CN106070321B - A kind of golden cluster-titanium dioxide-graphene composite material and its preparation method and application can be used for visible light efficient sterilization - Google Patents
A kind of golden cluster-titanium dioxide-graphene composite material and its preparation method and application can be used for visible light efficient sterilization Download PDFInfo
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Abstract
The present invention relates to a kind of golden cluster-titanium dioxide-graphene composite materials and its preparation method and application that can be used for visible light efficient sterilization, belong to technical field of composite materials.The composite material connects golden cluster and titanium dioxide nano-particle by way of electrostatic attraction first, then it is connected to golden cluster and titanium dioxide compound on graphene using the functional group on graphene, the mass ratio of golden cluster, titanium dioxide and graphene is (2.5-6.4) %: (78.6-92.5) %: (4.2-15) %.The present invention also provides the preparation method and application of above-mentioned composite material.Above-mentioned composite material allows titanium dioxide by excited by visible light by the visible absorption property of Aurum clusters, make to inspire in electronics transfer to graphene using the super Electronic Transport of Two Benzene of graphene, the recombination rate for reducing electrons and holes, to effectively improve the antibacterial action of composite material.The composite material can reach 80% to the eradicative rate of Escherichia coli, staphylococcus aureus under visible light.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of golden cluster-two that can be used for visible light efficient sterilization
Titanium oxide-graphene composite material and its preparation method and application.
Background technique
Antibacterial agent is a kind of to kill bacterium and inhibit bacterial growth as the material of major function, is mainly used for agricultural, doctor
The fields such as, industry.Its is many kinds of for antibacterial agent, can be mainly divided into organic antibacterial agent and inorganic antiseptic two major classes, organic
The disadvantages of anti-biotic material is decomposed there are poor heat resistance, easily and service life is short.As the development of nanotechnology is more and more at present
Inorganic material be applied to antibacterial field, wherein the antibacterial agent most to attract people's attention is exactly titanium dioxide, with nontoxic, nothing
Taste, nonirritant, heat resistance is good, the features such as being not easily decomposed, is not volatile, source is wide, is widely used in ceramics, coating, change
The industries such as fibre, cosmetics, electronics, plastics, rubber.
Titanium dioxide semiconductor material is primarily due to this kind of semiconductor material as antibacterial agent can be under the excitation of light
So that its valence-band electrons is transitted to conduction band, and leave hole in valence band simultaneously, free electron and hole respectively with the dissolution in environment
Oxygen and water reaction generate superoxide anion and hydroxyl radical free radical isoreactivity oxygen species.These active oxygen species can be attacked directly
Bacterial cell causes oxidativestress damage, to play the role of kill and inhibit bacterial growth.However, due to titanium dioxide
Forbidden bandwidth is 3.2eV, can only be excited by ultraviolet light, and there was only about 4% in natural light is ultraviolet light；And the electricity inspired
Son and hole be easy to happen it is compound, to reduce the anti-microbial property of titanium dioxide.Therefore how TiO 2 visible light is improved
Bactericidal property becomes hot topic.
Summary of the invention
The present invention provides a kind of gold that can be used for visible light efficient sterilization to improve TiO 2 visible light bactericidal property
Cluster-titanium dioxide-graphene composite material and its preparation method and application.
To achieve the goals above, technical solution of the present invention is specific as follows:
A kind of golden cluster-titanium dioxide-graphene composite material can be used for visible light efficient sterilization, the composite material is first
Golden cluster and titanium dioxide nano-particle are connected by way of electrostatic attraction, then make golden cluster using the functional group on graphene
It is connected on graphene with titanium dioxide compound, the mass ratio of golden cluster, titanium dioxide and graphene is (2.5-6.4) %:
(78.6-92.5) %:(4.2-15) %.
In the above-mentioned technical solutions, the mass ratio of the golden cluster, titanium dioxide and graphene is 6.4%:86.6%:7%.
