CN115711873A - Method for carrying out quantitative analysis by utilizing SERS file card - Google Patents
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Abstract
The invention relates to a method for carrying out quantitative analysis by utilizing an SERS file card, which comprises the following steps: 1) Preparing SERS file cards and SERS spectra, 2) selecting 1 to n characteristic peaks for a molecule I and 1 to m characteristic peaks for a molecule j for different molecules, and solving by using the following formula group I:
the method provides guidance for quantitative analysis of the SERS file card under different conditions, so that the application range of the SERS spectrum in the quantitative analysis is expanded.
Description
Technical Field
The invention relates to a method for carrying out quantitative analysis by utilizing an SERS file card, belonging to the field of material analysis.
Background
The Surface Enhanced Raman Scattering (SERS) spectrum belongs to the inelastic scattering spectrum technology, has the advantages of fingerprint identification, ultrahigh sensitivity, nondestructive detectability, simple sample preparation, high testing speed and the like, and has wide application prospect in a plurality of fields such as environmental pollutant detection, food addition and pesticide residue detection, biochemical medicine detection, criminal investigation and drug detection, biomarker detection and the like. In 1974, fleishmann et al observed SERS phenomena on the surface of rough silver electrodes. SERS spectroscopy has been developed to date for nearly a half century with continued exploration by researchers. The self Raman scattering intensity of the substance is far lower than that of Rayleigh scattering, the SERS substrate can obviously enhance Raman scattering signals and plays a role of a signal amplifier, and meanwhile, the Raman scattering of the substance is influenced by the surrounding environment, so that the shape of a Raman spectrum can be changed by the SERS substrate. Nowadays, many SERS substrates are designed and developed for SERS spectrum detection in various scenes, including traditional noble metal SERS substrates based on gold, silver, copper and alloy nanostructures thereof, oxygen/sulfide semiconductor SERS substrates, organic semiconductor SERS substrates, flexible SERS substrates, and the like. In addition, atomic force microscopy, electrochemistry, surface modification and the like are combined with the SERS substrate to generate a plurality of novel SERS spectrum-based technologies, and the application range of the SERS spectrum technology is widened. Although these developments have led to great advances in the design and preparation of SERS substrates and SERS spectra in detection and analysis, difficulties remain in quantitative analysis. The stability of the SERS substrate, the uniformity of the same SERS substrate, the repeatability among different SERS substrates in the same batch and the difference among the SERS substrates in different batches can cause the intensity of the SERS spectrum to fluctuate greatly, which generates serious interference to quantitative analysis, and makes the quantitative analysis based on the absolute intensity of the SERS spectrum face huge challenges.
Research shows that under a certain laser wavelength, when a SERS substrate material is fixed, a system formed by a molecule and the SERS substrate has a stable relative SERS scattering cross section, namely a stable relative scattering cross section exists between different SERS characteristic peaks in the same molecule, and meanwhile, stable relative SERS scattering capacity factors exist between different molecules, namely a stable relative scattering cross section exists between selected SERS characteristic peaks among different molecules. The two parameters of the relative SERS scattering cross section and the relative SERS scattering capacity factor are related to the laser wavelength and the material of the SERS substrate and are not related to the geometrical morphology of the nano structure of the SERS substrate. In addition, the normalization processing is carried out on the SERS spectrum, the absolute intensity fluctuation of the SERS spectrum can be removed, and the intramolecular scattering cross section and the intermolecular scattering capacity of the SERS spectrum are expressed by relative SERS scattering cross sections and relative SERS scattering capacity factors. The SERS file card can be constructed based on relative SERS scattering cross sections in the same molecule, relative SERS scattering capacity factors among different molecules and normalized SERS spectrum, and the file contains molecule quantified SERS spectrum information, so that the method can be used for constructing an SERS file card database similar to a powder diffraction file card in an X-ray diffraction (XRD) technology, and lays a foundation for quantitative analysis and semi-quantitative analysis based on the SERS spectrum.
However, currently, there is no systematic and comprehensive quantitative analysis application guidance in the development of the SERS file card database, and a method for performing quantitative analysis by using the SERS file card is urgently needed to better exert the function of the SERS file card in the field of quantitative analysis and promote the development of the quantitative analysis technology of SERS spectrum.
Disclosure of Invention
Problems to be solved by the invention
In view of the above-mentioned problems, an object of the present invention is to provide a method for performing quantitative analysis by using a SERS file card, which provides guidance for performing quantitative analysis on the SERS file card under different conditions, so as to expand the application range of SERS spectra in quantitative analysis, and provide reference for constructing a general quantitative analysis method and quantitative analysis software based on the SERS file card.
