CN103344731A - Method for qualitative and quantitative determination of sugar alcohols in foods by ion chromatograph-mass spectrometer - Google Patents
Method for qualitative and quantitative determination of sugar alcohols in foods by ion chromatograph-mass spectrometer Download PDFInfo
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Abstract
The invention discloses a method for qualitative and quantitative determination of sugar alcohols in foods by an ion chromatograph-mass spectrometer. The method is characterized in that a sample subjected to extraction purification pre-treatment is detected by the ion chromatograph-mass spectrometer; ion chromatography conditions comprise that 90mmoL/L of a sodium hydroxide solution as a separation column eluting solution is used for isocratic elution at a flow rate of 0.50mL/min; a suppressed conductance method comprising a suppressor electric current of 139mA, a feeding amount of 25.0 microliters and a suppressor water source constant flow pump flow rate of 1.0mL/min is adopted; mass spectrometry conditions comprise that an ionization mode APCI- is adopted and a temperature of fainting during acupuncture treatment is 450 DEG C; atomized gas is nitrogen and has purity of 99.9% and pressure of 55psi; and quantitative analysis adopts an external standard quantitative method. The method realizes on-line qualitative and quantitative detection of sugar alcohols in foods, utilizes a self-made SPE column and the ion chromatograph-mass spectrometer to carry out detection, and realizes simple and fast qualitative and quantitative detection of six sugar alcohols in foods.
Description
Technical field
The present invention relates to field of food and detect analysis field, especially to the analytical approach of the sugar alcohol composition in the food.
Background technology
At inspection and quarantine department, need carry out qualitative and quantitative detection to the content of sugar alcohol of food, but present detection method defective to some extent all.Domestic and international detection method to sugar alcohol in the food comprises at present: high performance liquid chromatography-evaporative light-scattering method, high performance liquid chromatography-differential refraction detection method
,Ion exclusion liquid phase chromatography, vapor-phase chromatography
,Gaschromatographic mass spectrometry method, liquid chromatography tandem mass spectrometry etc.Evaporative light-scattering method, differential refraction detection method, ion exclusion liquid phase chromatography, vapor-phase chromatography etc. all can't satisfy the requirement of European Union's 657 instructions.The positive findings of these detection methods must be again adds their confirmation with other separating column, detecting device.The method that adopts in the condition gaschromatographic mass spectrometry method, need with behind the analyte derivative again nitrogen blow redissolution, sample introduction is consuming time longer then.
Summary of the invention
Technical matters to be solved by this invention provide a kind of detect sugar alcohol in the food detection method, it can be quick, qualitative, quantitative carries out quantitative and qualitative to the sugar alcohol composition and detects.
For solving the problems of the technologies described above, technical scheme chromatography of ions GC-MS qualitative, quantitative provided by the invention is measured the method for sugar alcohol in the food, it comprises the steps: 1), sample pre-treatments contains sample constant volume behind acetonitrile precipitation and refrigerated centrifuge of albumen, grease; Other solid samples grind the back constant volume and handle through refrigerated centrifuge; Fruit juice, flavor drench, the direct constant volume of honey class I liquid I sample, and the sample behind the constant volume is crossed water film and SPE post, and filtrate is for detecting;
2) the chromatography of ions GC-MS detects, wherein, the chromatography of ions condition, the separating column leacheate is that the sodium hydroxide solution of 90mmoL/L carries out isocratic elution, flow velocity is 0.50 mL/min; Adopt and suppress conductance method, the rejector electric current is 139mA, and sample size is 25.0 μ L, rejector water source constant flow pump flow velocity 1.0 mL/min;
3) mass spectrum condition, ionization mode is APCI-, 450 ℃ of the temperature of having a fainting spell during acupuncture treatment; Atomization gas is nitrogen, and purity is 99.9%, pressure is 55 psi;
4) qualitative and quantitative analysis carries out the qualitative analysis of sugar alcohol molecule to sample according to retention time and sugar alcohol feature molion mass-to-charge ratio, utilizes standard law drawing standard curve to carry out quantitative test by external standard method.
