CN105665739B - Bismuth bovine serum albumin(BSA) platinum nano composite material and preparation method thereof - Google Patents
Bismuth bovine serum albumin(BSA) platinum nano composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of bismuth bovine serum albumin(BSA) platinum nano composite material and preparation method thereof, aqueous bismuth nitrate solution is added in the bovine serum albumin(BSA) platinum nano material aqueous solution, heating water bath after being mixed with phosphate buffer, the mixed solution after finishing is heated by ultrafiltration and washing obtains the bismuth bovine serum albumin(BSA) platinum nano composite material aqueous solution, the bismuth bovine serum albumin(BSA) platinum nano composite material aqueous solution is freeze-dried to the powder for obtaining bismuth bovine serum albumin(BSA) platinum nano composite material.The present invention is a kind of new platinum nano material and preparation method thereof, and with many advantages such as the high, good stability of simple, cheap, catalytic activity are prepared, extremely tempting application prospect is shown in terms of biology enzyme is simulated.
Description
Technical field
The present invention relates to bismuth-bovine serum albumin(BSA)-platinum nano composite material and preparation method thereof, belong to nanometer technology neck
Domain.
Background technology
Biomolecule composite nano materials are scientists on the basis of to biomineralization molecule fully study, and are utilized
The inorganic nano material of small peptide and protein design and preparation in mineralising molecule.Utilize compound the receiving that protein is template preparation
Rice material in three dimensions at least it is one-dimensional in nanoscale scope or by the range scale material be basic structure
Unit is constituted, wavelength of its yardstick already close to light and the special effects with large surface, therefore such material is a kind of
Typical Mesoscopic structure, with skin effect, small-size effect, macro quanta tunnel effect and quantum confined effect.
Noble metal（Gold, platinum etc.）Due to their good stability, the advantages of fusing point is high make its nano material preparation and
Widely studied in.Nano platinum particle relies on its strong anti-oxidation power, high surface energy, strong adsorption capacity, in fuel electricity
All it is widely used in terms of pond, biology sensor, chemical catalyst.In recent years, researcher is more the side of research
Upper to the preparation and application that are placed on many metal composite nano materials, many metal composite nano materials summarize the excellent of various metals
Point, makes up the deficiency of property between metal, stabilizing it property, dispersiveness, and catalytic activity, which has, significantly to be lifted, and is following nanometer
The trend of investigation of materials.
The present invention prepares a kind of three-system composite Nano of bismuth-bovine serum albumin(BSA)-platinum using bovine serum albumin(BSA) as template
Material.
The content of the invention
The purpose of the present invention is to prepare a kind of to be used as the new of core shell structure using bismuth-bovine serum albumin(BSA)-nano platinum particle
Three-system composite nano materials and preparation method thereof.
To achieve these goals, the present invention uses following technical scheme：
A kind of bismuth-bovine serum albumin(BSA)-platinum nano composite material of the present invention, is prepared from by following methods：
Bismuth nitrate solution and phosphate buffer are added in the aqueous solution of bovine serum albumin(BSA)-platinum nano material, water-bath adds after mixing
Heat, the mixed solution after heating is finished passes through ultrafiltration and washed, and obtains containing bismuth-bovine serum albumin(BSA)-platinum nano composite material
The aqueous solution, by the freeze-drying of the aqueous solution of bismuth-bovine serum albumin(BSA)-platinum nano composite material obtain bismuth-bovine serum albumin(BSA)-
The powder of platinum nano composite material.