Means for solving the problems
The invention provides a method for carrying out quantitative analysis by utilizing an SERS file card, which comprises the following steps:
1) Preparing a SERS document card and a SERS spectrum,
2) For different molecules, 1 to n characteristic peaks are selected for the molecule I, 1 to m characteristic peaks are selected for the molecule j, and the following formula group I is utilized to solve the problems:
wherein the content of the first and second substances,
I i,p : peak intensity of the p-th SERS characteristic peak of the i-th molecule,
I j,q : the peak intensity of the qth SERS characteristic peak of the jth molecule,
RSA i,j : the relative SERS scattering power factor of the ith molecule relative to the jth molecule,
for k molecules, any i, j belongs to the interval [1,k ], and i is not equal to j;
X i : the content of the (i) th molecule,
C i : the concentration of the i-th molecule(s),
X j : the content of the (j) th molecule,
C j : the concentration of the jth molecule is,
RSC i,p : the relative SERS scattering cross section of the p-th SERS characteristic peak selected by the ith molecule,
RSC j,q : the relative SERS scattering cross section of the qth SERS characteristic peak selected by the jth molecule,
l and m are the number of the selected SERS characteristic peaks respectively.
The invention also provides a method for carrying out quantitative analysis by utilizing the SERS file card, which comprises the following steps:
1) Preparing a SERS file card and a SERS spectrum,
2) For n molecules, 1 to p spectral intervals of the SERS spectrum are selected and solved using the following formula set II:
wherein the content of the first and second substances,
X i : the content of the (i) th molecule,
C i : the concentration of the i-th molecule(s),
X j : the content of the jth molecule is,
C j : the concentration of the jth molecule is,
RSA i,j : phase of molecule i relative to molecule jFor the SERS scattering power factor,
Anorm i,1-p : the integral area of the selected 1 to p SERS spectrum intervals in the ith molecular SERS file card,
Anorm j,1-p : the integral area of the selected 1 to p SERS spectral intervals in the jth molecule SERS file card,
PC A,i,1-p : the integral area of the ith molecule in the spectral interval from 1 to p normalizes the main component value corresponding to the SERS spectrum,
PC A,range,1-p : and normalizing the corresponding principal component numerical value of the SERS spectrum by the integral area of the spectrum to be analyzed in the spectral interval from 1 to p.
The invention further provides a method for carrying out quantitative analysis by utilizing the SERS file card, which comprises the following steps:
1) Preparing a SERS file card and a SERS spectrum,
2) For n molecules, selecting a complete spectral interval of the SERS spectrum or selecting a partial spectral interval of the SERS spectrum as the complete spectral interval, and solving by adopting the following formula group III:
wherein the content of the first and second substances,
X i : the content of the i-th molecule(s),
C i : the concentration of the (i) th molecule,
X j : the content of the jth molecule is,
C j : the concentration of the jth molecule is,
RSA i,j : the relative SERS scattering power factor of molecule i relative to molecule j,
α: the introduced common scale factor is used as a reference,
Spec i : normalized SERS spectra in the ith molecular SERS file card,
X i,M : when i is from 1 to n, α × RSA i,j ×X i The vector of the composition is then calculated,
Spec i,M : when i is from 1 to n, spec i The matrix of the composition is formed by the following components,
Spec mix : the SERS spectrum is to be analyzed.
According to the method, the laser wavelength and the substrate material of the SERS file card are the same as those of the SERS spectrum, and the background of the SERS spectrum is deducted.
According to the method, the relative SERS scattering capacity factor of the molecule is obtained through an SERS file card of the molecule or is obtained through indirect transfer calculation of the SERS file cards of other molecules, and the calculation of the relative SERS scattering capacity factor of the molecule through the SERS file cards of other molecules is realized through the following chain transfer formula IV:
RSA i,j ＝RSA i,p ×RSA p,q ×RSA q,r ×RSA r,s ×RSA r,t ×RSA t,j
wherein RSA i,j Is the relative SERS scattering power factor of molecule i relative to molecule j, RSA i,p Is the relative SERS scattering power factor of molecule i relative to molecule p, RSA p,q Is the relative SERS scattering power factor of molecule p relative to molecule q, RSA q,r Is the relative SERS scattering power factor of molecule q versus molecule r, RSA r,s Is the relative SERS scattering power factor of a molecule r relative to a molecule s, RSA s,t Is the relative SERS scattering power factor of molecule s relative to molecule t, RSA t,j Is the relative SERS scattering power factor of molecule t relative to molecule j.
According to the method of the invention, the transmission times of the chain transmission formula IV are less than or equal to 6.
ADVANTAGEOUS EFFECTS OF INVENTION
The method for carrying out quantitative analysis by utilizing the SERS file card can combine the SERS file card with different algorithms under various different conditions to carry out quantitative analysis on the content and the concentration of the selected molecules, effectively expands the general application range of the SERS technology in the aspect of quantitative analysis of micro-trace substances, simultaneously enables the quantitative analysis work based on the SERS technology to be simple and convenient, and has wide application prospect and important basic supporting effect in the field of the quantitative analysis of the micro-trace molecules.
