CN112798572B - Raman spectrum and ion mobility spectrum combined detection method and device - Google Patents
Raman spectrum and ion mobility spectrum combined detection method and device Download PDFInfo
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention relates to a Raman spectrum and ion mobility spectrometry combined detection method and a device, comprising the steps of collecting Raman spectrum data of a sample to be detected; mixing air and steam of a sample to be detected according to a plurality of preset ratios to obtain an ion mobility spectrum; processing the ion mobility spectrometry to obtain the number and the molecular weight range of volatile substances of the sample to be detected; the invention combines Raman spectrum and ion mobility spectrometry technology to detect volatile solid and liquid samples, greatly reduces the matching difficulty of Raman spectrum, improves the detection accuracy while reducing the detection operand, has great application potential in the application of detecting liquid and solid volatile toxic and harmful substances, and can be applied to the fields of reconnaissance detection and treatment of chemical weapons, reconnaissance and treatment of emergency incident sites, environmental protection inspection and the like.
Description
Technical Field
The invention relates to the technical field of substance detection, in particular to a combined detection method and device of Raman spectrum and ion mobility spectrum.
Background
The Ion Mobility Spectrometry (IMS) technique ionizes gaseous molecules to be detected by using radioactive substance rays (α or β rays) or a passive ionization method (ultraviolet ionization, high-voltage discharge ionization, or the like), and forms ion clusters under the action of water molecules and oxygen. Under the action of the electric field, these product ions enter the migration zone through the periodically opened ion gates. In the migration region, ions obtain energy from an electric field for directional drift, and on the other hand, the ions continuously collide with neutral migration gas molecules flowing reversely to lose energy. The composition of the object to be detected can be qualitatively and semi-quantitatively determined based on the difference in specific mobility of the specific substance. The method has the advantages that the device has excellent portability, high signal sensitivity, no need of sample preparation, high detection speed and long service life of consumable materials, and has the defects that the detection is easily interfered by the environment, and the directionality of the migration time is poor, so the detection library of the general ion migration device has fewer substances, only 10-20 substances are provided, and false alarm can be generated if the detected substances are not in the detection library.
On the other hand, in 1928, the Indian physicist Raman discovers the Raman scattering effect of light, a sample can generate a scattering spectrum with a frequency different from that of incident light, the Raman scattering spectrum is independent of the wavelength of the incident light, the spectrum is generated by vibration and rotation of chemical bonds of substances and has strong correlation with the chemical composition structure of a measured substance, and the characteristic of the molecular structure can be reflected, so that the Raman spectrum is a molecular vibration spectrum. The equipment based on Raman spectrum detection is convenient to miniaturize, can detect a large number of substances, can detect tens of thousands of substances under the condition of existence of standard substance spectrums, and is particularly suitable for rapid screening detection. However, when a material spectrum library is established for raman spectroscopy, the uncertainty and workload of library establishment are generally reduced by establishing a library with pure materials, so that the matching accuracy of the obtained spectrum and the spectrum in the library can be directly high when a raman spectroscopy technology detects pure materials, and when a mixture is detected, because the detected raman spectrum belongs to different materials, the standard spectrum of the spectrum library needs to be mixed and superposed according to different proportions, the matching calculation amount is rapidly increased in a geometric series mode, and because the spectrum can be detected once, the detection efficiency and accuracy of the raman spectrum to the mixture are not ideal, and the actual application effect of the raman spectrum is severely limited.