In described step 1) sample pre-treatments, contain the sample of albumen, grease, get 0.1～1g sample in the 50mL centrifuge tube, add the 25mL eddies of water and revolve mixing 3 min, ultrasonic extraction 10min; Get the 5mL supernatant in the 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove the normal hexane layer, 2mL gets in another centrifuge tube in lower floor, adds 3mL acetonitrile vortex, 5000 rpm, the following 15 ℃ of refrigerated centrifuge 15min of zero temperature, get supernatant 1.5mL, in another test tube, add 3.5mL deionized water dissolving vortex after nitrogen dries up, cross water film and SPE post, filtrate is for detecting; Fruit juice, honey, flavor drench, and get 0.1～1g sample and add the water constant volume in the 100mL volumetric flask, cross water film and SPE post, and filtrate is for detecting; Other solid samples are got 0.1～1g sample and are added to be transferred to after low amounts of water is fully ground and add deionized water in the 100mL volumetric flask and be settled to scale, inhale 10mL solution, at 5000 rpm, the following 15 ℃ of following refrigerated centrifuge 15min of zero temperature get the 5mL supernatant and cross water film and SPE post, and filtrate is for detecting.
The exchange filler of described SPE post is distributed in the SPE post according to the ratio of mass ratio 1:1 successively by mixed type ion-exchange packing and C18 filler to be formed.
Described mixed type ion-exchange packing is mixed according to the ratio of mass ratio 1:1 by cation exchange filler and anion exchange filler and forms.
Described cation exchange filler is the glytidyl methacrylate that finishing has quaternary ammonium salt; Described anion exchange filler is the glytidyl methacrylate that finishing has sulfonate.
Described SPE post adds 5mL methyl alcohol before use in styletable under the condition of negative pressure, cross post with the flow velocity of 3mL/ min and clean impurity; The methyl alcohol 5mL of adding 50% crosses post with the flow velocity of 3mL/ min and carries out activation processing in styletable.
Set up the method for sugar alcohol in the chromatography of ions mass spectrometry detection food.Sugar alcohol in the sample adopts diverse ways to extract, and crosses the SPE post and removes impurity.Extract separates through separating column, detects under selection ion monitoring (SIM) pattern, and external standard method is quantitative.Each object linear relationship within the specific limits is good, related coefficient (R
2) all greater than 0.99.(signal to noise ratio (S/N ratio) S/N=10) is respectively 0.98 mg/kg, 1.99 mg/kg, 2.24 mg/kg, 5.92 mg/kg, 13.56 mg/kg, 13.21 mg/kg to the quantitative limit of antierythrite, xylitol, D-D-sorbite, D-mannitol, lactitol, maltitol; (S/N=3) is respectively 0.28 mg/kg, 0.59 mg/kg, 0.71 mg/kg, 1.74mg/kg, 4.14 mg/kg, 4.03 mg/kg to detection limit.The recovery of standard addition of 6 kinds of sugar alcohols is 84.5% ~ 105.5%, and relative standard deviation (RSDs) is 1.5% ~ 7.6%.
By the method for qualitative and quantitative detection of sugar alcohol in the food of the present invention, solve the sample purification problem: any detection method no matter all needs the extraction solution purification to sample.According to bibliographical information, the employing solid phase extraction column (SPE) that has, the method that the employing liquid liquid that has distributes will be extracted solution purification.In this research process, laboratory oneself has prepared the purification of SPE post for sample extraction solution, has reduced the cost that detects, has shortened detection time.Set up the confirmation method of sugar alcohol positive findings in the sample.Utilize chromatography of ions to isomerization body good separating effect, characteristics that matrix interference is little, not only realized the quantitative test to sugar alcohol, also utilize mass spectrum that the molecular structure of sugar alcohol is identified, avoid false-positive generation.Compare with LC-MS, the chromatography of ions mass spectrometric hyphenated technique detects sugar alcohol, have certain technical advantage: at first chromatography of ions is owing to adopted 90mmoL/L NaOH as eluent solution, can realize effective separation of sugar alcohol, particularly particularly evident to the separating effect of isomerization body, such as the separation of D-sorbite, mannitol.Because the mass number of isomerization body is the same, structure is basic identical, separate the unclear erroneous judgement that tends to produce.Secondly target components enters rejector after separating through separating column, and its eluent solution has also become water, and the CD value generally can both be controlled below 4uS, can not produce adverse influence to mass spectrum.This point is being that the LC-MS instrument can't be realized, liquid matter can not be with highly basic as the phase that flows.
