CN103389336A - Mass spectrometry imaging method capable of rapidly identifying of handwriting authenticity - Google Patents

Mass spectrometry imaging method capable of rapidly identifying of handwriting authenticity Download PDF

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Publication number
CN103389336A
CN103389336A CN2013102994892A CN201310299489A CN103389336A CN 103389336 A CN103389336 A CN 103389336A CN 2013102994892 A CN2013102994892 A CN 2013102994892A CN 201310299489 A CN201310299489 A CN 201310299489A CN 103389336 A CN103389336 A CN 103389336A
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handwriting
mass spectrum
mass spectrometry
sample
person
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欧阳永中
洪锋
陈焕文
刘思莹
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East China Institute of Technology
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East China Institute of Technology
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Abstract

The invention relates to a mass spectrometry imaging method capable of rapidly identifying of handwriting authenticity. According to the mass spectrometry imaging method, a surface desorption chemical ionization mass spectrometry is adopted in combination of a three-dimensional high-precision automatic control mobile system to carry out two-dimensional spectrum scan on the handwriting without pre-treating the sample, and mass spectrometry images of character compounds in the handwriting are obtained according to changes of ion signal intensities of the character compounds in the handwriting. The mass spectrometry imaging method can directly realize rapid identification of the handwriting authenticity of files at a molecular level under a normal temperature and a normal pressure without pre-treating the sample. The mass spectrometry imaging method has the advantages of simple operations, fast analysis speed, high precision, high sensitivity and no damage to the sample, overcomes the limits of low precision, low sensitivity and slow analysis speed in a conventional handwriting identification method and has enormous potential application prospects in the technical fields related to forensic analysis, archeology, finance, justice, etc.

