CN113514529B - Method for rapidly detecting photoinitiator in cigarette paper - Google Patents
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Abstract
The invention discloses a method for rapidly detecting a photoinitiator in cigarette paper. The method adopts an in-situ mass spectrometry detection method to detect the 18 photoinitiators in the cigarette paper, and can realize the rapid detection of the 18 photoinitiator components in the cigarette paper without any pretreatment process on the cigarette paper. The method can be used for detecting the photoinitiator in a paper sample with a complex matrix, the sensitivity of the photoinitiator detection is high, the detection limit and the quantitative limit of the detection are far smaller than the numerical values measured by the traditional gas chromatography-mass spectrometry method, and the detected detection Limit (LOD) is 0.002-0.045 mg/m 2 The limit of quantitation (LOQ) is 0.006-0.15 mg/m 2 (ii) a The detection time is short, and high-throughput detection can be performed; the matrix effect is small, and the detection can be carried out on actual complex samples; the requirement of modern product quality safety management and control on rapid detection is met.
Description
Technical Field
The invention relates to a method for detecting harmful components in cigarette paper, in particular to a method for quickly and efficiently detecting 18 photoinitiators in the cigarette paper by using an in-situ mass spectrometry detection method, and belongs to the field of analysis of harmful components in the cigarette paper.
Background
The cigarette paper is an indispensable important component part for producing cigarette products, has important functions in the processes of developing new products, reducing tar release amount, reducing harmful substances and the like, and directly influences the quality and the production cost of the cigarette products.
The photoinitiator is also called as a light curing agent, is a compound which can absorb energy with certain wavelength in an ultraviolet light region or a visible light region to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers, and is a main component of printing ink. When photoinitiators harmful to human bodies are used in printing ink for cigarette box packaging paper, the photoinitiators are harmful to human health through contact with human bodies and other ways. Studies have shown that photoinitiators may have an effect on the secretory system in humans, and some of the photoinitiators have been shown to be carcinogenic, skin contact toxic, and reproductive toxic.
The mass spectrometry technology is known as the "gold standard" of chemical analysis because of its characteristics of high sensitivity, good specificity, fast response speed, easy automation and the like. The innovation and improvement of ion sources as the inlet and core components of mass spectrometry instruments continuously push the leap-over development of mass spectrometry technology, which represents the development of mass spectrometry technology to some extent.
The mass spectrometry ionization technology used by the existing detection method has the common characteristics that: 1) Closed ionization, in which a sample to be analyzed is enclosed in a certain tube (e.g. ESI, APCI) or a certain vacuum environment (e.g. EI, CI, MALDI, etc.); 2) The necessary sample pre-treatment, which often takes hours or more, consumes a lot of manpower, time and solvents.
After the generation of electro-spray desorption ion source (DESI) technology and real-time direct analysis technology (DART) in 2004, the arrival of the new era of research on the atmospheric rapid mass spectrometry technology was marked.
In 2015, chinese patent CN 110400740A disclosed a novel in situ ionization mass spectrometry technique, i.e., a flame ion source.
When the traditional detection method is used for qualitatively or quantitatively detecting the photoinitiator in the cigarette paper, due to the influence of a complex matrix, the complex pretreatment work of the object to be detected before ionization comprises the steps of paper sample cutting, soaking, extracting, oscillating, centrifuging and the like, and then the subsequent mass spectrometry detection can be carried out after the components of the object to be detected are separated by adopting the separation technology such as gas chromatography or liquid chromatography and the like, so that the time of hours or more is usually needed, and a large amount of manpower, solvents and time are consumed.
Disclosure of Invention
Aiming at the defects existing in the qualitative or quantitative detection of the photoinitiator in the cigarette paper in the prior art, the invention aims to provide a method for realizing the in-situ rapid detection of the photoinitiator in the cigarette paper. When the method provided by the invention is adopted to detect the photoinitiator in the cigarette paper, no pretreatment is needed, the detection sensitivity of the photoinitiator is high, and the detected detection limit and the quantitative limit are far smaller than the numerical values detected by the traditional gas chromatography-mass spectrometry method; the detection time is greatly shortened, and high-throughput detection can be carried out; the matrix effect is small, and the actual complex sample can be detected; the requirement of modern product quality safety control on rapid detection is met.
