阅读说明：本技术 一种邻苯二甲酸酯类化合物的检测方法 (Detection method of phthalate compound ) 是由 施佳康 李兰 马强 戴洪霞 于 2020-03-31 设计创作，主要内容包括：本发明公开了一种邻苯二甲酸酯类化合物的检测方法,属于检测技术领域。本发明的邻苯二甲酸酯类化合物的检测方法,包括如下步骤：将在锥形结构基底上复合Ag@β-CD纳米颗粒制备得到的表面增强拉曼光谱基底浸泡在待测溶液中0.5～2h,浸泡后取出表面增强拉曼光谱基底并干燥,置于拉曼光谱仪激光下扫描,得到表面增强拉曼光谱图,对邻苯二甲酸酯类化合物进行定性和定量分析。本发明通过采用锥形结构基底复合Ag@β-CD纳米颗粒作为表面增强拉曼光谱基底,能够有效增强拉曼信号,同时能够提高对入射光的利用效率,邻苯二甲酸酯类化合物富集效果增强,检测限和检测灵敏度较高。(The invention discloses a detection method of phthalate compounds, which belongs to the technical field of detection and comprises the following steps of soaking a surface-enhanced Raman spectrum substrate prepared by compounding Ag @ β -CD nano particles on a conical structure substrate in a solution to be detected for 0.5-2 h, taking out the surface-enhanced Raman spectrum substrate after soaking, drying, scanning under the laser of a Raman spectrometer to obtain a surface-enhanced Raman spectrum diagram, and carrying out qualitative and quantitative analysis on the phthalate compounds.)

1. A method for detecting phthalate compounds is characterized by comprising the following steps of soaking a surface-enhanced Raman spectrum substrate in a solution to be detected for 0.5-2 h, taking out the surface-enhanced Raman spectrum substrate after soaking, drying, scanning under the laser of a Raman spectrometer to obtain a surface-enhanced Raman spectrum, and qualitatively and quantitatively analyzing the phthalate compounds, wherein the surface-enhanced Raman spectrum substrate is prepared by compounding Ag @ β -CD nano particles on a conical structure substrate.

2. The method according to claim 1, wherein the method for preparing the surface-enhanced Raman spectroscopy substrate comprises the following steps:

(1) preparing a conical structure substrate: cleaning a silicon wafer to remove impurities, and then placing the silicon wafer in an alkaline solution to etch for 1-50 min to obtain the conical structure substrate;

(2) preparing nano silver colloid: cyclodextrin aqueous solution and AgNO₃Uniformly mixing the solution according to the volume ratio of 1: 10-100, adjusting the pH to be alkaline, heating to 80-120 ℃, and stirring for reaction for 20-50 min to obtain the nano-silver colloid;

(3) and (3) immersing the conical structure substrate prepared in the step (1) in the nano silver adhesive prepared in the step (2) for 10-30 min, taking out and drying to obtain the surface enhanced Raman spectrum substrate.

3. The method according to claim 2, wherein in step (1), the alkaline solution is an inorganic base, an organic base or a mixture thereof.

4. The method according to claim 2, wherein the etching temperature is 50-90 ℃.

5. The method according to claim 2, wherein the mass fraction of the cyclodextrin aqueous solution is 0.1-0.5 wt%.

6. The method of claim 2, wherein said AgNO₃The molar concentration of the solution is 10-100 mM.

7. The method according to claim 2, wherein in the step (2), the pH is adjusted to 8 to 10.

8. The method according to claim 1, further comprising measuring the surface enhanced Raman spectroscopy of the standard sample, soaking the surface enhanced Raman spectroscopy substrate in solutions of the phthalate compound standard samples with different concentrations for 0.5-2 h, taking out the surface enhanced Raman spectroscopy substrate after soaking, drying, and scanning under the laser of a Raman spectrometer to obtain a surface enhanced Raman spectroscopy of the standard sample.

9. The method according to claim 8, wherein the standard sample of phthalate-based compound is methyl phthalate, ethyl phthalate, propyl phthalate, pentyl phthalate or hexyl phthalate.

10. The method according to claim 8, wherein the concentration of the standard sample of phthalate compound is 1 × 10^-4M、1×10^-5M、1×10^-6M、1×10^-7M、1×10^-8M、1×10^-9M、1×10^-10M、1×10^-11M and 1 × 10^-12M。

Technical Field

The invention relates to a detection method of phthalate compounds, belonging to the technical field of detection.

Background

The phthalate ester compound is used as a plasticizer which is most commonly used in the polyvinyl chloride processing industry, and can also be used as a production raw material of pesticide carriers, cosmetics, lubricants, detergents and paints. Since such compounds are only attached to the plastic matrix by hydrogen bonds or van der waals forces, they are not polymerized to the polymeric carbon chains of the plastic and are easily released into the environment over time. Researches find that the phthalate compounds and the degradation products thereof have the effects of estrogen-like, interfere the endocrine system, have carcinogenic and mutagenic effects on both human beings and animals, and have potential health risks.

