CN117976097A - Establishment and application method, device and equipment of glucocorticoid mass spectrum database - Google Patents
Establishment and application method, device and equipment of glucocorticoid mass spectrum database Download PDFInfo
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Abstract
The invention belongs to the technical field of cosmetic detection, and discloses an automatic establishment method, device and equipment of a glucocorticoid mass spectrum database, wherein the method comprises the following steps: obtaining simplified molecular linear input standard text of a plurality of glucocorticoid compounds to be converted into a molecular structure, and obtaining mass-to-charge ratio of parent ions by hydrogenating ions; searching target specific groups according to a specific sequence to simulate breakage, and calculating the mass-to-charge ratio of characteristic fragment ions; the target specific groups are part or all of a plurality of preset specific fracture groups, the mass-to-charge ratio of parent ions and the mass-to-charge ratio of each characteristic fragment ion are summarized to obtain a simulated mass spectrogram, and the simulated mass spectrogram is arranged into csv files according to TRACEFINDER database format to form a glucocorticoid mass spectrum database, so that the coverage range of the database can be expanded to 7199 types; and discloses a quasi-targeting screening method for the glucocorticoid in the cosmetics based on the database, so that the glucocorticoid can be accurately screened from mass spectrum data of collected mass samples, and the screening efficiency and accuracy are improved.
Description
Technical Field
The invention belongs to the technical field of cosmetic detection, and particularly relates to a method, a device, equipment and a storage medium for establishing and applying a glucocorticoid mass spectrum database.
Background
In recent years, the problem of illegal addition of cosmetics has been attracting attention from consumers and market regulatory authorities. The cosmetic is easy to add glucocorticoid (glucocorticoids, GCs) illegally in freckle removing and whitening cosmetics and masks, skin is fast in whitening and fine in skin feel when the cosmetics are used in early stage, but long-term continuous use can cause local side effects such as skin vasodilation, hormone-dependent dermatitis and irreversible skin atrophy, and even can cause serious systematic damage such as osteoporosis, hypertension and diabetes, so that relevant regulations are made to prohibit the addition of glucocorticoid in the cosmetics. Glucocorticoids have pharmacological actions such as anti-inflammation and immunosuppression and are generally used for treating allergic and inflammatory diseases. Depending on the combination of different groups and the spatial configuration, the number of glucocorticoid compounds can reach thousands of, and the number of pairs of detection techniques and market supervision present great challenges.
Currently, the conventional methods for detecting glucocorticoids mainly include thin layer chromatography (THIN LAYER chromatography, TLC), gas chromatography mass spectrometry, high performance liquid chromatography (High Performance Liquid Chromatography, HPLC), liquid chromatography-mass spectrometry (liquid Chromatograph Mass Spectrometer, LC-MS/MS), liquid chromatography-high resolution mass spectrometry, and the like. The traditional detection method generally adopts standard substances for the qualitative and quantitative detection of the known glucocorticoids, has limited coverage, and is difficult to detect for the unknown glucocorticoids.
Disclosure of Invention
The invention aims to provide a method, a device, equipment and a storage medium for establishing and applying a glucocorticoid mass spectrum database, which can enlarge the coverage range of the glucocorticoid, thereby improving the accuracy of screening results.
The first aspect of the invention discloses a method for establishing a mass spectrum database of a glucocorticoid, wherein the method for establishing the mass spectrum database is executed by computer equipment, the computer equipment is provided with executable program codes, and the computer equipment calls the executable program codes to execute the method for establishing the mass spectrum database; the method for establishing the mass spectrum database comprises the following steps:
The computer device obtains simplified molecular linear input canonical texts of a plurality of sample objects, wherein the sample objects are glucocorticoid compounds and/or derivatives of glucocorticoid compounds;
the computer device converting the reduced molecular linear input specification text for each of the sample objects into a component structure;
The computer equipment hydrogenates the molecular structure to obtain positively charged molecular ions serving as parent ions, and calculates the mass-to-charge ratio of the parent ions;
The computer equipment searches target specific groups in a parent ion structure according to a specific sequence, sequentially carries out simulated fracture on the target specific groups, and calculates the mass-to-charge ratio of characteristic fragment ions obtained after each fracture; wherein the target specific group is part or all of a plurality of preset specific cleavage groups, and the plurality of specific cleavage groups comprise C=C ortho-ring-F, dihydro-oxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C5 or less ring alkanoyloxy, C=C non-ortho-ring-F, C6 or less non-ring alkanoyloxy, phosphate, oxazolidinyl, C-Cl, C alkoxy, C-Br, carbomethylcarbonium positive ions;
the computer equipment gathers the mass-to-charge ratio of the parent ions and the mass-to-charge ratio of each characteristic fragment ion to obtain a simulated mass spectrogram of each sample object;
The computer equipment sorts the simulated mass spectrograms of each sample object into a csv file according to TRACEFINDER database format to form a glucocorticoid mass spectrum database.
