CN106290615B - A kind of micro maleic acid hydrazide separation method - Google Patents

A kind of micro maleic acid hydrazide separation method Download PDF

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CN106290615B
CN106290615B CN201610608651.8A CN201610608651A CN106290615B CN 106290615 B CN106290615 B CN 106290615B CN 201610608651 A CN201610608651 A CN 201610608651A CN 106290615 B CN106290615 B CN 106290615B
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extraction
maleic acid
micro
acid hydrazide
separation method
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CN106290615A (en
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孔光辉
顾丽莉
师君丽
吕小刚
李勇
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Yunnan Academy of Tobacco Agricultural Sciences
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

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Abstract

The invention discloses a kind of micro maleic acid hydrazide separation methods, including pre-treatment, extraction and separation step, specifically include：By raw material through drying, pulverize and sieve；It is placed in extractor and uses supercritical CO2Fluid extraction obtains extract liquor；Extract liquor is concentrated by evaporation to obtain extraction concentrate, then material quality volume ratio 1 will be added in extraction concentrate：1~5 methanol crosses organic filter film and obtains extracting and purifying liquid after shaking up；Extracting and purifying liquid is detected maleic hydrazide content with high performance liquid chromatography.The present invention extracts micro maleic acid hydrazide in tobacco leaf using supercritical carbon dioxide fluid and specific adjuvant as extractant, and gained extract liquor is detected by concentration and purified treatment for efficient liquid phase chromatographic analysis.Operating process of the present invention is simple, and recovery rate is high, and organic reagent dosage is few, and pre-treatment is quick, and the rate of recovery is high, and stability is good, and will not destroy determination sample, can be used as the specific determination method of micro maleic acid hydrazide in tobacco and tobacco product.

