CN106732213B - A kind of gold nanoparticle/hydrogel composite material and its preparation method and application - Google Patents
A kind of gold nanoparticle/hydrogel composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of gold nanoparticle/hydrogel composite materials and its preparation method and application, it is a kind of gold nanoparticle/hydrogel complex microsphere；The gold nanoparticle/hydrogel complex microsphere is the hydrogel microsphere that ball interior is distributed with that the partial size of multiple gold nanoparticles is 10~1000 μm, and the partial size of the gold nanoparticle is 20~100nm.Preparation method includes: to disperse multiple gold nanoparticles in hydrogel reaction solution as dispersed phase, using oil-based liquid as continuous phase, and water-in-oil emulsion is prepared using microfluidic methods, it is placed under the ultraviolet lamp that wavelength is 311nm and irradiates again, the mixed colloidal solution in the water-in-oil emulsion is set to be cured as gold nanoparticle/hydrogel complex microsphere, it is cleaned using organic solvent again to get clean gold nanoparticle/hydrogel complex microsphere is arrived.The present invention can be realized the sensing of the visualization to environmental pH and concentration of glucose and detection.
Description
Technical field
The present invention relates to organic-inorganic nanocomposite field more particularly to a kind of gold nanoparticle/hydrogel are compound
Material and its preparation method and application.
Background technique
Hydrogel is the gel using water as decentralized medium, has macromolecule network system, and property is soft, is able to maintain certain
Shape, and a large amount of water can be absorbed.It is that hydrophobic grouping and parent are introduced 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 change of enough sensing external environments or stimulation (such as: pH value, temperature, pressure, electric field, magnetic field, ionic strength, ultraviolet light,
The variation of visible light, specific chemicals etc.), and by itself physically or chemically variation (such as: the volume sweell(ing) of itself or
Shrink) come respond these variation or stimulation.This spy that can be exchanged information with the external world and make a response of environmental sensitive hydrogels
Property, make its flexibly direct writing element, micromechanics, drug delivery system, seperation film, in terms of have huge application
Prospect.
PH sensitive aqueous gel, which refers to, changes the intelligent aqueous gel that can be responded to the pH value of environment.PH sensitive hydrogel
- COO is typically contained in the macromolecular network of glue-、—OPO3-、—NH3+、—SO3+Equal zwitterions group, they can be according to ring
Proton is captured or is discharged in the variation of border pH value, changes so as to cause volume.Utilize this property of pH sensitive aqueous gel
It can be convenient the diffusion and rate of release of drug in ground regulation and control hydrogel.But existing pH sensitive aqueous gel is mostly
Colorless and transparent, volume change is difficult to differentiate, and senses in particular for the pH value of micro solution, and individual this kind of hydrogel is more
Add and is difficult to realize pH value visualization sensing.
Summary of the invention
In order to solve the technical issues of independent pH sensitive aqueous gel in the prior art is difficult to realize pH value visualization sensing,
The present invention provides a kind of gold nanoparticle/hydrogel composite materials and its preparation method and application, so as to realize to ring
The visualization sensing of border pH value variation and detection.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of gold nanoparticle/hydrogel composite material, it is a kind of gold nanoparticle/hydrogel complex microsphere；The gold
Nanoparticle/hydrogel complex microsphere is the water-setting that ball interior is distributed with that the partial size of multiple gold nanoparticles is 10~1000 μm
Glue microballoon, and the partial size of the gold nanoparticle is 20~100nm.
Preferably, the ingredient of the hydrogel microsphere includes acrylamide and acrylic acid.
A kind of preparation method of above-mentioned gold nanoparticle/hydrogel composite material, comprising the following steps:
Step A, it disperses the gold nanoparticle that multiple partial sizes are 20~100nm in hydrogel reaction solution, to obtain
Mixed colloidal solution；
Step B, according to parts by volume meter, 100 parts of atoleines are mixed with 1.5 parts of emulsifiers, to obtain oil-based liquid；
Step C, using mixed colloidal solution obtained in step A as micro-fluidic dispersed phase, by oil obtained in step B
Property liquid as micro-fluidic continuous phase, and using microfluidic methods prepare water-in-oil emulsion, then by the water-in-oil emulsion
It is placed under the ultraviolet lamp that wavelength is 311nm and irradiates, so that the mixed colloidal solution in the water-in-oil emulsion be made to be cured as Jenner
Rice corpuscles/hydrogel complex microsphere；
Step D, gold nanoparticle/hydrogel complex microsphere after solidifying in step C is cleaned using organic solvent,
To obtain clean gold nanoparticle/hydrogel complex microsphere.