The invention discloses a quasi-targeting screening method of glucocorticoid in cosmetics, which is implemented by computer equipment, wherein the computer equipment is provided with a controller and a data memory which are connected with a liquid chromatograph high-resolution mass spectrometer, and TRACEFINDER software is installed on the computer equipment and used for implementing the quasi-targeting screening method; the quasi-targeting screening method comprises the following steps:
the computer equipment acquires mass spectrum data of a sample to be detected;
the computer equipment performs chromatographic peak extraction on mass spectrum data of a sample to be detected to obtain a primary mass spectrum peak and a secondary mass spectrum peak;
The computer equipment matches the primary mass spectrum peak with parent ions in a glucocorticoid mass spectrum database, and calculates the mass error of the parent ions and the matching degree of isotope distribution;
And if the mass error of the parent ion is smaller than the specified error and the isotope distribution matching degree is larger than the specified matching degree, the computer equipment matches the secondary mass spectrum peak with fragment ions in the glucocorticoid mass spectrum database to obtain a matching result.
The third aspect of the invention discloses a device for establishing a glucocorticoid mass spectrum database, which comprises the following steps:
A text acquisition unit for acquiring simplified molecular linear input canonical texts of several sample objects, wherein the sample objects are glucocorticoid compounds and/or derivatives of glucocorticoid compounds;
A conversion unit for converting the simplified molecular linear input specification text of each of the sample objects into a component structure;
The simulated ionization unit is used for hydrogenating the molecular structure to obtain positively charged molecular ions serving as parent ions, and calculating the mass-to-charge ratio of the parent ions;
The simulated breaking unit is used for searching target specific groups in the parent ion structure according to a specific sequence, sequentially performing simulated breaking on the target specific groups, and calculating the mass-to-charge ratio of the characteristic fragment ions obtained after each breaking; wherein the target specific group is part or all of a plurality of preset specific cleavage groups, and the plurality of specific cleavage groups comprise C=C ortho-ring-F, dihydro-oxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C5 or less ring alkanoyloxy, C=C non-ortho-ring-F, C6 or less non-ring alkanoyloxy, phosphate, oxazolidinyl, C-Cl, C alkoxy, C-Br, carbomethylcarbonium positive ions;
the summarizing unit is used for summarizing the mass-to-charge ratio of the parent ions and the mass-to-charge ratio of each characteristic fragment ion to obtain a simulated mass spectrogram of each sample object;
And the sorting unit is used for sorting the simulated mass spectrograms of each sample object into csv files according to TRACEFINDER database format to form a glucocorticoid mass spectrum database.
The fourth aspect of the invention discloses a quasi-targeting screening device for glucocorticoid in cosmetics, which is applied to the glucocorticoid mass spectrum database in the third aspect, and comprises the following components:
The data acquisition unit is used for acquiring mass spectrum data of the sample to be detected;
The extraction unit is used for extracting chromatographic peaks from the mass spectrum data of the sample to be detected to obtain a primary mass spectrum peak and a secondary mass spectrum peak;
the first matching unit is used for matching the primary mass spectrum peak with parent ions in the glucocorticoid mass spectrum database and calculating the mass error of the parent ions and the matching degree of isotope distribution;
and the second matching unit is used for matching the secondary mass spectrum peak with fragment ions in the glucocorticoid mass spectrum database when the mass error of the parent ions is smaller than the specified error and the isotope distribution matching degree is larger than the specified matching degree, so as to obtain a matching result.
A fifth aspect of the invention discloses a computer device comprising a memory storing executable program code and a processor coupled to the memory; the processor invokes the executable program code stored in the memory for performing the method of establishing a glucocorticoid mass spectrometry database as disclosed in the first aspect.
A sixth aspect of the present invention discloses a computer-readable storage medium storing a computer program, wherein the computer program causes a computer to execute the method of establishing a glucocorticoid mass spectrum database disclosed in the first aspect.
The beneficial effects of the invention include:
(1) The glucocorticoid has the same cyclopentanol phenanthrene mother nucleus structure, and has stronger mass spectrum fracture specificity. According to the invention, on the basis of researching and analyzing a plurality of glucocorticoid secondary mass spectrograms, the glucocorticoid specific property spectrum breaking rule is summarized and obtained, and a glucocorticoid specific property spectrum breaking algorithm program is independently developed by adopting a computer programming technology, so that the automatic establishment and screening method application of a glucocorticoid mass spectrum database are realized.
(2) The invention can automatically simulate the mass spectrum breaking process of the glucocorticoid and can generate glucocorticoid characteristic fragment ions in a one-bond batch mode. At the same time, expanding glucocorticoid compounds to 7199 species by means of the internet large-scale chemical substance database, the structure of which represents almost all available glucocorticoids and their derivatives, increases the coverage of screening.