Description

A kind of micro maleic acid hydrazide separation method
Technical field
The invention belongs to separation technology fields, and in particular to a kind of micro maleic acid hydrazide separation method.
Background technology
Maleic acid hydrazide, chemical name are maleic hydrazide（Maleic hydrazide, MH）, alias is maleic hydrazide, is made For a kind of selective vegetable depressor and herbicide, it is widely used in the fields such as plant, crops.Maleic acid hydrazide exists Three kinds of tautomers, room temperature（25℃）It is white crystal, density 1.60g/m down3, the substance is more stable, and fusing point exists Within the scope of 296-298 DEG C, it is insoluble in water and general solvent.Maleic acid hydrazide can reduce the photosynthesis of plant, hinder plant Inner cell divides, to inhibit axillary bud growth, such as garlic, the growth of potato and tobacco leaf axillary bud.Studies have reported that maleic acid hydrazide It is a kind of mutagenesis carcinogen, cell can be generated different degrees of toxic effect by being accumulated in organism after reaching a certain amount of.So MH persticide residues, which become leaf tobacco production, must monitor one of project.Effectively extracted from tobacco leaf maleic acid hydrazide persticide residue at For the important content of detection technique.
Invention content
The purpose of the present invention is to provide a kind of micro maleic acid hydrazide separation methods.
The object of the present invention is achieved like this, including pre-treatment, extraction and separation step, specifically includes：
A, pre-treatment：By raw material through drying, pulverize and sieve it is spare；
B, it extracts：Supercritical CO will be used in raw material merging extractor after pre-treatment2Fluid extraction obtains extract liquor；
C, it detaches：Extract liquor is concentrated by evaporation to obtain extraction concentrate, then material quality will be added in extraction concentrate Volume ratio 1：1~5 methanol crosses organic filter film and obtains extracting and purifying liquid after shaking up；
D, it detects：Extracting and purifying liquid is detected maleic hydrazide content with high performance liquid chromatography.
Standard curve and detection limit：
100mg maleic acid hydrazides accurately are weighed, 0.1mg is accurate to, is dissolved in 100mL methanol, obtain the Malaysia acyl of 1mg/mL Hydrazine mother liquor takes in 10mL mother liquors methanol constant volume to 100mL volumetric flasks.The standard solution of 100 μ g/mL is obtained, is being distilled respectively The 100 μ g/mL maleic acid hydrazide standard solution of 0.1,0.5,1,2,4,8 and 10mL are added in bottle, then presses and measures tobacco sample Step is handled, and is prepared 7 standard solution, is used the peak area of HPLC bioassay standard solution（See Fig. 1）, and with peak area (y) working curve is obtained to its corresponding concentration (x) mapping（See Fig. 2）, regression equation is obtained by regression analysis：Y = 8.7513X-1.615 related coefficient 0.99992.The detection of this method is limited to 2.7 μ g/g.
The present invention extracts micro Malaysia acyl in tobacco leaf using supercritical carbon dioxide fluid and specific adjuvant as extractant Hydrazine, gained extract liquor are detected by concentration and purified treatment for efficient liquid phase chromatographic analysis.Operating process of the present invention is simple, carries Take rate high, organic reagent dosage is few, and pre-treatment is quick, and the rate of recovery is high, and stability is good, and will not destroy determination sample, can make For the specific determination method of micro maleic acid hydrazide in tobacco and tobacco product.
Description of the drawings
Fig. 1 is the chromatogram of maleic acid hydrazide standard solution；
Fig. 2 is maleic acid hydrazide standard curve schematic diagram；
Fig. 3 is the HPLC chromatogram of 1 extraction and separation product of embodiment；
Fig. 4 is the HPLC chromatogram of 2 extraction and separation product of embodiment；
Fig. 5 is the HPLC chromatogram of 3 extraction and separation product of embodiment.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is further illustrated, but is not subject in any way to the present invention Limitation, based on present invention teach that made by it is any transform or replace, all belong to the scope of protection of the present invention.
Micro maleic acid hydrazide separation method of the present invention, including pre-treatment, extraction and separation step, specifically include：
A, pre-treatment：By raw material through drying, pulverize and sieve it is spare；
B, it extracts：Supercritical CO will be used in raw material merging extractor after pre-treatment2Fluid extraction obtains extract liquor；
