trivalent titanium doped titanium oxide nano particle, and the up-conversion particle is wrapped on the outside of the gold nanoparticle modified trivalent titanium doped titanium oxide nano particle.
The titanium in the titanium oxide nano material doped with trivalent titanium exists in the form of trivalent titanium and tetravalent titanium in TiO2In the crystal lattice, Ti is formed3+-O-Ti4+And (5) structure.
The photoresponse range of the antibacterial agent is 900-1100 nm.
The preparation method of the near-infrared light response antibacterial agent comprises the following steps:
step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method;
step 1.1, placing titanium dioxide in a hydrogen atmosphere for calcination, wherein the calcination temperature is 600 ℃, and the calcination time is 2 hours, so as to obtain a titanium oxide nano material doped with trivalent titanium;
step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles;
step 2.1, dispersing 0.01g of trivalent titanium doped titanium oxide nano material in a chloroauric acid solution with the concentration of 2mmol/L, and sufficiently stirring for 12 hours in a dark place to obtain a mixture A;
step 2.2, centrifuging the mixture A, removing supernatant, and dispersing in 10ml of deionized water again to obtain a mixture B;
step 2.3, placing the mixture B under a mercury lamp for irradiating for 30min, washing the obtained product with deionized water, and obtaining the gold nanoparticle modified trivalent titanium doped titanium oxide nano material;
3, wrapping the trivalent titanium doped titanium oxide nano material modified by the gold nano particles by using an up-conversion material;
step 3.1, 0.75 percent of yttrium nitrate hydrate, ytterbium nitrate hydrate and erbium nitrate hydrate by weight; 0.20% wt; dissolving 0.05 wt% of urea in 100ml of deionized water, stirring until the urea is fully mixed, and adding 1.5g of urea into the solution to obtain a mixture C;
step 3.2, adding the gold-modified trivalent titanium doped titanium oxide nano material into the mixture C, fully stirring, heating to react the mixture C with the gold-modified trivalent titanium doped titanium oxide nano material at the temperature of 70 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is finished to obtain a mixture D;
3.3, cleaning the mixture D with deionized water, transferring the mixture D into an oven for drying, and then calcining the mixture D at the calcining temperature of 600 ℃ for 2 hours to obtain a mixture E;
and 3.4, transferring the mixed solution of sodium fluoride, hydrofluoric acid and deionized water into a hydrothermal reaction kettle, wherein the concentration of the sodium fluoride is 0.1mol/L, the concentration of the hydrofluoric acid is 0.6 wt%, adding the mixture E, reacting for 2 hours at 80 ℃, naturally cooling a product obtained by the reaction to room temperature, then centrifugally washing and drying at 60 ℃ to obtain the near-infrared light response antibacterial agent.
2.0mL of 1.0X 105And (3) adding the CFU/mL methicillin-resistant staphylococcus aureus liquid into a quartz cup, and then adding 1.0mg of gold-modified trivalent titanium doped titanium oxide material wrapped by the up-conversion material. After stirring well, the mixture is treated with a 980nm laser (0.68W/cm)2) Samples were taken by irradiation for 60 min. 100 mu L of the diluted 100-fold bacterial liquid is dispersed on a solid culture medium and cultured for 24h at 37 ℃ to calculate the number of colonies, and then the sterilization efficiency is calculated to be more than 99.9 percent according to the number of the colonies. The experiment uses the untreated bacteria liquid as a blank, and each group of data is measured for three times on average to obtain an average value and calculate the error.
Example 3
The invention provides a near-infrared light response antibacterial agent, wherein the light response range is 900-1100 nm; the antibacterial agent is a composite material consisting of an up-conversion material and a gold nanoparticle modified trivalent titanium doped titanium oxide nano material, wherein the trivalent titanium doped titanium oxide nano material is a trivalent titanium doped titanium oxide nano particle, a gold nanoparticle is attached to the outside of the trivalent titanium doped titanium oxide nano particle to form a gold nanoparticle modified trivalent titanium doped titanium oxide nano particle, and the up-conversion particle is wrapped on the outside of the gold nanoparticle modified trivalent titanium doped titanium oxide nano particle.
The titanium in the titanium oxide nano material doped with trivalent titanium exists in the form of trivalent titanium and tetravalent titanium in TiO2In the crystal lattice, Ti is formed3+-O-Ti4+And (5) structure.
The photoresponse range of the antibacterial agent is 900-1100 nm.
