CN108359118A - A kind of preparation method and application of poly (arylene ether nitrile)-gold and silver nano compound film - Google Patents
A kind of preparation method and application of poly (arylene ether nitrile)-gold and silver nano compound film Download PDFInfo
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Abstract
A kind of preparation method of poly (arylene ether nitrile) gold and silver nano compound film, belongs to noble metal nano technical field of composite materials.Include the following steps：1) using poly (arylene ether nitrile) film as substrate, gold (Au) film of nanometer grade thickness and silver-colored (Ag) film are sequentially prepared on it using physical vaporous deposition；2) the poly (arylene ether nitrile) film containing Au films and Ag films that upper step obtains is placed in tube furnace, under inert gas atmosphere, rises to 250 DEG C~310 DEG C by room temperature with the heating rate of 10~50 DEG C/min, then cooled to room temperature.The present invention is heat-treated under conditions of higher than the glass transition temperature of poly (arylene ether nitrile), so that Au/Ag films are during fracture, migration, connection, it is fixed in the poly (arylene ether nitrile) film surface of softening, obtained nanoparticle composite film has very high stability, can be used for the immune detection to prostate specific antigen (PSA) after sessile antibody.
Description
Technical field
The invention belongs to noble metal nano technical field of composite materials, and in particular to a kind of poly (arylene ether nitrile)-gold and silver nanometer is multiple
Close the preparation method of film and its specificity in prostate specific antigen (prostate specific antigen, PSA)
Application in immune detection.
Background technology
Noble metal nanometer material have good optics, catalysis and electric property, be widely used in medicine, catalysis,
The multiple fields such as electronics, especially its unique optical property provide diversified signal for design optical biosensor
Conversion and method for amplifying signal.Such as when light is incident on noble metal nano particles surface, if incident photon frequency and your gold
The body vibration frequency of metal nano-particle free electron is consistent, i.e., is absorbed to incident photon energy, generates local surface etc.
Ion resonance body (Localized Surface Plasmon Resonance, LSPR) phenomenon.Any change noble metal nano
The factor of particle shape looks, interparticle distance and surface dielectric environment can all cause its LSPR spectrum to change.In bio-sensing application
In, when keeping the pattern of noble metal nano particles constant, biologic specificity recognition unit (antibody, nucleic acid are fixed on its surface
Deng), interface specific reaction occurs with test substance, the surface dielectric constant of noble metal nano particles can be increased, and then cause
Red shift occurs for its LSPR spectrum, and test substance concentration is directly proportional to LSPR spectral red shift degree, to complete to target substance
Unmarked (label-free) fast optical detection.Therefore, the optical bio based on noble metal nanometer material LSPR effects
Sensor has become one of the important research direction in detection field (Point-of-Care-Test, POCT) immediately.
Different types of noble metal nano particles are usual with different LSPR spectrum, such as the resonance absorbing peak of nanogold
Positioned at~520nm, and nano silver absorption peak is then usually located at~400nm.Currently, by preparing electrum nano material, adjust
The ratio of section wherein gold and silver component obtains different resonance absorbance spectrums, you can is applied to biology and chemical sensor field.Specially
Application No. is 201210492265.9 for profit《A kind of gold and silver adds up to the preparation method of nano-particle》, 201310348676.5
《LSPR sensing membranes and preparation method thereof for measuring mercury ion》, 201710219201.4《One kind is modified based on tartaric acid
Gold-silver alloy nanoparticles colorimetric detection water quality Cr3+Method》, 201510250664.8《A kind of glutathione-gold and silver conjunction
Gold nano-material and the preparation method and application thereof》And 201510947225.2《Interface transform in situ prepares electrum two
Ordered nano film and its method》In disclose by preparation with different gold and silver component ratios gold-silver alloy nanoparticles, adjust
Its optical property is saved, and is applied to biology/field of chemical detection.
In practical applications, for detect the noble metal nano particles of target substance need to be fixed on particular substrate it
On.However, the noble metal nano particles Presence of an interface stability prepared in the rigid basement (such as glass, silicon chip) of generally use
It difference, the problems such as being easy to fall off, therefore, it is necessary to add interface stability agent to enhance the binding force between nano-particle and substrate, leads
Cause processing step cumbersome, it is complicated for operation.In addition, using physical vacuum sedimentation on the glass substrate gold evaporation silver nanoparticle film,
Re-annealing heat treatment (K.Jia, et al, ACS Appl. Mater.Interfaces, 2014,6,219), and prepare gold and silver
The common method of nano-particle.Gold-silver alloy nanoparticles can be embedded in glass basic surface and are fixed by this method；But
Be, this method there are heat treatment temperature excessively high (be higher than 550 DEG C), heat treatment time is long the problems such as, increase manufacturing cost and energy
Consumption.Therefore, seek it is a kind of quickly, low cost, low energy consumption method metal nanoparticle is fixed in substrate, and applied to life
Object/chemical sensor field is current urgent problem.