C, it detaches：Extract liquor is concentrated by evaporation to obtain extraction concentrate, then material quality will be added in extraction concentrate Volume ratio 1：1~5 methanol crosses organic filter film and obtains extracting and purifying liquid after shaking up；
D, it detects：Extracting and purifying liquid is detected maleic hydrazide content with high performance liquid chromatography.
The raw material is tobacco or tobacco product.
Drying described in step A be by raw material at 35~45 DEG C dry 4~6h to moisture content be 2~8%.
Pulverizing and sieving described in step A is to crushed 40~100 mesh sieve.
Supercritical CO described in step B2The condition of fluid extraction is：20~80 DEG C of temperature；10~35MPa of pressure；It is special Determine the binary or ternary mixture that auxiliary agent is methanol, isopropanol and Acetonitrile combinations, ratio range is methanol：Isopropanol：Acetonitrile= a：b：C, wherein a are 0,1 or 2, and b is 0 or 1, and c is 0 or 1；CO2Flow be 10~25g/min, the dosage of specific adjuvant is CO2 The 2~5% of flow；Extraction mode is dynamic extraction；Extraction time is 50~100min.
Evaporation and concentration described in step C is that Rotary Evaporators are used at 70~90KPa of vacuum degree, 20~45 DEG C of temperature 5~15min of concentration obtains extraction concentrate.
The organic filter film that organic filter film described in step C is 0.22~0.45 μm.
High performance liquid chromatography detection condition described in D steps is：Chromatographic column:SBC18（4.6mm×250mm,5um）；Stream Dynamic phase：0.1moL/L ammonium acetate solutions（pH=4.8）；Detection wavelength 303nm；30 DEG C of column temperature；Flow rate of mobile phase 0.7mL/min；Into 5 μ L of sample amount, isocratic elution.
The specific implementation of micro maleic acid hydrazide separation method of the present invention is as follows：
Extraction and separation operate：
(1) the tobacco leaf crushed is dried 5 hours at 40 DEG C, be sieved, it is spare accurately to weigh dry 5 ~ 10g of offal.
(2) load weighted offal is put into extractor, setting operation parameter, extraction temperature, extracting pressure, CO2Flow, it is special Determine auxiliary agent.
(3) after parameter setting, CO is opened2Valve opens CO2Pump, extracting system are started to work.
When in extractor state reach setting value, while while having tail gas releasing, starts timing.
(5) extraction time is reached, extraction experiments are terminated, CO is closed in the operation of halt system2Pump closes CO2Valve.
(6) after extraction experiments, extracting system pressure is continuously decreased to atmospheric pressure, tank temperature to be extracted is down to 30 DEG C, is beaten The exhaust-valve at collecting tank bottom is opened, extract liquor is collected and is measured.
(7) supercritical CO is cleaned after testing2Equipment, playback.
Technological parameter：
Supercritical carbon dioxide fluid state range is：20 ~ 80 DEG C of temperature, 10 ~ 35MPa of pressure；
Specific adjuvant is：The binary or ternary mixture of methanol, isopropanol and Acetonitrile combinations, ratio range are methanol: Isopropanol:Acetonitrile=A:B:C,（A=0,1,2；B=0,1；C=0,1）；
Extracting operation condition：
Extraction temperature：20~80℃
Extracting pressure：10~35MPa
Extraction time：50~100min
Extraction mode：Dynamic extraction
CO2Flow：10~25g/min
Specific adjuvant dosage：Take CO2The 2 ~ 5% of flow
Tobacco sample：It is uniformly added into 20 μ g/g MH standard samples in the tobacco leaf powder without MH, and seals certain time up for safekeeping Allow MH fully penetrateds in tobacco leaf particulate, it is spare.
Tobacco leaf powder size：40 ~ 100 mesh
Extract liquor concentration mensuration：
Extract liquor concentrates condition：In 70 ~ 90kPa of vacuum degree, temperature is at 20 ~ 45 DEG C, using Rotary Evaporators concentration 5 ~ 15min obtains extraction concentrate；
Purified treatment：By above-mentioned extraction concentrate methanol constant volume to 10 ~ 50mL, 0.22 or 0.45 μm of organic filter is crossed Film obtains extracting and purifying liquid.
Separating resulting measures：
High performance liquid chromatography detection condition is：Chromatographic column:SBC18（4.6mm×250mm,5um）；Mobile phase：0.1moL/L Ammonium acetate solution（pH=4.8）；Detection wavelength 303nm；30 DEG C of column temperature；Flow rate of mobile phase 0.7mL/min；Sample size 5 μ L, it is isocratic Elution.
Standard curve and detection limit：
100mg maleic acid hydrazides accurately are weighed, 0.1mg is accurate to, is dissolved in 100mL methanol, obtain the Malaysia acyl of 1mg/mL Hydrazine mother liquor takes in 10mL mother liquors methanol constant volume to 100mL volumetric flasks.The standard solution of 100 μ g/mL is obtained, is being distilled respectively The 100 μ g/mL maleic acid hydrazide standard solution of 0.1,0.5,1,2,4,8 and 10mL are added in bottle, then presses and measures tobacco sample Step is handled, and is prepared 7 standard solution, is used the peak area of HPLC bioassay standard solution（See Fig. 1）, and with peak area (y) working curve is obtained to its corresponding concentration (x) mapping（See Fig. 2）, regression equation is obtained by regression analysis：Y = 8.7513X-1.615 related coefficient 0.99992.The detection of this method is limited to 2.7 μ g/g.
