CN108489942A - A kind of preparation method of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array - Google Patents
A kind of preparation method of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array Download PDFInfo
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- CN108489942A CN108489942A CN201810105634.1A CN201810105634A CN108489942A CN 108489942 A CN108489942 A CN 108489942A CN 201810105634 A CN201810105634 A CN 201810105634A CN 108489942 A CN108489942 A CN 108489942A
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/10—Integrating sample preparation and analysis in single entity, e.g. lab-on-a-chip concept
Abstract
The present invention relates to a kind of preparation methods of microchannel internal oxidition zinc Sodium Polyacrylate composite nanorod array, including:Microchannel inner surface is activated with liquor potassic permanganate, then zinc salt and ammonium hydroxide mixed solution, ethanolamine solutions are injected in microchannel simultaneously, it rinses, drying, then silane coupler solution is passed through into microchannel, it is incubated, it rinses, vacuum heat cure, be then alternately passed through sodium polyacrylate solution and cationic polyelectrolyte solution to get.The present invention utilizes wet chemical synthesis and microflow control technique, it realizes and constructs zinc oxide Sodium Polyacrylate composite nanorod array in microchannel inner surface, it is easy to operate, it is easy to repeat, constructed zinc oxide Sodium Polyacrylate composite nanorod array has large specific surface area, enhancement effect of fluorescence strong, the characteristics of non-specific adsorption is few and is easy to modify antibody, and combine microflow control technique, it is expected to become a kind of effective Immunofluorescence test tool, and applied to fields such as medical diagnosis on disease, Food Safety Analysis.
Description
Technical field
The invention belongs to Immunofluorescence test field, more particularly to a kind of microchannel internal oxidition zinc-Sodium Polyacrylate is compound
The preparation method of nanometer stick array.
Background technology
Microflow control technique typically refers in microchannel (size is tens of to hundreds of microns) processing or manipulates minute fluid
Related science involved by (volume be microlitre to nanoliter) and technology, are one and are related to chemistry, fluid physics, microelectronics, green wood
The emerging cross discipline of material, biology and biomedical engineering, wherein analysis detection is one of its application direction the most main.
Micro-fluidic detection technology generally has many advantages, such as that sample consumption is few, detection speed is fast, easy to operate and easy to carry, is suitable for i.e.
When diagnose.By microchannel inner surface carry out functional modification, as micro-nano structure array construct and the filling of function factor,
Nanometer material science can be combined well with microflow control technique, to effectively promote the performance of micro-fluidic device,
Middle microfluidic chemical method is considered as modification means in a kind of ideal microchannel, be may be implemented in closing microchannel
Construct micro-nano structure array.
Immunofluorescence test is a kind of widely used optical detection means, has high specificity, sensibility height, speed fast
The characteristics of, but non-specific fluorescence pollution is the problem that it is often faced, and is usually used in observing protein expression feelings in cell and tissue
Condition, because it also can effectively detect biomarker and pathogenic microorganism, Immunofluorescence test also become medical diagnosis on disease and
A kind of effective detection means of Food Safety Analysis.
Broad-band gap of the zinc oxide with 3.37eV and the at room temperature high excitation with 60meV combine can, be a kind of reason
The biological detection thought Fluorescence Increasing material.The significant Fluorescence Increasing performance of zinc oxide makes it can be used for a variety of biomedical tests
And high-throughput Protein Detection.Have studies have shown that there is nanometic zinc oxide rod array high-specific surface area to be provided for more
Binding site, greatly enhance fluorescent dye fluorescence intensity, improve fluorescence intensity and keep device sensitiveer, detection limit
It is lower.
Sodium Polyacrylate is a kind of hydrophilic anionic polyelectrolyte, can be reasonably resistant to the non-specific of albumen and inhale
Attached, to effectively be inhibited to occurring non-specific dyestuff in Immunofluorescence test, and it contains abundant carboxyl functional group
Also it is advantageous to associated antibodies and albumen further modification and functionalization, has been successfully applied to the immune glimmering of tumor markers
Light detection.