Description of drawings
Fig. 1, the selection ion detection figure of the standard mixed solution of each sugar alcohol.
Fig. 2,3 kinds of sugar alcohols and 3 kinds of organic acid samples are crossed IonPac AS11-HC anion-exchange column and are selected ionic monitoring figure.
Fig. 3,3 kinds of sugar alcohols and 3 kinds of organic acid samples are crossed self-control SPE post exchange column and are selected ionic monitoring figure.
Fig. 4,3 kinds of sugar alcohols and triethanolamine, sample of triethylamine are selected ion monitoring figure after crossing IonPac CS12-12A cation exchange separating column.
Fig. 5,3 kinds of sugar alcohols and triethanolamine, sample of triethylamine are selected ionic monitoring figure after crossing self-control SPE post exchange column.
Embodiment
Chemicals normal hexane, acetonitrile, the methyl alcohol that the present invention relates to are chromatographically pure, and German Merck company produces.Antierythrite, xylitol, D-D-sorbite, D-mannitol, lactitol, maltitol, lactic acid, malic acid, citric acid, triethanolamine, triethylamine are standard items, purity is greater than 99%, for Dr. Ehrenstorfer company produces, the detection water is ultrapure water.
The instrument model that relates to: Dionex ICS-3000 ion chromatograph (U.S. Dai An company), rejector (ASRS 300 4mm of U.S. Dai An company), CD detecting device (wear peace Conductivity Detector, DS6), single pole mass spectrometer MSQ PLUS(Thermo Scientific company).
Chromatography of ions mass spectrometry of the present invention detects the method for sugar alcohol in the food, and its step is as follows: 1, sample pre-treatments, 1) contain the sample of albumen, grease, get 0.1～1g sample in the 50mL centrifuge tube, add the 25mL eddies of water and revolve and mix 3 min, ultrasonic extraction 10min; Get the 5mL supernatant in the 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove the normal hexane layer, 2mL gets in another centrifuge tube in lower floor, adds 3mL acetonitrile vortex, 5000 rpm, the following 15 ℃ of refrigerated centrifuge 15min of zero temperature, get supernatant 1.5mL, in another test tube, add 3.5mL deionized water redissolution vortex after nitrogen dries up, cross water film and SPE post, filtrate is for detecting; 2) fruit juice, honey, flavor drench wind, get 0.1～1g sample and add the water constant volume in the 100mL volumetric flask, cross water film and SPE post, and filtrate is for detecting; 3) other solid samples are got 0.1～1g sample and are added to be transferred to after low amounts of water is fully ground and add deionized water in the 100mL volumetric flask and be settled to scale, inhale 10mL solution, at 5000 rpm, the following 15 ℃ of following refrigerated centrifuge 15min of zero temperature get the 5mL supernatant and cross water film and SPE post, and filtrate is for detecting.
2, the chromatography of ions GC-MS detects, wherein, the chromatography of ions condition, the separating column leacheate is that the sodium hydroxide solution of 90mmoL/L carries out isocratic elution, flow velocity is 0.50 mL/min; Adopt and suppress conductance method, the rejector electric current is 139mA, and sample size is 25.0 μ L, rejector water source constant flow pump flow velocity 1.0 mL/min.
