CN112858505A - Method for determining organic acid in reconstituted tobacco pulp and white water - Google Patents
Method for determining organic acid in reconstituted tobacco pulp and white water Download PDFInfo
- Publication number
- CN112858505A CN112858505A CN202110032044.2A CN202110032044A CN112858505A CN 112858505 A CN112858505 A CN 112858505A CN 202110032044 A CN202110032044 A CN 202110032044A CN 112858505 A CN112858505 A CN 112858505A
- Authority
- CN
- China
- Prior art keywords
- sodium
- sample
- column
- pulp
- reconstituted tobacco
- 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.)
- Pending
Links
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 33
- 241000208125 Nicotiana Species 0.000 title claims abstract description 31
- 235000002637 Nicotiana tabacum Nutrition 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 24
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 235000005985 organic acids Nutrition 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 6
- 229920002472 Starch Polymers 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000004744 fabric Substances 0.000 claims abstract description 5
- 229920002521 macromolecule Polymers 0.000 claims abstract description 5
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 5
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 5
- 235000019698 starch Nutrition 0.000 claims abstract description 5
- 239000008107 starch Substances 0.000 claims abstract description 5
- 239000000523 sample Substances 0.000 claims description 46
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000013068 control sample Substances 0.000 claims description 7
- DAEPDZWVDSPTHF-UHFFFAOYSA-M sodium pyruvate Chemical compound [Na+].CC(=O)C([O-])=O DAEPDZWVDSPTHF-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 238000004255 ion exchange chromatography Methods 0.000 claims description 5
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 229960003885 sodium benzoate Drugs 0.000 claims description 3
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- UDWXLZLRRVQONG-UHFFFAOYSA-M sodium hexanoate Chemical compound [Na+].CCCCCC([O-])=O UDWXLZLRRVQONG-UHFFFAOYSA-M 0.000 claims description 3
- 239000001540 sodium lactate Substances 0.000 claims description 3
- 235000011088 sodium lactate Nutrition 0.000 claims description 3
- 229940005581 sodium lactate Drugs 0.000 claims description 3
- 239000001394 sodium malate Substances 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims description 3
- 239000004324 sodium propionate Substances 0.000 claims description 3
- 235000010334 sodium propionate Nutrition 0.000 claims description 3
- 229960003212 sodium propionate Drugs 0.000 claims description 3
- 229940054269 sodium pyruvate Drugs 0.000 claims description 3
- 239000001433 sodium tartrate Substances 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- TWEGKFXBDXYJIU-UHFFFAOYSA-M sodium;2-methylpropanoate Chemical compound [Na+].CC(C)C([O-])=O TWEGKFXBDXYJIU-UHFFFAOYSA-M 0.000 claims description 3
- JJZAWYXASMCCLB-UHFFFAOYSA-M sodium;3-methylbutanoate Chemical compound [Na+].CC(C)CC([O-])=O JJZAWYXASMCCLB-UHFFFAOYSA-M 0.000 claims description 3
- UONCLBUDXCZIOK-UHFFFAOYSA-M sodium;3-methylpentanoate Chemical compound [Na+].CCC(C)CC([O-])=O UONCLBUDXCZIOK-UHFFFAOYSA-M 0.000 claims description 3
- ZTRIBXMDBFDMQW-UHFFFAOYSA-M sodium;4-methylpentanoate Chemical compound [Na+].CC(C)CCC([O-])=O ZTRIBXMDBFDMQW-UHFFFAOYSA-M 0.000 claims description 3
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012521 purified sample Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 239000011734 sodium Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- -1 formate ions Chemical class 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000011002 quantification Methods 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IGIDLTISMCAULB-UHFFFAOYSA-N 3-methylvaleric acid Chemical compound CCC(C)CC(O)=O IGIDLTISMCAULB-UHFFFAOYSA-N 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- 229940107700 pyruvic acid Drugs 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 229940005605 valeric acid Drugs 0.000 description 3
- OVBFMEVBMNZIBR-UHFFFAOYSA-N -2-Methylpentanoic acid Natural products CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 108010089934 carbohydrase Proteins 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 238000002045 capillary electrochromatography Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019505 tobacco product Nutrition 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The invention discloses a method for measuring organic acid in reconstituted tobacco pulp and white water, which comprises the steps of removing fibers and other solid particulate matters in the pulp by using filter cloth in the processes of pulp sample purification and sample stability treatment, centrifugally removing macromolecular substances such as starch, protein and the like, and adding a proper amount of sodium hydroxide aqueous solution; the on-line purification and separation process of the sample to be tested comprises the steps that alkali metal ions and transition metal ions are intercepted by a sodium type solid phase extraction column, an H type column is replaced by an ion exchange pretreatment column to intercept hydrophobic compounds in a matrix, the abundance of acetate ions and formate ions cannot be increased, a large quantitative ring of 1mL is added in front of the ion exchange pretreatment column, the samples flowing out of the Na solid phase extraction column are all collected and enter an analysis system, the analysis of the samples is not influenced by the pH value of the samples, and the accuracy of sample quantification is ensured. After the analysis, a map of the slurry organic acid can be obtained, and the content of 17 organic acids can be quantified simultaneously.