Specifically, for a test spectrum, the test spectrum is compared with the library spectrum and is marked as a primary match through correlation coefficient calculation, the quantity of the pure object spectrum library material is N, if the default is pure object, the calculation frequency is N, if the default is mixture, for binary mixture, the required calculation frequency is 10 XN assuming that the mixing ratio is 10% first grade, and the required calculation frequency is 10 XN 2 In addition to the names of the substances corresponding to the spectra, a substance ratio unknown needs to be solved, which is 100 XN for a ternary mixture 3 Besides the names of the substances corresponding to the spectra, the unknown proportion of the two substances needs to be solved, and so on. As the components increase, solutions are neededThe variation of (a) also increases, and similar results can be obtained by superposing different spectra in different spectral proportions. Consider the jth standard spectrum as a vector A j Coefficient of proportionality of alpha j The detected spectrum is A, and A j The vector has a large dimension, so [ alpha ] 1 ，α 2 ，...]The solution of (c) is not unique. Therefore, in the case of uncertain component quantity, the component quantity needs to be exhausted from 1 to the maximum component matching number m, and the total calculation quantity is N +10 multiplied by N 2 +100×N 3 +……+(10) m-1 ×N m . Accordingly, if the component quantity and part of the substance state information in the measured substance are known by other means, the uncertainty in the Raman spectrum matching process can be greatly reduced, and the matching accuracy and speed are improved.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a Raman spectrum and ion mobility spectrum combined detection method and device.
The technical scheme for solving the technical problems is as follows:
a Raman spectrum and ion mobility spectrum combined detection method is characterized by comprising the following steps:
acquiring a sample to be detected, and acquiring Raman spectrum data of the sample to be detected;
continuously collecting gas in a container, mixing air and steam of the sample to be detected according to a plurality of preset proportions in the container, and acquiring an ion mobility spectrum of the gas;
processing the ion mobility spectrometry to obtain the number of volatile substances in the sample to be detected and a corresponding molecular weight range;
and determining the material components of the sample to be detected according to the quantity of the volatile substances, the molecular weight range, a preset spectrum library and the Raman spectrum data of the sample to be detected.
The method has the beneficial effects that: the method comprises the steps of acquiring a sample to be detected, acquiring Raman spectrum data of the sample to be detected, continuously acquiring gas in a container, mixing air and steam of the sample to be detected according to a plurality of preset proportions in the container, acquiring an ion mobility spectrum of the gas, processing according to the ion mobility spectrum to obtain the number of volatile substances and a corresponding molecular weight range in the sample to be detected, and determining the substance components of the sample to be detected according to the molecular weight range, a preset spectrum library and the Raman spectrum data of the sample to be detected. The method combines Raman spectrum and ion mobility spectrometry technology to detect volatile solid and liquid samples, and determines the quantity and molecular mass range of volatile substances in the samples to be detected through ion mobility spectrometry, thereby reducing the matching range of a Raman database, greatly reducing the matching difficulty of Raman spectrum, simultaneously reducing the detection operand on a large scale, improving the detection accuracy while reducing the detection operand, having great application potential in the application of detecting liquid and solid volatile toxic and harmful substances, and being applied to the fields of detection and treatment of chemical weapons, reconnaissance and treatment of emergency incident sites, environmental protection inspection and the like.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the acquiring a sample to be detected and acquiring a raman spectrum of the sample to be detected specifically includes:
when the dosage of the sample to be detected is smaller than a preset value, putting the sample to be detected into a microscopic device, and focusing laser by the microscopic device to obtain the Raman spectrum;
and when the dosage of the sample to be detected is larger than a preset value, directly measuring the sample to be detected to obtain the Raman spectrum.
The beneficial effect of adopting the further scheme is that: when the dosage of the sample to be detected is smaller than the preset value, the sample to be detected is placed into the microscopic equipment, the microscopic equipment focuses laser to obtain a Raman spectrum, and when the dosage of the sample to be detected is larger than the preset value, the Raman spectrum is obtained after the sample to be detected is sampled, and the spectrum can be directly obtained without using the microscopic equipment.
Further, the processing the ion mobility spectrometry to obtain the molecular weight range corresponding to the volatile substance in the sample to be detected specifically includes:
identifying whether an ion peak in the ion mobility spectrum is a multimeric ion peak;
and if so, removing the polymer ion peak from the ion mobility spectrum, and determining the quantity and the molecular weight range of the volatile substances corresponding to the effective monomer ion peak in the ion mobility spectrum according to an ion mobility database.
The beneficial effect of adopting the further scheme is that: the molecular weight range corresponding to volatile substances in the sample to be detected is obtained by processing the ion mobility spectrometry, so that the area of a Raman spectrum library required to be compared is reduced, the calculated amount is reduced, and the detection accuracy is improved.
