CN113567532A - Method for rapidly detecting phthalate ester components in cigarette paper - Google Patents
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- CN113567532A CN113567532A CN202010273882.4A CN202010273882A CN113567532A CN 113567532 A CN113567532 A CN 113567532A CN 202010273882 A CN202010273882 A CN 202010273882A CN 113567532 A CN113567532 A CN 113567532A
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- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 59
- -1 phthalate ester Chemical class 0.000 title claims description 50
- 238000001514 detection method Methods 0.000 claims abstract description 74
- 238000011065 in-situ storage Methods 0.000 claims abstract description 30
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims description 161
- 239000000123 paper Substances 0.000 claims description 74
- 239000012634 fragment Substances 0.000 claims description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 28
- 230000005540 biological transmission Effects 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001819 mass spectrum Methods 0.000 claims description 21
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 20
- 238000000889 atomisation Methods 0.000 claims description 17
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 14
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 claims description 14
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 14
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 14
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 238000002552 multiple reaction monitoring Methods 0.000 claims description 11
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 10
- 229960001826 dimethylphthalate Drugs 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 9
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 7
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 7
- UAFXUVUVOTXFND-UHFFFAOYSA-N bis(4-methylpentan-2-yl) benzene-1,2-dicarboxylate Chemical compound CC(C)CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)CC(C)C UAFXUVUVOTXFND-UHFFFAOYSA-N 0.000 claims description 7
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 7
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 7
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 claims description 7
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 claims description 7
- TZJIQGWUUVNPDS-UHFFFAOYSA-N ethyl 2-methylperoxycarbonylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OOC TZJIQGWUUVNPDS-UHFFFAOYSA-N 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 238000002137 ultrasound extraction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 239000011087 paperboard Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000012490 blank solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004885 tandem mass spectrometry Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004147 desorption mass spectrometry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000000375 direct analysis in real time Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012063 dual-affinity re-targeting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000001428 peripheral nervous system Anatomy 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
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- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for rapidly detecting phthalate components in cigarette paper, which adopts an in-situ mass spectrometry detection method to detect 18 phthalate components in cigarette paper, and can realize rapid detection of the 18 phthalate components in cigarette paper without any pretreatment process on the cigarette paper. The method can be used for detecting the phthalate compounds in the paper sample with the complex matrix, has higher sensitivity for detecting the phthalate components, and has the detection limit and the quantitative limit far smaller than the values detected by the traditional gas chromatography-mass spectrometry method, wherein the detection Limit (LOD) is 0.008-0.30 mu g/g, and the quantitative Limit (LOQ) is 0.025-0.90 mu g/g; the detection time is greatly shortened, and high-throughput detection can be carried out; 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 phthalate plasticizers in cigarette paper by using an in-situ mass spectrometry detection method, and belongs to the field of analysis of harmful components in cigarette paper.
Background
The cigarette paper is an indispensable important component for producing cigarette products, has an important function 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.
Phthalate (PAEs) plasticizer is a widely used food packaging material additive, and when cigarette paper containing PAEs is used, the PAEs easily migrate from the plasticizer to harm the health of human bodies. Researches show that the phthalate ester compounds can cause functional changes of central nervous system and peripheral nervous system, and also can damage human reproductive system, so that the phthalate ester plasticizers in the cigarette paper are required to be detected quickly and accurately.
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, etc., and has been widely applied to various fields of chemistry, chemical industry, environment, energy, medicine, life science, etc., and has promoted the huge development of natural discipline.
In 2004, electrospray desorption ion source (DESI) technology and 2005, direct analysis technology (DART) were produced, and in-situ ionization mass spectrometry technology was developed explosively.
In 2015, a new in-situ ionization mass spectrometry technique, namely a flame ion source, was reported by the kingdom of shanghai organic institute, for example, patent CN 110400740 a.
When the phthalate ester component in the cigarette paper is qualitatively or quantitatively detected by an industry standard method, due to the influence of a complex matrix, complicated pretreatment work including soaking, extracting, ultrasonic processing, centrifuging and the like is required for an object to be detected before ionization, and then subsequent mass spectrometry detection can be carried out after the component of the object to be detected is separated by adopting separation technologies such as gas chromatography or liquid chromatography and the like, so that hours or more time is usually required, and a large amount of manpower, solvent and time are consumed.
