CN109187830A - The method of 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance - Google Patents
The method of 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance Download PDFInfo
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Abstract
The present invention relates to the methods of 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance, belong to technical field of analytical chemistry.The present invention use gas chromatograph-mass spectrometer (GC-MS), deuterated -1- propyl alcohol -1,1,3,3,3-d5For internal standard, 20:1 split sampling, temperature programming, the method that SIM scan pattern establishes 9 kinds of alcohol compound contents in the quick measurement flavors and fragrances of one kind.It analyzes by the method for the invention, 9 kinds of alcohol compounds have the good range of linearity in 0.2-50 mg/L, related coefficient is 0.993 or more, quantitative limit is between 0.65 ~ 1.01mg/kg, the average recovery rate of mark-on experiment is between 87.9% ~ 105.2%, relative standard deviation is between 2.01% ~ 4.83%, the results showed that this method is easy, quick, accurate, and method analyzes measurement suitable for edible essence fragrance while 9 kinds of alcohol compounds.
Description
Technical field
The invention belongs to technical field of analytical chemistry, and in particular to a kind of GC-MS method Rapid Simultaneous Determination edible essence is fragrant
The method of 9 kinds of alcohol compound contents in material.
Background technique
Edible essence fragrance would generally use ethyl alcohol as the solvent extracted in extraction and preparation process, and ethyl alcohol exists
A series of micro or trace miscellaneous by-product alcohols-fusel oil is inevitably resulted from its fermentation production process.This
Some alcohol compounds are easily adulterated and are mixed into edible essence fragrance with the use of ethyl alcohol, such as methanol, 1- propyl alcohol, Zhong Ding
Alcohol, isobutanol, n-butyl alcohol etc., they can generate the esters with unique perfume in conjunction with organic acid, meanwhile, and have one
Fixed toxicity, this is because its poisoning and anesthetic effect are very strong, toxicity increases with molecular weight and is increased, and can make nerveous system
System is congested, leads to number of people pain, dry.If isobutanol and isoamyl alcohol are slow compared with ethyl alcohol in the intracorporal oxidative metabolism reaction of people, when stop
Between it is long, can cause headache etc. symptoms.Therefore, the content of fusel oil seems for its safety evaluatio in Accurate Determining flavors and fragrances
It is most important.
There is not been reported for the method for fusel oil content in current measurement flavors and fragrances, and existing research focuses mostly in measurement wine
Fusel oil content in essence, and common method is mainly colorimetric method and gas chromatography.Colorimetric method operation is comparatively laborious, sensitive
Spend low, disturbing factor is more, and evaluated error is big, and can only measure one-component.Therefore how overcome the deficiencies in the prior art is mesh
The problem of preceding technical field of analytical chemistry urgent need to resolve.
Summary of the invention
It is edible that It is an object of the present invention to solve the deficiency of the existing technology and provide a kind of GC-MS method Rapid Simultaneous Determinations
The method of 9 kinds of alcohol compound contents in flavors and fragrances, this method is easy, quick, accurate, 9 suitable for edible essence fragrance
Analysis measurement, application easy to spread while kind miscellaneous alcohol compound.
To achieve the above object, The technical solution adopted by the invention is as follows:
The method of 9 kinds of alcohol compound contents, includes the following steps: in GC-MS method Rapid Simultaneous Determination edible essence fragrance
Step (1), with deuterated -1- propyl alcohol -1,1,3,3,3-d5 as internal standard compound, and it is molten to prepare the internal standard work containing internal standard compound
Liquid；
Step (2) is prepared the series standard working solution containing 9 kinds of alcohol compounds and internal standard compound, and is analyzed using GC-MS,
Draw the standard working curve of 9 kinds of alcohol compounds；
9 kinds of alcohol compounds are methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, positive penta
Pure and mild n-hexyl alcohol；
Step (3), flavors and fragrances sample is added in extractant containging interior traget, oscillation extraction, is stood, organic phase filter membrane
Filtering, filtrate carry out GC-MS analysis, calculate the perfume according to the standard working curve that step (2) obtains according to inner mark method ration
The content of 9 kinds of alcohol compounds in smart fragrance sample.
It is further preferred that the internal standard working solution containing internal standard compound is to contain 180-220 mg/L in step (1)
The ethanol solution of internal standard compound.
