CN106665695A - Antibacterial titanium dioxide composite micro-nano particle and preparation method thereof - Google Patents
Antibacterial titanium dioxide composite micro-nano particle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial titanium dioxide composite micro-nano particle and a preparation method thereof. The composite micro-nano particle is prepared by performing carbonization, acid pickling and crushing electrospun enteromorpha nano particles/titanium dioxide fiber into micro-nano particles, loading the micro-nano particles with an antibacterial solution and performing drying; the antibacterial solution is a traditional Chinese medicine antibacterial component extraction solution prepared from raw materials in parts by weight as follows: 12-15 parts of fresh camphor tree leaves, 10-15 parts of fresh mint leaves, 8-12 parts of fresh pheonix tree leaves, 5-9 parts of all grass of asparagus gobicus, 8-10 parts of fructus momordicae, 7-9 parts of fructus forsythiae, 9-11 parts of folium artemisiae argyi, 4-6 parts of fructus mume, 6-8 parts of clove, 4-6 parts of galla chinensis and 3-5 parts of radix glycyrrhizae preparata. Through material composition, the antibacterial efficiency of the titanium dioxide composite is effectively improved, so that the material has better antibacterial performance and application prospect.
Description
Technical field
The present invention relates to a kind of antibacterial titanium dioxide composite micro-nano rice grain and preparation method thereof.
Background technology
Titanium dioxide, chemical formula is TiO2, be commonly called as titanium dioxide, be used for photocatalyst, cosmetics, can by disinfection by ultraviolet light and
Sterilization, now positive extensive exploitation, has an opportunity to become new industry in the future.Titanium dioxide can decompose extraction by ilmenite acid, or by four
Titanium chloride decomposition is obtained.Titanium dioxide is stable in properties, a large amount of Chinese whites being used as in paint, and it has good covering energy
Power, it is similar with white lead, but unlike white lead can blackening；It has the same persistency of zinc white again.Titanium dioxide also serves as enamel
Delustering agent, can produce a kind of very bright, hard and acidproof vitreous enamel cover.Titanium dioxide can be fabricated to photocatalyst, only
Change air, eliminate in vehicle emission 25% to 45% nitrogen oxides, can be used to administer the too high sky of PM2.5 suspended particulate substances
Gas pollutes.
Photocatalysis antibacterial material with titanium dioxide as representative is that have important research value and wide DEVELOPMENT PROSPECT at present
Inorganic antiseptic.Titanium dioxide has photocatalytic effect, and being excited by light makes valence-band electrons transit to conduction band, is swashed in conduction band
The son that generates electricity has strong reproducibility, and the hole of valence band has strong oxidability, and such that it is able to play to kill antibacterial is suppressed
Effect, but, titanium dioxide anti-bacterial agent needs ultraviolet light, and photocatalysis efficiency is low, and in actual applications antibacterial action is weaker.
The content of the invention
It is an object of the invention to be improved to current material, there is provided a kind of antibacterial titanium dioxide composite micro-nano rice grain
And preparation method thereof, the material effectively increases the antimicrobial efficiency of titanic oxide material so that material has by Material cladding
More preferable anti-microbial property and application prospect.
To achieve these goals, the technical scheme that the present invention is provided is as follows：
A kind of antibacterial titanium dioxide composite micro-nano rice grain, the composite micro-nano rice grain by electrospinning Entermorpha nano-particle/
Titania fiber Jing carbonizations, pickling, be crushed to micro-nano granules, load antibacterial medicinal liquid, be dried be obtained；The antibacterial medicinal liquid is
Chinese medicine antibacterial constituents extraction liquid, the crude drug and its parts by weight for making the antibacterial medicinal liquid be：Folium cinnamomi camphorae fresh goods 12-15 part,
Mentha leave fresh goods 10-15 part, Folium firmianae fresh goods 8-12 part, Herba asparagi gobici herb 5-9 parts, Fructus Momordicae 8-10 parts, Fructus Forsythiae 7-9 parts, Chinese mugwort
Leaf 9-11 parts, Fructus Mume 4-6 parts, Flos Caryophylli 6-8 parts, Galla Chinensiss 4-6 parts, Radix Glycyrrhizae Preparata 3-5 parts.
Preferably, the crude drug and its parts by weight for making the antibacterial medicinal liquid be：14 parts of Folium cinnamomi camphorae fresh goods, mentha leave is fresh
12 parts of product, 10 parts of Folium firmianae fresh goods, 7 parts of Herba asparagi gobici herb, 9 parts of Fructus Momordicae, 8 parts of Fructus Forsythiae, 10 parts of Folium Artemisiae Argyi, 5 parts of Fructus Mume, Flos Caryophylli 7
Part, 5 parts of Galla Chinensiss, 4 parts of Radix Glycyrrhizae Preparata.