The volume ratio of the aqueous solution of the bovine serum albumin(BSA)-platinum nano material, bismuth nitrate solution and phosphate buffer
For 1:1:3；The concentration of the aqueous solution of the bovine serum albumin(BSA)-platinum nano material is 23.8 mg/mL, bismuth nitrate solution concentration
For 0.5 mmol/L, phosphate buffering liquid concentration is 10 mmol/L, and pH=7；Above-mentioned bovine serum albumin(BSA)-platinum nano material
It is molten after heating response in 80 DEG C of heating in water bath for reaction 2.5 hours after the aqueous solution, bismuth nitrate solution are mixed with phosphate buffer
Liquid loads the super filter tube that cutoff is 3k, 6000 r/min centrifugal ultrafiltrations, and washes 3 times；Obtain bismuth-bovine serum albumin
In vain-platinum nano composite material aqueous solution, by the freeze-drying of the bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution obtain bismuth-
The powder of bovine serum albumin(BSA)-platinum nano composite material；The bovine serum albumin(BSA)-platinum nano composite material is by following method systems
Standby：It is 16 mmol/L chlorine to add 5 mL concentration in 5 mL concentration are 50 mg/mL Bovine Serum Albumin in Aqueous Solution
Platinic acid solution and 0.5 mL concentration are 1.5 mol/L sodium hydroxide solutions, and 2 h are reacted at 80 DEG C of water-bath after mixing.
Described a kind of bismuth-bovine serum albumin(BSA)-platinum nano composite material, it is characterized in that Pt of the platinum by 87 %0With 13 %
Pt4+Composition, bismuth by 87 % Bi3+With 13 % Bi0Composition, the average grain diameter of nano-particle is 4 nm, and interplanar distance is
0.227 nm。
A kind of described bismuth-bovine serum albumin(BSA)-platinum nano composite material, it is characterized in that water can be dissolved in, aqueous solution room temperature
Lower place more than 1 month occurs without precipitum.
A kind of described bismuth-bovine serum albumin(BSA)-platinum nano composite material, it is characterized in that energy catalyzing hydrogen peroxide oxidation 3,
3 ', 5,5 '-tetramethyl biphenyl amine hydrochlorate generates blue product.
Described a kind of bismuth-bovine serum albumin(BSA)-platinum nano composite material, it is characterized in that its aqueous solution room temperature preservation 30 days
Afterwards, with good stability, relative catalytic activity reaches 98.9%.
The preparation method of a kind of bismuth-bovine serum albumin(BSA)-platinum nano composite material of the present invention, it is characterized in that 5
ML concentration is that to add 5 mL concentration in 50 mg/mL Bovine Serum Albumin in Aqueous Solution be 16 mmol/L platinum acid chloride solutions and 0.5
ML concentration is 1.5 mol/L sodium hydroxide solutions, and 2 h are reacted at 80 DEG C of water-bath after mixing；Solution loads cut-off molecule after reaction
The super filter tube for 3k, 6000 r/min centrifugal ultrafiltrations are measured, and are washed 3 times, bovine serum albumin(BSA)-platinum nano composite material water is obtained
Solution, the nano combined material of bovine serum albumin(BSA)-platinum is obtained by bovine serum albumin(BSA)-platinum nano composite material aqueous solution freeze-drying
The powder of material；0.6 is added in 0.6 mL concentration is 23.8 mg/mL bovine serum albumin(BSA)-platinum nano composite material aqueous solution
ML concentration is 0.5 mmol/L bismuth nitrate solutions and 1.8 mL concentration are 10 mmol/L, pH=7 phosphate buffer, after mixing
Solution after 2.5 h, reaction is reacted at 80 DEG C of water-bath and loads the super filter tube that cutoff is 3k, 6000 r/min centrifugal ultrafiltrations,
And wash 3 times, bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution is obtained, bismuth-bovine serum albumin(BSA)-platinum nanometer is multiple
The condensation material aqueous solution is freeze-dried the powder for obtaining bismuth-bovine serum albumin(BSA)-platinum nano composite material.
In resulting bismuth-bovine serum albumin(BSA)-platinum nano composite material platinum by 87% Pt0With 13% Pt4+Composition, bismuth
By 87% Bi3+With 13% Bi0Composition, the average grain diameter of nano-particle is 4 nm, and interplanar distance is 0.227 nm.