It is further preferred that in step (2), the preparation method of series standard working solution are as follows: use ethyl alcohol as molten
Agent, prepare containing etc. mass concentrations methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, n-amyl alcohol
With the series standard working solution of 9 kinds of alcohol compounds of n-hexyl alcohol, wherein the concentration of 9 kinds of alcohol compounds be 0.8mg/L,
4mg/L, 8mg/L, 16mg/L, 40mg/L, deuterated -1- propyl alcohol -1,1,3,3,3-d5 concentration are 2mg/L.
It is further preferred that preparing hybrid standard stock solution first when the preparation of series standard working solution: with etc.
Methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, n-amyl alcohol and the n-hexyl alcohol of quality are solute, so
It is added in ethyl alcohol together afterwards, is configured to the hybrid standard stock solution that every kind of solute concentration is 2000 mg/L；
Then it prepares level-one mixed standard solution: hybrid standard stock solution made from step (2) being added in ethyl alcohol, is configured to
Every kind of solute concentration is the level-one mixed standard solution of 80 mg/L；
It finally prepares series standard working solution: accurately pipetting 0.1mL, 0.5mL, 1mL, 2mL, 5mL level-one hybrid standard respectively
Solution is added 100 μ L internal standard stock solutions, is settled to 10mL with ethyl alcohol to get series standard working solution.
It is further preferred that in step (2), when standard working curve is drawn, with every kind of alcohol compound it is quantitative from
The ratio of sub- peak area and internal standard compound quota ion peak area is ordinate, dense with corresponding alcohol compound concentration and internal standard compound
The ratio of degree is abscissa, draws standard working curve.
It is further preferred that the flavors and fragrances sample is edible essence fragrance.
It is further preferred that in step (3), 0.45-0.55 g flavors and fragrances sample is added in step (3)
In the mixed liquor of 14-16 mL ethyl alcohol and the ethanol solution containing 180-220 mg/L internal standard compound of 140-160 μ L.
It is further preferred that the revolving speed of oscillation extraction is 140-160 r/min, time 9-11 in step (3)
min；Time of repose is 1.8-2.2min；Organic phase filter membrane is 0.22 μm of organic phase filter membrane.
It is further preferred that organic phase filter membrane is 0.22 μm of organic phase filter membrane in step (3).
It is further preferred that in step (3), calculation method specifically:
By following equation calculate separately methanol in flavors and fragrances sample, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol,
The content of isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol:
C=Ci×V/m；
Wherein, C --- the content of 9 kinds of alcohol compound kind one kind, unit mg/Kg in flavors and fragrances sample；
Ci --- according to the standard working curve of this kind of alcohol compound obtained by step (3), bring flavors and fragrances obtained by step (2) into
The quota ion peak area and the deuterated -1- propyl alcohol -1,1,3,3,3-d5 quota ion of internal standard compound of this in sample kind alcohol compound
The ratio of peak area calculates this kind of alcohol compound concentration and the deuterated -1- propyl alcohol -1,1 of internal standard compound, the ratio of 3,3,3-d5 concentration
Value, and then the concentration of this kind of alcohol compound is obtained, unit mg/L；
The volume of filtrate, unit L in V --- step (2)；
M --- weigh the quality of flavors and fragrances sample, unit Kg.
It is further preferred that when GC-MS is analyzed, the GC condition: chromatographic column: DB-624 capillary column；Carrier gas:
Helium；Flow velocity: 1.5mL/min；Temperature programming: 50 DEG C of initial temperature, 5min is kept, rises to 160 DEG C with 10 DEG C/min, then with 60
DEG C/min rises to 220 DEG C, keep 10min；Injector temperature: 230 DEG C；Split sampling, split ratio 20:1,1 μ L of sample volume；
The MS condition: ion source: EI；Ionize energy: 70eV；Ion source temperature: 230 DEG C；Transmission line temperature: 230 DEG C；
Solvent delay: 0-4.3min, 5.3-8.1min；Scanning of the mass spectrum range: 29m/z-300m/z；Scan pattern: SIM mode.
The present invention is analyzed using Capillary Column GC-mass spectrography, and faster, sample volume is also more for analysis speed
Few, total column effect is more preferable.
Compared with prior art, the present invention has the advantages that:
The present invention uses DB-624 capillary column direct injected, and deuterated -1- propyl alcohol -1,1,3,3,3-d5 be internal standard, establishes one
The content of 9 kinds of alcohol compounds in kind GC-MS method Rapid Simultaneous Determination flavors and fragrances, and the performance indicator of this method is examined
It examines, achieves good result.