Description
Technical Field
The invention relates to the technical field of detection of tobacco pulp and white water, in particular to a method for determining organic acid in reconstituted tobacco pulp and white water.
Background
Pulping is one of the key processes in the production of the papermaking industry, and the characteristics of the pulp directly influence the subsequent production process and the product quality. In the production and operation process, microorganisms can be bred in inorganic salt, polysaccharide and other organic substances in the slurry system under appropriate conditions, and the slurry can be acidified and deteriorated when the retention time is long, so that the production line is polluted, and the production efficiency is influenced. The industry generally adopts methods of adding a sterilization preservative, microorganisms, an enzyme preparation, a flocculating agent and the like to solve the problem of microbial pollution in a system.
The paper-making reconstituted tobacco is a sheet product which is close to natural tobacco and is formed by recombining and processing raw material components by using tobacco materials such as tobacco powder, tobacco stems, tobacco pieces and the like as raw materials through the process of extraction, concentration, pulping, papermaking, coating, baking, post-treatment and the like. Pulping is a process of obtaining paper pulp by separating fibers from fibers under the action of mechanical force by using a pulping machine, the freshness of the pulp in the production process of the paper-making reconstituted tobacco directly influences the sensory quality of the product, and the tobacco industry has requirements on the safety of the reconstituted tobacco product and has clear regulations in the list of substances permitted to be used by the reconstituted tobacco.
At present, the reconstituted tobacco industry generally adopts methods of increasing the operation temperature of the pulp, reducing the reuse of white water and the like to reduce the breeding of microorganisms, the measures are established according to production operation experience and product sensory quality evaluation, and the measures have uncertainty and postposition on control on the quality of the pulp. Anaerobic bacteria in the slurry system can be fermented into carbohydrase, metabolic byproducts such as volatile fatty acid and the like are released, the volatile fatty acid is a main component causing the slurry to be acidified and deteriorated, and the change of the content of the organic acid in the slurry reflects the freshness of the slurry to a certain extent. Therefore, establishing a method for measuring organic acid in the slurry is a common problem faced by the technical workers of the reconstituted tobacco at present.
Relevant research reports on organic acid determination include GC/MS, HPLC, capillary electrophoresis, pressurized capillary electrochromatography, ion chromatography and the like. The GC/MS method is mainly focused on the measurement of organic acids in solid samples, the HPLC method is mainly used for measuring organic acids which are difficult to volatilize, the research on the measurement of volatile organic acids is less, and the ion chromatography method for measuring organic acids is mainly focused on a simpler sample system. The reconstituted tobacco pulp system contains inorganic salt, polysaccharide, pigment, metal ions and other components such as cations and anions, the sample system is complex, and the determination of organic acid in the reconstituted tobacco pulp is not reported.