Description

The mass spectrum imaging method of the Rapid identification person's handwriting true and false
Technical field
The present invention relates to the correlative technology fields such as forensic analysis, archaeology, finance, the administration of justice, be specifically related to a kind of mass spectrum imaging method of the Rapid identification person's handwriting true and false.
Background technology
Handwriting verification is writing skill, custom, the feature according to the people, reflection in the writing of writing and drawing, differentiate a kind of technical skill of writing the people, its task is exactly will be by action of writing custom feature, text layout and the written language feature that reflects in the research person's handwriting, in order to situation analysis time, for lawsuit is given a clue and evidence.Handwriting verification is ingredient important in forensic analysis always, for lawsuit, gives a clue and evidence, has been widely used in the signature of authentication and vital document.Identify the handwriting authentication method and technology of the fast development of modern science and technology and economic society had higher requirement, in the urgent need to developing fast, harmless, handwriting verification method accurately and technology.
The method of tradition handwriting verification mainly comprises: thin-layered chromatography, high performance liquid chromatography (HPLC), vapor-phase chromatography (GC), inductively coupled plasma mass spectrometry (ICP-MS), HPLC-MS technology (HPLC-MS), gas chromatography-mass spectrography technology (GC-MS), Raman spectroscopy, fourier transform infrared spectroscopy, digit microscope relative method etc.Yet chromatography and hydrolysis and condensation, before sample analysis, all need through numerous and diverse sample pretreatment process, length consuming time (at least 1 one hour), and tend to occur some physical-chemical reactions in the sample preparation process, cause sample is caused to a certain degree damage.In addition, spectroscopic methodology sensitivity is not high, has greatly limited the handwriting verification technology and has applied in association area.
Summary of the invention
Purpose of the present invention just is to provide the mass spectrum imaging method of a kind of sensitivity, the Rapid identification person's handwriting true and false that harmless, accuracy is high.
The mass spectrum imaging method of the Rapid identification person's handwriting true and false of the present invention comprises the following steps:
1,, with the first alcohol and water ratio preparation mixed liquor of 1:1 by volume, inject reagent bottle, as ionization reagents, standby;
2, regulate surface desorption atmospheric chemical ionization source (DAPCI), and it is coupled on mass spectrometer: the angle α of spray point tip nozzle and sample load-bearing surface is 30 °, the vertical range of spray point tip nozzle and sample surfaces is 1.8mm, the distance of discharge needle point and mass spectrum entrance is 10 mm, the angle beta of sample surfaces and mass spectrum entrance is 12 °, the vertical range of sample surfaces and mass spectrum entrance is 2mm, the voltage of spray point is 3.5kV, the pressure of assist gas is 0.105 MP, utilize the mixed liquor of the above-mentioned first alcohol and water of nitrogen gasification, flow velocity with 250 mL/min passes into the reagent intake,
3, regulate the three-dimensional mobile platform of automatically controlling, the vertical range of regulating ion source discharge needle point nozzle and sample plummer and mass spectrum entrance by controller, the moving step length of then setting X, Y horizontal direction is 10-500 μ m;
4, the setting of mass spectrum condition: be set to the positive ion detecting pattern, the scanning of the mass spectrum scope is m/z 50-600, ion gun voltage is 3.5 kV, the ion transfer tube temperature is 200 ℃, the width of ion selection window is 1.2 Da, the scope of collision-induced cracking energy is 18-27%, and other parameter is by the mass spectrometer Automatic Optimal;
5, the file that will identify is placed on the sample plummer, nitrogen take air pressure as 0.2 MPa passes in the reagent bottle of the mixing material that fills the first alcohol and water, obtain gas-phase reagents and introduce solvent quartz wool spool road, utilize mass spectrometer to identify the handwriting and carry out two-dimentional scanning of the mass spectrum, utilize similarity algorithm to the characteristic imaging data analysis,, according to the variation of characterization compound ion signal intensity in person's handwriting, obtain the mass spectrum image of characterization compound in person's handwriting, thereby reach the purpose of the Rapid identification person's handwriting true and false.
Described surface desorption atmospheric chemical ionization source, comprise spray point and threeway stainless steel metal sleeve pipe, the spray point surface all scribbles insulation course, insulation course overcoat solvent quartz wool spool, solvent quartz wool spool overcoat is assisted the desorption gas sleeve pipe, termination operation valve before auxiliary desorption gas sleeve pipe, threeway stainless steel metal sleeve pipe is provided with reagent intake and auxiliary desorption gas intake.Use the nitrogen (lower than 0.2 MPa) of certain pressure intensity as carrier gas, through the carrier gas pipe, pass in the reagent bottle of the mixing material that the first alcohol and water is housed, adopt foaming to obtain gas-phase reagents, through the reagent intake, pass into solvent quartz wool spool.
The mass spectrum imaging method of the Rapid identification person's handwriting true and false of the present invention, to use a certain proportion of methyl alcohol and water mixed solution as ionization reagents, adopt the surface desorption chemical ionization mass spectrometry, in conjunction with three-dimensional high-accuracy automatic control mobile system, need not under the condition of sample pretreatment, directly identifying the handwriting and carry out two-dimentional scanning of the mass spectrum, according to the variation of characterization compound ion signal intensity in person's handwriting, obtain the mass spectrum image of characterization compound in person's handwriting, realize fast the evaluation of the person's handwriting true and false.Its principle of work is: the surface desorption atmospheric chemical ionization source mainly is comprised of spray point and threeway stainless steel metal sleeve pipe two parts, elementary reagent is by the nitrogen of certain pressure intensity, pass through to obtain gas-phase reagents from the reagent bottle that reagent mix liquid is housed, introduce solvent quartz wool spool through the reagent intake, the gas phase ionization reagents is covered with whole discharge needle point space, and the spray point needle point produces series of proton hydroxonium ion H by high-voltage corona discharge 3O +With water radical cation H 2O +Under desorption gas is auxiliary, then with the heteroion physical-chemical reaction of sample surfaces generation series of complex, and carry out the exchange of corresponding electric charge and the transfer process of energy, thereby obtain the ion signal of determinand, automatically control in three-dimensional under the regulating and controlling of mobile platform, realize the two-dimentional scanning of the mass spectrum of sample, utilize similarity algorithm to the characteristic imaging data analysis, variation according to characterization compound ion signal intensity in person's handwriting, obtain the mass spectrum image of characterization compound in person's handwriting, realize fast the evaluation of the person's handwriting true and false.
