CN116973341A - Visual fluorescent sensor - Google Patents
Visual fluorescent sensor Download PDFInfo
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- CN116973341A CN116973341A CN202310503822.0A CN202310503822A CN116973341A CN 116973341 A CN116973341 A CN 116973341A CN 202310503822 A CN202310503822 A CN 202310503822A CN 116973341 A CN116973341 A CN 116973341A
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- spiropyran
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- polydimethylsiloxane
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- 230000000007 visual effect Effects 0.000 title claims abstract description 16
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 102
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 102
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 102
- 239000002105 nanoparticle Substances 0.000 claims abstract description 36
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 25
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 15
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- 238000001514 detection method Methods 0.000 claims abstract description 12
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- 239000010949 copper Substances 0.000 claims description 10
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- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000005046 Chlorosilane Substances 0.000 claims description 8
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000012815 thermoplastic material Substances 0.000 claims description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000009832 plasma treatment Methods 0.000 claims description 4
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 abstract description 80
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- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
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- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
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- 241000238631 Hexapoda Species 0.000 description 1
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- GTXRYQGMNAPQDP-UHFFFAOYSA-N butyl-chloro-diphenylsilane Chemical group C=1C=CC=CC=1[Si](Cl)(CCCC)C1=CC=CC=C1 GTXRYQGMNAPQDP-UHFFFAOYSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
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- HEUIAKTUJMENAO-UHFFFAOYSA-N tert-butyl-chloro-phenylsilane Chemical compound CC(C)(C)[SiH](Cl)C1=CC=CC=C1 HEUIAKTUJMENAO-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
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Classifications
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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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The application discloses a visual fluorescent sensor, wherein a support body below PMMA in the fluorescent sensor is PDMS with a micron-sized inverted pyramid structure, and the whole is defined as PDMS/PMMA-Au/SP. PDMS/PMMA-Au/SP has a structure similar to that of an insect compound eye, has a large specific surface area and low reflectivity, can provide more attachment sites and higher light absorption efficiency for the spiropyran, and is beneficial to improving the fluorescence intensity of the ring-opened body MC of the spiropyran. Meanwhile, the electromagnetic field enhancement effect of the Au nano-particles can further improve the fluorescence intensity of the spiropyran open ring MC. The brand new PDMS/PMMA-Au/SP fluorescence sensor is successfully applied to trace detection of metal ions.
Description
Technical Field
The application belongs to the technical field of photoelectric materials, and particularly relates to a visual fluorescent sensor.
Background
Spiropyran derivatives are of great interest because of their ability to bind a variety of metal ions and provide a unique spectral response for each metal ion. As a typical representation of photochromic molecules, they can generate colored Merocyanine (MC) structures due to cleavage of c—o bonds under uv light induction, and can also undergo a ring closure reaction under visible light or thermal stimulus to return to their colorless initial State (SP). The MC form of spiropyran has negative charge phenolic oxygen radical to provide complexing site for metal ion to change its corresponding absorption spectrum and fluorescence spectrum, so that it may be used in colorimetry and fluorescence sensing. However, the spiropyran molecules have the defects of poor fatigue resistance caused by easy photodegradation, weak fluorescence caused by easy aggregation of MC forms, incapability of generating ring-closure reaction and the like, and limit the practical application value of the spiropyran molecules in the sensing field.
An effective method to solve this problem is to bond the spiropyran to a support (polymer chain, nanoparticle, etc.) by covalent bond. Because the support can influence the switching dynamics of the spiropyrans to a great extent, the aggregation of the spiropyrans is avoided, and the photostability, switchability and processability thereof are improved. Depending on the dispersed form of the spiropyran, two categories can be distinguished: the first is to modify the spiropyran inside the support by grafting reaction. For example: liu et al graft the spiropyran molecule into poly (N-vinylcaprolactam) by atom radical transfer (ATRP) method, wherein the phenolic oxygen bond of the ring-opened MC and the amino group of N-vinylcaprolactam form coordination bond with metal ion, thereby realizing Fe 2+ 、Cu 2+ 、Co 2+ Is a colorimetric sensor of (a). Sousa et al prepared a spiropyran grafted poly (epsilon-caprolactone) polymer by electrospinning into a nanofiber with photochromic properties, which can realize Mg treatment after ultraviolet light treatment 2+ 、Zn 2+ 、Ca 2+ 、Cd 2+ 、La 3+ 、Er 3+ Colorimetric and fluorescent responses of (a). However, the dense polymer network not only prolongs the response time of the spiropyran ring opening, but also has very difficult desorption process of metal ions from the inside of the polymer system, which reduces the recycling times. The second is to modify the spiropyran on the surface of the support by interfacial modification. For example, maclachlan et al modify spiropyrans on mesoporous silica surfaces by amino silylation agents, which exhibit excellent photochromic properties and are resistant to Zn due to the mesoporous nature of the substrate providing a large number of attachment sites for spiropyrans 2+ 、Cu 2+ 、Ni 2+ 、Sn 2+ Exhibiting a colorimetric response. However, the spiropyran modified on the surface of the support is usually a monomolecular film, and the colorimetric or fluorescent sensing signal is weak, so that trace detection of metal ions has not been achieved yet.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide a visual fluorescent sensor.