Disclosure of Invention
Aiming at the defects existing in qualitative or quantitative detection of the phthalate ester component in the cigarette paper in the prior art, the invention aims to provide an in-situ rapid detection method for the phthalate ester plasticizer in the cigarette paper. When the method provided by the invention is adopted to detect the phthalate plasticizer in the cigarette paper, no pretreatment is needed, the detection sensitivity of the phthalate component 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 detection time is greatly shortened, and high-throughput detection can be carried out; 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.
In order to achieve the technical purpose, the invention provides a method for rapidly detecting phthalate components in cigarette paper, which adopts an in-situ mass spectrometry detection method to detect 18 phthalate components in cigarette paper.
Preferably, the cigarette paper comprises at least one of cigarette tipping paper, cigarette lining paper, cigarette paperboard and cigarette box packaging paper.
As a preferred scheme, the 18 phthalate ester components in the cigarette paper comprise: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate and diallyl phthalate.
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 the 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 the ion transmission tube for detection to generate a signal peak.
As a preferred scheme, the size of the cut tobacco paper can be adjusted according to actual needs, mainly for the convenience of clamping by tweezers, but generally, the cut tobacco paper should be smaller than 2cm by 2cm, and preferably, the cut tobacco paper should be in a strip shape of 0.2-0.8 cm by 0.8-1.5 cm. Most preferably 0.5cm by 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 2.0 cm.
As a preferred scheme, the length of the hydrogen flame is 2.0-7.0 mm, the temperature is 350-520 ℃, and the further preferred length of the hydrogen flame is 3.5-5.0 mm, and the temperature is 400-430 ℃.
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 a full-sweep 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 scan time was 0.5s, the scan width was 1.0u, and the CID Gas was set to 1.5 mTorr.
As a preferred embodiment of the method, it is,the parent ions and qualitative and quantitative ions of the 18 phthalate components set in the positive ion detection mode are as follows: dimethyl phthalate: excimer ion [ M + H]+m/z: 195; characteristic fragment ions: 163; diethyl phthalate: excimer ion [ M + H]+m/z: 223; characteristic fragment ions: 149; diisobutyl phthalate: excimer ion [ M + H]+m/z: 279; characteristic fragment ions: 149; dibutyl phthalate: excimer ion [ M + H]+m/z: 279; characteristic fragment ions: 149, 205; di (2-methoxy) ethyl phthalate: excimer ion [ M + H]+m/z: 283; characteristic fragment ions: 59,207, respectively; di (4-methyl-2-pentyl) phthalate: excimer ion [ M + H]+m/z: 335; characteristic fragment ions: 149; di (2-ethoxy) ethyl phthalate: excimer ion [ M + H]+m/z: 311; characteristic fragment ions: 73; diamyl phthalate: excimer ion [ M + H]+m/z: 307; characteristic fragment ions: 149; dihexyl phthalate: excimer ion [ M + H]+m/z: 335; characteristic fragment ions: 149; butyl benzyl phthalate: excimer ion [ M + H]+m/z: 313; characteristic fragment ions: 149,91, 205; di (2-butoxy) ethyl phthalate: excimer ion [ M + H]+m/z: 367; characteristic fragment ions: 101,149,249, respectively; dicyclohexyl phthalate: excimer ion [ M + H]+m/z: 331; characteristic fragment ions: 167,149,249, respectively; di (2-ethyl) hexyl phthalate: excimer ion [ M + H]+m/z: 391; characteristic fragment ions: 149; diphenyl phthalate: excimer ion [ M + H]+m/z: 319; characteristic fragment ions: 225, a step of mixing; di-n-octyl phthalate: excimer ion [ M + H]+m/z: 391; characteristic fragment ions: 149; dinonyl phthalate: excimer ion [ M + H]+m/z: 419; characteristic fragment ions: 149,334, respectively; diisononyl phthalate: excimer ion [ M + H]+m/z: 419; characteristic fragment ions: 149; diallyl phthalate: excimer ion [ M + H]+m/z: 247; characteristic fragment ions: 189,41,149.