Preferably, the crude drug of the antibacterial medicinal liquid is obtained by following steps：
1) Herba asparagi gobici, Fructus Momordicae, Fructus Forsythiae, Folium Artemisiae Argyi, Fructus Mume, Flos Caryophylli, Galla Chinensiss, Radix Glycyrrhizae Preparata mixing is crushed to 100 after cleaning
Mesh powder, the water for adding 4 times of mixed-powder gross mass multiple soaks 1 minute, is cooked by slow fire 45 minutes, crosses 1000 mesh drainage screens and takes
Filtrate, the water that 4 times of mixed-powder gross mass is added again soaks 1 hour, is cooked by slow fire 1 hour, crosses 1000 mesh drainage screens and takes filter
Liquid, merges filtrate twice standby；
2) step 1) gained filtrate dry to relative density for 1.30 ± 0.02 (60 DEG C) thick paste；
3) mixed grinding adds slurry gross mass 4 into slurry after Folium cinnamomi camphorae fresh goods, mentha leave fresh goods, Folium firmianae fresh goods are cleaned
Ethanol again, after stirring mixes 2 hours under room temperature, stands 1 hour, crosses 1000 mesh filter screen filtrations and obtains filtrate；
4) step 2) gained thick paste add step 3) gained filtrate in, be sufficiently stirred for mix after gained liquid cross 1000 mesh mistakes
Strainer filtering gained filtrate is antibacterial medicinal liquid.
In making the crude drug of antibacterial medicinal liquid：
Folium cinnamomi camphorae：Bitter is pungent, temperature, wind-dispelling, dehumidifying, pain relieving, parasite killing, dispelling the wind and dampness pathogens osteodynia, traumatic injury, scabies, Folium cinnamomi camphorae
Extracting solution is a kind of broad spectrum activity antibacterial, and optimal to the fungistatic effect of gram positive bacteria；
Mentha leave：It is pungent, cool, dispelling wind-heat, refresh oneself, rash, for anemopyretic cold, pathogenic wind-warm is from the beginning of, headache, conjunctival congestion, larynx
Numbness, aphtha, rubella, measles, Breast bilges frowsty about, Herba Menthae plays the role of desensitization, antiinflammatory and antibacterial to mosquito bite skin, to upper breathing
Road infection also has obvious cough-relieving, antiinflammatory and bacteriostasis, plays the role of reducing swelling and alleviating pain, antiphlogistic antibacterial to hemorrhoid, anal fissure；
Folium firmianae：Bitter in the mouth, it is cold in nature, the effect of with expelling wind and removing dampness, removing toxic substances and promoting subsidence of swelling, blood pressure lowering, it is usually used in rheumatic arthralgia, fall
Beat and damage, ulcerative carbuncle pyogenic infections, hemorrhoid, infantile malnutrition, dysentery, hypertension；
Herba asparagi gobici：Acrid in the mouth, slight bitter is mild-natured, wind-dispelling, and parasite killing is antipruritic, carbuncle that disappears dissipating bind, main neurodermatitiss, psoriasiss, body
Tinea, furuncle carbuncle；
Fructus Momordicae：It is cool in nature, sweet in the mouth, clearing heat and moistening lung, cough-relieving, sore-throat relieving, laxation relieving constipation.For lung-fire cough caused by dryness, pharyngalgia aphonia, intestinal
Dry constipation, Fructus Momordicae and its extract possess antibacterial, anti-diabetic and remove the effect of three aspects such as free radical, so as to there is guarantor
Hepatoprotective cell, treatment diabetes, adjust immunologic function, blood circulation promoting and blood stasis dispelling, suppress Streptococcus mutans effect and have active anticancer,
The effect of antioxidant activity；
Fructus Forsythiae：Heat-clearing and toxic substances removing, dispersing swelling and dissipating binds, dispelling wind and heat pathogens, modern medicine study confirms that weeping forsythia concentrated decoction has in vitro
Antibacterial action, can suppress Bacillus typhi, Salmonella paratyphi, escherichia coli, dysentery bacterium, diphtheria corynebacterium and vibrio cholera, Fructus Vitis viniferae
Coccus, streptococcus etc.；
Folium Artemisiae Argyi：Warming the meridian and stop blooding, dispelling cold and removing dampness analgesia, have functions that hemostasis, bleeding and clotting time can be shortened.Folium Artemisiae Argyi
Decoct has faint antagonism to dermatophytosises；
Fructus Mume：Sour-puckery flavor, it is warm in nature, enter lung, spleen, large intestine channel.Astringe the lung, astringing intestine to stop diarrhea, promoting the production of body fluid to quench thirst, antibacterial, relieving colic caused by ascaris is cured mainly long
Cough, chronic diarrhea, chronic dysentery are had blood in stool, the ascariasis of biliary tract, excessive thirst, the disease such as vomiting, modern medicine study confirms that Fructus Mume can suppress the intestinals such as dysentery bacterium
Pathogenic bacterium and second kind Hemolytic streptococcuss；
Flos Caryophylli：Warming middle-JIAO to send down the adverse QI, dispersing cold for relieving pain, warming the kidney to activate YANG, its water extract has analgesic and anti-inflammatory effects, and its decoct is to Fructus Vitis viniferae ball
The bacillus such as bacterium, streptococcus and diphtheria, deformation, green pus, large intestine, dysentery, typhoid fever has inhibitory action, and has preferable mite killing to make
With；
Galla Chinensiss：It is cold in nature, it is sour in the mouth, puckery, it is main the effects such as with pathogenic fire reducing of astringing the lung, relieving diarrhea with astringents, arresting sweating hemostasis, removing dampness sore
The diseases such as chronic cough of deficiency lung, protracted dysentery and diarrhea, hemorrhoidal bleeding of having blood in stool, carbuncle sore tumefacting virus, Skin wet and rotten are controlled, Galla Chinensiss decoct is to Staphylococcus aureus
Bacterium, beta hemolytic streptococcuss, streptococcus pneumoniae, bacillus pyocyaneus, dysentery bacterium, anthrax bacillus, diphtheria corynebacterium, escherichia coli, wound
Cold and Salmonella paratyphi etc. has obvious antibacterial and bactericidal action；
Radix Glycyrrhizae Preparata：Containing various chemical compositions such as glycyrrhizin, enoxolone, Angelica Polysaccharide, with antiinflammatory and resistance state
Reagentia, scalable body's immunity, antitumor and analgesic effect, therefore the primary efficacy of Radix Glycyrrhizae Preparata is and middle emergency,
Lung moistening, removing toxic substances, coordinating the actions of various ingredients in a prescription.