Invention content
In view of the defects in the background art, the present invention proposes a kind of poly (arylene ether nitrile)-gold silver nanometer particles
(polyarylene ether nitrile-gold/silver nanoparticles, PEN-Au/Ag NPs) laminated film
Preparation method and application.It is thin with poly (arylene ether nitrile) in the preparation method of poly (arylene ether nitrile) provided by the invention-gold and silver nano compound film
Film is as flexible substrates, after the gold and silver metal layer of nano thickness is deposited on it using physical vaporous deposition, then higher than poly-
Short annealing heat treatment is carried out under the conditions of the glass transition temperature of aryl oxide nitrile, finally obtains PEN-Au/Ag NPs laminated films；
The nano compound film that the present invention obtains has the characteristics that particle diameter distribution is uniform, stability is strong, is easy to biological functional, can apply
In the high-technology fields such as biological immune detection, chemical sensitisation.
Technical scheme is as follows：
A kind of preparation method of poly (arylene ether nitrile)-gold and silver nano compound film, which is characterized in that include the following steps：
Step 1, using poly (arylene ether nitrile) film as substrate, be sequentially prepared on it using physical vaporous deposition nanoscale thickness
The Au films and Ag films of degree；
The poly (arylene ether nitrile) film containing Au films and Ag films that step 1 obtains is placed in tube furnace by step 2, in indifferent gas
Under body atmosphere, 250 DEG C~310 DEG C are risen to by room temperature with the heating rate of 10~50 DEG C/min, then cooled to room temperature, i.e.,
The poly (arylene ether nitrile)-gold and silver nano compound film can be obtained.
Further, when preparing Au films and Ag films using physical vaporous deposition described in step 1, using transmission electron microscope copper mesh
As mask plate, obtained Au films and Ag films are array structure.
Further, used described in step 1 physical vaporous deposition prepare the detailed process of Au films and Ag films for：With poly- virtue
Ether nitrile film covers transmission electron microscope copper mesh as mask plate as flexible substrates on it, using vacuum PVD method,
It is less than 1x10 in pressure-6Support, deposition velocity are 0.01nm s-1Under conditions of, 2~6nm is deposited on poly (arylene ether nitrile) film successively
The Ag films of thick Au films and 1~3nm thickness, you can the Au/Ag laminated films of array arrangement are obtained on poly (arylene ether nitrile) film.
Further, inert gas described in step 2 is nitrogen or argon gas.
The present invention also provides above-mentioned poly (arylene ether nitrile)-gold and silver nano compound films in prostate specific antigen (prostate
Specific antigen, PSA) specific detection in application.
The poly (arylene ether nitrile) that the method for the present invention obtains-gold and silver nanometer (PEN-Au/Ag NPs) laminated film is to prostate-specific
The detection process of antigen (prostate specific antigen, PSA) is specially：
Poly (arylene ether nitrile)-gold and silver nano compound film that the present invention obtains is impregnated 30min or more by step 1 in ethanol,
The floating dust of film surface and extra unstable nano-particle are removed, is then dried；
Step 2, by obtained laminated film after step 1 processing at room temperature, 11- Mercaptoundecanoic acids (MUA) reagent
10~16h is impregnated in ethanol solution, is cleaned using ethyl alcohol after taking-up, it is dry；By the laminated film after above-mentioned drying at room temperature,
40 are impregnated in 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides/n-hydroxysuccinimide (EDC/NHS) reagent
~80min is cleaned after taking-up using deionized water, dry；
Step 3, the laminated film obtained after handling step 2 are at a temperature of 4 DEG C, in PSA antibody (Anti-PSA) solution
It is taken out after impregnating 4~8h, phosphate buffer, deionized water is successively used to clean, it is dry；
Step 4, compound concentration are 100ng mL-1PSA solution, with secure the PEN-Au/Ag NPs of Anti-PSA into
Row reaction, the variation of the front and back PEN-Au/Ag NPs laminated film LSPR spectrum of detection reaction, including resonance peak intensity, resonance frequency
The variation of rate.
Beneficial effects of the present invention are：
Compared with prior art, the present invention is using poly (arylene ether nitrile) film as substrate, on it using physical vaporous deposition
Prepare Au/Ag films, then under the glass transition temperature higher than substrate carry out short annealing heat treatment, obtained nanoscale,
The uniform gold silver nanometer particle laminated film of particle diameter distribution.Condition of the present invention in the glass transition temperature higher than poly (arylene ether nitrile)
Under be heat-treated so that Au/Ag films are fixed in the poly (arylene ether nitrile) film table of softening during fracture, migration, connection
Face, obtained nanoparticle composite film have very high stability, can be used for prostate specific antigen after sessile antibody
The immune detection of (prostate specific antigen, PSA).Meanwhile the present invention introduces silver in laminated film preparation,
Compared with the laminated film of proof gold component, the particle diameter distribution of nano-particle is more uniform, and LSPR absorption peak half-peak breadths are narrower, quality
Factor higher.