In order to solve the technical problems, the application provides the following technical scheme: a visual fluorescence sensor, characterized in that: the sensor consists of a three-layer structure, wherein the bottom layer is a flexible substrate prepared from polydimethylsiloxane, the middle layer is a metal particle film coated by a thermoplastic material and metal nano particles, and the upper layer is a chlorosilane or alkoxysilane and spiropyran modified induction layer.
The application further aims to overcome the defects in the prior art and provide a preparation method of the visual fluorescent sensor.
In order to solve the technical problems, the application provides the following technical scheme:
preparing a flexible substrate: etching monocrystalline silicon by adopting alkali liquor, carrying out hydrophobic treatment, pouring a polydimethylsiloxane prepolymer and an initiator on a silicon template after the treatment, solidifying, cooling to room temperature after solidification is completed, and stripping polydimethylsiloxane to obtain the polydimethylsiloxane substrate with the inverted pyramid microstructure;
coating a metal nanoparticle film: dissolving gold nano particles and a thermoplastic material in a solvent, continuously stirring after ultrasonic dispersion, spin-coating the stirred mixed solution on the surface of polydimethylsiloxane, and drying to obtain a polydimethylsiloxane/thermoplastic material-metal nano particle substrate;
first monolayer surface modification: performing plasma treatment on a polydimethylsiloxane/thermoplastic material-metal nanoparticle substrate to enable the surface of the polydimethylsiloxane/thermoplastic material-metal nanoparticle substrate to be attached with hydroxyl groups, and performing first monolayer surface modification;
second monolayer surface modification: carrying out second monomolecular layer surface modification on the substrate subjected to the first surface modification, and putting the substrate subjected to the second surface modification into an organic solvent containing spiropyran and an activating agent for spiropyran functional modification to obtain a polydimethylsiloxane/thermoplastic material-metal nano particle/spiropyran composite substrate;
finally, the polydimethyl siloxane/thermoplastic material-metal nano particle/spiropyran composite substrate is cleaned and dried to obtain the fluorescent sensor.
As a preferred embodiment of the preparation process according to the application, there is provided: the thermoplastic material comprises polymethyl methacrylate, polystyrene, polyvinylidene chloride, polyurethane and derivatives of the above materials.
As a preferred embodiment of the preparation process according to the application, there is provided: the spiropyran includes spiropyran containing carboxyl and spiropyran derivative.
As a preferred embodiment of the preparation process according to the application, there is provided: the metal nano particles comprise gold nano particles, silver nano particles and copper nano particles; the addition amount was 3.5X10 -5 M～5.6×10 -4 M。
As a preferred embodiment of the preparation process according to the application, there is provided: the polydimethylsiloxane substrate with inverted pyramid microstructure has an included angle of about 54.7 degrees between the side surface and the top surface in side view, and the inverted pyramid height is 5 μm.
As a preferred embodiment of the preparation process according to the application, there is provided: when the first monomolecular layer is subjected to surface modification, one or two chlorosilane or alkoxy silane containing alkyl and benzene rings is/are adopted for surface modification, and the chlorosilane comprises tert-butylphenyl chlorosilane.
As a preferred embodiment of the preparation process according to the application, there is provided: and in the second monolayer surface modification, the surface modification adopts chlorosilane or alkoxy silane containing amino, including 3-aminopropyl trimethoxy silane.
As a preferred embodiment of the preparation process according to the application, there is provided: the growth time of the spiropyran in the spiropyran functional modification is 3-12 hours.
It is a further object of the present application to overcome the deficiencies of the prior art and to provide an application of a visual fluorescence sensor.
As an application of the visual fluorescence sensor of the present application, wherein: the application of the fluorescent sensor in visual trace detection of metal ions.