3, the mass spectrum condition, ionization mode is APCI-, 450 ℃ of the temperature of having a fainting spell during acupuncture treatment; Atomization gas is nitrogen, and purity is 99.9%, pressure is 55 psi.
4, qualitative and quantitative analysis carries out the qualitative analysis of sugar alcohol molecule to sample according to retention time and sugar alcohol feature molion mass-to-charge ratio, utilizes standard law drawing standard curve to carry out quantitative test by external standard method.
Now be illustrated at method of the present invention.
The preparation of standard reserving solution and standard operation liquid: at first carry out the standard reserving solution of antierythrite, xylitol, D-D-sorbite, D-mannitol, lactitol, 6 kinds of sugar alcohols of maltitol and the preparation of standard operation liquid, these six kinds of sugar alcohol standard items purity are all greater than 99%, for Dr. Ehrenstorfer company produces.Accurately take by weighing 6 kinds of each 100mg of sugar alcohol standard items, 6 kinds of sugar alcohol standard items that take by weighing are total to 600mg are settled to 100ml with the ultrapure water dissolving, be mixed with the hybrid standard storing solution that concentration is 1000 mg/L with ultrapure water then; Be diluted to the hybrid standard working fluid that mass concentration is 200mg/L with ultrapure water again.Above solution all places 4 ℃ of refrigerators to preserve.
Adopt ICS-MS to detect, wherein ICS condition (chromatography of ions condition): to adopt CarboPar MA1 separating column (4 * 250mm, Dionex company); CarboPar MA1 guard column (4 * 50mm, Dionex company); Adopt quaternary gradient pump sample introduction, the sodium hydroxide solution of separating column leacheate: 90mmoL/L, isocratic elution, flow velocity: 0.50 mL/min, sample size: 25.0 μ L; Provide the constant flow pump flow velocity at water source for rejector: 1.0 mL/min, rejector electric current: 139mA; Detecting device is the CD detecting device.
MS condition (mass spectrum condition): ionization mode adopts APCI
-, 450 ℃ of the temperature of having a fainting spell during acupuncture treatment; Atomization gas is nitrogen, and purity is 99.9%, pressure 55 psi.The characteristic ion of each sugar alcohol, retention time parameter see Table 1, the selection ion detection figure of the standard mixed solution of each sugar alcohol sees Fig. 1, in the spectrogram 1: 1. antierythrite, 2. xylitol, 3. the left side seam is the D-mannitol for D-D-sorbite, right side seam, and 4. the left side seam is maltitol for lactitol, right side seam.
The characteristic ion of each sugar alcohol of table one, retention time parameter.
| Sequence number | Compound | Retention time (min) | Ion mass-to-charge ratio (m/z) |
| 1 | Antierythrite | 10.3 | 121.1 |
| 2 | Xylitol | 12.5 | 151.2 |
| 3 | The D-D-sorbite | 19.3 | 181.2 |
| 4 | The D-mannitol | 24.3 | 181.2 |
| 5 | Lactitol | 32.9 | 343.3 |
| 6 | Maltitol | 57.3 | 343.3 |
Preparation SPE post, i.e. solid phase extraction column.Commercially available SPE base for post originally has two kinds at present, and a kind of is to keep target compound with special filler, removes chaff interference through drip washing, and the solvent with small size elutes measured matter at last.Such as in melamine detection, just adopting this mode; Another is to keep impurity with filler, and target compound does not keep on filler or minute quantity keeps, and just begins to collect the target compound component behind the last sample, such as with the pigment in the Graphon pillar removal food etc.
Because it is extraordinary water-soluble that sugar alcohol has, after sample dissolved with pure water, albumen wherein, grease can be removed respectively with the method for acetonitrile precipitation and refrigerated centrifuge respectively.Sample extracting solution can effectively be removed impurity such as pigment, organic acid, kation after the SPE post, can obtain good clean-up effect.