Description of the drawings
Fig. 1 is the structural schematic diagram for poly (arylene ether nitrile)-gold and silver nano compound film that the method for the present invention obtains；
Fig. 2 is the chemical structural formula of the substrate poly (arylene ether nitrile) of laminated film of the present invention；
Fig. 3 is obtained poly (arylene ether nitrile)-gold and silver nano compound film of the invention when carrying out LSPR spectrum assignment tests
Optical microscope photograph；
Poly (arylene ether nitrile)-gold thin film before and after the annealing that Fig. 4 is embodiment 3, comparative example 1-3 is obtained and poly (arylene ether nitrile)-gold and silver
The LSPR spectrum of laminated film；Wherein, PEN-Au film are poly (arylene ether nitrile)-gold continuous film before comparative example 1 is annealed, PEN-
Au NPs are poly (arylene ether nitrile)-gold nanometer film after comparative example 2 is annealed, and PEN-Au/Ag film are poly- before comparative example 3 is annealed
Aryl oxide nitrile-electrum continuous film, PEN-Au/Ag NPs are that poly (arylene ether nitrile)-electrum nanometer after embodiment 3 is annealed is multiple
Close film；
Fig. 5 is the LSPR spectrum comparison diagram (A) for poly (arylene ether nitrile)-gold and silver nano compound film that embodiment 1-4 is obtained, with
And the scanning electron microscope diagram piece (B-E) of laminated film that embodiment 1-4 is obtained；Wherein, B corresponding embodiments 1, C correspond to real
Apply example 2, D corresponding embodiments 3, E corresponding embodiments 4；
Fig. 6 is the grain size distribution (A) and embodiment for poly (arylene ether nitrile)-gold and silver nano compound film that embodiment 3 obtains
3 obtained laminated films impregnate different time (15min, 30min, 1h, 2h, 4h, 8h, 12h) LSPR absorption peaks afterwards in ethanol
Change curve (B) after intensity normalization；
Fig. 7 is the obtained poly (arylene ether nitrile)-gold and silver nano compound film of embodiment 3 to prostate specific antigen (prostate
Specific antigen, PSA) carry out specific immunity detection LSPR spectrum (A), heterogenetic antigen as a comparison
LSPR spectrum (B) when (bovine serum albumin(BSA), albumin from bovine serum, BSA) is detected, what embodiment 3 obtained
The scanning electron microscope diagram (C) of poly (arylene ether nitrile)-gold and silver nano compound film, and to prostate specific antigen (prostate
Specific antigen, PSA) carry out specific immunity detection after nano compound film scanning electron microscope diagram (D).
Specific implementation mode
With reference to the accompanying drawings and examples, technical scheme of the present invention is described in detail.
A kind of preparation method of poly (arylene ether nitrile)-gold and silver nano compound film, which is characterized in that include the following steps：
The preparation of step 1, flexible poly (arylene ether nitrile) transparent membrane：Precise 1g poly (arylene ether nitrile)s are put into three-necked bottle, so
11mLN is added in backward three-necked bottle, N- dimethylacetylamides (N, N-dimethylacetamide, DMAc) stir at 80 DEG C
30min is mixed, poly (arylene ether nitrile) solution is obtained；Then, obtained poly (arylene ether nitrile) solution is slowly fallen on glass plate, is positioned over baking oven
In, setting temperature program keeps 2h under 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C of each temperature spots, after the completion, natural
It is cooled to room temperature, film is taken off from glass plate, you can obtain flexible poly (arylene ether nitrile) transparent membrane；
The preparation of step 2, Au/Ag films：Using the flexible poly (arylene ether nitrile) transparent membrane that step 1 obtains as substrate, use
Physical vaporous deposition is sequentially prepared Au films and Ag films on it；Detailed process is：In the flexible polyarylether that step 1 obtains
Transmission electron microscope copper mesh is covered on nitrile transparent membrane as mask plate, is put into the evaporation coating device for being equipped with film-thickness monitoring, is used
Vacuum PVD method is less than 1x10 in pressure-6Support, deposition velocity are 0.01nm s-1Under conditions of, successively in poly- virtue
The Ag films of the Au films and 1~3nm thickness of 2~6nm thickness are deposited on ether nitrile film, you can array arrangement is obtained on poly (arylene ether nitrile)
Au/Ag laminated films, structure are as shown in Figure 1；
Step 3, annealing heat-treats process：The poly (arylene ether nitrile) film of film containing Au and Ag films that step 2 obtains is placed in tubular type
In stove, under inert gas atmosphere, 250 DEG C~310 DEG C are risen to by room temperature with the heating rate of 10~50 DEG C/min, at once certainly
It is so cooled to room temperature, you can obtain the poly (arylene ether nitrile)-gold and silver nano compound film.Wherein, annealing temperature is above polyarylether
The glass transition temperature of nitrile, it is therefore an objective to make Au/Ag films that fracture, migration occur, connect and then form stable nano-particle
In the process, it is fixed on the poly (arylene ether nitrile) film surface of softening, obtains the nanoparticle composite film of high stability.
