阅读说明：本技术 一种基于PMMA膜的自组装Au@Ag点阵用于检测溶液中F-离子 (PMMA film-based self-assembled Au @ Ag dot matrix for detecting F-ions in solution ) 是由 颜梅 魏全勇 张晶 王妍 王文寿 刘云霞 李增军 于 2019-11-05 设计创作，主要内容包括：本发明公开了一种基于自组装在PMMA膜上的金核银壳点阵来检测溶液中F<Sup>?</Sup>离子。通过在PMMA膜上自组装金核银壳纳米复合材料、制备4-巯基苯硼酸修饰的金核银壳纳米粒子,利用硼酸基对F<Sup>?</Sup>离子的特异性选择及Au@Ag/PMMA传感器灵敏的SERS信号响应,实现了对F<Sup>?</Sup>离子的超灵敏检测。该传感体系与其他传统方法相比,有效的降低了F<Sup>?</Sup>离子的检测限,且操作简单,检测效率高。(The invention discloses a method for detecting F in a solution based on a gold-core silver-shell dot matrix self-assembled on a PMMA film − Ions. The gold-core silver-shell nano-composite material is self-assembled on a PMMA film to prepare 4-mercaptophenylboronic acid modified gold-core silver-shell nano-particles, and F is subjected to boric acid group pairing − Ion specificity selection and sensitive SERS signal response of Au @ Ag/PMMA sensor, and F is realized − Ultrasensitive detection of ions. Compared with other traditional methods, the sensing system effectively reduces F − The detection limit of the ions, the operation is simple, and the detection efficiency is high.)

1. The invention detects F in solution based on Au @ Ag dot matrix self-assembled on a PMMA film⁻An ion, characterized by the steps of:

(1) synthesizing gold nanoparticles;

(2) preparing Au @ Ag nano particles;

(3) preparing a PMMA film with a self-assembled Au @ Ag nano particle lattice;

(4) preparing 4-mercaptophenylboronic acid modified Au @ Ag nanoparticles;

(5) using prepared Au @ Ag/PMMA flake pairs F⁻Performing SERS detection on the ions;

(6) and (4) analyzing the SERS signal.

2. The ultra-sensitive detection solution for F based on PMMA film with self-assembled Au @ Ag nano particle lattice according to claim 1⁻Ion, the synthesis of gold nanoparticles described in step (1), characterized by: 0.023 g of 99.99 percent pure gold is weighed and dissolved in aqua regia to prepare chloroauric acid solution, 45 mL of 1 mM chloroauric acid solution is kept in a state of vigorous boiling and uniform stirring, 5.5 mL of 38.8 mM sodium citrate solution is weighed and rapidly added into the solution from the upper end of a condensing tube, the color change and the time of the solution are recorded,boiling and stirring for 10min, turning off the power supply, cooling and stirring for 15 min.

3. The ultra-sensitive detection solution for F based on PMMA film with self-assembled Au @ Ag nano particle lattice according to claim 1⁻And (3) preparing Au @ Ag nanoparticles as described in step (2), wherein the Au @ Ag nanoparticles are characterized in that: 3mL of Au NPs 60. mu.L of 1% trisodium citrate was measured in 120. mu.L of 10 mM ascorbic acid solution, and 120. mu.L of 10 mM AgNO was measured₃The solution was dropwise added to the above solution to allow silver shells to be deposited on the Au NPs, and the above solution was continuously shaken in a dark environment at 25 ℃ for 30 min.

4. The ultra-sensitive detection solution for F based on PMMA film with self-assembled Au @ Ag nano particle lattice according to claim 1⁻Ion, the preparation of PMMA film with self-assembled Au @ Ag nano particle lattice described in the step (3), is characterized in that: soaking a glass beaker with an interface containing a self-assembled Au @ Ag/PMMA plasma array in acetone for 2 hours, then washing the glass beaker with ultrapure water, drying the glass beaker at 60 ℃, respectively measuring 3mL of newly prepared nano colloid and 1 mL of PMMA toluene solution, injecting the nano colloid and the PMMA toluene solution into the treated glass beaker, measuring 1.5 mL of ethanol, and quickly injecting the ethanol into the solution by using an injector so as to trap Au @ Ag NPs to an organic/water interface, and forming a thin new PMMA template after the toluene naturally evaporates at room temperature.