Self-control SPE post, the sieve plate of packing in the bottom of 10mL syringe, the 100mg mixed type of packing into ion-exchange packing.The mixed type ion-exchange packing is mixed by cation exchange filler and the anion exchange filler ratio according to mass ratio 1:1.Wherein, the cation exchange filler is the glytidyl methacrylate that finishing has quaternary ammonium salt; Anion exchange filler is the glytidyl methacrylate that finishing has sulfonate.Dress sieve plate behind the mixed type ion-exchange packing dress post is compressed; The material of the positively charged picture organic amine of the overwhelming majority, metal cation etc., negative charge all can mixed type ion-exchange packing absorption as organic acid, amino acid etc.The 100mg C18 filler of packing into subsequently, the dress sieve plate compresses.The SPE post activates before use: activation procedure: add 5mL methyl alcohol in styletable under the condition of negative pressure, cross post with the flow velocity of 3mL/ min and clean impurity; The methyl alcohol 5mL of adding 50% crosses post in styletable with the flow velocity of 3mL/ min.
In order to investigate hybrid ionic exchange filler to the adsorption effect of organic acid negative ion and sugar alcohol, having selected 3 kinds of sugar alcohols (antierythrite, xylitol, D-D-sorbite) and 3 kinds of organic acids (lactic acid, malic acid, citric acid) is that matrix is made into mixed solution with fruit juice, crosses SPE post and the IonPac AS11-HC anion-exchange column of the making of C18 and hybrid ionic exchange filler and does the contrast of investigation effect.Test shows, (1) not so good through the effect of IonPac AS11-HC anion-exchange column separation sugar alcohol, under the condition that adopts isocratic elution, 3 kinds of sugar alcohols almost go out the peak at one time, the results are shown in Figure 2, in the spectrogram 2,1 is that antierythrite, 2 is that xylitol, 3 is that D-D-sorbite, 4 is that lactic acid, 5 is that malic acid, 6 is citric acid
(2) cross the homemade SPE post of being made by C18 and hybrid ionic exchange filler, 3 kinds of organic acids all are adsorbed after crossing C18 and hybrid ionic exchange filler, and sugar alcohol still exists, the results are shown in Figure 3,1 is that antierythrite, 2 is that xylitol, 3 is that D-D-sorbite, 4 is that lactic acid, 5 is that malic acid, 6 is citric acid in the spectrogram 3.Illustrate that hybrid ionic exchange filler does not adsorb sugar alcohol, and it is relatively good that negative ion is kept effect, 3 kinds of sugar alcohols, 3 kinds of organic acid retention times, characteristic ion parameters see Table 2.
Table two, 3 kinds of sugar alcohols, 3 kinds of organic acid retention times, characteristic ion parameter.
| Sequence number | Compound | Retention time (min) | Ion mass-to-charge ratio (m/z) |
| 1 | Antierythrite | 10.3 | 121.1 |
| 2 | Xylitol | 12.5 | 151.2 |
| 3 | The D-D-sorbite | 19.3 | 181.2 |
| 4 | Lactic acid | 10.6 | 89.0 |
| 5 | Malic acid | 17.2 | 133.4 |
| 6 | Citric acid | 25.1 | 191.7 |
In order to investigate hybrid ionic exchange filler to the adsorption effect of kation such as amine and sugar alcohol, we have selected 3 kinds of sugar alcohols (antierythrite, xylitol, D-D-sorbite) and triethanolamine, triethylamine, be that matrix is made into mixed solution with fruit juice, cross SPE post that C18 and hybrid ionic exchange filler makes and separates with IonPac CS12-12A cation exchange separating column and carry out the effect contrast, select ion monitoring behind the mistake post.Test findings shows that the effect of (1) IonPac CS12-12A cation exchange separating column separation sugar alcohol is also not so good, under the condition that adopts isocratic elution, 3 kinds of sugar alcohols almost go out the peak at one time, the results are shown in Figure 4,1 is that antierythrite, 2 is that xylitol, 3 is that D-D-sorbite, 4 is that triethanolamine, 5 is triethylamine in the spectrogram 4, length and flow velocity according to whole PEEK pipe calculate, and sugar alcohol does not almost keep.(2) sample extraction solution is behind the SPE post of crossing the making of C18 and hybrid ionic exchange filler, and triethanolamine wherein all is adsorbed, and the adsorption rate of triethylamine reaches 92%.And sugar alcohol is not adsorbed, and the results are shown in Figure 5, and 1 is that antierythrite, 2 is that xylitol, 3 is that D-D-sorbite, 4 is that triethanolamine, 5 is triethylamine in the spectrogram 5.Illustrate that hybrid ionic exchange filler does not have adsorptive power to sugar alcohol, and also relatively good to cationic reservation effect, 3 kinds of sugar alcohols, triethanolamine, triethylamine retention time, characteristic ion parameters see Table 3.