In order to ensure that there is film the higher transparency, poly (arylene ether nitrile) to use phenolphthalin biphenol monomer and 2,6- dichloro-benzenes
It is fine, it is obtained by nucleophilic displacement of fluorine polycondensation reaction.The chemical structural formula of poly (arylene ether nitrile) is as shown in Figure 2.
As shown in figure 3, carrying out detection and localization its LSPR spectrum to the obtained PEN-Au/Ag NPs laminated films of the present invention
When, localization method is the square array configuration obtained for mask plate based on transmission electron microscope copper mesh, and an array cell sizes are
110 μm * 110 μm, using the light microscope for being equipped with halogen positioning aperture, spectrometer and test software, in 10 times of eyepiece, object
Detection and localization LSPR spectrum are carried out under conditions of 10 times of mirror to it.Positioning survey is carried out based on array structure laminated film of the present invention
When examination, the uniformity of test zone can be effectively ensured, avoid the spectral ripple caused by test zone difference is possible.
Embodiment 1
A kind of preparation method of poly (arylene ether nitrile)-gold and silver nano compound film, includes the following steps：
The preparation of step 1, flexible poly (arylene ether nitrile) transparent membrane：Precise 1g poly (arylene ether nitrile)s (chemical structural formula such as Fig. 2
It is shown) it is put into three-necked bottle, 11mL n,N-dimethylacetamide (N, N- are then added into three-necked bottle
Dimethylacetamide, DMAc), 30min is stirred at 80 DEG C, obtains poly (arylene ether nitrile) solution；Then, the poly- virtue that will be obtained
Ether nitrile solution slowly fall on clean glass plate, is positioned in baking oven, setting temperature program 80 DEG C, 100 DEG C, 120 DEG C,
140 DEG C, keep 2h under 160 DEG C of each temperature spots, after the completion, cooled to room temperature takes film off from glass plate, you can
To flexible poly (arylene ether nitrile) transparent membrane；
The preparation of step 2, Au/Ag films：The flexible poly (arylene ether nitrile) transparent membrane that step 1 obtains is cut out as 1.4cm*
1.4cm sizes, then covering transmission electron microscope copper mesh is put into the evaporation coating device for being equipped with film-thickness monitoring as mask plate on it
In, using vacuum PVD method, it is less than 1x10 in pressure-6Support, deposition velocity are 0.01nm s-1Under conditions of, first exist
The Au films that a layer thickness is 2nm are deposited on poly (arylene ether nitrile) film, then the Ag films that a layer thickness is 1nm are deposited on Au films, you can
The Au/Ag laminated films of array arrangement are obtained on poly (arylene ether nitrile), structure is as shown in Figure 1；
Step 3, annealing heat-treats process：The poly (arylene ether nitrile) film of film containing Au and Ag films that step 2 obtains is placed in tubular type
In stove, in a nitrogen atmosphere, 250 DEG C are risen to by room temperature with the heating rate of 30 DEG C/min, at once cooled to room temperature, you can
Obtain the poly (arylene ether nitrile)-gold and silver nano compound film.
Embodiment 2
The present embodiment compared with Example 1, difference lies in：It is risen to by room temperature with the heating rate of 30 DEG C/min in step 3
270 DEG C, remaining step is same as Example 1.
Embodiment 3
The present embodiment compared with Example 1, difference lies in：It is risen to by room temperature with the heating rate of 30 DEG C/min in step 3
290 DEG C, remaining step is same as Example 1.
Embodiment 4
The present embodiment compared with Example 1, difference lies in：It is risen to by room temperature with the heating rate of 30 DEG C/min in step 3
310 DEG C, remaining step is same as Example 1.
Comparative example 1
A kind of preparation method of poly (arylene ether nitrile)-gold continuous film (PEN-Au film), includes the following steps：
The preparation of step 1, flexible poly (arylene ether nitrile) transparent membrane：Precise 1g poly (arylene ether nitrile)s (chemical structural formula such as Fig. 2
It is shown) it is put into three-necked bottle, 11mL n,N-dimethylacetamide (N, N- are then added into three-necked bottle
Dimethylacetamide, DMAc), 30min is stirred at 80 DEG C, obtains poly (arylene ether nitrile) solution；Then, the poly- virtue that will be obtained
Ether nitrile solution slowly fall on clean glass plate, is positioned in baking oven, setting temperature program 80 DEG C, 100 DEG C, 120 DEG C,
140 DEG C, keep 2h under 160 DEG C of each temperature spots, after the completion, cooled to room temperature takes film off from glass plate, you can
To flexible poly (arylene ether nitrile) transparent membrane；
The preparation of step 2, Au films：The flexible poly (arylene ether nitrile) transparent membrane that step 1 obtains is cut out as 1.4 cm*
1.4cm sizes, then covering transmission electron microscope copper mesh is put into the evaporation coating device for being equipped with film-thickness monitoring as mask plate on it
In, using vacuum PVD method, it is less than 1x10 in pressure-6Support, deposition velocity are 0.01nm s-1Under conditions of, poly-
The Au films that a layer thickness is 2nm are deposited on aryl oxide nitrile film, obtain poly (arylene ether nitrile)-gold continuous film.