Further, the identifying of the ion peak in the ion mobility spectrometry is a multimeric ion peak, and specifically includes:
determining the effective monomer ion peak in the ion mobility spectrum;
if an ion peak with the opposite intensity change trend appears synchronously in the process of the effective monomer ion peak intensity along with the change of the concentration, the ion peak is a polymer ion peak of the effective monomer ion peak.
The further scheme has the advantages that polymer ion peaks in the ion mobility spectrometry are identified, detection accuracy is improved, and misjudgment is reduced.
Further, the determining the substance components of the sample to be detected according to the quantity of the volatile substance, the molecular weight range, the preset spectrum library and the raman spectrum data of the sample to be detected specifically includes:
determining a substance list participating in spectrum matching in the preset spectrum library according to the molecular weight range;
and comparing the Raman spectrum in the matching material list with the Raman spectrum data of the sample to be detected to obtain the material components of the sample to be detected.
The beneficial effect of adopting the further scheme is that: according to the quantity of the volatile substances, the molecular weight range, the preset spectrum library and the Raman spectrum data of the sample to be detected, the substance components of the sample to be detected are determined, the area of the Raman spectrum library to be compared is reduced, the calculated amount is reduced, and the detection accuracy is improved.
Further, after the raman spectrum in the matching substance list is compared with the raman spectrum data of the sample to be detected to obtain the substance component of the sample to be detected, the method further includes:
denoising the Raman spectrum data of the sample to be detected, and then subtracting the fitting spectrum of the material components to obtain a spectrum residual error;
and determining whether components of the non-volatile substances exist in the sample to be detected according to the residual energy of the spectrum residual error.
The beneficial effect of adopting the further scheme is that: the method comprises the steps of denoising Raman spectrum data of a sample to be detected, subtracting a fitting spectrum of material components to obtain a spectrum residual error, and determining whether the component of a non-volatile material exists in the sample to be detected according to the residual energy of the spectrum residual error, so that the material identification capability is improved, the detection accuracy is improved while the detection operation amount is reduced.
Another technical solution of the present invention for solving the above technical problems is as follows: a raman spectroscopy and ion mobility spectroscopy combined detection apparatus, the apparatus comprising:
the device comprises a collecting device, a processing device and a control device, wherein the collecting device is used for acquiring a sample to be detected and collecting Raman spectrum data of the sample to be detected;
the flow distribution device is used for continuously collecting gas in a container, mixing air and steam of the sample to be detected according to a plurality of preset ratios in the container, and acquiring an ion mobility spectrum of the gas;
the identification device is used for processing the ion mobility spectrometry to obtain a molecular weight range corresponding to volatile substances in the sample to be detected; and determining the material components of the sample to be detected according to the quantity of the volatile substances, the molecular weight range, a preset spectrum library and the Raman spectrum data of the sample to be detected.
The method has the beneficial effects that: the method comprises the steps of acquiring a sample to be detected, acquiring Raman spectrum data of the sample to be detected, mixing air and steam of the sample to be detected according to a plurality of preset proportions to acquire an ion mobility spectrum of the gas, processing according to the ion mobility spectrum to obtain the number of volatile substances in the sample to be detected and a corresponding molecular weight range, and determining the substance components of the sample to be detected according to the molecular weight range, a preset spectrum library and the Raman spectrum data of the sample to be detected. The method combines Raman spectrum and ion mobility spectrometry technology to detect volatile solid and liquid samples, and determines the quantity and molecular mass range of volatile substances of the samples to be detected through ion mobility spectrometry, so that the matching range of a Raman database is narrowed, the matching difficulty of the Raman spectrum is greatly reduced, the detection operand is also greatly reduced, the detection accuracy is improved while the detection operand is reduced, and the method has great application potential in the application of detecting liquid and solid volatile toxic and harmful substances, and can be applied to the fields of detection and treatment of chemical weapons, reconnaissance and treatment of emergency incident sites, environmental protection, inspection and the like.