Measuring method provided by the invention can be used to measure 9 kinds of alcohol compounds in flavors and fragrances sample, fill up existing
Blank in technology.The present invention is 2.01%-4.83% through the relative standard deviation of 6 parallel determinations, and recovery of standard addition is
87.9%-105.2%, this method detection limit is low, and precision is good, accurately and reliably, has application value.
Detailed description of the invention
Fig. 1 is the selection chromatography of ions figure of 9 kinds of alcohol compound standard solution and internal standard compound standard solution；Wherein.IS is
Deuterated -1- the propyl alcohol -1,1 of internal standard compound, 3,3,3-d5,1 ~ 9 is respectively methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butyl alcohol, secondary penta
Alcohol, isoamyl alcohol, 1- amylalcohol, n-hexyl alcohol.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and it should not be regarded as limiting this hair
Bright range.In the examples where no specific technique or condition is specified, described technology or conditions according to the literature in the art
Or it is carried out according to product description.Production firm person is not specified in material therefor or equipment, is that can be obtained by purchase
Conventional products.
Embodiment 1
The method of 9 kinds of alcohol compound contents, includes the following steps: in GC-MS method Rapid Simultaneous Determination edible essence fragrance
Step (1), with deuterated -1- propyl alcohol -1,1,3,3,3-d5 as internal standard compound, and it is molten to prepare the internal standard work containing internal standard compound
Liquid；
Step (2) is prepared the series standard working solution containing 9 kinds of alcohol compounds and internal standard compound, and is analyzed using GC-MS,
Draw the standard working curve of 9 kinds of alcohol compounds；
9 kinds of alcohol compounds are methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, positive penta
Pure and mild n-hexyl alcohol；
Step (3), flavors and fragrances sample is added in extractant containging interior traget, oscillation extraction, is stood, organic phase filter membrane
Filtering, filtrate carry out GC-MS analysis, calculate the perfume according to the standard working curve that step (2) obtains according to inner mark method ration
The content of 9 kinds of alcohol compounds in smart fragrance sample.
Embodiment 2
The method of 9 kinds of alcohol compound contents, includes the following steps: in GC-MS method Rapid Simultaneous Determination edible essence fragrance
Step (1), as internal standard compound, prepares the ethyl alcohol containing 180 mg/L internal standard compounds with deuterated -1- propyl alcohol -1,1,3,3,3-d5
Solution；
Step (2) is prepared the series standard working solution containing 9 kinds of alcohol compounds and internal standard compound, and is analyzed using GC-MS,
Draw the standard working curve of 9 kinds of alcohol compounds；
9 kinds of alcohol compounds are methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, positive penta
Pure and mild n-hexyl alcohol；
The preparation method of series standard working solution are as follows: use ethyl alcohol as solvent, prepare containing etc. mass concentrations methanol, 1- third
The series standard work of alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, 9 kinds of isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol alcohol compounds
Make solution, wherein the concentration of 9 kinds of alcohol compounds is 0.8mg/L, 4mg/L, 8mg/L, 16mg/L, 40mg/L, deuterated -1-
The concentration of propyl alcohol -1,1,3,3,3-d5 is 2mg/L；When standard working curve is drawn, with the quota ion of every kind of alcohol compound
The ratio of peak area and internal standard compound quota ion peak area is ordinate, with corresponding alcohol compound concentration and internal standard compound concentration
Ratio be abscissa, draw standard working curve.
Step (3) contains 180 mg/L for what 0.45 g of edible essence fragrance sample was added to 14 mL ethyl alcohol and 140 μ L
In the mixed liquor of the ethanol solution of internal standard compound, 9min is extracted with the speed oscillation of 140 r/min, stands 1.8min, 0.22 μm has
Machine phase membrane filtration, filtrate carries out GC-MS analysis, according to inner mark method ration, according to the standard working curve that step (2) obtains,
Calculate the content of 9 kinds of alcohol compounds in the flavors and fragrances sample.