Preferably, by multiple partial sizes be 20~100nm gold nanoparticle be scattered in include: in hydrogel reaction solution will be more
A partial size is that the gold nanoparticle of 20~100nm is mixed with hydrogel reaction solution, and is uniformly dispersed using ultrasonic treatment.
Preferably, the raw material of the hydrogel reaction solution includes acrylamide and acrylic acid, and acrylamide and propylene
The molar ratio of acid is 1~4:1.
Preferably, the hydrogel reaction solution is made of following methods: according to mole of acrylamide and acrylic acid
Than the ratio for 1~4:1, acrylamide and acrylic acid are dissolved in deionized water, and crosslinking agent and photoinitiator is added, is mixed
Uniformly, to obtain hydrogel reaction solution.
Preferably, the gold nanoparticle is made of following methods: using 1.4mL poly- two according to every 70mL ethylene glycol
Allyl dimethyl ammonium chloride and 35 μ L concentration are the ratio of 1mol/L gold chloride, by ethylene glycol, diallyl dimethyl chlorine
Change ammonium to mix with gold chloride, be placed in oil bath pan and react 30min, oil bath temperature is 195~220 DEG C, to be made
Mixed liquor comprising golden octahedra nanoparticle；It then the use of 17.5 μ L concentration is 1mol/L gold chloride according to 70mL ethylene glycol
Ratio is added gold chloride into the mixed liquor comprising the octahedra nanoparticle of gold, and reacts 2~5 minutes at room temperature, then into
Row centrifugal treating, to obtain the gold nanoparticle that partial size is 20~100nm.
Preferably, emulsifier uses polyether modified silicon oil KF6038；The organic solvent uses petroleum ether or ethyl alcohol.
Gold nanoparticle/hydrogel composite material in above-mentioned technical proposal is directly used in the visualization sensing and inspection of pH value
It surveys.
The visualization that gold nanoparticle/hydrogel composite material in above-mentioned technical proposal is directly used in concentration of glucose passes
Sense and detection.
As seen from the above technical solution provided by the invention, gold nanoparticle/hydrogel provided by the present invention is multiple
Condensation material be by by multiple partial sizes be 20~100nm gold nanoparticle be scattered in hydrogel reaction solution, and use miniflow
Water-in-oil emulsion is made in prosecutor method, then carries out polymerizing curable, the ball prepared by the hydrogel reaction solution in water-in-oil emulsion
Internal body portion is furnished with the hydrogel microsphere that the partial size of multiple gold nanoparticles is 10~1000 μm.Due to the hydrogel microsphere at
Dividing includes acrylamide and acrylic acid, therefore the hydrogel microsphere has certain sensibility to pH value, when the pH value of external environment
When variation, the volume of the hydrogel microsphere can change, and then make between the gold nanoparticle inside the hydrogel microsphere
Distance changes, so as to convert the variation of the pH value of external environment to the change of absorption and scattering of these gold nanoparticles to light
Change, which achieves the visualization changed to environmental pH sensing and detections.As it can be seen that gold nanoparticle provided by the present invention/
Hydrogel composite material can not only solve independent pH sensitive aqueous gel in the prior art and be difficult to realize pH value visualization sensing
The technical issues of, realize the visualization sensing and detection change to environmental pH, and can reuse, be conducive to saving at
This, is avoided the waste of material.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the electron scanning micrograph of regular spherical gold nanoparticle made from step d in the embodiment of the present invention 1
And abosrption spectrogram.
Fig. 2 is that the optical microscopy of final gold nanoparticle/hydrogel complex microsphere obtained 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 made in the embodiment of the present invention 2 using Zeiss optical microscopy (Axio Lab.A1)
Gold nanoparticle/hydrogel complex microsphere pattern size obtained from optical microscope photograph.
Fig. 4 is to be observed under different pH value using Zeiss optical microscopy (Axio Lab.A1) in the embodiment of the present invention 1~3
Gold nanoparticle/hydrogel under difference pH value obtained from gold nanoparticle obtained/hydrogel complex microsphere pattern size
Complex microsphere change of size curve graph.
Fig. 5 is using Morpho spectrometer respectively to gold nanoparticle/hydrogel obtained in the single embodiment of the present invention 1
Absorption spectrum performance comparison figure obtained from the absorption spectrum performance of complex microsphere at various ph values is detected.
Fig. 6 is using Morpho spectrometer respectively to gold nanoparticle/hydrogel obtained in the single embodiment of the present invention 2
Absorption spectrum performance comparison figure obtained from the absorption spectrum performance of complex microsphere at various ph values is detected.