(3) The invention utilizes a developed mass spectrum fracture algorithm program to simulate fracture of a glucocorticoid compound, constructs a large-scale glucocorticoid mass spectrum database, adopts ultra-high performance liquid chromatography-quadrupole-electrostatic field orbit ion trap mass spectrum (UHPLC-Q-Orbitrap MS) to collect data, utilizes TRACEFINDER software to perform data processing, and establishes a glucocorticoid quasi-targeting screening analysis technology. The technology can accurately screen out the glucocorticoid and the derivatives thereof in mass high-resolution mass spectrum data.
(4) Compared with the prior art, the method greatly improves the coverage of the glucocorticoid compound, and the constructed glucocorticoid mass spectrum database is used for rapidly screening and identifying the glucocorticoid in cosmetics. The invention sets parameters of <5ppm of parent ion mass error, more than 90% of isotope distribution matching, <5ppm of secondary fragment mass error, more than or equal to 2 of matching quantity, reaches 7 identification points, is far more than at least 4 Identification Points (IPs) required by regulations, and greatly improves identification accuracy. The method can directly output the screening result, greatly reduces manual intervention, reduces analysis difficulty and time investment, and greatly improves screening efficiency and accuracy.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles and effects of the invention.
Unless specifically stated or otherwise defined, the same reference numerals in different drawings denote the same or similar technical features, and different reference numerals may be used for the same or similar technical features.
FIG. 1 is a flow chart of a method of establishing a glucocorticoid mass spectrometry database in accordance with the present disclosure;
FIG. 2 is a schematic representation of the chemical structure of the glucocorticoids disclosed in the present invention;
FIG. 3 is a flow chart illustrating the detailed execution of step 140 of FIG. 1 in accordance with the present disclosure;
FIG. 4 is a flow chart of a method of quasi-targeted screening of glucocorticoids in cosmetics according to the present disclosure;
FIG. 5 is a schematic diagram of a device for establishing a mass spectrum database of glucocorticoids according to the present invention;
FIG. 6 is a schematic diagram of a quasi-targeting screening device for glucocorticoids in cosmetics according to the present invention;
fig. 7 is a schematic structural diagram of a computer device according to the present disclosure.
Reference numerals illustrate:
401. A text acquisition unit; 402. a conversion unit; 403. a simulated ionization unit; 404. simulating a breaking unit; 405. a summarizing unit; 406. a finishing unit; 501. a data acquisition unit; 502. an extraction unit; 503. a first matching unit; 504. a second matching unit; 601. a memory; 602. a processor.
Detailed Description
Unless defined otherwise or otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In the context of a realistic scenario in connection with the technical solution of the invention, all technical and scientific terms used herein may also have meanings corresponding to the purpose of the technical solution of the invention. The terms "first" and "second" … "as used herein are used merely for distinguishing between names and not necessarily for describing a particular amount or sequence. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
It will be understood that when an element is referred to as being "fixed" to another element, it can be directly fixed to the other element or intervening elements may also be present; when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present; when an element is referred to as being "mounted to" another element, it can be directly mounted to the other element or intervening elements may also be present. When an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present.
As used herein, unless specifically stated or otherwise defined, "the" means that the feature or technical content mentioned or described before in the corresponding position may be the same or similar to the feature or technical content mentioned. Furthermore, the terms "comprising," "including," and "having," as well as any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.
The embodiment of the invention discloses a method for establishing a glucocorticoid mass spectrum database, which realizes automatic establishment of the glucocorticoid mass spectrum database through computer programming. The execution subject of the method is computer equipment or a device for establishing a glucocorticoid mass spectrum database embedded in the computer equipment, and the invention is not limited to the method. In order to facilitate understanding of the present invention, a computer device will be used as a main body for execution, and specific embodiments of the present invention will be described in more detail with reference to the accompanying drawings. Wherein the computer device is provided with executable program code, which is called by the computer device for executing the method for establishing the mass spectrum database.
As shown in fig. 1, the method for establishing the mass spectrum database includes the following steps 110 to 160:
110. The computer device obtains a reduced molecular linear input specification for several sample objects, wherein the sample objects are glucocorticoid compounds and/or derivatives of glucocorticoid compounds.
Wherein the sample object may be a glucocorticoid and its derivative range extended by means of an internet large-scale chemical substance database covering almost all available glucocorticoid compounds. Illustratively, 100 glucocorticoid compounds are used as a parent nucleus structure, an Internet large compound database PubChem is used as a data source, glucocorticoids and derivatives thereof are obtained through structural similarity matching, a list is downloaded, repetition and structural confirmation are removed, enantiomers are combined, and 7199 types of available glucocorticoids and derivatives thereof are finally obtained, wherein the available glucocorticoids cover almost all types of available glucocorticoids and derivatives thereof.
120. The computer device converts the reduced molecular linear input specification text for each sample object into a molecular structure.