In step (3), calculation method specifically:
By following equation calculate separately methanol in flavors and fragrances sample, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol,
The content of isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol:
C=Ci×V/m；
Wherein, C --- the content of 9 kinds of alcohol compound kind one kind, unit mg/Kg in flavors and fragrances sample；
Ci --- according to the standard working curve of this kind of alcohol compound obtained by step (3), bring flavors and fragrances obtained by step (2) into
The quota ion peak area and the deuterated -1- propyl alcohol -1,1,3,3,3-d5 quota ion of internal standard compound of this in sample kind alcohol compound
The ratio of peak area calculates this kind of alcohol compound concentration and the deuterated -1- propyl alcohol -1,1 of internal standard compound, the ratio of 3,3,3-d5 concentration
Value, and then the concentration of this kind of alcohol compound is obtained, unit mg/L；
The volume of filtrate, unit L in V --- step (2)；
M --- weigh the quality of flavors and fragrances sample, unit Kg.
When GC-MS is analyzed, the GC condition: chromatographic column: DB-624 capillary column；Carrier gas: helium；Flow velocity: 1.5mL/
min；Temperature programming:, keeping 5min, rise to 160 DEG C with 10 DEG C/min, then rise to 220 DEG C with 60 DEG C/min by 50 DEG C of initial temperature,
Keep 10min；Injector temperature: 230 DEG C；Split sampling, split ratio 20:1,1 μ L of sample volume；
The MS condition: ion source: EI；Ionize energy: 70eV；Ion source temperature: 230 DEG C；Transmission line temperature: 230 DEG C；
Solvent delay: 0-4.3min, 5.3-8.1min；Scanning of the mass spectrum range: 29m/z-300m/z；Scan pattern: SIM mode.
Embodiment 3
The method of 9 kinds of alcohol compound contents, includes the following steps: in GC-MS method Rapid Simultaneous Determination edible essence fragrance
Step (1), as internal standard compound, prepares the ethyl alcohol containing 220 mg/L internal standard compounds with deuterated -1- propyl alcohol -1,1,3,3,3-d5
Solution；
Step (2) is prepared the series standard working solution containing 9 kinds of alcohol compounds and internal standard compound, and is analyzed using GC-MS,
Draw the standard working curve of 9 kinds of alcohol compounds；
9 kinds of alcohol compounds are methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, positive penta
Pure and mild n-hexyl alcohol；
The preparation method of series standard working solution are as follows: use ethyl alcohol as solvent, prepare containing etc. mass concentrations methanol, 1- third
The series standard work of alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, 9 kinds of isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol alcohol compounds
Make solution, wherein the concentration of 9 kinds of alcohol compounds is 0.8mg/L, 4mg/L, 8mg/L, 16mg/L, 40mg/L, deuterated -1-
The concentration of propyl alcohol -1,1,3,3,3-d5 is 2mg/L；When standard working curve is drawn, with the quota ion of every kind of alcohol compound
The ratio of peak area and internal standard compound quota ion peak area is ordinate, with corresponding alcohol compound concentration and internal standard compound concentration
Ratio be abscissa, draw standard working curve.
When the preparation of series standard working solution, prepare hybrid standard stock solution first: with etc. quality methanol, 1- third
Alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol are solute, are then added to ethyl alcohol together
In, it is configured to the hybrid standard stock solution that every kind of solute concentration is 2000 mg/L；
Then it prepares level-one mixed standard solution: hybrid standard stock solution made from step (2) being added in ethyl alcohol, is configured to
Every kind of solute concentration is the level-one mixed standard solution of 80 mg/L；
It finally prepares series standard working solution: accurately pipetting 0.1mL, 0.5mL, 1mL, 2mL, 5mL level-one hybrid standard respectively
Solution is added 100 μ L internal standard stock solutions, is settled to 10mL with ethyl alcohol to get series standard working solution.
Step (3) contains 220 mg/L for what 0.55 g of edible essence fragrance sample was added to 16 mL ethyl alcohol and 160 μ L
In the mixed liquor of the ethanol solution of internal standard compound, 11min is extracted with the speed oscillation of 150 r/min, stands 2.2min, 0.22 μm has
Machine phase membrane filtration, filtrate carries out GC-MS analysis, according to inner mark method ration, according to the standard working curve that step (2) obtains,
Calculate the content of 9 kinds of alcohol compounds in the flavors and fragrances sample.