Case is embodied, the invention will be further described below：
Embodiment 1
It accurately weighs 60 mesh offal of 10g grain sizes to be put in extractor, supercritical CO is set2Fluid extraction condition：Extraction pressure Power 20MPa, 55 DEG C of extraction temperature, CO2Flow 20g/min, specific adjuvant are methanol:Isopropanol=1:1（V:V）, dosage CO2 The 4% of flow.Open CO2Valve opens CO2Pump, starts extraction and separation system, and the dynamic extraction 60min under setting condition terminates CO is closed in extraction experiments, the operation of halt system2Pump.After extraction experiments, system pressure is continuously decreased to atmospheric pressure, is waited for Extractor temperature is down to 30 DEG C, and the exhaust-valve for opening collecting tank bottom collects extract liquor and weighs.Gained extract liquor is placed in vacuum Rotary Evaporators concentrate 10min at being 40 DEG C in 0.08MPa and temperature, obtain extraction concentrate；Above-mentioned extraction concentrate is used Methanol constant volume crosses 0.45 μm of organic filter film, obtains extracting and purifying liquid to 10mL.With high performance liquid chromatography detection extracting and purifying liquid Middle maleic hydrazide content, testing conditions are：Chromatographic column:SBC18（4.6mm×250mm,5um）；Mobile phase：0.1moL/L acetic acid Ammonium salt solution（pH=4.8）；Detection wavelength 303nm；30 DEG C of column temperature；Flow rate of mobile phase 0.7mL/min；5 μ L of sample size, isocratic elution. The rate of recovery that MH is obtained by testing result is 95.08%, RSD 4.87%.
Embodiment 2
It accurately weighs 80 mesh offal of 10g grain sizes to be put in extractor, supercritical CO is set2Fluid extraction condition：Extraction pressure Power 25MPa, 50 DEG C of extraction temperature, CO2Flow 25g/min, specific adjuvant are methanol:Isopropanol:Acetonitrile=1:1:1（V:V:V）, Its dosage is CO2The 3% of flow.Open CO2Valve opens CO2Pump starts extraction and separation system, dynamically extracts under setting condition 80min is taken, extraction experiments are terminated, CO is closed in the operation of halt system2Pump.After extraction experiments, system pressure is continuously decreased To atmospheric pressure, tank temperature to be extracted is down to 30 DEG C, and the exhaust-valve for opening collecting tank bottom collects extract liquor and weighs.Gained is extracted Liquid is placed in vacuum rotary evaporator, concentrates 5min at being 30 DEG C in 0.09MPa and temperature, obtains extraction concentrate；By above-mentioned extraction It takes concentrate methanol constant volume to 10mL, crosses 0.45 μm of organic filter film, obtain extracting and purifying liquid.Use high performance liquid chromatography detection Maleic hydrazide content in extracting and purifying liquid, testing conditions are：Chromatographic column:SBC18（4.6mm×250mm,5um）；Mobile phase： 0.1moL/L ammonium acetate solutions（pH=4.8）；Detection wavelength 303nm；30 DEG C of column temperature；Flow rate of mobile phase 0.7mL/min；Sample size 5 μ L, isocratic elution.The rate of recovery that MH is obtained by testing result is 99.16%, RSD 2.37%.
Embodiment 3
It accurately weighs 80 mesh offal of 5g grain sizes to be put in extractor, supercritical CO is set2Fluid extraction condition：Extracting pressure 20MPa, 50 DEG C of extraction temperature, CO2Flow 15g/min, specific adjuvant are methanol:Isopropanol=1:1（V:V）, dosage CO2Stream The 4% of amount.Open CO2Valve opens CO2Pump, starts extraction and separation system, and the dynamic extraction 60min under setting condition terminates extraction Experiment, the operation of halt system is taken to close CO2Pump.After extraction experiments, system pressure is continuously decreased to atmospheric pressure, waits extracting Tank temperature is taken to be down to 30 DEG C, the exhaust-valve for opening collecting tank bottom collects extract liquor and weighs.Gained extract liquor is placed in vacuum rotation Turn evaporimeter, concentrates 8min at being 40 DEG C in 0.08MPa and temperature, obtain extraction concentrate；By above-mentioned extraction concentrate first Alcohol is settled to 10mL, crosses 0.45 μm of organic filter film, obtains extracting and purifying liquid.With in high performance liquid chromatography detection extracting and purifying liquid Maleic hydrazide content, testing conditions are：Chromatographic column:SBC18（4.6mm×250mm,5um）；Mobile phase：0.1moL/L ammonium acetates Solution（pH=4.8）；Detection wavelength 303nm；30 DEG C of column temperature；Flow rate of mobile phase 0.7mL/min；5 μ L of sample size, isocratic elution.By The rate of recovery that testing result obtains MH is 98.08%, RSD 2.45%.