Structural information of the glucocorticoid compound to be broken is entered in a simplified molecular linear input specification (SMILES) text and converted by a computer device into a computer-recognizable molecular structure mol. The glucocorticoid structure is shown in figure 2.
130. The computer equipment hydrogenates the molecular structure to obtain the molecular ion with positive charge as the parent ion, and calculates the mass-to-charge ratio of the parent ion.
In this step, in order to simulate ESI + ionization, the computer device adds H + to the molecular structure to obtain glucocorticoid molecular ions, uses the glucocorticoid molecular ions as glucocorticoid parent ions, and can calculate and output the mass-to-charge ratio m/z of the parent ions.
140. The computer equipment searches target specific groups in the parent ion structure according to a specific sequence, sequentially carries out simulated fracture on the target specific groups, and calculates the mass-to-charge ratio of the characteristic fragment ions obtained after each fracture.
It should be noted that the target specific group may have one or more, and may be a part or all of a plurality of preset specific cleavage groups. The preset specific cleavage groups can be summarized according to the molecular structure of the glucocorticoid compound and the corresponding secondary mass spectrum data of the glucocorticoid compound and the cleavage process of the glucocorticoid specific cleavage groups. The predetermined plurality of specific cleavage groups may include C=C ortho-ring-F, dihydrooxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C < 5 ring alkanoyloxy, C < 6 non-ring alkanoyloxy, phosphate, oxazolidinyl, ring-Cl, ring alkoxy, ring-Br, carbomethyl carbonium. Illustratively, the following table 1 shows 16 groups:
TABLE 1 glucocorticoid-specific cleavage groups and cleavage process thereof
As glucocorticoid molecules form positively charged excimer ions after ionization of ESI + ion sources, the excimer ions are broken by collisions with 10-30NCE energy in a high energy collision cell. The breaking process of the glucocorticoid molecules is researched, and if 16 groups in the table 1 exist in the glucocorticoid molecules, the breaking process can be carried out, and when two or more groups appear, the breaking of different groups can be carried out in a certain sequence and is related to the molecular structure.
The plurality of preset specific cleavage groups in table 1 may be combined into three cleavage sequences, each comprising a plurality of specific cleavage groups and their cleavage sequences, e.g., a first cleavage sequence a, a second cleavage sequence B, and a third cleavage sequence C. Wherein the first cleavage sequence A is { dihydro-oxazolyl, -OH on the ring, alkanoyloxy on the ring with a number of carbon atoms not less than 5, acyclic alkanoyloxy with a number of carbon atoms not less than 6, acetal, alkanoyloxy on the ring, cyclic-F other than C=C ortho; the second cleavage sequence B is { -F, dihydro-oxazolyl, C.gtoreq.5-ring alkanoyloxy, C.gtoreq.6-ring-not-ring alkanoyloxy, acetal, C.gtoreq.C.o-ring-F, C.gtoreq.o-ring-OH }; the third cleavage sequence C is { cyclic alkanoyloxy, phosphate, oxazolidinyl, acyclic alkanoyloxy, cyclic-Cl, cyclic alkoxy, -OH, cyclic-Br, -OH, carbomethylcarbonium }.
Thus, the specific sequence may be a combination of the first and third fragmentation sequences, or the specific sequence may also be a combination of the second and third fragmentation sequences. In step 140, it may be first determined whether a specific cleavage group-F is present on the c=c ortho ring of the parent ion structure; if no specific cleavage group-F is present on the ring ortho to c=c, then the specific sequence of the combination of the first cleavage sequence a and the third cleavage sequence C is employed; if a specific cleavage group-F is present on the ring in the ortho position to C=C, the specific sequence of the combination of the second cleavage sequence B and the third cleavage sequence C is used.
The first fragmentation sequence a has a higher priority than the third fragmentation sequence C, and the second fragmentation sequence B has a higher priority than the third fragmentation sequence C. That is, if no specific cleavage group-F appears on the C=C ortho ring, the specific sequence is { dihydro-oxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetals, ring alkanoyloxy, ring-F other than the C=C ortho position, ring alkanoyloxy, phosphate, oxazolidinyl, non-ring alkanoyloxy, ring-Cl, ring alkoxy, -OH, ring-Br, -OH, carbomethylcarbonium }; if a specific cleavage group-F appears on the C=C ortho ring, the specific sequence is { C=C ortho ring-F, dihydro oxazolyl, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, ring alkanoyloxy, non-c=c ortho ring-F, ring-OH, ring alkanoyloxy, phosphate, oxazolidinyl, non-ring alkanoyloxy, ring-Cl, ring alkoxy, -OH, ring-Br, -OH, carbomethylcarbonium }.