In step (3), calculation method specifically:
By following equation calculate separately methanol in flavors and fragrances sample, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol,
The content of isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol:
C=Ci×V/m；
Wherein, C --- the content of 9 kinds of alcohol compound kind one kind, unit mg/Kg in flavors and fragrances sample；
Ci --- according to the standard working curve of this kind of alcohol compound obtained by step (3), bring flavors and fragrances obtained by step (2) into
The quota ion peak area and the deuterated -1- propyl alcohol -1,1,3,3,3-d5 quota ion of internal standard compound of this in sample kind alcohol compound
The ratio of peak area calculates this kind of alcohol compound concentration and the deuterated -1- propyl alcohol -1,1 of internal standard compound, the ratio of 3,3,3-d5 concentration
Value, and then the concentration of this kind of alcohol compound is obtained, unit mg/L；
The volume of filtrate, unit L in V --- step (2)；
M --- weigh the quality of flavors and fragrances sample, unit Kg.
When GC-MS is analyzed, the GC condition: chromatographic column: DB-624 capillary column；Carrier gas: helium；Flow velocity: 1.5mL/
min；Temperature programming:, keeping 5min, rise to 160 DEG C with 10 DEG C/min, then rise to 220 DEG C with 60 DEG C/min by 50 DEG C of initial temperature,
Keep 10min；Injector temperature: 230 DEG C；Split sampling, split ratio 20:1,1 μ L of sample volume；
The MS condition: ion source: EI；Ionize energy: 70eV；Ion source temperature: 230 DEG C；Transmission line temperature: 230 DEG C；
Solvent delay: 0-4.3min, 5.3-8.1min；Scanning of the mass spectrum range: 29m/z-300m/z；Scan pattern: SIM mode.
Embodiment 4
1.1 instruments and reagent
Perkin Elmer Clarus 600T type gas chromatography-mass spectrometry (Perkin Elmer company of the U.S.)；DB-
624 capillary columns (60m × 0.32mm × 1.8 μm, Agilent company of the U.S.)；AE200 type electronic analytical balance (German plum
Teller company)；HY-5A convolution adjusts the speed multi-purpose oscillator (Shanghai Lan Yi Industrial Co., Ltd.).
Anhydrous sodium sulfate (analysis is pure, is placed in spare in drier after cooling with preceding 550 DEG C of bakings 2-3 h), ethyl alcohol (color
Compose pure, purity 99.9%)；Methanol (purity 99.9%)；1- propyl alcohol (purity 99.9%)；Sec-butyl alcohol (purity 99.5%)；
Isobutanol (purity 99.8%)；N-butyl alcohol (purity 99.8%)；Sec-amyl alcohol (purity 99.5%)；(purity is isoamyl alcohol
99.6%)；1- amylalcohol (purity 99.5%)；N-hexyl alcohol (purity 99.8%)；Deuterated -1- propyl alcohol -1,1,3,3,3-d5(CAS
Number: 188894-71-5, purity 99.3%).
1.2 standard solution are prepared
50 mg, 9 kinds of alcohol compounds are accurately weighed in same 25 mL brown volumetric flask, are settled to scale with ethyl alcohol, are prepared
The hybrid standard stock solution for being 2000 mg/L at concentration；
Accurately weigh the deuterated -1- propyl alcohol -1,1,3,3,3-d of 10 mg5In 50 mL brown volumetric flasks, quarter is settled to ethyl alcohol
Degree is configured to the internal standard stock solution that concentration is 200 mg/L；
2 mL hybrid standard stock solutions accurately are pipetted into 50 mL brown volumetric flasks, are settled to scale with ethyl alcohol, are configured to concentration
For the level-one mixed standard solution of 80 mg/L；
The series standard working solution of suitable concentration is prepared according to sample actual content；Recommend following preparation method: accurate respectively
0.1 mL, 0.5 mL, 1 mL, 2 mL, 5 mL level-one mixed standard solutions are pipetted in 10 mL brown volumetric flasks, 100 μ are added
L internal standard stock solution is settled to scale with ethyl alcohol to get series standard working solution.
1.3 sample pre-treatments
0.5 g flavors and fragrances sample is accurately weighed in 50 mL stuffed conical flasks, is accurate to 0.1 mg, it is accurate respectively to be added 15
The internal standard working solution of mL ethyl alcohol and 150 μ L extracts 10 min on the oscillator with 150 r/min speed oscillations, stands 2
Min takes supernatant liquor to filter through 0.22 μm of organic phase filter membrane, and filtrate carries out GC-MS analysis.
