CN109497088A - A kind of antibacterial agent and preparation method thereof of near infrared light response - Google Patents
A kind of antibacterial agent and preparation method thereof of near infrared light response Download PDFInfo
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- CN109497088A CN109497088A CN201811611971.4A CN201811611971A CN109497088A CN 109497088 A CN109497088 A CN 109497088A CN 201811611971 A CN201811611971 A CN 201811611971A CN 109497088 A CN109497088 A CN 109497088A
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- trivalent
- titanium
- titanium dioxide
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 41
- 230000004298 light response Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 171
- 239000010936 titanium Substances 0.000 claims abstract description 104
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 92
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 69
- 239000002086 nanomaterial Substances 0.000 claims abstract description 65
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052737 gold Inorganic materials 0.000 claims abstract description 57
- 239000010931 gold Substances 0.000 claims abstract description 57
- 239000002105 nanoparticle Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000012986 modification Methods 0.000 claims abstract description 48
- 230000004048 modification Effects 0.000 claims abstract description 48
- 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 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 66
- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- ISEXWJYBJMXWCC-UHFFFAOYSA-N erbium;hydrate Chemical compound O.[Er] ISEXWJYBJMXWCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 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
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- AFUKLFQBWVGSJH-UHFFFAOYSA-N ytterbium;hydrate Chemical compound O.[Yb] AFUKLFQBWVGSJH-UHFFFAOYSA-N 0.000 claims description 6
- BEDFIBPNPHRGDO-UHFFFAOYSA-N yttrium;hydrate Chemical compound O.[Y] BEDFIBPNPHRGDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 4
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000002068 microbial inoculum Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 241000894006 Bacteria Species 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 11
- 235000013339 cereals Nutrition 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000002070 germicidal effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000005070 sampling Methods 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
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 229910003087 TiOx Inorganic materials 0.000 description 3
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 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
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000369 enteropathogenic effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
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Abstract
A kind of preparation method of the antibacterial agent of near infrared light response, comprising the following steps: step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；Step 3 wraps up the titanium dioxide nano material titanium doped by the trivalent of gold nano particle modification with up-conversion；Contain up-conversion in composite material of the invention, near infrared light can be converted into visible light and ultraviolet light by up-conversion, and the doping of titanous and the modification of gold nano grain can be by TiO2Optical response range expand to visible region, thus visible/ultraviolet light that efficient absorption up-conversion issues, the final photocatalysis antibacterial effect for realizing the present invention in deep layer biological tissue.
Description
Technical field
The invention belongs to photocatalysis antibacterial technical fields, and in particular to a kind of antibacterial agent of near infrared light response and its preparation
Method.
Background technique
A kind of important microorganism of bacterium, some pathogenic bacterias seriously threaten the life and health of people: pathogenic thin
Bacterium can invade the blood circulation of human body by wound, cause systemic complication, such as infectious shock, heart failure.
Such as enteropathogenic E. Coli, the enteron aisle organ of human body can be entered by approach such as food and water environments, causes serious abdomen
Rush down or even can directly result in death.
TiO2It is a kind of photocatalyst-type inorganic antiseptic, works as TiO2After absorbing ultraviolet light of the wavelength less than 387nm, valence band
Electronics, which is excited to conduction band, becomes the electronics e with greater activity-, meanwhile, positively charged hole h is formed in valence band+；High activity
Electronics can be with the O in solution2Generate superoxide radical O2 -, meanwhile, hole and H2O reaction generates hydroxyl radical free radical OH；
These active oxygen species destroy the cell wall of bacterium first, are destroyed the overall structure of bacterium；After cell wall is destroyed, activity
Species can readily pass through cell membrane, cut off the phosphodiester bond between DNA base, the double-spiral structure of DNA is caused to be destroyed,
Influence the breeding of bacterium.Photocatalyst-type inorganic antiseptic has a broad antifungal spectrum, will not generate bacterial drug resistance, be a kind of with huge latent
The antibacterial agent of power.