When searching target specific groups according to a specific sequence, traversing each preset specific cleavage group in the specific sequence, sequentially searching the same target specific groups in the molecular structure, and performing simulated cleavage every time one target specific group is searched in the molecular structure. Sequentially until all specific cleavage groups in a particular sequence are traversed. Specifically, the execution flow of step 140 may be as shown in fig. 3. Searching the groups in the molecular structure according to the sequence of FIG. 3, if the groups in the table 1 exist, performing simulated fracture according to the fracture process, namely, breaking chemical bonds, losing corresponding groups, calculating broken fragment ions m/z, and continuously performing operations of searching the groups- > breaking the groups- > outputting fragments after the fragments are broken until all the groups are searched.
150. The computer equipment gathers the mass-to-charge ratio of the parent ions and the mass-to-charge ratios of the individual characteristic fragment ions to obtain simulated mass spectrograms of each sample object.
160. The computer equipment sorts the simulated mass spectrograms of each sample object into csv files according to TRACEFINDER database format to form a glucocorticoid mass spectrum database.
Wherein the csv file is a table with ID of each sample object, reduced molecular linear input canonical text, parent ion and feature fragment ion m/z. In the subsequent data analysis method, the glucocorticoid mass spectrum database has a decisive effect on the matching result, and the more glucocorticoid compounds are contained in the glucocorticoid mass spectrum database, the wider the screening range is, so that the accuracy of the screening result can be improved. In order to realize automation of glucocorticoid screening, a glucocorticoid mass spectrum database is imported into TRACEFINDER 4.1.1 software in a specific format to realize automation of screening of actual sample data.
In summary, the embodiment of the invention realizes the large-scale expansion of the glucocorticoid mass spectrum database by summarizing the breaking rule of the glucocorticoid compound specific property spectrum, and greatly improves the screening coverage of the glucocorticoid compound in cosmetics.
As shown in fig. 4, the embodiment of the invention also discloses a glucocorticoid quasi-targeting screening method in cosmetics, which is implemented by a computer device provided with a controller and a data memory connected with a liquid chromatograph high-resolution mass spectrometer, and is implemented by TRACEFINDER software, wherein the glucocorticoid mass spectrum database constructed by the embodiment is applied to the glucocorticoid quasi-targeting screening method in cosmetics; the quasi-targeting screening method comprises the following steps 310-330:
310. the computer equipment acquires mass spectrum data of the sample to be detected, and performs chromatographic peak extraction on the mass spectrum data of the sample to be detected to obtain a primary mass spectrum peak and a secondary mass spectrum peak.
Specifically, a Hypersil Gold C18 column (50 mm. Times.2.1 mm,1.9 μm) was used as the HPLC column. The gradient elution procedure was adjusted according to the column adaptation, under which conditions 100 glucocorticoid compounds were efficiently separated and peak-shaped symmetrically. The method can effectively elute most of glucocorticoid compounds by setting 100% acetonitrile elution for 2min aiming at the fact that unknown glucocorticoid compounds possibly have larger log P values.
By adopting an ESI + mode, the first-level resolution is 70000, the second-level resolution is 17500, and the mass scanning range m/z is 200-1500,3 different Normalized Collision Energies (NCEs) 10, 20 and 35 are respectively overlapped after collision. Under the condition of mass spectrum, most glucocorticoid compounds have certain response and can normally collect primary mass spectrum peaks and secondary mass spectrum peaks.
320. The computer equipment matches the primary mass spectrum peak with the parent ions in the glucocorticoid mass spectrum database, and calculates the mass error of the parent ions and the matching degree of isotope distribution.
Specifically, the manner in which the computer device calculates the mass error of the parent ion in step 320 may be:
The computer equipment matches the primary mass spectrum peak with parent ions in the glucocorticoid mass spectrum database, and then calculates the mass error of the parent ions according to the actually measured mass-to-charge ratio of the ions and the theoretical mass-to-charge ratio of the ions. For example, by the following formula (1):
where E represents the parent ion mass error, m c represents the ion measured mass-to-charge ratio, and m 0 represents the ion theoretical mass-to-charge ratio.
The manner in which the computer device calculates the isotope distribution match in step 320 may be:
The computer equipment matches the primary mass spectrum peak with parent ions in a glucocorticoid mass spectrum database, calculates the similarity between the actual measurement intensities of a plurality of isotope mass spectrum peaks and the theoretical intensities of corresponding isotope mass spectrum peaks, and determines the similarity as isotope distribution matching degree. Preferably, a plurality of isotope mass spectrometry peaks with measured intensities > 2% can be selected for calculation.
By way of example, it can be calculated by the following formula (2):
Wherein MA represents the matching degree of isotope distribution, mi represents the actual measurement intensity of the ith isotope mass spectrometry peak, ti represents the theoretical intensity of the ith isotope mass spectrometry peak, and n represents the total number of isotope mass spectrometry peaks.