The application has the beneficial effects that:
(1) My application provides a method of modifying spiropyrans to the surface of a PMMA film containing Au nanoparticles therein, the support under PMMA being PDMS with a micron-sized inverted pyramid structure, the whole being defined as PDMS/PMMA-Au/SP. PDMS/PMMA-Au/SP has a structure similar to that of an insect compound eye, has a large specific surface area and low reflectivity, can provide more attachment sites and higher light absorption efficiency for the spiropyran, and is beneficial to improving the fluorescence intensity of the ring-opened body MC of the spiropyran.
(2) Meanwhile, the electromagnetic field enhancement effect of the Au nano-particles can further improve the fluorescence intensity of the spiropyran open ring MC; the novel PDMS/PMMA-Au/SP successfully prepares a fluorescence sensor, can be applied to trace visual detection of metal ions, and can be recycled.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic illustration of the preparation flow of PDMS/PMMA-Au/SP substrate according to example 1 of the present application;
FIG. 2 is a graph showing SEM characterization of the surface of a substrate according to example 2, wherein the (a, d) pyramids are arranged in an array; (b, e) a PDMS surface imprinted with an inverted cone structure; (c, f) PDMS/PMMA-Au; (g) substrate surface EDS characterization;
FIG. 3 is a graph showing the UV-Vis spectrum of the PDMS/PMMA-Au surface of example 2 of the present application after sequential grafting of different functionalized materials;
FIG. 4 is a graph showing the change of contact angle of PDMS/PMMA-Au surface according to example 2 of the present application after sequentially grafting different functionalized materials;
FIG. 5 shows (a) an absorption spectrum and (b) a fluorescence spectrum of a PDMS/PMMa-Au/SP composite substrate coated with Au nanoparticles having different concentrations in example 3 of the present application;
FIG. 6 is a graph showing (a) transmission spectrum and (b) fluorescence spectrum of PDMS/PMMA-Au/SP composite substrate grafted with different TBDS addition amounts in example 4 of the present application;
FIG. 7 is a graph showing (a) transmission spectrum and (b) fluorescence spectrum of PDMS/PMMA-Au/SP composite substrate grafted with different ATMS addition amounts in example 5 of the present application;
FIG. 8 is a graph showing (a) transmission spectrum and (b) fluorescence spectrum of PDMS/PMMA-Au/SP composite substrates according to the present application for different spiro pyran grafting times in example 6;
FIG. 9 shows fluorescence spectra of different structures under (a) UV irradiation in example 7 of the present application; (b) absorbance spectra (black line) of PDMS/PMMA-Au; absorption spectrum of MC (red line); (c) fluorescence spectra of different structures; (d) time resolved emission spectrum contrast plots of different structures;
FIG. 10 shows fluorescence spectra of (a) PDMS/PMMA-Au/SP substrates and 10-3M different metal ions complexed with Zn at different concentrations in example 8 of the present application 2+ (b) fluorescence spectrum when bound to a substrate; (c) linear fitting; (d) PDMS/PMMA-Au/SP substrate detection of Zn 2+ Fatigue resistance at the time; (e) And (f) PDMS/PMMA-Au/SP detection of transmission spectra and corresponding macroscopic photographs of different metal ions.
Fig. 11 is a schematic side view of an array of micropyramids in example 2 of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Preparation of PDMS substrate containing inverted pyramid microstructure
Firstly, etching for 30min by utilizing the anisotropic etching property of monocrystalline silicon in KOH solution to obtain the silicon template with the micro pyramid structure on the surface. The silicon template is then subjected to a hydrophobic treatment with a fluoro silylating agent to facilitate subsequent peeling of the PDMS. PDMS prepolymer and initiator were then cast on the hydrophobically treated silicon template and cured at 68 ℃ for 3 hours. And after solidification, cooling to room temperature and peeling off the PDMS to obtain the PDMS substrate containing the inverted pyramid microstructure.
(2) Preparation of PDMS/PMMA-Au substrates
First, 20mL of chloroauric acid (0.01 wt%) was added to a round bottom flask and boiled under stirring and reflux. Then, 0.14mL sodium citrate (1 wt%) was added quickly to the boiling solution and the solution was boiled for an additional 30min. Subsequently, the above solution was cooled to room temperature, and centrifuged to obtain Au nanoparticles. Then, 0.0455g of PMMA is dissolved in 20g of methylene dichloride, au nano-particles with different contents are added, the mixture is uniformly dispersed by ultrasonic, and the mixture is stirred for 5 hours at room temperature after sealing. Finally, 50 mu L of mixed solution of PMMA and Au is spin-coated on the surface of PDMS, spin-coating speed and time are 4500r/min and 30s respectively, and the spin-coated sample is dried in an oven at 60 ℃ for 1h, so that the PDMS/PMMa-Au substrate is obtained.