All medicine compatibilities are proper, and sharing can improve the antibacterial effectiveness of medicinal liquid, play broad-spectrum antibacterial action, to antibacterial, funguses etc.
Microorganism has certain suppression killing action.
The invention also discloses the preparation method of described antibacterial titanium dioxide composite micro-nano rice grain, it is characterised in that
Comprise the following steps：
(1) Entermorpha nanometer dry powder is prepared：The cleaning of Entermorpha fresh goods removes the impurity such as the grains of sand, and Jing natural air dryings or lyophilization are obtained
Dry product, gained dry product micronizing to micropowder it is last be placed in ball grinder carry out high-energy ball milling post-drying obtain Entermorpha nanometer do
Powder；
(2) spinning precursor liquid is prepared：Prepare containing tetrabutyl titanate, the Entermorpha nanometer dry powder of gained in step (1), anhydrous
Ethanol, the high molecular polymer for being dissolved in ethanol, the uniform suspension of organic acid are used as spinning precursor liquid；
(3) electrospinning preparation fibrous membrane：Spinning precursor liquid obtained by step (2) adds the liquid storage mechanism of electrostatic spinning apparatus
In, spinning nozzle connection high-voltage power cathode, collector connection high voltage power supply negative pole, adjusting spinning voltage and spinning distance is carried out
Electrostatic spinning, spinning precursor liquid forms fibrous membrane and is preparation fibrous membrane in the presence of electric field force on collector；
(4) carbonization treatment：Preparation fibre film Jing high-temperature heat treatments under anoxia or oxygen-free environment of gained make waterside in step (3)
Tongue nanometer dry powder is carbonized to obtain activated carbon, and the process eliminates high molecular polymer and residual solvent in prepared fibrous membrane simultaneously,
Obtain Entermorpha activated carbon/dioxide composite nanofiber film；
(5) pickling impurity removal：By sample Jing molar concentrations 5mol/L obtained by step (4) under the constant temperature that temperature is 60 DEG C
Soak with hydrochloric acid is taken out sample from acid solution with removing impurity for 10 hours, then is soaked in deionized water every 2 hours more
Change and once soak the deionized water of sample, and test the ph values of the deionized water for soaking sample, to soaked sample go from
When sub- water is neutral, sample is taken out to be placed in 60 DEG C of baking ovens and is dried；
(6) pulverized particles：Drying sample obtained by step (5) is crushed to into 2000 mesh powder；
(7) medicinal liquid is loaded：Step (6) gained powder is mixed homogeneously with appropriate antibacterial medicinal liquid, makes powder particle abundant
Absorbing load medicinal liquid；
(8) it is dried：Step (7) resulting material dries to obtain thick paste, and gained thick paste lyophilization obtains dry solids and is
Antibacterial titanium dioxide composite micro-nano rice grain.
