Intelligent screening method and apparatus for sulfate / sulfonate surfactant, and device

Abstract

The present invention relates to the technical field of detection and analysis of daily chemical products. Disclosed are an intelligent screening method and apparatus for a sulfate / sulfonate surfactant, a device, and a storage medium. The method comprises: performing pretreatment and ultra-high performance liquid chromatography high-resolution mass spectrometry scanning on a sample to be tested; performing conversion to obtain an mzXML file; screening for a target secondary mass spectrum peak containing characteristic ions from among all secondary mass spectrum peaks in the file; extracting corresponding masses and peak intensities of all precursor ions; when a mass difference between two precursor ions is within a sulfur isotope mass difference range, and a peak intensity ratio is within a specified ratio range, selecting the precursor ion with the lower mass as a quasi-molecular ion; generating a prediction molecular formula, and retrieving matching structural information from a database; performing simulated fragmentation to obtain a simulated secondary mass spectrum; comparing the simulated secondary mass spectrum with an actual secondary mass spectrum to determine a prediction structure; and identifying as a sulfate / sulfonate surfactant. The present invention can achieve intelligent processing of high-resolution mass spectrum data, improve the data processing efficient, and improve the sensitivity and accuracy.

Description

Intelligent screening method and device for sulfur / sulfonate surfactants, and equipment

[0001] The present application claims priority to the Chinese patent application No. 2024104572516, filed on April 16, 2024, and entitled "Intelligent screening method and device for sulfur / sulfonate surfactants, and equipment", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application belongs to the technical field of daily chemical product detection and analysis, and specifically relates to an intelligent screening method and device for sulfur / sulfonate surfactants, equipment, and a storage medium. BACKGROUND

[0003] Sulfur / sulfonate surfactants have two distinct parts: a hydrophilic (water-soluble) head and a hydrophobic (fat-soluble) tail. The hydrophilic head is composed of a sulfur / sulfonate group, which can interact with water molecules, allowing the surfactant molecules to dissolve in water. The hydrophobic tail is composed of long-chain fatty acids, which repel water molecules, allowing the surfactant molecules to form a thin film on the water surface. This structure allows sulfur / sulfonate surfactants to act as a bridge between water and oil. When sulfur / sulfonate surfactant molecules form a thin film on the water surface, they encapsulate water molecules inside the film, reducing the attraction between water molecules. This allows water to better wet surfaces and interact with other substances, such as cleaning dirt or increasing foam. Therefore, sulfur / sulfonate surfactants are widely used in daily life. For example, in personal care products, they are commonly found in shampoos, body washes, toothpaste, and facial cleansers due to their ability to produce abundant foam and effectively remove oil and dirt. In addition, they are also used in laundry detergent, dishwashing detergent, and other cleaning products to enhance their ability to remove dirt.

[0004] However, their use is also accompanied by some potential hazards. In particular, at high concentrations or with long-term exposure, these compounds can cause skin and eye irritation. Long-term use of products containing sulfur / sulfonate surfactants can cause dry skin and hair, as they remove natural oils. In addition, people sensitive to these chemicals may experience dermatitis or other allergic reactions. From an environmental perspective, although sulfur / sulfonate surfactants are relatively easy to biodegrade, their extensive use in water bodies can have a negative impact on aquatic ecosystems.

[0005] There are multiple methods for analyzing sulfur / sulfate surfactants, each with certain limitations. Traditional methods include spectrophotometry, electrochemistry, and chromatography. One common method is the Methylene Blue Active Substances (MBAS) test, which involves the formation of blue salts of anionic surfactants with the Methylene Blue dye and is determined by spectrophotometry. However, these methods often lack sufficient selectivity to distinguish different anionic groups or alkyl chain structures, making them ineffective for detailed analysis of alkyl and alkoxyl ether sulfur / sulfate surfactants in complex mixtures.

[0006] In recent years, with the advancement of technology, triple quadrupole tandem mass spectrometry is used to analyze sulfur / sulfate surfactants in Prec (precursor ion scanning) mode based on characteristic ions of sulfur / sulfate surfactants. By comparing the parent ion information scanned by each scanning channel, it is determined whether sulfur / sulfate surfactants are present in the sample. However, in the prior art, the mass spectrometry resolution is not high, which can easily lead to high false positives, and the baseline of the collected data is too high, there are too many impurity peaks, and the sensitivity is insufficient. The collected data still needs to be manually distinguished after being processed by software to obtain the results. In addition, the targeted screening technology using triple quadrupole tandem mass spectrometry can only target known components for targeted screening, and cannot cover a wide variety of sulfur / sulfate surfactants. SUMMARY

[0007] The purpose of the present application is to provide a sulfur / sulfate surfactant intelligent screening method and device, equipment, and storage medium, which can intelligently process high-resolution mass spectrometry data, improve data processing efficiency, reduce manual dependence, and at the same time improve sensitivity, accuracy, and reduce false positive rate.