Anaerobic bacteria in the reconstituted tobacco slurry are fermented into carbohydrase, and metabolic byproducts such as volatile fatty acids and the like are released, wherein the volatile fatty acids comprise formic acid, acetic acid, propionic acid, butyric acid, pyruvic acid, isobutyric acid, valeric acid, methyl valeric acid, caproic acid and the like. In the preparation process of the slurry, organic acids such as lactic acid, malic acid, benzoic acid, tartaric acid, oxalic acid, citric acid and the like in tobacco enter a slurry circulating system, and the citric acid is one of the fermented organic acids. Since the change of the organic acid in the slurry reflects the freshness of the slurry to some extent, research on a method for measuring 17 kinds of organic acids such as lactic acid, acetic acid, propionic acid, formic acid, isobutyric acid, butyric acid, isovaleric acid, pyruvic acid, valeric acid, 3-methylvaleric acid, 4-methylvaleric acid, hexanoic acid, tartaric acid, malic acid, oxalic acid, benzoic acid, citric acid, and the like in the slurry by ion chromatography has been carried out.
Disclosure of Invention
The invention aims to provide a method for measuring organic acid in reconstituted tobacco pulp and white water, which solves the problem that the organic acid in reconstituted tobacco is difficult to measure in the prior art.
The invention is realized by the following technical scheme:
a method for measuring organic acid in reconstituted tobacco pulp and white water comprises the following steps:
s1 purifying and stabilizing slurry sample
Filtering a pulp sample to remove fibers and other solid particulate matters in the pulp, adding 0.2-0.02mL of 1-10mol/L sodium hydroxide aqueous solution into 25mL of filtrate, centrifuging to remove starch, protein and other macromolecular substances, and passing supernatant through a water-based needle filter to obtain a purified sample;
s2, injecting the sample into the quantitative ring, bringing the sample into the Na-type solid phase extraction column by pure water to remove alkali metal ions and transition metal ions in the sample, allowing the sample to flow out of the Na-type solid phase extraction column and enter a 1ml large quantitative ring, allowing the sample to enter an ion exchange pre-column to remove hydrophobic substances, allowing the sample flowing out of the ion exchange pre-column to enter an ion chromatographic column for separation, and allowing the separated anions to enter a conductivity detector for detection.
Preferably, the slurry sample is filtered using a filter cloth in step S1.
Preferably, the ion exchange pre-column in the step S2 is an AG11-HC column, and the ion chromatographic column is an IonPac AS11-HC ion exchange column.
Preferably, in step S2, the Na-type solid-phase extraction column and the ion exchange pre-column are washed with an organic solvent.
Preferably, the preparation of the control sample solution is also included, and the method comprises the following steps: accurately weighing sodium lactate, sodium acetate, sodium formate, sodium propionate, sodium butyrate, sodium valerate, sodium pyruvate, sodium caproate, sodium isobutyrate, sodium iso-valerate, sodium 3-methyl valerate, sodium 4-methyl valerate, sodium benzoate, sodium tartrate, sodium oxalate, sodium malate and sodium citrate serving as standard samples, and dissolving with ultrapure water to obtain a control sample solution.
Preferably, the working parameters of the ion chromatographic column are that the column temperature is 30 ℃; the temperature of the constant temperature box is 30 ℃; the temperature of the detection pool is 35 ℃; the suppressor current was 160 mA; the column flow rate is 1.5 mL/min; the sample injection amount is 25 mu L; and potassium hydroxide solution was used as the rinse.
Preferably, the eluent is eluted with a gradient.
Preferably, the control sample is added with Cl-、NO3 －、SO4 2－And PO4 3－Four ionic species.
