CN104458987B - 25 kinds of neutrality in heroin or the detection method of acid impurities - Google Patents
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Abstract
Relate to the detection method of 25 kinds of neutrality or acid impurities in heroin sample, particularly relate to the method for 25 kinds of neutrality or acid impurities in a kind of Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) Simultaneously test heroin, the method is in acid condition by sherwood oil: methylene chloride mixed solvent centering or acid impurities extract, and adopts Ultra Performance Liquid Chromatography series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) centering or acid impurities to measure.This method has the advantage that sample pre-treatments is simple, testing cost is low, analysis time is short, selectivity is good compared with existing neutrality or acid impurities detection method.
Description
Technical field
The present invention relates to the detection method of 25 kinds of neutrality in heroin sample or acid impurities, particularly relate to the method that a kind of Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) detects 25 kinds of neutrality in heroin or acid impurities simultaneously.
Background technology
Heroin, is also called diacetylmorphine, is a kind of semi-synthetic drugs, is obtained after acetylation by the main alkaloid morphine in opium.Heroin also generates a large amount of neutrality or acid impurities in illegal process, and these neutral or acid impurities are that the alkaloid such as morphine, codeine, papaverine, thebaine, narcotine in acetic anhydride and opium reacts and generates.The kind of these impurity contained in heroin and quantity, directly reflect the processing technology of heroin, some degree also can reflect the place of production of opium.Utilize these distinctive neutrality or the acid impurities in heroin, the discriminant classification on heroin separate sources ground can be carried out.
In heroin, detection method that is neutral or acid impurities comprises CE method, GC-ECD method, GC-FID method, GC-MS method.Although CE method, GC-ECD method, GC-FID method are highly sensitive, selectivity is not strong, sometimes can meet difficulty when the ownership at peak.So the forensic science laboratory of the current U.S. and Australia all adopts GC-MS method to detect neutral or acid impurities.The sensitive height of GC-MS method, selectivity are strong, and method is ripe, stable; Shortcoming is that sample needs to carry out derivatization treatment, and pre-treatment complex operation, data redundancy are poor, and the analysis time of sample is long.
Summary of the invention
In order to solve the technical matters that in heroin, neutrality or acid impurities fast, accurately detect, the object of this invention is to provide the method for 25 kinds of neutrality or acid impurities in a kind of Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) Simultaneously test heroin, the method has the advantage that sample pre-treatments is simple, testing cost is low, analysis time is short, sensitivity for analysis is high, resolution is high, selectivity is good.
In order to realize above-mentioned object, present invention employs following technical scheme.
25 kinds of neutrality in Simultaneously test heroin or a method for acid impurities, adopt Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF), the method comprises the following steps:
(1) extraction of neutrality to be measured or acid impurities in heroin sample
Take heroin sample, as in glass centrifuge tube, add acidified solvent, ultrasonic process, adds Extraction solvent, and concussion is centrifugal after extracting, and through filter membrane process, obtains sample solution;
Reagent blank is done in company with sample;
(2) mensuration of neutrality or acid impurities
Set corresponding liquid phase chromatogram condition and Mass Spectrometry Conditions, comprise the molecular formula of setting, retention time, secondary fragment ion parameters, by Ultra Performance Liquid Chromatography-series connection level Four bar time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF), Integral Processing is carried out to be measured 25 kinds of neutrality or acid impurities compound, obtains the peak area numerical value of each compound.
Preferably, acidified solvent is selected from HCl solution, HNO
3solution, H
2sO
4solution, is more preferably H
2sO
4solution.
Preferably, Extraction solvent is sherwood oil, methylene chloride mixed solvent, is more preferably sherwood oil: the mixed liquor of methylene chloride=3mL:2mL.
Preferably, ultrasonic time is 5-20min, further preferred 10min.
Preferably, concussion extraction time is 20-40min, further preferred 30min.
