CN103344731B - 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
- Publication number
- CN103344731B CN103344731B CN201310239643.7A CN201310239643A CN103344731B CN 103344731 B CN103344731 B CN 103344731B CN 201310239643 A CN201310239643 A CN 201310239643A CN 103344731 B CN103344731 B CN 103344731B
- Authority
- CN
- China
- Prior art keywords
- sample
- qualitative
- quantitative
- sugar alcohol
- chromatography
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000005846 sugar alcohols Chemical class 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 35
- 235000013305 food Nutrition 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000004445 quantitative analysis Methods 0.000 claims abstract description 9
- 238000002203 pretreatment Methods 0.000 claims abstract description 8
- 238000010829 isocratic elution Methods 0.000 claims abstract description 7
- 238000001467 acupuncture Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 5
- 206010042772 syncope Diseases 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 47
- 239000000945 filler Substances 0.000 claims description 31
- 238000004587 chromatography analysis Methods 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 230000014759 maintenance of location Effects 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 11
- 238000005349 anion exchange Methods 0.000 claims description 9
- 238000005341 cation exchange Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 239000004519 grease Substances 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 235000015203 fruit juice Nutrition 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000004451 qualitative analysis Methods 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019640 taste Nutrition 0.000 claims description 6
- 238000010812 external standard method Methods 0.000 claims description 5
- 235000012907 honey Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 4
- 238000012113 quantitative test Methods 0.000 claims description 4
- 238000002137 ultrasound extraction Methods 0.000 claims description 4
- 238000001994 activation Methods 0.000 claims description 3
- 238000012512 characterization method Methods 0.000 claims description 3
- 150000001793 charged compounds Chemical class 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000004255 ion exchange chromatography Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 14
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 14
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 14
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 14
- 239000000811 xylitol Substances 0.000 description 14
- 235000010447 xylitol Nutrition 0.000 description 14
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 14
- 229960002675 xylitol Drugs 0.000 description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- 150000007524 organic acids Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000832 lactitol Substances 0.000 description 6
- 235000010448 lactitol Nutrition 0.000 description 6
- VQHSOMBJVWLPSR-JVCRWLNRSA-N lactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-JVCRWLNRSA-N 0.000 description 6
- 229960003451 lactitol Drugs 0.000 description 6
- 239000000845 maltitol Substances 0.000 description 6
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 6
- 235000010449 maltitol Nutrition 0.000 description 6
- 229940035436 maltitol Drugs 0.000 description 6
- 238000002098 selective ion monitoring Methods 0.000 description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 239000001630 malic acid Substances 0.000 description 5
- 235000011090 malic acid Nutrition 0.000 description 5
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229960002052 salbutamol Drugs 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000105 evaporative light scattering detection Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 238000000581 reactive spray deposition Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 albumen wherein Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000014651 chocolate spreads Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003859 hyphenated technique Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
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 component in food.
Background technology
At inspection and quarantine department, need to carry out qualitative and quantitative detection to the content of sugar alcohol of food, but current detection method defect all to some extent.Domestic and international at present the detection method of sugar alcohol in food to be comprised: HPLC ELSD method, high performance liquid chromatography-differential pulse polarograpll method
,ion exclusion liquid phase chromatography, vapor-phase chromatography
,gC-MS, liquid chromatography tandem mass spectrometry etc.Evaporative light-scattering method, differential pulse polarograpll method, ion exclusion liquid phase chromatography, vapor-phase chromatography etc. all cannot meet the requirement of European Union 657 instruction.The positive findings of these detection methods must add their confirmation with other separating column, detecting device again.The method adopted in condition GC-MS, need by after analyte derivative again nitrogen blow redissolution, then sample introduction, consuming time longer.
Summary of the invention
Technical matters to be solved by this invention be to provide a kind of detect sugar alcohol in food detection method, what it can be quick, qualitative, quantitative carries out quantitative and qualitative detection to sugar alcohol component.