(3) TBDS functionalization of PDMS/PMMA-Au substrates
First, the dried PDMS/PMMA-Au substrate was subjected to oxygen plasma treatment for 5min to attach a large number of hydroxyl groups to the surface. Then, the above treated substrate was put into DMF solutions of different TBDS contents, and left to stand at room temperature for 30min. Finally, the substrate was washed thoroughly with DMF to modify the TBDS monolayer on the substrate surface.
(4) Preparation of PDMS/PMMA-Au/SP substrates
First, PDMS/PMMA-Au substrates with surface modified TBDS were placed in DMF solutions with different ATMS contents and allowed to stand at room temperature for 30min. Next, the substrate was washed thoroughly with ethanol and water using a grafted amino silylation reagent to modify the ATMS monolayer on the substrate surface. Then, the substrate after ATMS modification is put into 20mL ethanol solution containing 35mgEDC and 5mg spiropyran for reaction, and the substrate is stood for different times under the condition of room temperature and darkness, so as to finish the spiropyran functional modification of the surface of the substrate. Finally, washing the spiropyran modified sample with ethanol to obtain the PDMS/PMMA-Au/SP composite substrate, and finally obtaining the fluorescence sensor.
Example 2
Preparation method verification and morphology characterization of PDMS/PMMA-Au/SP substrate
The preparation flow of the PDMS/PMMA-Au/SP substrate is shown in figure 1, and firstly, a silicon substrate containing a micro pyramid array is obtained on the surface of planar silicon by an alkali liquid anisotropic etching method. The average height of the micro pyramids was 5 μm, and the side-to-plane angle was about 54.7 °, as shown in fig. 2 (a), (d) and fig. 11. And then pouring the PDMS prepolymer on the surface of the silicon substrate, and curing to obtain the PDMS substrate with the inverted pyramid structure on the surface. As shown in fig. 2 (b) and (e), the inverse pyramid structure of the PDMS surface was complementary to the pyramid structure of the silicon substrate surface, indicating that the PDMS substrate was successfully replicated.
Compared with a planar structure, the PDMS substrate not only has larger specific surface area, but also has excellent anti-reflection capability, which is beneficial to improving the light absorption efficiency and enhancing the isomerism efficiency and the excitation efficiency of the spiropyran. And then, spin-coating the PMMA film containing the Au nano particles on the surface of the PDMS substrate, wherein the PMMA dielectric layer can effectively reduce the probability of direct contact between the Au nano particles and the spiropyran molecules and reduce non-radiative energy transfer between the Au and the spiropyran molecules.
In addition, tertiary butyl diphenyl chlorosilane (TBDS) containing rigid groups is modified on the PMMA surface, so that the space between spiropyran molecules can be increased, and a large enough free space is provided for spiropyran ring-opening isomerization. Finally, SP-COOH was covalently grafted onto PMMA surface unoccupied by TBDS by an amino silylating agent as bridging molecule. FIGS. 2 (c) and (f) show the morphology of PDMS/PMMA-Au/SP substrates with overall structure similar to that of insect complex eyes. Meanwhile, fig. 2 (e) shows the EDS spectrum of the PDMS/PMMA-Au/SP substrate, with the elements uniformly distributed on the substrate surface, again demonstrating the success of the composite substrate preparation.
To further demonstrate the success of the modification of the functional molecules on the surface of the composite substrate, the inventors performed UV-Vis transmission spectrum tracking of the samples involved in the modification process, as shown in fig. 3. First, after the TBDS is modified on the surface of the composite substrate, two characteristic peaks appear at 250nm and 365nm in the transmission spectrum. Then, after modifying ATMS, the characteristic peak at 365nm of the transmission spectrum of the composite substrate surface disappears. Finally, after the spiropyran is grafted on the surface of the composite substrate, the characteristic peak at 250nm of the transmission spectrum disappears, and two characteristic peaks appear at 265nm and 340 nm. After the spiropyran modified composite substrate is irradiated by ultraviolet light, a strong characteristic peak appears in a transmission spectrum of 550nm, which shows that spiropyran isomerizes from a closed-loop SP form to an open-loop MC form, and the composite substrate is proved to be successfully prepared.