The invention has the beneficial effects that:
in the process of purifying a slurry sample and stably treating the sample, fiber and other solid particle substances in the slurry are removed by using filter cloth, macromolecular substances such as starch, protein and the like are removed by centrifugation, a proper amount of sodium hydroxide aqueous solution is added to destroy the environment of the sample, and the breeding of microorganisms is slowed down or stopped; the on-line purification and separation process of the sample to be tested comprises the steps that alkali metal ions and transition metal ions are intercepted by a sodium type solid phase extraction column, an H type column is replaced by an ion exchange pretreatment column to intercept hydrophobic compounds in a matrix, the abundance of acetate ions and formate ions cannot be increased, a large quantitative ring of 1mL is added in front of the ion exchange pretreatment column, the samples flowing out of the Na solid phase extraction column are all collected and enter an analysis system, the analysis of the samples is not influenced by the pH value of the samples, and the accuracy of sample quantification is ensured.
Drawings
FIG. 1 is a schematic view of the organic acid purification and separation process of the present invention;
FIG. 2 is an ion chromatogram of 17 organic acids;
FIG. 3 is an ion chromatogram for a standard solution concentration of 4. mu.g/mL;
FIG. 4 is a chromatogram of a sample of the spiked slurry of the present invention.
Description of the reference numerals
01. A sample to be tested, 02, waste liquid, 03, a quantitative ring, 04, a solid phase extraction Na type column, 05, a large quantitative ring, 06, leacheate, 07, an ion chromatographic column, 08, an ion exchange pre-column, 09 and a conductivity detector.
Detailed Description
The technical solutions of the present invention are described in detail below by examples, and the following examples are only exemplary and can be used only for explaining and explaining the technical solutions of the present invention, but not construed as limiting the technical solutions of the present invention.
The technical scheme of the application is a method aiming at the content of 17 organic acids in tobacco pulp and white water, and the technical scheme mainly comprises the following steps:
s1 purifying and stabilizing slurry sample
The slurry sample is filtered through 400-mesh filter cloth to remove fibers and other solid particulate matters in the slurry, and 0.1ml of 4mol/L sodium hydroxide aqueous solution is added into 25ml of filtrate to destroy the sample environment and slow down or stop the growth of microorganisms. And centrifuging to remove starch, protein and other macromolecular substances, and taking the centrifuged supernatant to pass through a water-based needle filter to obtain the purified test sample 01.
S2, as shown in fig. 1, wherein the solid line is the load line, the dotted line is the injection line, a is deionized water, and B is acetonitrile. Injecting a sample to be tested into a quantitative ring 03 (valve 2), introducing pure water into the valve 2 through a quaternary gradient pump, leading the sample to be tested into a Na-type solid-phase extraction column 04 by the pure water to remove alkali metal ions and transition metal ions in the sample to be tested, intercepting the alkali metal ions and the transition metal ions in the sample to the Na-type solid-phase extraction column, leading the sample to be tested, from which the metal ions are removed, to flow out of the Na-type solid-phase extraction column, then to a 1ml large quantitative ring 05 (valve 1), and then to an ion exchange pre-column 08, wherein in the technical scheme of the application, the ion exchange pre-column is an AG11-HC column (4mm multiplied by 50mm) to remove hydrophobic substances in the sample, the hydrophobic substances in the sample to be tested are intercepted on the ion exchange pre-column, organic acid ions are not intercepted, and the sample to flow out of the ion exchange pre-column enters an ion chromatographic column 07 for separation, the separated anions enter a conductivity detector 09 for detection.
In the technical scheme of this application, will be detained in the sample matrix washing of Na type solid phase extraction post and ion exchange pre-column to waste liquid 02 with organic phase solvent, realize the washing regeneration of Na type solid phase extraction post and ion exchange pre-column, in this example, organic phase solution is acetonitrile.
Preparation of control solutions:
accurately weighing standard sodium lactate, sodium acetate, sodium formate, sodium propionate, sodium butyrate, sodium valerate, sodium pyruvate, sodium caproate, sodium isobutyrate, sodium iso-valerate, sodium 3-methyl valerate, sodium 4-methyl valerate, sodium benzoate, sodium tartrate, sodium oxalate, sodium malate and sodium citrate, and dissolving with ultrapure water to obtain the final product. In the technical scheme of the application, the various organic acids can be purchased commercially, and reagent pure products can also be purchased in a reagent sales department.