Drawings
FIG. 1 is a general illustration of a SERS document card;
FIG. 2 is a flow chart of a method for quantitative analysis using SERS file cards under different circumstances;
FIG. 3 is a graph showing the results of the quantitative analysis of example 1;
FIG. 4 is a graph showing the results of the quantitative analysis of example 2;
FIG. 5 is a graph showing the results of the quantitative analysis in example 3.
Detailed Description
Preparation method of SERS (surface enhanced Raman scattering) file card
Measuring a Surface Enhanced Raman Scattering (SERS) spectrum of a selected molecule, selecting a characteristic peak with the strongest peak intensity in the spectrum as a reference peak, and calculating relative values of the peak intensities of other characteristic peaks and the peak intensity of the reference peak to obtain a relative scattering cross section of surface enhanced Raman scattering;
respectively measuring the surface enhanced Raman scattering spectra of the selected molecules and the reference molecules, respectively selecting the characteristic peak with the strongest peak intensity in the spectra of the selected molecules and the reference molecules as the reference peak of the selected molecules and the reference molecules, measuring the surface enhanced Raman scattering spectra of the mixture of the selected molecules and the reference molecules, and calculating the relative value of the peak intensity of the reference peaks of the selected molecules and the reference molecules to obtain the relative scattering ability factor of the surface enhanced Raman scattering.
Determination of the relative Scattering Cross-sections of "surface enhanced Raman Scattering
According to the preparation method, the characteristic peak with the strongest peak intensity in the spectrum is selected as the reference peak, the intensity value of the reference peak is set as 100, the peak intensities of other characteristic peaks are normalized, and the peak intensities of the other characteristic peaks after normalization are relative scattering cross sections of the surface enhanced raman scattering.
Preferably, for the relative scattering cross section (RCS) of the SERS spectrum of the selected molecule, a certain SERS characteristic peak can be selected as a reference peak, and the relative scattering cross sections of SERS of other peaks are calculated. The method comprises the following specific operations: measuring the spectrum of the selected molecule on the SERS substrate, deducting background signals such as fluorescence and the like from the SERS spectrum obtained by testing, selecting a characteristic peak with the strongest peak intensity of the SERS spectrum as a reference peak, carrying out normalization processing, and calculating the relative intensity of any other characteristic peak to obtain the relative scattering cross section of SERS.
Relative scattering of "surface enhanced Raman ScatteringAbility toDetermination of factors
According to the preparation method, the selected molecules and the reference molecules are mixed according to different molar ratios, surface enhanced Raman scattering spectra of different molar ratios are respectively determined, the characteristic peak with the strongest peak intensity in the spectra of the selected molecules and the reference molecules is respectively selected as the reference peak of the selected molecules and the reference molecules, the intensity ratio of the reference peaks of the selected molecules and the reference molecules is calculated, and the linear regression coefficient between the intensity ratio and the molar ratio is calculated through a least square regression method, namely the relative scattering ability factor of the surface enhanced Raman scattering between the molecules.
When the surface enhanced Raman scattering spectrum is measured, the molecules to be measured are dripped on the surface of the substrate in the form of solution, the spectrum is measured after the solvent is naturally dried, and the fluorescence background signal is deducted to obtain the surface enhanced Raman scattering spectrum. The intensity ratio is in the range of 0.1 to 10. The total concentration of the solution was 10 -8 ～10 -5 mol/L, the average in-plane volume range of the dropping amount is 0.1 to 5 mu L/mm 2 。
The resulting SERS document card is shown in fig. 1, and includes a plurality of regions. Numbering each region from top to bottom is described: the area 1 is a serial number area of the SERS file card; the region 2 is a laser wavelength and SERS material established by the SERS file card; region 3 is the chemical nomenclature of the selected molecule and the reference molecule and the raman shift of the respective selected strongest SERS characteristic peak; region 4 is the relative SERS scattering power factor (RSA) of the strongest SERS signature peak selected for the selected molecule and the strongest SERS signature peak selected for the reference molecule; region 5 is the normalized SERS spectrum of the selected molecule; region 6 is the structural formula of the selected molecule; the region 7 is a relative SERS scattering cross section (RSC) in the selected molecule and is divided into 3 parts, the region 7-1 is a Raman displacement of each main SERS characteristic peak of the selected molecule, the region 7-2 is a relative SERS scattering cross section between each main SERS characteristic peak in the selected molecule, and the region 7-3 is a vibration mode of each main SERS characteristic peak of the selected molecule. For the SERS file card, the main parameters for carrying out quantitative analysis are relative SERS scattering capacity factor, relative SERS scattering cross section and normalized SERS spectrum. In the SERS file card, relative SERS scattering ability factors show that under the condition of determined laser wavelength and SERS substrate material, the strength ratio of the selected strongest SERS characteristic peak of the selected molecule to the selected strongest SERS characteristic peak of the reference molecule is irrelevant to the geometric shape of the SERS substrate nano structure; the relative SERS scattering cross section is the relative intensity relation among all SERS characteristic peaks in the selected molecule, the strongest peak in the SERS spectrum is generally defined as 100, the relative intensities of other SERS characteristic peaks can be calculated, and the value is irrelevant to the geometrical morphology of the nano structure of the SERS substrate because the molecule has stable SERS spectrum on the SERS substrate with the determined laser wavelength and the same material; the normalized SERS spectrum is obtained by normalizing the SERS spectrum of the selected molecule and defining the normalized intensity of the strongest peak as 100, and is a supplement of the intramolecular relative SERS scattering cross section.