Table three, 3 kinds of sugar alcohols, triethanolamine, triethylamine retention time, characteristic ion parameter
| Sequence number | Compound | Retention time (min) | Ion mass-to-charge ratio (m/z) |
| 1 | Antierythrite | 10.3 | 121.1 |
| 2 | Xylitol | 12.5 | 151.2 |
| 3 | The D-D-sorbite | 19.3 | 181.2 |
| 4 | Triethanolamine | 7.7 | 150.2 |
| 5 | Triethylamine | 21.5 | 102.2 |
As known from the above, the homemade SPE post isolation of purified of being made by C18 filler and hybrid ionic exchange filler is effective, and it can finely adsorb kation in the sample and negative ion, and to not absorption of sugar alcohol, realize good clean-up effect, guaranteed the result that follow-up chromatography of ions detects.
Embodiment 1
Sample pre-treatments:
Get German chocolate cream biscuit 0.5g sample in the 50mL centrifuge tube, add the 25mL eddies of water and revolve mixing 3 min, ultrasonic extraction 10min.Get the 5mL supernatant in the 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove the normal hexane layer, 2mL gets in another centrifuge tube in lower floor, add 3mL acetonitrile vortex, on refrigerated centrifuge in temperature-15 ℃, with the rotating speed refrigerated centrifuge 15min of 5000 rpm, get supernatant 1.5mL, in another test tube, after drying up, nitrogen adds 3.5mL water redissolution vortex, cross water film and SPE post.Get 25.0 μ L filtrates and detect for ICS-MS, the ICS-MS testing conditions is identical with the chromatography of ions Mass Spectrometer Method condition of above-mentioned standard hybrid working liquid, and six kinds of sugar alcohols are carried out qualitative and quantitative analysis.
Embodiment 2
Drenching with China's flavor is sample, gets the 0.2g sample and add the water constant volume in the 100mL volumetric flask, crosses water film and SPE post, and filtrate is detected for ICS-MS.Get 25.0 μ L filtrates and detect for ICS-MS, the ICS-MS testing conditions is identical with the chromatography of ions Mass Spectrometer Method condition of above-mentioned standard hybrid working liquid, and six kinds of sugar alcohols are carried out qualitative and quantitative analysis, and six kinds of sugar alcohols are carried out qualitative and quantitative analysis.
Embodiment 3
Be sample with Indonesia's ginger sugar, get the 0.8g sample in mortar, add to be transferred to after low amounts of water is fully ground and add water in the 100mL volumetric flask and be settled to scale.Absorption 10mL solution at-15 ℃, with the centrifugal 15min of 5000 rpm rotating speeds, is got the 5mL supernatant and is crossed water film and SPE post on refrigerated centrifuge, and filtrate is detected for ICS-MS.Get 25.0 μ L filtrates and detect for ICS-MS, the ICS-MS testing conditions is identical with the chromatography of ions Mass Spectrometer Method condition of above-mentioned standard hybrid working liquid, and six kinds of sugar alcohols are carried out qualitative and quantitative analysis.