The antibacterial titanium dioxide composite micro-nano rice grain of the present invention be loaded with the titanium dioxide of Chinese medicine antibacterial effective ingredient/
Activated carbon composite micro-nano nano antibacterial granule.Photocatalysis antibacterial material with titanium dioxide as representative is that have important research valency at present
It is worth the inorganic antiseptic with wide DEVELOPMENT PROSPECT, titanium dioxide has photocatalytic effect, and exciting by light makes valence-band electrons transition
To conduction band, the electronics that is excited in conduction band has strong reproducibility, and the hole of valence band has strong oxidability, such that it is able to rise
To the effect for killing the microorganisms such as suppression antibacterial, funguses.By containing tetrabutyl titanate, Entermorpha nanometer dry powder, dehydrated alcohol, be dissolved in
Preparation fibrous membrane is TiO obtained in the high molecular polymer of ethanol, the spinning precursor liquid method of electrostatic spinning of organic acid2/ macromolecule
The fibrous membrane that polymer/Entermorpha nano-particle (Entermorpha nanometer dry powder) composite nano fiber is constituted, wherein Entermorpha nano-particle is equal
It is even to be embedded in TiO2In/high molecular polymer composite nano fiber, preparation fibre film Jing carbonizations under anoxia or oxygen free condition of gained
Process, make Entermorpha nano-particle be carbonized into the activated carbon nano-particle of porous, heat treatment process eliminates prepared fibrous membrane simultaneously
In high molecular polymer and residual solvent, be uniformly embedded with many crystal titanium dioxide/activity of Entermorpha activated carbon nano-particle
Carbon nanofibers film, then through the Titanium dioxide/active carbon composite particles obtained by pickling impurity removal, micronizing, combine dioxy
Change the advantage performance of titanium and Entermorpha activated carbon, the loose structure of Entermorpha activated carbon granule, with preferable adsorption, can be inhaled
The antibiotic effective ingredient in load antibacterial medicinal liquid is received, to improve the sterilization effect of titanium dioxide, and by electrostatic spinning technique and is surpassed
The composite particles of micro/nano level have larger specific surface area obtained in Crushing of Ultrafine technology, can fully have the contact of antibacterial medicinal liquid negative
Medicinal liquid is carried, medicinal liquid is fully loaded, the antibacterial bacteriostatic effect of antibacterial, the Entermorpha activated carbon that composite particles are embedded with preferably is improved
Grain is the activated carbon granule that nano-scale is obtained by the carbonization of Entermorpha nano-particle, and the absorbability of absorbent charcoal material is because its hole
With absorption potential, formed by carbon molecule and the gravitation of adsorbed molecule, aperture is less, and absorption potential is stronger, active raw material of wood-charcoal
The absorbability of material is stronger, therefore compared to Entermorpha activated carbon obtained in commonsense method, the activated carbon of this Nano grade
The hole of grain is less, with higher absorbability, can effectively strengthen the efficiency that composite loads medicinal liquid, improves the anti-of material
Bacterium performance, the complex antimicrobials preparation method is simpler, and product property is superior, and takes full advantage of coastal waters Entermorpha resource, becomes useless
For treasured.The material effectively increases the antimicrobial efficiency of titanic oxide material by Material cladding so that material has preferably anti-
Bacterium performance and application prospect.
Preferably, described step (1) prepares Entermorpha nanometer dry powder：The cleaning of Entermorpha fresh goods is removed after the impurity such as the grains of sand, cold
Lyophilizing is dry to obtain dry product, and gained dry product micronizing is last to 500 mesh micropowder, and gained micron powder is placed in ball grinder to be carried out
High-energy ball milling, wherein zirconia ball:Micron powder:The mass ratio of water is 8:4:1,2000 revs/min of rotating speed, Ball-milling Time 4 is little
When, gained powder is placed in 60 DEG C of baking ovens dries to obtain Entermorpha nanometer dry powder.
Preferably, described step (2) prepares spinning precursor liquid：3.4g tetrabutyl titanates are added with 2g sulfosalicylic acids
In 9ml dehydrated alcohol, the Entermorpha nanometer dry powder obtained by 2.2g steps (1), magnetic force is added to stir after 1 hour mix homogeneously of magnetic agitation
Mix 1 hour, be configured to suspension A；3.5g polyvinylpyrrolidones are added in 9ml dehydrated alcohol, and magnetic agitation mixing in 2 hours is equal
It is even to obtain solution B；After suspension A and solution B are mixed into magnetic agitation 40 minutes, ultrasonic vibration 10 minutes, after ultrasonic vibration again
Magnetic agitation 30 minutes, then ultrasonic vibration 10 minutes again, obtain final product uniform suspension for spinning precursor liquid.
Preferably, the spinning voltage in described step (3) electrospinning preparation fibrous membrane is 22kV, and spinning distance is 18cm,
The spinning time is 30 minutes.
Preferably, described step (4) carbonization treatment：The preparation fibre film of gained is placed in tube furnace in step (3), in nitrogen
Under gas atmosphere, with 3 DEG C/min 500 DEG C are warming up to, after insulation 1 hour, are cooled to room temperature and take out sample, obtain final product Entermorpha activated carbon/
Dioxide composite nanofiber film.
Preferably, described step (7) load medicinal liquid：By step (6) gained powder and the antimicrobial drug of 4 times of powder gross mass
Liquid mixed magnetic agitation after 30 minutes, ultrasonic vibration 10 minutes, and again magnetic agitation obtains suspension after 24 hours.