In order to achieve the technical purpose, the invention provides a method for rapidly detecting 18 photoinitiators in cigarette paper, which adopts an in-situ mass spectrometry detection method to detect the 18 photoinitiators in the cigarette paper.
As a preferred scheme, the cigarette paper is cigarette case wrapping paper containing an ink coating.
As a preferred scheme, the 18 kinds of photoinitiators in the cigarette paper include: 2-hydroxy-2-methyl-1-phenylacetone, methyl benzoylformate, benzophenone, 2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-N, N-dimethylaminobenzoate, 3-methylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-2-phenylacetophenone, methyl benzoylbenzoate, isooctyl p-dimethylaminobenzoate, 2-methyl-1- (4-methylthio) phenyl 2-morpholinyl-1-propanone, 4-isopropylthioxanthone, 2-isopropylthioxanthone, biphenyl benzophenone, 2,4-diethylthioxanthone, 4,4-bis (dimethylamino) benzophenone, and 4,4-bis (diethylamino) benzophenone.
As a preferable scheme, the in-situ mass spectrometry detection method adopts a hydrogen flame desorption ion source and a triple quadrupole mass analyzer. The technical scheme of the invention selects hydrogen flame to analyze the state of the ion source to have no special requirements on the state of the target substance, has rapid detection and high sensitivity, can tolerate various solvents, but can also detect more non-target compound peaks, and can make qualitative and quantitative determination more accurate by combining various different working modes of the triple quadrupole mass analyzer on the basis.
As a preferable scheme, the in-situ mass spectrum detection method adopts a forceps handle sample introduction method or an in-situ ultrasonic extraction method.
As a preferred scheme, when the forceps handle sample injection method is adopted, the in-situ mass spectrum detection method comprises the following steps:
1) Cutting cigarette paper into strips;
2) Adjusting the length of a hydrogen flame of the hydrogen flame desorption ion source device and the distance parameter from the tail end of a hydrogen flame pipeline to an ion transmission pipe;
3) Setting an acquisition mode and mass spectrum parameters of a triple quadrupole mass analyzer;
4) And clamping strip cigarette paper by using tweezers, placing the strip cigarette paper on a hydrogen flame for detection, and analyzing data according to a signal peak detected and displayed by an instrument.
As a preferred scheme, when the in-situ ultrasonic extraction method is adopted, the in-situ mass spectrum detection method comprises the following steps:
1) Making cigarette paper into a wafer through a puncher;
2) An ultrasonic atomization sheet is arranged between the hydrogen flame desorption ion source device and the ion transmission pipe;
3) Placing a cigarette paper wafer on an ultrasonic atomization sheet, and dropwise adding an extracting agent on the cigarette paper wafer;
4) Setting an acquisition mode and mass spectrum parameters of a triple quadrupole mass analyzer;
5) The plasma generated by the hydrogen flame desorption ion source device and the spray generated by the ultrasonic atomization sheet under the ultrasonic action are subjected to charge transfer and energy transfer to generate ions, and the ions enter an ion transmission pipe for detection to generate a signal peak.
As a preferable scheme, the size of the cut cigarette paper can be adjusted according to actual needs, mainly for the convenience of clamping by tweezers, but generally the cut cigarette paper should be smaller than 2cm x 2cm, and preferably 0.2-0.8cm x 0.8-1.5 cm strips. Most preferably 0.5cm x 1.0 cm.
As a preferable scheme, the vertical distance from the ultrasonic atomization sheet to the ion transmission tube is 1.0-1.3 cm.
As a preferable scheme, the diameter of the ultrasonic atomization sheet is 1.6 cm-2.5 cm, and the diameter of the round sheet of the paper for the cigarette is smaller than that of the ultrasonic atomization sheet. The ultrasonic atomization plate preferably has a diameter of 2.0cm.