The mass spectrum imaging method of the Rapid identification person's handwriting true and false of the present invention, can sample be carried out under pre-service and normal temperature and pressure conditions need not, on molecular level, directly realize the Rapid identification of the file person's handwriting true and false, have simple to operate, analysis speed is fast, degree of accuracy is high, highly sensitive, to advantages such as sample nondestructive evils, solved that traditional person's handwriting authentication method degree of accuracy is low, sensitivity is low, analysis speed waits limitation slowly, will have huge potential application foreground at correlative technology fields such as forensic analysis, archaeology, finance, the administration of justice.
Description of drawings
Fig. 1 is principle of work schematic diagram of the present invention;
Fig. 2 is the mass spectrogram of A4 white print paper blue watercolor person's handwriting " Q ": (a) one-level scanning of the mass spectrum figure; (b) the second order ms figure of feature compound ions m/z 126;
Fig. 3 is the true and false that mass spectrum imaging method of the present invention is identified A4 white paper blue watercolor person's handwriting " Q ": (a) and (b) be same person writing's person's handwriting, (c) be the person's handwriting of another one people imitation; (d), (e), and (f) be respectively (a) and (b), and (c) utilize the mass spectrum imaging image of feature compound ions m/z 126;
Fig. 4 is the result that fast mass spectrum imaging method of the present invention is identified burnt black ink pen person's handwriting " Ding " true and false on the A4 blank sheet of paper: (a) and (b) be same person writing's person's handwriting, (c) be the person's handwriting of another one people imitation; (d), (e), and (f) be respectively (a) and (b), and (c) with the image of characteristic ion m/z 126 mass spectrum imagings; (g) and (h) be respectively the firsts and seconds mass spectrogram of burnt black ink pen mark on the A4 blank sheet of paper;
Fig. 5 is the result that fast mass spectrum imaging method of the present invention is identified gel pen person's handwriting " Ben " true and false on scratch paper: (a) and (b) be same person writing's person's handwriting, (c) be the person's handwriting of another one people imitation; (d), (e), and (f) be respectively (a) and (b), and (c) with the image of m/z 80 characteristic ion mass spectrum imagings; (g) be the one-level scanning of the mass spectrum figure of gel pen person's handwriting on the A4 scratch paper.
Embodiment
As Fig. 1, the basic comprising of the mass spectrum imaging method device of the Rapid identification person's handwriting true and false of the present invention comprises: 1, threeway stainless steel metal sleeve pipe, 2, operation valve, 3, auxiliary desorption gas sleeve pipe, 4, solvent quartz wool spool, 5, spray point, 6, the carrier gas intake, 7, the reagent intake, 8, carrier gas pipe, 9, reagent bottle, 10, the sample plummer, 11, the three-dimensional platform of controlling, 12, self-actuated controller, 13, the mass spectrum entrance.
A kind of mass spectrum imaging method of the Rapid identification person's handwriting true and false comprises following experimental procedure:
(1), with the first alcohol and water ratio preparation mixed liquor of 1:1 by volume, inject reagent bottle, as ionization reagents, standby;
(2), optimizing surface desorption atmospheric chemical ionization source (DAPCI), and it is coupled on the LTQ-XL mass spectrometer: the angle α that regulates spray point tip nozzle and sample load-bearing surface is 30 °, the vertical range of spray point tip nozzle and sample surfaces is 1.8mm, the distance of discharge needle point and mass spectrum entrance is 10 mm, the angle beta of sample surfaces and mass spectrum entrance is 12 °, the vertical range of sample surfaces and mass spectrum entrance is 2mm, the voltage of spray point is 3.5kV, the pressure of assist gas is 0.105 MP, utilize the mixed liquor of the above-mentioned first alcohol and water of nitrogen gasification, flow velocity with 250 mL/min passes into the reagent intake,
(3), the three-dimensional adjusting of automatically controlling mobile platform; Regulate the vertical range of ion gun needle point nozzle and sample plummer and mass spectrum entrance by controller, the moving step length of then setting X, Y horizontal direction is 10-500 μ m, and the time of a point of scanning is 5 seconds;
(4), the setting of mass spectrum condition: be set to the positive ion detecting pattern; The scanning of the mass spectrum scope is m/z 50-600, and ion gun voltage is 3.5 kV, and the ion transfer tube temperature is 200 ℃, and the width of ion selection window is 1.2Da, and the scope of collision-induced cracking energy is 18-27%, and other parameter is by the mass spectrometer Automatic Optimal;
(5), the file that will identify is placed on the sample plummer, nitrogen take air pressure as 0.2 MPa passes in the reagent bottle of the mixing material that fills the first alcohol and water, obtain gas-phase reagents and introduce solvent quartz wool spool road, utilize mass spectrometer to identify the handwriting and carry out two-dimentional scanning of the mass spectrum, utilize computing machine to process the mass spectrum scan-data,, according to the variation of characterization compound ion signal intensity in person's handwriting, obtain the mass spectrum image of characterization compound in person's handwriting, thereby reach the purpose of the Rapid identification person's handwriting true and false.
Fig. 3 and Fig. 4 are the person's handwriting mass spectrum imaging figure of same paper variety classes ink.Fig. 3 a, 3b is same person writing's person's handwriting " Q ", Fig. 3 c is the person's handwriting " Q " that the another one people imitates, can not differentiate original and apish person's handwriting fully from Fig. 3 a-3c, but utilize method of the present invention, select characteristic ion m/z 126 to carry out mass spectrum imaging, obtain respectively mass spectrum imaging Fig. 3 d-3f of person's handwriting " Q ", can distinguish clearly person's handwriting original and that imitate from mass spectrum imaging Fig. 3 e-3f.In like manner, after the person's handwriting in Fig. 4 " Ding " utilizes method of the present invention to carry out mass spectrum imaging, can significantly identify apish person's handwriting.
Fig. 5 is person's handwriting " Ben " the mass spectrum imaging figure of pen on paper.Original person's handwriting with imitating in Fig. 5 a-5c that naked eyes can not be identified, but after the DAPCI mass spectrum imaging, obtain respectively 5d-5f imaging mass spectrogram, can significantly distinguish same person and apish person's handwriting.Result shows, method of the present invention can not be subjected to the interference of the complicated substrates such as different sample supporting bodies and ink marks, accurately, fast, harmless, the true and false of distinguishing delicately person's handwriting.