Fig. 4 shows a photograph of the change in the surface contact angle during sample preparation. PDMS and PMMA are both hydrophobic polymers, so the contact angles of the surfaces of the PDMS substrate and the PDMS/PMMA-Au substrate are about 120 degrees, and the contact angles are not changed obviously. After the PDMS/PMMA-Au is subjected to oxygen plasma treatment, a large number of hydroxyl groups are generated on the surface of the PDMS/PMMA-Au, the contact angle reaches 30 degrees, and the PDMS/PMMA-Au shows certain hydrophilicity. After the PDMS/PMMA-Au surface is modified by TBDS, the contact angle reaches 106.1 degrees. This is because the modified TBDS contains a large number of benzene rings, which makes the sample surface exhibit a certain hydrophobicity. After grafting the ATMS, the contact angle of the substrate surface was reduced to 60.4 again, since ATMS contains a large amount of amino groups, making the substrate surface hydrophilic. After grafting the spiropyran onto the substrate surface by ATMS, its contact angle reaches 103.4 °, because the spiropyran that is not ring-opened isomerized is hydrophobic. Finally, the spiropyran ring-opening isomerism on the surface of the substrate under the irradiation of ultraviolet light is in an MC form with a zwitterionic form, and the spiropyran ring-opening isomerism shows hydrophilic property, so that the contact angle is only 37.0 degrees. The variation of the contact angle is completely matched with the functionalization of the substrate surface in each step, and the preparation success of the composite substrate is fully proved.
Example 3
My application investigated the effect of Au nanoparticle content on the fluorescence enhancement performance of PDMS/PMMa-Au/SP composite substrates, and the following discussion relates to composite substrates that were all subjected to uv irradiation for 90 s.
As shown in fig. 5, when Au nanoparticles are not contained, the fluorescence intensity of the composite substrate is very weak under excitation of incident light.
As the concentration of Au nanoparticles increases, the fluorescence intensity of the composite substrate increases as well, because of the plasmonic effect of the Au nanoparticles.
At an Au nanoparticle concentration of 1.4X10 -4 And in the M process, the fluorescence intensity of the composite substrate reaches the maximum, and the corresponding plasma resonance absorption peak is the strongest. However, as the concentration of Au nanoparticles continues to increase, the fluorescence intensity decreases because Au nanoparticles at too high a concentration accumulate, weakening the electromagnetic field effect.
Example 4
My application investigated the effect of TBDS addition on the fluorescence enhancement performance of PDMS/PMMA-Au/SP composite substrates, and the following discussion relates to composite substrates that have been subjected to UV irradiation for 90 seconds.
As shown in FIG. 6, at a TBDS addition of 100. Mu.L, the transmittance of the composite substrate was the lowest, i.e., the spiropyran discoloration effect of the substrate surface was the most pronounced, while the fluorescence intensity was also the greatest. This is because the addition of TBDS affects the intermolecular spacing of the spiropyrans and thus the steric hindrance of their ring opening.
When the TBDS addition amount is too small, the molecular spacing of the spiropyran is too short, so that a sufficient space cannot be increased for isomerization of the spiropyran, the spiropyran ring opening is slow and even so that the spiropyran ring opening cannot be performed, and further, the composite substrate is small in transmittance change and weak in fluorescence intensity. However, when the TBDS is excessively added, the effective modification amount of the subsequent spiropyran on the surface of the composite substrate is reduced, so that the change of the transmittance of the composite substrate is small and the fluorescence intensity is weak.
Example 5
My application investigated the effect of ATMS addition on the fluorescence enhancement performance of PDMS/PMMA-Au/SP composite substrates, and the following discussion relates to composite substrates that have been subjected to UV irradiation for 90 seconds.
The amount of ATMS added will have a significant effect on the grafting sites of the spiropyrans. As shown in fig. 7, when the addition amount of ATMS is too small, it cannot provide sufficient active sites required for spiropyran grafting on the surface of the composite substrate, so that the spiropyran grafting amount is low, and thus the transmittance of the composite substrate becomes small and the fluorescence intensity is weak.
With the increase of the ATMS addition amount, the transmissivity of the composite substrate is continuously reduced, and the fluorescence intensity is gradually enhanced. At an ATMS addition of 10. Mu.L, the transmittance of the composite substrate was the lowest and the fluorescence enhancement was the greatest. However, when the ATMS addition amount exceeds 10. Mu.L, the fluorescence intensity of the composite substrate tends to decrease because the density of grafting active sites is too high, so that the grafted spiropyran is quenched by fluorescence aggregation.