As a preferred scheme, the length of the hydrogen flame is 2.0-7.0 mm, and the temperature is 350-520 ℃; more preferably, the hydrogen flame length is 3.5 to 5.0mm and the temperature is 400 to 430 ℃.
As a preferred scheme, the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe is 1.3-1.7 cm, the hydrogen flame and the ion transmission pipe are on the same horizontal line, and a selective reaction monitoring mode can be adopted for detecting and colliding characteristic fragment ions to collect data.
As a preferred scheme, a positive ion detection mode is selected for collection by a triple quadrupole mass analyzer, no voltage is applied, and the temperature of an ion transmission tube is set to 275 ℃; under the full-scanning mode, the scanning mass range is m/z 50-m/z 600, the scanning width of Q1 is 0.7u, the auxiliary solvent is methanol or acetone, and the flow rate is set to be 5-70 mu L/min; in the multiple reaction monitoring mode, the peak width of Q1 was 0.70u, the scanning time was 0.5s, the scanning width was 1.0u, and the CID Gas was set to 1.5mTorr.
As a preferred scheme, the parent ions and qualitative and quantitative ions of the 18 photoinitiator components set in the positive ion detection mode are as follows: 2-hydroxy-2-methyl-1-phenylacetone: excimer ion [ M + H] + m/z:165; characteristic fragment ions: 119,91,129,147; methyl benzoylformate: excimer ion [ M + H] + m/z:165; characteristic fragment ions: 105,77; IIBenzophenone: excimer ion [ M + H] + m/z:183; characteristic fragment ions: 105,77; 2-methylbenzophenone: excimer ion [ M + H] + m/z:197; characteristic fragment ions: 105,119,77; 1-hydroxycyclohexyl phenyl ketone: excimer ion [ M + H] + m/z:205; characteristic fragment ions: 105,149,77,187, 184; ethyl p-N, N-dimethylaminobenzoate: excimer ion [ M + H] + m/z:194; characteristic fragment ions: 151,166,134,179; 3-methylbenzophenone: excimer ion [ M + H] + m/z:197; characteristic fragment ions: 105,119,77; 4-methylbenzophenone: excimer ion [ M + H] + m/z:197; characteristic fragment ions: 105,119;2,2-dimethoxy-2-phenylacetophenone: excimer ion [ M + H] + m/z:257; characteristic fragment ions: 215,186; methyl o-benzoylbenzoate: excimer ion [ M + H] + m/z:241, a first electrode and a second electrode; characteristic fragment ions: 209,153; isooctyl p-dimethylaminobenzoate: excimer ion [ M + H] + m/z:278; characteristic fragment ions: 151,166; 2-methyl-1- (4-methylthio) phenyl-2-morpholinyl-1-propanone: excimer ion [ M + H] + m/z:280 parts of; characteristic fragment ions: 165; 4-isopropylthioxanthone: excimer ion [ M + H] + m/z:255; characteristic fragment ions: 213,184; 2-isopropyl thioxanthone: excimer ion [ M + H] + m/z:255; characteristic fragment ions: 213; biphenyl benzophenone: excimer ion [ M + H] + m/z:259; characteristic fragment ions: 105,77,153,181;2,4-diethylthioxanthone: excimer ion [ M + H] + m/z:269; characteristic fragment ions: 213,241;4,4-bis (dimethylamino) benzophenone: excimer ion [ M + H] + m/z:269; characteristic fragment ions: 148,210;4,4-bis (diethylamino) benzophenone: excimer ion [ M + H] + m/z:325; characteristic fragment ions: 281,176.
As a preferred scheme, the optimal collision energy of 18 photoinitiator components set in the positive ion detection mode: 2-hydroxy-2-methyl-1-phenylacetone: 15eV; methyl benzoylformate: 15eV; benzophenone: 20eV; 2-methylbenzophenone: 20eV; 1-hydroxycyclohexyl phenyl ketone: 18eV; ethyl p-N, N-dimethylaminobenzoate: 25eV; 3-methylbenzophenone: 18eV; 4-methylbenzophenone: 20eV;2,2-dimethoxy-2-phenylacetophenone: 30eV; methyl o-benzoylbenzoate: 25eV; isooctyl p-dimethylaminobenzoate: 25eV; 2-methyl-1- (4-methylthio) phenyl-2-morpholinyl-1-propanone: 25eV; 4-isopropylthioxanthone: 25eV; 2-isopropyl thioxanthone: 20eV; biphenyl benzophenone: 25eV;2,4-diethylthioxanthone: 30eV;4,4-bis (dimethylamino) benzophenone: 30eV;4,4-bis (diethylamino) benzophenone: 28eV.