With examination criteria hybrid working liquid phase ICS-MS chromatography of ions mass spectrum condition together sample is analyzed, set up the method for sugar alcohol in the chromatography of ions mass spectrometry detection food.Sugar alcohol in the sample adopts diverse ways to extract, and crosses the SPE post and removes impurity.Sample filtrate is separated through CarboPar MA1 separating column, detects under selection ion monitoring (SIM) pattern, and external standard method is quantitative.The equation of linear regression of each sugar alcohol, detection limit and quantitative limit see Table four.
The equation of linear regression of each sugar alcohol of table four, linearly dependent coefficient (R
2), detection limit (LOD) and quantitative limit (LOQ)
Each object linear relationship within the specific limits is good, related coefficient (R
2) all greater than 0.99.(signal to noise ratio (S/N ratio) S/N=10) is respectively 0.98 mg/kg, 1.99 mg/kg, 2.24 mg/kg, 5.92 mg/kg, 13.56 mg/kg, 13.21 mg/kg to the quantitative limit of antierythrite, xylitol, D-D-sorbite, D-mannitol, lactitol, maltitol; (S/N=3) is respectively 0.28 mg/kg, 0.59 mg/kg, 0.71 mg/kg, 1.74mg/kg, 4.14 mg/kg, 4.03 mg/kg to detection limit.The recovery of standard addition of 6 kinds of sugar alcohols is 84.5% ~ 105.5%, and relative standard deviation (RSDs) is 1.5% ~ 7.6%.See Table five, three kinds of sample detection results' the recovery and the coefficient of variation.
Three kinds of sample detection results' of table five the recovery and the coefficient of variation
Wherein, a in the table five, b represent each sample and do six parallel experiments; C is difference mark-on 20 mg/kg, 40mg/kg.
As known from the above, homemade SPE post isolation of purified is effective, is conducive to sugar alcohol and detects.The sugar alcohol chromatography of ions Mass Spectrometer Method method that the present invention sets up is carried out sample pre-treatments by homemade SPE separating column and is purified, and coupled ion chromatogram Mass Spectrometer Method can effectively be carried out the detection of qualitative, quantitative to six kinds of sugar alcohols that contain in the food.
Claims (6)
1. chromatography of ions GC-MS qualitative, quantitative is measured the method for sugar alcohol in the food, and it comprises the steps: 1), sample pre-treatments contains sample constant volume behind acetonitrile precipitation and refrigerated centrifuge of albumen, grease; Other solid samples grind the back constant volume and handle through refrigerated centrifuge; Fruit juice, flavor drench, the direct constant volume of honey class I liquid I sample, and the sample behind the constant volume is crossed water film and SPE post, and filtrate is for detecting;
2) the chromatography of ions GC-MS detects, wherein, the chromatography of ions condition, the separating column leacheate is that the sodium hydroxide solution of 90mmoL/L carries out isocratic elution, flow velocity is 0.50 mL/min; Adopt and suppress conductance method, the rejector electric current is 139mA, and sample size is 25.0 μ L, rejector water source constant flow pump flow velocity 1.0 mL/min;
3) mass spectrum condition, ionization mode is APCI-, 450 ℃ of the temperature of having a fainting spell during acupuncture treatment; Atomization gas is nitrogen, and purity is 99.9%, pressure is 55 psi;
4) qualitative and quantitative analysis carries out the qualitative analysis of sugar alcohol molecule to sample according to retention time and sugar alcohol feature molion mass-to-charge ratio, utilizes standard law drawing standard curve to carry out quantitative test by external standard method.
