CN106732213A - A kind of golden nanometer particle/hydrogel composite material and its preparation method and application - Google Patents
A kind of golden nanometer particle/hydrogel composite material and its preparation method and application Download PDFInfo
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- CN106732213A CN106732213A CN201611225987.2A CN201611225987A CN106732213A CN 106732213 A CN106732213 A CN 106732213A CN 201611225987 A CN201611225987 A CN 201611225987A CN 106732213 A CN106732213 A CN 106732213A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0056—Preparation of gels containing inorganic material and water
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/49—Scattering, i.e. diffuse reflection within a body or fluid
Abstract
The invention discloses a kind of golden nanometer particle/hydrogel composite material and its preparation method and application, it is a kind of golden nanometer particle/hydrogel complex microsphere；The golden nanometer particle/hydrogel complex microsphere is the hydrogel microsphere that the particle diameter that ball interior is distributed with multiple golden nanometer particles is 10~1000 μm, and the particle diameter of the golden nanometer particle is 20~100nm.Its preparation method includes：Multiple golden nanometer particles are scattered in hydrogel reaction solution as dispersed phase, using oil-based liquid as continuous phase, and prepare water-in-oil emulsion using microfluidic methods, irradiation under the uviol lamp that wavelength is 311nm is placed in again, the mixed colloidal solution in the water-in-oil emulsion is set to be cured as golden nanometer particle/hydrogel complex microsphere, cleaned using organic solvent again, that is, obtained clean golden nanometer particle/hydrogel complex microsphere.The present invention can realize the visualization sensing and detection to environmental pH and concentration of glucose.
Description
Technical field
It is compound the present invention relates to organic-inorganic nanocomposite field, more particularly to a kind of golden nanometer particle/hydrogel
Material and its preparation method and application.
Background technology
Hydrogel is the gel with water as decentralized medium, and with macromolecule network system, property is soft, can keep certain
Shape, and substantial amounts of water can be absorbed.It is introducing hydrophobic grouping and the parent in the water soluble polymer with cross-linked network
Water base group, and hydrophilic radical and water molecules make hydrone be connected to netted inside, and the friendship of hydrophobic grouping water-swellable
Linked polymer.
Hydrogel can be divided into Common hydrogels and environmental sensitive hydrogels (i.e. intelligent aqueous gel).Environmental sensitive hydrogels energy
The minor variations of enough sensing external environments stimulate (for example：PH value, temperature, pressure, electric field, magnetic field, ionic strength, ultraviolet light,
The change of visible ray, specific chemicals etc.), and by the physically or chemically change of itself (for example：The volume sweell(ing) of itself or
Shrink) come respond these change or stimulate.This of environmental sensitive hydrogels can be with the extraneous spy for exchanging information and responding
Property, it is had huge application at aspects such as flexibly direct writing element, micromechanics, drug delivery system, seperation film, biomaterials
Prospect.
PH sensitive aqueous gels refer to change the intelligent aqueous gel that can be responded to the pH value of environment.PH sensitive hydrogels
- COO is typically contained in the macromolecular network of glue-、—OPO3-、—NH3+、—SO3+Deng zwitterion group, they can be according to ring
Proton is captured or is discharged in the change of border pH value, so as to cause volume to change.Using this property of pH sensitive aqueous gels
Can be conveniently adjusted and control the diffusion of medicine and rate of release in hydrogel.But existing pH sensitive aqueous gels are mostly
Water white transparency, its Volume Changes is difficult to differentiate, and in particular for the pH value sensing of micro solution, single this kind of hydrogel is more
Plus it is difficult to pH value visualization sensing.
The content of the invention
In order to solve the technical problem that independent pH sensitive aqueous gels in the prior art are difficult to pH value visualization sensing,
The invention provides a kind of golden nanometer particle/hydrogel composite material and its preparation method and application such that it is able to realize to ring
The visualization sensing of border pH value change and detection.
The purpose of the present invention is achieved through the following technical solutions：
A kind of golden nanometer particle/hydrogel composite material, it is a kind of golden nanometer particle/hydrogel complex microsphere；The gold
Nano-particle/hydrogel complex microsphere is the water-setting that the particle diameter that ball interior is distributed with multiple golden nanometer particles is 10~1000 μm
Glue microballoon, and the particle diameter of the golden nanometer particle is 20~100nm.
Preferably, the composition of the hydrogel microsphere includes acrylamide and acrylic acid.
A kind of preparation method of above-mentioned golden nanometer particle/hydrogel composite material, comprises the following steps：
Step A, the golden nanometer particle that multiple particle diameters are 20~100nm is scattered in hydrogel reaction solution, so as to obtain
Mixed colloidal solution；
Step B, according to parts by volume meter, 100 parts of atoleines are mixed with 1.5 parts of emulsifying agents, so as to obtain oil-based liquid；
Step C, the mixed colloidal solution that will be obtained in step A are used as micro-fluidic dispersed phase, the oil that will be obtained in step B
Property liquid prepares water-in-oil emulsion as micro-fluidic continuous phase using microfluidic methods, then by the water-in-oil emulsion
Irradiation under the uviol lamp that wavelength is 311nm is placed in, so that the mixed colloidal solution in the water-in-oil emulsion is cured as Jenner
Rice corpuscles/hydrogel complex microsphere；
Step D, using organic solvent in step C solidify after golden nanometer particle/hydrogel complex microsphere clean,
So as to obtain clean golden nanometer particle/hydrogel complex microsphere.