In the process of directly detecting the photoinitiator in the paper sample for the cigarette by adopting an in-situ mass spectrometry detection method, when a forceps handle sample introduction method is utilized, the method comprises the following steps:
(1) Firstly, cutting a strip with a proper size from the cigarette paper according to the test requirement;
(2) The ion source device is well built, the length of the hydrogen flame is adjusted to be 5mm, and the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe is 1.3cm;
(3) The mass spectrum acquisition adopts an MRM mode, detected parent ions, qualitative and quantitative ions and corresponding collision energy are filled in the mass spectrum parameter setting, and the scanning width is as follows: 1.0u; scanning time: 0.5s; peak width of Q1: 0.7u; q2 CID gas:1.5mTorr. The paper strips are clamped by tweezers and are put on a hydrogen flame for detection, an instrument detects and displays signal peaks, and then data are analyzed.
In the process of directly detecting the photoinitiator in the paper sample for the cigarette by adopting an in-situ mass spectrometry detection method, the method comprises the following steps of:
(1) The ion source device is well built, an ultrasonic atomization sheet is arranged between the hydrogen flame ion source and the ion transmission tube, and the vertical distance from the ultrasonic atomization sheet to the ion transmission tube is about 1.2cm;
(2) Putting the tobacco paper round sheet punched by the puncher on the atomizing sheet;
(3) And (3) dropping an extracting agent on the paper during testing, and detecting the spray generated by extraction. The mass spectrum acquisition adopts an MRM mode, detected parent ions, qualitative and quantitative ions and corresponding collision energy are filled in the mass spectrum parameter setting, and the scanning width is as follows: 1.0u; scanning time: 0.5s; peak width of Q1: 0.7u; q2 CID gas:1.5mTorr. The plasma generated by the ion source and the spray generated by the atomization sheet in an ultrasonic mode generate charge transfer and energy transfer, and the generated ions enter the ion transmission pipe to be detected to generate a signal peak.
In the process of directly detecting the photoinitiator in the paper sample for the cigarette by adopting an in-situ mass spectrometry detection method, the method for judging the detection conclusion comprises the following steps: comparing the MRM total ion flow diagram of the sample to be detected with the total ion flow diagram in the blank solution to judge whether the paper for cigarettes contains the photoinitiator; namely, if the intensity of the secondary fragment ions of the sample to be detected is not changed compared with the intensity of the blank solution, judging that the photoinitiator is not contained in the sample to be detected; namely, if the intensity of the secondary fragment ions of the sample to be detected is higher than that of the blank solution, the photoinitiator in the sample to be detected is judged.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the technical scheme of the invention adopts an in-situ ionization mass spectrometry technology to realize in-situ real-time and high-flux detection of 18 photoinitiators in cigarette paper, solves the problems of complicated detection pretreatment process, long detection time, large solvent consumption and the like of 18 photoinitiators in cigarette paper by an original standard method through optimization of ion source parameters and selection of a proper extracting agent and a sample introduction method, and has irreplaceable advantages in detection efficiency; the sensitivity is high, the detected detection limit and the quantitative limit are far smaller than the numerical values detected by the traditional gas chromatography-mass spectrometry, and the detected detection Limit (LOD) is 0.002-0.045 mg/m 2 The limit of quantitation (LOQ) is 0.006-0.15 mg/m 2 (ii) a The matrix effect is small when the developed method is applied to testing, and the method can be used for detecting actual complex samples. The requirement of modern product quality safety management and control on rapid detection is met.