1.4 gaschromatographic mass spectrometry conditions
Chromatographic condition: chromatographic column: DB-624 capillary column；Carrier gas: helium (He)；Flow velocity: 1.5 mL/min；Temperature programming: just
50 DEG C of beginning temperature, 5 min are kept, 160 DEG C is risen to 10 DEG C/min, then rise to 220 DEG C with 60 DEG C/min, keeps 10
min；Injector temperature: 230 DEG C；Split sampling, split ratio 20:1,1 μ L of sample volume.
Mass Spectrometry Conditions: ion source: EI；Ionize energy: 70eV；Ion source temperature: 230 DEG C；Transmission line temperature: 230
℃；Solvent delay: 0-4.3 min, 5.3-8.1 min；Scanning of the mass spectrum range: 29 m/z-300 m/z；Scan pattern: SIM mould
Formula.
Using NIST map library searching, the retention time and abundance of ions ratio at reference standards and sample chromatogram peak are determined
Property, inner mark method ration.
2 results and discussion
Analysis condition when testing and analyzing is optimized, mainly from chromatographic condition, Selection of internal standard, sample pre-treatments condition etc.
Aspect is studied respectively and is optimized.
The optimization of 2.1 analysis conditions
2.1.1 the selection of chromatographic condition
Target compound is the substance of polar volatile, preferably polar column is selected to be analyzed, which selects to be suitble to alcohols
The stationary phase of analysis is the DB-624 capillary column of polyethylene glycol, specification are as follows: 60m × 0.32mm × 1.8 μm, the results showed that, 9 kinds
Alcohol compound fully achieves baseline separation.
Object is a kind of compound, and the boiling spread of object is between 64.7 DEG C -157 DEG C, the boiling of combining target object
Point has selected initial temperature to be tested respectively for 40,50,60,70,80 DEG C.When experiment shows 40 DEG C, the peak of alcohols appearance
Broadening phenomenon is serious, and with the raising of initial temperature, the peak shape of alcohols gradually becomes sharply, and peak width is more and more narrow, retention time
It gradually shortens, the separating degree of ethyl alcohol and propyl alcohol is deteriorated, and after 70 DEG C, ethyl alcohol and propyl alcohol can not achieve baseline separation, and the guarantor of methanol
The time is stayed to shorten, appearance is too fast, and when initial temperature 50 C, alcohols peak shape is preferable, realization baseline separation, while using program
Heating, adjusts split ratio, and injection port, detector temperature and flow rate of carrier gas etc. obtain Optimum separation condition, 9 kinds of compounds and internal standard
The selection chromatography of ions figure of object standard solution is detailed in Fig. 1.
2.1.2 interior target selection
Internal standard is made using substance similar in the chemical property with object, it is possible to reduce sample loss bring analytical error mentions
The accuracy of high detection result.Comprehensively considering physical property, the chemical property of object, this method selects deuterated propyl alcohol-1-1-,
1,3,3,3-d5 as internal standard, internal standard selection the reason is as follows that: 1, Isotopic Internal Standard is not present in sample to be tested；2, it is completely molten
It is kept completely separate in sample and with the chromatographic peak of each component；3, its peak position out is among 9 objects；4, internal standard and object
Belong to a substance, instrument, external environmental condition etc. influence consistent accordingly.Therefore deuterated -1- propyl alcohol -1,1,3,3,3-d5 is selected
As internal standard.
2.1.3 sample pre-treatments condition optimizing
2.1.3.1 sample weighting amount is investigated
Sample weighting amount in 1.3 is investigated, remaining parameter is constant, and sample weighting amount is respectively 0.2,0.5,1 g, each sample weighting amount into
The horizontal measurement of row 5, the results showed that, when sample weighting amount is 0.2g, between 2.78-6.21%, sample weighting amount is the RSD of 9 kinds of compounds
When 0.5 g, the RSD of 9 kinds of compounds is between 1.36%-4.31%, and when sample weighting amount is 1g, the RSD of 9 kinds of compounds is in 3.12%-
Between 4.72%.Comprehensively consider sample weighting amount selection 0.5g.
2.1.3.2 the optimization of solvent volume
The dosage (extraction volume) of ethyl alcohol in 1.3 is investigated, remaining parameter is constant, selects 5,10,15,20,25 mL extraction
Volume is taken to optimize, the experimental results showed that, when extraction volume is 15mL, extraction efficiency is best.