Currently, TiO2Photocatalysis antibacterial agent has been achieved for many outstanding achievements, however its there are still certain limitations；
If Chinese patent CN201010609018.3 discloses the antibacterial agent that can have bactericidal effect under a kind of indoor conventional lighting sources, so
And indoor conventional lighting sources belong to visible light, penetration depth is limited, cannot achieve the antibacterial in deep layer biological tissue.
Summary of the invention
The present invention provides a kind of antibacterial agents and preparation method thereof of near infrared light response, can be effectively by TiO2Light ring
It answers range to expand to near-infrared region, realizes photocatalysis antibacterial effect of the nano-titanium dioxide in deep layer biological tissue, technology
Scheme is as follows:
A kind of antibacterial agent of near infrared light response, the antibacterial agent is the trivalent of up-conversion and gold nano particle modification
The composite material of titanium doped titanium dioxide nano material composition, the titanium doped titanium dioxide nano material of the trivalent are mixed for titanous
Miscellaneous titanium oxide nanoparticles, the titanium doped titanium oxide nanoparticles of trivalent are attached with gold nanoparticle outside, form Jenner's grain of rice
The titanium doped titanium oxide nanoparticles of the trivalent of son modification, the titanium doped TiOx nano of the trivalent of the gold nanoparticle modification
Conversion particles are enclosed on the outside of particle.
Titanium in the titanium doped titanium dioxide nano material of the trivalent is present in TiO in the form of titanous and titanic2
In lattice, Ti is formed3+-O-Ti4+Structure.
The optical response range of the antibacterial agent is 900~1100nm.
A kind of preparation method of the antibacterial agent of near infrared light response above-mentioned, comprising the following steps:
Step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；
Titanium dioxide is placed in hydrogen atmosphere and calcines by step 1.1, and calcination temperature is 500~700 DEG C, and calcination time is
0.5~3h obtains the titanium doped titanium dioxide nano material of trivalent；
Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；
The titanium doped titanium dioxide nano material of trivalent is placed in the gold chloride that concentration is 0.5~5.0mmol/L by step 2.1
It in solution, is protected from light and is sufficiently stirred, obtain mixture A；
Mixture A is centrifuged by step 2.2, after abandoning supernatant, is dispersed in deionized water again, is obtained mixture B；
Mixture B is placed under mercury lamp and irradiates 15~30min by step 2.3, and obtained product is rinsed with deionized water, obtained
Obtain the titanium doped titanium dioxide nano material of the trivalent of gold nano particle modification；
Step 3 wraps up the titanium dioxide nano material titanium doped by the trivalent of gold nano particle modification with up-conversion；
Step 3.1, by nitric hydrate yttrium, nitric hydrate ytterbium, nitric hydrate erbium and urea with (0.75~0.80) %w,
(0.15~0.20) %wt, (0.01~0.05) %wt, 1.5~3%wt are soluble in water, and stirring is to being sufficiently mixed to obtain mixture
C；
The titanium doped titanium dioxide nano material of trivalent by gold modification is added into mixture C step 3.2, sufficiently
After stirring, heating makes the two react, and the temperature of the reaction is 70~90 DEG C, and heating time is 2~3h, after reaction
Cooled to room temperature obtains mixture D；
Step 3.3 is transferred to drying in baking oven after cleaning mixture D with deionized water, then calcined, calcining temperature
Degree is 400~800 DEG C, and calcination time is 2~3h, obtains mixture E；
The mixed solution of sodium fluoride, hydrofluoric acid and deionized water is transferred in hydrothermal reaction kettle by step 3.4, wherein fluorine
The concentration for changing sodium is 0.1mol/L, and the concentration of hydrofluoric acid is 0.6~1%wt., and mixture E is added wherein, 80~100 DEG C
2~4h is reacted, the product cooled to room temperature reacted is then centrifuged for washing and dry, and obtains near infrared light response
Antibacterial agent.
Drying temperature in the step 3.4 is 60~80 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
Contain up-conversion in composite material of the invention, near infrared light can be converted into visible light by up-conversion
And ultraviolet light；The doping of titanous and the modification of gold nano grain can be by TiO2Optical response range expand to visible light
Area, thus visible/ultraviolet light that efficient absorption up-conversion issues, the final light for realizing the present invention in deep layer biological tissue
Catalytic antimicrobial effect.