Preferably, centrifugal speed is 3000-15000r/min, more preferably 4000-8000r/min, is more preferably 5000r/min.
Preferably, centrifugation time is 5-20min, more preferably 10min.
Preferably, filter membrane is 0.22 μm of organic system filter membrane.
Preferably, described liquid phase chromatogram condition is:
Chromatographic column: AgilentEclipsePlusC
18rRHD (1.8 μm, 2.1 × 100mm); Sample introduction concentration: 40mg/mL; Sampling volume: 0.5 μ L; Column temperature: 40 DEG C; Mobile phase A: acetonitrile, Mobile phase B: 10mmol/L ammonium formate solution; Flow velocity: 0.4mL/min, gradient elution program sees the following form,
Gradient elution program
| Time/min | A(％) | B(％) |
| 0 | 30 | 70 |
| 1 | 30 | 70 |
| 10 | 55 | 45 |
| 11 | 95 | 5 |
| 12 | 95 | 5 |
| 12.5 | 30 | 70 |
| 17 | 30 | 70 |
Preferably, described Mass Spectrometry Conditions is:
First mass spectrometric, adopts ESI ion gun, positive ion mode; Ion spray voltage: 5.5kV; Remove a bunch voltage (DP): 80V; Vapo(u)rizing temperature: 600 DEG C; Atomization gas (N
2, GS
1) the front pressure of post: 50psi; Desolventizing gas (N
2, GS
2) the front pressure of post: 50psi; Gas curtain gas (N
2, CUR) and the front pressure of post: 30psi; Collision energy (CE): 10V; Mass axes: 100 ~ 1000amu;
Second order ms, adopts ESI ion gun, positive ion mode; MS/MS switched scan (IDA); Ion spray voltage: 5.5kV; Remove a bunch voltage (DP): 80V; Vapo(u)rizing temperature: 600 DEG C; Atomization gas (N
2, GS
1) the front pressure of post: 50psi; Desolventizing gas (N
2, GS
2) the front pressure of post: 50psi; Gas curtain gas (N
2, CUR) and the front pressure of post: 30psi; Collision energy (CE): 40V, collision energy expansion (CES): 15V; Mass axes: 100 ~ 1000amu.
Under corresponding Parameter Conditions, see table 2, Integral Processing is carried out to 25 kinds of neutrality or acid impurities compound, obtain the peak area numerical value of each compound.
Table 2 is liquid matter parameter lists of 25 kinds of neutrality or each compound of acid impurities.
The liquid matter parameter list of table 225 kind of neutrality or each compound of acid impurities
In table 2, neutrality or its title of acid impurities variable of known structure represent, the neutrality of unknown structure or acid impurities variable represent with " extracting mass number/retention time " ".
The method is extracted by sherwood oil, methylene chloride mixed solvent centering or acid compound in acid condition, and Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) centering or acid compound measure.This method has the advantage that pre-treatment is simple, testing cost is low, analysis time is short, selectivity is good compared with existing neutrality or acid impurities detection method, meets the demand of batch heroin sample source ground Quick.
Accompanying drawing explanation
Fig. 1 is that heroin sample UPLC-Q-TOFTIC schemes; Each numbering that is neutral or acid impurities in figure in the corresponding table 2 of numeral number;
Fig. 2 .1-Fig. 2 .25 is respectively the secondary fragment ion figure of 25 kinds of neutrality or acid impurities; Such as Fig. 2 .1 represents the secondary fragment ion figure of Hydrocotarnine, and Fig. 2 .2 represents the secondary fragment ion figure of 356/1.5, and Fig. 2 .25 represents the secondary fragment ion figure of 4-O-Acetylthebaol.