As a preferred technical solution, the optimal collision energy of 18 phthalate components set in the positive ion detection mode: dimethyl phthalate: 15 eV; diethyl phthalate: 15 eV; diisobutyl phthalate: 15 eV; dibutyl phthalate: 15 eV; di (2-methoxy) ethyl phthalate: 15 eV; di (4-methyl-2-pentyl) phthalate: 28 eV; di (2-ethoxy) ethyl phthalate: 18 eV; diamyl phthalate: 20 eV; dihexyl phthalate: 18 eV; butyl benzyl phthalate: 15 eV; di (2-butoxy) ethyl phthalate: 15 eV; dicyclohexyl phthalate: 15 eV; di (2-ethyl) hexyl phthalate: 25 eV; diphenyl phthalate: 13 eV; di-n-octyl phthalate: 23 eV; dinonyl phthalate: 30 eV; diisononyl phthalate: 25 eV; diallyl phthalate: 15 eV.
In the process of directly detecting the phthalate ester compounds in the paper samples for cigarettes by adopting an in-situ mass spectrometry detection method, the method for sampling by using the forceps handle comprises the following steps:
(1) cutting a strip with a proper size from cigarette paper according to a test requirement;
(2) the ion source device is built, the length of the hydrogen flame is adjusted to be 4mm, and the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe is 1.5 cm;
(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: 1.0 u; scanning time: 0.5 s; peak width of Q1: 0.7 u; q2CID gas: 1.5 mTorr. 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 phthalate ester compounds in the paper samples for cigarettes by adopting an in-situ mass spectrometry detection method, the in-situ ultrasonic extraction method comprises the following steps:
(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 1.2 cm;
(2) putting the cigarette paper round piece punched by the puncher on the atomizing piece;
(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: 1.0 u; scanning time: 0.5 s; peak width of Q1: 0.7 u; q2CID gas: 1.5 mTorr. The plasma generated by the ion source and the spray generated by the ultrasonic atomization of the atomization sheet generate charge transfer and energy transfer, and the generated ions enter the ion transmission tube for detection to generate a signal peak.
In the process of directly detecting the phthalate ester compounds in the cigarette paper sample by adopting an in-situ mass spectrometry detection method, the detection conclusion judgment method 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 phthalate components; namely, if the strength of the secondary fragment ions of the sample to be detected is not changed compared with the strength of the blank solution, judging that no phthalate component exists in the sample to be detected; namely, if the strength of the secondary fragment ions of the sample to be detected is higher than that of the blank solution, the phthalate component is judged to be contained in the sample to be detected.
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 phthalate compounds in cigarette paper, solves the problems of complicated detection pretreatment process, long detection time, large solvent consumption and the like of 18 phthalate compounds 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 values detected by the traditional gas chromatography-mass spectrometry, the detected detection Limit (LOD) is 0.008-0.30 mu g/g, and the quantitative Limit (LOQ) is 0.025-0.90 mu g/g; the developed method has small matrix effect when being used for testing, and 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 showing optimization of the distance condition from the end of the hydrogen gas pipe to the ion transport tube;
FIG. 3 is a mass spectrum of 18 phthalate compounds in a full scan mode;
FIG. 4 is a MS/MS mass spectrum of dimethyl phthalate.