Detailed description of the invention
Fig. 1 is the titanium doped titanium dioxide nano material of the compound trivalent via gold nano particle modification of up-conversion
X-ray diffraction pattern；
Fig. 2 is that the titanium doped titanium dioxide nano material of the compound trivalent via gold nano particle modification of up-conversion exists
Transmission electron microscope picture under different resolution.
Specific embodiment
Embodiment 1
As depicted in figs. 1 and 2, the present invention provides a kind of antibacterial agent of near infrared light response, optical response ranges 900
~1100nm；A kind of antibacterial agent of near infrared light response, the antibacterial agent is the three of up-conversion and gold nano particle modification
The composite material of the titanium doped titanium dioxide nano material composition of valence, the titanium doped titanium dioxide nano material of the trivalent is titanous
The titanium oxide nanoparticles of doping, the titanium doped titanium oxide nanoparticles of trivalent are attached with gold nanoparticle outside, form gold nano
The titanium doped titanium oxide nanoparticles of the trivalent of particle modification, the titanium oxide that the trivalent of the gold nanoparticle modification is titanium doped are received
Conversion particles are enclosed on the outside of rice corpuscles.
Titanium in the titanium doped titanium dioxide nano material of the trivalent is present in TiO in the form of titanous and titanic2
In lattice, Ti is formed3+-O-Ti4+Structure.
The optical response range of the antibacterial agent is 900~1100nm.
A kind of preparation method of the antibacterial agent of near infrared light response above-mentioned, comprising the following steps:
Step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；
Titanium dioxide is placed in hydrogen atmosphere and calcines by step 1.1, and calcination temperature is 600 DEG C, and calcination time 2h is obtained
The titanium dioxide nano material titanium doped to trivalent；
Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；
Step 2.1 disperses the titanium doped titanium dioxide nano material of the trivalent of 0.01g in the chlorine gold that concentration is 2mmol/L
It in acid solution, is protected from light and 12h is sufficiently stirred, obtain mixture A；
Mixture A is centrifuged by step 2.2, after abandoning supernatant, is dispersed in 10ml deionized water again, is obtained mixture
B；
Mixture B is placed under mercury lamp and irradiates 30min by step 2.3, and obtained product is rinsed with deionized water, obtains gold
The titanium doped titanium dioxide nano material of nano-particle modified trivalent；
Step 3 wraps up the titanium dioxide nano material titanium doped by the trivalent of gold nano particle modification with up-conversion；
Step 3.1, by nitric hydrate yttrium, nitric hydrate ytterbium, nitric hydrate erbium with 0.75%wt；0.20%wt；0.05%
Wt is dissolved in 100ml deionized water, and stirring is to being sufficiently mixed, then 1.5g urea is added into solution and obtains mixture C；
The titanium doped titanium dioxide nano material of trivalent by gold modification is added into mixture C step 3.2, sufficiently
After stirring, heating makes the two react, and the temperature of the reaction is 70 DEG C, heating time 2h, naturally cold after reaction
But to room temperature, mixture D is obtained；
Step 3.3 is transferred to drying in baking oven after cleaning mixture D with deionized water, then calcined, calcining temperature
Degree is 600 DEG C, and calcination time 2h obtains mixture E；
The mixed solution of sodium fluoride, hydrofluoric acid and deionized water is transferred in hydrothermal reaction kettle by step 3.4, wherein fluorine
The concentration for changing sodium is 0.1mol/L, and the concentration of hydrofluoric acid is 0.6%wt, and mixture E is added wherein, 80 DEG C of reaction 2h, instead
The product cooled to room temperature that should be obtained is then centrifuged for washing and drying at 60 DEG C, obtains the antibacterial of near infrared light response
Agent.