Embodiment
Embodiment 1: 25 kinds of neutrality or acid impurities in Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) Simultaneously test heroin, the method comprises the following steps:
(1) extraction of neutrality to be measured or acid impurities in heroin sample
Take " South-West Asia " heroin sample 100mg, be placed in 8mL glass centrifuge tube, pipette 2mL acidified solvent in glass centrifuge tube with 5mL bottleneck pipettor, acidified solvent is: 0.25MH
2sO
4solution, ultrasonic 10min.Pipette 2.5mL Extraction solvent with 5mL bottleneck pipettor and add above-mentioned glass centrifuge tube, Extraction solvent is: sherwood oil: the mixed liquor of methylene chloride=3mL:2mL, and 30min is extracted in concussion.With the centrifugal 10min of 5000r/min rotating speed.Pipette upper organic phase 1mL, avoid carrying water layer secretly, cross 0.22 μm of organic system filter membrane, be transferred in 1.5mL sample injection bottle, sample introduction analysis.
Reagent blank is done in company with sample.
(2) mensuration of neutrality or acid impurities
Sample solution sample introduction analysis under the liquid phase and Mass Spectrometry Conditions of the Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) (UPLC-Q-TOF) of setting.
The liquid chromatography parameter set in method is as follows:
Chromatographic column: AgilentEclipsePlusC
18rRHD (1.8 μm, 2.1 × 100mm); Sample introduction concentration: 40mg/mL; Sampling volume: 0.5 μ L; Column temperature: 40 DEG C; Mobile phase A: acetonitrile, Mobile phase B: ammonium formate (10mmol/L); Flow velocity: 0.4mL/min.Gradient elution program is in table 1.
The Mass Spectrometry Conditions parameter set in method is as follows:
First mass spectrometric.Adopt ESI ion gun, positive ion mode; Ion spray voltage: 5.5kV; Remove a bunch voltage (DP): 80V; Vapo(u)rizing temperature: 600 DEG C; Atomization gas (N
2, GS
1) the front pressure of post: 50psi; Desolventizing gas (N
2, GS
2) the front pressure of post: 50psi; Gas curtain gas (N
2, CUR) and the front pressure of post: 30psi; Collision energy (CE): 10V; Mass axes: 100 ~ 1000amu.
Second order ms.Adopt ESI ion gun, positive ion mode; MS/MS switched scan (IDA); Ion spray voltage: 5.5kV; Remove a bunch voltage (DP): 80V; Vapo(u)rizing temperature: 600 DEG C; Atomization gas (N
2, GS
1) the front pressure of post: 50psi; Desolventizing gas (N
2, GS
2) the front pressure of post: 50psi; Gas curtain gas (N
2, CUR) and the front pressure of post: 30psi; Collision energy (CE): 40V, (CES): 15V; Mass axes: 100 ~ 1000amu.
Under the molecular formula set, retention time, secondary fragment ion parameters condition, see table 2, Integral Processing is carried out to given 25 kinds of neutrality or acid impurities compound, obtains the peak area numerical value of each compound.
Use the method, detect for each neutrality or acid impurities in 150 parts " Golden Triangle " and " Golden Crescent " maternal heroin, the mean value of its peak area and relative standard deviation RSD data are in table 4.
Table 4150 part " Golden Triangle " and " Golden Crescent " heroin maternal sample peak area average and relative standard deviation RSD statistical form
The application establishes the method that employing Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS) measures 25 kinds of neutrality/acid impurities in heroin first, this method has the advantage that pre-treatment is simple, testing cost is low, analysis time is short, selectivity is good compared with existing neutrality/acid impurities detection method, meets the demand of batch heroin sample source ground Quick.