330. If the mass error of the parent ion is smaller than the specified error and the isotope distribution matching degree is larger than the specified matching degree, the computer equipment matches the secondary mass spectrum peak with fragment ions in the glucocorticoid mass spectrum database to obtain a matching result.
For example, if the mass error of the parent ion is <5ppm and the isotope distribution matching degree is > 90%, the first-order mass spectrum peak is judged to pass through the matching. After the primary mass spectrum peak is matched, automatically running and matching according to set parameters (the mass error of the secondary fragments is less than 5ppm and the matching quantity is more than or equal to 2), if the mass error of the secondary fragments is less than 5ppm, the matching of the fragments is successful, if the matching quantity is more than or equal to 2, the matching of the secondary mass spectrum peak and the compounds in the database is successful, the more the number of the secondary fragments is successful, the higher the accuracy is, and finally the matched compounds in the database are output as matching results.
In summary, the method uses software TRACEFINDER 4.1.1, sets parameters such as mass error of parent ion <5ppm, isotope distribution matching > 90%, mass error of secondary fragments <5ppm, matching quantity is more than or equal to 2, reaches 7 identification points, is far more than at least 4 Identification Points (IPs) required by regulations, and greatly improves identification accuracy. The method can directly output the screening result, greatly reduces manual intervention, reduces analysis difficulty and time investment, and greatly improves screening efficiency and accuracy.
The quasi-targeting screening method provided by the invention is used for screening 955 batches of glucocorticoids in the circulating cosmetics, and 12 batches (see Table 2) of positive samples are detected to totally relate to 10 glucocorticoids. 6 of the compositions are common glucocorticoids, and the content is 6.1 mg/kg-16.2 mg/kg. In addition, the crude glucocorticoids are novel glucocorticoids screened for the first time from actual samples on the market, the content of the novel glucocorticoids is 5.4 mg/kg-28.6 mg/kg, and related departments can strengthen supervision on illegal addition of the novel glucocorticoids. The result shows that the method is applied to large-scale rapid screening of the glucocorticoid in the cosmetics, has great technical advantages in the aspects of screening coverage, accuracy and automation degree, and has wide application prospect.
TABLE 2 screening of actual samples for Positive results
The quasi-targeting screening method established by the invention is adopted to screen and analyze the actual sample of the cosmetics. Screening results show extracted ion flow chromatograms and partial matching conditions, wherein bishydroxyfluocinolone acetonide shows parent ions [ C 21H26F2O6+H]+ (m/z 413.1770, error-1.59 ppm), parent ion isotope matching score is 100%, parent ion isotope distribution mass spectrum peaks match all 5, secondary mass spectrum peaks match 5, and the display results are matched. The fragment M/z 393.1708 and error-3.86ppm are [ M+H-HF ] + fragment ions obtained by neutral losing HF of [ M+H ] + parent ions; fragment M/z 373.1646, error-0.05ppm [ M+H-2HF ] + fragment ion obtained by continuing neutral loss of HF for [ M+H-HF ] + ion; h 2 O (fragment m/z 355.1540, error-3.12 ppm), (fragment m/z 337.1434,error 1.61ppm), (fragment m/z 319.1329,error 0.01ppm) was continuously lost, and as a result 1 parent ion, 5 secondary fragments, discrimination point=2+2.5×5=14.5, i.e. a total of 14.5 discrimination points were reached, far greater than the 4 discrimination points required by the regulations. Meanwhile, the screening result is consistent with the control validation result, which shows that the method has the characteristics of high accuracy and high automation degree, can automatically match to obtain a correct result and has a huge coverage of compounds.
As shown in fig. 5, the embodiment of the invention discloses a device for establishing a glucocorticoid mass spectrum database, which comprises a text acquisition unit 401, a conversion unit 402, a simulated ionization unit 403, a simulated fracture unit 404, a summarization unit 405 and a finishing unit 406, wherein,
A text acquisition unit 401 for acquiring simplified molecular linear input canonical texts of several sample objects, wherein the sample objects are glucocorticoid compounds and/or derivatives of glucocorticoid compounds;
a conversion unit 402 for converting the simplified molecular linear input specification text of each sample object into a component structure;
The simulated ionization unit 403 is used for hydrogenating the molecular structure to obtain positively charged molecular ions as parent ions, and calculating the mass-to-charge ratio of the parent ions;
The simulated breaking unit 404 is configured to search a target specific group in the parent ion structure according to a specific sequence, sequentially perform simulated breaking on the target specific group, and calculate a mass-to-charge ratio of the characteristic fragment ion obtained after each breaking; wherein the target specific group is part or all of a plurality of preset specific cleavage groups, and the plurality of specific cleavage groups comprise C=C ortho-ring-F, dihydro-oxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C5 or less ring alkanoyloxy, C=C non-ortho-ring-F, C6 or less non-ring alkanoyloxy, phosphate, oxazolyl, C-Cl, C alkoxy, C-Br, and carbomethyl carbonium.