Taking 2.0mL concentration is 1.0 × 105Then the Escherichia coli bacteria liquid of CFU/mL is added on 1.0mg and turns into quartz curette
The titanium doped titanic oxide material of the trivalent of the gold modification of conversion materials package.After mixing evenly, in 980nm laser (0.68W/
cm2) irradiation 60min sampling.Bacterium solution is dispersed on solid medium and cultivates for 24 hours to calculate bacterium for 37 DEG C after taking 100 μ L to dilute 100 times
Number is fallen, then calculating germicidal efficiency by colony count is 99.9% or more.Experiment is using the bacterium solution without any processing as sky
White, every group of data average measurement is averaged three times and calculates error.
Embodiment 2
As depicted in figs. 1 and 2, the present invention provides a kind of antibacterial agent of near infrared light response, optical response ranges 900
~1100nm；A kind of antibacterial agent of near infrared light response, the antibacterial agent is the three of up-conversion and gold nano particle modification
The composite material of the titanium doped titanium dioxide nano material composition of valence, the titanium doped titanium dioxide nano material of the trivalent is titanous
The titanium oxide nanoparticles of doping, the titanium doped titanium oxide nanoparticles of trivalent are attached with gold nanoparticle outside, form gold nano
The titanium doped titanium oxide nanoparticles of the trivalent of particle modification, the titanium oxide that the trivalent of the gold nanoparticle modification is titanium doped are received
Conversion particles are enclosed on the outside of rice corpuscles.
Titanium in the titanium doped titanium dioxide nano material of the trivalent is present in TiO in the form of titanous and titanic2
In lattice, Ti is formed3+-O-Ti4+Structure.
The optical response range of the antibacterial agent is 900~1100nm.
A kind of preparation method of the antibacterial agent of near infrared light response above-mentioned, comprising the following steps:
Step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；
Titanium dioxide is placed in hydrogen atmosphere and calcines by step 1.1, and calcination temperature is 600 DEG C, and calcination time 2h is obtained
The titanium dioxide nano material titanium doped to trivalent；
Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；
Step 2.1 disperses the titanium doped titanium dioxide nano material of the trivalent of 0.01g in the chlorine gold that concentration is 2mmol/L
It in acid solution, is protected from light and 12h is sufficiently stirred, obtain mixture A；
Mixture A is centrifuged by step 2.2, after abandoning supernatant, is dispersed in 10ml deionized water again, is obtained mixture
B；
Mixture B is placed under mercury lamp and irradiates 30min by step 2.3, and obtained product is rinsed with deionized water, obtains gold
The titanium doped titanium dioxide nano material of nano-particle modified trivalent；
Step 3 wraps up the titanium dioxide nano material titanium doped by the trivalent of gold nano particle modification with up-conversion；
Step 3.1, by nitric hydrate yttrium, nitric hydrate ytterbium, nitric hydrate erbium with 0.75%wt；0.20%wt；0.05%
Wt is dissolved in 100ml deionized water, and stirring is to being sufficiently mixed, then 1.5g urea is added into solution and obtains mixture C；
The titanium doped titanium dioxide nano material of trivalent by gold modification is added into mixture C step 3.2, sufficiently
After stirring, heating makes the two react, and the temperature of the reaction is 70 DEG C, heating time 2h, naturally cold after reaction
But to room temperature, mixture D is obtained；
Step 3.3 is transferred to drying in baking oven after cleaning mixture D with deionized water, then calcined, calcining temperature
Degree is 600 DEG C, and calcination time 2h obtains mixture E；
The mixed solution of sodium fluoride, hydrofluoric acid and deionized water is transferred in hydrothermal reaction kettle by step 3.4, wherein fluorine
The concentration for changing sodium is 0.1mol/L, and the concentration of hydrofluoric acid is 0.6%wt., and mixture E is added wherein, 80 DEG C of reaction 2h, instead
The product cooled to room temperature that should be obtained is then centrifuged for washing and drying at 60 DEG C, obtains the antibacterial of near infrared light response
Agent.
Taking 2.0mL concentration is 1.0 × 105The methicillin-resistant staphylococcus aureus bacterium solution of CFU/mL into quartz curette,
Then the titanium doped titania meterial of the trivalent of the gold modification of 1.0mg up-conversion package is added.After mixing evenly, exist
980nm laser (0.68W/cm2) irradiation 60min sampling.Bacterium solution is dispersed on solid medium after taking 100 μ L to dilute 100 times
For 24 hours to calculate bacterium colony number, then calculating germicidal efficiency by colony count is 99.9% or more for 37 DEG C of cultures.Experiment is without appointing
As blank, every group of data average measurement is averaged three times and calculates error the bacterium solution of where reason.