[ invention of the first aspect ]
The invention provides a method for carrying out quantitative analysis by utilizing an SERS file card, which comprises the following steps:
1) Preparing a SERS document card and a SERS spectrum,
2) For different molecules, 1 to n characteristic peaks are selected for the molecule I, 1 to m characteristic peaks are selected for the molecule j, and the following formula group I is utilized to solve the problems:
wherein, the first and the second end of the pipe are connected with each other,
I i,p : peak intensity of the p-th SERS characteristic peak of the i-th molecule,
I j,q : the peak intensity of the qth SERS characteristic peak of the jth molecule,
RSA i,j : the relative SERS scattering power factor of the ith molecule relative to the jth molecule,
for k molecules, any i, j belongs to the interval [1,k ], and i is not equal to j;
X i : the content of the i-th molecule(s),
C i : the concentration of the i-th molecule(s),
X j : the content of the jth molecule is,
C j : the concentration of the jth molecule is,
RSC i,p : the relative SERS scattering cross section of the p-th SERS characteristic peak selected by the ith molecule,
RSC j,q : the relative SERS scattering cross section of the qth SERS characteristic peak selected by the jth molecule,
l and m are the number of the selected SERS characteristic peaks respectively.
For different molecules, when the molecule I selects 1 characteristic peak, the molecule j selects 1 characteristic peak, and the formula set I is as follows:
preferably, when the SERS characteristic peak between molecules is easily resolved in the SERS spectrum, the method of the first aspect is selected for quantitative analysis.
[ invention of the second aspect ]
The invention provides a method for carrying out quantitative analysis by utilizing an SERS file card, which comprises the following steps:
1) Preparing a SERS file card and a SERS spectrum,
2) For n molecules, 1 to p spectral intervals of the SERS spectrum are selected and solved using the following formula set II:
wherein the content of the first and second substances,
X i : the content of the (i) th molecule,
C i : the concentration of the (i) th molecule,
X j : the content of the jth molecule is,
C j : the concentration of the jth molecule is,
RSA i,j : the relative SERS scattering power factor of molecule i relative to molecule j,
Anorm i,1-p : the integral area of the selected 1 to p SERS spectrum intervals in the ith molecular SERS file card,
Anorm j,1-p : the integral area of the selected 1 to p SERS spectral intervals in the jth molecule SERS file card,
PC A,i,1-p : the integral area of the ith molecule in the spectral interval from 1 to p normalizes the corresponding principal component value of the SERS spectrum,
PC A,range,1-p : and normalizing the corresponding principal component numerical value of the SERS spectrum by the integral area of the spectrum to be analyzed in the spectral interval from 1 to p.
Specifically, with S range,1-p Representing selected intervals 1 to p in the SERS spectrum using RSA i,j Representing the relative SERS scattering power factor, snorm, of the ith molecule relative to the jth molecule i,1-p Denotes the corresponding 1 st to p intervals, X, in the ith molecular normalized SERS spectrum i For the content of molecule i, a Principal Component Analysis (PCA) algorithm was used.
For the PCA algorithm, it can filter system noise and can represent the spatial positional relationship with few principal components. For normalized SERS spectra in SERS file cards, first calculate the total integrated area value of selected interval 1 to p, use Anorm i,1-p Represents the integrated area values of the 1 st to p th intervals in the ith molecular normalized SERS spectrum. For n molecules, the integral area normalization SE of the SERS spectrum in the selected interval divided by the total integral area in the selected interval is calculated by the formula (2-1)RS spectrum Snorm A,i,1-p ：
Also for S range,1-p With A range,1-p An integrated area normalized SERS spectrum S representing the total integrated area of the selected interval, the spectrum of the selected interval divided by the total integrated area A,range,1-p As shown in formula (2-2):
then according to Snorm A,i,1-p Directly solving a load matrix L, multiplying the load matrix L by the integral area normalized SERS spectrum of the selected interval to obtain each principal component of the SERS spectrum of the selected interval, and for S A,range,1-p Using PC A,range,1-p The expression (2-3) holds when it indicates the main component:
PC A,range,1-p ＝L×S A,range,1-p (2-3)
for the same reason, for Snorm A,i,1-p Using PC A,i,1-p The expression (2-4) holds when it indicates the main component:
PC A,i,1-p ＝L×Snorm A,i,1-p (2-4)
for S range,1-p The relationship (2-5) holds:
wherein E is F Denotes the SERS enhancement factor, again for A range,1-p There is (2-6) a relation:
substituting expressions (2-5) and (2-6) into expression (2-2) can obtain the following expression (2-7):
converting equation (2-7) to equation (2-8):
substituting the formula (2-1) into the formula (2-8) to obtain the formula (2-9):
multiplying the load matrix by the expression (2-9) and substituting the expressions (2-3) and (2-4) to obtain the following expression (2-10):
the formula (2-10) can be converted into the formula (2-11):
like the formula (1-3), the following formula (2-12) holds:
PC obtained by calculation A,i,1-p And PC A,range,1-p Relative SERS Scattering Capacity factor RSA in SERS File cards i,j Normalized integral area Anorm of selected interval in SERS spectrum i,1-p And Anorm j,1-p Substituting into the formula (2-11) and combining with the formula (2-12) to obtain the content X of each molecule i Likewise, when a certain known concentration of molecule j is selected or added as a reference, its concentration is set to C j Then the concentration of any i molecules can be solved using the equation (1-4).