For solving the problems of the technologies described above, technical scheme chromatography of ions GC-MS qualitative, quantitative provided by the invention measures the method for sugar alcohol in food, it comprises the steps: 1), sample pre-treatments, containing sample constant volume after acetonitrile precipitation and refrigerated centrifuge of albumen, grease; Other solid samples, after grinding, constant volume is again through refrigerated centrifuge process; Fruit juice, taste drench, the direct constant volume of honey class I liquid I sample, the sample after constant volume are crossed aqueous phase film and SPE post, and filtrate is for detecting;
2) chromatography of ions GC-MS detects, wherein, chromatography of ions condition, separating column leacheate is that the sodium hydroxide solution of 90mmoL/L carries out isocratic elution, and flow velocity is 0.50 mL/min; Adopt suppress conductivity method, 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 Spectrometry Conditions, ionization mode is APCI-, temperature of having a fainting spell during acupuncture treatment 450 DEG C; Atomization gas is nitrogen, and purity is 99.9%, pressure is 55 psi;
4) qualitative and quantitative analysis, carries out the analysis of sugar alcohol Molecular characterization to sample according to retention time and sugar alcohol characteristic molecular ion 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, containing the sample of albumen, grease, get 0.1 ~ 1g sample in 50mL centrifuge tube, add 25mL water vortex mixed 3 min, ultrasonic extraction 10min; Get 5mL supernatant in 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove normal hexane layer, 2mL gets in another centrifuge tube in lower floor, adds 3mL acetonitrile vortex, 5000 rpm, the lower 15 DEG C of refrigerated centrifuge 15min of zero temperature, get supernatant 1.5mL, in another test tube, after nitrogen dries up, add 3.5mL deionized water dissolving vortex, cross aqueous phase film and SPE post, filtrate is for detecting; Fruit juice, honey, taste drench, and get 0.1 ~ 1g sample and to add water in 100mL volumetric flask constant volume, cross aqueous phase film and SPE post, and filtrate is for detecting; Other solid samples, get 0.1 ~ 1g sample and add to be transferred to after a small amount of water fully grinds and add deionized water in 100mL volumetric flask and be settled to scale, inhale 10mL solution, at 5000 rpm, refrigerated centrifuge 15min at lower 15 DEG C of zero temperature, gets 5mL supernatant and crosses aqueous phase film and SPE post, and filtrate is for detecting.
The exchange filler of described SPE post to be distributed in successively in SPE post according to the ratio of mass ratio 1:1 by mixed type ion-exchange packing and C18 filler and to form.
Described mixed type ion-exchange packing is made up of according to the ratio mixing of mass ratio 1:1 cation exchange filler and anion exchange filler.
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 before use, adds 5mL methyl alcohol in styletable under the condition of negative pressure, crosses post cleaning impurity with the flow velocity of 3mL/ min; Add the methyl alcohol 5mL of 50% in styletable, cross post with the flow velocity of 3mL/ min and carry out activation process.
Establish the method that chromatography of ions mass spectrometry detects sugar alcohol in food.Sugar alcohol in sample adopts diverse ways to extract, and crosses SPE post and removes impurity.Extract is separated through separating column, detects, quantified by external standard method under Salbutamol Selected Ion Monitoring (SIM) pattern.Each object within the specific limits linear relationship is good, related coefficient (R
2) be all greater than 0.99.The quantitative limit (signal to noise ratio (S/N ratio) S/N=10) of antierythrite, xylitol, D-D-sorbite, D-mannital, lactitol, maltitol 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; Detection limit (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.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 food of the present invention, solve sample purification problem: no matter any detection method, all needs the extraction solution purification to sample.According to bibliographical information, some employing solid phase extraction columns (SPE), the method that some employing liquid liquid distributes will extract solution purification.In this research process, the purification of SPE post for sample extraction solution has been prepared in laboratory oneself, reduces the cost of detection, shortens detection time.Establish the confirmation method of sugar alcohol positive findings in sample.Utilize chromatography of ions to isomerization body good separating effect, feature that matrix interference is little, not only achieve the quantitative test to sugar alcohol, also utilize the molecular structure of mass spectrum to sugar alcohol to identify, avoid false-positive generation.Compare with LC-MS, chromatography of ions mass spectrometric hyphenated technique detects sugar alcohol, there is certain technical advantage: first chromatography of ions is owing to have employed 90mmoL/L NaOH as eluent solution, effective separation of sugar alcohol can be realized, particularly particularly evident to the separating effect of isomerization body, the such as separation of D-sorbite, mannitol.Because the mass number of isomerization body is the same, structure is substantially identical, is separated and unclearly often produces erroneous judgement.Secondly target components enters rejector after separating column is separated, and its eluent solution also becomes water, and CD value generally can control at below 4uS, can not produce adverse influence to mass spectrum.This point is being that LC-MS instrument cannot realize, and liquid matter can not with highly basic as mobile phase.