Specifically, a kind of bismuth-bovine serum albumin(BSA)-platinum nano composite material of the present invention, is by following methods
It is prepared from：Chloroplatinic acid aqueous solution is added in Bovine Serum Albumin in Aqueous Solution, sodium hydrate aqueous solution is added after mixing and is obtained
Mixed solution, heating in water bath for reaction, ultrafiltration is simultaneously washed, and obtains bovine serum albumin(BSA)-platinum nano material aqueous solution；It is pure in ox blood
Heating water bath after aqueous bismuth nitrate solution, mixing is added in the aqueous solution of albumen-platinum nano material, the mixed solution after finishing is heated
By ultrafiltration and wash, bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution is obtained, by bismuth-bovine serum albumin(BSA)-platinum
The nano composite material aqueous solution is freeze-dried the powder for obtaining bismuth-bovine serum albumin(BSA)-platinum nano composite material.
Described bovine serum albumin(BSA)-platinum concentration of aqueous solution is 23.8 mg/mL, and bismuth nitrate solution concentration is preferably 0.5
mmol/L。
The volume ratio of the bovine serum albumin(BSA)-platinum aqueous solution, aqueous bismuth nitrate solution and phosphate buffer is preferably 1:1:
3。
After the bovine serum albumin(BSA)-platinum nano material, bismuth nitrate, phosphate buffer are mixed successively, in preferably 80 DEG C water
It is 2.5 hours to bathe the heating response preferred time.
Solution loads the super filter tube that cutoff is preferably 3k after heating response, and preferably rotating speed centrifuges for 6000 r/min
Ultrafiltration, and preferred number of times is washed for 3 times.
In described bismuth-bovine serum albumin(BSA)-platinum nano composite material nano platinum particle by 87 % Pt0With 13 % Pt4 +Composition, the particle diameter of nano platinum particle is 4.0 ± 0.4 nm, and the interplanar distance of nano platinum particle is 0.227 nm, brilliant corresponding to platinum
111 crystal faces of body.Bismuth by 87 % Bi3+With 13 % Bi0Composition.
The water-soluble liquid energy of described bismuth-bovine serum albumin(BSA)-platinum nano composite material places at least one month, no precipitum
Occur.
Advantages of the present invention：
（1）Preparation method environmental protection of the present invention, it is easy to operate quick, it is not necessary to use reducing agent.
（2）Bismuth-bovine serum albumin(BSA)-platinum nano composite material particle diameter prepared by the present invention is small, and aqueous dispersion is good, steady
Qualitative height, remains in that good catalytic activity after being long placed in.
（3）Bismuth-bovine serum albumin(BSA)-platinum nano composite material prepared by the present invention can efficiently catalyzing hydrogen peroxide oxygen
Change peroxidase substrate, and catalytic activity is significantly increased compared with bovine serum albumin(BSA)-platinum nano material, therefore the present invention
Bismuth-bovine serum albumin(BSA)-platinum nano composite material can be as Mimetic enzyme of peroxidase to hydrogen peroxide and associated biochemical thing
Matter is accurately determined, and its application is more extensive.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of bismuth-bovine serum albumin(BSA)-platinum nano composite material.
Fig. 2 is Pt (4f) x-ray photoelectron power spectrum of bismuth-bovine serum albumin(BSA)-platinum nano composite material.
Fig. 3 is Bi (4f) x-ray photoelectron power spectrum of bismuth-bovine serum albumin(BSA)-platinum nano composite material.
Fig. 4 is the relative catalytic work of obtained bismuth-bovine serum albumin(BSA)-platinum nano composite material under differential responses temperature conditionss
Property figure.
Fig. 5 is the relative catalytic work of obtained bismuth-bovine serum albumin(BSA)-platinum nano composite material under differential responses time conditions
Property figure.
Fig. 6 is the relative catalytic of obtained bismuth-bovine serum albumin(BSA)-platinum nano composite material under different bismuth nitrate concentration conditions
Activity figure.