Beneficial effects of the present invention are：The invention discloses a kind of antibacterial titanium dioxide composite micro-nano rice grain and its preparation
Method, the material effectively increases the antimicrobial efficiency of titanic oxide material by Material cladding so that material has preferably anti-
Bacterium performance and application prospect.Specifically：
1st, antibacterial titanium dioxide composite micro-nano rice grain of the invention is the titanium dioxide for being loaded with Chinese medicine antibacterial effective ingredient
Titanium/activated carbon composite micro-nano nano antibacterial granule.Photocatalysis antibacterial material with titanium dioxide as representative is that have important grinding at present
Study carefully the inorganic antiseptic being worth with wide DEVELOPMENT PROSPECT, titanium dioxide has photocatalytic effect, and exciting by light makes valence-band electrons
Conduction band is transitted to, the electronics that is excited in conduction band has strong reproducibility, and the hole of valence band has strong oxidability, so as to can
Suppress the microorganisms such as antibacterial, funguses to play a part of to kill.By containing tetrabutyl titanate, Entermorpha nanometer dry powder, dehydrated alcohol,
It is TiO to be dissolved in preparation fibrous membrane obtained in the high molecular polymer of ethanol, the spinning precursor liquid method of electrostatic spinning of organic acid2/ high
The fibrous membrane that Molecularly Imprinted Polymer/Entermorpha nano-particle (Entermorpha nanometer dry powder) composite nano fiber is constituted, wherein Entermorpha nanometer
Grain is uniformly embedded in TiO2In/high molecular polymer composite nano fiber, preparation fibre film Jing under anoxia or oxygen free condition of gained
Carbonization treatment, makes Entermorpha nano-particle be carbonized into the activated carbon nano-particle of porous, and heat treatment process eliminates preparation fibre simultaneously
High molecular polymer and residual solvent in dimension film, be uniformly embedded with many crystal titanium dioxides of Entermorpha activated carbon nano-particle/
Activated carbon nano fibrous membrane, then through the Titanium dioxide/active carbon composite particles obtained by pickling impurity removal, micronizing, combine
The advantage performance of titanium dioxide and Entermorpha activated carbon, the loose structure of Entermorpha activated carbon granule, with preferable adsorption, energy
Antibiotic effective ingredient in enough absorbing load antibacterial medicinal liquids, to improve the sterilization effect of titanium dioxide, the material is multiple by material
Close, effectively increase the antimicrobial efficiency of titanic oxide material so that material has more preferable anti-microbial property and application prospect.
2nd, the composite particles of micro/nano level by obtained in electrostatic spinning technique and superfine communication technique have larger ratio table
Area, can fully there is antibacterial medicinal liquid contact load medicinal liquid, fully load medicinal liquid, preferably improve the antibacterial bacteriostatic effect of antibacterial
Really, the Entermorpha activated carbon granule that composite particles are embedded with is the activated carbon granule that nano-scale is obtained by the carbonization of Entermorpha nano-particle,
The absorbability of absorbent charcoal material, because its hole has absorption potential, is formed by carbon molecule and the gravitation of adsorbed molecule
, aperture is less, and absorption potential is stronger, and the absorbability of absorbent charcoal material is stronger, therefore compared to waterside obtained in commonsense method
Tongue activated carbon, the hole of the activated carbon granule of this Nano grade is less, with higher absorbability, can effectively strengthen compound
The efficiency of material load medicinal liquid, improves the anti-microbial property of material, and the complex antimicrobials preparation method is simpler, and product property is excellent
More, and coastal waters Entermorpha resource is taken full advantage of, is turned waste into wealth.
3rd, make that all medicine compatibilities of antibacterial medicinal liquid are proper, sharing can improve the antibacterial effectiveness of medicinal liquid, play broad-spectrum antibacterial action,
There is certain suppression killing action to microorganisms such as antibacterial, funguses.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the specific material proportion described by example, process conditions and its result be merely to illustrate the present invention and should not also without limitation on
The present invention described in detail in claims.
Embodiment 1
A kind of antibacterial titanium dioxide composite micro-nano rice grain, the composite micro-nano rice grain by electrospinning Entermorpha nano-particle/
Titania fiber Jing carbonizations, pickling, be crushed to micro-nano granules, load antibacterial medicinal liquid, be dried be obtained；The antibacterial medicinal liquid is
Chinese medicine antibacterial constituents extraction liquid, the crude drug and its parts by weight for making the antibacterial medicinal liquid be：12 parts of Folium cinnamomi camphorae fresh goods, Herba Menthae
10 parts of leaf fresh goods, 8 parts of Folium firmianae fresh goods, 5 parts of Herba asparagi gobici herb, 8 parts of Fructus Momordicae, 7 parts of Fructus Forsythiae, 9 parts of Folium Artemisiae Argyi, 4 parts of Fructus Mume, Flos Caryophylli
6 parts, 4 parts of Galla Chinensiss, 3 parts of Radix Glycyrrhizae Preparata.
The crude drug of the antibacterial medicinal liquid is obtained by following steps：
1) Herba asparagi gobici, Fructus Momordicae, Fructus Forsythiae, Folium Artemisiae Argyi, Fructus Mume, Flos Caryophylli, Galla Chinensiss, Radix Glycyrrhizae Preparata mixing is crushed to 100 after cleaning
Mesh powder, the water for adding 4 times of mixed-powder gross mass multiple soaks 1 minute, is cooked by slow fire 45 minutes, crosses 1000 mesh drainage screens and takes
Filtrate, the water that 4 times of mixed-powder gross mass is added again soaks 1 hour, is cooked by slow fire 1 hour, crosses 1000 mesh drainage screens and takes filter
Liquid, merges filtrate twice standby；
2) step 1) gained filtrate dry to relative density for 1.30 ± 0.02 (60 DEG C) thick paste；
3) mixed grinding adds slurry gross mass 4 into slurry after Folium cinnamomi camphorae fresh goods, mentha leave fresh goods, Folium firmianae fresh goods are cleaned
Ethanol again, after stirring mixes 2 hours under room temperature, stands 1 hour, crosses 1000 mesh filter screen filtrations and obtains filtrate；
4) step 2) gained thick paste add step 3) gained filtrate in, be sufficiently stirred for mix after gained liquid cross 1000 mesh mistakes
Strainer filtering gained filtrate is antibacterial medicinal liquid.