Accompanying drawing explanation
Fig. 1, the Select ion monitor figure of the standard mixed solution of each sugar alcohol.
Fig. 2, IonPac AS11-HC anion-exchange column Selective ion mode monitoring figure crossed by 3 kinds of sugar alcohols and 3 kinds of organic acid samples.
Fig. 3, self-control SPE post exchange column Selective ion mode monitoring figure crossed by 3 kinds of sugar alcohols and 3 kinds of organic acid samples.
Fig. 4,3 kinds of sugar alcohols and triethanolamine, sample of triethylamine cross Salbutamol Selected Ion Monitoring figure after IonPac CS12-12A Cation exchange separation post.
Fig. 5,3 kinds of sugar alcohols and triethanolamine, sample of triethylamine cross Selective ion mode monitoring figure after self-control SPE post exchange column.
Embodiment
The chemicals normal hexane that the present invention relates to, acetonitrile, methyl alcohol are chromatographically pure, and German Merck company produces.Antierythrite, xylitol, D-D-sorbite, D-mannital, lactitol, maltitol, lactic acid, malic acid, citric acid, triethanolamine, triethylamine are standard items, purity is greater than 99%, for Dr. Ehrenstorfer company produces, detection water is ultrapure water.
The INSTRUMENT MODEL related to: Dionex ICS-3000 ion chromatograph (Dai An company of the U.S.), rejector (Dai An company of U.S. ASRS 300 4mm), CD detecting device (wearing 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 food, and its step is as follows: 1, sample pre-treatments, 1) containing the sample of albumen, grease, get 0.1 ~ 1g sample in 50mL centrifuge tube, add 25mL water vortex mixed 3 min, ultrasonic extraction 10min; Get 5mL supernatant in 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove normal hexane layer, 2mL gets in another centrifuge tube in lower floor, adds 3mL acetonitrile vortex, 5000 rpm, the lower 15 DEG C of refrigerated centrifuge 15min of zero temperature, get supernatant 1.5mL, in another test tube, after nitrogen dries up, add 3.5mL deionized water redissolution vortex, cross aqueous phase film and SPE post, filtrate is for detecting; 2) fruit juice, honey, taste drench wind, get 0.1 ~ 1g sample and to add water in 100mL volumetric flask constant volume, cross aqueous phase film and SPE post, and filtrate is for detecting; 3) other solid samples, get 0.1 ~ 1g sample and add to be transferred to after a small amount of water fully grinds and add deionized water in 100mL volumetric flask and be settled to scale, inhale 10mL solution, at 5000 rpm, refrigerated centrifuge 15min at lower 15 DEG C of zero temperature, gets 5mL supernatant and crosses aqueous phase film and SPE post, and filtrate is for detecting.
2, chromatography of ions GC-MS detects, wherein, chromatography of ions condition, separating column leacheate is that the sodium hydroxide solution of 90mmoL/L carries out isocratic elution, and flow velocity is 0.50 mL/min; Adopt suppress conductivity method, 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 Spectrometry Conditions, ionization mode is APCI-, temperature of having a fainting spell during acupuncture treatment 450 DEG C; Atomization gas is nitrogen, and purity is 99.9%, pressure is 55 psi.
4, qualitative and quantitative analysis, carries out the analysis of sugar alcohol Molecular characterization to sample according to retention time and sugar alcohol characteristic molecular ion mass-to-charge ratio, utilizes standard law drawing standard curve to carry out quantitative test by external standard method.
Now be illustrated for method of the present invention.