Preferably, the golden nanometer particle that multiple particle diameters are 20~100nm is scattered in into hydrogel reaction solution includes：To be many
Individual particle diameter is that the golden nanometer particle of 20~100nm mixes with hydrogel reaction solution, and is uniformly dispersed using ultrasonically treated.
Preferably, the raw material of the hydrogel reaction solution includes acrylamide and acrylic acid, and acrylamide and propylene
The mol ratio of acid is 1~4:1.
Preferably, described hydrogel reaction solution is made of following methods：According to acrylamide with acrylic acid mole
Than being 1~4:1 ratio, acrylamide and acrylic acid are dissolved in deionized water, and add crosslinking agent and light trigger, mixing
Uniformly, so as to obtain hydrogel reaction solution.
Preferably, described golden nanometer particle is made of following methods：1.4mL poly- two is used according to every 70mL ethylene glycol
Allyl dimethyl ammonium chloride and 35 μ L concentration are the ratio of 1mol/L gold chlorides, by ethylene glycol, diallyl dimethyl chlorine
Change ammonium to be mixed with gold chloride, be placed in reacting 30min in oil bath pan, oil bath temperature is 195~220 DEG C, so as to be obtained
Mixed liquor comprising golden octahedron nano-particle；Then it is 1mol/L gold chlorides to use 17.5 μ L concentration according to 70mL ethylene glycol
Ratio, to adding gold chloride in the mixed liquor comprising gold octahedron nano-particle, and reacts 2~5 minutes, then enter at room temperature
Row centrifugal treating, so as to the golden nanometer particle that particle diameter is 20~100nm is obtained.
Preferably, emulsifying agent uses polyether modified silicon oil KF6038；Described organic solvent uses petroleum ether or ethanol.
Golden nanometer particle/hydrogel composite material in above-mentioned technical proposal is directly used in visualization sensing and the inspection of pH value
Survey.
The visualization that golden nanometer particle/hydrogel composite material in above-mentioned technical proposal is directly used in concentration of glucose is passed
Sense and detection.
As seen from the above technical solution provided by the invention, golden nanometer particle/hydrogel provided by the present invention is multiple
Condensation material is scattered in hydrogel reaction solution by by the golden nanometer particle that multiple particle diameters are 20~100nm, and uses miniflow
Prosecutor method is made water-in-oil emulsion, then carries out polymerizing curable to the hydrogel reaction solution in water-in-oil emulsion, from prepared by ball
The particle diameter that internal body portion is furnished with multiple golden nanometer particles is 10~1000 μm of hydrogel microsphere.Due to the hydrogel microsphere into
Dividing includes acrylamide and acrylic acid, therefore the hydrogel microsphere has certain sensitiveness to pH value, when the pH value of external environment
During change, the volume of the hydrogel microsphere can change, and then make between the golden nanometer particle inside the hydrogel microsphere
Distance changes, such that it is able to the change of the pH value of external environment is converted into change of these golden nanometer particles to absorption with the scattering of light
Change, which achieves the visualization sensing and the detection that change to environmental pH.It can be seen that, golden nanometer particle provided by the present invention/
Hydrogel composite material can not only solve independent pH sensitive aqueous gels in the prior art and be difficult to pH value visualization sensing
Technical problem, realize the visualization sensing to environmental pH change and detection, and can reuse, be conducive to saving into
This, it is to avoid the waste of material.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will use needed for embodiment description
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the electron scanning micrograph of regular spherical golden nanometer particle obtained in step d in the embodiment of the present invention 1
And abosrption spectrogram.
Fig. 2 is that the light microscope of final obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 1 shines
Piece, electron scanning micrograph, abosrption spectrogram.
Fig. 3 is to observe under different pH value being obtained in the embodiment of the present invention 2 using Zeiss light microscope (Axio Lab.A1)
Golden nanometer particle/hydrogel complex microsphere pattern size obtained from optical microscope photograph.
Fig. 4 is to be observed under different pH value in the embodiment of the present invention 1~3 using Zeiss light microscope (Axio Lab.A1)
Golden nanometer particle/hydrogel under different pH value obtained from the pattern size of obtained golden nanometer particle/hydrogel complex microsphere
Complex microsphere change of size curve map.
Fig. 5 is respectively to obtained golden nanometer particle/hydrogel in the single embodiment of the present invention 1 using Morpho spectrometers
Complex microsphere absorption spectrum performance at various ph values detected obtained from absorption spectrum performance comparison figure.