Further, the collecting device is specifically configured to, when the dose of the sample to be detected is smaller than a preset value, place the sample to be detected into a microscopic device, and the microscopic device focuses laser to obtain the raman spectrum;
and when the dosage of the sample to be detected is larger than a preset value, directly measuring the sample to be detected to obtain the Raman spectrum after sampling.
Further, the identification device is specifically used for identifying whether the ion peak in the ion mobility spectrometry is a polymer ion peak;
and if so, removing the polymer ion peak from the ion mobility spectrum, and determining the quantity and the molecular weight range of the volatile substances corresponding to the effective monomer ion peak in the ion mobility spectrum according to an ion mobility database.
Further, the identification means, in particular, is configured to determine the effective monomer ion peak in the ion mobility spectrum;
if an ion peak with the opposite intensity change trend appears synchronously in the process of the effective monomer ion peak intensity along with the change of the concentration, the ion peak is a polymer ion peak of the effective monomer ion peak.
Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention or in the description of the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flowchart of a raman spectroscopy and ion mobility spectroscopy combined detection method according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an ion mobility spectrum and a Raman spectrum obtained by applying a Raman spectrum and ion mobility spectrum combined detection method according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of an ion mobility spectrum and a Raman spectrum obtained by applying a Raman spectrum and ion mobility spectrum combined detection method according to another embodiment of the present invention;
FIG. 4 is a schematic diagram of an ion mobility spectrum and a Raman spectrum obtained by applying a Raman spectroscopy and ion mobility spectrometry combined detection method according to another embodiment of the present invention;
fig. 5 is a schematic block diagram of a raman spectroscopy and ion mobility spectroscopy combined detection apparatus according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.
As shown in fig. 1, a schematic flow chart of a raman spectroscopy and ion mobility spectroscopy joint detection method according to an embodiment of the present invention is shown, where a raman spectroscopy and ion mobility spectroscopy joint detection method includes the following steps:
110. acquiring a sample to be detected, and acquiring Raman spectrum data of the sample to be detected.
120. And continuously collecting gas in a container, mixing air and steam of a sample to be detected in the container according to a plurality of preset ratios, and acquiring an ion mobility spectrum of the gas.
130. And processing the ion mobility spectrometry to obtain the number of volatile substances in the sample to be detected and a corresponding molecular weight range, and determining the material components of the sample to be detected according to the number of the volatile substances, the molecular weight range, a preset spectrum library and Raman spectrum data of the sample to be detected.
It will be appreciated that the sample to be tested in the present application is a solid or liquid and does not support a gaseous component. When the sample to be detected is 1 microgram to 100 milligram, the sample to be detected can be observed by using a microscopic module, the microscopic module further focuses laser and Raman scattering light returns along the same optical path, so that a Raman spectrum is collected, wherein when the sample to be detected is more than 100 milligram, a glass sample bottle can be used for sampling, then the sample is directly loaded and detected, and meanwhile, a Raman spectrometer is used for collecting the Raman spectrum.
Firstly, air is mixed into a container in a detection sampling product in a high proportion, gas in the container is sampled, then the proportion is continuously reduced, top gas with different concentrations is obtained, and an ion mobility spectrum of the gas is collected.
When the gas flow is increased, the position of an effective monomer ion peak is increased and then decreased, and a slowly-increased peak is synchronously generated at a position with larger migration time in the peak decreasing process, the peak is a polymer ion peak of the effective monomer ion peak, the polymer ion peak is often generated when the concentration of volatile substances is very large, the purpose of using different proportions is to count the polymer ion peak by mistake when counting substances is eliminated, after the polymer ion peak is eliminated, the number of the effective monomer ion peaks in an ion migration spectrum is counted, and the number and the molecular weight range of the corresponding volatile substances are determined according to the effective monomer ion peaks.
The molecular range of the corresponding volatile substance is determined according to the ion migration information, so that the area required to be compared by the Raman spectrum library is reduced, the possibility of correct matching is improved from two aspects of components and the library, and the calculation amount is reduced.