The preparation of standard reserving solution and standard working solution: first carry out antierythrite, xylitol, D-D-sorbite, D-mannital, lactitol, the standard reserving solution of maltitol 6 kinds of sugar alcohols and the preparation of standard working solution, these six kinds of sugar alcohol standard items purity are all greater than 99%, for Dr. Ehrenstorfer company produces.Accurately take 6 kinds of each 100mg of sugar alcohol standard items, take 6 kinds of sugar alcohol standard items are total to the dissolving of 600mg ultrapure water and are settled to 100ml, be then mixed with ultrapure water the hybrid standard storing solution that concentration is 1000 mg/L; The hybrid standard working fluid that mass concentration is 200mg/L is diluted to again with ultrapure water.Above solution is all placed in 4 DEG C of refrigerators and preserves.
ICS-MS is adopted 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; For rejector provides the constant flow pump flow velocity at water source: 1.0 mL/min, rejector electric current: 139mA; Detecting device is CD detecting device.
MS condition (Mass Spectrometry Conditions): ionization mode adopts APCI
-, temperature of having a fainting spell during acupuncture treatment 450 DEG C; Atomization gas is nitrogen, and purity is 99.9%, pressure 55 psi.The characteristic ion of each sugar alcohol, retention time parameter are in table 1, the Select ion monitor figure of the standard mixed solution of each sugar alcohol is shown in Fig. 1, in spectrogram 1: 1. antierythrite, 2. xylitol, 3. on the left of, seam is D-D-sorbite, right side is stitched is D-mannital, stitches as lactitol, right side seam are maltitol 4..
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 | D-D-sorbite | 19.3 | 181.2 |
| 4 | D-mannital | 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.SPE base for post commercially available at present originally has two kinds, and a kind of is retain target compound with special filler, through drip washing removing chaff interference, is finally eluted by measured matter with the solvent of small size.Such as just adopt in this way in the detection of melamine; Another retains impurity with filler, and target compound does not retain on filler or minute quantity retains, and just starts to collect target compound component after loading, such as removes the pigment etc. in food with Graphon pillar.
Because sugar alcohol has extraordinary water-soluble, after sample dissolves with pure water, albumen wherein, grease can be removed by the method for acetonitrile precipitation and refrigerated centrifuge respectively respectively.Sample extracting solution can effectively remove the impurity such as pigment, organic acid, kation after SPE post, can obtain good clean-up effect.
Self-control SPE post, loads sieve plate in the bottom of 10mL syringe, loads 100mg mixed type ion-exchange packing.Mixed type ion-exchange packing is mixed according to the ratio of mass ratio 1:1 by cation exchange filler and anion exchange filler.Wherein, cation exchange filler is the glytidyl methacrylate that finishing has quaternary ammonium salt; Anion exchange filler is the glytidyl methacrylate that finishing has sulfonate.Compress filling sieve plate after mixed type ion-exchange packing dress post; The material of the overwhelming majority positively charged picture organic amine, metal cation etc., negative charge all can mixed type ion-exchange packing absorption as organic acid, amino acid etc.Load 100mg C18 filler subsequently, dress sieve plate compresses.SPE post activates before use: activation procedure: under the condition of negative pressure, add 5mL methyl alcohol in styletable, crosses post cleaning impurity with the flow velocity of 3mL/ min; Add the methyl alcohol 5mL of 50% in styletable, cross post with the flow velocity of 3mL/ min.
The adsorption effect of filler to organic acid negative ion and sugar alcohol is exchanged in order to investigate hybrid ionic, have selected 3 kinds of sugar alcohols (antierythrite, xylitol, D-D-sorbite) and 3 kinds of organic acids (lactic acid, malic acid, citric acid) are that matrix is made into mixed solution with fruit juice, cross C18 and hybrid ionic and exchange SPE post that filler makes and IonPac AS11-HC anion-exchange column does investigation Contrast on effect.Test shows, (1) effect through IonPac AS11-HC anion-exchange column separation sugar alcohol is not so good, under the condition adopting isocratic elution, 3 kinds of sugar alcohols almost go out peak at one time, the results are shown in Figure 2, in spectrogram 2,1 be antierythrite, 2 be xylitol, 3 be D-D-sorbite, 4 be lactic acid, 5 be malic acid, 6 for citric acid
; (2) the homemade SPE post being exchanged filler making by C18 and hybrid ionic is crossed, 3 kinds of organic acids are all adsorbed after crossing C18 and hybrid ionic exchange filler, and sugar alcohol still exists, the results are shown in Figure 3,1 be antierythrite, 2 be xylitol in spectrogram 3,3 be D-D-sorbite, 4 be lactic acid, 5 be malic acid, 6 for citric acid.Illustrate that hybrid ionic exchanges filler and do not adsorb sugar alcohol, and relatively good to negative ion retention, 3 kinds of sugar alcohols, 3 kinds of organic acid retention times, characteristic ion parameter are in table 2.