5. The ultra-sensitive detection solution for F based on PMMA film with self-assembled Au @ Ag nano particle lattice according to claim 1⁻And (4) preparing 4-mercaptophenylboronic acid modified Au @ Ag nanoparticles, wherein the preparation method is characterized by comprising the following steps: putting the PMMA template obtained in the step (3) at 1.0 multiplied by 10⁻³The M4-MPBA in ethanol solution was soaked for 12 hours to obtain a 4-MPBA modified template, and then the 4-MPBA modified template was thoroughly rinsed with ethanol and dried under a nitrogen atmosphere.

6. The ultra-sensitive detection of PMMA films with self-assembled Au @ Ag nano particle lattices of claim 1Measuring F in solution⁻Ionic preparation of Au @ Ag/PMMA flakes and pairing F as described in step (5)⁻SERS detection of ions characterized by: serial dilution 1.0 × 10 with pH = 7 PBS solution⁻³KF stock solution of M to obtain different concentrations of F⁻Ion solution, soaking SERS slice modified by 4-MPBA in the solution containing F with different concentrations⁻Collecting SERS spectrum signal after 100 s in ionic solution, collecting data every 10 s, and soaking 4-MPBA modified SERS sheet in corresponding F⁻In ionic solution.

7. The ultra-sensitive detection solution for F based on PMMA film with self-assembled Au @ Ag nano particle lattice according to claim 1⁻Ion, SERS signal analysis described in step (6), characterized by: and (5) combining the SERS signal analysis.

Technical Field

The invention relates to F^-The technical field of ion detection, in particular to an Au @ Ag dot matrix detection solution self-assembled on a PMMA film^-Ions.

Background

The surface enhanced raman scattering refers to an abnormal surface optical phenomenon that an analyte adsorbed on the surface of a rough metal nano structure obtains a remarkably enhanced raman spectrum under the irradiation of light. In recent years, SERS technology has been widely used for research such as substance detection and biosensing, and has shown great application potential and achieved remarkable research results in the biomedical field. More importantly, SERS has the outstanding advantages of high sensitivity, fingerprint analysis characteristics, difficult photobleaching, narrow spectral line width, suitability for multi-element detection, capability of being excited by infrared light, small interference by biological sample autofluorescence and water, suitability for biological application and the like.

The components in the nano composite material system can generate strong mutual coupling effect, not only can enhance the respective intrinsic characteristics of the material, but also can show a plurality of novel physicochemical characteristics, thereby breaking through the limitation of the material performance of a single component, and having wide application in the fields of novel functional material research and development, energy conversion and storage, environmental protection and pollution treatment, biological medicine and the like.

Fluorine is widely present in natural water bodies, and human tissues contain fluorine, but mainly accumulate in teeth and bone tendons. Proper fluorine is necessary for human body, excessive fluorine is harmful to human body, the lethal dose of sodium fluoride to human body is 6-12 g, and the drinking water containing 2.4-5 mg/L can cause fluorosis. The toxicity mechanism is that fluoride ions combine with calcium ions in blood to form insoluble calcium fluoride, which further causes hypocalcemia. Since calcium is critical to the nervous system, its reduction in concentration can be fatal. What is needed at this stage is a more sensitive assay for F by improving or innovating the assay^-The content of ions.

Disclosure of Invention

The invention aims to solve the technical problem of providing an Au @ Ag dot matrix detection solution in which F is self-assembled on a PMMA film^-The ion SERS analysis detection method can be easily realized in most laboratories without complex and cumbersome large-scale equipment support. The specific preparation scheme is as follows:

(1) synthesizing gold nanoparticles: weighing 0.023 g of 99.99 percent pure gold, dissolving the pure gold in aqua regia to prepare a chloroauric acid solution, keeping 45 mL of the chloroauric acid solution with 1 mM in a state of vigorous boiling and uniform stirring, weighing 5.5 mL of a sodium citrate solution with 38.8 mM, quickly adding the sodium citrate solution into the solution from the upper end of a condensing tube, recording the color change and the time of the solution, boiling and stirring for 10min, turning off a power supply, cooling and stirring for 15 min.

(2) Preparing Au @ Ag nanoparticles: 3mL of Au NPs 60. mu.L of 1% trisodium citrate was measured in 120. mu.L of 10 mM ascorbic acid solution, and 120. mu.L of 10 mM AgNO was measured₃The solution was dropwise added to the above solution to allow silver shells to be deposited on the Au NPs, and the above solution was continuously shaken in a dark environment at 25 ℃ for 30 min.

(3) Preparing a PMMA film with a self-assembled Au @ Ag nano particle lattice: soaking a glass beaker with an interface containing a self-assembled Au @ Ag/PMMA plasma array in acetone for 2 hours, then washing the glass beaker with ultrapure water, drying the glass beaker at 60 ℃, respectively measuring 3mL of newly prepared nano colloid and 1 mL of PMMA toluene solution, injecting the nano colloid and the PMMA toluene solution into the treated glass beaker, measuring 1.5 mL of ethanol, and quickly injecting the ethanol into the solution by using an injector so as to trap Au @ Ag NPs to an organic/water interface, and forming a thin new PMMA template after the toluene naturally evaporates at room temperature.