Claims (16)
1. 25 kinds of neutrality in Simultaneously test heroin or a method for acid impurities, adopt Ultra Performance Liquid Chromatography-series connection quadrupole rod time-of-flight mass spectrometry (TOFMS), the method comprises the following steps:
(1) extraction of neutrality to be measured or acid impurities in heroin sample
Take heroin sample, be placed in glass centrifuge tube, add acidified solvent, ultrasonic process, adds Extraction solvent, and concussion is centrifugal after extracting, and through filter membrane process, obtains sample solution;
Reagent blank is done in company with sample;
(2) mensuration of neutrality or acid impurities
Set corresponding liquid phase chromatogram condition and Mass Spectrometry Conditions, comprise the molecular formula of setting, retention time, secondary fragment ion parameters, by Ultra Performance Liquid Chromatography-series connection level Four bar time-of-flight mass spectrometry (TOFMS), Integral Processing is carried out to be measured 25 kinds of neutrality or acid impurities compound, obtains the peak area numerical value of each compound; Wherein, described liquid phase chromatogram condition is:
Chromatographic column: AgilentEclipsePlusC
18rRHD, 1.8 μm, 2.1 × 100mm; Sample introduction concentration: 40mg/mL; Sampling volume: 0.5 μ L; Column temperature: 40 DEG C; Mobile phase A: acetonitrile, Mobile phase B: 10mmol/L ammonium formate solution; Flow velocity: 0.4mL/min, gradient elution program sees the following form,
Gradient elution program
；
Wherein, the retention time set in step (2), secondary fragment ion parameters are as follows:
In upper table, the neutrality of known structure or its title of acid impurities variable represent, the neutrality of unknown structure or acid impurities variable represent with " extracting mass number/retention time ".
2. method according to claim 1, is characterized in that, acidified solvent is selected from HCl solution, HNO
3solution or H
2sO
4solution.
3. method according to claim 2, is characterized in that, acidified solvent is H
2sO
4solution.
4. method according to claim 1 and 2, is characterized in that, Extraction solvent is sherwood oil, methylene chloride mixed solvent.
5. method according to claim 4, its feature is being, Extraction solvent is sherwood oil: the mixed liquor of methylene chloride=3mL:2mL.
6. according to the method one of claim 1-3 Suo Shu, it is characterized in that, described Mass Spectrometry Conditions is:
First mass spectrometric, adopts ESI ion gun, positive ion mode; Ion spray voltage: 5.5kV; Remove a bunch voltage: 80V; Vapo(u)rizing temperature: 600 DEG C; Atomization gas is N
2, pressure: 50psi before post; Desolventizing gas is N
2, pressure: 50psi before post; Gas curtain gas is N
2, pressure: 30psi before post; Collision energy: 10V; Mass axes: 100 ~ 1000amu;
Second order ms, adopts ESI ion gun, positive ion mode; MS/MS switched scan; Ion spray voltage: 5.5kV; Remove a bunch voltage: 80V; Vapo(u)rizing temperature: 600 DEG C; Atomization gas is N
2, pressure: 50psi before post; Desolventizing gas is N
2, pressure: 50psi before post; Gas curtain gas is N
2, pressure: 30psi before post; Collision energy: 40V, collision energy is expanded: 15V; Mass axes: 100 ~ 1000amu.
7. according to the method one of claim 1-3 Suo Shu, it is characterized in that, described sonication treatment time is 5-20min.
8. method according to claim 7, is characterized in that, described sonication treatment time is 10min.
9. according to the method one of claim 1-3 Suo Shu, it is characterized in that, described concussion extraction time is 20-40min.
10. method according to claim 9, is characterized in that, described concussion extraction time is 30min.
11., according to the method one of claim 1-3 Suo Shu, is characterized in that, described centrifugal speed is 3000-15000r/min.
12. methods according to claim 11, is characterized in that, described centrifugal speed is 4000-8000r/min.
13. methods according to claim 12, is characterized in that described centrifugal speed is 5000r/min.
14., according to the method one of claim 1-3 Suo Shu, is characterized in that, described centrifugation time is 5-20min.
15. methods according to claim 14, is characterized in that, described centrifugation time is 10min.
16., according to the method one of claim 1-3 Suo Shu, is characterized in that, described filter membrane is 0.22 μm of organic system filter membrane.
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