Table two, 3 kinds of sugar alcohols, 3 kinds of organic acid retention times, characteristic ion parameters.
| 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 | 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 |
The adsorption effect of filler to the kations such as amine and sugar alcohol is exchanged in order to investigate hybrid ionic, 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 C18 and hybrid ionic to exchange SPE post that filler makes and is separated with IonPac CS12-12A Cation exchange separation post and carries out Contrast on effect, Salbutamol Selected Ion Monitoring after mistake post.The effect that test findings display (1) IonPac CS12-12A Cation exchange separation post is separated sugar alcohol is also not so good, under the condition adopting isocratic elution, 3 kinds of sugar alcohols almost go out peak at one time, the results are shown in Figure 4,1 be antierythrite, 2 be xylitol in spectrogram 4,3 be D-D-sorbite, 4 be triethanolamine, 5 for triethylamine, according to length and the flow relocity calculation of whole PEEK pipe, sugar alcohol does not almost retain.(2) sample extraction solution is after the SPE post crossing C18 and the making of hybrid ionic exchange filler, and triethanolamine wherein is all adsorbed, and the adsorption rate of triethylamine reaches 92%.And sugar alcohol is not adsorbed, the results are shown in Figure 5,1 be antierythrite, 2 be xylitol in spectrogram 5,3 be D-D-sorbite, 4 be triethanolamine, 5 for triethylamine.Illustrate that hybrid ionic exchanges filler and do not have adsorptive power to sugar alcohol, and also relatively good to cationic retention, 3 kinds of sugar alcohols, triethanolamine, triethylamine retention time, characteristic ion parameter are in table 3.
Table three, 3 kinds of sugar alcohols, triethanolamine, triethylamine retention time, characteristic ion parameters
| 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 | 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 be made up of C18 filler and hybrid ionic exchange filler is effective, and it can adsorb sample cationic and negative ion very well, and does not adsorb sugar alcohol, realize good clean-up effect, ensure that the result that subsequent ion chromatogram detects.
Embodiment 1
Sample pre-treatments:
Get German chocolate cream biscuit 0.5g sample in 50mL centrifuge tube, add 25mL water vortex mixed 3 min, ultrasonic extraction 10min.Get 5mL supernatant in 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove normal hexane layer, 2mL gets in another centrifuge tube in lower floor, add 3mL acetonitrile vortex, temperature-15 DEG C on refrigerated centrifuge, with the rotating speed refrigerated centrifuge 15min of 5000 rpm, get supernatant 1.5mL, in another test tube, add 3.5mL water redissolution vortex after nitrogen dries up, cross aqueous phase film and SPE post.Get 25.0 μ L filtrates to detect for ICS-MS, ICS-MS testing conditions is identical with the chromatography of ions Mass Spectrometer Method condition of above-mentioned standard hybrid working liquid, carries out qualitative and quantitative analysis to six kinds of sugar alcohols.
Embodiment 2
Drench for sample with Chinese taste, get 0.2g sample and to add water in 100mL volumetric flask constant volume, cross aqueous phase film and SPE post, filtrate is detected for ICS-MS.Get 25.0 μ L filtrates to detect for ICS-MS, ICS-MS testing conditions is identical with the chromatography of ions Mass Spectrometer Method condition of above-mentioned standard hybrid working liquid, carries out qualitative and quantitative analysis to six kinds of sugar alcohols, carries out qualitative and quantitative analysis to six kinds of sugar alcohols.