The specific measurement of the application is ion chromatography, and the specific steps are as follows:
the sample solution and the control solution are sucked up, respectively, and injected into the quantitative loop (valve 2) as shown in FIG. 1, and the control chromatogram of the 17 organic acids and the chromatograms of the sample are obtained by the sequential operations, as shown in FIGS. 2 and 3.
The ion chromatographic analysis conditions of the ion chromatographic method are that a chromatographic column is an IonPac AS11-HC ion exchange column with the specification of (250mm multiplied by 4.0mm), and leacheate 06 introduced by a high-pressure pump is KOH solution; the column temperature is 30 ℃; the temperature of the constant temperature box is 30 ℃; the temperature of the detection pool is 35 ℃; the suppressor current was 160 mA; the column flow rate is 1.5 mL/min; the amount of sample was 25. mu.L. The elution gradient of the eluate is shown in Table 1.
TABLE 1 gradient elution procedure for leacheate
The slurry sample purification and stability treatment conditions are that the ion exchange pre-column is an ion exchange column IonPac AG11-HC with the specification of 50mm multiplied by 4.0mm, and in the figure 1, a mobile phase A is deionized water and a mobile phase B is acetonitrile; the mobile phase elution gradient in the quantitation loop is shown in table 2.
The ion chromatogram of the 17 organic acids in the control solution is shown in fig. 2, and the peak numbers in fig. 2 are respectively: 1. lactic acid (10.120 min); 2. acetic acid (10.923 min); 3. propionic acid (13.087 min); 4. formic acid (15.047 min); 5. isobutyric acid (15.553 min); 6. butyric acid (17.013 min); 7. isovaleric acid (19.463 min); 8. pyruvic acid (20.417 min); 9. valeric acid (23.837 min); 10. 3-methylvaleric acid (26.753 min); 11. 4-Methylpentanoic acid (29.093 min); 12. hexanoic acid (30.843 min); 13. benzoic acid (45.940 min); 14. malic acid (49.557 min); 15. tartaric acid (53.777 min); 16. oxalic acid (56.180 min); 17. citric acid (59.397 min).
In the preparation process of the sizing agent, Cl is introduced into the tobacco raw material and the process additive-、NO3 －、SO4 2－、PO4 3－Plasma, to avoid interference of these anions in the matrix with the detection peak, Cl was added to the control sample solution-、NO3 －、SO4 2－、PO4 3－The ion chromatogram of the four ion standard substances is shown in FIG. 3.
The chromatogram for a typical spiked slurry sample is shown in FIG. 4.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for measuring organic acid in reconstituted tobacco pulp and white water is characterized by comprising the following steps:
s1 purifying and stabilizing slurry sample
Filtering a pulp sample to remove fibers and other solid particulate matters in the pulp, adding 0.2-0.02mL of 1-10mol/L sodium hydroxide aqueous solution into 25mL of filtrate, centrifuging to remove starch, protein and other macromolecular substances, and passing supernatant through a water-based needle filter to obtain a purified sample;
s2, injecting the sample into the quantitative ring, bringing the sample into the Na-type solid phase extraction column by pure water to remove alkali metal ions and transition metal ions in the sample, allowing the sample to flow out of the Na-type solid phase extraction column and enter a 1ml large quantitative ring, allowing the sample to enter an ion exchange pre-column to remove hydrophobic substances, allowing the sample flowing out of the ion exchange pre-column to enter an ion chromatographic column for separation, and allowing the separated anions to enter a conductivity detector for detection.
2. The method for measuring organic acids in reconstituted tobacco pulp and white water according to claim 1, wherein the pulp sample is filtered using a filter cloth in step S1.
3. The method for measuring organic acid in reconstituted tobacco pulp and white water according to claim 1, wherein the ion exchange pre-column in step S2 is an AG11-HC column, and the ion chromatography column is an ion pac AS11-HC ion exchange column.
4. The method for measuring organic acid in reconstituted tobacco pulp and white water according to claim 1, wherein in step S2, an organic phase solvent is used to clean the Na-type solid-phase extraction column and the ion exchange pre-column.