The preparation method of described antibacterial titanium dioxide composite micro-nano rice grain, comprises the following steps：
(1) Entermorpha nanometer dry powder is prepared：The cleaning of Entermorpha fresh goods is removed after the impurity such as the grains of sand, and lyophilization obtains dry product, gained
Dry product micronizing is last to 500 mesh micropowder, and gained micron powder is placed in ball grinder carries out high-energy ball milling, wherein aoxidizing
Zirconium ball:Micron powder:The mass ratio of water is 8:4:1,2000 revs/min of rotating speed, Ball-milling Time 4 hours, gained powder is placed in 60
Entermorpha nanometer dry powder is dried to obtain in DEG C baking oven；
(2) spinning precursor liquid is prepared：3.4g tetrabutyl titanates are added in 9ml dehydrated alcohol with 2g sulfosalicylic acids, magnetic force
The Entermorpha nanometer dry powder obtained by 2.2g steps (1), magnetic agitation 1 hour is added to be configured to suspended after 1 hour mix homogeneously of stirring
Liquid A；3.5g polyvinylpyrrolidones are added in 9ml dehydrated alcohol, and 2 hours mix homogeneously of magnetic agitation obtain solution B；By suspension
A and solution B mixed magnetic agitation after 40 minutes, ultrasonic vibration 10 minutes, magnetic agitation 30 minutes again after ultrasonic vibration, then
Again ultrasonic vibration 10 minutes, obtain final product uniform suspension for spinning precursor liquid；
(3) electrospinning preparation fibrous membrane：Spinning precursor liquid obtained by step (2) adds the liquid storage mechanism of electrostatic spinning apparatus
In, spinning nozzle connection high-voltage power cathode, collector connection high voltage power supply negative pole, adjusting spinning voltage and spinning distance is carried out
Electrostatic spinning, spinning precursor liquid forms fibrous membrane as preparation fibrous membrane in the presence of electric field force on collector, wherein, spin
Filament voltage is 22kV, and spinning distance is 18cm, and the spinning time is 30 minutes；
(4) carbonization treatment：The preparation fibre film of gained is placed in tube furnace in step (3), in a nitrogen atmosphere, with 3 DEG C/minute
Clock is warming up to 500 DEG C, after being incubated 1 hour, is cooled to room temperature and takes out sample, obtains final product Entermorpha activated carbon/titanium dioxide composite Nano
Fibrous membrane；
(5) pickling impurity removal：By sample Jing molar concentrations 5mol/L obtained by step (4) under the constant temperature that temperature is 60 DEG C
Soak with hydrochloric acid is taken out sample from acid solution with removing impurity for 10 hours, then is soaked in deionized water every 2 hours more
Change and once soak the deionized water of sample, and test the ph values of the deionized water for soaking sample, to soaked sample go from
When sub- water is neutral, sample is taken out to be placed in 60 DEG C of baking ovens and is dried；
(6) pulverized particles：Drying sample obtained by step (5) is crushed to into 2000 mesh powder；
(7) medicinal liquid is loaded：4 times of antibacterial medicinal liquid of step (6) gained powder and powder gross mass is mixed into magnetic agitation 30
Minute after, ultrasonic vibration 10 minutes, again magnetic agitation after 24 hours suspension；
(8) it is dried：Step (7) resulting material dries to obtain thick paste, and gained thick paste lyophilization obtains dry solids and is
Antibacterial titanium dioxide composite micro-nano rice grain.
Embodiment 2
A kind of antibacterial titanium dioxide composite micro-nano rice grain, the composite micro-nano rice grain by electrospinning Entermorpha nano-particle/
Titania fiber Jing carbonizations, pickling, be crushed to micro-nano granules, load antibacterial medicinal liquid, be dried be obtained；The antibacterial medicinal liquid is
Chinese medicine antibacterial constituents extraction liquid, the crude drug and its parts by weight for making the antibacterial medicinal liquid be：14 parts of Folium cinnamomi camphorae fresh goods, Herba Menthae
12 parts of leaf fresh goods, 10 parts of Folium firmianae fresh goods, 7 parts of Herba asparagi gobici herb, 9 parts of Fructus Momordicae, 8 parts of Fructus Forsythiae, 10 parts of Folium Artemisiae Argyi, 5 parts of Fructus Mume, fourth
It is fragrant 7 parts, 5 parts of Galla Chinensiss, 4 parts of Radix Glycyrrhizae Preparata.The preparation method of the antibacterial medicinal liquid and antibacterial titanium dioxide composite micro-nano rice grain
It is same as Example 1.
Embodiment 3
A kind of antibacterial titanium dioxide composite micro-nano rice grain, the composite micro-nano rice grain by electrospinning Entermorpha nano-particle/
Titania fiber Jing carbonizations, pickling, be crushed to micro-nano granules, load antibacterial medicinal liquid, be dried be obtained；The antibacterial medicinal liquid is
Chinese medicine antibacterial constituents extraction liquid, the crude drug and its parts by weight for making the antibacterial medicinal liquid be：15 parts of Folium cinnamomi camphorae fresh goods, Herba Menthae
15 parts of leaf fresh goods, 12 parts of Folium firmianae fresh goods, 9 parts of Herba asparagi gobici herb, 10 parts of Fructus Momordicae, 9 parts of Fructus Forsythiae, 11 parts of Folium Artemisiae Argyi, 6 parts of Fructus Mume,
8 parts of Flos Caryophylli, 6 parts of Galla Chinensiss, 5 parts of Radix Glycyrrhizae Preparata.The preparation side of the antibacterial medicinal liquid and antibacterial titanium dioxide composite micro-nano rice grain
Method is same as Example 1.
Illustrative embodiments listed above are only not to technical scheme described in the invention for understanding that the present invention is used
Restriction, about the those of ordinary skill in field, on the basis of technical scheme described in claim, various changes can also be made
Change or deform, the change or deformation of all equivalents all should be covered within the claims of the present invention.The present invention is not
Part is described in detail in detail, the known technology of those skilled in the art of the present technique is.
Claims (8)
1. a kind of antibacterial titanium dioxide composite micro-nano rice grain, it is characterised in that the composite micro-nano rice grain is by electrospinning Entermorpha
The Jing carbonizations of Nano granule/titanium dioxide fiber, pickling, be crushed to micro-nano granules, load antibacterial medicinal liquid, be dried be obtained；It is described
Antibacterial medicinal liquid is Chinese medicine antibacterial constituents extraction liquid, and the crude drug and its parts by weight for making the antibacterial medicinal liquid is：Folium cinnamomi camphorae is fresh
Product 12-15 parts, mentha leave fresh goods 10-15 part, Folium firmianae fresh goods 8-12 part, Herba asparagi gobici herb 5-9 parts, Fructus Momordicae 8-10 parts, even
Stick up 7-9 parts, Folium Artemisiae Argyi 9-11 parts, Fructus Mume 4-6 parts, Flos Caryophylli 6-8 parts, Galla Chinensiss 4-6 parts, Radix Glycyrrhizae Preparata 3-5 parts.
2. a kind of antibacterial titanium dioxide composite micro-nano rice grain as claimed in claim 1, it is characterised in that make the antibacterial
The crude drug and its parts by weight of medicinal liquid be：14 parts of Folium cinnamomi camphorae fresh goods, 12 parts of mentha leave fresh goods, 10 parts of Folium firmianae fresh goods posts horse
7 parts of herb of stake, 9 parts of Fructus Momordicae, 8 parts of Fructus Forsythiae, 10 parts of Folium Artemisiae Argyi, 5 parts of Fructus Mume, 7 parts of Flos Caryophylli, 5 parts of Galla Chinensiss, 4 parts of Radix Glycyrrhizae Preparata.
3. a kind of antibacterial titanium dioxide composite micro-nano rice grain as claimed in claim 1, it is characterised in that the antibacterial medicinal liquid
Crude drug be obtained by following steps：
1) Herba asparagi gobici, Fructus Momordicae, Fructus Forsythiae, Folium Artemisiae Argyi, Fructus Mume, Flos Caryophylli, Galla Chinensiss, Radix Glycyrrhizae Preparata mixing is crushed to 100 mesh powder after cleaning
End, the water for adding 4 times of mixed-powder gross mass multiple soaks 1 minute, is cooked by slow fire 45 minutes, crosses 1000 mesh drainage screens and takes filter
Liquid, the water that 4 times of mixed-powder gross mass is added again soaks 1 hour, is cooked by slow fire 1 hour, crosses 1000 mesh drainage screens and takes filtrate,
Merge filtrate twice standby；
2) step 1) gained filtrate dry to relative density for 1.30 ± 0.02 (60 DEG C) thick paste；
3) mixed grinding adds 4 times of slurry gross mass into slurry after Folium cinnamomi camphorae fresh goods, mentha leave fresh goods, Folium firmianae fresh goods are cleaned
Ethanol, after stirring mixes 2 hours under room temperature, stands 1 hour, crosses 1000 mesh filter screen filtrations and obtains filtrate；
4) step 2) gained thick paste add step 3) gained filtrate in, be sufficiently stirred for mix after gained liquid cross 1000 mesh drainage screens
Filter gained filtrate and be antibacterial medicinal liquid.
4. as claimed any one in claims 1 to 3 a kind of preparation method of antibacterial titanium dioxide composite micro-nano rice grain, its
It is characterised by, comprises the following steps：
(1) Entermorpha nanometer dry powder is prepared：The cleaning of Entermorpha fresh goods removes the impurity such as the grains of sand, and Jing natural air dryings or lyophilization must be done
Product, gained dry product micronizing to last being placed in ball grinder of micropowder carries out high-energy ball milling post-drying and obtains Entermorpha nanometer dry powder；
(2) spinning precursor liquid is prepared：Prepare Entermorpha nanometer dry powder, anhydrous second containing gained in tetrabutyl titanate, step (1)
Alcohol, the high molecular polymer for being dissolved in ethanol, the uniform suspension of organic acid are used as spinning precursor liquid；
(3) electrospinning preparation fibrous membrane：Spinning precursor liquid obtained by step (2) is added in the liquid storage mechanism of electrostatic spinning apparatus, is spun
Silk shower nozzle connection high-voltage power cathode, collector connection high voltage power supply negative pole, adjusting spinning voltage and spinning distance carries out electrostatic
Spinning, spinning precursor liquid forms fibrous membrane and is preparation fibrous membrane in the presence of electric field force on collector；
(4) carbonization treatment：Preparation fibre film Jing high-temperature heat treatments under anoxia or oxygen-free environment of gained make Entermorpha receive in step (3)
Rice dry powder is carbonized to obtain activated carbon, and the process eliminates high molecular polymer and residual solvent in prepared fibrous membrane, obtains waterside simultaneously
Tongue activated carbon/dioxide composite nanofiber film；
(5) pickling impurity removal：By the hydrochloric acid of sample Jing molar concentrations 5mol/L obtained by step (4) under the constant temperature that temperature is 60 DEG C
Immersion is taken out sample from acid solution with removing impurity for 10 hours, then is soaked in deionized water every replacing one in 2 hours
The deionized water of secondary immersion sample, and the ph values of the deionized water for soaking sample are tested, to the deionized water for soaking sample
For neutrality when, by sample take out be placed in 60 DEG C of baking ovens dry；
(6) pulverized particles：Drying sample obtained by step (5) is crushed to into 2000 mesh powder；
(7) medicinal liquid is loaded：Step (6) gained powder is mixed homogeneously with appropriate antibacterial medicinal liquid, powder particle is fully absorbed
Load medicinal liquid；
(8) it is dried：Step (7) resulting material dries to obtain thick paste, and gained thick paste lyophilization obtains dry solids and is antibacterial
Titanium dioxide composite micro-nano rice grain.
5. the preparation method of a kind of antibacterial titanium dioxide composite micro-nano rice grain as claimed in claim 4 described, its feature
It is that described step (1) prepares Entermorpha nanometer dry powder：The cleaning of Entermorpha fresh goods is removed after the impurity such as the grains of sand, and lyophilization must be done
Product, gained dry product micronizing is last to 500 mesh micropowder, and gained micron powder is placed in ball grinder carries out high-energy ball milling,
Wherein zirconia ball:Micron powder:The mass ratio of water is 8:4:1,2000 revs/min of rotating speed, Ball-milling Time 4 hours, gained powder
End is placed in 60 DEG C of baking ovens dries to obtain Entermorpha nanometer dry powder.
6. the preparation method of a kind of antibacterial titanium dioxide composite micro-nano rice grain as claimed in claim 4 described, its feature
It is that described step (2) prepares spinning precursor liquid：3.4g tetrabutyl titanates add 9ml dehydrated alcohol with 2g sulfosalicylic acids
In, add the Entermorpha nanometer dry powder obtained by 2.2g steps (1), magnetic agitation 1 hour to match somebody with somebody after 1 hour mix homogeneously of magnetic agitation
Make suspension A；3.5g polyvinylpyrrolidones are added in 9ml dehydrated alcohol, and 2 hours mix homogeneously of magnetic agitation obtain solution B；
After suspension A and solution B mixing magnetic agitation 40 minutes, ultrasonic vibration 10 minutes, magnetic agitation 30 again after ultrasonic vibration
Minute, then ultrasonic vibration 10 minutes again, obtain final product uniform suspension for spinning precursor liquid；Described step (3) electrospinning preparation
Spinning voltage in fibrous membrane is 22kV, and spinning distance is 18cm, and the spinning time is 30 minutes.
7. the preparation method of a kind of antibacterial titanium dioxide composite micro-nano rice grain as claimed in claim 4 described, its feature
It is, described step (4) carbonization treatment：The preparation fibre film of gained is placed in tube furnace in step (3), in a nitrogen atmosphere,
500 DEG C are warming up to 3 DEG C/min, after being incubated 1 hour, room temperature are cooled to and are taken out sample, obtain final product Entermorpha activated carbon/titanium dioxide
Composite nano-fiber membrane.
8. the preparation method of a kind of antibacterial titanium dioxide composite micro-nano rice grain as claimed in claim 4 described, its feature
It is, described step (7) load medicinal liquid：By 4 times of antibacterial medicinal liquid mixing magnetic force of step (6) gained powder and powder gross mass
Stirring 30 minutes after, ultrasonic vibration 10 minutes, again magnetic agitation after 24 hours suspension.
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| CN113795149A (en) * | 2019-04-04 | 2021-12-14 | 印摩列求尔国际有限公司 | Various uses of nanoparticle compounds of functionalized titanium dioxide |
| CN113875783A (en) * | 2021-11-05 | 2022-01-04 | 淮南联合大学 | Photocatalyst for expelling mites and preparation method thereof |
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| CN102586948A (en) * | 2011-12-15 | 2012-07-18 | 江南大学 | Anatase type titanium dioxide nano-fiber photocatalyst and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113795149A (en) * | 2019-04-04 | 2021-12-14 | 印摩列求尔国际有限公司 | Various uses of nanoparticle compounds of functionalized titanium dioxide |
| CN113795149B (en) * | 2019-04-04 | 2023-12-12 | 印摩列求尔国际有限公司 | Various uses of nanoparticle compounds of functionalized titanium dioxide |
| CN113875783A (en) * | 2021-11-05 | 2022-01-04 | 淮南联合大学 | Photocatalyst for expelling mites and preparation method thereof |
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