Fig. 6 is respectively to obtained golden nanometer particle/hydrogel in the single embodiment of the present invention 2 using Morpho spectrometers
Complex microsphere absorption spectrum performance at various ph values detected obtained from absorption spectrum performance comparison figure.
Fig. 7 is respectively to obtained golden nanometer particle/hydrogel in the single embodiment of the present invention 3 using Morpho spectrometers
Complex microsphere absorption spectrum performance at various ph values detected obtained from absorption spectrum performance comparison figure.
Fig. 8 is respectively to obtained golden nanometer particle/water in the single embodiment of the present invention 1~3 using Morpho spectrometers
Gel complex microsphere absorption peak strength obtained from absorption spectrum performance is detected at various ph values is with pH value change curve
Figure.
Fig. 9 is respectively to obtained golden nanometer particle/hydrogel in the single embodiment of the present invention 2 using Morpho spectrometers
Absorption spectrum performance of the complex microsphere under different concentration of glucose detected obtained from absorption spectrum performance comparison figure.
Figure 10 is respectively to obtained golden nanometer particle/water-setting in the single embodiment of the present invention 2 using Morpho spectrometers
Absorption spectrum performance of the glue complex microsphere under different concentration of glucose detected obtained from absorption peak strength with glucose
Concentration curve figure.
Specific embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Inventive embodiment, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not paid
Example, belongs to protection scope of the present invention.
Golden nanometer particle/hydrogel composite material in the present invention and its preparation method and application is retouched in detail below
State.
(1) a kind of golden nanometer particle/hydrogel composite material
A kind of golden nanometer particle/hydrogel composite material, it is a kind of golden nanometer particle/hydrogel complex microsphere；The gold
Nano-particle/hydrogel complex microsphere is the water-setting that the particle diameter that ball interior is distributed with multiple golden nanometer particles is 10~1000 μm
Glue microballoon, and the particle diameter of the golden nanometer particle is 20~100nm.Wherein, the composition of the hydrogel microsphere includes propylene
Acid amides and acrylic acid.
Specifically, in the golden nanometer particle/hydrogel composite material, the inside of hydrogel microsphere is distributed with multiple gold nanos
Particle, because the composition of hydrogel microsphere includes acrylamide and acrylic acid, therefore the hydrogel microsphere has necessarily to pH value
Sensitiveness, when the pH value of external environment changes, the volume of the hydrogel microsphere can change, and then make the hydrogel microsphere
The distance between internal golden nanometer particle changes, such that it is able to the change of the pH value of external environment is converted into these Jenner's grain of rices
Change of the son to absorption with the scattering of light, which achieves the visualization sensing and the detection that change to environmental pH.Using single
The golden nanometer particle/hydrogel complex microsphere carry out absorption spectrum measurement it can be found that the single golden nanometer particle/water-setting
Glue complex microsphere can be used for the visualization sensing and detection to the change of micro solution pH value, and this has expanded organic-inorganic nano and has answered
The application field of condensation material.
(2) preparation method of above-mentioned golden nanometer particle/hydrogel composite material
Multiple golden nanometer particles first can be distributed to water by the preparation method of above-mentioned golden nanometer particle/hydrogel composite material
In gel reaction liquid, water-in-oil emulsion then is made using microfluidic methods of the prior art, then using light polymerization process pair
Hydrogel reaction solution in water-in-oil emulsion carries out polymerizing curable, so as to golden nanometer particle/hydrogel complex microsphere is obtained；And
The golden nanometer particle can use and gold chloride preparation gold octahedron nano-particle is reduced in ethylene glycol, then will using gold chloride
Golden octahedron nano-particle is etched into the color of spherical gold of rule.The preparation of the golden nanometer particle/hydrogel composite material
Method specifically may comprise steps of：
Step A, the golden nanometer particle that multiple particle diameters are 20~100nm is scattered in hydrogel reaction solution, so as to obtain
Mixed colloidal solution.In actual applications, can be by golden nanometer particle that multiple particle diameters are 20~100nm and hydrogel reaction solution
Mixing, and be uniformly dispersed using ultrasonically treated, so as to obtain mixed colloidal solution.
Wherein, the raw material of the hydrogel reaction solution includes acrylamide and acrylic acid, and acrylamide and acrylic acid
Mol ratio be 1~4:1.Described hydrogel reaction solution can be prepared from using following methods：According to acrylamide and third
The mol ratio of olefin(e) acid is 1~4:1 ratio, acrylamide and acrylic acid are dissolved in deionized water, and add crosslinking agent (described
Crosslinking agent can use N of the prior art, N '-methylene-bisacrylamide) and light trigger (described light trigger can
To use 2- hydroxy-2-methyls phenyl-propane -1- ketone of the prior art), it is well mixed, so as to obtain hydrogel reaction solution.