A kind of golden cluster-titanium dioxide-graphene composite material preparation method can be used for visible light efficient sterilization, including
Following steps:
(1) it weighs 3-15mg graphene powder to be added in the mixed solution of ultrapure water and dehydrated alcohol, ultrasonic disperse obtains
To graphene dispersing solution；
(2) the golden cluster solution for taking 10-50mL glutathione to protect, weighs 0.1g titania powder and stirs at room temperature；From
The above solution of the heart is precipitated, and cleans precipitating with ultrapure water, is dried precipitating after being repeated 3 times and is obtained golden cluster-titanium dioxide sample；
(3) golden cluster-titanium dioxide sample that step (2) synthesize is added in above-mentioned graphene dispersing solution, ultrasound, room temperature
After stirring at 100-150 DEG C after hydro-thermal reaction 3h, centrifugation is precipitated, and cleans precipitating with ultrapure water, will precipitating after being repeated 3 times
Drying obtains golden cluster-titanium dioxide-graphene composite material.
In the above-mentioned technical solutions, the graphene is made by following methods:
(1) weigh 1g graphite powder, 0.5g sodium nitrate is added to 250mL round-bottomed flask, then be added the 25mL concentrated sulfuric acid, stirring
It is uniformly mixed it；
(2) above-mentioned reaction mixture is placed in ice bath, weighs 3g potassium permanganate, is slowly added into mixed liquor；
(3) round-bottomed flask is moved into oil bath, temperature is set as 35 DEG C, stirs 2h；
(4) 46ml ultrapure water is added, temperature is controlled at 98 DEG C, 15min is stirred；
(5) hydrogen peroxide solution of 140mL 15% is added, centrifuging and taking precipitates the hydrochloric acid with 10% after temperature drops to room temperature
Precipitating, is dispersed in ultrapure water by solution cleaning after being repeated 5 times, and freeze-drying obtains graphene powder.
In the above-mentioned technical solutions, the golden cluster solution of the glutathione protection is made by following methods:
(1) the Milli-Q ultrapure water of 75mL 18.2M Ω is added in 250ml round-bottomed flask, 4.125mL is then added
48.56mM chlorauric acid solution, stirring are uniformly mixed it；
(2) it weighs 0.092g glutathione to be added in above-mentioned reaction solution, reaction is transferred to oil after stirring 20min
Bath, temperature are set as 75 DEG C, are stirred at reflux and stop reaction for 24 hours.
With the method for above-mentioned golden cluster-titanium dioxide-graphene composite material antibacterial, comprising the following steps:
Step 1, Bacteria Culture
(1) preparation of liquid bacterial culture solution: weigh that 10g tryptone, 5g yeast powder, that 5g sodium chloride is added to 1L is ultrapure
In water, pH value is adjusted to 7.2 with the sodium hydroxide solution of 5M, is put into high-pressure sterilizing pot and sterilizes, take out spare；
(2) preparation of solid bacteria culture solution: 10g tryptone, 5g yeast powder, 5g sodium chloride, 20g agar are weighed and is added
Into 1L ultrapure water, pH value is adjusted to 7.2 with the sodium hydroxide solution of 5M, is put into high-pressure sterilizing pot and sterilizes, 60 DEG C are taken out
Enter in culture product, it is spare after cooling；
(3) antibiotic is added in the culture medium after taking sterilizing, and final concentration of 20 μ g/mL takes 15 μ L of the bacteria culture frozen to add
Enter into 20mL culture solution, 37 DEG C of shaking table cultures are stayed overnight, revolution 150rpm；
Step 2 weighs 5mg Aurum clusters-titanium dioxide-graphene composite material and is added in 1mL inoculum, prepares
At the solution of 5mg/mL；
Step 3 takes the bacterial solution grown dilution different multiples to survey absorption value its 600nm at, and adjusting absorption value=
After 0.1, for use；
Step 4, Aurum clusters-titanium dioxide-graphene composite material antibacterial detection
Take Aurum clusters-titanium dioxide-graphene inoculum of the 144 prepared 5mg/mL of μ L that 156 μ L bacteriums are added
Culture solution is configured to the solution of 2.4mg/mL, respectively by its two-fold dilution obtain concentration be 1.2,0.6,0.3,0.15,0.75,
The solution of 0.375mg/mL respectively takes 50 μ L to be added to 96 orifice plates, wherein every hole is in triplicate, then every hole is separately added into 100 μ L
The bacterial solution of absorption value=0.1 is placed under sunlight simulator after irradiating 20min and moves into Bacteria Culture shaking table, 37 DEG C,
150rpm culture, the absorption value at 1h detection bacterium growth 600nm, draws growth curve.