Fig. 7 is using Morpho spectrometer respectively to gold nanoparticle/hydrogel obtained in the single embodiment of the present invention 3
Absorption spectrum performance comparison figure obtained from the absorption spectrum performance of complex microsphere at various ph values is detected.
Fig. 8 is using Morpho spectrometer respectively to gold nanoparticle/water obtained in the single embodiment of the present invention 1~3
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 using Morpho spectrometer respectively to gold nanoparticle/hydrogel obtained in the single embodiment of the present invention 2
Absorption spectrum performance comparison figure obtained from complex microsphere is detected in the absorption spectrum performance under different concentration of glucose.
Figure 10 is using Morpho spectrometer respectively to gold nanoparticle/water-setting obtained in the single embodiment of the present invention 2
Absorption peak strength obtained from glue complex microsphere is detected in the absorption spectrum performance under different concentration of glucose is with glucose
Concentration curve figure.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, those of ordinary skill in the art's every other implementation obtained under that premise of not paying creative labor
Example, belongs to protection scope of the present invention.
Gold nanoparticle/hydrogel composite material and its preparation method and application in the present invention is retouched in detail below
It states.
(1) a kind of gold nanoparticle/hydrogel composite material
A kind of gold nanoparticle/hydrogel composite material, it is a kind of gold nanoparticle/hydrogel complex microsphere；The gold
Nanoparticle/hydrogel complex microsphere is the water-setting that ball interior is distributed with that the partial size of multiple gold nanoparticles is 10~1000 μm
Glue microballoon, and the partial size of the gold nanoparticle is 20~100nm.Wherein, the ingredient of the hydrogel microsphere includes propylene
Amide and acrylic acid.
Specifically, in the gold nanoparticle/hydrogel composite material, multiple gold nanos are distributed in the inside of hydrogel microsphere
Particle, since the ingredient of hydrogel microsphere includes acrylamide and acrylic acid, which has pH value certain
Sensibility, when the variation of the pH value of external environment, the volume of the hydrogel microsphere can change, and then make the hydrogel microsphere
The distance between internal gold nanoparticle changes, so as to convert these Jenner's grain of rices for the variation of the pH value of external environment
Variation of the son to the absorption and scattering of light, which achieves the visualization changed to environmental pH sensing and detections.Using single
The gold nanoparticle/hydrogel complex microsphere carry out absorption spectrum measurement it can be found that the single gold nanoparticle/water-setting
The visualization sensing and detection that glue complex microsphere can be used for changing micro solution pH value, it is multiple that this has expanded organic-inorganic nano
The application field of condensation material.
(2) preparation method of above-mentioned gold nanoparticle/hydrogel composite material
Multiple gold nanoparticles first can be distributed to water by the preparation method of above-mentioned gold nanoparticle/hydrogel composite material
In gel reaction liquid, water-in-oil emulsion then is made using microfluidic methods in the prior art, then use light polymerization process pair
Hydrogel reaction solution in water-in-oil emulsion carries out polymerizing curable, to obtain gold nanoparticle/hydrogel complex microsphere；And
The gold nanoparticle can prepare the octahedra nanoparticle of gold using gold chloride is restored in ethylene glycol, then will using gold chloride
Golden octahedron nanoparticle is etched into the color of spherical gold of rule.Gold nanoparticle/hydrogel composite material preparation
Method can specifically include following steps:
Step A, it disperses the gold nanoparticle that multiple partial sizes are 20~100nm in hydrogel reaction solution, to obtain
Mixed colloidal solution.In practical applications, the gold nanoparticle and hydrogel reaction solution that can be 20~100nm by multiple partial sizes
Mixing, and be uniformly dispersed using ultrasonic treatment, to obtain mixed colloidal solution.
Wherein, the raw material of the hydrogel reaction solution includes acrylamide and acrylic acid, and acrylamide and acrylic acid
Molar ratio be 1~4:1.The hydrogel reaction solution can be prepared using following methods: according to acrylamide and third
The molar ratio of olefin(e) acid is the ratio of 1~4:1, acrylamide and acrylic acid is dissolved in deionized water, and it is (described that crosslinking agent is added
Crosslinking agent can use N in the prior art, N '-methylene-bisacrylamide) and photoinitiator (photoinitiator can
To use 2- hydroxy-2-methyl phenyl-propane -1- ketone in the prior art), it is uniformly mixed, to obtain hydrogel reaction solution.