A summarizing unit 405, configured to summarize the mass-to-charge ratio of the parent ion and the mass-to-charge ratio of each characteristic fragment ion, and obtain a simulated mass spectrogram of each sample object;
And the sorting unit 406 is configured to sort the simulated mass spectrograms of each sample object into a csv file according to TRACEFINDER database format, so as to form a glucocorticoid mass spectrum database.
As shown in fig. 6, an embodiment of the present invention discloses a quasi-targeting screening device for glucocorticoids in cosmetics, which comprises a data acquisition unit 501, an extraction unit 502, a first matching unit 503, and a second matching unit 504, wherein,
A data acquisition unit 501, configured to acquire mass spectrum data of a sample to be measured;
the extraction unit 502 is configured to perform chromatographic peak extraction on mass spectrum data of a sample to be detected, so as to obtain a primary mass spectrum peak and a secondary mass spectrum peak;
A first matching unit 503, configured to match the primary mass spectrum peak with parent ions in the glucocorticoid mass spectrum database, and calculate a parent ion mass error and an isotope distribution matching degree;
And the second matching unit 504 is configured to match the secondary mass spectrum peak with fragment ions in the glucocorticoid mass spectrum database when the mass error of the parent ion is smaller than the specified error and the isotope distribution matching degree is greater than the specified matching degree, so as to obtain a matching result.
As shown in fig. 7, an embodiment of the present invention discloses a computer apparatus including a memory 601 storing executable program codes and a processor 602 coupled to the memory 601;
Wherein the processor 602 invokes the executable program code stored in the memory 601 to perform the method of establishing a glucocorticoid mass spectrometry database as described in the above embodiments.
The embodiment of the invention also discloses a computer readable storage medium storing a computer program, wherein the computer program enables a computer to execute the establishment of the glucocorticoid mass spectrum database or the quasi-targeting screening method of the glucocorticoids in cosmetics described in the above embodiments.
The foregoing embodiments are provided for the purpose of exemplary reproduction and deduction of the technical solution of the present invention, and are used for fully describing the technical solution, the purpose and the effects of the present invention, and are used for enabling the public to understand the disclosure of the present invention more thoroughly and comprehensively, and are not used for limiting the protection scope of the present invention.
The above examples are also not an exhaustive list based on the invention, and there may be a number of other embodiments not listed. Any substitutions and modifications made without departing from the spirit of the invention are within the scope of the invention.
Claims (10)
1. The method for establishing the glucocorticoid mass spectrum database is characterized in that the method for establishing the mass spectrum database is executed by computer equipment, the computer equipment is provided with executable program codes, and the computer equipment calls the executable program codes and is used for executing the method for establishing the mass spectrum database; the method for establishing the mass spectrum database comprises the following steps:
The computer device obtains simplified molecular linear input canonical texts of a plurality of sample objects, wherein the sample objects are glucocorticoid compounds and/or derivatives of glucocorticoid compounds;
the computer device converting the reduced molecular linear input specification text for each of the sample objects into a component structure;
The computer equipment hydrogenates the molecular structure to obtain positively charged molecular ions serving as parent ions, and calculates the mass-to-charge ratio of the parent ions;
The computer equipment searches target specific groups in a parent ion structure according to a specific sequence, sequentially carries out simulated fracture on the target specific groups, and calculates the mass-to-charge ratio of characteristic fragment ions obtained after each fracture; wherein the target specific group is part or all of a plurality of preset specific cleavage groups, and the plurality of specific cleavage groups comprise C=C ortho-ring-F, dihydro-oxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C5 or less ring alkanoyloxy, C=C non-ortho-ring-F, C6 or less non-ring alkanoyloxy, phosphate, oxazolidinyl, C-Cl, C alkoxy, C-Br, carbomethylcarbonium positive ions;
the computer equipment gathers the mass-to-charge ratio of the parent ions and the mass-to-charge ratio of each characteristic fragment ion to obtain a simulated mass spectrogram of each sample object;
The computer equipment sorts the simulated mass spectrograms of each sample object into a csv file according to TRACEFINDER database format to form a glucocorticoid mass spectrum database.
2. A method of establishing a glucocorticoid mass spectrometry database according to claim 1,
If no specific cleavage group-F appears on the C=C ortho ring of the parent ion structure, the specific sequence is { dihydro-oxazolyl group, -OH on the ring, alkanoyloxy on the ring with the number of carbon atoms being more than or equal to 5, acyclic alkanoyloxy with the number of carbon atoms being more than or equal to 6, acetals, ring alkanoyloxy, ring-F other than the C=C ortho position, ring alkanoyloxy, phosphate, oxazolidinyl, non-ring alkanoyloxy, ring-Cl, ring alkoxy, -OH, ring-Br, -OH, carbomethylcarbonium }.