Specifically, described golden nanometer particle can be prepared from using following methods：Used according to every 70mL ethylene glycol
1.4mL diallyl dimethyl ammoniumchlorides and 35 μ L concentration are the ratio of 1mol/L gold chlorides, by ethylene glycol, polydiene propyl group
Alkyl dimethyl ammonium chloride is mixed with gold chloride, is placed in reacting 30min in oil bath pan, and oil bath temperature is 195~220 DEG C,
So as to the mixed liquor comprising gold octahedron nano-particle is obtained；Then it is 1mol/L to use 17.5 μ L concentration according to 70mL ethylene glycol
The ratio of gold chloride, to adding gold chloride in the mixed liquor comprising gold octahedron nano-particle, and reacts 2~5 at room temperature
Minute, performed etching with to golden octahedron nano-particle, then centrifugal treating is carried out using supercentrifuge of the prior art, from
And can be prepared by the regular color of spherical gold that particle diameter is 20~100nm.
Step B, according to parts by volume meter, by 100 parts of atoleines and 1.5 parts of emulsifying agents, (emulsifying agent uses prior art
In polyether modified silicon oil KF6038) mixing, so as to obtain oil-based liquid.
Step C, the mixed colloidal solution that will be obtained in step A are used as micro-fluidic dispersed phase, the oil that will be obtained in step B
Property liquid as micro-fluidic continuous phase, the flow velocity of micro-fluidic dispersed phase is 100 μ L/h, and the flow velocity of micro-fluidic continuous phase is
500 μ L/min, and water-in-oil emulsion is prepared using microfluidic methods of the prior art, then the water-in-oil emulsion is placed in
Wavelength is irradiation under the uviol lamp of 311nm, so that the mixed colloidal solution in the water-in-oil emulsion is cured as Jenner's grain of rice
Son/hydrogel complex microsphere.
Step D, using organic solvent (described organic solvent using petroleum ether or ethanol) to solidifying in step C after gold
Nano-particle/hydrogel complex microsphere is cleaned, so as to obtain clean golden nanometer particle/hydrogel complex microsphere.
As fully visible, golden nanometer particle/hydrogel composite material provided by the present invention can not only solve prior art
In individually pH sensitive aqueous gels be difficult to pH value visualization sensing technical problem, realize to environmental pH change it is visual
Change sensing and detection, or even the visualization sensing to the change of micro solution pH value and detection can be realized, and profit can be repeated
With being conducive to the saving of cost, it is to avoid the waste of material.And golden nanometer particle/hydrogel composite material provided by the present invention
Preparation method not only process is simple, and without valuable preparation processing instrument.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with tool
Golden nanometer particle/hydrogel composite material that body embodiment is provided the present invention and its preparation method and application is retouched in detail
State.
Embodiment 1
A kind of golden nanometer particle/hydrogel composite material, is prepared from using following steps：
Step a, the gold chloride that 35 μ L concentration are 1mol/L is pipetted with 20~200 μ L liquid-transfering guns, and with 1~5mL liquid-transfering guns
1.4mL diallyl dimethyl ammoniumchlorides are pipetted, both of which is put in 100mL vials；Measured with the graduated cylinder of 100mL again
70mL ethylene glycol is added in described 100mL vials, is stirred, so as to obtain golden nanometer particle reaction solution.Now, institute
The color for stating liquid in 100mL vials is uniform light green color.
Step b, the golden nanometer particle reaction solution in step a is placed in 30min is reacted in oil bath pan, oil bath temperature is 195
~220 DEG C, so as to the mixed liquor comprising gold octahedron nano-particle is obtained.In this step, liquid in the 100mL vials
Color is changed into purple from light green color, then is changed into kermesinus from purple.
Step c, the mixed liquor comprising golden octahedron nano-particle in step b is down to room temperature, and with 2~20 μ L liquid reliefs
Rifle pipettes the gold chloride that 17.5 μ L concentration are 1mol/L and is added in the mixed liquor comprising gold octahedron nano-particle, in room temperature
Lower reaction 2~5 minutes, performs etching, with to golden octahedron nano-particle so as to can be prepared by comprising regular spherical Jenner's grain of rice
The mixed liquor of son.
Step d, the mixed liquor 200mL comprising regular spherical golden nanometer particle taken in step c, and use supercentrifuge
The centrifugal treating of 30min is carried out to it with the rotating speed of 13000r/min, to remove the liquid such as ethylene glycol, so as to can be prepared by particle diameter
It is the regular spherical golden nanometer particle of 20~100nm.
Step e, with electronic balance weighing 0.5g acrylamides, the N of 20mg, N '-methylene-bisacrylamide is added to 5mL
Deionized water in, then (now acrylamide and acrylic acid mol ratio are about 1 to 480 μ L acrylic acid are added in the deionized water:
1) with 30 μ L 2- hydroxy-2-methyl phenyl-propane -1- ketone, stir, so as to obtain hydrogel reaction solution.