The existing spectrum is denoised, the spectrum is fitted to obtain a spectrum residual, if the total residual energy of the residual is not or very little, all volatile and Raman-active substances are matched, volatile components can be confirmed, common substances which are non-volatile and have no Raman activity, such as water, cellulose and the like, are non-toxic and harmless, and the result is that the volatile components are given. If the total residual energy of the residual is large, indicating that volatile substances are removed, still non-volatile raman-active substances are present in the solid or liquid, and it is necessary to indicate that the volatile components are still difficult to volatilize chemical substances.
The method comprises the steps of obtaining a sample to be detected, collecting Raman spectrum data of the sample to be detected, mixing air and steam of the sample to be detected according to a plurality of preset proportions to obtain an ion mobility spectrum of the gas, processing according to the ion mobility spectrum to obtain the number of volatile substances in the sample to be detected and a corresponding molecular weight range, and determining material components of the sample to be detected according to the number of the volatile substances, the molecular weight range, a preset spectrum library and the Raman spectrum data of the sample to be detected. The method combines Raman spectrum and ion mobility spectrometry technology to detect volatile solid and liquid samples, and determines the quantity and molecular mass range of volatile substances of the samples to be detected through ion mobility spectrometry, thereby reducing the matching range of a Raman database, greatly reducing the matching difficulty of Raman spectrum, simultaneously reducing the detection operand on a large scale, improving the detection accuracy while reducing the detection operand, having great application potential in the application of detecting liquid and solid volatile toxic and harmful substances, and being applied to the fields of detection and treatment of chemical weapons, reconnaissance and treatment of emergency incident sites, environmental protection, inspection and the like.
Further, step 110 specifically includes:
when the dosage of the sample to be detected is smaller than a preset value, putting the sample to be detected into a microscopic device, and focusing laser by the microscopic device to obtain the Raman spectrum;
and when the dosage of the sample to be detected is larger than a preset value, directly measuring the sample to be detected to obtain the Raman spectrum after sampling.
Further, step 130 specifically includes:
identifying a multimeric ion peak in the ion mobility spectrum.
And removing polymer ion peaks from the ion mobility spectrometry, and determining the number and the molecular weight range of volatile substances corresponding to effective monomer ion peaks in the ion mobility spectrometry according to an ion mobility database.
Wherein the method of identifying a multimeric ion peak in an ion mobility spectrometry comprises:
determining effective monomer ion peaks in an ion mobility spectrum;
an ion peak having an opposite trend to the intensity variation, which appears in synchronization with the variation of the intensity of the effective monomer ion peak with the concentration variation, is a polymer ion peak of the effective monomer ion peak.
Further, according to the molecular weight range, determining a substance list participating in spectrum matching in a preset spectrum library.
And comparing the Raman spectrum in the matching material list with the Raman spectrum data of the sample to be detected to obtain the material components of the sample to be detected.
Further, denoising the Raman spectrum data of the sample to be detected, and then subtracting the fitted spectrum of the material components to obtain a spectrum residual error.
And determining whether components of the non-volatile substances exist in the sample to be detected according to the residual energy of the spectrum residual error.
How to apply the present embodiment for detection is described in detail below.
As shown in fig. 2, the ion mobility spectrum and the raman spectrum obtained by the raman spectrum and ion mobility spectrum joint detection method according to the embodiment of the present invention are schematic diagrams, a raman spectrum method is adopted to directly test a mixture of imidazole and dinitroaniline, the obtained mixed spectrum is very similar to the raman spectrum of trinitroaniline, and if the mixed spectrum is directly matched with the raman spectrum of trinitroaniline, the similarity between the standard spectrum of trinitroaniline and the mixture spectrum exceeds 95%, so that the detection result is trinitroaniline. However, two effective monomer mobility spectrum peaks of dinitroaniline and imidazole can be detected by adopting ion mobility spectrometry, so that the Raman matching algorithm is guided to improve the grabbing of small peaks, such as 902cm -1 、1149cm -1 、1190cm -1 、1452cm -1 And equal position, thereby being capable of successfully matching imidazole and dinitroaniline, and the similarity of the mixed spectrum to the simulated mixed spectrum of the final standard substance is 91 percent.