The preparation method of the near-infrared light response antibacterial agent comprises the following steps:
step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method;
step 1.1, placing titanium dioxide in a hydrogen atmosphere for calcination at 500 ℃ for 0.5h to obtain a titanium oxide nano material doped with trivalent titanium;
step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles;
step 2.1, dispersing 0.01g of trivalent titanium doped titanium oxide nano material in a chloroauric acid solution with the concentration of 0.5mmol/L, and sufficiently stirring for 12 hours in a dark place to obtain a mixture A;
step 2.2, centrifuging the mixture A, removing supernatant, and dispersing in 10ml of deionized water again to obtain a mixture B;
step 2.3, placing the mixture B under a mercury lamp for irradiating for 15min, washing the obtained product with deionized water, and obtaining a gold nanoparticle modified titanium dioxide nano material doped with trivalent titanium;
3, wrapping the trivalent titanium doped titanium oxide nano material modified by the gold nano particles by using an up-conversion material;
step 3.1, 0.70 wt% of yttrium nitrate hydrate, ytterbium nitrate hydrate and erbium nitrate hydrate; 0.28% wt; dissolving 0.02 wt% in 100ml of deionized water, stirring until the mixture is fully mixed, and then adding 1.5g of urea into the solution to obtain a mixture C;
step 3.2, adding the gold-modified trivalent titanium doped titanium oxide nano material into the mixture C, fully stirring, heating to react the mixture C with the gold-modified trivalent titanium doped titanium oxide nano material at 90 ℃ for 3 hours, and naturally cooling to room temperature after the reaction is finished to obtain a mixture D;
3.3, cleaning the mixture D with deionized water, transferring the mixture D into an oven for drying, and then calcining the mixture D at 400 ℃ for 2 hours to obtain a mixture E;
and 3.4, transferring the mixed solution of sodium fluoride, hydrofluoric acid and deionized water into a hydrothermal reaction kettle, wherein the concentration of the sodium fluoride is 0.1mol/L, the concentration of the hydrofluoric acid is 1% wt, adding the mixture E, reacting for 4 hours at 100 ℃, naturally cooling a product obtained by the reaction to room temperature, then centrifugally washing and drying at 60 ℃ to obtain the near-infrared light response antibacterial agent.
2.0mL of 1.0X 105And (3) adding the Escherichia coli liquid of CFU/mL into a quartz cup, and then adding 1.0mg of gold-modified trivalent titanium doped titanium dioxide material wrapped by the upconversion material. After stirring well, the mixture is treated with a 980nm laser (0.68W/cm)2) Samples were taken by irradiation for 60 min. 100 mu L of the diluted 100-fold bacterial liquid is dispersed on a solid culture medium and cultured for 24h at 37 ℃ to calculate the number of colonies, and then the sterilization efficiency is calculated to be more than 99.9 percent according to the number of the colonies. The experiment uses the untreated bacteria liquid as a blank, and each group of data is measured for three times on average to obtain an average value and calculate the error.
Example 4
The invention provides a near-infrared light response antibacterial agent, wherein the light response range is 900-1100 nm; the antibacterial agent is a composite material consisting of an up-conversion material and a gold nanoparticle modified trivalent titanium doped titanium oxide nano material, wherein the trivalent titanium doped titanium oxide nano material is a trivalent titanium doped titanium oxide nano particle, a gold nanoparticle is attached to the outside of the trivalent titanium doped titanium oxide nano particle to form a gold nanoparticle modified trivalent titanium doped titanium oxide nano particle, and the up-conversion particle is wrapped on the outside of the gold nanoparticle modified trivalent titanium doped titanium oxide nano particle.
The titanium in the titanium oxide nano material doped with trivalent titanium exists in the form of trivalent titanium and tetravalent titanium in TiO2In the crystal lattice, Ti is formed3+-O-Ti4+And (5) structure.
The photoresponse range of the antibacterial agent is 900-1100 nm.
The preparation method of the near-infrared light response antibacterial agent comprises the following steps:
step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method;
step 1.1, placing titanium dioxide in a hydrogen atmosphere for calcination, wherein the calcination temperature is 700 ℃, and the calcination time is 3 hours, so as to obtain a titanium oxide nano material doped with trivalent titanium;
step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles;
step 2.1, dispersing 0.01g of trivalent titanium doped titanium oxide nano material in 5mmol/L chloroauric acid solution, and stirring for 12 hours in a dark place to obtain a mixture A;
step 2.2, centrifuging the mixture A, removing supernatant, and dispersing in 10ml of deionized water again to obtain a mixture B;
step 2.3, placing the mixture B under a mercury lamp for irradiating for 20min, washing the obtained product with deionized water, and obtaining the gold nanoparticle modified trivalent titanium doped titanium oxide nano material;
3, wrapping the trivalent titanium doped titanium oxide nano material modified by the gold nano particles by using an up-conversion material;
step 3.1, 0.78 wt% of yttrium nitrate hydrate, ytterbium nitrate hydrate and erbium nitrate hydrate; 0.17% wt; dissolving 0.05 wt% of urea in 100ml of deionized water, stirring until the urea is fully mixed, and adding 1.5g of urea into the solution to obtain a mixture C;
step 3.2, adding the gold-modified trivalent titanium doped titanium oxide nano material into the mixture C, fully stirring, heating to react the mixture C with the gold-modified trivalent titanium doped titanium oxide nano material at the temperature of 80 ℃ for 2.5 hours, and naturally cooling to room temperature after the reaction is finished to obtain a mixture D;
3.3, cleaning the mixture D with deionized water, transferring the mixture D into an oven for drying, and then calcining the mixture D at 800 ℃ for 2.5 hours to obtain a mixture E;
and 3.4, transferring the mixed solution of sodium fluoride, hydrofluoric acid and deionized water into a hydrothermal reaction kettle, wherein the concentration of the sodium fluoride is 0.1mol/L, the concentration of the hydrofluoric acid is 0.8 wt%, adding the mixture E, reacting for 3 hours at 90 ℃, naturally cooling a product obtained by the reaction to room temperature, then centrifugally washing and drying at 60 ℃ to obtain the near-infrared light response antibacterial agent.