Step f, the hydrogel reaction solution taken in 1mL steps e, and the regular spherical golden nanometer particle in step d is added
To the hydrogel reaction solution, being subsequently placed in supersonic cleaning machine carries out ultrasonically treated, makes the regular spherical golden nanometer particle steady
Surely it is scattered in the hydrogel reaction solution, is formed without precipitation, the mixed colloidal solution do not reunited.
Step g, according to parts by volume meter, 100 parts of atoleines are mixed with 1.5 parts of polyether modified silicon oil KF6038 so that
Obtain oil-based liquid.
Step h, mixed colloidal solution 1mL in step f is taken with 1mL syringes as micro-fluidic dispersed phase, use 100mL
Syringe takes oil-based liquid 80mL in step g as micro-fluidic continuous phase, and the flow velocity of micro-fluidic dispersed phase is whole
It is 100 μ L/h, it is 500 μ L/min that the flow velocity of micro-fluidic continuous phase is whole, uses T-shape glass micro chip, internal channel depth
Be 50 μm, a width of 200 μm, the polyfluortetraethylene pipe of 0.6 × 1.6mm as outer connecting pipe, so as to prepare water-in-oil emulsion；So
The water-in-oil emulsion is placed under the uviol lamp that wavelength is 311nm is afterwards irradiated, the polytetrafluoroethylene (PTFE) length of tube of irradiation area is 1
~2m, so that the mixed colloidal solution in the water-in-oil emulsion is cured as golden nanometer particle/hydrogel complex microsphere.
Step i, the golden nanometer particle/hydrogel complex microsphere after solidifying in step h is carried out using petroleum ether and ethanol
Alternately clean, and with the rotating speed centrifugal treating 4~5 times of 4000r/min, each 5min, to clean the golden nanometer particle/hydrogel
The oil-based liquid on complex microsphere surface, so as to can obtain clean golden nanometer particle/hydrogel complex microsphere.
Embodiment 2
A kind of golden nanometer particle/hydrogel composite material, employs the preparation method of the embodiments of the present invention 1, its area
It is not only that：Acrylic acid consumption in step e is changed into 240 μ L from 480 μ L in embodiment 1, now acrylamide and acrylic acid
Mol ratio is about 2:1.
Embodiment 3
A kind of golden nanometer particle/hydrogel composite material, employs the preparation method of the embodiments of the present invention 1, its area
It is not only that：Acrylic acid consumption in step e is changed into 120 μ L from 480 μ L in embodiment 1, now acrylamide and acrylic acid
Mol ratio is about 4:1.
Pattern and performance detection
Morphology observation and performance detection are carried out during the embodiments of the present invention 1~3 are implemented, concrete outcome is such as
Under：
(1) when oil bath temperature uses 215 DEG C in b the step of the embodiment of the present invention 1, d the step of to the embodiment of the present invention 1
Obtained regular spherical golden nanometer particle is observed and measured, and is shone so as to can obtain SEM as shown in Figure 1
Piece and abosrption spectrogram；Wherein, Fig. 1 a are to oil bath temperature in the embodiment of the present invention 1 using JEM-2010 transmission electron microscopes
Electron scanning micrograph obtained from being observed using regular spherical golden nanometer particle obtained in step d at 215 DEG C；Figure
1b is step d systems when using 215 DEG C to oil bath temperature in the embodiment of the present invention 1 using SU8020 field emission scanning electron microscopes
Regular spherical golden nanometer particle observed obtained from electron scanning micrograph；Fig. 1 c are using Morpho spectrum
Instrument oil bath temperature in the embodiment of the present invention 1 is measured using regular spherical golden nanometer particle obtained in step d at 215 DEG C and
The abosrption spectrogram for obtaining, its abscissa is wavelength (i.e. wavelength, unit is nm), and its ordinate is absorbance
(i.e. absorbance).Be can be seen that by such as Fig. 1 a, Fig. 1 b and Fig. 1 c：Regular spherical Jenner obtained in step d in the embodiment of the present invention 1
Rice corpuscles form is more regular, and granular size is very homogeneous, size about 67nm, has well to the spectrum that wavelength is 540nm or so
Assimilation effect.