Embodiment 3
The present invention provides a kind of antibacterial agent of near infrared light response, optical response range is 900~1100nm；It is a kind of close
The antibacterial agent of infrared optical response, the antibacterial agent titanium oxide titanium doped for the trivalent of up-conversion and gold nano particle modification
The composite material of nano material composition, the titanium doped titanium dioxide nano material of the trivalent are the titanium doped TiOx nano of trivalent
Particle, the titanium doped titanium oxide nanoparticles of trivalent are attached with gold nanoparticle outside, form the titanous of gold nanoparticle modification
The titanium oxide nanoparticles of doping, the titanium oxide nanoparticles outside that the trivalent of the gold nanoparticle modification is titanium doped are enclosed with
Upper conversion particles.
Titanium in the titanium doped titanium dioxide nano material of the trivalent is present in TiO in the form of titanous and titanic2
In lattice, Ti is formed3+-O-Ti4+Structure.
The optical response range of the antibacterial agent is 900~1100nm.
A kind of preparation method of the antibacterial agent of near infrared light response above-mentioned, comprising the following steps:
Step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；
Titanium dioxide is placed in hydrogen atmosphere and calcines by step 1.1, and calcination temperature is 500 DEG C, calcination time 0.5h,
Obtain the titanium doped titanium dioxide nano material of trivalent；
Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；
Step 2.1 disperses the titanium doped titanium dioxide nano material of the trivalent of 0.01g in the chlorine that concentration is 0.5mmol/L
It in auric acid solution, is protected from light and 12h is sufficiently stirred, obtain mixture A；
Mixture A is centrifuged by step 2.2, after abandoning supernatant, is dispersed in 10ml deionized water again, is obtained mixture
B；
Mixture B is placed under mercury lamp and irradiates 15min by step 2.3, and obtained product is rinsed with deionized water, obtains gold
The titanium doped titanium dioxide nano material of nano-particle modified trivalent；
Step 3 wraps up the titanium dioxide nano material titanium doped by the trivalent of gold nano particle modification with up-conversion；
Step 3.1, by nitric hydrate yttrium, nitric hydrate ytterbium, nitric hydrate erbium with 0.70%wt；0.28%wt；0.02%
Wt is dissolved in 100ml deionized water, and stirring is to being sufficiently mixed, then 1.5g urea is added into solution and obtains mixture C；
The titanium doped titanium dioxide nano material of trivalent by gold modification is added into mixture C step 3.2, sufficiently
After stirring, heating makes the two react, and the temperature of the reaction is 90 DEG C, heating time 3h, naturally cold after reaction
But to room temperature, mixture D is obtained；
Step 3.3 is transferred to drying in baking oven after cleaning mixture D with deionized water, then calcined, calcining temperature
Degree is 400 DEG C, and calcination time 2h obtains mixture E；
The mixed solution of sodium fluoride, hydrofluoric acid and deionized water is transferred in hydrothermal reaction kettle by step 3.4, wherein fluorine
The concentration for changing sodium is 0.1mol/L, and the concentration of hydrofluoric acid is 1%wt, and mixture E is added wherein, 100 DEG C of reaction 4h, reaction
Obtained product cooled to room temperature is then centrifuged for washing and drying at 60 DEG C, obtains the antibacterial agent of near infrared light response.
Taking 2.0mL concentration is 1.0 × 105Then the Escherichia coli bacteria liquid of CFU/mL is added on 1.0mg and turns into quartz curette
The titanium doped titanic oxide material of the trivalent of the gold modification of conversion materials package.After mixing evenly, in 980nm laser (0.68W/
cm2) irradiation 60min sampling.Bacterium solution is dispersed on solid medium and cultivates for 24 hours to calculate bacterium for 37 DEG C after taking 100 μ L to dilute 100 times
Number is fallen, then calculating germicidal efficiency by colony count is 99.9% or more.Experiment is using the bacterium solution without any processing as sky
White, every group of data average measurement is averaged three times and calculates error.