Fig. 7 is that bismuth-bovine serum albumin(BSA)-platinum nano composite material catalyzing hydrogen peroxide aoxidizes 3,3 ', 5,5 '-tetramethyl connection
The ultraviolet-visible absorption spectroscopy figure of anilinechloride system.
Embodiment
Example 1：
It is 16 mmol/L chlorine to add 5 mL concentration in 5 mL concentration are 50 mg/mL Bovine Serum Albumin in Aqueous Solution
Platinic acid solution and 0.5 mL concentration are 1.5 mol/L sodium hydroxide solutions, and 2 h are reacted at 80 DEG C of water-bath after mixing.It is molten after reaction
Liquid loads the super filter tube that cutoff is 3k, 6000 r/min centrifugal ultrafiltrations, and washes 3 times, obtains bovine serum albumin(BSA)-platinum
The nano composite material aqueous solution, bovine serum albumin is obtained by bovine serum albumin(BSA)-platinum nano composite material aqueous solution freeze-drying
The powder of in vain-platinum nano composite material.
Example 2：
It is water-soluble for bovine serum albumin(BSA)-platinum nano composite material prepared by 23.8 mg/mL example 1 in 0.6 mL concentration
Add that 0.6 mL concentration is 0.5 mmol/L bismuth nitrate solutions and 1.8 mL concentration are 10 mmol/L, pH=7 phosphate in liquid
Solution after 2.5 h, reaction is reacted after buffer solution, mixing at 80 DEG C of water-bath and loads the super filter tube that cutoff is 3k, 6000
R/min centrifugal ultrafiltrations, and wash 3 times, bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution is obtained, by bismuth-cow's serum
Albumin-platinum nano composite material aqueous solution freeze-drying obtains the powder of bismuth-bovine serum albumin(BSA)-platinum nano composite material
（Also referred to as：Bovine serum albumin(BSA)-platinum/bismuth composite nano materials）.
Example 3：
Bismuth-bovine serum albumin(BSA) prepared by example 2-water-soluble drop-coated of platinum nano composite material is taken to be transmitted on copper mesh
Electronic Speculum is detected.As shown in figure 1, nano platinum particle average grain diameter is 4 nm, the interplanar distance of gained nano-particle is 0.227 nm.
Example 4：
Bismuth-bovine serum albumin(BSA) prepared by example 2-platinum nano composite powder is taken to carry out x-ray photoelectron power spectrum survey
It is fixed.As shown in Fig. 2 Pt of the resulting platinum by 87 %0With 13 % Pt4+Composition.As shown in figure 3, resulting bismuth is by 87 %
Bi3+With 13 % Bi0Composition.Above-mentioned % refers to atomicity percentage.
Example 5：
0.6 is added in 0.6 mL concentration is 23.8 mg/mL bovine serum albumin(BSA)-platinum nano composite material aqueous solution
ML concentration is 0.5 mmol/L bismuth nitrate solutions and 1.8 mL concentration are 10 mmol/L, and pH=7 phosphate buffer is mixed
Afterwards in different temperature（20-80 ℃）It is lower to prepare 2.5 h of reaction.As shown in figure 4, resulting bovine serum albumin(BSA)-platinum nanometer
Composite catalytic activity strengthens with the rise for preparing reaction temperature, and when reaction temperature reaches 80 DEG C, its catalytic activity is most
It is high.
Example 6：
0.6 is added in 0.6 mL concentration is 23.8 mg/mL bovine serum albumin(BSA)-platinum nano composite material aqueous solution
ML concentration is 0.5 mmol/L bismuth nitrate solutions and 1.8 mL concentration are 10 mmol/L, and pH=7 phosphate buffer is mixed
0-200 min are reacted in 80 DEG C of water-bath afterwards.As shown in figure 5, resulting bovine serum albumin(BSA)-platinum nano composite material catalysis is lived
Property with prepare the reaction time extension and strengthen, the reaction time reach 2.5 h after, its catalytic activity reaches highest.