Comparative example 2
A kind of preparation method of poly (arylene ether nitrile)-gold nanometer film (PEN-Au NPs), includes the following steps：
The preparation of step 1, flexible poly (arylene ether nitrile) transparent membrane：Precise 1g poly (arylene ether nitrile)s (chemical structural formula such as Fig. 2
It is shown) it is put into three-necked bottle, 11mL n,N-dimethylacetamide (N, N- are then added into three-necked bottle
Dimethylacetamide, DMAc), 30min is stirred at 80 DEG C, obtains poly (arylene ether nitrile) solution；Then, the poly- virtue that will be obtained
Ether nitrile solution slowly fall on clean glass plate, is positioned in baking oven, setting temperature program 80 DEG C, 100 DEG C, 120 DEG C,
140 DEG C, keep 2h under 160 DEG C of each temperature spots, after the completion, cooled to room temperature takes film off from glass plate, you can
To flexible poly (arylene ether nitrile) transparent membrane；
The preparation of step 2, Au films：The flexible poly (arylene ether nitrile) transparent membrane that step 1 obtains is cut out as 1.4 cm*
1.4cm sizes, then covering transmission electron microscope copper mesh is put into the evaporation coating device for being equipped with film-thickness monitoring as mask plate on it
In, using vacuum PVD method, it is less than 1x10 in pressure-6Support, deposition velocity are 0.01nm s-1Under conditions of, poly-
The Au films that a layer thickness is 2nm are deposited on aryl oxide nitrile film；
Step 3, annealing heat-treats process：The poly (arylene ether nitrile) film for the band Au films that step 2 obtains is placed in tube furnace,
Under nitrogen atmosphere, 290 DEG C are risen to by room temperature with the heating rate of 30 DEG C/min, at once cooled to room temperature, you can obtain institute
State poly (arylene ether nitrile)-gold nanometer film (PEN-Au NPs).
Comparative example 3
A kind of preparation method of poly (arylene ether nitrile)-electrum continuous film (PEN-Au/Ag film), includes the following steps：
The preparation of step 1, flexible poly (arylene ether nitrile) transparent membrane：Precise 1g poly (arylene ether nitrile)s (chemical structural formula such as Fig. 2
It is shown) it is put into three-necked bottle, 11mL n,N-dimethylacetamide (N, N- are then added into three-necked bottle
Dimethylacetamide, DMAc), 30min is stirred at 80 DEG C, obtains poly (arylene ether nitrile) solution；Then, the poly- virtue that will be obtained
Ether nitrile solution slowly fall on clean glass plate, is positioned in baking oven, setting temperature program 80 DEG C, 100 DEG C, 120 DEG C,
140 DEG C, keep 2h under 160 DEG C of each temperature spots, after the completion, cooled to room temperature takes film off from glass plate, you can
To flexible poly (arylene ether nitrile) transparent membrane；
The preparation of step 2, Au/Ag films：The flexible poly (arylene ether nitrile) transparent membrane that step 1 obtains is cut out as 1.4cm*
1.4cm sizes, then covering transmission electron microscope copper mesh is put into the evaporation coating device for being equipped with film-thickness monitoring as mask plate on it
In, using vacuum PVD method, it is less than 1x10 in pressure-6Support, deposition velocity are 0.01nm s-1Under conditions of, first exist
The Au films that a layer thickness is 2nm are deposited on poly (arylene ether nitrile) film, then the Ag films that a layer thickness is 1nm are deposited on Au films, you can
Obtain poly (arylene ether nitrile)-electrum continuous film (PEN-Au/Ag film).
The film obtained to embodiment 3, comparative example 1-3 carries out detection and localization its LSPR spectrum；Localization method is based on saturating
Radio speculum metal net is the square array configuration that mask plate obtains, and an array cell sizes are 110 μm * 110 μm, utilize dress
Light microscope equipped with halogen positioning aperture, spectrometer and test software, to it under conditions of 10 times of eyepiece, 10 times of object lens
Carry out detection and localization LSPR spectrum.When carrying out assignment test based on array structure laminated film, test zone can be effectively ensured
Uniformity, avoid because test zone difference may caused by spectral ripple.Test mode pictorial diagram is as shown in figure 3, test knot
Fruit is as shown in Figure 4.