(2) final obtained golden nanometer particle-hydrogel complex microsphere in the embodiment of the present invention 1 is completely dried, and it is right
The golden nanometer particle being completely dried-hydrogel complex microsphere is observed and measured, and is shown so as to can obtain optics as shown in Figure 2
Micro mirror photo, electron scanning micrograph, abosrption spectrogram；Wherein, Fig. 2 a are using Zeiss light microscope (Axio
Lab.A1 obtained from) observing the golden nanometer particle-hydrogel complex microsphere in the embodiment of the present invention 1 that is completely dried
Optical microscope photograph；Fig. 2 b and Fig. 2 c are using SU8020 field emission scanning electron microscopes to the present invention that is completely dried
Golden nanometer particle-hydrogel complex microsphere in embodiment 1 observed obtained from optical microscope photograph；Fig. 2 d are use
Morpho spectrometers the golden nanometer particle-hydrogel complex microsphere in the embodiment of the present invention 1 that is completely dried is measured and
The abosrption spectrogram for obtaining, its abscissa is wavelength (i.e. wavelength, unit is nm), and its ordinate is absorbance
(i.e. absorbance).Be can be seen that by such as Fig. 2 a：Final obtained golden nanometer particle-hydrogel is combined micro- in the embodiment of the present invention 1
Ball is spherical in more rule, and granular size is homogeneous；Be can be seen that by such as Fig. 2 b and Fig. 2 c：Finally made in the embodiment of the present invention 1
Golden nanometer particle-hydrogel complex microsphere the particle diameter for obtaining is 210 μm or so, and surface is smooth, and this explanation golden nanometer particle is equal
Inside in hydrogel, hydrogel effectively can prevent it from coming off comprising golden nanometer particle；Be can be seen that by such as Fig. 2 d：This hair
Final obtained golden nanometer particle in bright embodiment 1-hydrogel complex microsphere its absworption peak is right as golden nanometer particle, all
Wavelength is that the spectral absorption effect of 540nm or so is best.
(3) obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 2 is distributed in 5mL water, so that
Obtain golden nanometer particle/hydrogel complex microsphere solution；It is multiple 200 μ L nano-particles/hydrogel to be pipetted with 20~200 μ L liquid-transfering guns
Close microspheres solution, be put in 12 2ml centrifuge tubes, then successively in this 12 2ml centrifuge tubes add 1mL pH=2,3,4,5,
6th, 7,8,9,10,11,12,13 buffer solution；After about 10-30 minutes, observed not with Zeiss light microscope (Axio Lab.A1)
With the pattern size of golden nanometer particle under pH value/hydrogel complex microsphere, so as to obtain Jenner under different pH value as shown in Figure 3
The microphotograph of rice corpuscles/hydrogel complex microsphere.As seen from Figure 3：Obtained Jenner's grain of rice in the embodiment of the present invention 2
Son/hydrogel complex microsphere state in shrinking in low ph value solution, and expansion shape is substantially in high ph-values solution
State；Obtained golden nanometer particle/hydrogel complex microsphere is in the solution that pH value is 2~9 in the embodiment of the present invention 2, its particle diameter
Size increases with the increase of pH value, and in solution of the pH value more than 9, due to being influenceed by ionic strength, its grain size
Reduce with the increase of pH value on the contrary；Obtained golden nanometer particle/hydrogel complex microsphere can in this explanation embodiment of the present invention 2
PH value is detected as 2~9 solution with being applied to.Further, in the method respectively in the embodiment of the present invention 1~3
Obtained golden nanometer particle/hydrogel complex microsphere pattern size at various ph values is detected, so as to obtain such as Fig. 4 institutes
Golden nanometer particle/hydrogel complex microsphere change of size curve map under the different pH value shown；Wherein, the abscissa of Fig. 4 is pH
The ordinate of value (i.e. pH value), Fig. 4 is diameter (i.e. diameter), " AAm in Fig. 4:AA=1:1 " acrylamide is represented
Mol ratio with both acrylic acid consumption is about 1:1 is (i.e. multiple to obtained golden nanometer particle/hydrogel in the embodiment of the present invention 1
Close microballoon), " AAm in Fig. 4:AA=2:1 " represent that the mol ratio of both acrylamide and acrylic acid consumption is about 2:1 is (i.e. right
Obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 2), " AAm in Fig. 4:AA=4:1 " propylene is represented
The mol ratio of both acid amides and acrylic acid consumption is about 4:1 (i.e. to obtained golden nanometer particle/water-setting in the embodiment of the present invention 3
Glue complex microsphere).Be can be seen that with reference to Fig. 3 and Fig. 4：Obtained golden nanometer particle/hydrogel is multiple in the embodiment of the present invention 1~3
Closing microballoon its grain size in the solution that pH value is 2~9 is increased with the increase of pH value；It can be seen that, the embodiment of the present invention
Obtained golden nanometer particle/hydrogel complex microsphere may apply to pH value as 2~9 solution are detected.