Claims (1)

1. the mass spectrum imaging method of a Rapid identification person's handwriting true and false, it is characterized in that: it comprises the following steps:
(1), with the first alcohol and water ratio preparation mixed liquor of 1:1 by volume, inject reagent bottle, as ionization reagents, standby;
(2), regulate the surface desorption atmospheric chemical ionization source, and it is coupled on mass spectrometer: the angle α of spray point tip nozzle and sample load-bearing surface is 30 °, the vertical range of spray point tip nozzle and sample surfaces is 1.8mm, the distance of discharge needle point and mass spectrum entrance is 10 mm, the angle beta of sample surfaces and mass spectrum entrance is 12 °, the vertical range of sample surfaces and mass spectrum entrance is 2mm, the voltage of spray point is 3.5kV, the pressure of assist gas is 0.105 MP, utilize the mixed liquor of the above-mentioned first alcohol and water of nitrogen gasification, flow velocity with 250 mL/min passes into the reagent intake,
(3), regulate the three-dimensional mobile platform of automatically controlling, the vertical range of regulating ion source discharge needle point nozzle and sample plummer and mass spectrum entrance by controller, the moving step length of then setting X, Y horizontal direction is 10-500 μ m;
(4), the setting of mass spectrum condition: be set to the positive ion detecting pattern, the scanning of the mass spectrum scope is m/z 50-600, ion gun voltage is 3.5 kV, the ion transfer tube temperature is 200 ℃, the width of ion selection window is 1.2 Da, the scope of collision-induced cracking energy is 18-27%, and other parameter is by the mass spectrometer Automatic Optimal;
(5), the file that will identify is placed on the sample plummer, nitrogen take air pressure as 0.2 MPa passes in the reagent bottle of the mixing material that fills the first alcohol and water, obtain gas-phase reagents and introduce solvent quartz wool spool road, utilize mass spectrometer to identify the handwriting and carry out two-dimentional scanning of the mass spectrum, utilize similarity algorithm to the characteristic imaging data analysis,, according to the variation of characterization compound ion signal intensity in person's handwriting, obtain the mass spectrum image of characterization compound in person's handwriting;
Described surface desorption atmospheric chemical ionization source, comprise spray point (5) and threeway stainless steel metal sleeve pipe (1), spray point (5) overcoat solvent quartz wool spool (3), solvent quartz wool spool (3) overcoat is assisted desorption gas sleeve pipe (4), the auxiliary front termination operation valve of desorption gas sleeve pipe (4) (2), threeway stainless steel metal sleeve pipe is provided with reagent intake (7) and auxiliary desorption gas intake (6).
CN2013102994892A 2013-07-17 2013-07-17 Mass spectrometry imaging method capable of rapidly identifying of handwriting authenticity Pending CN103389336A (en)