The LSPR spectrum for the film that Fig. 4 is embodiment 3, comparative example 1-3 is obtained；Wherein, PEN-Au film are comparative example 1
Poly (arylene ether nitrile)-gold continuous film before annealing, PEN-Au NPs are poly (arylene ether nitrile)-gold nanometer film after comparative example 2 is annealed,
PEN-Au/Ag film are poly (arylene ether nitrile)-electrum continuous film before comparative example 3 is annealed, and PEN-Au/Ag NPs are to implement
Poly (arylene ether nitrile)-electrum nano compound film after the annealing of example 3.As shown in Figure 4, the PEN-Au film before annealing have compared with
The unconspicuous RESONANCE ABSORPTION of width, this is because the golden film thinner thickness of 2nm, caused by surface irregularity；It anneals by 290 DEG C
After processing (comparative example 2), occur being located at the typical LSPR absorption peaks at 613nm, half-peak breadth 220nm.And before annealing
PEN-Au/Ag film occur without apparent resonance absorbing peak, this is because the silverskin of 1nm is deposited in the golden film of 2nm, make metal
Film surface is more smooth；And after 290 DEG C of annealings (embodiment 3), there is being located at the LSPR at 532nm and absorbs
Peak, half-peak breadth 142nm.Show that Au/Ag films occur to be broken during heat treatment, migration, connect and then form stabilization
Nano-particle is fixed on the poly (arylene ether nitrile) film surface of softening, and the absorption peak wavelength of PEN-Au/Ag NPs is shorter than PEN-Au
The half-peak breadth of NPs, PEN-Au/Ag NPs show that PEN-Au/Ag NPs have more uniform grain again smaller than PEN-Au NPs
Diameter is distributed.
The test of LSPR spectrum is carried out to the laminated film that embodiment 1-4 is obtained, the results are shown in Figure 5.Fig. 5 is to implement
What the LSPR spectrum comparison diagram (A) and embodiment 1-4 for poly (arylene ether nitrile)-gold and silver nano compound film that example 1-4 is obtained obtained answers
Close the scanning electron microscope diagram piece (B-E) of film；Wherein, B corresponding embodiments 1, C corresponding embodiments 2, D corresponding embodiments 3, E
Corresponding embodiment 4.By Fig. 5 A it is found that the LSPR absorption peaks for the laminated film that different temperatures is thermally treated resulting in are：536nm(250
DEG C), 538nm (270 DEG C), 530nm (290 DEG C), 529nm (310 DEG C) show the absorption peak of laminated film with heat treatment temperature
The raising of degree and there is the trend of blue shift, absorption intensity increases with the raising of heat treatment temperature.Wherein, 310 DEG C of heat treatment
Obtained laminated film is obviously increased in the pervious absorptions of 490nm, this is because at such a temperature, poly (arylene ether nitrile) film has occurred
Decomposed causes film to turn to be yellow.By Fig. 5 B-E it is found that with heat treatment temperature raising, the size of gold silver nanometer particle is presented
Gradual increased trend；And in 310 DEG C of laminated films being thermally treated resulting in, nano particle diameter is slightly less than 290 DEG C and is heat-treated
The laminated film arrived, this may be to lead to its molecular chain movement since decomposing on a small quantity has occurred in poly (arylene ether nitrile) film at 310 DEG C
Speed is accelerated, and metal nanoparticle is absorbed in rapidly poly (arylene ether nitrile) film surface, limits its further fracture and migration.
The nano-particle on the poly (arylene ether nitrile) obtained to embodiment 3-gold and silver nano compound film surface carries out particle diameter distribution meter
Calculation and stability test, the results are shown in Figure 6.Fig. 6 is the grain for poly (arylene ether nitrile)-gold and silver nano compound film that embodiment 3 obtains
The laminated film that diameter distribution map (A) and embodiment 3 obtain impregnate in ethanol different time (15min, 30min, 1h, 2h,
4h, 8h, 12h) after LSPR absorption peak strengths normalization after change curve.By Fig. 6 A it is found that the polyarylether that embodiment 3 obtains
The average grain diameter of nano-particle is~35nm in nitrile-gold and silver nano compound film, and is evenly distributed.By Fig. 6 B it is found that implementing
The laminated film that example 3 obtains impregnate in ethanol different time (15min, 30min, 1h, 2h, 4h, 8h, 12 h) after same position
It sets and carries out assignment test its LSPR spectrum, after taking the resonance peak intensity of spectrum to be normalized, with ethyl alcohol soaking time
Increase, resonance absorbing peak Strength Changes are minimum；Show that annealing heat-treats temperature uses the vitrifying higher than poly (arylene ether nitrile) to turn
Temperature can make Au/Ag films be embedded in the poly (arylene ether nitrile) film surface of softening during fracture, migration, connection, enhancing
The stability of nano thin-film.