Drawings
FIG. 1 is a schematic diagram of the optimization of flame temperature and flame length conditions;
FIG. 2 is a schematic diagram illustrating optimization of the distance condition from the end of the hydrogen pipe to the ion transport tube;
FIG. 3 is a mass spectrum of 18 photoinitiators in full sweep mode;
FIG. 4 is a MS/MS mass spectrum of the photoinitiator.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The invention adopts an in-situ mass spectrometry detection method to directly detect the photoinitiator in the paper sample for cigarettes:
1) Firstly, optimizing detection conditions: the photoinitiator is detected by utilizing a hydrogen flame ion source, benzophenone with the concentration of 10 mu g/mL is selected as a target compound at the initial stage to carry out an experiment, different auxiliary solvents are screened (methanol, acetone, acetonitrile, dichloromethane and the like are tried, the effect of acetonitrile and dichloromethane is found to be poor because the intermiscibility of the benzophenone with the target compound is poor, the effect of methanol and acetone is good, but the dissolving capacity of acetone to ink is stronger, and the acetone is finally selected), different hydrogen and nitrogen ratios (the flame length is different and the flame temperature is different by adjusting the different ratios of hydrogen and nitrogen), the distance from the tail end of a hydrogen pipeline to an ion transmission pipe and other conditions are adjusted, so that the excimer ion peak m/z 183 of the benzophenone with high strength is obtained. A schematic diagram for optimizing the conditions of flame temperature and flame length is shown in fig. 1 (fig. 1 can see that the size is about 5mm, the temperature is about 420 ℃, which is the optimal condition, and the distance from the end of the hydrogen pipe to the ion transport pipe is adjusted on the basis of the optimal condition), and a schematic diagram for optimizing the conditions of the distance from the end of the hydrogen pipe to the ion transport pipe is shown in fig. 2. The optimal detection conditions obtained after optimization are as follows: the mass analyzer is a triple quadrupole and is set to be in a positive ion detection mode, no voltage is applied, and the temperature of an ion transmission tube is set to be 275 ℃; in a full-scanning mode, the scanning mass range is m/z 50-m/z 600, the scanning width of Q1 is 0.7u, the auxiliary solvent is acetone, and the flow rate is set to be 25 mu L/min; in the multiple reaction monitoring mode, the peak width of Q1 was 0.70u, the scanning time was 0.5s, the scanning width was 1.0u, and the CID Gas was set to 1.5mTorr; the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe is 1.3cm; the size of the hydrogen flame is about 5mm, and the temperature is about 420 ℃; the hydrogen flame and the ion transmission pipe are on the same horizontal line; data can be collected using a selective reaction monitoring mode for detection and collision of characteristic fragment ions.
2) Finding out the characteristic secondary fragment ions and the optimal collision energy of each photoinitiator under the optimized condition; because the mass spectrum is a low-resolution mass spectrum, the existence of the detected substance cannot be determined only by detecting the molecular ion peak, and the detection condition of the mass spectrum is as follows: the mass analyzer is a triple quadrupole (Thermo Fisher Scientific, TSQ Quantum Access); the auxiliary solvent is acetone, and the flow rate is set to be 25 mu L/min; the temperature of the ion transmission tube is set to 275 ℃; the peak width of Q1 was 0.70u; CID Gas is set to be 1.5mTorr; without voltage, in the test, a full scan mode is firstly used by using a peristaltic pump direct sample injection mode, a photoinitiator mixed standard solution with the concentration of 10 mu g/mL is used as a test object, and the [ M + H ] of each photoinitiator is found by using an in-situ ultrasonic extraction sample injection mode] + Peak, as shown in fig. 3, the ion source has different hardness and hardness, and the characteristic fragment ions generated by MS/MS analysis on the same substance are also different, and the characteristic fragment ions generated by using the method are shown in table 1; FIG. 4 illustrates an example of p-benzophenone excimer ion [ M + H ]] + MS/MS analysis was performed to obtain the major characteristic fragment ions m/z 105 and m/z 77.
TABLE 1 qualitative and quantitative ions of 18 photoinitiators
Because the paper substrate for the cigarette is complex, when the photoinitiator exists or not, the MRM (multiple reaction monitoring) mode is selected to determine through secondary characteristic fragment ions.