Embodiment 3
With Indonesia ginger sugar for sample, get 0.8g sample in mortar, add to be transferred in 100mL volumetric flask to add water after a small amount of water fully grinds and be settled to scale.Draw 10mL solution at-15 DEG C on refrigerated centrifuge, with the centrifugal 15min of 5000 rpm rotating speed, get 5mL supernatant and cross aqueous phase film and SPE post, filtrate is detected for ICS-MS.Get 25.0 μ L filtrates to detect for ICS-MS, ICS-MS testing conditions is identical with the chromatography of ions Mass Spectrometer Method condition of above-mentioned standard hybrid working liquid, carries out qualitative and quantitative analysis to six kinds of sugar alcohols.
The ICS-MS chromatography of ions Mass Spectrometry Conditions same with examination criteria hybrid working liquid phase is analyzed sample, establishes the method that chromatography of ions mass spectrometry detects sugar alcohol in food.Sugar alcohol in sample adopts diverse ways to extract, and crosses SPE post and removes impurity.Sample filtrate is separated through CarboPar MA1 separating column, detects, quantified by external standard method under Salbutamol Selected Ion Monitoring (SIM) pattern.The equation of linear regression of each sugar alcohol, detection limit and quantitative limit are in 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 within the specific limits linear relationship is good, related coefficient (R
2) be all greater than 0.99.The quantitative limit (signal to noise ratio (S/N ratio) S/N=10) of antierythrite, xylitol, D-D-sorbite, D-mannital, lactitol, maltitol 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; Detection limit (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.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%.In table five, the recovery of three kinds of sample detection results and the coefficient of variation.
The recovery of table five three kinds of sample detection results and the coefficient of variation
Wherein, a, b in table five 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 Spectrometry detection method that the present invention sets up, carries out sample pre-treatments purification by homemade SPE separating column, and coupled ion chromatographic mass spectrometry detects, and effectively can carry out the detection of qualitative, quantitative to the six kinds of sugar alcohols contained in food.
Claims (5)
1. chromatography of ions GC-MS qualitative, quantitative measures the method for sugar alcohol in food, and it comprises the steps: 1), sample pre-treatments, containing sample constant volume after acetonitrile precipitation and refrigerated centrifuge of albumen, grease; Not containing the solid sample of albumen, grease, after grinding, constant volume is again through refrigerated centrifuge process; Fruit juice, taste drench, the direct constant volume of honey class I liquid I sample, the sample after constant volume are crossed aqueous phase film and SPE post, and filtrate is for detecting;
2) chromatography of ions GC-MS detects, wherein, chromatography of ions condition, separating column leacheate is that the sodium hydroxide solution of 90mmoL/L carries out isocratic elution, and flow velocity is 0.50 mL/min; Adopt suppress conductivity method, 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 Spectrometry Conditions, ionization mode is APCI-, temperature of having a fainting spell during acupuncture treatment 450 DEG C; Atomization gas is nitrogen, and purity is 99.9%, pressure is 55 psi;
4) qualitative and quantitative analysis, carries out the analysis of sugar alcohol Molecular characterization to sample according to retention time and sugar alcohol characteristic molecular ion 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, containing the sample of albumen, grease, get 0.1 ~ 1g sample in 50mL centrifuge tube, add 25mL water vortex mixed 3 min, ultrasonic extraction 10min; Get 5mL supernatant in 10mL centrifuge tube, add 5mL normal hexane vortex mixed, with the centrifugal 10min of 5000 rpm, remove normal hexane layer, 2mL gets in another centrifuge tube in lower floor, adds 3mL acetonitrile vortex, 5000 rpm, the lower 15 DEG C of refrigerated centrifuge 15min of zero temperature, get supernatant 1.5mL, in another test tube, after nitrogen dries up, add 3.5mL deionized water dissolving vortex, cross aqueous phase film and SPE post, filtrate is for detecting; Fruit juice, honey, taste drench, and get 0.1 ~ 1g sample and to add water in 100mL volumetric flask constant volume, cross aqueous phase film and SPE post, and filtrate is for detecting; Not containing the solid sample of albumen, grease, get 0.1 ~ 1g sample to add to be transferred to after a small amount of water fully grinds and add deionized water in 100mL volumetric flask and be settled to scale, inhale 10mL solution, at 5000 rpm, the lower 15 DEG C of refrigerated centrifuge 15min of zero temperature, get 5mL supernatant and cross aqueous phase film and SPE post, filtrate is for detecting.