2.1.3.3 the optimization of mode is extracted
Extraction mode in 1.3 is investigated, remaining parameter is constant, and ultrasound, oscillation, the three kinds of modes that are vortexed are optimized and examined
It examines, the experimental results showed that, ultrasound only allows sample molecule to vibrate in a small range, and mixed effect is poor, and the fever in ultrasonic procedure
The loss for easily causing volatility object, especially for the high methanol of recall rate, the extraction mode of vortex oscillation is also easily caused
The loss of object.Comprehensively consider the extraction mode of selection oscillation.
2.1.3.4 the optimization of extraction time
Extraction time in 1.3 is investigated, remaining parameter is constant, and 2,5,10,15,20 min is selected to carry out time-optimized choosing
It selects, the experimental results showed that.Comprehensively consider and selects 10min for optimum extraction time.
2.2 methodological study
2.2.1 linear relationship, detection limit and quantitative limit
Using the chromatographic condition and Mass Spectrometry Conditions of optimization, prepared series standard solution is measured respectively, 9 kinds of objects
And the selection chromatography of ions figure of internal standard compound standard solution is shown in Fig. 1, using selection ion scan mode to 9 kinds of compounds and internal standard compound
It is detected, table 1 summarizes the information such as the qualitatively and quantitatively selection ion of 9 kinds of compounds and internal standard compound.
Table 1
Linear regression is carried out to component to be measured and interior target concentration ratio x with component to be measured and interior target chromatographic peak area ratio y.From table
As can be seen that 9 kinds of components to be measured linear relationship in the range of 0.2-50 mg/L is good in 2, related coefficient is greater than 0.993,9
The detection limit of kind object is between 0.19-0.30 mg/kg, and quantitative limit is between 0.65-1.01 mg/kg.See Table 2 for details.
Table 2
Note: y- peak area ratio；X- concentration ratio.
2.2.2 the rate of recovery and precision
Basic, normal, high 3 concentration levels: 4,9 kinds of standard items of 8,10 mg/L are added to edible essence fragrance sample, according to optimization
Method carries out pre-treatment to sample, is measured in parallel 6 times, measures average recovery rate and relative standard deviation (RSD), measurement result is detailed
It is shown in Table 3.From experimental result as can be seen that the average recovery rate of mark-on experiment is between 87.9%-105.2%, relative standard deviation
Between 2.01%-4.83%, method has good reproducibility and the rate of recovery.
Table 3
2.3 the detection of actual sample
Using chromatographic condition, Mass Spectrometry Conditions and the pre-treating method after above-mentioned optimization, 25 flavors and fragrances samples are detected,
The result shows that sec-butyl alcohol, sec-amyl alcohol and n-hexyl alcohol are not detected；And methanol, normal propyl alcohol, isobutanol, n-butyl alcohol, isoamyl alcohol, 1-
6 kinds of alcohol of amylalcohol have detection, and detection content range is 3.88-134.02mg/kg.In addition, during sample introduction, often into 10 samples
Product are inserted into a solvent blank sample and are measured, do not find sample carryover on a column, and after sample introduction 50 times,
The position of retention time illustrates that this method is stable, reliable there is no drift.
The method of the present invention establishes the detection method of 9 kinds of alcohol compounds in GC-MS-SIM method measurement edible essence fragrance,
And to being studied and optimized respectively in terms of the analysis conditions such as the chromatographic condition, Selection of internal standard, sample pre-treatments of method.It should
Method separating capacity is strong, detection flux height, high sensitivity, analyzes that speed is fast, and method is able to satisfy 9 kinds of alcohols objects while detecting
Requirement, and pre-treatment is easy to operate, and safety is good, and the batch daily suitable for edible essence fragrance sample quickly detects.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
- The method of 9 kinds of alcohol compound contents in 1.GC-MS method Rapid Simultaneous Determination edible essence fragrance, which is characterized in that packet Include following steps:Step (1), with deuterated -1- propyl alcohol -1,1,3,3,3-d5 as internal standard compound, and it is molten to prepare the internal standard work containing internal standard compound Liquid；Step (2) is prepared the series standard working solution containing 9 kinds of alcohol compounds and internal standard compound, and is analyzed using GC-MS, Draw the standard working curve of 9 kinds of alcohol compounds；9 kinds of alcohol compounds are methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, positive penta Pure and mild n-hexyl alcohol；Step (3), flavors and fragrances sample is added in extractant containging interior traget, oscillation extraction, is stood, organic phase filter membrane Filtering, filtrate carry out GC-MS analysis, calculate the perfume according to the standard working curve that step (2) obtains according to inner mark method ration The content of 9 kinds of alcohol compounds in smart fragrance sample.