2.0mL of 1.0X 105Adding the Escherichia coli liquid of CFU/mL into a quartz cup, and then adding 1.0mg of upconversion material for wrappingThe gold-modified trivalent titanium doped titanium oxide material. After stirring well, the mixture is treated with a 980nm laser (0.68W/cm)2) Samples were taken by irradiation for 60 min. 100 mu L of the diluted 100-fold bacterial liquid is dispersed on a solid culture medium and cultured for 24h at 37 ℃ to calculate the number of colonies, and then the sterilization efficiency is calculated to be more than 99.9 percent according to the number of the colonies. The experiment uses the untreated bacteria liquid as a blank, and each group of data is measured for three times on average to obtain an average value and calculate the error.
The above examples are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above examples, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (5)
1. The near-infrared light response antibacterial agent is characterized in that the antibacterial agent is a composite material formed by an up-conversion material and a gold nanoparticle modified trivalent titanium doped titanium oxide nano material, the trivalent titanium doped titanium oxide nano material is trivalent titanium doped titanium oxide nano particles, gold nanoparticles are attached to the outside of the trivalent titanium doped titanium oxide nano particles to form gold nanoparticle modified trivalent titanium doped titanium oxide nano particles, and up-conversion particles wrap the outside of the gold nanoparticle modified trivalent titanium doped titanium oxide nano particles.
2. The near-infrared light-responsive antibacterial agent according to claim 1, wherein the titanium in the trivalent titanium-doped titanium oxide nanomaterial is present in the form of trivalent titanium and tetravalent titanium in the TiO2In the crystal lattice, Ti is formed3+-O-Ti4+And (5) structure.
3. The near-infrared light-responsive antibacterial agent according to claim 1, wherein the antibacterial agent has a light-responsive range of 900 to 1100 nm.
4. A method for producing a near-infrared light-responsive antibacterial agent according to any one of claims 1 to 3, characterized by comprising the steps of:
step 1, preparing a titanium oxide nano material doped with trivalent titanium by adopting a hydrogen reduction method;
step 1.1, placing titanium dioxide in a hydrogen atmosphere for calcination at the temperature of 500-700 ℃ for 0.5-3 h to obtain a titanium oxide nano material doped with trivalent titanium;
step 2, modifying the titanium oxide nano material doped with trivalent titanium by using gold nano particles;
step 2.1, placing the titanium oxide nano material doped with the trivalent titanium into a chloroauric acid solution with the concentration of 0.5-5.0 mmol/L, and sufficiently stirring in a dark place to obtain a mixture A;
step 2.2, centrifuging the mixture A, removing supernatant, and dispersing in deionized water again to obtain a mixture B;
step 2.3, placing the mixture B under a mercury lamp for irradiating for 15-30 min, washing the obtained product with deionized water, and obtaining a gold nanoparticle modified titanium dioxide nano material doped with trivalent titanium;
3, wrapping the gold nanoparticle modified trivalent titanium doped titanium oxide nano material with an up-conversion material;
step 3.1, dissolving yttrium nitrate hydrate, ytterbium nitrate hydrate, erbium nitrate hydrate and urea in water according to (0.75-0.80)% w, (0.15-0.20)% wt, (0.01-0.05)% wt and 1.5-3% wt, and stirring until the materials are fully mixed to obtain a mixture C;
step 3.2, adding the gold-modified trivalent titanium doped titanium oxide nano material into the mixture C, fully stirring, heating to react the mixture C with the gold-modified trivalent titanium doped titanium oxide nano material at the temperature of 70-90 ℃ for 2-3 hours, and naturally cooling to room temperature after the reaction is finished to obtain a mixture D;
3.3, cleaning the mixture D with deionized water, transferring the mixture D into an oven for drying, and then calcining the mixture D at the calcining temperature of 400-800 ℃ for 2-3 h to obtain a mixture E;
and 3.4, transferring the mixed solution of sodium fluoride, hydrofluoric acid and deionized water into a hydrothermal reaction kettle, wherein the concentration of the sodium fluoride is 0.1mol/L, the concentration of the hydrofluoric acid is 0.6-1% by weight, adding the mixture E into the hydrothermal reaction kettle, reacting for 2-4 hours at 80-100 ℃, naturally cooling a product obtained by the reaction to room temperature, and then centrifugally washing and drying to obtain the near-infrared light response antibacterial agent.
5. The method for preparing a near-infrared light-responsive antibacterial agent according to claim 4, wherein the drying temperature in the step 3.4 is 60-80 ℃.
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