The existing phthalate compound detection mainly depends on a precise detection instrument for detection, the existing commonly used detection instruments mainly comprise a gas chromatograph or a high performance liquid chromatograph, a combination instrument of the gas chromatograph or the high performance liquid chromatograph and a mass spectrum, and the like, the standard degree and the precision of the instruments reach high standards, and then, the sample enrichment extraction and the pretreatment are complex and time-consuming, and become a restriction factor for detecting phthalate.

In the last 70 th century, Van Duyne et al found that the Raman signal of the molecule to be detected adsorbed on the surface of the rough gold and silver nano-material can be enhanced by more than 106. This discovery has evolved into a new technology, Surface-Enhanced Raman Spectroscopy (SERS). SERS can provide fingerprint information at the molecular level to determine the fine structure of the molecule to be measured. The method overcomes the defect of low sensitivity of the traditional Raman spectrum, has extremely high sensitivity, can realize the detection of trace substances, and even can reach the single molecule detection level under the optimized condition. Meanwhile, SERS also has the advantages of no need of sample pretreatment (or simple pretreatment), high detection speed, easy realization of field detection and the like.

Cyclodextrin is a generic term for D-pyran-type cyclic oligosaccharides linked by α -1, 4-glycosidic bonds, generally containing 6-12D-glucopyranose units, cyclodextrin is a macrocyclic molecule, and its structure is characterized in that it has a tapered hollow cylindrical stereo ring structure with a hydrophobic inner cavity and a hydrophilic outer cavity, and its hydrophobic cavity can be used as a binding site for an object, cyclodextrin can mimic a hydrophobic pocket of an enzyme in an aqueous phase, and a cavity Host (Host) can bind a variety of appropriate objects (Guest), such as hydrophobic small molecules, ions, oligonucleotides, proteins, and the like.

Disclosure of Invention

By adopting the conical structure substrate and Ag @ β -CD nano particles compounded on the substrate as the surface enhanced Raman spectrum substrate, Raman signals can be effectively enhanced, meanwhile, the utilization efficiency of incident light can be improved, the enrichment effect of phthalate compounds is enhanced, and the detection limit and the detection sensitivity are higher.

The invention provides a method for detecting phthalate compounds, which comprises the following steps of soaking a surface-enhanced Raman spectrum substrate in a solution to be detected for 0.5-2 h, taking out the surface-enhanced Raman spectrum substrate after soaking, drying, scanning under the laser of a Raman spectrometer to obtain a surface-enhanced Raman spectrum image, and performing qualitative and quantitative analysis on the phthalate compounds, wherein the surface-enhanced Raman spectrum substrate is prepared by compounding Ag @ β -CD nanoparticles on a conical structure substrate.

Further, the preparation method of the surface-enhanced Raman spectrum substrate comprises the following steps:

(1) preparing a conical structure substrate: cleaning a silicon wafer to remove impurities, and then placing the silicon wafer in an alkaline solution to etch for 1-50 min to obtain the conical structure substrate;

(2) preparing nano silver colloid: cyclodextrin aqueous solution and AgNO₃Uniformly mixing the solution according to the volume ratio of 1: 10-100, adjusting the pH to be alkaline, heating to 80-120 ℃, and stirring for reaction for 20-50 min to obtain the nano-silver colloid;

(3) and (3) immersing the conical structure substrate prepared in the step (1) in the nano silver adhesive prepared in the step (2) for 10-30 min, taking out and drying to obtain the surface enhanced Raman spectrum substrate.

Further, in the step (1), the alkaline solution is an inorganic base, an organic base or a mixture thereof.

Further, the etching temperature is 50-90 ℃.

Further, the mass fraction of the cyclodextrin water solution is 0.1-0.5 wt%.

Further, the AgNO₃The molar concentration of the solution is 10-100 mM.

Further, in the step (2), the pH is adjusted to 8-10.

Further, the method comprises the step of measuring the surface enhanced Raman spectrum of the standard sample, namely soaking the surface enhanced Raman spectrum substrate in solutions of the phthalate compound standard samples with different concentrations for 0.5-2 h, taking out the surface enhanced Raman spectrum substrate after soaking, drying, and scanning under the laser of a Raman spectrometer to obtain a surface enhanced Raman spectrum of the standard sample.

Further, the standard sample of the phthalate ester compound is methyl phthalate, ethyl phthalate, propyl phthalate, pentyl phthalate or hexyl phthalate.

Further, the concentration of the standard sample of the phthalate ester compound is 1 × 10^-4M、1×10^-5M、1×10^-6M、1×10^-7M、1×10^-8M、1×10^-9M、1×10^-10M、1×10^-11M and 1 × 10^-12M。

The invention has the beneficial effects that:

according to the invention, the surface enhanced Raman spectrum substrate is formed by compounding the Ag @ β -CD nanoparticles on the conical structure substrate, so that Raman signals can be effectively enhanced, the utilization efficiency of incident light can be improved, the enrichment effect of phthalate compounds is enhanced, and the detection limit and the detection sensitivity are higher.

Drawings

Figure 1 is a graph of the surface enhanced raman substrate sensitivity to methyl phthalate.

Detailed Description

The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.