2. chromatography of ions GC-MS qualitative, quantitative according to claim 1 measures the method for sugar alcohol in food, it is characterized in that the exchange filler of described SPE post to be distributed in described SPE post according to the ratio of mass ratio 1:1 successively by mixed type ion-exchange packing and C18 filler and forms.
3. chromatography of ions GC-MS qualitative, quantitative according to claim 2 measures the method for sugar alcohol in food, it is characterized in that described mixed type ion-exchange packing is made up of according to the ratio mixing of mass ratio 1:1 cation exchange filler and anion exchange filler.
4. chromatography of ions GC-MS qualitative, quantitative according to claim 3 measures the method for sugar alcohol in food, it 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.
5. chromatography of ions GC-MS qualitative, quantitative according to claim 4 measures the method for sugar alcohol in 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 cleaning impurity with the flow velocity of 3mL/ min; Add the methyl alcohol 5mL of 50% in styletable, cross post with the flow velocity of 3mL/ min and carry out activation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310239643.7A CN103344731B (en) | 2013-06-18 | 2013-06-18 | Method for qualitative and quantitative determination of sugar alcohols in foods by ion chromatograph-mass spectrometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310239643.7A CN103344731B (en) | 2013-06-18 | 2013-06-18 | Method for qualitative and quantitative determination of sugar alcohols in foods by ion chromatograph-mass spectrometer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103344731A CN103344731A (en) | 2013-10-09 |
| CN103344731B true CN103344731B (en) | 2015-01-28 |
Family
ID=49279545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310239643.7A Expired - Fee Related CN103344731B (en) | 2013-06-18 | 2013-06-18 | Method for qualitative and quantitative determination of sugar alcohols in foods by ion chromatograph-mass spectrometer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103344731B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104297232A (en) * | 2014-09-05 | 2015-01-21 | 安徽蜂献蜂业有限公司 | High-fructose syrup detection system |
| CN104833761B (en) * | 2015-06-01 | 2017-04-26 | 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 |
| 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 |
| CN110514777B (en) * | 2019-09-25 | 2021-06-11 | 日照海关综合技术服务中心 | Method for simultaneously and rapidly detecting various sugars, sugar alcohols and alcohols 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 |
| CN115728421A (en) * | 2022-12-06 | 2023-03-03 | 浙江省检验检疫科学技术研究院 | Method for simultaneously determining sugar and sugar alcohol in infant formula milk powder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06167486A (en) * | 1992-11-30 | 1994-06-14 | Shimadzu Corp | Analyzing method for alcohols and sugars |
| JP4574669B2 (en) * | 2007-12-25 | 2010-11-04 | 独立行政法人科学技術振興機構 | Comprehensive analysis of sugar phosphates in higher plants |
-
2013
- 2013-06-18 CN CN201310239643.7A patent/CN103344731B/en not_active Expired - Fee Related
Non-Patent Citations (7)
| Title |
|---|
| An investigation of the chemical stability of arsenosugars in simulated gastric juice and acidic environments using IC-ICP-MS and IC-ESI-MS/MS;Bryan M.Gamble等;《Analyst》;20020423;第127卷;第781～785页 * |
| Analysis of oligosaccharides in lignocellulosic biomass hydrolysates by high-performance anion-exchange chromatography coupled with mass spectrometry(HPAEC-MS);Leon Coulier等;《Bioresource Technology》;20130128;第133卷;第221～231页 * |
| JP特开2008-122404A 2008.05.29 * |
| JP特开平6-167486A 1994.06.14 * |
| 唐坤甜等.无糖和低糖食品中的糖和糖醇同时分析的阴离子交换色谱-脉冲安培检测法研究.《食品科学》.2008,第29卷(第6期),第327～331页. * |
| 液相色谱串联质谱法测定食品中甘露糖醇、麦芽糖、木糖醇、山梨糖醇;马书民等;《中国食品添加剂》;20111015(第5期);第207页 * |
| 淋洗液发生器离子色谱抑制电导法测定甜味剂;郭莹莹等;《浙江大学学报》;20040731;第31卷(第4期);第435～437页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103344731A (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103344731B (en) | Method for qualitative and quantitative determination of sugar alcohols in foods by ion chromatograph-mass spectrometer | |