As shown in FIG. 3, which is a schematic diagram of an ion mobility spectrometry and a Raman spectrum obtained by a combined Raman spectroscopy and ion mobility spectrometry detection method according to an embodiment of the present invention, a mixture of ethyl acetate and isopropyl alcohol is directly tested by the Raman spectroscopy method, and the mixed spectrum is very similar to that of isobutyl acetate, mainly because the isopropoxy structure of isopropyl alcohol is the same as that of the isopropoxy of isobutyl acetate, and the acetoxy group of ethyl acetate and the acetoxy group of isobutyl acetate are the same phaseThe same as above. If there is a direct match, the standard spectrum of isobutyl acetate will have a similarity of more than 80% to the spectrum of the mixture, and therefore the detection result will be isobutyl acetate. However, two effective monomer mobility spectrum peaks of ethyl acetate and isopropanol can be detected by using IMS (ion mobility spectrometry), so that a Raman matching algorithm is guided to improve the grabbing of a small peak, for example 778cm -1 、846cm -1 、1116cm -1 Equal positions, so that ethyl acetate and isopropanol can be successfully matched, and the similarity of the mixed spectrum to the simulated mixed spectrum of the final standard substance is 85%.
As shown in fig. 4, which is a schematic diagram of an ion mobility spectrometry and a raman spectrometry obtained by a raman spectrometry and an ion mobility spectrometry combined detection method according to an embodiment of the present invention, when a mixture of dimethyl sulfoxide and ethanol is directly tested by using the raman spectrometry, because raman activity of dimethyl sulfoxide is very strong, signals of ethanol with similar volumes are weak in a mixed spectrum, so that the mixed spectrum is very similar to dimethyl sulfoxide, and if the mixed spectrum is directly matched with the dimethyl sulfoxide, similarity between a standard spectrum of dimethyl sulfoxide and the mixed spectrum exceeds 85%, so that a detection result is dimethyl sulfoxide. However, two effective monomer mobility spectrum peaks of ethanol and dimethyl sulfoxide can be detected by adopting the ion mobility spectrometry, so that the Raman matching algorithm is guided to improve the grabbing of small peaks, such as 432cm -1 、882cm -1 、1094cm -1 、1274cm -1 、1478cm -1 And the positions are equal, so that the dimethyl sulfoxide and the ethanol can be successfully matched, and the similarity of the mixed spectrum to the simulated mixed spectrum of the final standard substance is 90%.
Based on the embodiment, the Raman spectrum and the ion mobility spectrum are used for detecting volatile substances together, the identification capability of the Raman spectrum on the mixture is improved by using the combination method and the corresponding algorithm, the size of a database of the ion mobility spectrum is expanded, and the accuracy and the speed of matching are improved from more than ten substances to tens of thousands of substances of the Raman spectrum.
As shown in fig. 5, a schematic block diagram of a raman spectroscopy and ion mobility spectroscopy combined detection apparatus according to an embodiment of the present invention includes:
the device comprises a collecting device, a processing device and a control device, wherein the collecting device is used for acquiring a sample to be detected and collecting Raman spectrum data of the sample to be detected;
the flow distribution device is used for continuously collecting gas in a container, mixing air and steam of the sample to be detected according to a plurality of preset ratios in the container, and acquiring an ion mobility spectrum of the gas;
the identification device is used for processing the ion mobility spectrometry to obtain a molecular weight range corresponding to a volatile substance in the sample to be detected; and determining the material components of the sample to be detected according to the quantity of the volatile substances, the molecular weight range, the preset spectrum library and the Raman spectrum data of the sample to be detected.
Further, the collecting device is specifically configured to, when the dose of the sample to be detected is smaller than a preset value, place the sample to be detected in a microscopic device, and the microscopic device focuses laser to obtain the raman spectrum;
and when the dosage of the sample to be detected is larger than a preset value, directly measuring the sample to be detected to obtain the Raman spectrum after sampling.
Further, the identification device is specifically used for identifying whether the ion peak in the ion mobility spectrometry is a polymer ion peak;
and if so, removing the polymer ion peak from the ion mobility spectrum, and determining the quantity and the molecular weight range of the volatile substances corresponding to the effective monomer ion peak in the ion mobility spectrum according to an ion mobility database.
Further, the identification means, in particular, is configured to determine the effective monomer ion peak in the ion mobility spectrum;
and an ion peak which is opposite to the intensity change trend and synchronously appears in the process of changing the intensity of the effective monomer ion peak along with the concentration change is a polymer ion peak of the effective monomer ion peak.
It should be understood that, for convenience and simplicity of description, the foregoing division of the functional units and modules is only used for illustration, and in practical applications, the above distribution of functions may be performed by different functional units and modules as needed, that is, the internal structure of the apparatus may be divided into different functional units or modules to perform all or part of the above described functions. Each functional unit and module in the embodiments may be integrated in one processing unit, or each unit may exist alone physically, or two or more units are integrated in one unit, and the integrated unit may be implemented in a form of hardware, or in a form of software functional unit. In addition, specific names of the functional units and modules are only for convenience of distinguishing from each other, and are not used for limiting the protection scope of the present application. The specific working processes of the units and modules in the system may refer to the corresponding processes in the foregoing method embodiments, and are not described herein again.
In the above embodiments, the description of each embodiment has its own emphasis, and reference may be made to the related description of other embodiments for parts that are not described or recited in any embodiment.
Those of ordinary skill in the art will appreciate that the various illustrative elements and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware or combinations of computer software and electronic hardware. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the implementation. Skilled artisans may implement the described functionality in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the present invention.
In the embodiments provided in the present invention, it should be understood that the disclosed apparatus/terminal system and method can be implemented in other ways. For example, the above-described embodiments of the apparatus/terminal system are merely illustrative, and for example, the division of the modules or units is only one logical division, and other divisions may be realized in practice, for example, a plurality of units or components may be combined or integrated into another system, or some features may be omitted, or not executed. In addition, the shown or discussed mutual coupling or direct coupling or communication connection may be through some interfaces, indirect coupling or communication connection of devices or units, and may be in an electrical, mechanical or other form.
The units described as separate parts may or may not be physically separate, and parts displayed as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the units can be selected according to actual needs to achieve the purpose of the solution of the embodiment.
In addition, functional units in the embodiments of the present invention may be integrated into one processing unit, or each unit may exist alone physically, or two or more units are integrated into one unit. The integrated unit may be implemented in the form of hardware, or may also be implemented in the form of a software functional unit.
The integrated modules/units, if implemented in the form of software functional units and sold or used as separate products, may be stored in a computer readable storage medium.
Based on such understanding, all or part of the flow of the method according to the embodiments of the present invention may also be implemented by a computer program, which may be stored in a computer-readable storage medium, and when the computer program is executed by a processor, the steps of the method embodiments may be implemented. Wherein the computer program comprises computer program code, which may be in the form of source code, object code, an executable file or some intermediate form, etc. The computer-readable medium may include: any entity or device capable of carrying the computer program code, recording medium, U.S. disk, removable hard disk, magnetic diskette, optical disk, computer Memory, read-Only Memory (ROM), random Access Memory (RAM), electrical carrier wave signal, telecommunications signal, and software distribution medium, etc. It should be noted that the computer readable medium may contain other components which may be suitably increased or decreased as required by legislation and patent practice in jurisdictions, for example, in some jurisdictions, computer readable media which may not include electrical carrier signals and telecommunications signals in accordance with legislation and patent practice.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A Raman spectrum and ion mobility spectrum combined detection method is characterized by comprising the following steps:
acquiring a sample to be detected, and acquiring Raman spectrum data of the sample to be detected;
collecting gas in a container, mixing air and steam of the sample to be detected according to a plurality of preset proportions in the container, and acquiring an ion mobility spectrum of the gas;
processing the ion mobility spectrometry to obtain the number of volatile substances in the sample to be detected and a corresponding molecular weight range;
determining the material components of the sample to be detected according to the quantity of volatile substances, the molecular weight range, a preset spectrum library and Raman spectrum data of the sample to be detected;
the step of processing the ion mobility spectrometry to obtain the molecular weight range corresponding to the volatile substance in the sample to be detected specifically comprises the following steps:
identifying whether an ion peak in the ion mobility spectrum is a multimeric ion peak;
and if so, removing the polymer ion peak from the ion mobility spectrometry, and determining the number and the molecular weight range of volatile substances corresponding to the effective monomer ion peak in the ion mobility spectrometry according to an ion mobility database.
2. The method for jointly detecting a raman spectrum and an ion mobility spectrum according to claim 1, wherein the acquiring a sample to be detected and acquiring a raman spectrum of the sample to be detected specifically comprises:
when the dosage of the sample to be detected is smaller than a preset value, putting the sample to be detected into a microscopic device, and focusing laser by the microscopic device to obtain the Raman spectrum;
and when the dosage of the sample to be detected is larger than a preset value, directly measuring the sample to be detected to obtain the Raman spectrum after sampling.
3. The method for detecting Raman spectrum and ion mobility spectrum in combination according to claim 2, wherein the identifying the ion peaks in the ion mobility spectrum is a polymer ion peak, specifically comprises:
determining the effective monomer ion peak in the ion mobility spectrum;
if an ion peak with the intensity opposite to the intensity change trend appears synchronously in the process of changing the intensity of the effective monomer ion peak along with the concentration, the ion peak is a polymer ion peak of the effective monomer ion peak.
4. The raman spectroscopy and ion mobility spectroscopy combined detection method of claim 1, wherein the determining the volatile substance component of the sample to be detected according to the amount of the volatile substance, the molecular weight range, the preset spectral library and the raman spectroscopy data of the sample to be detected specifically comprises:
determining a substance list participating in spectrum matching in the preset spectrum library according to the molecular weight range;
and comparing the Raman spectrum in the matching material list with the Raman spectrum data of the sample to be detected to obtain the material components of the sample to be detected.
5. The method for combined detection of raman spectrum and ion mobility spectrum according to claim 4, wherein after comparing the raman spectrum in the matching material list with the raman spectrum data of the sample to be detected to obtain the material component of the sample to be detected, the method further comprises:
denoising the Raman spectrum data of the sample to be detected, and then subtracting the fitted spectrum of the material components to obtain a spectrum residual error;
and determining whether components of the non-volatile substances exist in the sample to be detected according to the residual energy of the spectrum residual error.
6. A combined raman spectroscopy and ion mobility spectroscopy detection apparatus, the apparatus comprising:
the acquisition device is used for acquiring a sample to be detected and acquiring Raman spectrum data of the sample to be detected;
the flow distribution device is used for continuously collecting gas in a container, mixing air and steam of the sample to be detected in the container according to a plurality of preset ratios, and acquiring an ion mobility spectrum of the gas;
the identification device is used for processing the ion mobility spectrometry to obtain a molecular weight range corresponding to a volatile substance in the sample to be detected; determining the material components of the sample to be detected according to the quantity of volatile substances, the molecular weight range, a preset spectrum library and the Raman spectrum data of the sample to be detected;
the identification device is specifically used for identifying whether the ion peak in the ion mobility spectrometry is a polymer ion peak or not;
and if so, removing the polymer ion peak from the ion mobility spectrum, and determining the quantity and the molecular weight range of the volatile substances corresponding to the effective monomer ion peak in the ion mobility spectrum according to an ion mobility database.
7. The apparatus for Raman spectroscopy and ion mobility spectroscopy combined detection according to claim 6,
the acquisition device is specifically used for placing the sample to be detected into a microscopic device when the dosage of the sample to be detected is smaller than a preset value, and the microscopic device focuses laser to obtain the Raman spectrum;
and when the dosage of the sample to be detected is larger than a preset value, directly measuring the sample to be detected to obtain the Raman spectrum after sampling.
8. The apparatus for joint detection of Raman spectroscopy and ion mobility spectroscopy according to claim 6,
the identification means, in particular, for determining the effective monomer ion peak in the ion mobility spectrum;
if an ion peak with the opposite intensity change trend appears synchronously in the process of the effective monomer ion peak intensity along with the change of the concentration, the ion peak is a polymer ion peak of the effective monomer ion peak.
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