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 phthalate compounds in paper samples for cigarettes:
1) firstly, optimizing detection conditions: the method comprises the steps of detecting phthalate compounds by using a hydrogen flame ion source, selecting dimethyl phthalate with the concentration of 10 mu g/mL at the initial stage as a target compound to perform experiments, screening different auxiliary solvents (methanol, acetone, acetonitrile, dichloromethane and the like are tried, the acetonitrile and dichloromethane are found to have poor effects because of poor compatibility with the target compound and good effects of the methanol and the acetone, considering that the methanol is a proton type solvent, the methanol is finally selected), different hydrogen and nitrogen proportions (the flame length is different and the flame temperature is different by adjusting the different proportions of the hydrogen and the nitrogen), adjusting the distance from the tail end of a hydrogen pipeline to an ion transmission pipe and other conditions, and obtaining the excimer ion peak m/z 195 of the high-strength dimethyl phthalate. A schematic diagram for optimizing the conditions of flame temperature and flame length is shown in fig. 1 (it can be seen from fig. 1 that the size is about 4mm, the temperature is about 400 ℃, which is the optimal condition, and the distance from the end of the hydrogen pipe to the ion transmission 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 transmission pipe is shown in fig. 2. The optimal detection conditions obtained after optimization are as follows: the mass analyzer is set to be in a positive ion detection mode by a triple quadrupole, no voltage is applied, and the temperature of an ion transmission tube is set to be 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, 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 scan time was 0.5s, the scan width was 1.0u, and the CID Gas was set to 1.5 mTorr; the distance from the tail end of the hydrogen flame pipeline to the ion transmission pipe is 1.5 cm; the size of the hydrogen flame is about 4mm, and the temperature is about 400 ℃; 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 phthalate compound 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 methanol, 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 0.70 u; CID Gas is set to 1.5 mTorr; without voltage, during testing, a full scan mode is firstly used by utilizing a peristaltic pump direct sample injection mode, a mixed standard solution of phthalate compounds with the concentration of 10 mu g/mL is used as a test object, and a sample injection mode of in-situ ultrasonic extraction is adopted to find the [ M + H ] of each plasticizer]+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 dimethyl terephthalate excimer ion [ M + H ]]+MS/MS analysis was performed to obtain the major characteristic fragment ion m/z 163.
TABLE 118 qualitative and quantitative ions of phthalate plasticizers
Due to the fact that the paper substrate for the cigarette is complex, when whether the plasticizer exists or not is tested, 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 phthalate components in the detection using the hydrogen flame desorption mass spectrometry technique was optimized, and the results are shown in table 2 below.
TABLE 218 optimal Collision energy of plasticizers when Using the 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 phthalic acid ester 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 raw paper of paper for cigarettes, drying the paper, and then detecting the paper by using a forceps handle sample injection mode, wherein secondary fragment ions of the plasticizer 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: 1.0 u; scanning time: 0.5 s; peak width of Q1: 0.7 u; q2CID gas: 1.5 mTorr.
(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 in the blank solution to judge whether the paper for cigarettes contains phthalate components; namely, if the strength of the secondary fragment ions of the sample to be detected is not changed compared with the strength of the blank solution, judging that no phthalate component exists in the sample to be detected; namely, if the strength of the secondary fragment ions of the sample to be detected is higher than that of the blank solution, the phthalate component is judged to be contained in the sample to be detected. The main types of phthalate components in the paper for cigarettes include dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diallyl phthalate, and the like.
The detection limit and the quantitative limit of each phthalate in the tipping paper for cigarettes and the detection results of the gas chromatography-mass spectrometry used in the traditional standard method GB/T37860-2019 determination of phthalate of paper, paperboard and paper products are shown in the following table 3.
Detection limit and quantitative limit of 318 phthalic acid ester compounds in table
The method realizes the in-situ real-time and high-flux detection of the 18 phthalate compounds in the cigarette paper, solves the problems of complicated pretreatment process, long detection time, large solvent consumption and the like of the original standard method for the detection of the 18 phthalate compounds 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 (14)
1. A method for rapidly detecting phthalate ester components in cigarette paper is characterized by comprising the following steps: and detecting 18 phthalate components in the cigarette paper by adopting an in-situ mass spectrometry detection method.
2. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 1, which is characterized in that: the cigarette paper comprises at least one of cigarette tipping paper, cigarette lining paper, cigarette paperboard and cigarette box packaging paper.
3. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 1, which is characterized in that: the 18 phthalate ester components comprise: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate and diallyl phthalate.
4. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 1, which is characterized in that: the in-situ mass spectrometry detection method adopts a hydrogen flame desorption ion source and a triple quadrupole mass analyzer.
5. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 1, which is characterized in that: the in-situ mass spectrum detection method adopts a forceps handle sample introduction method or an in-situ ultrasonic extraction method.
6. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 5, wherein the method comprises the following steps:
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 the ion transmission pipe;
3) setting an acquisition mode and mass spectrum parameters of a triple quadrupole mass analyzer;
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;
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 the ion transmission tube for detection to generate a signal peak.
7. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 6, which is characterized in that: the cigarette paper is cut into strips with the size of 0.2-0.8 cm x 0.8-1.5 cm.
8. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 6, which is characterized in that: the vertical distance from the ultrasonic atomization sheet to the ion transmission tube is 1.0-1.3 cm.
9. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 6, which is characterized in that: the diameter of the ultrasonic atomization sheet is 1.6 cm-2.5 cm, and the diameter of the round piece of paper for cigarettes is smaller than that of the ultrasonic atomization sheet.
10. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 6, which is characterized in that: the length of the hydrogen flame is 2.0-7.0 mm, and the temperature is 350-520 ℃.
11. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 6, which is characterized in that: 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 collecting data for detection and collision of characteristic fragment ions.
12. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 6, which is characterized in that: the quality analyzer of the triple quadrupole rod selects a positive ion detection mode without voltage, and the temperature of an ion transmission tube is set to 275 ℃; under a full-sweep 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 scan time was 0.5s, the scan width was 1.0u, and the CID Gas was set to 1.5 mTorr.
13. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 12, wherein the method comprises the following steps: the parent ions and qualitative and quantitative ions of the 18 phthalate components set in the positive ion detection mode are as follows:
dimethyl phthalate: excimer ion [ M + H]+m/z: 195; characteristic fragment ions: 163;
diethyl phthalate: excimer ion [ M + H]+m/z: 223; characteristic fragment ions: 149;
diisobutyl phthalate: excimer ion [ M + H]+m/z: 279; characteristic fragment ions: 149;
dibutyl phthalate: excimer ion [ M + H]+m/z: 279; characteristic fragment ions: 149, 205;
di (2-methoxy) ethyl phthalate: excimer ion [ M + H]+m/z: 283; characteristic fragment ions: 59,207, respectively;
di (4-methyl-2-pentyl) phthalate: excimer ion [ M + H]+m/z: 335; characteristic fragment ions: 149;
di (2-ethoxy) ethyl phthalate: excimer ion [ M + H]+m/z: 311; characteristic fragment ions: 73;
diamyl phthalate: excimer ion [ M + H]+m/z: 307; characteristic fragment ions: 149;
dihexyl phthalate: excimer ion [ M + H]+m/z: 335; characteristic fragment ions: 149;
butyl benzyl phthalate: excimer ion [ M + H]+m/z：313; characteristic fragment ions: 149,91, 205;
di (2-butoxy) ethyl phthalate: excimer ion [ M + H]+m/z: 367; characteristic fragment ions: 101,149,249, respectively;
dicyclohexyl phthalate: excimer ion [ M + H]+m/z: 331; characteristic fragment ions: 167,149,249, respectively;
di (2-ethyl) hexyl phthalate: excimer ion [ M + H]+m/z: 391; characteristic fragment ions: 149;
diphenyl phthalate: excimer ion [ M + H]+m/z: 319; characteristic fragment ions: 225, a step of mixing;
di-n-octyl phthalate: excimer ion [ M + H]+m/z: 391; characteristic fragment ions: 149;
dinonyl phthalate: excimer ion [ M + H]+m/z: 419; characteristic fragment ions: 149,334, respectively;
diisononyl phthalate: excimer ion [ M + H]+m/z: 419; characteristic fragment ions: 149;
diallyl phthalate: excimer ion [ M + H]+m/z: 247; characteristic fragment ions: 189,41,149.
14. The method for rapidly detecting the phthalate ester component in the cigarette paper as claimed in claim 12, wherein the method comprises the following steps: optimum collision energy for 18 phthalate-based components set in positive ion detection mode:
dimethyl phthalate: 15 eV;
diethyl phthalate: 15 eV;
diisobutyl phthalate: 15 eV;
dibutyl phthalate: 15 eV;
di (2-methoxy) ethyl phthalate: 15 eV;
di (4-methyl-2-pentyl) phthalate: 28 eV;
di (2-ethoxy) ethyl phthalate: 18 eV;
diamyl phthalate: 20 eV;
dihexyl phthalate: 18 eV;
butyl benzyl phthalate: 15 eV;
di (2-butoxy) ethyl phthalate: 15 eV;
dicyclohexyl phthalate: 15 eV;
di (2-ethyl) hexyl phthalate: 25 eV;
diphenyl phthalate: 13 eV;
di-n-octyl phthalate: 23 eV;
dinonyl phthalate: 30 eV;
diisononyl phthalate: 25 eV;
diallyl phthalate: 15 eV.
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