| Li et al. | Enantioselective determination of triazole fungicide simeconazole in vegetables, fruits, and cereals using modified QuEChERS (quick, easy, cheap, effective, rugged and safe) coupled to gas chromatography/tandem mass spectrometry | |
| CN107247105B (en) | A kind of method that Solid Phase Extraction-high performance liquid chromatography-tandem mass method detects perchlorate in tealeaves | |
| Qin et al. | Automated multi-plug filtration cleanup for liquid chromatographic–tandem mass spectrometric pesticide multi-residue analysis in representative crop commodities | |
| JP6208866B2 (en) | Analytical method for detecting sulfated oligosaccharides | |
| Cao et al. | Molecularly imprinted polymer-based solid phase clean-up for analysis of ochratoxin A in ginger and LC-MS/MS confirmation | |
| González-Domínguez et al. | Development of a metabolomic approach based on urine samples and direct infusion mass spectrometry | |
| Dyke et al. | Sample processing method for the determination of perchlorate in milk | |
| Vu et al. | Clinical screening of paraquat in plasma samples using capillary electrophoresis with contactless conductivity detection: towards rapid diagnosis and therapeutic treatment of acute paraquat poisoning in Vietnam | |
| Shan et al. | A fully automated system with on-line micro solid-phase extraction combined with capillary liquid chromatography–tandem mass spectrometry for high throughput analysis of microcystins and nodularin-R in tap water and lake water | |
| Hamada et al. | Construction of on-line supercritical fluid extraction with reverse phase liquid chromatography–tandem mass spectrometry for the determination of capsaicin | |
| Jiang et al. | Determination of carboplatin in human plasma using HybridSPE-precipitation along with liquid chromatography–tandem mass spectrometry | |
| Song et al. | Automated multi-plug filtration cleanup method for analysis of 48 pesticide residues in green tea using liquid chromatography-tandem mass spectrometry | |
| Long et al. | A non-derivative method for the quantitative analysis of isosteroidal alkaloids from Fritillaria by high performance liquid chromatography combined with charged aerosol detection | |
| Vijay et al. | Capillary electromigration techniques coupled to mass spectrometry: Applications to food analysis | |
| Ge et al. | Trace residue analysis of dicyandiamide, cyromazine, and melamine in animal tissue foods by ultra-performance liquid chromatography | |
| Zhu et al. | Determination of spices in food samples by ionic liquid aqueous solution extraction and ion chromatography | |
| Wei et al. | A rapid ion chromatography column-switching method for online sample pretreatment and determination of L-carnitine, choline and mineral ions in milk and powdered infant formula | |
| Chen et al. | Development of a high-performance liquid chromatography method for the simultaneous quantification of four organoarsenic compounds in the feeds of swine and chicken | |
| CN107529337A (en) | The HPLC analyses of impurity in two to the water wei ling alcohol | |
| CN107688072B (en) | Detection method of Xingnaojing injection | |
| CN114509509A (en) | Method for detecting full-spectrum vitamins in serum | |
| Qin et al. | Multi-residue method for determination of selected neonicotinoid insecticides in traditional Chinese medicine using modified dispersive solid-phase extraction combined with ultra-performance liquid chromatography tandem mass spectrometry | |
| Yao et al. | A fluorinated chitosan‐based QuEChERS method for simultaneous determination of 20 organophosphorus pesticide residues in ginseng using GC–MS/MS | |
| Chang et al. | Online eluent-switching technique coupled anion-exchange liquid chromatography–ion trap tandem mass spectrometry for analysis of non-steroidal anti-inflammatory drugs in pig serum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150128 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |