CN111413313A - Detection method of phthalate compound - Google Patents
Detection method of phthalate compound Download PDFInfo
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- CN111413313A CN111413313A CN202010245213.6A CN202010245213A CN111413313A CN 111413313 A CN111413313 A CN 111413313A CN 202010245213 A CN202010245213 A CN 202010245213A CN 111413313 A CN111413313 A CN 111413313A
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Images
Classifications
-
- 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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
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.
Description
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.
Example 1: preparation of surface enhanced Raman spectroscopy substrate
(1) Preparing a conical structure substrate, namely cutting a silicon wafer into pieces with the size of 1cm × 2cm, cleaning the silicon wafer, removing impurities on the surface of the silicon wafer, performing clear water modification on the clean silicon wafer, finally placing the processed silicon wafer in a KOH solution, performing etching reaction at the temperature of 80 ℃, and obtaining the conical structure substrate after 30min of reaction;
(2) preparing nano silver colloid: mixing 0.2 wt% cyclodextrin water solution with 50mM AgNO3Uniformly mixing the solution according to the volume ratio of 1:50, adjusting the pH to 8, heating to 80 ℃, and stirring for reaction for 30min to obtain 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 20min, taking out and drying to obtain the surface enhanced Raman spectrum substrate.
Example 2: raman detection of methyl phthalate standard sample
Methyl phthalate standard sample solutions (1 × 10) of different concentrations were prepared-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) surface enhanced Raman Spectroscopy prepared in example 1And (2) respectively soaking the substrate in the solution for 1h, adsorbing the methyl phthalate standard sample molecules on the surface of the surface enhanced Raman spectrum substrate, taking out the surface enhanced Raman spectrum substrate, drying, scanning under the laser of a Raman spectrometer after drying to obtain a surface enhanced Raman spectrum chart of each concentration gradient solution, analyzing the characteristic peak of the methyl phthalate as shown in figure 1, and further establishing a standard curve between the Raman signal intensity and the corresponding concentration.
As can be seen from the results, the detection limit of the method of the invention for methyl phthalate can reach 1 × 10-12M, the detection sensitivity is higher. In the invention, the absorption and enrichment effects of cyclodextrin are utilized to effectively enrich the methyl phthalate compounds, the composite substrate has a larger specific surface area, the utilization efficiency of incident laser is improved, and meanwhile, the metal nanoparticles are adopted, so that the substrate has more electromagnetic field enhancement hot spots.
According to the same method, a surface enhanced Raman spectrum of ethyl phthalate, propyl phthalate, pentyl phthalate or hexyl phthalate can be obtained, and a standard curve can be further established.
Example 3:
taking an environmental water sample, respectively soaking the surface enhanced Raman spectroscopy substrates prepared in the embodiment 1 in the water sample to be detected for 1 hour, adsorbing phthalate molecules on the surface of the surface enhanced Raman spectroscopy substrates, taking out the surface enhanced Raman spectroscopy substrates, drying, scanning under the laser of a Raman spectrometer after drying to obtain a surface enhanced Raman spectrogram, and detecting to obtain the content of the phthalate compounds in the water sample to be detected by referring to the surface enhanced Raman spectrogram and a standard curve of the standard sample in the embodiment 2.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
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。
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2020
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