In the above-mentioned technical solutions, step (4) is with spread plate method to Aurum clusters-titanium dioxide-graphene composite material
Carry out antibacterial detection, the specific steps are as follows:
Aurum clusters-titanium dioxide-graphene the inoculum for taking the 160 prepared 5mg/mL of μ L is added to 840 μ L suction
In the bacterial solution of receipts value=0.1；The bacterial solution of 840 absorption value=0.1 μ L is taken to add 160 μ L inoculums as a comparison；
Aurum clusters-titanium dioxide-graphene composite material inoculum spoke under sunlight simulator is not added in above-mentioned adduction
According to immigration Bacteria Culture shaking table after 20min, 37 DEG C, 150rpm culture 30min；Aurum clusters-titanium dioxide-is not added in above-mentioned adduction
The inoculum of graphene composite material dilutes 10000 times respectively, and 30 μ L is taken to be added in solid medium, after coating uniformly
Be put into 37 DEG C, 150rpm culture for 24 hours, take pictures.
The beneficial effects of the present invention are:
Golden cluster-titanium dioxide-the graphene composite material provided by the invention that can be used for visible light efficient sterilization is with paddy
The sweet peptide protection Aurum clusters of Guang are photosensitizer, graphene is electron transfer material, are made by the visible absorption property of Aurum clusters
Titanium dioxide can make to inspire electronics transfer to graphene using the super Electronic Transport of Two Benzene of graphene by excited by visible light
On, the recombination rate of electrons and holes is reduced, to effectively improve the antibacterial action of composite material.The composite material is to large intestine bar
The eradicative rate of bacterium, staphylococcus aureus under visible light can reach 80%.
Detailed description of the invention
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the transmission electron microscope photo that glutathione protects golden cluster.
Fig. 2 is golden cluster-titanium dioxide-graphene composite material transmission electron microscope photo.
Fig. 3 is the inspection that spread plate method inhibits Escherichia coli Growth performance to golden cluster-titanium dioxide-graphene composite material
Survey photo.
Fig. 4 is that spread plate method inhibits staphylococcus aureus growth to golden cluster-titanium dioxide-graphene composite material
The detection photo of energy.
Fig. 5 is the growth curve of bacteria that golden cluster-titanium dioxide-graphene composite material inhibits Escherichia coli Growth effect
Figure.
Fig. 6 is the bacterial growth that golden cluster-titanium dioxide-graphene composite material inhibits staphylococcus aureus growth effect
Curve graph.
Fig. 7 is the Survival probability of bacteria curve that golden cluster-titanium dioxide-graphene composite material inhibits Escherichia coli Growth effect
Figure.
Fig. 8 is the bacteria living that golden cluster-titanium dioxide-graphene composite material inhibits staphylococcus aureus growth effect
Rate curve graph.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
A kind of golden cluster-titanium dioxide-graphene composite material can be used for visible light efficient sterilization provided by the invention
Specific step is as follows for preparation method:
1, the synthesis of glutathione protection Aurum clusters:
(1) the Milli-Q ultrapure water of 75mL 18.2M Ω is added in 250ml round-bottomed flask, 4.125mL is then added
Chlorauric acid solution (48.56mM), stirring are uniformly mixed it；
(2) it weighs 0.092g glutathione to be added in reaction solution, reaction is transferred to oil bath after stirring 20min, temperature
Degree is set as 75 DEG C, is stirred at reflux and stops reaction for 24 hours.
Fig. 1 is the transmission electron microscope photo that glutathione protects Aurum clusters, the bright Aurum clusters synthesized of the chart
Size is 1-2nm.
2, the synthesis of graphene:
(1) weigh 1g graphite powder, 0.5g sodium nitrate is added to 250mL round-bottomed flask, then be added the 25mL concentrated sulfuric acid, stirring
It is uniformly mixed it；
(2) above-mentioned reaction mixture is placed in ice bath, weighs 3g potassium permanganate, is slowly added into mixed liquor；
(3) round-bottomed flask is moved into oil bath, temperature is set as 35 DEG C, stirs 2h；
(4) 46ml ultrapure water is added, temperature is controlled at 98 DEG C, 15min is stirred；
(5) hydrogen peroxide solution of 140mL 15% is added, centrifuging and taking precipitates the hydrochloric acid with 10% after temperature drops to room temperature
Precipitating, is dispersed in ultrapure water by solution cleaning after being repeated 5 times, and freeze-drying obtains graphene powder.
3, Aurum clusters-titanium dioxide-graphene composite material synthesis
(1) it weighs 3-15mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasound
Dispersion；
(2) the Aurum clusters solution for the glutathione protection for taking 10-50mL to synthesize, weighs 0.1g titania powder at room temperature
Stir 5h；It is centrifuged the above solution to be precipitated, cleans precipitating with ultrapure water, precipitating is placed in 60 DEG C of drying box bakings after being repeated 3 times
It is dry to obtain powder sample.
(3) above-mentioned synthetic Aurum clusters-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasound
20min is stirred at room temperature after 20min；After moving to 100-150 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, clear with ultrapure water
Precipitating is washed, precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains powder sample.
Fig. 2 is Aurum clusters-titanium dioxide-graphene composite material transmission electron microscope photo, and figure explanation uses this
Kind method can successfully synthesize Aurum clusters-titanium dioxide-graphene composite material.
Embodiment 1: mass ratio is Aurum clusters-titanium dioxide-graphene composite material conjunction of 6.4%:86.6%:7%
At
(1) it weighs 5mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasound point
It dissipates；
(2) the Aurum clusters solution for the glutathione protection for taking 25mL to synthesize, weighs 0.1g titania powder and stirs at room temperature
Mix 5h；It is centrifuged the above solution to be precipitated, cleans precipitating with ultrapure water, precipitating is placed in 60 DEG C of drying box drying after being repeated 3 times
Obtain powder sample.
(3) above-mentioned synthetic Aurum clusters-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasound
20min is stirred at room temperature after 20min；After moving to 120 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, and it is heavy to be cleaned with ultrapure water
It forms sediment, precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains powder sample.
Embodiment 2: mass ratio is Aurum clusters-titanium dioxide-graphene composite material of 6.4%:89.4%:4.2%
Synthesis
(1) it weighs 3mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasound point
It dissipates；
(2) the Aurum clusters solution for the glutathione protection for taking 50mL to synthesize, weighs 0.1g titania powder and stirs at room temperature
Mix 5h；It is centrifuged the above solution to be precipitated, cleans precipitating with ultrapure water, precipitating is placed in 60 DEG C of drying box drying after being repeated 3 times
Obtain powder sample.
(3) above-mentioned synthetic Aurum clusters-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasound
20min is stirred at room temperature after 20min；After moving to 150 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, and it is heavy to be cleaned with ultrapure water
It forms sediment, precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains powder sample.
Embodiment 3: mass ratio is Aurum clusters-titanium dioxide-graphene composite material conjunction of 2.5%:82.5%:15%
At
(1) it weighs 15mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasound point
It dissipates；
(2) the Aurum clusters solution for the glutathione protection for taking 10mL to synthesize, weighs 0.1g titania powder and stirs at room temperature
Mix 5h；It is centrifuged the above solution to be precipitated, cleans precipitating with ultrapure water, precipitating is placed in 60 DEG C of drying box drying after being repeated 3 times
Obtain powder sample.
(3) above-mentioned synthetic Aurum clusters-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasound
20min is stirred at room temperature after 20min；After moving to 100 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, and it is heavy to be cleaned with ultrapure water
It forms sediment, precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains powder sample.
Embodiment 4: mass ratio is Aurum clusters-titanium dioxide-graphene composite material conjunction of 6.4%:78.6%:15%
At
(1) it weighs 15mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasound point
It dissipates；
(2) the Aurum clusters solution for the glutathione protection for taking 50mL to synthesize, weighs 0.1g titania powder and stirs at room temperature
Mix 5h；It is centrifuged the above solution to be precipitated, cleans precipitating with ultrapure water, precipitating is placed in 60 DEG C of drying box drying after being repeated 3 times
Obtain powder sample.
(3) above-mentioned synthetic Aurum clusters-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasound
20min is stirred at room temperature after 20min；After moving to 120 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, and it is heavy to be cleaned with ultrapure water
It forms sediment, precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains powder sample.
Embodiment 5: mass ratio is Aurum clusters-titanium dioxide-graphene composite material conjunction of 2.5%:92.5%:5%
At
(1) it weighs 4mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasound point
It dissipates；
(2) the Aurum clusters solution for the glutathione protection for taking 10mL to synthesize, weighs 0.1g titania powder and stirs at room temperature
Mix 5h；It is centrifuged the above solution to be precipitated, cleans precipitating with ultrapure water, precipitating is placed in 60 DEG C of drying box drying after being repeated 3 times
Obtain powder sample.
(3) above-mentioned synthetic Aurum clusters-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasound
20min is stirred at room temperature after 20min；After moving to 130 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, and it is heavy to be cleaned with ultrapure water
It forms sediment, precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains powder sample.
With embodiment 1 prepare golden cluster-titanium dioxide-graphene composite material antibacterial embodiment of the method:
1, Bacteria Culture
The preparation of liquid bacterial culture solution: 10g tryptone, 5g yeast powder, 5g sodium chloride are weighed and is added to 1L ultrapure water
In, pH value is adjusted to 7.2 with the sodium hydroxide solution of 5M, is put into high-pressure sterilizing pot and is sterilized, takes out spare；
The preparation of solid bacteria culture solution: 10g tryptone, 5g yeast powder, 5g sodium chloride, 20g agar are weighed and is added to
In 1L ultrapure water, pH value is adjusted to 7.2 with the sodium hydroxide solution of 5M, is put into high-pressure sterilizing pot and sterilizes, 60 DEG C of taking-ups are poured into
It is spare after cooling in culture product；
Antibiotic is added in culture medium after taking sterilizing, and final concentration of 20 μ g/mL takes the Escherichia coli frozen or golden yellow respectively
15 μ L of color staphylococcus is added in 20mL culture solution, and 37 DEG C of shaking table cultures are stayed overnight, revolution 150rpm；
2, spread plate method inhibits the detection of bacterial growth performance to Aurum clusters-titanium dioxide-graphene composite material:
(1) it weighs 5mg Aurum clusters-titanium dioxide-graphene composite material to be added in 1mL inoculum, be configured to
The solution of 5mg/mL；
(2) it takes the Escherichia coli grown or staphylococcus aureus solution to dilute different multiples respectively to survey at its 600nm
Absorption value, adjust absorption value=0.1 after, for use；
(3) Aurum clusters-titanium dioxide-graphene inoculum for taking the 160 prepared 5mg/mL of μ L, is added to 840 μ
In the Escherichia coli of absorption value=0.1 L or staphylococcus aureus solution；Take Escherichia coli or the gold of 840 absorption value=0.1 μ L
Staphylococcus aureus solution adds 160 μ L inoculums as a comparison, and Aurum clusters-titanium dioxide-graphite is not added in above-mentioned adduction
The inoculum of alkene composite material irradiates under sunlight simulator and moves into Bacteria Culture shaking table after 20min, 37 DEG C,
150rpm cultivates 30min；Aurum clusters-titanium dioxide-graphene composite material Escherichia coli or golden yellow are not added in above-mentioned adduction
Color staphylococcus solution dilutes 10000 times respectively, and 30 μ L is taken to be added in solid medium, coating uniformly after be put into 37 DEG C,
150rpm is cultivated for 24 hours, is taken pictures.
Fig. 3 is that spread plate method inhibits Escherichia coli Growth performance to Aurum clusters-titanium dioxide-graphene composite material
Detect photo, as can be seen from the figure be added composite material nanometer particle after E. coli clones grow it is less, show compound
Material has good inhibiting effect to Escherichia coli.
Fig. 4 is that spread plate method inhibits staphylococcus aureus growth to Aurum clusters-titanium dioxide-graphene composite material
The detection photo of performance, as can be seen from the figure be added composite material nanometer particle after S. aureus colonies grow compared with
It is few, show that composite material has good inhibiting effect to staphylococcus aureus.
3, Aurum clusters-titanium dioxide-graphene composite material inhibits growth curve of bacteria test
(1) it weighs 5mg Aurum clusters-titanium dioxide-graphene composite material to be added in 1mL inoculum, be configured to
The solution of 5mg/mL；
(2) it takes the Escherichia coli grown or staphylococcus aureus solution to dilute different multiples respectively to survey at its 600nm
Absorption value, adjust absorption value=0.1 after, for use；
(3) take Aurum clusters-titanium dioxide-graphene inoculum of the 144 prepared 5mg/mL of μ L that 156 μ L are added thin
Bacteria culture fluid is configured to the solution of 2.4mg/mL, respectively by its two-fold dilution obtain concentration be 1.2,0.6,0.3,0.15,0.75,
The solution of 0.375mg/mL respectively takes 50 μ L to be added to 96 orifice plates, wherein every hole is in triplicate.Then every hole is separately added into 100 μ L
The Escherichia coli of absorption value=0.1 or staphylococcus aureus solution are placed under sunlight simulator after irradiating 20min and move into
Bacteria Culture shaking table, 37 DEG C, 150rpm culture.Absorption value at 1h detection bacterium growth 600nm, draws growth curve.
Fig. 5 is that Aurum clusters-titanium dioxide-graphene composite material inhibits the bacterial growth of Escherichia coli Growth effect bent
Line illustrates multiple it can be seen from the figure that E. coli growth rates are slowed down under the composite material effect of various concentration
Condensation material plays the role of inhibiting growth, and composite material concentration is higher, inhibits growth efficiency higher.
Fig. 6 is that Aurum clusters-titanium dioxide-graphene composite material inhibits the bacterium of staphylococcus aureus growth effect raw
Long curve, it can be seen from the figure that staphylococcus aureus growth rate is subtracted under the composite material effect of various concentration
Slowly, illustrate that composite material plays the role of inhibiting growth, and composite material concentration is higher, inhibits growth efficiency higher.
Fig. 7 is that Aurum clusters-titanium dioxide-graphene composite material inhibits the Survival probability of bacteria of Escherichia coli Growth effect bent
Line, as can be seen from the figure composite material increases the inhibiting effect of Escherichia coli Growth with the increase of concentration, wherein most
Big inhibitory effect can be greatly to 77.39%.
Fig. 8 is that Aurum clusters-titanium dioxide-graphene composite material inhibits the bacterium of staphylococcus aureus growth effect to deposit
Motility rate curve, as can be seen from the figure composite material to the inhibiting effect of staphylococcus aureus growth with the increase of concentration and
Increase, wherein maximum suppression effect can be greatly to 73.28%.