Example 6
The effect of the spiropyran growth time on the fluorescence enhancement performance of PDMS/PMMA-Au/SP composite substrates was studied, and the following discussion relates to composite substrates that were all subjected to UV irradiation for 90 s.
The growth time of the spiropyran is closely related to the grafting quantity of the spiropyran on the surface of the composite substrate. As shown in fig. 8, the number of spiropyran grafts is smaller as the growth time is shorter, so that the change in transmittance of the composite substrate is smaller. With the increase of the grafting time of the spiropyran, the transmissivity of the composite substrate is continuously reduced, and the fluorescence intensity is gradually enhanced. The transmittance change of the composite substrate is most obvious when the grafting time is 12 hours.
However, it should be noted that the fluorescence intensity of the composite substrate has reached a maximum value at 3 hours, and then tends to decrease. This is probably because the grafting density was too high and aggregation quenching occurred after 3 hours as the growth time of the spiropyran continued to increase.
In the present application, the inventors selected the optimum condition for the spiropyran growth time of 3 hours for the subsequent study, because the transmittance of the composite substrate was 3% lower in 3 to 12 hours, but the fluorescence intensity was reduced by 1.5 times.
Meanwhile, the composite substrate needs to be used for trace detection of subsequent metal ions, so that excellent fluorescence performance is important for practical application of the substrate.
Example 7
My application has demonstrated that PDMS/PMMA-Au/SP substrates exhibit very excellent fluorescence properties at a spiropyran grafting time of 3h in a one-factor optimization process. This fluorescence enhancement comes mainly from three aspects, an inverted pyramid structure with anti-reflection capability, au nanoparticles with plasmon resonance effect, and PMMA spacer layer with low non-radiative energy transfer probability, respectively.
The inverted pyramid structure has excellent anti-reflection capability, and can improve the excitation efficiency of the spiropyran on the surface of the substrate, thereby improving the fluorescence intensity of the spiropyran.
To demonstrate this, the substrate P with inverted pyramid structure was compared sample (PDMS/PMMA-Au/SP) and a substrate F having no inverted pyramid structure sample As shown in fig. 9 (a), the fluorescence intensity of the former is 19 times that of the latter, and the enhancement factor is as high as 5.06.
The Au nano particles can generate enhanced local electromagnetic fields under the action of incident light, so that more rapid attenuation channels are provided for the spiropyran on the surface of the substrate, the fluorescence lifetime of the spiropyran is reduced, the spontaneous radiation rate of the spiropyran is increased, and the fluorescence intensity of the spiropyran is enhanced. To demonstrate this, the fluorescence intensity and fluorescence lifetime of the Au nanoparticle-containing substrate PDMS/PMMa-Au/SP and the Au nanoparticle-free substrate PDMS/SP were compared, the fluorescence intensity of the PDMS/PMMa-Au/SP being significantly greater than that of the PDMS/SP, and the fluorescence lifetime of the PDMS/PMMa-Au/SP being shorter than that of the PDMS/SP, as shown in fig. 9 (c) and (d).
In addition, the resonant coupling between the Au nanoparticles and the fluorescent molecules can significantly enhance the fluorescence intensity of the latter, and the enhancement effect is maximized when the plasmon resonance peak of the metal nanoparticles overlaps with the absorption peak or excitation peak of the fluorescent molecules. As shown in fig. 9 (b), the plasmon resonance absorption peak of the Au nanoparticle has a relatively high overlap with the absorption peak of the spiropyran, which will significantly increase the excitation efficiency and the radiation rate of the spiropyran on the substrate surface, thereby increasing the fluorescence intensity thereof.
The PMMA spacer layer reduces the probability of non-radiative energy transfer caused by direct contact of Au and MC, thereby improving the fluorescence intensity of the substrate. To demonstrate this, the fluorescence intensity and fluorescence lifetime of the PMMA-containing substrate PDMS/PMMa-Au/SP and the PMMA-free substrate PDMS/Au/SP were compared, as shown in FIGS. 9 (c) and (d). The fluorescence intensity of PDMS/PMMa-Au/SP is larger than that of PDMS/Au/SP, and meanwhile, the fluorescence lifetime of PDMS/PMMa-Au/SP is longer than that of PDMS/Au/SP, which indicates that more electron transfer exists between metal nano particles of the PDMS/Au/SP substrate and the spiropyran, and fluorescence emission of MC is quenched.