- 2. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that in step (1), the internal standard working solution containing internal standard compound is to contain 180-220 mg/L internal standard compound Ethanol solution.
- 3. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that in step (2), the preparation method of series standard working solution are as follows: use ethyl alcohol as solvent, preparation contains Methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, n-amyl alcohol and the n-hexyl alcohol 9 of mass concentrations such as have The series standard working solution of kind alcohol compound, wherein the concentration of 9 kinds of alcohol compounds is 0.8mg/L, 4mg/L, 8mg/ L, 16mg/L, 40mg/L, deuterated -1- propyl alcohol -1,1,3,3,3-d5 concentration are 2mg/L.
- 4. 9 kinds of alcohol compounds contain in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 or 3 The method of amount, which is characterized in that when the preparation of series standard working solution, prepare hybrid standard stock solution first: with etc. quality Methanol, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol be solute, then one It rises and is added in ethyl alcohol, be configured to the hybrid standard stock solution that every kind of solute concentration is 2000 mg/L；Then it prepares level-one mixed standard solution: hybrid standard stock solution made from step (2) being added in ethyl alcohol, is configured to Every kind of solute concentration is the level-one mixed standard solution of 80 mg/L；It finally prepares series standard working solution: accurately pipetting 0.1mL, 0.5mL, 1mL, 2mL, 5mL level-one hybrid standard respectively Solution is added 100 μ L internal standard stock solutions, is settled to 10mL with ethyl alcohol to get series standard working solution.
- 5. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that in step (2), when standard working curve is drawn, with the quota ion peak area of every kind of alcohol compound Ratio with internal standard compound quota ion peak area is ordinate, with the ratio of corresponding alcohol compound concentration and internal standard compound concentration For abscissa, standard working curve is drawn.
- 6. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that the flavors and fragrances sample is edible essence fragrance.
- 7. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that in step (3), 0.45-0.55 g flavors and fragrances sample is added to 14-16 mL ethyl alcohol and 140- In the mixed liquor of the ethanol solution containing 180-220 mg/L internal standard compound of 160 μ L.
- 8. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that in step (3), the revolving speed of oscillation extraction is 140-160 r/min, and the time is 9-11 min；When standing Between be 1.8-2.2min；Organic phase filter membrane is 0.22 μm of organic phase filter membrane.
- 9. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that in step (3), calculation method specifically:By following equation calculate separately methanol in flavors and fragrances sample, 1- propyl alcohol, sec-butyl alcohol, isobutanol, n-butanol, sec-amyl alcohol, The content of isoamyl alcohol, n-amyl alcohol and n-hexyl alcohol:C=Ci×V/m；Wherein, C --- the content of 9 kinds of alcohol compound kind one kind, unit mg/Kg in flavors and fragrances sample；Ci --- according to the standard working curve of this kind of alcohol compound obtained by step (3), bring flavors and fragrances obtained by step (2) into The quota ion peak area and the deuterated -1- propyl alcohol -1,1,3,3,3-d5 quota ion of internal standard compound of this in sample kind alcohol compound The ratio of peak area calculates this kind of alcohol compound concentration and the deuterated -1- propyl alcohol -1,1 of internal standard compound, the ratio of 3,3,3-d5 concentration Value, and then the concentration of this kind of alcohol compound is obtained, unit mg/L；The volume of filtrate, unit L in V --- step (2)；M --- weigh the quality of flavors and fragrances sample, unit Kg.
- 10. 9 kinds of alcohol compound contents in GC-MS method Rapid Simultaneous Determination edible essence fragrance according to claim 1 Method, which is characterized in that GC-MS analyze when, the GC condition: chromatographic column: DB-624 capillary column；Carrier gas: helium；Stream Speed: 1.5mL/min；Temperature programming: 50 DEG C of initial temperature, 5min is kept, rises to 160 DEG C with 10 DEG C/min, then with 60 DEG C/min 220 DEG C are risen to, 10min is kept；Injector temperature: 230 DEG C；Split sampling, split ratio 20:1,1 μ L of sample volume；The MS condition: ion source: EI；Ionize energy: 70eV；Ion source temperature: 230 DEG C；Transmission line temperature: 230 DEG C； Solvent delay: 0-4.3min, 5.3-8.1min；Scanning of the mass spectrum range: 29m/z-300m/z；Scan pattern: SIM mode.
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