In order to make the relative abundance of the qualitative and quantitative ions as high as possible and improve the detection sensitivity, the collision energy of the above 18 photoinitiators was optimized when they were detected using the hydrogen flame desorption mass spectrometry technique, and the results are shown in table 2 below.
TABLE 2 optimal Collision energy of 18 photoinitiators when using a Hydrogen flame ion Source
3) And detecting the actual sample, and inspecting the influence magnitude of the matrix effect and the detection limit and the quantification limit of each compound. A batch of positive samples was first prepared in situ. The method comprises the steps of firstly preparing a series of mixed standard solutions of photoinitiators with different concentrations, specifically, firstly preparing the mixed standard solution with the concentration of 100 mu g/mL, diluting the mixed standard solution step by step according to a conventional method, then dropwise adding the diluted mixed standard solution onto base paper of paper for cigarettes, drying the base paper, and then detecting the base paper by using a forceps handle sample injection mode, wherein secondary fragment ions of the photoinitiators can be detected by using an MRM mode, which shows that an in-situ mass spectrometry method can be used for detecting actual samples with complex matrixes.
When the forceps handle sample injection method is adopted, the method comprises the following steps:
(1) The ion source device is built, and the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe and the length adjustment of the hydrogen flame are adjusted according to the preferred scheme;
(2) The mass spectrum acquisition adopts an MRM mode, detected parent ions, qualitative and quantitative ions and corresponding collision energy are filled in the mass spectrum parameter setting, and the scanning width is as follows: 1.0u; scanning time: 0.5s; peak width of Q1: 0.7u; q2 CID gas:1.5mTorr.
(3) And (4) clamping the paper slip by using tweezers, putting the paper slip on a hydrogen flame for detection, detecting and displaying a signal peak by using an instrument, and finally analyzing.
The detection conclusion judging method compares the MRM total ion flow diagram of the sample to be detected with the total ion flow diagram of a blank solution to judge whether the paper for the cigarette contains the photoinitiator; namely, if the intensity of the secondary fragment ions of the sample to be detected is not changed compared with the intensity of the blank solution, judging that the photoinitiator is not contained in the sample to be detected; namely, if the intensity of the secondary fragment ions of the sample to be detected is higher than that of the blank solution, the photoinitiator in the sample to be detected is judged. The main types of photoinitiators in the paper for cigarettes include 2-hydroxy-2-methyl-1-phenylacetone, methyl benzoylformate, benzophenone, 2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-N, N-dimethylaminobenzoate, 3-methylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-2-phenylacetophenone, methyl o-benzoylbenzoate, isooctyl p-dimethylaminobenzoate, 2-methyl-1- (4-methylthio) phenyl 2-morpholinyl-1-propanone, 4-isopropylthioxanthone, 2-isopropylthioxanthone, biphenylbenzophenone, 2,4-diethylthioxanthone, 4,4-bis (dimethylamino) benzophenone, and 4,4-bis (diethylamino) benzophenone.
The detection limit and the quantification limit of each photoinitiator in the cigarette box packaging paper are compared with the detection results measured by the enterprise standard gas chromatography-mass spectrometry combination method for measuring the photoinitiators in YQ/T31-2013 cigarette strips and the cigarette box packaging paper, which is shown in the following table 3.
TABLE 3 detection and quantitation limits for 18 photoinitiators
The method realizes the in-situ real-time and high-flux detection of the 18 photoinitiators in the cigarette paper, solves the problems of complicated pretreatment process, long detection time, high solvent consumption and the like of the original standard method for the detection of the 18 photoinitiators in the cigarette paper, and has irreplaceable advantages in detection efficiency; the sensitivity is high, and the detected detection limit and the quantitative limit are far smaller than the values detected by the traditional gas chromatography-mass spectrometry method; the matrix effect is small, and the detection can be carried out on actual complex samples. The requirement of modern product quality safety management and control on rapid detection is met.