The poly (arylene ether nitrile) that the embodiment of the present invention 3 obtains-gold and silver nano compound film is to prostate specific antigen
(prostate specific antigen, PSA) carries out specific detection, and detailed process is：
Step 1 impregnates poly (arylene ether nitrile)-gold and silver nano compound film that the embodiment of the present invention 3 obtains in ethanol
30min is simultaneously rinsed 3 times, the floating dust of film surface and extra unstable nano-particle is removed, then 25 DEG C in vacuum drying oven
Under be dried；
Step 2, PEN-Au/Ag NPs surface biological functionalization：By the laminated film obtained after step 1 processing in room temperature
Under, 11- Mercaptoundecanoic acids (11-Mercaptoundecanoic Acid, MUA, 1mmol L-1) alcohol solution dipping
12h carries out the modification of carboxylated unimolecule assembled layers, ethyl alcohol is used after then taking out using MUA in nanoparticle surface self assembly
Cleaning 3 times, removes the MUA of excess surface, dry at 25 DEG C in vacuum drying oven；Then, by the laminated film after above-mentioned drying
At room temperature, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (0.4mmol L-1)/N- hydroxysuccinimidyls acyl is sub-
Amine (0.1mmol L-1) reagent (N- (3-Dimethylaminopropyl)-N'-Ethylcarbodiimide
Hydrochloride/N-Hydroxysuccinimide, EDC/NHS) in impregnate 60min, carry out surface carboxyl groups activation；Most
Afterwards, it is rinsed 3 times using deionized water, is dried at 25 DEG C in vacuum drying oven；
Step 3, the surfaces PEN-Au/Ag NPs sessile antibody protein molecule：The laminated film that will be obtained after step 2 processing
At a temperature of 4 DEG C, PSA antibody (Anti-PSA, 100ng mL-1) 5h is impregnated in reagent, phosphate buffer is first used after taking-up
(Phosphate Buffered Saline, PBS, 0.01mol L-1) rinse 3 times, use deionized water rinsing 3 times again, finally
25 DEG C of dryings in vacuum drying oven；
Step 4, PEN-Au/Ag NPs specific recognition antigen molecules：Compound concentration is 100ng mL-1PSA solution,
It is reacted with the PEN-Au/Ag NPs for securing Anti-PSA, the front and back PEN-Au/Ag NPs laminated films of detection reaction
The variation of LSPR spectrum, including resonance peak intensity, the variation of resonant frequency.
The poly (arylene ether nitrile) that the embodiment of the present invention 3 is obtained-gold and silver nano compound film to the detection of BSA as a comparison, tool
Body is：Compound concentration is 100ng mL-1BSA solution, reacted with the PEN-Au/Ag NPs for securing Anti-PSA, examine
Survey the variation of the front and back PEN-Au/Ag NPs laminated film LSPR spectrum of reaction, including resonance peak intensity, the variation of resonant frequency.
In this, as check experiment, the specificity that laminated film of the present invention detects PSA is verified, obtains that the results are shown in Figure 7.
Fig. 7 is the obtained poly (arylene ether nitrile)-gold and silver nano compound film of embodiment 3 to prostate specific antigen (prostate
Specific antigen, PSA) carry out specific immunity detection LSPR spectrum (A), heterogenetic antigen as a comparison
LSPR spectrum (B) when (bovine serum albumin(BSA), albumin from bovine serum, BSA) is detected, what embodiment 3 obtained
The scanning electron microscope diagram (C) of poly (arylene ether nitrile)-gold and silver nano compound film, and to prostate specific antigen (prostate
Specific antigen, PSA) carry out specific immunity detection after laminated film scanning electron microscope diagram (D).By scheming
7A-B is it is found that resonant frequency red shift and absorption intensity enhancing occur after MUA and Anti-PSA processing in PEN-Au/Ag NPs
The phenomenon that；After being reacted with BSA, laminated film LSPR spectrum do not occur significant change；And after being reacted with PSA, laminated film occurs
The phenomenon that resonant frequency further red shift enhances with absorption intensity, and its resonance spectrum occurs with before non-biological functional
The red shift of 10nm and the absorption of 0.08 unit strength increase.The result shows that using Anti-PSA treated PEN-Au/Ag
NPs has the specific detection to PSA.It is by Fig. 7 C-D it is found that different from the microstructure that crystal grain before non-biological functional is clearly demarcated,
It carries out the laminated film surface after immune detection and the trace covered by MUA, Anti-PSA and PSA molecule occurs.
In the preparation method of poly (arylene ether nitrile) provided by the invention-gold and silver nano compound film, using poly (arylene ether nitrile) as flexibility
Substrate, after utilizing physical vaporous deposition gold evaporation silver metal layer on it, then higher than poly (arylene ether nitrile) glass transition temperature
Under conditions of carry out short annealing heat treatment, gold silver nanometer particle laminated film is prepared；The gold and silver nanometer that the present invention obtains
Particles dispersed film has the characteristics that particle diameter distribution is uniform, stability is strong, is easy to biological functional, can be applied to biological immune inspection
In the high-technology fields such as survey, chemical sensitisation.In the method for the present invention when heat treatment temperature relatively low (250 DEG C~310 DEG C), heat treatment
Between it is short, greatly reduce preparation time and energy consumption；Meanwhile poly (arylene ether nitrile) substrate has good as a kind of high molecular material
Transparency, flexibility and machinability flexibly can be cut out and be taken, and the immune inspection of prostate specific antigen is convenient for
It surveys.
Claims (6)
1. a kind of preparation method of poly (arylene ether nitrile)-gold and silver nano compound film, which is characterized in that include the following steps：
Step 1, the Au films and Ag films for being sequentially prepared nanometer grade thickness on poly (arylene ether nitrile) film using physical vaporous deposition；
The poly (arylene ether nitrile) film containing Au films and Ag films that step 1 obtains is placed in tube furnace by step 2, in inert gas gas
Under atmosphere, 250 DEG C~310 DEG C are risen to by room temperature with the heating rate of 10~50 DEG C/min, then cooled to room temperature, you can
To the poly (arylene ether nitrile)-gold and silver nano compound film.