2. chromatography of ions GC-MS qualitative, quantitative according to claim 1 is measured the method for sugar alcohol in the food, it is characterized in that in described step 1) sample pre-treatments, the sample that contains albumen, grease, get 0.1～1g sample in the 50mL centrifuge tube, add the 25mL eddies of water and revolve mixing 3 min, ultrasonic extraction 10min; Get the 5mL supernatant in the 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove the normal hexane layer, 2mL gets in another centrifuge tube in lower floor, adds 3mL acetonitrile vortex, 5000 rpm, the following 15 ℃ of refrigerated centrifuge 15min of zero temperature, get supernatant 1.5mL, in another test tube, add 3.5mL deionized water dissolving vortex after nitrogen dries up, cross water film and SPE post, filtrate is for detecting; Fruit juice, honey, flavor drench, and get 0.1～1g sample and add the water constant volume in the 100mL volumetric flask, cross water film and SPE post, and filtrate is for detecting; Other solid samples are got 0.1～1g sample and are added to be transferred to after low amounts of water is fully ground and add deionized water in the 100mL volumetric flask and be settled to scale, inhale 10mL solution, at 5000 rpm, the following 15 ℃ of following refrigerated centrifuge 15min of zero temperature get the 5mL supernatant and cross water film and SPE post, and filtrate is for detecting.
3. measure the method for sugar alcohol in the food according to claim 1 and 2 arbitrary described chromatography of ions GC-MS qualitative, quantitatives, the exchange filler that it is characterized in that described SPE post is distributed in the described SPE post according to the ratio of mass ratio 1:1 successively by mixed type ion-exchange packing and C18 filler to be formed.
4. chromatography of ions GC-MS qualitative, quantitative according to claim 3 is measured the method for sugar alcohol in the food, it is characterized in that described mixed type ion-exchange packing is mixed according to the ratio of mass ratio 1:1 by cation exchange filler and anion exchange filler to form.
5. the method for sugar alcohol in qualitative, the quantitative measurement food of chromatography of ions GC-MS according to claim 4 is characterized in that described cation exchange filler is the glytidyl methacrylate that finishing has quaternary ammonium salt; Described anion exchange filler is the glytidyl methacrylate that finishing has sulfonate.
6. chromatography of ions GC-MS qualitative, quantitative according to claim 5 is measured the method for sugar alcohol in the food, it is characterized in that described SPE post before use, adds 5mL methyl alcohol in styletable under the condition of negative pressure, crosses post with the flow velocity of 3mL/ min and cleans impurity; The methyl alcohol 5mL of adding 50% crosses post with the flow velocity of 3mL/ min and carries out activation processing in styletable.
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| CN104833761A (en) * | 2015-06-01 | 2015-08-12 | 华质泰科生物技术（北京）有限公司 | Method for quickly analyzing carbohydrates in samples |
| CN108181403A (en) * | 2018-01-31 | 2018-06-19 | 安徽泓顺源生物科技有限公司 | A kind of efficient liquid-phase chromatography method of rapidly quantifying honey quality |
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| CN104297232A (en) * | 2014-09-05 | 2015-01-21 | 安徽蜂献蜂业有限公司 | High-fructose syrup detection system |
| CN104833761A (en) * | 2015-06-01 | 2015-08-12 | 华质泰科生物技术（北京）有限公司 | Method for quickly analyzing carbohydrates in samples |
| CN108181403A (en) * | 2018-01-31 | 2018-06-19 | 安徽泓顺源生物科技有限公司 | A kind of efficient liquid-phase chromatography method of rapidly quantifying honey quality |
| CN108426965A (en) * | 2018-06-06 | 2018-08-21 | 胡贝贞 | The detection method of isomaltose, Isomaltotriose, maltose, panose in yellow rice wine |
| CN108426965B (en) * | 2018-06-06 | 2021-02-09 | 绍兴海关综合技术服务中心 | Method for detecting isomaltose, isomaltotriose, maltose and panose in yellow wine |
| CN110514777A (en) * | 2019-09-25 | 2019-11-29 | 日照海关综合技术服务中心 | A kind of method that a variety of sugar, sugar alcohols and alcohols quickly detect simultaneously in beer |
| CN111474249A (en) * | 2020-03-11 | 2020-07-31 | 台州学院 | Method for detecting organic alcohol amine compounds in environmental water sample |
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