Claims (4)
1. A method for rapidly detecting photoinitiator in cigarette paper is characterized by comprising the following steps: detecting 18 photoinitiators in the cigarette paper by adopting an in-situ mass spectrometry detection method;
the in-situ mass spectrum detection method adopts a forceps handle sample introduction method or an in-situ ultrasonic extraction method;
when the forceps handle sample injection method is adopted, the in-situ mass spectrum detection method comprises the following steps:
1) Cutting the cigarette paper into strips; cutting a cigarette paper into strips with the size of 0.2-0.8cm x 0.8-1.5cm;
2) Adjusting the length of a hydrogen flame of the hydrogen flame desorption ion source device and the distance parameter from the tail end of a hydrogen flame pipeline to the ion transmission pipe; the length of the hydrogen flame is 2.0 to 7.0mm, and the temperature is 350 to 520 ℃; the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe is 1.3-1.7 cm, the hydrogen flame and the ion transmission pipe are on the same horizontal line, and a selective reaction monitoring mode can be adopted for detecting and colliding characteristic fragment ions to collect data;
3) Setting an acquisition mode and mass spectrum parameters of a triple quadrupole mass analyzer; a positive ion detection mode is selected for collection by a triple quadrupole mass analyzer, no voltage is applied, and the temperature of an ion transmission tube is set to 275 ℃; under a full-scanning mode, the scanning mass range is m/z50 to m/z600, the scanning width of Q1 is 0.7u, an auxiliary solvent is methanol or acetone, and the flow rate is set to be 5 to 70 mu L/min; in the multiple reaction monitoring mode, the peak width of Q1 is 0.70u, the scanning time is 0.5s, the scanning width is 1.0u, and the CID Gas is set to be 1.5mTorr;
4) Clamping strip cigarette paper by using tweezers, placing the cigarette paper on a hydrogen flame for detection, and analyzing data according to a signal peak detected and displayed by an instrument;
when the in-situ ultrasonic extraction method is adopted, the in-situ mass spectrum detection method comprises the following steps:
1) Making cigarette paper into a wafer through a puncher;
2) An ultrasonic atomization sheet is arranged between the hydrogen flame desorption ion source device and the ion transmission pipe; the vertical distance from the ultrasonic atomization sheet to the ion transmission tube is 1.0-1.3cm; the diameter of the ultrasonic atomization sheet is 1.6cm to 2.5cm, and the diameter of the round sheet of the paper for the cigarette is smaller than that of the ultrasonic atomization sheet;
3) Placing a cigarette paper wafer on an ultrasonic atomization sheet, and dropwise adding an extracting agent on the cigarette paper wafer;
4) Setting an acquisition mode and mass spectrum parameters of a triple quadrupole mass analyzer; a positive ion detection mode is selected for collection by a triple quadrupole mass analyzer, no voltage is applied, and the temperature of an ion transmission tube is set to 275 ℃; under a full-scanning mode, the scanning mass range is m/z50 to m/z600, the scanning width of Q1 is 0.7u, an auxiliary solvent is methanol or acetone, and the flow rate is set to be 5 to 70 mu L/min; in the multiple reaction monitoring mode, the peak width of Q1 is 0.70u, the scanning time is 0.5s, the scanning width is 1.0u, and the CID Gas is set to 1.5mTorr;
5) The plasma generated by the hydrogen flame desorption ion source device and the spray generated by the ultrasonic atomization sheet under the ultrasonic action are subjected to charge transfer and energy transfer to generate ions, and the ions enter an ion transmission tube for detection to generate a signal peak;
the 18 photoinitiators comprise: 2-hydroxy-2-methyl-1-phenylacetone, methyl benzoylformate, benzophenone, 2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-N, N-dimethylaminobenzoate, 3-methylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-2-phenylacetophenone, methyl benzoylbenzoate, isooctyl p-dimethylaminobenzoate, 2-methyl-1- (4-methylthio) phenyl 2-morpholinyl-1-propanone, 4-isopropylthioxanthone, 2-isopropylthioxanthone, biphenyl benzophenone, 2,4-diethylthioxanthone, 4,4-bis (dimethylamino) benzophenone, and 4,4-bis (diethylamino) benzophenone.