Example 8
After the spiropyran is ring-opened and isomerized into a merocyanine MC form under ultraviolet light irradiation, fluorescence and colorimetric sensing of metal ions can be realized through the combination of the phenolic oxygen group of the merocyanine MC and the metal ions.
As shown in FIG. 10 (a), 10 drops of PDMS/PMMA-Au/SP were respectively applied to the surface of the substrate -3 M Zn 2+ 、Ni 2+ 、Sn 2+ 、Cu 2+ The fluorescence peak of MC of the ethanol solution is shifted from 620nm to 615nm, 610nm, 625nm and 630nm respectively, and the fluorescence intensity is obviously quenched. And the fluorescence intensity of PDMS/PMMA-Au/SP substrate is linear with the concentration of metal ions.
By Zn 2+ For example, as shown in FIGS. 10 (b) and (c), the fluorescence intensity of the substrate is compared with Zn 2+ The linear analytical equation for the concentration is: y= -307433X-319506 (10 -1 M～10 -6 M) with a detection Limit (LOD) of 0.281 μm (lod=3s) b /S，S b = 0.08613), which indicates that the substrate canThe trace detection of metal ions is realized.
In addition, because the complex bond formed between MC and metal ion is unstable, can release metal ion because the spiropyran isomerizes back to the open-loop state under exposing to visible light, and make the basement can realize recycling.
As shown in fig. 10 (d), the PDMS/PMMA-Au/SP substrate did not show any decay of sensitivity for 6 cycles. PDMS/PMMA-Au/SP substrates can be realized by colorimetry in addition to detection of different metal ions by fluorescence. In order to have obvious colorimetric response effect, the ultraviolet irradiation pretreatment time of the substrate is prolonged to 150s.
FIGS. 10 (e) and (f) show colourimetric photographs and transmission spectra of PDMS/PMMA-Au/SP substrates in response to different metal ions. The spiropyran on the surface of the substrate isomerizes from a colorless closed-loop form SP to a dark purple open-loop form MC after 150s of ultraviolet light irradiation, so that the whole substrate shows obvious color change, which corresponds to a transmission peak at 560nm corresponding to MC.
Then when the substrate complexes different metal ions, the absorption peak has a distinct blue shift, and thus shows different color changes. In this way, different metal ions can be distinguished through macroscopic color change, and the visual identification method greatly reduces the cost in the ion detection process.
Example 9
Example 9 differs from example 1 in that during the preparation of the PDMS/PMMA-Au substrate, polystyrene was used instead of PMMa as the substrate material, with the remaining conditions being the same as example 1.
Example 10
Example 10 differs from example 1 in that polyvinylidene chloride was used as the substrate material in place of PMMa during the preparation of the PDMS/PMMA-Au substrate, with the remaining conditions being the same as example 1.
Example 11
Example 11 differs from example 1 in that polyurethane was used as the substrate material instead of PMMa during the preparation of the PDMS/PMMA-Au substrate, and the remaining conditions were the same as example 1.
Zn was added dropwise to the fluorescence sensors in examples 9 to 11 2+ 、Ni 2+ 、Sn 2+ Which produces a significant shift in fluorescence peak, indicating that the fluorescence sensor has been successfully prepared.
Example 13
Example 13 differs from example 1 in that in the process of preparation of PDMS/PMMa-Au substrate, ag nanoparticles are used as a substrate material instead of Au nanoparticles, wherein the preparation method of Ag nanoparticles is as follows:
will 9mgAgNO 3 Dissolved in 49mL H 2 O and heating the solution to boiling with vigorous stirring; 1mL of 38.8mmol/L trisodium citrate was added dropwise, and the mixture was kept at boiling for half an hour; cooling the reaction solution to room temperature; the prepared silver colloid was centrifuged at 500 rpm for 10 minutes to remove larger sized particles, thereby obtaining Ag nanoparticles, and the other conditions were the same as in example 1.
Example 14
Example 14 differs from example 1 in that in the process of preparation of PDMS/PMMa-Au substrate, cu nanoparticles are used as a substrate material instead of Au nanoparticles, wherein the preparation method of Cu nanoparticles is as follows: first, 20mL of distilled water was added to a round-bottomed flask having a volume of 100mL, and 3mL of 50mmol L was added with continuous stirring -1 Cu (NO) 3 ) 2 The solution was transferred to an ice bath and stirred for 1 hour; 6mL of freshly configured 50mmol L-1 NaBH was added 4 The solution was stirred for 1 hour; the product was collected by centrifugation through a high-speed centrifuge (10000 rpm, 20 minutes) and then washed three times with distilled water and absolute ethanol, respectively. Finally, drying the obtained Cu nano particles in a vacuum drying oven for 4 hours at 50 ℃; cu nanoparticles were obtained, and the other conditions were the same as in example 1.