Aurum clusters-titanium dioxide-the graphene composite material prepared with embodiment 2,3,4,5 is used to inhibit bacterial growth,
Good inhibitory effect can also be obtained, is no longer enumerated here.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (6)
1. a kind of golden cluster-titanium dioxide-graphene composite material that can be used for visible light efficient sterilization, which is characterized in that this is multiple
Condensation material connects the golden cluster and titanium dioxide nano-particle of glutathione protection by way of electrostatic attraction first, then utilizes
The golden cluster and titanium dioxide compound that functional group on graphene protects glutathione are connected on graphene, glutathione
The mass ratio of the golden cluster of protection, titanium dioxide and graphene is 6.4%:86.6%:7%.
2. the golden cluster-titanium dioxide-graphene composite material according to claim 1 that can be used for visible light efficient sterilization
Preparation method, which comprises the following steps:
(1) it weighs 5mg graphene powder to be added in the mixed solution of 30mL ultrapure water and 9mL dehydrated alcohol, ultrasonic disperse obtains
To graphene dispersing solution；
(2) the Aurum clusters solution for taking 25mL glutathione to protect, weighs 0.1g titania powder and stirs 5h at room temperature；Centrifugation with
Upper solution is precipitated, and cleans precipitating with ultrapure water, and precipitating is placed in 60 DEG C of drying of drying box after being repeated 3 times and obtains golden cluster-two
Titanium oxide sample；
(3) above-mentioned synthetic golden cluster-titanium dioxide sample is added in above-mentioned graphene dispersing solution, ultrasonic 20min rear chamber
Temperature stirring 20min；After moving to 120 DEG C of hydro-thermal reaction 3h of reaction kettle, centrifugation is precipitated, and is cleaned precipitating with ultrapure water, is repeated 3 times
Precipitating is placed in 60 DEG C of drying of drying box afterwards and obtains powder sample gold cluster-titanium dioxide-graphene composite material.
3. the golden cluster-titanium dioxide-graphene composite material according to claim 2 that can be used for visible light efficient sterilization
Preparation method, which is characterized in that the graphene is made by following methods:
(1) weigh 1g graphite powder, 0.5g sodium nitrate is added to 250mL round-bottomed flask, then be added the 25mL concentrated sulfuric acid, stirring make it
It is uniformly mixed；
(2) above-mentioned reaction mixture is placed in ice bath, weighs 3g potassium permanganate, is slowly added into mixed liquor；
(3) round-bottomed flask is moved into oil bath, temperature is set as 35 DEG C, stirs 2h；
(4) 46ml ultrapure water is added, temperature is controlled at 98 DEG C, 15min is stirred；
(5) hydrogen peroxide solution of 140mL 15% is added, centrifuging and taking precipitates the hydrochloric acid solution with 10% after temperature drops to room temperature
Precipitating, is dispersed in ultrapure water by cleaning after being repeated 5 times, and freeze-drying obtains graphene powder.
4. the golden cluster-titanium dioxide-graphene composite material according to claim 2 that can be used for visible light efficient sterilization
Preparation method, which is characterized in that the golden cluster solution of the glutathione protection is made by following methods:
(1) the Milli-Q ultrapure water of 75mL 18.2M Ω is added in 250ml round-bottomed flask, 4.125mL is then added
48.56mM chlorauric acid solution, stirring are uniformly mixed it；
(2) it weighs 0.092g glutathione to be added in above-mentioned reaction solution, reaction is transferred to oil bath after stirring 20min, temperature
Degree is set as 75 DEG C, is stirred at reflux and stops reaction for 24 hours.