Specifically, the gold nanoparticle can be prepared using following methods: be used according to every 70mL ethylene glycol
1.4mL diallyl dimethyl ammoniumchloride and 35 μ L concentration are the ratio of 1mol/L gold chloride, by ethylene glycol, polydiene propyl
Alkyl dimethyl ammonium chloride is mixed with gold chloride, is placed in oil bath pan and is reacted 30min, and oil bath temperature is 195~220 DEG C,
To which the mixed liquor comprising the octahedra nanoparticle of gold be made；It then the use of 17.5 μ L concentration is 1mol/L according to 70mL ethylene glycol
The ratio of gold chloride is added gold chloride into the mixed liquor comprising the octahedra nanoparticle of gold, and reacts 2~5 at room temperature
Minute, to perform etching to golden octahedra nanoparticle, then centrifugal treating is carried out using supercentrifuge in the prior art, from
And it can be prepared by the color of spherical gold for the rule that partial size is 20~100nm.
Step B, according to parts by volume meter, by 100 parts of atoleines and 1.5 parts of emulsifiers, (emulsifier uses the prior art
In polyether modified silicon oil KF6038) mixing, to obtain oil-based liquid.
Step C, using mixed colloidal solution obtained in step A as micro-fluidic dispersed phase, by oil 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 in the prior art, then the water-in-oil emulsion is placed in
It is irradiated under the ultraviolet lamp that wavelength is 311nm, so that the mixed colloidal solution in the water-in-oil emulsion be made to be cured as Jenner's grain of rice
Son/hydrogel complex microsphere.
Step D, using organic solvent (organic solvent is using petroleum ether or ethyl alcohol) to the gold after solidifying in step C
Nanoparticle/hydrogel complex microsphere is cleaned, to obtain clean gold nanoparticle/hydrogel complex microsphere.
To sum up, gold nanoparticle/hydrogel composite material provided by the present invention can not only solve the prior art
In individually pH sensitive aqueous gel be difficult to realize pH value visualization sensing the technical issues of, realization environmental pH is changed it is visual
Change sensing and detection, or even can be realized to the visualization sensing of micro solution pH value variation and detection, and benefit can be repeated
With being conducive to the saving of cost, avoid the waste of material.And gold nanoparticle/hydrogel composite material provided by the present invention
Preparation method not only simple process, but also process instrument without valuable preparation.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
Body embodiment retouches gold nanoparticle/hydrogel composite material provided by the invention and its preparation method and application in detail
It states.
Embodiment 1
A kind of gold nanoparticle/hydrogel composite material, is prepared 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 gun
1.4mL diallyl dimethyl ammoniumchloride is pipetted, is both put in 100mL vial；It is measured again with the graduated cylinder of 100mL
70mL ethylene glycol is added in the 100mL vial, is stirred evenly, to obtain gold nanoparticle reaction solution.At this point, institute
The color for stating liquid in 100mL vial is uniform light green color.
Step b, the gold nanoparticle reaction solution in step a is placed in oil bath pan and reacts 30min, oil bath temperature 195
~220 DEG C, so that the mixed liquor comprising the octahedra nanoparticle of gold be made.In this step, liquid in the 100mL vial
Color becomes purple from light green color, then becomes kermesinus from purple.
Step c, the mixed liquor comprising the octahedra nanoparticle of gold 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 that this includes the octahedra nanoparticle of gold, in room temperature
Lower reaction 2~5 minutes, to be performed etching to golden octahedra nanoparticle, to can be prepared by comprising the regular spherical Jenner grain of rice
The mixed liquor of son.
Step d, the mixed liquor 200mL comprising regular spherical gold nanoparticle in step c is taken, and uses supercentrifuge
The centrifugal treating of 30min is carried out to it with the revolving speed of 13000r/min, to remove the liquid such as ethylene glycol, to can be prepared by partial size
For the regular spherical gold nanoparticle of 20~100nm.
Step e, with electronic balance weighing 0.5g acrylamide, the N of 20mg, N '-methylene-bisacrylamide is added to 5mL
Deionized water in, then be added into the deionized water 480 μ L acrylic acid (acrylamide and acrylic acid molar ratio are about 1 at this time:
1) it with 30 μ L 2- hydroxy-2-methyl phenyl-propane -1- ketone, stirs evenly, to obtain hydrogel reaction solution.
Step f, the hydrogel reaction solution in 1mL step e is taken, and the regular spherical gold nanoparticle in step d is added
It to the hydrogel reaction solution, is subsequently placed in supersonic cleaning machine and is ultrasonically treated, keep the regular spherical gold nanoparticle steady
Surely it is scattered in the hydrogel reaction solution, is formed without precipitating, the mixed colloidal solution that do not reunite.
Step g, according to parts by volume meter, 100 parts of atoleines are mixed with 1.5 parts of polyether modified silicon oil KF6038, thus
Obtain oil-based liquid.
Step h, it uses 1mL syringe to take the mixed colloidal solution 1mL in step f as micro-fluidic dispersed phase, uses 100mL
Syringe takes the oil-based liquid 80mL in step g as micro-fluidic continuous phase, and the flow velocity of micro-fluidic dispersed phase is whole
For 100 μ L/h, the flow velocity whole process of micro-fluidic continuous phase is 500 μ L/min, and using T-shape glass micro chip, internal channel is deep
It is 200 μm for 50 μm, width, the polyfluortetraethylene pipe of 0.6 × 1.6mm is as outer connecting pipe, to prepare water-in-oil emulsion；So
The water-in-oil emulsion is placed under the ultraviolet lamp that wavelength is 311nm afterwards and is 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 be made to be cured as gold nanoparticle/hydrogel complex microsphere.
Step i, the gold nanoparticle after solidifying in step h/hydrogel complex microsphere is carried out using petroleum ether and ethyl alcohol
It alternately cleans, and with the revolving speed centrifugal treating of 4000r/min 4~5 times, each 5min, to clean the gold nanoparticle/hydrogel
The oil-based liquid on complex microsphere surface, so that clean gold nanoparticle/hydrogel complex microsphere can be obtained.
Embodiment 2
A kind of gold nanoparticle/hydrogel composite material, using the preparation method of the embodiments of the present invention 1, area
Be not only that: the acrylic acid dosage in step e becomes 240 μ L from 480 μ L in embodiment 1, at this time acrylamide and acrylic acid
Molar ratio is about 2:1.
Embodiment 3
A kind of gold nanoparticle/hydrogel composite material, using the preparation method of the embodiments of the present invention 1, area
Be not only that: the acrylic acid dosage in step e becomes 120 μ L from 480 μ L in embodiment 1, at this time acrylamide and acrylic acid
Molar 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 the step b of the embodiment of the present invention 1, to the step d of the embodiment of the present invention 1
Regular spherical gold nanoparticle obtained is observed and is measured, and is shone so that scanning electron microscope as shown in Figure 1 can be obtained
Piece and abosrption spectrogram；Wherein, Fig. 1 a is using JEM-2010 transmission electron microscope to oil bath temperature in the embodiment of the present invention 1
Electron scanning micrograph obtained from being observed using regular spherical gold nanoparticle made from step d at 215 DEG C；Figure
1b is step d system when using 215 DEG C to oil bath temperature in the embodiment of the present invention 1 using SU8020 field emission scanning electron microscope
Electron scanning micrograph obtained from the regular spherical gold nanoparticle obtained is observed；Fig. 1 c is using Morpho spectrum
When instrument uses 215 DEG C to oil bath temperature in the embodiment of the present invention 1 regular spherical gold nanoparticle made from step d measure and
Obtained abosrption spectrogram, abscissa are wavelength (i.e. wavelength, unit nm), ordinate absorbance
(i.e. absorbance).As such as Fig. 1 a, Fig. 1 b and Fig. 1 c it can be seen that regular spherical Jenner made from step d in the embodiment of the present invention 1
Rice corpuscles form is more regular, and granular size is very uniform, size about 67nm, has well to the spectrum that wavelength is 540nm or so
Assimilation effect.
(2) gold nanoparticle-hydrogel complex microsphere obtained final in the embodiment of the present invention 1 is completely dried, and right
The gold nanoparticle being completely dried-hydrogel complex microsphere is observed and is measured, so that it is aobvious that optics as shown in Figure 2 can be obtained
Micro mirror photo, electron scanning micrograph, abosrption spectrogram；Wherein, Fig. 2 a is using Zeiss optical microscopy (Axio
Lab.A1 obtained from) observing the gold nanoparticle in the embodiment of the present invention 1 being completely dried-hydrogel complex microsphere
Optical microscope photograph；Fig. 2 b and Fig. 2 c are using SU8020 field emission scanning electron microscope to the present invention being completely dried
Optical microscope photograph obtained from gold nanoparticle-hydrogel complex microsphere in embodiment 1 is observed；Fig. 2 d is to use
Morpho spectrometer the gold nanoparticle in the embodiment of the present invention 1 being completely dried-hydrogel complex microsphere is measured and
Obtained abosrption spectrogram, abscissa are wavelength (i.e. wavelength, unit nm), ordinate absorbance
(i.e. absorbance).By such as Fig. 2 a it can be seen that final gold nanoparticle-hydrogel obtained is compound micro- in the embodiment of the present invention 1
For ball in more regular spherical shape, granular size is uniform；By such as Fig. 2 b and Fig. 2 c it can be seen that finally being made in the embodiment of the present invention 1
Gold nanoparticle-hydrogel complex microsphere the partial size obtained is 210 μm or so, and surface is smooth, this illustrates that gold nanoparticle is equal
Inside in hydrogel, hydrogel effectively can prevent it from falling off comprising gold nanoparticle；By such as Fig. 2 d it can be seen that this hair
Its absorption peak of final gold nanoparticle obtained-hydrogel complex microsphere is all pair as gold nanoparticle in bright embodiment 1
Wavelength is that the spectral absorption effect of 540nm or so is best.
(3) gold nanoparticle/hydrogel complex microsphere obtained in the embodiment of the present invention 2 is distributed in 5mL water, thus
Obtain gold nanoparticle/hydrogel complex microsphere solution；It is multiple that 200 μ L nanoparticles/hydrogel is pipetted with 20~200 μ L liquid-transfering guns
Close microspheres solution, be put in 12 2ml centrifuge tubes, then successively into this 12 2ml centrifuge tubes be added 1mL pH=2,3,4,5,
6,7,8,9,10,11,12,13 buffer；After about 10-30 minutes, not with Zeiss optical microscopy (Axio Lab.A1) observation
With gold nanoparticle under pH value/hydrogel complex microsphere pattern size, to obtain Jenner under different pH value as shown in Figure 3
Rice corpuscles/hydrogel complex microsphere microscope photo.As seen from Figure 3: Jenner's grain of rice obtained in the embodiment of the present invention 2
State of the son/hydrogel complex microsphere in contraction in low ph value solution, and expansion shape is substantially in high ph-values solution
State；Gold nanoparticle/hydrogel complex microsphere obtained is in the solution that pH value is 2~9 in the embodiment of the present invention 2, partial size
Size increases with the increase of pH value, and in solution of the pH value greater than 9, due to being influenced by ionic strength, particle size
Reduce instead with the increase of pH value；This illustrates that gold nanoparticle/hydrogel complex microsphere obtained can in the embodiment of the present invention 2
It is that 2~9 solution detect to pH value to be applied to.Further, in the method respectively in the embodiment of the present invention 1~3
The pattern size of gold nanoparticle obtained/hydrogel complex microsphere at various ph values is detected, to obtain such as Fig. 4 institute
Gold nanoparticle/hydrogel complex microsphere change of size curve graph under the different pH value shown；Wherein, the abscissa of Fig. 4 is pH
The ordinate of value (i.e. pH value), Fig. 4 are diameter (i.e. diameter), and " AAm:AA=1:1 " in Fig. 4 indicates acrylamide
Molar ratio with both acrylic acid dosage is about 1:1 (i.e. multiple to gold nanoparticle/hydrogel obtained in the embodiment of the present invention 1
Close microballoon), " AAm:AA=2:1 " in Fig. 4 indicate both acrylamide and acrylic acid dosage molar ratio be about 2:1 (i.e. pair
Gold nanoparticle/hydrogel complex microsphere obtained in the embodiment of the present invention 2), " AAm:AA=4:1 " in Fig. 4 indicates propylene
The molar ratio of both amide and acrylic acid dosage is about 4:1 (i.e. to gold nanoparticle/water-setting obtained in the embodiment of the present invention 3
Glue complex microsphere).In conjunction with Fig. 3 and Fig. 4 it can be seen that gold nanoparticle/hydrogel obtained is multiple in the embodiment of the present invention 1~3
Microballoon is closed in pH value as its particle size in 2~9 solution is the increase with pH value and increases；As it can be seen that the embodiment of the present invention
It is that 2~9 solution detect that obtained gold nanoparticle/hydrogel complex microsphere, which can be applied to pH value,.
(4) following behaviour is carried out to gold nanoparticle obtained in the embodiment of the present invention 1~3/hydrogel complex microsphere respectively
Make: gold nanoparticle obtained/hydrogel complex microsphere being distributed in 5mL water, and pipettes 200 μ with 20~200 μ L liquid-transfering guns
The L solution is put in 12 2ml centrifuge tubes, then successively into this 12 2ml centrifuge tubes be added 1mL pH=2,3,4,5,6,
7,8,9,10,11,12,13 buffer.After about 10-30 minutes, using Morpho spectrometer respectively to this 12 2ml centrifuge tubes
In gold nanoparticle/hydrogel complex microsphere absorption spectrum performance at various ph values detected, to obtain such as Fig. 5
To absorption spectrum performance comparison figure shown in Fig. 7 and absorption peak strength shown in Fig. 8 with pH value change curve.In Fig. 5,
Its abscissa is wavelength (i.e. wavelength, unit nm), and ordinate is absorbance (i.e. absorbance), in figure
" AAm:AA=1:1 " indicates that the molar ratio of both acrylamide and acrylic acid dosage is about 1:1 (i.e. in the embodiment of the present invention 1
Gold nanoparticle obtained/hydrogel complex microsphere)；In Fig. 6, abscissa is that (i.e. wavelength, unit are wavelength
Nm), ordinate is absorbance (i.e. absorbance), and " AAm:AA=2:1 " indicates both acrylamide and acrylic acid in figure
The molar ratio of dosage is about 2:1 (i.e. to gold nanoparticle/hydrogel complex microsphere obtained in the embodiment of the present invention 2)；In Fig. 7
In, abscissa is wavelength (i.e. wavelength, unit nm), and ordinate is absorbance (i.e. absorbance), in figure
" AAm:AA=4:1 " indicates that the molar ratio of both acrylamide and acrylic acid dosage is about 4:1 (i.e. in the embodiment of the present invention 3
Gold nanoparticle obtained/hydrogel complex microsphere)；In fig. 8, abscissa is pH value (i.e. pH value), ordinate
For absorbance (i.e. absorbance), " AAm:AA=1:1 " in figure indicates mole of both acrylamide and acrylic acid dosage
" AAm:AA=than being about 1:1 (i.e. to gold nanoparticle/hydrogel complex microsphere obtained in the embodiment of the present invention 1), in figure
2:1 " indicates that the molar ratio of both acrylamide and acrylic acid dosage is about 2:1 (i.e. to Jenner obtained in the embodiment of the present invention 2
Rice corpuscles/hydrogel complex microsphere), " AAm:AA=4:1 " in figure indicates mole of both acrylamide and acrylic acid dosage
Than being about 4:1 (i.e. to gold nanoparticle/hydrogel complex microsphere obtained in the embodiment of the present invention 3).It can be with by Fig. 5 to Fig. 8
Find out: gold nanoparticle/hydrogel complex microsphere obtained can realize pH solution visual in the embodiment of the present invention 1~3
Change sensing, wherein the gold nanoparticle in the embodiment of the present invention 2/hydrogel complex microsphere performance is the most superior.
(5) gold nanoparticle/hydrogel complex microsphere obtained in the embodiment of the present invention 2 is performed the following operation respectively:
Gold nanoparticle obtained/hydrogel complex microsphere is distributed in 5mL water, and pipetting 200 μ L with 20~200 μ L liquid-transfering guns should
Solution is put in 9 2ml centrifuge tubes；Then 20 μ L 2g/L glucose oxidases are added into this 9 2ml centrifuge tubes, then
It is separately added into the 100mmol/L glucose solution 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,
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 converted to glucose by glucose oxidase
Acid；Later, using Morpho spectrometer respectively to gold nanoparticle/hydrogel complex microsphere in this 9 2ml centrifuge tubes not
It is detected with the absorption spectrum performance in concentration of glucose solution, to obtain the single embodiment of the present invention 2 as shown in Figure 9
In absorption spectrum performance comparison figure under different concentration of glucose of gold nanoparticle/hydrogel complex microsphere obtained and such as
Gold nanoparticle/hydrogel complex microsphere obtained is in different concentration of glucose in the single embodiment of the present invention 2 shown in Fig. 10
Under absorption peak strength with concentration of glucose change curve.In Fig. 9, abscissa is wavelength (i.e. wavelength, unit
For nm), ordinate is absorbance (i.e. absorbance), and " 0mM " indicates that concentration is the glucose solution of 0mmol/L in figure,
" 1mM " indicates that concentration is the glucose solution of 1mmol/L in figure, and " 2mM " indicates that the glucose that concentration is 2mmol/L is molten in figure
Liquid, " 4mM " indicates that concentration is the glucose solution of 4mmol/L in figure, and " 6mM " indicates that concentration is the glucose of 6mmol/L in figure
Solution, " 8mM " indicates that concentration is the glucose solution of 8mmol/L in figure, and " 10mM " indicates that concentration is the Portugal of 10mmol/L in figure
Grape sugar juice, " 20mM " indicates that concentration is the glucose solution of 20mmol/L in figure, and " 50mM " indicates that concentration is 50mmol/ in figure
The glucose solution of L；In Figure 10, abscissa is concentration (i.e. concentration, unit mM, i.e. mmol/L), is indulged
Coordinate is absorbance (i.e. absorbance).By Fig. 9 and Figure 10 it can be seen that gold nanoparticle/water in the embodiment of the present invention 2
Gel complex microsphere can be realized the detection to glucose.
To sum up, the present invention is able to solve independent pH sensitive aqueous gel in the prior art and is difficult to realize pH value visualization
The technical issues of sensing, so as to realize to the visualization sensing of environmental pH variation and detection, or even can be realized to micro-
Measure the visualization sensing and detection of solution ph variation.Further, since glucose is converted to gluconic acid by glucose oxidase,
Therefore this performance to pH sensitive of gold nanoparticle/hydrogel composite material provided by the invention is utilized, may be implemented pair
The detection of glucose sugar.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (4)
1. a kind of preparation method of gold nanoparticle/hydrogel composite material, it is characterised in that:
Gold nanoparticle/the hydrogel composite material is a kind of gold nanoparticle/hydrogel complex microsphere；Jenner's grain of rice
Son/hydrogel complex microsphere be ball interior be distributed with multiple gold nanoparticles partial size be 10~1000 μm hydrogel it is micro-
Ball, and the partial size of the gold nanoparticle is 20~100nm；
The ingredient of the hydrogel microsphere includes acrylamide and acrylic acid；
The preparation method comprises the following steps:
Step A, it disperses the gold nanoparticle that multiple partial sizes are 20~100nm in hydrogel reaction solution, to be mixed
Colloidal solution；
Step B, according to parts by volume meter, 100 parts of atoleines are mixed with 1.5 parts of emulsifiers, to obtain oil-based liquid；
Step C, using mixed colloidal solution obtained in step A as micro-fluidic dispersed phase, by oiliness liquid obtained in step B
Body prepares water-in-oil emulsion as micro-fluidic continuous phase, and using microfluidic methods, then the water-in-oil emulsion is placed in
It is irradiated under the ultraviolet lamp that wavelength is 311nm, so that the mixed colloidal solution in the water-in-oil emulsion be made to be cured as Jenner's grain of rice
Son/hydrogel complex microsphere；
Step D, gold nanoparticle/hydrogel complex microsphere after solidifying in step C is cleaned using organic solvent, thus
Obtain clean gold nanoparticle/hydrogel complex microsphere；
Described disperse the gold nanoparticle that multiple partial sizes are 20~100nm in hydrogel reaction solution includes: by multiple grains
Diameter is that the gold nanoparticle of 20~100nm is mixed with hydrogel reaction solution, and is uniformly dispersed using ultrasonic treatment；
The raw material of the hydrogel reaction solution includes acrylamide and acrylic acid, and the molar ratio of acrylamide and acrylic acid is
1~4:1；
The hydrogel reaction solution uses following methods to be made: according to the molar ratio of acrylamide and acrylic acid for 1~4:1's
Acrylamide and acrylic acid are dissolved in deionized water by ratio, and crosslinking agent and photoinitiator is added, and are uniformly mixed, thus
To hydrogel reaction solution；
The gold nanoparticle is made of following methods: using 1.4mL polydiene dimethylamine according to every 70mL ethylene glycol
Ammonium chloride and 35 μ L concentration are the ratio of 1mol/L gold chloride, by ethylene glycol, diallyl dimethyl ammoniumchloride and chlorine gold
Acid-mixed is combined, and is placed in oil bath pan and is reacted 30min, and oil bath temperature is 195~220 DEG C, to be made comprising golden octahedral
The mixed liquor of body nanoparticle；It then is the ratio of 1mol/L gold chloride using 17.5 μ L concentration according to 70mL ethylene glycol, to this
Gold chloride is added in mixed liquor comprising golden octahedra nanoparticle, and reacts 2~5 minutes at room temperature, then carry out at centrifugation
Reason, to obtain the gold nanoparticle that partial size is 20~100nm.
2. the preparation method of gold nanoparticle/hydrogel composite material according to claim 1, which is characterized in that described
Emulsifier use polyether modified silicon oil KF6038；The organic solvent uses petroleum ether or ethyl alcohol.
3. gold nanoparticle/hydrogel composite material of preparation method preparation according to claim 1 is directly used in pH value
Visualization sensing and detection.
4. gold nanoparticle/hydrogel composite material of preparation method preparation according to claim 1 is directly used in grape
The visualization sensing of sugared concentration and detection.
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