(4) following behaviour is carried out to obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 1~3 respectively
Make：Obtained golden nanometer particle/hydrogel complex microsphere is distributed in 5mL water, and 200 μ are pipetted with 20~200 μ L liquid-transfering guns
The L solution, is put in 12 2ml centrifuge tubes, then successively to added in this 12 2ml centrifuge tubes 1mL pH=2,3,4,5,6,
7th, 8,9,10,11,12,13 buffer solution.After about 10-30 minutes, using Morpho spectrometers respectively to this 12 2ml centrifuge tubes
In golden nanometer particle/hydrogel complex microsphere absorption spectrum performance at various ph values detected, so as to obtain such as Fig. 5
Absorption peak strength shown in the absorption spectrum performance comparison figure and Fig. 8 shown in Fig. 7 is with pH value change curve.In Figure 5,
Its abscissa is wavelength (i.e. wavelength, unit is nm), and its ordinate is absorbance (i.e. absorbance), in figure
“AAm:AA=1:1 " represent that the mol ratio of both acrylamide and acrylic acid consumption is about 1:1 (i.e. in the embodiment of the present invention 1
Obtained golden nanometer particle/hydrogel complex microsphere)；In figure 6, its abscissa is that (i.e. wavelength, unit is wavelength
Nm), its ordinate is absorbance (i.e. absorbance), " AAm in figure:AA=2:1 " both acrylamide and acrylic acid are represented
The mol ratio of consumption is about 2:1 (i.e. to obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 2)；In Fig. 7
In, its abscissa is wavelength (i.e. wavelength, unit is nm), and its ordinate is absorbance (i.e. absorbance), in figure
“AAm:AA=4:1 " represent that the mol ratio of both acrylamide and acrylic acid consumption is about 4:1 (i.e. in the embodiment of the present invention 3
Obtained golden nanometer particle/hydrogel complex microsphere)；In fig. 8, its abscissa is pH value (i.e. pH value), its ordinate
It is absorbance (i.e. absorbance), " AAm in figure:AA=1:1 " represent both acrylamide and acrylic acid consumption mole
Than being about 1:1 (i.e. to obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 1), " AAm in figure:AA=
2:1 " represent that the mol ratio of both acrylamide and acrylic acid consumption is about 2:1 (i.e. to obtained Jenner in the embodiment of the present invention 2
Rice corpuscles/hydrogel complex microsphere), " AAm in figure:AA=4:1 " represent both acrylamide and acrylic acid consumption mole
Than being about 4:1 (i.e. to obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 3).Can be with by Fig. 5 to Fig. 8
Find out：Obtained golden nanometer particle/hydrogel complex microsphere can be realized visual to pH solution in the embodiment of the present invention 1~3
Change sensing, wherein the golden nanometer particle in the embodiment of the present invention 2/hydrogel complex microsphere performance is the most superior.
(5) following operation is carried out to obtained golden nanometer particle/hydrogel complex microsphere in the embodiment of the present invention 2 respectively：
Obtained golden nanometer particle/hydrogel complex microsphere is distributed in 5mL water, and 200 μ L are pipetted with 20~200 μ L liquid-transfering guns and be somebody's turn to do
Solution, is put in 9 2ml centrifuge tubes；Then to adding 20 μ L 2g/L glucose oxidases in this 9 2ml centrifuge tubes, then
The 100mmol/L glucose solutions of 0 μ L, 10 μ L, 20 μ L, 40 μ L, 60 μ L, 80 μ L, 100 μ L, 200 μ L and 500 μ L are separately added into,
And 780 μ L, 770 μ L, 760 μ L, 740 μ L, 720 μ L, 700 μ L, 680 μ L, 560 μ L and 280 μ L water are separately added into, make this 9 2ml
The ultimate density of glucose is respectively 0mmol/L, 1mmol/L, 2mmol/L, 4mmol/L, 6mmol/L, 8mmol/ in centrifuge tube
L, 10mmol/L, 20mmol/L and 50mmol/L；About 0.5~2 hour, glucose was changed into glucose by glucose oxidase
Acid；Afterwards, using Morpho spectrometers respectively to the golden nanometer particle/hydrogel complex microsphere in this 9 2ml centrifuge tubes not
Detected with the absorption spectrum performance in concentration of glucose solution, so as to obtain the single embodiment of the present invention 2 as shown in Figure 9
In absorption spectrum performance comparison figure of the obtained golden nanometer particle/hydrogel complex microsphere under different concentration of glucose and such as
Obtained golden nanometer particle/hydrogel complex microsphere is in different concentration of glucose in the single embodiment of the present invention 2 shown in Figure 10
Under absorption peak strength with concentration of glucose change curve.In fig .9, its abscissa is wavelength (i.e. wavelength, unit
It is nm), its ordinate is absorbance (i.e. absorbance), and " 0mM " represents that concentration is the glucose solution of 0mmol/L in figure,
" 1mM " represents that concentration is the glucose solution of 1mmol/L in figure, and " 2mM " represents that concentration is molten for the glucose of 2mmol/L in figure
Liquid, " 4mM " represents that concentration is the glucose solution of 4mmol/L in figure, and " 6mM " represents that concentration is the glucose of 6mmol/L in figure
Solution, " 8mM " represents that concentration is the glucose solution of 8mmol/L in figure, and " 10mM " represents that concentration is the Portugal of 10mmol/L in figure
Grape sugar juice, " 20mM " represents that concentration is the glucose solution of 20mmol/L in figure, and " 50mM " represents that concentration is 50mmol/ in figure
The glucose solution of L；In Fig. 10, its abscissa is concentration (i.e. concentration, unit is mM, i.e. mmol/L), and it is indulged
Coordinate is absorbance (i.e. absorbance).Be can be seen that by Fig. 9 and Figure 10：Golden nanometer particle/water in the embodiment of the present invention 2
Gel complex microsphere can realize the detection to glucose.