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
CN103760221A (en) * 2014-02-14 2014-04-30 厦门大学 Needle tip discharge device for solid surface denudation
CN104299883A (en) * 2014-10-09 2015-01-21 东华理工大学 Top entry type polar coordinate adjusting device
CN104849392A (en) * 2015-06-08 2015-08-19 公安海警学院 Relative writing time identification method
CN105758930A (en) * 2016-03-31 2016-07-13 东华理工大学 Gas heat assisting surface desorption normal-pressure chemical ionization source and mass spectrometry method
WO2017041696A1 (en) * 2015-09-09 2017-03-16 张华俊 Mass spectrometric detection and analysis method
CN107238654A (en) * 2017-05-26 2017-10-10 北京师范大学 A kind of ionization apparatus
CN108152360A (en) * 2018-02-08 2018-06-12 中国检验检疫科学研究院 The dielectric barrier discharge ionization mass spectrometry method of perfluorochemical in textile
CN109633187A (en) * 2018-12-25 2019-04-16 司法鉴定科学研究院 A kind of data detection system and method for documents
CN111678974A (en) * 2020-02-04 2020-09-18 公安部物证鉴定中心 Mass spectrum imaging analysis method for sequential identification or auxiliary identification of vermilion and black
CN112816739A (en) * 2019-11-18 2021-05-18 中国科学院大连化学物理研究所 Scanning chemical reaction microscopic imaging method and application
CN113176325A (en) * 2021-04-14 2021-07-27 北京师范大学 Normal-pressure mass spectrum online monitoring system for accelerated degradation of organic pollutants by plasmas in millisecond

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103760221B (en) * 2014-02-14 2015-12-02 厦门大学 A kind of needle point electric discharge device degraded for solid surface
CN103760221A (en) * 2014-02-14 2014-04-30 厦门大学 Needle tip discharge device for solid surface denudation
CN104299883A (en) * 2014-10-09 2015-01-21 东华理工大学 Top entry type polar coordinate adjusting device
CN104849392A (en) * 2015-06-08 2015-08-19 公安海警学院 Relative writing time identification method
WO2017041696A1 (en) * 2015-09-09 2017-03-16 张华俊 Mass spectrometric detection and analysis method
CN105758930B (en) * 2016-03-31 2018-08-21 东华理工大学 A kind of gas hot auxiliary surface desorption atmospheric chemical ionization source and mass spectrometric analysis method
CN105758930A (en) * 2016-03-31 2016-07-13 东华理工大学 Gas heat assisting surface desorption normal-pressure chemical ionization source and mass spectrometry method
CN107238654A (en) * 2017-05-26 2017-10-10 北京师范大学 A kind of ionization apparatus
CN108152360A (en) * 2018-02-08 2018-06-12 中国检验检疫科学研究院 The dielectric barrier discharge ionization mass spectrometry method of perfluorochemical in textile
CN108152360B (en) * 2018-02-08 2020-12-11 中国检验检疫科学研究院 Dielectric barrier discharge ionization mass spectrometry analysis method for perfluorinated compounds in textiles
CN109633187A (en) * 2018-12-25 2019-04-16 司法鉴定科学研究院 A kind of data detection system and method for documents
CN112816739A (en) * 2019-11-18 2021-05-18 中国科学院大连化学物理研究所 Scanning chemical reaction microscopic imaging method and application
CN111678974A (en) * 2020-02-04 2020-09-18 公安部物证鉴定中心 Mass spectrum imaging analysis method for sequential identification or auxiliary identification of vermilion and black
CN111678974B (en) * 2020-02-04 2023-08-15 公安部物证鉴定中心 Mass spectrum imaging analysis method for time sequence identification or auxiliary identification of cinnabar
CN113176325A (en) * 2021-04-14 2021-07-27 北京师范大学 Normal-pressure mass spectrum online monitoring system for accelerated degradation of organic pollutants by plasmas in millisecond

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Application publication date: 20131113