Claims (7)

1. a kind of micro maleic acid hydrazide separation method, it is characterised in that including pre-treatment, extraction and separation step, specifically include：
A, pre-treatment：By raw material through drying, pulverize and sieve it is spare；
B, it extracts：Supercritical CO will be used in raw material merging extractor after pre-treatment2Fluid extraction obtains extract liquor；It is described super Critical CO2The condition of fluid extraction is：20 ~ 80 DEG C of temperature；10 ~ 35MPa of pressure；Specific adjuvant is methanol, isopropanol and acetonitrile The binary or ternary mixture of combination, ratio range are methanol:Isopropanol:Acetonitrile=a:b:C, wherein a are 0,1 or 2, b 0 Or 1, c is 0 or 1；CO2Flow be 10 ~ 25g/min, the dosage of specific adjuvant is CO2The 2 ~ 5% of flow；Extraction mode is dynamic Extraction；Extraction time is 50 ~ 100min；
C, it detaches：Extract liquor is concentrated by evaporation to obtain extraction concentrate, then material quality volume will be added in extraction concentrate Than 1：1 ~ 5 methanol crosses organic filter film and obtains extracting and purifying liquid after shaking up；
D, it detects：Extracting and purifying liquid is detected maleic hydrazide content with high performance liquid chromatography.
2. micro maleic acid hydrazide separation method according to claim 1, it is characterised in that the raw material is tobacco or cigarette Straw-made articles.
3. micro maleic acid hydrazide separation method according to claim 1, it is characterised in that the drying described in step A be by Raw material at 35 ~ 45 DEG C dry 4 ~ 6h to moisture content be 2 ~ 8%.
4. micro maleic acid hydrazide separation method according to claim 1, it is characterised in that pulverizing and sieving described in step A It is that crushed 40 ~ 100 mesh sieve.
5. micro maleic acid hydrazide separation method according to claim 1, it is characterised in that the evaporation and concentration described in step C It is to concentrate 5 ~ 15min using Rotary Evaporators at 70 ~ 90KPa of vacuum degree, 20 ~ 45 DEG C of temperature to obtain extraction concentrate.
6. micro maleic acid hydrazide separation method according to claim 1, it is characterised in that the organic filter described in step C The organic filter film that film is 0.22 ~ 0.45 μm.
7. micro maleic acid hydrazide separation method according to claim 1, it is characterised in that the efficient liquid phase described in D steps Chromatographic test strip part is：Chromatographic column:SBC18,4.6mm × 250mm, 5 μm；Mobile phase：0.1moL/L ammonium acetate solutions pH= 4.8；Detection wavelength 303nm；30 DEG C of column temperature；Flow rate of mobile phase 0.7mL/min；5 μ L of sample size, isocratic elution.
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CN107807188B (en) * 2017-10-30 2020-02-07 云南省烟草农业科学研究院 Tobacco maleic hydrazide and glucoside quantitative analysis method thereof based on liquid chromatography-high resolution mass spectrometry

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