As fully visible, the present invention can solve the problem that independent pH sensitive aqueous gels are difficult to pH value visualization in the prior art
The technical problem of sensing such that it is able to realize the visualization sensing to environmental pH change and detection, or even can realize to micro-
The visualization sensing of amount solution ph change and detection.Further, since glucose is changed into gluconic acid by glucose oxidase,
Therefore this performance to pH sensitive of golden nanometer particle/hydrogel composite material for being provided using the present invention, it is possible to achieve right
The detection of glucose sugar.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
Should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of golden nanometer particle/hydrogel composite material, it is characterised in that it is that a kind of golden nanometer particle/hydrogel is combined
Microballoon；The golden nanometer particle/hydrogel complex microsphere be ball interior be distributed with the particle diameter of multiple golden nanometer particles for 10~
1000 μm of hydrogel microsphere, and the particle diameter of the golden nanometer particle is 20~100nm.
2. golden nanometer particle/hydrogel composite material according to claim 1, it is characterised in that the hydrogel microsphere
Composition include acrylamide and acrylic acid.
3. the preparation method of the golden nanometer particle/hydrogel composite material any one of a kind of the claims 1 to 2,
It is characterised in that it includes following steps：
Step A, the golden nanometer particle that multiple particle diameters are 20~100nm is scattered in hydrogel reaction solution, so as to be mixed
Colloidal solution；
Step B, according to parts by volume meter, 100 parts of atoleines are mixed with 1.5 parts of emulsifying agents, so as to obtain oil-based liquid；
Step C, the mixed colloidal solution that will be obtained in step A are used as micro-fluidic dispersed phase, the oiliness liquid that will be obtained in step B
Body prepares water-in-oil emulsion as micro-fluidic continuous phase using microfluidic methods, then the water-in-oil emulsion is placed in
Wavelength is irradiation under the uviol lamp of 311nm, so that the mixed colloidal solution in the water-in-oil emulsion is cured as Jenner's grain of rice
Son/hydrogel complex microsphere；
Step D, using organic solvent in step C solidify after golden nanometer particle/hydrogel complex microsphere clean so that
Obtain clean golden nanometer particle/hydrogel complex microsphere.
4. the preparation method of golden nanometer particle/hydrogel composite material according to claim 3, it is characterised in that described
The golden nanometer particle that multiple particle diameters are 20~100nm be scattered in hydrogel reaction solution include：By multiple particle diameters be 20~
The golden nanometer particle of 100nm mixes with hydrogel reaction solution, and is uniformly dispersed using ultrasonically treated.
5. the preparation method of the golden nanometer particle/hydrogel composite material according to claim 3 or 4, it is characterised in that institute
Stating the raw material of hydrogel reaction solution includes acrylamide and acrylic acid, and acrylamide and acrylic acid mol ratio are 1~4:
1。
6. the preparation method of the golden nanometer particle/hydrogel composite material according to claim 3 or 4, it is characterised in that institute
The hydrogel reaction solution stated is made of following methods：It is 1~4 according to acrylamide and acrylic acid mol ratio:1 ratio,
Acrylamide and acrylic acid are dissolved in deionized water, and add crosslinking agent and light trigger, be well mixed, so as to obtain water-setting
Glue reaction solution.
7. the preparation method of the golden nanometer particle/hydrogel composite material according to claim 3 or 4, it is characterised in that institute
The golden nanometer particle stated is made of following methods：1.4mL diallyl dimethyl chlorinations are used according to every 70mL ethylene glycol
Ammonium and 35 μ L concentration are the ratio of 1mol/L gold chlorides, and ethylene glycol, diallyl dimethyl ammoniumchloride are mixed with gold chloride
Together, it is placed in reacting 30min in oil bath pan, oil bath temperature is 195~220 DEG C, so as to be obtained comprising gold octahedron nanometer
The mixed liquor of particle；Then gold is included to this using the ratio that 17.5 μ L concentration are 1mol/L gold chlorides according to 70mL ethylene glycol
Gold chloride is added in the mixed liquor of octahedra nano-particle, and is reacted 2~5 minutes at room temperature, then carry out centrifugal treating, so that
The golden nanometer particle that particle diameter is 20~100nm is obtained.
8. the preparation method of the golden nanometer particle/hydrogel composite material according to claim 3 or 4, it is characterised in that institute
The emulsifying agent stated uses polyether modified silicon oil KF6038；Described organic solvent uses petroleum ether or ethanol.
9. what the golden nanometer particle/hydrogel composite material any one of the claims 1 to 2 was directly used in pH value can
Depending on changing sensing with detection.
10. golden nanometer particle/the hydrogel composite material any one of the claims 1 to 2 is directly used in glucose
Visualization sensing and the detection of concentration.
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| CN114669746A (en) * | 2022-03-07 | 2022-06-28 | 合肥工业大学 | Preparation method of porous metal microspheres for 3D printing |
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