Embodiment 4
The present invention provides a kind of antibacterial agent of near infrared light response, optical response range is 900~1100nm；It is a kind of close
The antibacterial agent of infrared optical response, the antibacterial agent titanium oxide titanium doped for the trivalent of up-conversion and gold nano particle modification
The composite material of nano material composition, the titanium doped titanium dioxide nano material of the trivalent are the titanium doped TiOx nano of trivalent
Particle, the titanium doped titanium oxide nanoparticles of trivalent are attached with gold nanoparticle outside, form the titanous of gold nanoparticle modification
The titanium oxide nanoparticles of doping, the titanium oxide nanoparticles outside that the trivalent of the gold nanoparticle modification is titanium doped are enclosed with
Upper conversion particles.
Titanium in the titanium doped titanium dioxide nano material of the trivalent is present in TiO in the form of titanous and titanic2
In lattice, Ti is formed3+-O-Ti4+Structure.
The optical response range of the antibacterial agent is 900~1100nm.
A kind of preparation method of the antibacterial agent of near infrared light response above-mentioned, comprising the following steps:
Step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；
Titanium dioxide is placed in hydrogen atmosphere and calcines by step 1.1, and calcination temperature is 700 DEG C, and calcination time 3h is obtained
The titanium dioxide nano material titanium doped to trivalent；
Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；
Step 2.1 disperses the titanium doped titanium dioxide nano material of the trivalent of 0.01g in the chlorine gold that concentration is 5mmol/L
It in acid solution, is protected from light and 12h is sufficiently stirred, obtain mixture A；
Mixture A is centrifuged by step 2.2, after abandoning supernatant, is dispersed in 10ml deionized water again, is obtained mixture
B；
Mixture B is placed under mercury lamp and irradiates 20min by step 2.3, and obtained product is rinsed with deionized water, obtains gold
The titanium doped titanium dioxide nano material of nano-particle modified trivalent；
Step 3 wraps up the titanium dioxide nano material titanium doped by the trivalent of gold nano particle modification with up-conversion；
Step 3.1, by nitric hydrate yttrium, nitric hydrate ytterbium, nitric hydrate erbium with 0.78%wt；0.17%wt；0.05%
Wt is dissolved in 100ml deionized water, and stirring is to being sufficiently mixed, then 1.5g urea is added into solution and obtains mixture C；
The titanium doped titanium dioxide nano material of trivalent by gold modification is added into mixture C step 3.2, sufficiently
After stirring, heating makes the two react, and the temperature of the reaction is 80 DEG C, heating time 2.5h, natural after reaction
It is cooled to room temperature, obtains mixture D；
Step 3.3 is transferred to drying in baking oven after cleaning mixture D with deionized water, then calcined, calcining temperature
Degree is 800 DEG C, and calcination time 2.5h obtains mixture E；
The mixed solution of sodium fluoride, hydrofluoric acid and deionized water is transferred in hydrothermal reaction kettle by step 3.4, wherein fluorine
The concentration for changing sodium is 0.1mol/L, and the concentration of hydrofluoric acid is 0.8%wt., and mixture E is added wherein, 90 DEG C of reaction 3h, instead
The product cooled to room temperature that should be obtained is then centrifuged for washing and drying at 60 DEG C, obtains the antibacterial of near infrared light response
Agent.
Taking 2.0mL concentration is 1.0 × 105Then the Escherichia coli bacteria liquid of CFU/mL is added on 1.0mg and turns into quartz curette
The titanium doped titania meterial of the trivalent of the gold modification of conversion materials package.After mixing evenly, in 980nm laser (0.68W/
cm2) irradiation 60min sampling.Bacterium solution is dispersed on solid medium and cultivates for 24 hours to calculate bacterium for 37 DEG C after taking 100 μ L to dilute 100 times
Number is fallen, then calculating germicidal efficiency by colony count is 99.9% or more.Experiment is using the bacterium solution without any processing as sky
White, every group of data average measurement is averaged three times and calculates error.