Preferably, when the SERS spectrum does not readily distinguish between two or more peaks characteristic of SERS between molecules, the method of the second aspect is used for quantitative analysis.
[ invention of third aspect ]
The invention provides a method for carrying out quantitative analysis by utilizing an SERS file card, which comprises the following steps:
1) Preparing a SERS file card and a SERS spectrum,
2) For n molecules, selecting a complete spectral interval of the SERS spectrum or selecting a partial spectral interval of the SERS spectrum as the complete spectral interval, and solving by adopting the following formula group III:
wherein the content of the first and second substances,
X i : the content of the i-th molecule(s),
C i : the concentration of the i-th molecule(s),
X j : the content of the jth molecule is,
C j : the concentration of the (j) th molecule,
RSA i,j : the relative SERS scattering power factor of molecule i relative to molecule j,
α: the introduced common scale factor is used as a reference,
Spec i : normalized SERS spectra in the ith molecular SERS file card,
X i,M : when i is from 1 to n, α × RSA i,j ×X i The vector of the composition is then calculated,
Spec i,M : when i is from 1 to n, spec i The matrix of the composition is formed by the following components,
Spec mix : the SERS spectrum is to be analyzed.
Using Spec mix Representing the SERS spectrum to be analyzed, using Spec i Representing normalized SERS spectra in the ith molecular SERS document card, using RSA i,j To representRelative SERS scattering power factor, X, of ith molecule relative to jth molecule i And (3) performing quantitative analysis by combining a multivariate linear regression algorithm and an SERS file card for the content of the molecule i.
For a multiple linear regression algorithm, the estimated value of the regression coefficient is more stable with the increase of the observation times, and for the SERS spectrum, each Raman shift corresponds to one observation, so that the full SERS spectrum is more stable for multiple linear regression. For Spec mix When the intermolecular interaction is not significant, the following relation (3-1) holds:
where α represents the common proportionality coefficient due to variations in test conditions, SERS substrate uniformity, repeatability, and lot-to-lot variability, and μ is a constant term related to noise. According to the principle of least square method, the estimated value of its parameters can be calculated, for convenient expression, using X i,M Denotes a value of α × RSA when i is from 1 to n i,j ×X i Column vector represented, spec i,M Represents Spec when i is from 1 to n i The formed matrix can express the formula (3-1) as the following formula (3-2):
Spec mix ＝Spec i,M ×X i,M +μ (3-2)
then X can be known according to the principle of least squares i,M The estimated value of (2) is (3-3):
the following equations (3-4) hold, as with equations (1-3) and (2-12):
according to the calculated X i,M And (3-4), can be solved toTo the content X of each molecule i (ii) a Likewise, when a certain known concentration of molecule j is selected or added as a reference, its concentration is set to C j Then the concentration of any i molecules can be solved using the equation (1-4).
Preferably, when the SERS characteristic peak between two or more molecules is not easily distinguished in the SERS spectrum, and the characteristic peaks of the respective molecules are relatively dispersed, the quantitative analysis is performed by using the method of the third aspect.
According to the method, the laser wavelength and the substrate material of the SERS file card are the same as those of the SERS spectrum, and the background of the SERS spectrum is deducted.
According to the method, the relative SERS scattering capacity factor of the molecule is obtained through an SERS file card of the molecule or is obtained through indirect transfer calculation of the SERS file cards of other molecules, and the calculation of the relative SERS scattering capacity factor of the molecule through the SERS file cards of other molecules is realized through the following chain transfer formula IV:
RSA i,j ＝RSA i,p ×RSA p,q ×RSA q,r ×RSA r,s ×RSA r,t ×RSA t,j
wherein RSA i,j Is the relative SERS scattering power factor of molecule i relative to molecule j, RSA i,p Is the relative SERS scattering power factor of molecule i relative to molecule p, RSA p,q Is the relative SERS scattering power factor of molecule p relative to molecule q, RSA q,r Is the relative SERS scattering power factor of molecule q versus molecule r, RSA r,s Is the relative SERS scattering power factor of a molecule r relative to a molecule s, RSA s,t Is the relative SERS scattering power factor of molecule s relative to molecule t, RSA t,j Is the relative SERS scattering power factor of molecule t relative to molecule j.