The replacement of metal ions can partially influence the performance of the fluorescence sensor, the performance of the fluorescence sensor is not obviously changed by replacing Au with Ag, and the fluorescence sensor is opposite to Cu by replacing Au with Cu 2+ Is more sensitive and is not interfered by other metal ions.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (10)
1. A visual fluorescence sensor, characterized in that: the sensor consists of a three-layer structure, wherein the three-layer structure is respectively a bottom layer, a middle layer and an upper layer according to the up-down distribution;
the bottom layer is a flexible substrate prepared from polydimethylsiloxane, the middle layer is a metal particle film coated by a thermoplastic material and metal nano particles, and the upper layer is an induction layer modified by chlorosilane or alkoxy silane and spiropyran;
the middle layer is of a membranous structure and covers the bottom layer, the upper layer is connected with the middle layer through chemical reaction, and each layer of the bottom layer, the middle layer and the upper layer is tightly attached.
2. A preparation method of a visual fluorescence sensor is characterized by comprising the following steps: the method comprises the following steps:
preparing a flexible substrate: etching monocrystalline silicon by adopting alkali liquor, carrying out hydrophobic treatment, pouring a polydimethylsiloxane prepolymer and an initiator on a silicon template after the treatment, solidifying, cooling to room temperature after solidification is completed, and stripping polydimethylsiloxane to obtain the polydimethylsiloxane substrate with the inverted pyramid microstructure;
coating a metal nanoparticle film: dissolving gold nano particles and a thermoplastic material in a solvent, continuously stirring after ultrasonic dispersion, spin-coating the stirred mixed solution on the surface of polydimethylsiloxane, and drying to obtain a polydimethylsiloxane/thermoplastic material-metal nano particle substrate;
first monolayer surface modification: performing plasma treatment on a polydimethylsiloxane/thermoplastic material-metal nanoparticle substrate to enable the surface of the polydimethylsiloxane/thermoplastic material-metal nanoparticle substrate to be attached with hydroxyl groups, and performing first monolayer surface modification;
second monolayer surface modification: carrying out second monomolecular layer surface modification on the substrate subjected to the first surface modification;
spiropyran functionalization modification: putting the substrate with the twice surface modification into an organic solvent containing spiropyran and an activating agent for spiropyran functional modification to obtain a polydimethylsiloxane/thermoplastic material-metal nano particle/spiropyran composite substrate;
finally, the polydimethyl siloxane/thermoplastic material-metal nano particle/spiropyran composite substrate is cleaned and dried to obtain the fluorescent sensor.
3. The method of manufacturing as claimed in claim 2, wherein: the thermoplastic material comprises one or more of polymethyl methacrylate, polystyrene, polyvinylidene chloride, polyurethane and derivatives of the above materials.
4. The method of manufacturing as claimed in claim 2, wherein: the spiropyran is a spiropyran or spiropyran derivative containing carboxyl.
5. The method of manufacturing as claimed in claim 2, wherein: the metal nano particles comprise one of gold nano particles, silver nano particles and copper nano particles; the addition amount was 3.5X10 -5 M～5.6×10 -4 M。
6. The method of manufacturing as claimed in claim 2, wherein: the polydimethylsiloxane substrate containing the inverted pyramid microstructure has an included angle of 54.7 degrees between the side face and the top face of the inverted pyramid microstructure and a height of 5 mu m.
7. The method of manufacturing as claimed in claim 2, wherein: the first monolayer surface modification is carried out by adopting one or two of alkyl, benzene ring chlorosilane or alkoxy silane, wherein the benzene ring chlorosilane is tert-butylene phenyl chlorosilane.
8. The method of manufacturing as claimed in claim 2, wherein: the second monomolecular layer is modified by adopting chlorosilane or alkoxy silane containing amino, and the alkoxy silane is 3-aminopropyl trimethoxy silane.
9. The method of manufacturing as claimed in claim 2, wherein: the growth time of the spiropyran in the spiropyran functional modification is 3-12 hours.
10. The use of a visual fluorescence sensor according to claim 1, wherein: the fluorescent sensor is applied to visual trace detection of metal ions.
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