Example 7：
0.6 is added in 0.6 mL concentration is 23.8 mg/mL bovine serum albumin(BSA)-platinum nano composite material aqueous solution
ML various concentrations bismuth nitrate solutions（0-1 mmol/L）With 1.8 mL concentration be 10 mmol/L, pH=7 phosphate buffer,
80 DEG C of 2.5 h of reaction of water-bath after mixing.As shown in fig. 6, resulting bovine serum albumin(BSA)-platinum nano composite material catalysis is lived
Property strengthen with the increase of nitric acid bi concns, nitric acid bi concns be more than 0.5 mmo/L when, its catalytic activity reaches highest.
Example 8：
0.6 is added in 0.6 mL concentration is 23.8 mg/mL bovine serum albumin(BSA)-platinum nano composite material aqueous solution
ML concentration is 0.5 mmol/L bismuth nitrate solutions and 1.8 mL concentration are 10 mmol/L, and pH=7 phosphate buffer is mixed
Solution after 2.5 h, reaction is reacted at 80 DEG C of water-bath afterwards and loads the super filter tube that cutoff is 3k, 6000 r/min centrifugations are super
Filter, and wash 3 times, obtain bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution and place without precipitum to go out for more than 1 month
It is existing.
Example 9：
It is 2 to sequentially add 1 mL concentration in 2.79 mL concentration are 100 mmol/L, pH=5 phosphate buffer
Mol/L hydrogen peroxide, 0.2 mL concentration are dense for 16 mmol/L 3,3 ', 5,5 '-tetramethyl biphenyl amine hydrochlorate and 10 μ L
Bismuth-bovine serum albumin(BSA)-platinum composite nano materials aqueous solution for 4.76 mg/mL is spent, 37 DEG C of warm bath 10 minutes after mixing are surveyed
Determine ultraviolet-visible absorption spectroscopy.As shown in fig. 7, bismuth-bovine serum albumin(BSA)-platinum composite nano materials energy catalyzing hydrogen peroxide oxidation
TMB hydrochloride generates blue product, has absorption maximum at 652 nm wavelength.
Example 10：
Bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution room temperature preservation determines catalysis after 30 days, by example 9 and lived
Property, as a result show that bismuth-bovine serum albumin(BSA)-platinum nano composite material has good long-time stability, preserves 30 at room temperature
After it, relative catalytic activity can reach 98.9%.
The exemplary embodiments of the present invention are the foregoing is only, are not intended to limit the invention, all essences in the present invention
God and any modification made within principle, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of bismuth-bovine serum albumin(BSA)-platinum nano composite material, is prepared from by following methods：Bovine serum albumin(BSA)-
Bismuth nitrate solution and phosphate buffer, heating water bath after mixing, after heating is finished are added in the aqueous solution of platinum nano material
Mixed solution is by ultrafiltration and washes, and the aqueous solution containing bismuth-bovine serum albumin(BSA)-platinum nano composite material is obtained, by bismuth-ox
The aqueous solution freeze-drying of seralbumin-platinum nano composite material obtains bismuth-bovine serum albumin(BSA)-platinum nano composite material
Powder；The volume ratio of the aqueous solution of the bovine serum albumin(BSA)-platinum nano material, bismuth nitrate solution and phosphate buffer is 1:
1:3；The concentration of the aqueous solution of the bovine serum albumin(BSA)-platinum nano material is 23.8 mg/mL, and bismuth nitrate solution concentration is 0.5
Mmol/L, phosphate buffering liquid concentration is 10 mmol/L, and pH=7；Above-mentioned bovine serum albumin(BSA)-platinum nano material is water-soluble
After liquid, bismuth nitrate solution are mixed with phosphate buffer, in 80 DEG C of heating in water bath for reaction 2.5 hours, solution was filled after heating response
Enter the super filter tube that cutoff is 3k, 6000 r/min centrifugal ultrafiltrations, and wash 3 times；Obtain bismuth-bovine serum albumin(BSA)-platinum
The nano composite material aqueous solution, bismuth-ox blood is obtained by bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution freeze-drying
The powder of pure albumen-platinum nano composite material；The bovine serum albumin(BSA)-platinum nano composite material prepared by following methods and
Into：It is 16 mmol/L chloroplatinic acids to add 5 mL concentration in 5 mL concentration are 50 mg/mL Bovine Serum Albumin in Aqueous Solution
Solution and 0.5 mL concentration are 1.5 mol/L sodium hydroxide solutions, and 2 h are reacted at 80 DEG C of water-bath after mixing.