According to the method of the invention, the transmission times of the chain transmission formula IV are less than or equal to 6.
Examples
Production of SERS file card between 2-MPY molecule and 4-MBA molecule
and 6, combining the substrate material in the step 1, the test wavelength of the laser in the step 2, the reference peak information in the step 3, the normalized SERS spectrum in the step 3, the relative scattering cross section of SERS in the step 3, the relative scattering capacity factor of SERS in the step 5 and the Raman vibration mode of each SERS characteristic peak according to a form shown in a figure 1, and establishing an SERS file card between 2-MPY molecules and 4-MBA molecules.
Based on the above discussion and the measured relative scattering cross section of SERS and the relative scattering ability factor of SERS, a SERS file card as shown in fig. 1 can be constructed, which is only an example, and in the figure, the serial number of the SERS file card, the material and the measured wavelength of the SERS substrate used, the name of the molecule, and the SERS reference peak of the selected molecule are shown from top to bottom. The lower part of the SERS file card continues to show relative scattering ability factors of two parameters SERS and relative scattering cross sections of SERS which can be used for quantitative analysis, and a normalized SERS spectrum of a molecule and a structural formula of the molecule are listed in the middle position. For easier and more straightforward qualitative and quantitative analysis, the table at the very bottom of the SERS file card lists the major SERS characteristic peaks of the 2-MPY molecules and their relative intensities, as well as their corresponding raman vibrational modes.
Example 1
1. The method comprises the following steps of (1) taking an SERS substrate with a high-purity silver nanostructure as an SERS substrate for quantitative analysis, and taking a mixed solution of 4-mercaptobenzoic acid (4-MBA) molecules and 2-mercaptopyridine (2-MPY) molecules as a target analysis system;
2. preparing a mixed solution of 4-MBA molecules and 2-MPY molecules, wherein the ratio of the number of the 4-MBA molecules to the number of the 2-MPY molecules in the mixed solution is 1;
3. measuring different mixed solutions configured in the step 2 by adopting the SERS substrate selected in the step 1, selecting the laser wavelength of 785nm, the light spot of 80 microns and the power of 15mW, dropwise adding 10 microliter of the mixed solution onto the SERS substrate with the size not more than 10mm multiplied by 10mm in the step 1, and testing an SERS spectrum after the SERS substrate is naturally dried;
4. subtracting the background from the SERS spectra of different mixed solutions obtained by testing in the step 3, and searching an SERS file card between the 2-MPY molecule and the 4-MBA molecule according to the substrate material in the step 1 and the laser wavelength in the step 3;
5. obtaining relative SE of the 2-MPY molecule relative to the 4-MBA molecule according to the SERS file card of the 2-MPY molecule and the 4-MBA moleculeRS scattering power factor, 2-MPY molecule 1002cm -1 Relative SERS scattering cross section of characteristic peak, 4-MBA molecule 1074cm -1 Relative SERS scattering cross-sections of characteristic peaks;
6. extracting 1074cm from the SERS spectrum with the background deducted in the step 4 -1 And 1002cm -1 And (4) combining the characteristic peak intensity with the relative SERS scattering capacity factor obtained from the SERS file card in the step (5), substituting the relative SERS scattering capacity factor into the following formula group, and directly calculating to obtain the content value of the 2-MPY molecule.
The measured SERS spectrum is as shown in fig. 3 (a), the spectral lines of different 2-MPY molecular contents change in sequence, the 2-MPY molecular content value calculated according to the SERS file card and the above formula set in step 6 is compared with the content value of the actual solution in step 2, and the result is as shown in fig. 3 (b), and it can be seen that the two match well.