(4) Preparing 4-mercaptophenylboronic acid modified Au @ Ag nanoparticles: putting the PMMA template obtained in the step (3) at 1.0 multiplied by 10⁻³The M4-MPBA in ethanol solution was soaked for 12 hours to obtain a 4-MPBA modified template, and then the 4-MPBA modified template was thoroughly rinsed with ethanol and dried under a nitrogen atmosphere.

(5) Using prepared Au @ Ag/PMMA flake pairs F⁻SERS detection is carried out on ions: serial dilution 1.0 × 10 with pH = 7 PBS solution⁻³KF stock solution of M to obtain different concentrations of F⁻Ion solution, soaking SERS slice modified by 4-MPBA in the solution containing F with different concentrations⁻Collecting SERS spectrum signal after 100 s in ionic solution, collecting data every 10 s, and soaking 4-MPBA modified SERS sheet in corresponding F⁻In ionic solution.

(6) SERS signal analysis: and (5) combining the SERS signal analysis.

The invention has the beneficial effects that:

(1) the method has the advantages of low cost, simple experimental operation and easily controlled reaction conditions;

(2) compared with an Au or Ag nano-particle substrate, the Au @ Ag composite nano-material has good stability, excellent dispersibility, difficult aggregation and outstanding signal enhancement performance.

(3) Based on self-assembly on PMMA, highly packed ordered nanoparticle arrays can produce dense hot spots and uniform SERS signals.

The following is a description of detailed embodiments of the present invention: f in Au @ Ag dot matrix detection solution self-assembled on PMMA film^-Ions.

Example 1 (detection of F in aqueous solution^-）

(1) Synthesizing gold nanoparticles: weighing 0.023 g of 99.99 percent pure gold, dissolving the pure gold in aqua regia to prepare a chloroauric acid solution, keeping 45 mL of the chloroauric acid solution with 1 mM in a state of vigorous boiling and uniform stirring, weighing 5.5 mL of a sodium citrate solution with 38.8 mM, quickly adding the sodium citrate solution into the solution from the upper end of a condensing tube, recording the color change and the time of the solution, boiling and stirring for 10min, turning off a power supply, cooling and stirring for 15 min.

(2) Preparing Au @ Ag nanoparticles: 3mL of Au NPs 60. mu.L of 1% trisodium citrate was measured in 120. mu.L of 10 mM ascorbic acid solution, and 120. mu.L of 10 mM AgNO was measured₃The solution was dropwise added to the above solution to allow silver shells to be deposited on the Au NPs, and the above solution was continuously shaken in a dark environment at 25 ℃ for 30 min.

(3) Preparing a PMMA film with a self-assembled Au @ Ag nano particle lattice: soaking a glass beaker with an interface containing a self-assembled Au @ Ag/PMMA plasma array in acetone for 2 hours, then washing the glass beaker with ultrapure water, drying the glass beaker at 60 ℃, respectively measuring 3mL of newly prepared nano colloid and 1 mL of PMMA toluene solution, injecting the nano colloid and the PMMA toluene solution into the treated glass beaker, measuring 1.5 mL of ethanol, and quickly injecting the ethanol into the solution by using an injector so as to trap Au @ Ag NPs to an organic/water interface, and forming a thin new PMMA template after the toluene naturally evaporates at room temperature.

(4) Preparing 4-mercaptophenylboronic acid modified Au @ Ag nanoparticles: putting the PMMA template obtained in the step (3) at 1.0 multiplied by 10⁻³The M4-MPBA in ethanol solution was soaked for 12 hours to obtain a 4-MPBA modified template, and then the 4-MPBA modified template was thoroughly rinsed with ethanol and dried under a nitrogen atmosphere.

(5) Using prepared Au @ Ag/PMMA flake pairs F⁻SERS detection is carried out on ions: serial dilution 1.0 × 10 with pH = 7 PBS solution⁻³KF stock solution of M to obtain different concentrations of F⁻Ion solution, soaking SERS slice modified by 4-MPBA in the solution containing F with different concentrations⁻Collecting SERS spectrum signal after 100 s in ionic solution, collecting data every 10 s, and soaking 4-MPBA modified SERS sheet in corresponding F⁻In ionic solution.

(6) SERS signal analysis: and (5) combining the SERS signal analysis.