2. bismuth-bovine serum albumin(BSA)-platinum nano composite material according to claim 1, it is characterized in that Pt of the platinum by 87 %0
With 13 % Pt4+Composition, bismuth by 87 % Bi3+With 13 % Bi0Composition, the average grain diameter of nano-particle is 4 nm, crystal face
Spacing is 0.227 nm.
3. bismuth-bovine serum albumin(BSA)-platinum nano composite material according to claim 1, it is characterized in that water can be dissolved in, it is water-soluble
Liquid is placed more than 1 month at room temperature to be occurred without precipitum.
4. bismuth-bovine serum albumin(BSA)-platinum nano composite material according to claim 1, it is characterized in that peroxidating can be catalyzed
3,3 ', 5,5 '-tetramethyl biphenyl of hydroxide amine hydrochlorate generates blue product.
5. bismuth-bovine serum albumin(BSA)-platinum nano composite material according to claim 1, it is characterized in that its aqueous solution room temperature
After preserving 30 days, with good stability, relative catalytic activity reaches 98.9%.
6. a kind of preparation method of bismuth-bovine serum albumin(BSA)-platinum nano composite material, it is characterized in that being 50 mg/ in 5 mL concentration
Add that 5 mL concentration are 16 mmol/L platinum acid chloride solutions and 0.5 mL concentration is 1.5 in mL Bovine Serum Albumin in Aqueous Solution
After mol/L sodium hydroxide solutions, mixing 2 h are reacted at 80 DEG C of water-bath；Solution loads the ultrafiltration that cutoff is 3k after reaction
Pipe, 6000 r/min centrifugal ultrafiltrations, and wash 3 times, bovine serum albumin(BSA)-platinum nano composite material aqueous solution is obtained, by ox blood
Pure albumen-platinum nano composite material aqueous solution freeze-drying obtains the powder of bovine serum albumin(BSA)-platinum nano composite material；
Adding 0.6 mL concentration in the bovine serum albumin(BSA) that 0.6 mL concentration is 23.8 mg/mL-platinum nano composite material aqueous solution is
0.5 mmol/L bismuth nitrate solutions and 1.8 mL concentration are 10 mmol/L, pH=7 phosphate buffer, water-bath 80 after mixing
Solution after 2.5 h, reaction is reacted at DEG C and loads the super filter tube that cutoff is 3k, 6000 r/min centrifugal ultrafiltrations, and washes 3
It is secondary, bismuth-bovine serum albumin(BSA)-platinum nano composite material aqueous solution is obtained, by bismuth-bovine serum albumin(BSA)-platinum nano composite material
The aqueous solution is freeze-dried the powder for obtaining bismuth-bovine serum albumin(BSA)-platinum nano composite material.
7. the preparation method of bismuth-bovine serum albumin(BSA)-platinum nano composite material according to claim 6, it is characterized in that institute
In obtained bismuth-bovine serum albumin(BSA)-platinum nano composite material platinum by 87% Pt0With 13% Pt4+Composition, bismuth is by 87%
Bi3+With 13% Bi0Composition, the average grain diameter of nano-particle is 4 nm, and interplanar distance is 0.227 nm.
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