Example 2
1. The method comprises the following steps of (1) taking an SERS substrate with a high-purity silver nanostructure as an SERS substrate for quantitative analysis, and taking a mixed solution of 4-mercaptobenzoic acid (4-MBA) molecules and 2-mercaptopyridine (2-MPY) molecules as a target analysis system;
2. preparing a mixed solution of 4-MBA molecules and 2-MPY molecules, taking the 4-MBA molecules as added reference substances, wherein the ratio of the number of the 4-MBA molecules to the number of the 2-MPY molecules in the mixed solution is 1 -6 mol/L(M)，4×10 -6 M，6×10 -6 M，8×10 -6 M；
3. Measuring different mixed solutions configured in the step 2 by adopting the SERS substrate selected in the step 1, selecting the laser wavelength of 785nm, the light spot of 80 microns and the power of 30mW, dropwise adding 5 muL of the mixed solution onto the SERS substrate with the size not more than 5mm multiplied by 5mm in the step 1, and testing an SERS spectrum after the SERS substrate is naturally dried;
4. deducting the SERS spectra of different mixed solutions obtained by testing in the step 3, searching an SERS file card between the 2-MPY molecules and the 4-MBA molecules according to the substrate material in the step 1 and the laser wavelength in the step 3, and calculating relative SERS scattering capacity factors of the SERS file card in a mode of transferring molecular profile;
5. indirectly calculating to obtain a relative SERS scattering capacity factor of the 2-MPY molecule relative to the 4-MBA molecule according to the SERS file cards of the 2-MPY molecule and the 4-MBA molecule, and obtaining a normalized SERS spectrum of the 2-MPY molecule and a normalized SERS spectrum of the 4-MBA molecule;
6. SERS spectra of 2-MPY and 4-MBA molecules are found to be 900-1250cm -1 The characteristic peak is most concentrated, so that 988cm is selected from the SERS spectrum after the background is deducted in the step 4 -1 To 1202cm -1 Combining the relative SERS scattering ability factor and the normalized SERS spectrum acquired from the SERS file card in the step 5, substituting the relative SERS scattering ability factor and the normalized SERS spectrum into the following formula group, directly calculating to obtain the content value of the 2-MPY molecule, and substituting the content value of the 2-MPY molecule and the concentration of the added reference molecule 4-MBA into the following formula group to obtain the concentration of the 2-MPY molecule;
the measured SERS spectrum is as shown in fig. 4 (a), spectral lines of different 2-MPY molecule contents are sequentially changed, the spectrum of a selected interval is subjected to integral area normalization, the calculated first principal component is as shown in fig. 4 (b), the 2-MPY molecule content value calculated according to the SERS file card and the formula set is as shown in fig. 4 (c), the result is well matched with the content value of the actual solution in step 2, and the 2-MPY molecule concentration calculated according to the 4-MBA molecule serving as the added reference molecule in step 2 is as shown in fig. 4 (d), which is well matched with the actual molecule concentration.
Example 3
1. The method comprises the following steps of (1) taking an SERS substrate with a high-purity silver nanostructure as an SERS substrate for quantitative analysis, and taking a mixed solution of 4-mercaptobenzoic acid (4-MBA) molecules and 2-mercaptopyridine (2-MPY) molecules as a target analysis system;
2. preparing a mixed solution of 4-MBA molecules and 2-MPY molecules, wherein the ratio of the number of the 4-MBA molecules to the 2-MPY molecules in the mixed solution is 1 -6 M，2×10 -6 M，3×10 -6 M，4×10 -6 M，5×10 -6 M，6×10 -6 M，7×10 -6 M，8×10 -6 M，9×10 -6 M；
3. Measuring different mixed solutions configured in the step 2 by adopting the SERS substrate selected in the step 1, selecting a laser wavelength of 785nm, a light spot of 80 microns and power of 15mW, dropwise adding 20 muL of the mixed solution onto the SERS substrate with the size not more than 10mm multiplied by 10mm in the step 1, and testing an SERS spectrum after the SERS substrate is naturally dried;
4. deducting the SERS spectra of different mixed solutions obtained by testing in the step 3, searching an SERS file card between the 2-MPY molecules and the 4-MBA molecules according to the substrate material in the step 1 and the laser wavelength in the step 3, and calculating relative SERS scattering capacity factors of the SERS file card in a mode of transferring molecular profile;
5. indirectly calculating to obtain a relative SERS scattering capacity factor of the 2-MPY molecule relative to the 4-MBA molecule according to the SERS file cards of the 2-MPY molecule and the 4-MBA molecule, and obtaining a normalized SERS spectrum of the 2-MPY molecule and a normalized SERS spectrum of the 4-MBA molecule;
6. and (3) substituting the full spectrum range of the SERS spectrum selector with the background subtracted in the step (4) and combining the relative SERS scattering capacity factor obtained by indirect calculation from the SERS file card in the step (5) into the following formula group, directly calculating to obtain the content value of the 2-MPY molecule, and then calculating together with the concentration of the added reference molecule 4-MBA to obtain the concentration of the 2-MPY molecule.
The calculated value of the content of 2-MPY molecules is shown in FIG. 5 (a), and the result is in good agreement with the value of the content of the actual solution in step 2, and the calculated concentration of 2-MPY molecules based on the formula (1-4) and the 4-MBA molecule as the addition reference in step 2 is shown in FIG. 5 (b), which is in good agreement with the concentration of the actual 2-MPY molecules.
According to the application method of the SERS file card in quantitative analysis, provided by the invention, the relative SERS scattering capacity factor, the relative SERS scattering cross section and the three core parameters of the normalized SERS spectrum in the SERS file card are combined with corresponding algorithms under different conditions, so that the quantitative analysis of micro-trace substances is realized, the adverse effects of the uniformity, stability, repeatability and test condition fluctuation of the SERS substrate on the quantitative analysis can be effectively reduced, the SERS spectrum technology can conveniently perform quantitative analysis as the X-ray diffraction technology by using the powder diffraction file card, and the application prospect and the important basic supporting effect are wide in the field of micro-trace molecular quantitative analysis.