5. with the method for golden cluster-titanium dioxide-graphene composite material antibacterial described in claim 1, which is characterized in that including
Following steps:
Step 1, Bacteria Culture
(1) preparation of liquid bacterial culture solution: 10g tryptone, 5g yeast powder, 5g sodium chloride are weighed and is added to 1L ultrapure water
In, pH value is adjusted to 7.2 with the sodium hydroxide solution of 5M, is put into high-pressure sterilizing pot and is sterilized, takes out spare；
(2) preparation of solid bacteria culture solution: 10g tryptone, 5g yeast powder, 5g sodium chloride, 20g agar are weighed and is added to 1L
In ultrapure water, pH value is adjusted to 7.2 with the sodium hydroxide solution of 5M, is put into high-pressure sterilizing pot and sterilizes, training is poured into 60 DEG C of taking-ups
It is spare after cooling in the product of supporting；
(3) antibiotic is added in the culture medium after taking sterilizing, and final concentration of 20 μ g/mL takes 15 μ L of the bacteria culture frozen to be added to
In 20mL culture solution, 37 DEG C of shaking table cultures are stayed overnight, revolution 150rpm；
Step 2 weighs 5mg Aurum clusters-titanium dioxide-graphene composite material and is added in 1mL inoculum, is configured to
The solution of 5mg/mL；
Step 3 takes the bacterial solution grown dilution different multiples to survey the absorption value at its 600nm, adjusts absorption value=0.1
Afterwards, for use；
Step 4, Aurum clusters-titanium dioxide-graphene composite material antibacterial detection
Take Aurum clusters-titanium dioxide-graphene inoculum of the 144 prepared 5mg/mL of μ L that 156 μ L Bacteria Cultures are added
Liquid is configured to the solution of 2.4mg/mL, respectively by its two-fold dilution obtain concentration be 1.2,0.6,0.3,0.15,0.75,
The solution of 0.375mg/mL respectively takes 50 μ L to be added to 96 orifice plates, wherein every hole is in triplicate, then every hole is separately added into 100 μ L
The bacterial solution of absorption value=0.1 is placed under sunlight simulator after irradiating 20min and moves into Bacteria Culture shaking table, 37 DEG C,
150rpm culture, the absorption value at 1h detection bacterium growth 600nm, draws growth curve.
6. the method that gold cluster-titanium dioxide-graphene composite material according to claim 5 inhibits bacterial growth, special
Sign is that step (4) carries out antibacterial detection to Aurum clusters-titanium dioxide-graphene composite material with spread plate method, specific to walk
It is rapid as follows:
Aurum clusters-titanium dioxide-graphene the inoculum for taking the 160 prepared 5mg/mL of μ L is added to 840 μ L absorption values
In=0.1 bacterial solution；The bacterial solution of 840 absorption value=0.1 μ L is taken to add 160 μ L inoculums as a comparison；It will be upper
Adduction is stated Aurum clusters-titanium dioxide-graphene composite material inoculum is not added to irradiate under sunlight simulator
Bacteria Culture shaking table, 37 DEG C, 150rpm culture 30min are moved into after 20min；Aurum clusters-titanium dioxide-stone is not added in above-mentioned adduction
The inoculum of black alkene composite material dilutes 10000 times respectively, and 30 μ L is taken to be added in solid medium, puts after coating uniformly
Enter 37 DEG C, 150rpm culture for 24 hours, take pictures.
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| CN102125837A (en) * | 2011-01-11 | 2011-07-20 | 湖南大学 | Metal-graphene-titanium dioxide nanotube array photocatalyst and preparation and application method thereof |
| CN104472542A (en) * | 2014-12-18 | 2015-04-01 | 中山大学 | Method for preparing graphene/silver/titanium dioxide composite material |
| CN105215352A (en) * | 2015-10-26 | 2016-01-06 | 吉林大学 | By the preparation method of the cationic polymer modified gold nanoclusters of coated with silica |
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| CN104472542A (en) * | 2014-12-18 | 2015-04-01 | 中山大学 | Method for preparing graphene/silver/titanium dioxide composite material |
| CN105215352A (en) * | 2015-10-26 | 2016-01-06 | 吉林大学 | By the preparation method of the cationic polymer modified gold nanoclusters of coated with silica |
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