3. A method of establishing a glucocorticoid mass spectrometry database according to claim 1,
If a specific cleavage group-F appears on the C=C ortho ring of the parent ion structure, the specific sequence is { C=C ortho ring-F, dihydrooxazolyl, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C=C ortho ring-F, C-OH, C-alkanoyloxy, phosphate, oxazolyl, C-C, C-Cl, C-alkoxy, -OH, C-Br, -OH, carbomethyl carbonium }.
4. A quasi-targeted screening method of glucocorticoid in cosmetics, applying the glucocorticoid mass spectrometry database of any one of claims 1 to 3, characterized in that the quasi-targeted screening method is performed by a computer device provided with a controller and a data memory connected to a liquid chromatography high resolution mass spectrometer, the computer device being installed with TRACEFINDER software for performing the quasi-targeted screening method, the quasi-targeted screening method comprising:
the computer equipment acquires mass spectrum data of a sample to be detected;
the computer equipment performs chromatographic peak extraction on mass spectrum data of a sample to be detected to obtain a primary mass spectrum peak and a secondary mass spectrum peak;
The computer equipment matches the primary mass spectrum peak with parent ions in a glucocorticoid mass spectrum database, and calculates the mass error of the parent ions and the matching degree of isotope distribution;
And if the mass error of the parent ion is smaller than the specified error and the isotope distribution matching degree is larger than the specified matching degree, the computer equipment matches the secondary mass spectrum peak with fragment ions in the glucocorticoid mass spectrum database to obtain a matching result.
5. The method for quasi-targeted screening of glucocorticoids in cosmetics according to claim 4, wherein the specified error is 5ppm and the specified matching degree is 90%.
6. A device for establishing a glucocorticoid mass spectrometry database, comprising:
A text acquisition unit for acquiring simplified molecular linear input canonical texts of several sample objects, wherein the sample objects are glucocorticoid compounds and/or derivatives of glucocorticoid compounds;
A conversion unit for converting the simplified molecular linear input specification text of each of the sample objects into a component structure;
The simulated ionization unit is used for hydrogenating the molecular structure to obtain positively charged molecular ions serving as parent ions, and calculating the mass-to-charge ratio of the parent ions;
The simulated breaking unit is used for searching target specific groups in the parent ion structure according to a specific sequence, sequentially performing simulated breaking on the target specific groups, and calculating the mass-to-charge ratio of the characteristic fragment ions obtained after each breaking; wherein the target specific group is part or all of a plurality of preset specific cleavage groups, and the plurality of specific cleavage groups comprise C=C ortho-ring-F, dihydro-oxazolyl, ring-OH, C5 or more ring alkanoyloxy, C6 or more non-ring alkanoyloxy, acetal, C5 or less ring alkanoyloxy, C=C non-ortho-ring-F, C6 or less non-ring alkanoyloxy, phosphate, oxazolidinyl, C-Cl, C alkoxy, C-Br, carbomethylcarbonium positive ions;
the summarizing unit is used for summarizing the mass-to-charge ratio of the parent ions and the mass-to-charge ratio of each characteristic fragment ion to obtain a simulated mass spectrogram of each sample object;
And the sorting unit is used for sorting the simulated mass spectrograms of each sample object into csv files according to TRACEFINDER database format to form a glucocorticoid mass spectrum database.
7. A quasi-targeted screening device for glucocorticoids in cosmetics, applying the mass spectrum database of glucocorticoids according to claim 6, characterized in that the quasi-targeted screening device comprises:
The data acquisition unit is used for acquiring mass spectrum data of the sample to be detected;
The extraction unit is used for extracting chromatographic peaks from the mass spectrum data of the sample to be detected to obtain a primary mass spectrum peak and a secondary mass spectrum peak;
the first matching unit is used for matching the primary mass spectrum peak with parent ions in the glucocorticoid mass spectrum database and calculating the mass error of the parent ions and the matching degree of isotope distribution;
and the second matching unit is used for matching the secondary mass spectrum peak with fragment ions in the glucocorticoid mass spectrum database when the mass error of the parent ions is smaller than the specified error and the isotope distribution matching degree is larger than the specified matching degree, so as to obtain a matching result.
8. A computer device comprising a memory storing executable program code and a processor coupled to the memory; the processor invokes the executable program code stored in the memory for performing the method of establishing a glucocorticoid mass spectrometry database according to any one of claims 1 to 3.
9. Computer device, characterized in that it comprises a controller connected to a liquid chromatograph high-resolution mass spectrometer and a data memory, said data memory being equipped with TRACEFINDER software, said controller calling said TRACEFINDER software for performing the quasi-targeted screening method of glucocorticoids in cosmetics according to claim 4 or 5.
10. A computer-readable storage medium, characterized in that the computer-readable storage medium stores a computer program, wherein the computer program causes a computer to execute the method of establishing a glucocorticoid mass spectrum database according to any one of claims 1 to 3.
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