The method for quantitative analysis using SERS file cards according to the present invention is described above by way of example with reference to the accompanying drawings. However, it will be understood by those skilled in the art that various modifications can be made to the method for quantitative analysis using SERS file cards of the present invention without departing from the scope of the present invention.
Claims (6)
1. A method for quantitative analysis by using an SERS file card is characterized by comprising the following steps:
1) Preparing a SERS file card and a SERS spectrum,
2) For different molecules, 1 to n characteristic peaks are selected for the molecule I, 1 to m characteristic peaks are selected for the molecule j, and the following formula group I is utilized to solve the problem:
wherein the content of the first and second substances,
I i,p : peak intensity of the p-th SERS characteristic peak of the i-th molecule,
I j,q : the peak intensity of the qth SERS characteristic peak of the jth molecule,
RSA i,j : the relative SERS scattering power factor of the ith molecule relative to the jth molecule,
for k molecules, any i, j belongs to the interval [1,k ], and i is not equal to j;
X i : the content of the i-th molecule(s),
C i : the concentration of the i-th molecule(s),
X j : the content of the jth molecule is,
C j : the concentration of the jth molecule is,
RSC i,p : the relative SERS scattering cross section of the p-th SERS characteristic peak selected by the ith molecule,
RSC j,q : the relative SERS scattering cross section of the qth SERS characteristic peak selected by the jth molecule,
l and m are the number of the selected SERS characteristic peaks respectively.
2. A method for quantitative analysis by using an SERS file card is characterized by comprising the following steps:
1) Preparing a SERS document card and a SERS spectrum,
2) For n molecules, 1 to p spectral intervals of the SERS spectrum are selected, and the solution is performed by using the following formula set II:
wherein the content of the first and second substances,
X i : the content of the i-th molecule(s),
C i : the concentration of the i-th molecule(s),
X j : the content of the jth molecule is,
C j : the concentration of the jth molecule is,
RSA i,j : moleculeThe relative SERS scattering power factor of i relative to molecule j,
Anorm i,1-p : the integral area of the selected 1 to p SERS spectrum intervals in the ith molecular SERS file card,
Anorm j,1-p : the integral area of the selected 1 to p SERS spectral intervals in the jth molecule SERS file card,
PC A,i,1-p : the integral area of the ith molecule in the spectral interval from 1 to p normalizes the corresponding principal component value of the SERS spectrum,
PC A,range,1-p : and normalizing the corresponding principal component numerical value of the SERS spectrum by the integral area of the spectrum to be analyzed in the spectral interval from 1 to p.
3. A method for quantitative analysis by using an SERS file card is characterized by comprising the following steps:
1) Preparing a SERS file card and a SERS spectrum,
2) For n molecules, selecting a complete spectral interval of the SERS spectrum or selecting a partial spectral interval of the SERS spectrum as the complete spectral interval, and solving by adopting the following formula group III:
wherein the content of the first and second substances,
X i : the content of the i-th molecule(s),
C i : the concentration of the (i) th molecule,
X j : the content of the jth molecule is,
C j : the concentration of the (j) th molecule,
RSA i,j : the relative SERS scattering power factor of molecule i relative to molecule j,
α: the introduced common scale factor is used as a reference,
Spec i : normalized SERS spectra in the ith molecular SERS file card,
X i,M : when i is from 1 to n, α × RSA i,j ×X i The vector of the composition is then calculated,
Spec i,M : when i is from 1 to n, spec i The matrix of the composition is formed by the following components,
Spec mix : the SERS spectrum is to be analyzed.
4. The method of any one of claims 1-3, wherein the laser wavelength and substrate material of the SERS document card are the same as the SERS spectrum, and the SERS spectrum is subtracted from the background.
5. The method according to any one of claims 1 to 3, wherein the relative SERS scattering power factor of the molecule is obtained by SERS file cards of the molecule, or is obtained by indirect transfer calculation through SERS file cards of other molecules, and the calculation of the relative SERS scattering power factor of the molecule through the SERS file cards of other molecules is realized by the following chain transfer formula IV:
RSA i，j ＝RSA i，p ×RSA p，q ×RSA q，r ×RSA r，s ×RSA r，t ×RSA t，j
wherein RSA i,j Is the relative SERS scattering power factor of molecule i relative to molecule j, RSA i,p Is the relative SERS scattering power factor of molecule i relative to molecule p, RSA p,q RSA, the relative SERS Scattering Capacity factor of molecule p relative to molecule q q,r Is the relative SERS scattering power factor of molecule q versus molecule r, RSA r,s Is the relative SERS scattering power factor of a molecule r relative to a molecule s, RSA s,t Is the relative SERS scattering power factor of molecule s relative to molecule t, RSA t,j Is the relative SERS scattering power factor of molecule t relative to molecule j.
6. The method of claim 5, wherein the number of transfers of the chain transfer formula IV is less than or equal to 6.
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