5. The method for measuring organic acids in reconstituted tobacco pulp and white water according to claim 1, further comprising the step of preparing a control sample solution, comprising the steps of: accurately weighing sodium lactate, sodium acetate, sodium formate, sodium propionate, sodium butyrate, sodium valerate, sodium pyruvate, sodium caproate, sodium isobutyrate, sodium iso-valerate, sodium 3-methyl valerate, sodium 4-methyl valerate, sodium benzoate, sodium tartrate, sodium oxalate, sodium malate and sodium citrate serving as standard samples, and dissolving with ultrapure water to obtain a control sample solution.
6. The method of claim 5, wherein the control sample is added with Cl-、NO3 －、SO4 2－And PO4 3－Four ionic species.
7. The method for measuring organic acid in reconstituted tobacco pulp and white water according to claim 1, wherein the operating parameters of the ion chromatographic column are that the column temperature is 30 ℃; the temperature of the constant temperature box is 30 ℃; the temperature of the detection pool is 35 ℃; the suppressor current was 160 mA; the column flow rate is 1.5 mL/min; the sample injection amount is 25 mu L; and potassium hydroxide solution was used as the rinse.
8. The method of claim 7, wherein the leacheate is eluted in a gradient manner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110032044.2A CN112858505A (en) | 2021-01-11 | 2021-01-11 | Method for determining organic acid in reconstituted tobacco pulp and white water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110032044.2A CN112858505A (en) | 2021-01-11 | 2021-01-11 | Method for determining organic acid in reconstituted tobacco pulp and white water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112858505A true CN112858505A (en) | 2021-05-28 |
Family
ID=76002466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110032044.2A Pending CN112858505A (en) | 2021-01-11 | 2021-01-11 | Method for determining organic acid in reconstituted tobacco pulp and white water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112858505A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113514583A (en) * | 2021-07-09 | 2021-10-19 | 河南卷烟工业烟草薄片有限公司 | Method for representing freshness of reconstituted tobacco pulp |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09138226A (en) * | 1995-11-16 | 1997-05-27 | Sumika Bunseki Center:Kk | Analytical method for drugs in sample containing protein |
| CN101131378A (en) * | 2007-09-29 | 2008-02-27 | 中国烟草总公司郑州烟草研究院 | Method for detecting volatile and semi-volatile organic acid in tobacco leaf or cut tobacco |
| CN101566607A (en) * | 2009-06-03 | 2009-10-28 | 川渝中烟工业公司 | Method for measuring organic acid radicals in cigarette paper |
| CN102128885A (en) * | 2010-12-08 | 2011-07-20 | 广东中烟工业有限责任公司 | Method for quickly and simultaneously detecting 16 inorganic anions and organic acids in tobacco |
| CN102507806A (en) * | 2011-10-12 | 2012-06-20 | 贵州省烟草科学研究所 | Solid phase micro-extraction device and method for measuring volatile organic acid in tobacco leaf |
| CN104345099A (en) * | 2013-08-05 | 2015-02-11 | 红塔辽宁烟草有限责任公司 | Method for determining nonvolatile organic acid in tobacco |
| CN104865332A (en) * | 2014-10-24 | 2015-08-26 | 深圳市科玺化工有限公司 | Method for rapidly detecting content of multiple organic acid radical ions |
| CN106841440A (en) * | 2017-01-20 | 2017-06-13 | 山东省分析测试中心 | The detection method of organic acid in a kind of environment |
| CN109212066A (en) * | 2018-09-21 | 2019-01-15 | 中国烟草总公司郑州烟草研究院 | The measuring method of non-fat class organic acid in a kind of tobacco and tobacco product |