In conclusion in conjunction with microflow control technique, zinc oxide is combined with Sodium Polyacrylate to can be used as and a kind of is more managed
The fluoroscopic examination material thought first constructs nanometic zinc oxide rod array using fluid chemistry method in microchannel, using layer by layer from group
Thus dress method completes constructing for composite nanorod array, finally in its surface modification Sodium Polyacrylate in microchannel inner surface
The modification that corresponding antibodies can be carried out according to target detection albumen, so as to be applied to medical diagnosis on disease and Food Safety Analysis.
Invention content
Technical problem to be solved by the invention is to provide a kind of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorods
The preparation method of array, this method utilize wet chemical synthesis and microflow control technique, realize and constructed in microchannel inner surface
Zinc oxide-Sodium Polyacrylate composite nanorod array, this method is easy to operate, is easy to repeat, constructed zinc oxide-polypropylene
Sour sodium composite nanorod array has large specific surface area, enhancement effect of fluorescence strong, and non-specific adsorption is few and is easy to modify antibody
The characteristics of, and microflow control technique is combined, it is expected to become a kind of effective Immunofluorescence test tool, and examine applied to disease
The fields such as disconnected, Food Safety Analysis.
A kind of preparation method of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array of the present invention is specific to walk
Suddenly it is:
(1) liquor potassic permanganate is injected in microchannel, activation, in the microchannel activated, by zinc salt and ammonium hydroxide
Mixing, is obtained zinc salt mixed liquor, is injected in the microchannel activated and reacted simultaneously with identical speed with ethanolamine solutions, is rushed
It washes, dries, obtain the microchannel that inner surface constructs nanometic zinc oxide rod array, the wherein a concentration of 5- of liquor potassic permanganate
10mM, a concentration of 0.025-0.1M of zinc salt in zinc salt mixed liquor, the volume fraction of ammonium hydroxide is 7.5-30% in zinc salt mixed liquor
v/v;
(2) into step (1), inner surface constructs in the microchannel of nanometic zinc oxide rod array that be passed through silane coupling agent molten
Liquid is incubated, and is rinsed, vacuum heat cure, is then alternately passed through sodium polyacrylate solution and cationic polyelectrolyte solution, is obtained micro-
Channel internal oxidition zinc-Sodium Polyacrylate composite nanorod array, wherein the mass ratio of silane coupling agent and zinc salt in step (1)
It is 0.7~0.8:0.005~0.01, the mass ratio of silane coupling agent, Sodium Polyacrylate and cationic polyelectrolyte is 0.7~
0.8:0.0003~0.001:0.0002~0.001.
The reducing agent of liquor potassic permanganate is n-butanol in the step (1);A concentration of 4-6M of ammonium hydroxide;Ethanolamine solutions
A concentration of 25-75%v/v;Zinc salt is zinc nitrate, zinc sulfate or zinc acetate.
It is activated in the step (1) and is specially:20-45min is stopped at 60-90 DEG C.
The injection rate of zinc solution and ethanolamine solutions is 5-50 μ L/min in the step (1);Reaction temperature is
70-90 DEG C, reaction time 1-10min;Drying temperature is 70-90 DEG C, and drying time is 1~2h.
Rinsed in the step (1) is to use distilled water or deionized water.
The length of zinc oxide nano rod is 300-1000nm, a diameter of 50-200nm in the step (1).
Silane coupling agent is 3- aminopropyl triethoxysilanes in the step (2);The solvent of silane coupler solution is
Ethyl alcohol;A concentration of 5-10%v/v of silane coupler solution.
The temperature being incubated in the step (2) is 25-60 DEG C, and the time of incubation is 1~3h;Flushing be successively use ethyl alcohol and
Deionized water is rinsed.
The cured temperature of Vacuum Heat is 100~120 DEG C in the step (2), and the Vacuum Heat cured time is 1~3h.
Alternately be passed through in the step (2) sodium polyacrylate solution and cationic polyelectrolyte solution the specific steps are:
First sodium polyacrylate solution is passed through in microchannel, after it stops 5-20min in microchannel, is rinsed with deionized water, then
It is passed through cationic polyelectrolyte solution, after it stops 5-20min in microchannel, is rinsed with deionized water, it is alternately logical with this
Enter and recycled for one, carries out 1-5 cycle, be finally passed through sodium polyacrylate solution, deionized water is used in combination to rinse.
A concentration of 0.5-2.0g/L of sodium polyacrylate solution in the step (2);The average molecular weight of Sodium Polyacrylate
For 10000-100000.
A concentration of 0.5-2.0g/L of cationic polyelectrolyte solution in the step (2);Cationic polyelectrolyte is poly-
Allylamine hydrochloride or polydiallyldimethyl ammonium chloride, average molecular weight 10000-100000.
Microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array is applied to fluoroscopic examination in the step (2).
The present invention first constructs nanometic zinc oxide rod array using fluid chemistry method on the microchannel inner surface being activated,
Use the method for LBL self-assembly in zinc oxide nano rod surface modification hydrophilic polyelectrolyte layer polypropylene acid sodium again.
The present invention can be by controlling reaction solution concentration, reaction time and the polyelectrolyte electrostatic self-assembled number of plies, can be micro- logical
Zinc oxide-Sodium Polyacrylate composite nanorod array of function admirable is prepared in road.
The present invention has preparation method simple based on microflow control technique, and production cost is low, the characteristics of being easy to repeat;
Fluorescent dye because of characteristic of the micro-nano structure zinc oxide with large specific surface area and to its neighbouring certain distance is with Fluorescence Increasing
Effect, while Sodium Polyacrylate decorative layer can not only efficiently reduce nonspecific proteins absorption, but also it is easy to grafting not homospecificity
Identify antibody, the two, which combines, can effectively promote detection sensitivity and specificity, so this zinc oxide-Sodium Polyacrylate is compound receives
Rice stick array can be applied in multiple fields such as biology, preclinical medicine, medical diagnosis on disease and Food Safety Analysis.
Advantageous effect
(1) present invention has the capillary glass tube of zinc oxide nano rod as microfluidic channel using inner surface growth, then to oxidation
Polyelectrolyte layer (poly- sodium propionate/polyallylamine hydrochloride of the zinc nanometer rods modification with anti-albumen non-specific adsorption effect
Or poly- sodium propionate/polydiallyldimethyl ammonium chloride), Sodium Polyacrylate is greatly reducing zinc oxide nano rod albumen non-specificity
Different specific recognition antibody can be grafted while absorption again, then fluorescent marker is resisted by the Fluorescence Enhancement of zinc oxide
Body carries out signal amplification, finally carries out quantitative analysis to the biomarker of various concentration using detection technique of fluorescence.This method
Based on microflow control technique, the device prepared using composite organic-inorganic material realizes the quantitative detection to biomarker,
Achievable detection limit is low, high sensitivity, takes short instant detection, has in terms of biological marker analyte detection and medical diagnosis on disease
It is widely applied foreground.
(2) present invention based on microflow control technique, have it is easy to operate, production cost is low, be easy to repeat the characteristics of.
Description of the drawings
Fig. 1 is the SEM figures of capillary internal oxidition zinc nanometer stick array in embodiment 1;
Fig. 2 is the oxygen in capillary after the poly- sodium propionate/polyallylamine hydrochloride polyelectrolyte layer of modification in embodiment 1
Change the SEM figures of zinc nanometer stick array;
Fig. 3 is that nanometic zinc oxide rod array (a) simple in embodiment 1 and poly- sodium propionate/polyallylamine hydrochloride are poly-
The shows fluorescent microscopy images that the non-specific adsorption power of the nanometic zinc oxide rod array (b) of electrolyte layer modification compares;
Fig. 4 is the shows fluorescent microscopy images a-f of the micro-fluidic device detection various concentration CEA of functional modification in embodiment 1
(a-f corresponds to CEA a concentration of 10 respectively5, 103, 10,1,0.1,0pg/mL);
Fig. 5 is that the standard that the micro-fluidic device of functional modification in embodiment 1 detects tumor markers CEA is bent
Line;
Fig. 6 is the shows fluorescent microscopy images a-f of the micro-fluidic device detection various concentration AFP of functional modification in embodiment 2
(a-f distinguishes corresponding A FP a concentration of 105, 103, 10,1,0.1,0pg/mL);
Fig. 7 is the shows fluorescent microscopy images a-f of the micro-fluidic device detection various concentration PSA of functional modification in embodiment 3
(a-f corresponds to PSA a concentration of 10 respectively5, 103, 10,1,0.1,0pg/mL).
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) preparation of micro-fluidic device
Selecting 10mM liquor potassic permanganates handle the capillary glass tube of 45min at 85 DEG C, (internal diameter is 500 μm, and outer diameter is
550 μm, length 5cm) it is used as microfluidic channel, select polyfluortetraethylene pipe (internal diameter is 300 μm, and outer diameter is 350 μm) conduct
Polyfluortetraethylene pipe and capillary glass tube are bonded using epoxy resin, are thus completed micro- by injection port and outlet material
The preparation of fluidic devices.
(2) functional modification of micro-fluidic device
It is passed through A liquid (zinc nitrate (0.05M), a concentration of 4M ammonium hydroxide (7.5%v/ simultaneously in micro-fluidic device tetrafluoroethene pipe
V)), B liquid (ethanol amine 50% (v/v)), flow velocity are 25 μ L/min, and the reaction time is 4min at 90 DEG C;It is used at once after the completion of reaction
Distilled water or deionized water wash unreacted solution, and the inner tubal wall scanning electron microscope of capillary is shot (see figure
1) it, dries.
The 3- aminopropyl triethoxysilane ethanol solutions that volume is 15mL will be immersed in capillary after above-mentioned drying
(5% (v/v)), is incubated at room temperature 2h, and 60 DEG C of incubation 40min use ethyl alcohol and deionized water to rinse, 110 DEG C of vacuum heat cures successively
2h.Then to the polyallylamine hydrochloric acid for sodium polyacrylate solution 100 the μ L and 2.0g/L for alternately injecting 2.0g/L in microchannel
100 μ L of salting liquid after it is stopped 10min in microchannel respectively, then are rinsed with deionized water, are recycled as one, into
After 3 cycles of row, it is finally passed through sodium polyacrylate solution, deionized water is used in combination to rinse, thus constructs to obtain oxygen in microchannel
Change zinc-Sodium Polyacrylate composite nanorod array (see Fig. 2).
1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride solution is filled into above-mentioned capillary, is incubated at room temperature
40min is passed through identification antibody incubation 8h after deionized water cleaning.This is the functionalization process of entire device.
(3) detection-phase
Sample (such as CEA) containing marker is passed through capillary 5min with 50 μ L/min, then by polyclonal antibody with 50 μ
L/min is passed through 5min in capillary, then the Cy3-IgG of 1 μ g/mL is passed through 5min, ultra-pure water cleaning with 50 μ L/min, and nitrogen is blown
It is dry.Finally micro-fluidic device is placed in clap under fluorescence microscope and takes fluorescence microscope picture.
Fig. 1 and Fig. 2 show:Nanometic zinc oxide rod array surface is covered with polyelectrolyte, to prove poly- electrolysis successfully
Matter is modified to the surface of zinc oxide nano rod.
Fig. 3 shows:The non-specific fluorescence intensity of nanometic zinc oxide rod array after modified polyelectrolyte layer is far low
In the nanometic zinc oxide rod array of unmodified polyelectrolyte layer, non-specific adsorption obviously weakens.
Fig. 4 and Fig. 5 show:Fluorescence intensity tapers off trend with the reduction of marker CEA concentration.
Embodiment 2
(1) preparation of micro-fluidic device
Selecting 5mM liquor potassic permanganates handle the capillary glass tube of 45min at 85 DEG C, (internal diameter is 300 μm, and outer diameter is
350 μm, length 5cm) it is used as microfluidic channel, select polyfluortetraethylene pipe (internal diameter is 300 μm, and outer diameter is 350 μm) conduct
Polyfluortetraethylene pipe and capillary glass tube are bonded using epoxy resin, are thus completed micro- by injection port and outlet material
The preparation of fluidic devices.
(2) functional modification of micro-fluidic device
In micro-fluidic device tetrafluoroethene pipe simultaneously be passed through A liquid (zinc nitrate (0.1M), a concentration of 4M ammonium hydroxide (15%v/
V)), B liquid (ethanol amine 50% (v/v)), flow velocity are 50 μ L/min, and the reaction time is 2min at 90 DEG C;It is used at once after the completion of reaction
Distilled water or deionized water wash unreacted solution, drying.
The 3- aminopropyl triethoxysilanes ethanol solution (5% that volume is 15mL will be immersed in the capillary of above-mentioned drying
(v/v)) it, is incubated at room temperature 2h, 60 DEG C of incubation 40min use ethyl alcohol and deionized water to rinse, 110 DEG C of vacuum heat cure 2h successively.With
The polyallylamine hydrochloride solution of sodium polyacrylate solution 150 the μ L and 1.0g/L of 1.0g/L are alternately injected in backward microchannel
150 μ L after it is stopped 10min in microchannel respectively, then are rinsed with deionized water, are recycled as one, are carried out 4 and are followed
After ring, it is finally passed through sodium polyacrylate solution, deionized water is used in combination to rinse, it is poly- thus to construct to obtain zinc oxide-in microchannel
Sodium acrylate composite nanorod array.
1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride solution is filled into above-mentioned capillary incubation at room temperature
40min is passed through identification antibody incubation 8h after deionized water cleaning.This is the functionalization process of entire device.
(3) detection-phase
Sample (such as AFP) containing marker is passed through capillary 5min with 50 μ L/min, then by polyclonal antibody with 50 μ
L/min is passed through 5min in capillary, then the Cy3-IgG of 1 μ g/mL is passed through 5min, ultra-pure water cleaning with 50 μ L/min, and nitrogen is blown
It is dry.Finally micro-fluidic device is placed in clap under fluorescence microscope and takes fluorescence microscope picture.
Fig. 6 shows:Fluorescence intensity tapers off trend with the reduction of marker AFP concentration.
Embodiment 3
(1) preparation of micro-fluidic device
Selecting 10mM liquor potassic permanganates handle the capillary glass tube of 45min at 85 DEG C, (internal diameter is 220 μm, and outer diameter is
270 μm, length 5cm) it is used as microfluidic channel, select polyfluortetraethylene pipe (internal diameter is 300 μm, and outer diameter is 350 μm) conduct
Polyfluortetraethylene pipe and capillary glass tube are bonded using epoxy resin, are thus completed micro- by injection port and outlet material
The preparation of fluidic devices.
(2) functional modification of micro-fluidic device
In micro-fluidic device tetrafluoroethene pipe simultaneously be passed through A liquid (zinc nitrate (0.075M), a concentration of 4M ammonium hydroxide (10%
V/v)), B liquid (ethanol amine 50% (v/v)), flow velocity are 40 μ L/min, and the reaction time at 90 DEG C is 2min;It is vertical after the completion of reaction
Quarter is washed unreacted solution with distilled water or deionized water, drying.
The 3- aminopropyl triethoxysilanes ethanol solution (5% that volume is 15mL will be immersed in the capillary of above-mentioned drying
(v/v)) it, is incubated at room temperature 2h, 60 DEG C of incubation 40min use ethyl alcohol and deionization to rinse, 110 DEG C of vacuum heat cure 2h successively.Then
The polyallylamine hydrochloride solution of sodium polyacrylate solution 100 the μ L and 0.5g/L of 0.5g/L are alternately injected into microchannel
100 μ L after it is stopped 10min in microchannel respectively, then are rinsed with deionized water, are recycled as one, are carried out 5 and are followed
After ring, it is finally passed through sodium polyacrylate solution, deionized water is used in combination to rinse, it is poly- thus to construct to obtain zinc oxide-in microchannel
Sodium acrylate composite nanorod array.
1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride solution is filled into above-mentioned capillary incubation at room temperature
40min is passed through identification antibody incubation 8h after deionized water cleaning.This is the functionalization process of entire device.
(3) detection-phase
Sample (such as PSA) containing marker is passed through capillary 5min with 50 μ L/min, then by polyclonal antibody with 50 μ
L/min is passed through 5min in capillary, then the Cy3-IgG of 1 μ g/mL is passed through 5min, ultra-pure water cleaning with 50 μ L/min, and nitrogen is blown
It is dry.Finally micro-fluidic device is placed in clap under fluorescence microscope and takes fluorescence microscope picture.
Fig. 7 shows:Fluorescence intensity tapers off trend with the reduction of marker PSA concentration.
Claims (9)
1. a kind of preparation method of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array, the specific steps are:
(1) liquor potassic permanganate is injected in microchannel, activation, zinc salt is mixed with ammonium hydroxide, obtained by the microchannel activated
It to zinc salt mixed liquor, is injected in the microchannel activated and is reacted simultaneously with identical speed with ethanolamine solutions, rinsed, drying,
Obtain the microchannel that inner surface constructs nanometic zinc oxide rod array, the wherein a concentration of 5-10mM of liquor potassic permanganate, zinc salt
A concentration of 0.025-0.1M of zinc salt in mixed liquor, the volume fraction of ammonium hydroxide is 7.5-30%v/v in zinc salt mixed liquor;
(2) into step (1), inner surface is constructed and is passed through silane coupler solution in the microchannel of nanometic zinc oxide rod array, incubates
It educates, rinses, vacuum heat cure, be then alternately passed through sodium polyacrylate solution and cationic polyelectrolyte solution, obtain microchannel
Internal oxidition zinc-Sodium Polyacrylate composite nanorod array, wherein the mass ratio of silane coupling agent and zinc salt in step (1) is 0.7
~0.8:0.005~0.01, the mass ratio of silane coupling agent, Sodium Polyacrylate and cationic polyelectrolyte is 0.7~0.8:
0.0003~0.001:0.0002~0.001.
2. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that the reducing agent of liquor potassic permanganate is n-butanol in the step (1);A concentration of 4-6M of ammonium hydroxide;Ethyl alcohol
A concentration of 25-75%v/v of amine aqueous solution;Zinc salt is zinc nitrate, zinc sulfate or zinc acetate.
3. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that in the step (1) activation be specially:20-45min is stopped at 60-90 DEG C;Zinc solution and ethyl alcohol
The injection rate of amine aqueous solution is 5-50 μ L/min;Reaction temperature is 70-90 DEG C, reaction time 1-10min.
4. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that silane coupling agent is 3- aminopropyl triethoxysilanes in the step (2);Silane coupler solution
Solvent is ethyl alcohol;A concentration of 5-10%v/v of silane coupler solution.
5. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that the temperature being incubated in the step (2) is 25-60 DEG C, and the time of incubation is 1~3h;Flushing is to use successively
Ethyl alcohol and deionized water are rinsed;The cured temperature of Vacuum Heat is 100~120 DEG C, and the Vacuum Heat cured time is 1~3h.
6. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that the specific step of sodium polyacrylate solution and cationic polyelectrolyte solution is alternately passed through in the step (2)
Suddenly it is:First sodium polyacrylate solution is passed through in microchannel, after stopping 5-20min, is rinsed with deionized water, then be passed through cation
Polyelectrolyte solution is rinsed after stopping 5-20min with deionized water, is alternately passed through with this and is recycled for one, is carried out 1-5 and is followed
Ring is finally passed through sodium polyacrylate solution, and deionized water is used in combination to rinse.
7. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that a concentration of 0.5-2.0g/L of sodium polyacrylate solution in the step (2);Sodium Polyacrylate is averaged
Molecular weight is 10000-100000.
8. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that a concentration of 0.5-2.0g/L of cationic polyelectrolyte solution in the step (2);The poly- electrolysis of cation
Matter is polyallylamine hydrochloride or polydiallyldimethyl ammonium chloride, average molecular weight 10000-100000.
9. a kind of preparation side of microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array described in accordance with the claim 1
Method, which is characterized in that microchannel internal oxidition zinc-Sodium Polyacrylate composite nanorod array is applied to fluorescence in the step (2)
Detection.
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