2. The method for rapidly detecting the photoinitiator in the cigarette paper according to claim 1, characterized by comprising the following steps: the cigarette paper is cigarette case wrapping paper containing an ink coating.
3. The method for rapidly detecting the photoinitiator in the cigarette paper as claimed in claim 1, wherein the method comprises the following steps: the parent ions and qualitative and quantitative ions of the 18 photoinitiator components set in the positive ion detection mode are as follows:
2-hydroxy-2-methyl-1-phenylacetone: excimer ion [ M + H] + m/z:165; characteristic fragment ions: 119,91,129,147;
methyl benzoylformate: excimer ion [ M + H] + m/z:165; characteristic fragment ions: 105,77;
benzophenone: excimer ion [ M + H] + m/z:183; characteristic fragment ions: 105,77;
2-methylbenzophenone: excimer ion [ M + H] + m/z:197; characteristic fragment ions: 105,119,77;
1-hydroxycyclohexyl phenyl ketone: excimer ion [ M + H] + m/z:205; characteristic fragment ions: 105,149,77,187, 184;
ethyl p-N, N-dimethylaminobenzoate: excimer ion [ M + H] + m/z:194; characteristic fragment ions: 151,166,134,179;
3-methylbenzophenone: excimer ion [ M + H] + m/z:197; characteristic fragment ions: 105,119,77;
4-methylbenzophenone: excimer ion [ M + H] + m/z:197; characteristic fragment ions: 105,119;
2,2-dimethoxy-2-phenylacetophenone: excimer ion [ M + H] + m/z:257; characteristic fragment ions: 215,186;
methyl o-benzoylbenzoate: excimer ion [ M + H] + m/z:241, a first electrode and a second electrode; characteristic fragment ions: 209,153;
isooctyl p-dimethylaminobenzoate: excimer ion [ M + H] + m/z:278; characteristic fragment ions: 151,166;
2-methyl-1- (4-methylthio) phenyl-2-morpholinyl-1-propanone: excimer ion [ M + H] + m/z:280 parts of; characteristic fragment ions: 165;
4-isopropylthioxanthone: excimer ion [ M + H] + m/z:255; characteristic fragment ions: 213,184;
2-isopropyl thioxanthone: excimer ion [ M + H] + m/z:255; characteristic fragment ions: 213;
biphenyl benzophenone: excimer ion [ M + H] + m/z:259; characteristic fragment ions: 105,77,153,181;
2,4-diethylthioxanthone: excimer ion [ M + H] + m/z:269; characteristic fragment ions: 213,241;
4,4-bis (dimethylamino) benzophenone: excimer ion [ M + H] + m/z:269; characteristic fragment ions: 148,210;
4,4-bis (diethylamino) benzophenone: excimer ion [ M + H] + m/z:325; characteristic fragment ions: 281,176.
4. The method for rapidly detecting the photoinitiator in the cigarette paper as claimed in claim 3, wherein the method comprises the following steps: optimal collision energy for 18 photoinitiator components set for positive ion detection mode:
2-hydroxy-2-methyl-1-phenylacetone: 15eV;
methyl benzoylformate: 15eV;
benzophenone: 20eV;
2-methylbenzophenone: 20eV;
1-hydroxycyclohexyl phenyl ketone: 18eV;
ethyl p-N, N-dimethylaminobenzoate: 25eV;
3-methylbenzophenone: 18eV;
4-methylbenzophenone: 20eV;
2,2-dimethoxy-2-phenylacetophenone: 30eV;
methyl o-benzoylbenzoate: 25eV;
isooctyl p-dimethylaminobenzoate: 25eV;
2-methyl-1- (4-methylsulfanyl) phenyl 2-morpholinyl-1-propanone: 25eV;
4-isopropylthioxanthone: 25eV;
2-isopropylthioxanthone: 20eV;
biphenyl benzophenone: 25eV;
2,4-diethylthioxanthone: 30eV;
4,4-bis (dimethylamino) benzophenone: 30eV;
4,4-bis (diethylamino) benzophenone: 28eV.
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