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, although referring to above-described embodiment pair
The present invention is described in detail, and the those of ordinary skill in field is it is understood that still can be to specific embodiment party of the invention
Formula is modified or replaced equivalently, and without departing from any modification of spirit and scope of the invention or equivalent replacement, it should all
Cover in present claims range.
Claims (5)
1. a kind of antibacterial agent of near infrared light response, which is characterized in that the antibacterial agent is up-conversion and gold nano grain
The composite material of the titanium doped titanium dioxide nano material composition of the trivalent of modification, the titanium doped titanium dioxide nano material of the trivalent
For the titanium doped titanium oxide nanoparticles of trivalent, the titanium doped titanium oxide nanoparticles of trivalent are attached with gold nanoparticle, shape outside
At the titanium doped titanium oxide nanoparticles of the trivalent of gold nanoparticle modification, the trivalent of the gold nanoparticle modification is titanium doped
Conversion particles are enclosed on the outside of titanium oxide nanoparticles.
2. a kind of antibacterial agent of near infrared light response according to claim 1, which is characterized in that the trivalent is titanium doped
Titanium in titanium dioxide nano material is present in TiO in the form of titanous and titanic2In lattice, Ti is formed3+-O-Ti4+Structure.
3. a kind of antibacterial agent of near infrared light response according to claim 1, which is characterized in that the light of the antibacterial agent is rung
Answering range is 900~1100nm.
4. a kind of preparation method of the antibacterial agent of near infrared light response, feature described in claims 1 to 3 any one exist
In, comprising the following steps:
Step 1 prepares the titanium doped titanium dioxide nano material of trivalent using hydrogen reduction method；
Titanium dioxide is placed in hydrogen atmosphere and calcines by step 1.1, calcination temperature be 500~700 DEG C, calcination time be 0.5~
3h obtains the titanium doped titanium dioxide nano material of trivalent；
Step 2, the titanium dioxide nano material titanium doped to trivalent carry out the modification of gold nano grain；
The titanium doped titanium dioxide nano material of trivalent is placed in the chlorauric acid solution that concentration is 0.5~5.0mmol/L by step 2.1
In, it is protected from light and is sufficiently stirred, obtain mixture A；
Mixture A is centrifuged by step 2.2, after abandoning supernatant, is dispersed in deionized water again, is obtained mixture B；
Mixture B is placed under mercury lamp and irradiates 15~30min by step 2.3, and obtained product is rinsed with deionized water, obtains gold
The titanium doped titanium dioxide nano material of nano-particle modified trivalent；
Step 3, with the titanium doped titanium dioxide nano material of trivalent of up-conversion package gold nano particle modification；
Step 3.1, by nitric hydrate yttrium, nitric hydrate ytterbium, nitric hydrate erbium and urea with (0.75~0.80) %w, (0.15
~0.20) %wt, (0.01~0.05) %wt, 1.5~3%wt are soluble in water, and stirring is to being sufficiently mixed to obtain mixture C；
The titanium doped titanium dioxide nano material of trivalent by gold modification is added into mixture C step 3.2, is sufficiently stirred
Afterwards, heating makes the two react, and the temperature of reaction is 70~90 DEG C, and heating time is 2~3h, after reaction natural cooling
To room temperature, mixture D is obtained；
Step 3.3 is transferred to drying in baking oven after cleaning mixture D with deionized water, then calcined, calcination temperature is
400~800 DEG C, calcination time is 2~3h, obtains mixture E；
The mixed solution of sodium fluoride, hydrofluoric acid and deionized water is transferred in hydrothermal reaction kettle by step 3.4, wherein sodium fluoride
Concentration be 0.1mol/L, the concentration of hydrofluoric acid is 0.6~1%wt., and mixture E is added wherein, 80~100 DEG C of reactions 2
~4h, the product cooled to room temperature reacted, is then centrifuged for washing and dry, and obtains the anti-of the near infrared light response
Microbial inoculum.
5. a kind of preparation method of the antibacterial agent of near infrared light response according to claim 4, which is characterized in that the step
Drying temperature in rapid 3.4 is 60~80 DEG C.
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