[0008] The first aspect of the present application discloses a sulfur / sulfate surfactant intelligent screening method, comprising:

[0009] The raw data of the sample to be tested is obtained by pretreating and ultra-high performance liquid chromatography high-resolution mass spectrometry scanning the sample to be tested;

[0010] The raw data is converted into an mzXML format file, and all secondary mass spectrometry peaks in the mzXML format file are screened and filtered to select target secondary mass spectrometry peaks containing characteristic ions;

[0011] The primary mass spectrometry data corresponding to the target secondary mass spectrometry peaks is extracted from the mzXML format file, and the primary mass spectrometry data includes the mass of all parent ions and peak intensity;

[0012] The mass difference of two parent ions is calculated, and if the mass difference of the two parent ions is within the mass difference range of sulfur isotopes, the peak intensity ratio of the two parent ions is calculated;

[0013] If the peak intensity ratio is within the specified ratio range, the parent ion with lower mass among the two parent ions is selected as the quasi-molecular ion of the potential target compound;

[0014] According to the mass of the quasi-molecular ion of the potential target compound, a predicted molecular formula of the potential target compound is generated according to the molecular formula assignment rule, and matched structure information is retrieved in a database according to the predicted molecular formula;

[0015] According to the matched structure information, simulated fragmentation is performed to obtain a simulated secondary mass spectrum;

[0016] The simulated secondary mass spectrum is compared with the actual secondary mass spectrum of the quasi-molecular ion, and the predicted structure of the potential target compound is determined according to the comparison result;

[0017] According to the actual secondary mass spectrum of the quasi-molecular ion, the potential target compound is identified as a sulfate surfactant or a sulfonate surfactant.

[0018] The second aspect of the present application discloses a sulfate / sulfonate surfactant intelligent screening device, comprising:

[0019] The scanning unit is used for pretreating and performing ultra-high performance liquid chromatography-high resolution mass spectrometry scanning on the to-be-tested sample to obtain raw data of the to-be-tested sample;

[0020] The filtering unit is used for converting the raw data into an mzXML format file, screening and filtering all secondary mass spectrum peaks in the mzXML format file, and selecting target secondary mass spectrum peaks containing characteristic ions;

[0021] The extraction unit is used for extracting primary mass spectrum data corresponding to the target secondary mass spectrum peaks from the mzXML format file, and the primary mass spectrum data includes the mass and peak intensity of all parent ions;

[0022] The calculation unit is used for calculating the mass difference of the two parent ions, and if the mass difference of the two parent ions is within the range of the mass difference of sulfur isotopes, the peak intensity ratio of the potential target compound containing the two parent ions is calculated;

[0023] The selection unit is used for selecting the parent ion with lower mass among the two parent ions as the quasi-molecular ion of the potential target compound if the peak intensity ratio is within the specified ratio range;

[0024] The generation unit is used for generating a predicted molecular formula of the potential target compound according to the mass of the quasi-molecular ion of the potential target compound according to the molecular formula assignment rule, and retrieving matched structure information in a database according to the predicted molecular formula;

[0025] The simulation unit is used for performing simulated fragmentation according to the matched structure information to obtain a simulated secondary mass spectrum;

[0026] a comparison unit configured to compare the simulated secondary mass spectrum with an actual secondary mass spectrum of the quasi-molecular ion, and determine a predicted structure of the potential target compound according to a comparison result;

[0027] a recognition unit configured to recognize the potential target compound as a sulfate surfactant or a sulfonate surfactant according to the actual secondary mass spectrum of the quasi-molecular ion.

[0028] A third aspect of the present application discloses an electronic device, comprising a memory storing executable program codes and a processor coupled with the memory; the processor invokes the executable program codes stored in the memory to execute the sulfate / sulfonate surfactant intelligent screening method disclosed in the first aspect.

[0029] A fourth aspect of the present application discloses a computer readable storage medium storing a computer program, wherein the computer program enables a computer to execute the sulfate / sulfonate surfactant intelligent screening method disclosed in the first aspect.

[0030] The beneficial effects of the present application are that, by performing mass spectrum scanning on the sample to be measured, the original raw data of the sample to be measured are obtained; the original raw data are converted into an mzXML format file, all secondary mass spectrum peaks in the file are screened and filtered, target secondary mass spectrum peaks containing characteristic ions are selected, and primary mass spectrum data corresponding to the target secondary mass spectrum peaks are extracted, the primary mass spectrum data including the mass of all parent ions and peak intensity; the mass difference of two parent ions is calculated, if the mass difference of the two parent ions is within the mass difference range of sulfur isotopes, the peak intensity ratio of the two parent ions is calculated; if the peak intensity ratio is within a specified ratio range, the parent ion with the lower mass among the two parent ions is selected as the quasi-molecular ion of the potential target compound; according to the mass of the quasi-molecular ion of the potential target compound, a predicted molecular formula is generated according to the molecular formula distribution rule, matched structure information is obtained by searching in a database, simulated fragmentation is performed according to the matched structure information, simulated secondary mass spectrum diagrams are obtained, and the simulated secondary mass spectrum diagrams are compared with the actual secondary mass spectrum diagram of the quasi-molecular ion to determine the predicted structure of the potential target compound, and the actual secondary mass spectrum diagram of the quasi-molecular ion is used to identify the potential target compound as a sulfate surfactant or a sulfonate surfactant, so that intelligent processing of high-resolution mass spectrum data can be realized, the data processing efficiency is improved, the dependence on manual operation is reduced, the sensitivity and accuracy are improved, and the false positive rate is reduced. Moreover, by setting the mass difference range of sulfur isotopes and the specified peak intensity ratio range, the efficiency of non-target screening can be effectively improved in a large mass spectrum data set. In addition, the accurate mass measurement of high-resolution mass spectrometry further ensures the certainty of the determination of the molecular formula of the compound, significantly reduces the possibility of the structure of the potential compound, and simplifies the compound structure identification process by combining the secondary mass spectrum data and the simulated fragmentation secondary mass spectrum analysis. The present application can be widely applied to the identification of sulfate / sulfonate surfactants, and the screening range is expanded. BRIEF DESCRIPTION OF DRAWINGS

[0031] The drawings herein show specific examples of the technical solutions of the present application, and constitute a part of the specification together with the specific embodiments, for explaining the technical solutions, principles and effects of the present application.

[0032] Unless specifically stated or defined otherwise, the same reference signs in different drawings represent the same or similar technical features, and different reference signs may also be used to represent the same or similar technical features.

[0033] Fig. 1 is a flowchart of a sulfate / sulfonate surfactant intelligent screening method disclosed by an embodiment of the present application;

[0034] Fig. 2 is a secondary chromatogram of the characteristic ion m / z = 79.9567 in the R language data processing program disclosed by an embodiment of the present application;

[0035] Fig. 3 to 5 are structural schematic diagrams of three potential quasi-molecular ions disclosed by embodiments of the present application;

[0036] Fig. 6 is a structural schematic diagram of a sulfur / sulfonate surfactant intelligent screening device disclosed by an embodiment of the present application;

[0037] Fig. 7 is a structural schematic diagram of an electronic device disclosed by an embodiment of the present application.

[0038] Legend: 601, scanning unit; 602, filtering unit; 603, extraction unit; 604, calculation unit; 605, selection unit; 606, generation unit; 607, simulation unit; 608, comparison unit; 609, identification unit; 701, memory; 702, processor. DETAILED DESCRIPTION

[0039] Unless specifically stated or otherwise understood, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In the context of the technical solutions of the present application in a real scenario, all technical and scientific terms used herein can also have meanings corresponding to the purposes of implementing the technical solutions of the present application. The terms "first, second, …" used herein are only used to distinguish names and do not represent specific quantities or sequences. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0040] It should be noted that when an element is considered to be "fixed to" another element, it can be directly fixed to the other element or there can be a middle element; when an element is considered to be "connected to" another element, it can be directly connected to the other element or there can be a middle element; when an element is considered to be "mounted on" another element, it can be directly mounted on the other element or there can be a middle element. When an element is considered to be "provided in" another element, it can be directly provided in the other element or there can be a middle element.

[0041] Unless specifically stated or otherwise understood, "the", "this" used herein refers to the technical features or technical contents mentioned or described before the corresponding position, which can be the same as or similar to the technical features or technical contents mentioned. In addition, the terms "include" and "have" used herein and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device including a series of steps or units is not limited to the listed steps or units, but optionally also includes steps or units not listed, or optionally also includes other steps or units inherent to the process, method, product or device.

[0042] The embodiment of the present application discloses a kind of sulphur / sulphonate surfactant intelligent screening method, the method can be realized by computer programming.The execution main body of the method can be as computer, notebook computer, tablet computer etc.Electronic equipment, or sulphur / sulphonate surfactant intelligent screening device (hereinafter referred to as intelligent screening device) embedded in electronic equipment, the present application does not limit this.The executable program code is arranged in electronic equipment or intelligent screening device, and the executable program code is called by electronic equipment or intelligent screening device, to execute sulphur / sulphonate surfactant intelligent screening method.In order to facilitate understanding of the present application, the specific embodiments of the present application will be described in more detail below with reference to the drawings of the specification.As shown in Figure 1, the method comprises the following steps 110-180:

[0043] 110, mass spectrum scanning is carried out on the sample to be measured, and the original raw data of the sample to be measured is obtained.

[0044] In order to screen out all sulphur / sulphonate surfactants as much as possible, the pretreatment process of all samples will reduce loss as much as possible, first, methanol is mixed with the sample, vortex mixing is uniform, and then ultrasonic is 10-15 min, and after being reduced to room temperature, it is filtered through 0.22 μm filter membrane to form the sample to be measured.

[0045] Then control ultra-high performance liquid chromatography with high resolution mass spectrometry (UPLC-HRMS) according to the preset mass spectrum condition to carry out mass spectrum scanning on the sample to be measured, and the preset mass spectrum condition is set, including the selection of cyan column, the mass spectrum scanning mode is Full-scan / AIF mode, and the ionization mode is selected as negative ion mode.Under the preset mass spectrum condition, the chromatographic mass spectrum data of the sample to be measured is scanned, and the data format is raw file, also known as original raw data.

[0046] Among them, by selecting cyan column based on the polarity of sulphur / sulphonate surfactant, the chromatographic separation effect can be significantly improved, and the identification accuracy is enhanced.In combination with ultra-high performance liquid chromatography with high resolution mass spectrometry (UPLC-HRMS), the identification accuracy of sulphur / sulphonate surfactant can be improved, and false positive can be reduced.

[0047] In some embodiments, the preset mass spectrum condition further comprises:

[0048] H-ESI ion source, negative ion detection mode;

[0049] Spray voltage: 2500V;

[0050] Sheath gas: nitrogen, flow rate 45Arb;

[0051] Auxiliary gas: nitrogen, flow rate 11Arb, temperature 300 DEG C;

[0052] Purge gas: nitrogen 0Arb;

[0053] Ion transfer tube temperature: 350°C;

[0054] Evaporation temperature: 300℃;

[0055] S-lens RF level: 50;

[0056] Full-scan range: 75-1125Da;

[0057] AIF scanning range: 50-200 Da.

[0058] 120. Convert the original raw data into an mzXML format file, filter all the secondary mass spectrum peaks in the mzXML format file, and select the target secondary mass spectrum peaks containing characteristic ions.

[0059] In an embodiment of the present invention, data processing is realized using R language data processing program. For the convenience of importing original raw data into R Studio software, data filtering process is carried out using R language data processing program, and it is necessary to convert original raw data into the file of mzXML format. For realizing the object of the present invention, the R language package used includes xcms, mzR, faahko, pander, MSnbase, magrittr, dplyr, BiocStyle, RMSPeak. Specifically, ProteoWizard-MSConvert software can be utilized to convert original raw data into mzXML format file, and then import R Studio software to carry out data filtering process.

[0060] The sulfonic acid group and sulfate group of the hydrophilic head of the sulfur / sulfonate surfactant are their functional groups, so the fragment ion [SO3] with a mass-to-charge ratio of m / z = 79.9567 can be set. - 、Fragment ion [HSO4] with m / z = 96.9588 - The target secondary mass spectrum peak containing the characteristic ion is selected by screening and filtering the secondary mass spectrum peak.

[0061] 130. Extract the primary mass spectrum data corresponding to the target secondary mass spectrum peak from the mzXML format file, where the primary mass spectrum data includes the masses and peak intensities of all parent ions.

[0062] Among them, the time corresponding to the target secondary mass spectrum peak containing the characteristic ion is first determined, and then all the parent ion information in the primary mass spectrum peak within the corresponding time, that is, the mass and peak intensity of the parent ion, are selected as the primary mass spectrum data.

[0063] 140、Traverse all parent ions two by two combination, calculate the mass difference of each two parent ions, if the mass difference of two parent ions is in the range of sulfur element isotope mass difference, calculate the peak intensity ratio of the two parent ions; if the peak intensity ratio is in the specified ratio range, select the parent ion with lower mass in the two parent ions as the quasi-molecular ion of the potential target compound.

[0064] It should be noted that according to the provisions of Commission Decision 2002 / 657 / EC of 12 August 2002 implementing Council Directive 96 / 23 / EC concerning the performance of analytical methods and the interpretation of results, the relative ion peak intensity ratio is less than 10% of the maximum allowable limit range ± 50%, and the theoretical value of S isotope mass difference is 1.99580, so in the embodiment of the present application, the sulfur element isotope mass difference range is set to [1.99475, 1.99685], and because 34 S and 32 The relative ion peak intensity ratio of S is 4.52%, and the set value should be 4.52% ± 50%, that is, the specified peak intensity ratio range is set to [2.26%, 6.78%]. Thus, the sulfur element isotope mass difference range can be used to further filter and screen the parent ions, if the mass difference of two parent ions is in the range of [1.99475, 1.99685], then the next step of isotope ratio test is performed, that is, the peak intensity ratio of potential containing the two parent ions is calculated, if the peak intensity ratio is in [2.26%, 6.78%], the parent ion with lower mass is selected as the quasi-molecular ion. Among them, the peak intensity ratio of two parent ions refers to the ratio obtained by dividing the peak intensity of the parent ion with larger mass by the peak intensity of the parent ion with smaller mass.

[0065] In the embodiment of the present application, the quasi-molecular ions meeting the conditions screened out by the computer program are shown in the following Table 1.

[0066] Table 1 Quasi-molecular ions meeting the conditions screened out

[0067] 150、According to the mass of the quasi-molecular ion of the potential target compound, the predicted molecular formula of the potential target compound is generated according to the molecular formula distribution rule, and the matched structure information is retrieved in the database according to the predicted molecular formula.

[0068] Specifically, the mass of the quasi-molecular ion can be input into the Xcalibur software, and a predicted molecular formula of the potential target compound can be generated according to a preset molecular formula distribution rule. In an embodiment of the present application, the preset molecular formula distribution rule is: C 0-100 H 0-100 O 3-100 N 0-3 S 1-2 The number of oxygen atoms in the theoretical molecular formula should be greater than 3 because the purpose of the present application is to find a sulfur / sulfonic acid surfactant. It should also be noted that the parameter settings in the Xcalibur software, for example, the charge should be negative, and the unsaturation degree (RDBE) should be greater than 0.5 because the unsaturation degree of the sulfuric acid sulfonic ion is 0.5, and the error range is 5 ppm.

[0069] The obtained predicted molecular formula can be searched in the Pubchem database to obtain matched structure information (International Chemical Identifier, InChI), which is a possible structural formula.

[0070] 160、According to the matched structure information, simulated fragmentation is performed to obtain a simulated secondary mass spectrum.

[0071] The simulated fragmentation can be one or more, and the obtained simulated secondary mass spectrum can also include one or more. Specifically, the structure information InChI is imported into the Mass Froniter software and / or the CFM-ID website for simulated fragmentation to obtain a simulated secondary mass spectrum, which includes simulated fragment ion information such as structure, accurate mass, and fragmentation pathway. When using the Mass Froniter software, it should be noted that the negative mode is selected. In addition, when performing simulated fragmentation in the CFM-ID website, because the original data is obtained in the negative ion mode, the ion source should be selected as ESI-source in the CFM-ID website.

[0072] 170、The simulated secondary mass spectrum is compared with the actual secondary mass spectrum of the quasi-molecular ion, and the predicted structure of the potential target compound is determined according to the comparison result.

[0073] After the simulation fragmentation, the simulated secondary mass spectrum of each quasi-molecular ion obtained is compared with the actual secondary mass spectrum of the quasi-molecular ion, and the prediction structure of the potential target compound is determined according to the comparison result. When the simulated secondary mass spectrum of the quasi-molecular ion includes multiple, the multiple simulated secondary mass spectrums need to be compared with the actual secondary mass spectrum respectively. Specifically, the comparison result is specifically the number of mass spectrum peak matches, the simulated secondary mass spectrum of each quasi-molecular ion obtained is compared with the actual secondary mass spectrum of the quasi-molecular ion to count the number of mass spectrum peak matches between the simulated secondary mass spectrum of each quasi-molecular ion and the actual secondary mass spectrum of the quasi-molecular ion, and the structure information corresponding to the quasi-molecular ion with the most number of mass spectrum peak matches is determined as the prediction structure of the potential target compound. Wherein, the most number of mass spectrum peak matches indicates that the structure is most consistent with the actual situation.

[0074] Wherein, in order to obtain the actual secondary mass spectrum of the quasi-molecular ion of the real potential target compound, the sample will be tested and analyzed again in the ultra-high performance liquid chromatography coupled with high resolution mass spectrometer (UPLC-HRMS). The mass spectrum condition is reset, the scanning mode is parallel reaction monitoring (PRM) mode, and the ionization mode is still selected as negative ion mode, and the mass of the potential quasi-molecular ion is introduced into the inclusion list of UPLC-HRMS.

[0075] Specifically, the actual fragment ion information can be obtained by the following implementation: introducing the mass of the quasi-molecular ion of the potential target compound into the inclusion list of UPLC-HRMS to obtain the actual secondary mass spectrum of the quasi-molecular ion of the potential target compound in the PRM mode.

[0076] 180、According to the actual secondary mass spectrum of the quasi-molecular ion, the potential target compound is identified as a sulfated surfactant or a sulfonated surfactant.

[0077] Wherein, if the first preset fragment ion and the second fragment ion exist in the actual secondary mass spectrum of the quasi-molecular ion at the same time, the potential target compound is a sulfated surfactant; if only the first preset fragment ion exists in the actual secondary mass spectrum of the quasi-molecular ion, and the second fragment ion does not exist, the potential target compound is a sulfonated surfactant. Wherein, the first preset fragment ion refers to the fragment ion with m / z=79.9567, and the second fragment ion refers to the fragment ion with m / z=96.9588. Finally, the identification result that the target compound is a sulfated surfactant or a sulfonated surfactant and its prediction structure are output as a screening result together. Through the prediction structure, a possible structural formula output can be provided in addition to identifying sulfated / sulfonated surfactants, which is more accurate.

[0078] In the actual sample case, the data file raw file obtained by the instrument is converted into an mzXML format file by using software ProteoWizard-MSConvert, and then is imported into an R language data processing program for screening, and a total of 20 potential quasi-molecular ion information (including retention time, accurate mass, and peak intensity) is obtained. First, a secondary chromatogram of a characteristic ion m / z = 79.9567 is obtained, as shown in FIG. 2.

[0079] The time corresponding to the peak of the characteristic ion obtained by the chromatogram is obtained, and in the present application, a total of 6 peaks are obtained by using a centwave function in an xcms package of R language, and then the primary mass spectrum data corresponding to the six peak times is screened and filtered.

[0080] Taking one of the peaks as an example, the peak has a total of 818 parent ion information (including accurate mass and peak intensity), and the parent ions are further filtered and screened by using the mass difference of sulfur element isotopes 1.99475-1.99685. Finally, the peak intensity ratio of two parent ions containing sulfur isotopes is calculated, and if the ratio is located in 2.26%-6.78%, the parent ion with smaller mass is selected as the quasi-molecular ion. Finally, three parent ions are selected from the 818 parent ions as quasi-molecular ions of potential target compounds, and the masses of the three parent ions are 309.1742, 297.153, and 265.1479, respectively. The mass of the quasi-molecular ion is brought into software Xcalibur to assign a molecular formula, and the assignment rule is C 0-100 H 0-100 O 3-100 N 0-3 S 1-2 , charge is selected as negative electricity, unsaturation (RDBE) is greater than 0.5, and the error range is 5ppm. Finally, the molecular formulas of the three parent ions are C 14 H 29 O5S, C 16 H 25 O3S, and C 12 H 25 O4S. The obtained molecular formula is searched for possible molecular formula structures in a Pubchem website.

[0081] InChI containing structure information is imported into Mass Froniter software and / or CFM-ID website to simulate fragmentation to obtain possible fragment ion information, that is, to simulate a secondary mass spectrum. The mass of the obtained potential quasi-molecular ion is imported into an inclusion list, and an actual secondary mass spectrum is obtained by a PRM mode of the instrument UPLC-HRMS.

[0082] The actual obtained secondary mass spectrum information is matched with the simulated secondary mass spectrum information obtained by the Mass Froniter software and / or the CFM-ID website to determine the predicted structures of the three potential parent ions, as shown in FIGS. 3 to 5. Meanwhile, according to their actual secondary mass spectrum diagrams, it is known that their categories are sulfate, sulfonate and sulfonate, respectively.

[0083] The above steps are repeated to analyze all peaks. Finally, 19 sulfur / sulfonate compounds are found in the sample, and the specific information is shown in Table 2 below.

[0084] Table 2 Basic information of compounds obtained in the sample

[0085] In addition, 20 products are selected as research objects. The categories are mainly shampoo, shower gel, facial cleanser and other washing and protecting products. Among them, 10 products have the use of sulfur / sulfonate surfactants marked on the raw material label and are set as positive samples. Another ten samples have no mark of using sulfur / sulfonate surfactants on the label and are set as negative samples. Finally, by using the method for screening, it is found that some products or raw material labels of the positive samples only mark the content of sodium lauryl sulfate or sodium laureth sulfate, but the test results show that there are other kinds of sulfur / sulfonate surfactants in the products. At the same time, low content of sulfur / sulfonate surfactants is also found in the negative samples. Finally, a total of 38 sulfur / sulfonate surfactant compounds are screened out. The results are shown in Table 3 below:

[0086] Table 3 38 sulfur / sulfonate surfactant compounds

[0087] As shown in FIG. 6, the embodiment of the present application discloses a sulfur / sulfonate surfactant intelligent screening device, which comprises:

[0088] The scanning unit 601 is used for pretreating and performing ultra-high performance liquid chromatography-high resolution mass spectrometry on the to-be-tested sample to obtain raw data of the to-be-tested sample;

[0089] The filtering unit 602 is used for converting the raw data into an mzXML format file, screening and filtering all secondary mass spectrum peaks in the mzXML format file, and selecting target secondary mass spectrum peaks containing characteristic ions;

[0090] The extraction unit 603 is used for extracting primary mass spectrum data corresponding to the target secondary mass spectrum peaks from the mzXML format file, and the primary mass spectrum data includes the mass and peak intensity of all parent ions.

[0091] The computing unit 604 is configured to calculate the mass difference of the two parent ions, and if the mass difference of the two parent ions is within the range of the mass difference of sulfur element isotopes, calculate the peak intensity ratio of the two parent ions.

[0092] The selecting unit 605 is configured to select the parent ion with lower mass as the quasi-molecular ion of the potential target compound if the peak intensity ratio is within the specified range.

[0093] The generating unit 606 is configured to generate the predicted molecular formula of the potential target compound according to the mass of the quasi-molecular ion of the potential target compound, and search for the matched structure information in the database according to the predicted molecular formula.

[0094] The simulating unit 607 is configured to simulate fragmentation according to the matched structure information to obtain a simulated secondary mass spectrum.

[0095] The comparing unit 608 is configured to compare the simulated secondary mass spectrum with the actual secondary mass spectrum of the quasi-molecular ion, and determine the predicted structure of the potential target compound according to the comparison result.

[0096] The identifying unit 609 is configured to identify the potential target compound as a sulfate surfactant or a sulfonate surfactant according to the actual secondary mass spectrum of the quasi-molecular ion.

[0097] Optionally, the apparatus further comprises an acquisition unit (not shown) configured to introduce the mass of the quasi-molecular ion of the potential target compound into the inclusion list of the UPLC-HRMS before the comparing unit compares the simulated secondary mass spectrum with the actual secondary mass spectrum of the quasi-molecular ion, so as to acquire the actual secondary mass spectrum of the quasi-molecular ion of the potential target compound in the PRM mode.

[0098] Optionally, the identifying unit is specifically configured to determine that the potential target compound is a sulfate surfactant when the first preset fragment ion and the second preset fragment ion both exist in the actual secondary mass spectrum of the quasi-molecular ion, and determine that the potential target compound is a sulfonate surfactant when only the first preset fragment ion exists in the actual secondary mass spectrum of the quasi-molecular ion without the second preset fragment ion.

[0099] Optionally, the first fragment ion refers to a fragment ion with m / z=79.9567, and the second fragment ion refers to a fragment ion with m / z=96.9588.

[0100] As shown in FIG. 7, the embodiment of the present application discloses an electronic device, which comprises a memory 701 storing executable program codes and a processor 702 coupled with the memory 701.

[0101] The processor 702 invokes the executable program code stored in the memory 701 to execute the intelligent screening method of the sulfur / sulfonate surfactant described in the above embodiments.

[0102] The embodiment of the present application also discloses a computer readable storage medium which stores a computer program, wherein the computer program enables a computer to execute the intelligent screening method of the sulfur / sulfonate surfactant described in the above embodiments.

[0103] The above embodiments are intended to exemplarily reproduce and deduce the technical solutions of the present application, and to completely describe the technical solutions, objects and effects of the present application, so as to make the public more thoroughly and comprehensively understand the disclosed content of the present application, and not to limit the protection scope of the present application.

[0104] The above embodiments are not exhaustive enumeration based on the present application, and there can be a plurality of other embodiments not listed. Any replacement and improvement made without violating the concept of the present application is within the protection scope of the present application.

Claims

1. A method for intelligent screening of sulfur / sulfonate surfactants, characterized by, The method comprises the following steps: performing pretreatment and UPLC-HRMS scanning on the sample to be tested to obtain raw data of the sample to be tested; converting the raw data into an mzXML format file, screening and filtering all secondary mass spectrometry peaks in the mzXML format file, and selecting target secondary mass spectrometry peaks containing characteristic ions; extracting primary mass spectrometry data corresponding to the target secondary mass spectrometry peaks from the mzXML format file, wherein the primary mass spectrometry data comprises mass and peak intensity of all parent ions; calculating the mass difference between two parent ions, and if the mass difference between the two parent ions is within the mass difference range of sulfur isotopes, calculating the peak intensity ratio of the two parent ions; if the peak intensity ratio is within a specified ratio range, selecting the parent ion with lower mass among the two parent ions as a quasi-molecular ion of a potential target compound; generating a predicted molecular formula of the potential target compound according to the mass of the quasi-molecular ion of the potential target compound, searching for matched structure information in a database according to the predicted molecular formula, and simulating fragmentation according to the matched structure information to obtain a simulated secondary mass spectrometry diagram; comparing the simulated secondary mass spectrometry diagram with an actual secondary mass spectrometry diagram of the quasi-molecular ion, and determining the predicted structure of the potential target compound according to the comparison result; identifying the potential target compound as a sulfate surfactant or a sulfonate surfactant according to the actual secondary mass spectrometry diagram of the quasi-molecular ion. Before the step of comparing the simulated secondary mass spectrometry diagram with the actual secondary mass spectrometry diagram of the quasi-molecular ion, the method further comprises:

2. The sulfur / sulfonate surfactant intelligent screening method of claim 1, wherein, importing the mass of the quasi-molecular ion of the potential target compound into an inclusion list of UPLC-HRMS to obtain the actual secondary mass spectrometry diagram of the quasi-molecular ion of the potential target compound in a PRM mode. The step of identifying the potential target compound as a sulfate surfactant or a sulfonate surfactant according to the actual secondary mass spectrometry diagram of the quasi-molecular ion comprises:

3. The sulfur / sulfonate surfactant intelligent screening method of claim 1, wherein, if the first preset fragment ion and the second preset fragment ion both exist in the actual secondary mass spectrometry diagram of the quasi-molecular ion, determining that the potential target compound is a sulfate surfactant; if only the first preset fragment ion exists in the actual secondary mass spectrometry diagram of the quasi-molecular ion, determining that the potential target compound is a sulfonate surfactant. The first fragment ion refers to a fragment ion with m / z=79.9567, and the second fragment ion refers to a fragment ion with m / z=96.9588.

4. The sulfur / sulfonate surfactant intelligent screening method according to claim 3, wherein, The method comprises the following steps:

5. A sulfur / sulfonate surfactant intelligent screening device, characterized in that, a scanning unit for performing pretreatment and UPLC-HRMS scanning on a sample to be tested to obtain raw data of the sample to be tested; a filtering unit for converting the raw data into an mzXML format file, screening and filtering all secondary mass spectrometry peaks in the mzXML format file, and selecting target secondary mass spectrometry peaks containing characteristic ions; an extraction unit for extracting primary mass spectrometry data corresponding to the target secondary mass spectrometry peaks from the mzXML format file, wherein the primary mass spectrometry data comprises mass and peak intensity of all parent ions; ​ The computing unit is configured to calculate the mass difference of the two parent ions, and if the mass difference of the two parent ions is within the range of the mass difference of sulfur element isotopes, calculate the peak intensity ratio of the two parent ions. The selecting unit is configured to select the parent ion with lower mass as the quasi-molecular ion of the potential target compound if the peak intensity ratio is within a specified range. The generating unit is configured to generate a predicted molecular formula of the potential target compound according to the mass of the quasi-molecular ion of the potential target compound, and search for matched structure information in a database according to the predicted molecular formula. The simulating unit is configured to simulate fragmentation according to the matched structure information to obtain a simulated secondary mass spectrum. The comparing unit is configured to compare the simulated secondary mass spectrum with an actual secondary mass spectrum of the quasi-molecular ion, and determine the predicted structure of the potential target compound according to the comparison result. The identifying unit is configured to identify the potential target compound as a sulfate surfactant or a sulfonate surfactant according to the actual secondary mass spectrum of the quasi-molecular ion.

6. The sulfur / sulfonate surfactant intelligent screening device of claim 5, wherein, Further comprising: The acquiring unit is configured to import the mass of the quasi-molecular ion of the potential target compound into the inclusion list of the UPLC-HRMS before the comparing unit compares the simulated secondary mass spectrum with the actual secondary mass spectrum of the quasi-molecular ion, so as to acquire the actual secondary mass spectrum of the quasi-molecular ion of the potential target compound in the PRM mode.

7. The sulfur / sulfonate surfactant intelligent screening device of claim 5, wherein, The identifying unit is specifically configured to determine that the potential target compound is a sulfate surfactant when the first preset fragment ion and the second preset fragment ion exist simultaneously in the actual secondary mass spectrum of the quasi-molecular ion, and determine that the potential target compound is a sulfonate surfactant when only the first preset fragment ion exists in the actual secondary mass spectrum of the quasi-molecular ion without the second preset fragment ion.

8. The sulfur / sulfonate surfactant intelligent screening device of claim 7, wherein, The first fragment ion refers to a fragment ion with m / z=79.9567, and the second fragment ion refers to a fragment ion with m / z=96.9588.

9. An electronic device, comprising: The computer readable storage medium stores a computer program, wherein the computer program enables the computer to execute the intelligent screening method of the sulfate surfactant.

10. A computer-readable storage medium, characterized in that, The computer readable storage medium stores a computer program, wherein the computer program enables the computer to execute the intelligent screening method of the sulfate surfactant.

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