2. the preparation method of poly (arylene ether nitrile) according to claim 1-gold and silver nano compound film, which is characterized in that step 1
It is described Au films to be prepared using physical vaporous deposition and when Ag films, using transmission electron microscope copper mesh as mask plate, obtained Au films
It is array structure with Ag films.
3. the preparation method of poly (arylene ether nitrile) according to claim 1-gold and silver nano compound film, which is characterized in that step 1
The detailed process for using physical vaporous deposition to prepare Au films and Ag films for：Using poly (arylene ether nitrile) film as flexible substrates,
Covering transmission electron microscope copper mesh is as mask plate on it, using vacuum PVD method, is less than 1x10 in pressure-6Support is sunk
Product speed is 0.01nm s-1Under conditions of, successively on poly (arylene ether nitrile) film deposit 2~6nm thickness Au films and 1~3nm thickness
Ag films, you can the Au/Ag laminated films of array arrangement are obtained on poly (arylene ether nitrile) film.
4. the preparation method of poly (arylene ether nitrile) according to claim 1-gold and silver nano compound film, which is characterized in that step 2
The inert gas is nitrogen or argon gas.
5. the poly (arylene ether nitrile) that any one of Claims 1-4 the method obtains-gold and silver nano compound film is anti-in prostate-specific
Application in former specific detection.
6. the poly (arylene ether nitrile) that any one of Claims 1-4 the method obtains-gold and silver nano compound film is anti-to prostate-specific
Former detection process is specially：
Step 1, the poly (arylene ether nitrile)-gold and silver nano compound film for obtaining any one of Claims 1-4 the method are in ethanol
30min or more is impregnated, the floating dust of film surface and extra unstable nano-particle is removed, then dries；
Step 2, by obtained laminated film after step 1 processing at room temperature, in the ethanol solution of 11- mercapto-undecanoic acid reagents
10~16h is impregnated, is cleaned using ethyl alcohol after taking-up, it is dry；By the laminated film after above-mentioned drying at room temperature, 1- (3- diformazans
Aminopropyl) 40~80min is impregnated in -3- ethyl-carbodiimide hydrochlorides/n-hydroxysuccinimide reagent, it is used after taking-up
Deionized water is cleaned, dry；
Step 3 takes the laminated film obtained after step 2 processing at a temperature of 4 DEG C, after impregnating 4~8h in PSA antibody-solutions
Go out, phosphate buffer, deionized water is successively used to clean, it is dry；
Step 4, compound concentration are 100ng mL-1PSA solution, carried out with the PEN-Au/Ag NPs for securing Anti-PSA anti-
It answers, the variation of the front and back PEN-Au/Ag NPs laminated film LSPR spectrum of detection reaction, including resonance peak intensity, resonant frequency
Variation.
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| CN110057438A (en) * | 2019-04-16 | 2019-07-26 | 中国地质大学（武汉） | Embedded double-layer sensitive film and preparation method for FP chamber optical fiber acoustic sensor |
| CN111230139A (en) * | 2020-02-07 | 2020-06-05 | 深圳大学 | Gold nanoplate and preparation method thereof |
| CN111766222A (en) * | 2020-07-24 | 2020-10-13 | 江苏致微光电技术有限责任公司 | LSPR sensor based on flexible substrate and preparation method and application thereof |
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| CN107561054A (en) * | 2017-06-02 | 2018-01-09 | 南京大学 | Doré metal three-dimensional ordered macroporous structure detects simultaneously as SERS substrates for Cardiorenal syndrome multiple proteins |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110057438A (en) * | 2019-04-16 | 2019-07-26 | 中国地质大学（武汉） | Embedded double-layer sensitive film and preparation method for FP chamber optical fiber acoustic sensor |
| CN110057438B (en) * | 2019-04-16 | 2023-08-29 | 中国地质大学（武汉） | Embedded double-layer sensitive film for FP cavity optical fiber acoustic sensor and preparation method |
| CN111230139A (en) * | 2020-02-07 | 2020-06-05 | 深圳大学 | Gold nanoplate and preparation method thereof |
| CN111766222A (en) * | 2020-07-24 | 2020-10-13 | 江苏致微光电技术有限责任公司 | LSPR sensor based on flexible substrate and preparation method and application thereof |
| CN111766222B (en) * | 2020-07-24 | 2022-03-15 | 江苏致微光电技术有限责任公司 | LSPR sensor based on flexible substrate and preparation method and application thereof |
| CN115487686A (en) * | 2022-09-01 | 2022-12-20 | 成都博睿兴材科技有限公司 | Multifunctional electrospun fiber composite membrane and preparation method and application thereof |
| CN115487686B (en) * | 2022-09-01 | 2023-08-29 | 成都博睿兴材科技有限公司 | Multifunctional electrospun fiber composite membrane and preparation method and application thereof |
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