| CN109406704A (en) * | 2018-11-20 | 2019-03-01 | 中国烟草总公司郑州烟草研究院 | A method of a variety of organic acid contents in measurement tobacco and tobacco product |
| CN111122715A (en) * | 2019-11-14 | 2020-05-08 | 浙江工业大学 | Method for simultaneously determining contents of various trace anions in sodium carboxymethylcellulose by using ion chromatography |
-
2021
- 2021-01-11 CN CN202110032044.2A patent/CN112858505A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09138226A (en) * | 1995-11-16 | 1997-05-27 | Sumika Bunseki Center:Kk | Analytical method for drugs in sample containing protein |
| CN101131378A (en) * | 2007-09-29 | 2008-02-27 | 中国烟草总公司郑州烟草研究院 | Method for detecting volatile and semi-volatile organic acid in tobacco leaf or cut tobacco |
| CN101566607A (en) * | 2009-06-03 | 2009-10-28 | 川渝中烟工业公司 | Method for measuring organic acid radicals in cigarette paper |
| EP2650680A1 (en) * | 2010-12-08 | 2013-10-16 | China Tobacco Guangdong Industrial Co., Ltd. | Method for rapidly determining 16 species of inorganic anions and organic acids in tobacco simultaneously |
| WO2012075950A1 (en) * | 2010-12-08 | 2012-06-14 | 广东中烟工业有限责任公司 | Method for rapidly determining 16 species of inorganic anions and organic acids in tobacco simultaneously |
| CN102128885A (en) * | 2010-12-08 | 2011-07-20 | 广东中烟工业有限责任公司 | Method for quickly and simultaneously detecting 16 inorganic anions and organic acids in tobacco |
| CN102507806A (en) * | 2011-10-12 | 2012-06-20 | 贵州省烟草科学研究所 | Solid phase micro-extraction device and method for measuring volatile organic acid in tobacco leaf |
| CN104345099A (en) * | 2013-08-05 | 2015-02-11 | 红塔辽宁烟草有限责任公司 | Method for determining nonvolatile organic acid in tobacco |
| CN104865332A (en) * | 2014-10-24 | 2015-08-26 | 深圳市科玺化工有限公司 | Method for rapidly detecting content of multiple organic acid radical ions |
| CN106841440A (en) * | 2017-01-20 | 2017-06-13 | 山东省分析测试中心 | The detection method of organic acid in a kind of environment |
| CN109212066A (en) * | 2018-09-21 | 2019-01-15 | 中国烟草总公司郑州烟草研究院 | The measuring method of non-fat class organic acid in a kind of tobacco and tobacco product |
| CN109406704A (en) * | 2018-11-20 | 2019-03-01 | 中国烟草总公司郑州烟草研究院 | A method of a variety of organic acid contents in measurement tobacco and tobacco product |
| CN111122715A (en) * | 2019-11-14 | 2020-05-08 | 浙江工业大学 | Method for simultaneously determining contents of various trace anions in sodium carboxymethylcellulose by using ion chromatography |
Non-Patent Citations (1)
| Title |
|---|
| 李华雨等: "再造烟叶浆料中有机酸质量分数随振荡时间的变化", 《烟草科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113514583A (en) * | 2021-07-09 | 2021-10-19 | 河南卷烟工业烟草薄片有限公司 | Method for representing freshness of reconstituted tobacco pulp |
| CN113514583B (en) * | 2021-07-09 | 2023-03-07 | 河南卷烟工业烟草薄片有限公司 | Method for representing freshness of reconstituted tobacco pulp |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Michalkiewicz et al. | Solid-phase extraction procedure for determination of phenolic acids and some flavonols in honey | |
| Cherchi et al. | Solid-phase extraction and high-performance liquid chromatographic determination of organic acids in honey | |
| CN106645502B (en) | Ion chromatograph based on off-line and on-line analysis of multi-valve switching and detection method thereof | |
| Valto et al. | Overview of analytical procedures for fatty and resin acids in the papermaking process | |
| Mongay et al. | Determination of carboxylic acids and inorganic anions in wines by ion-exchange chromatography | |
| CN112858505A (en) | Method for determining organic acid in reconstituted tobacco pulp and white water | |
| Monaghan et al. | Determination of nitrite and nitrate in human serum | |
| Ahrer et al. | Analysis of low-molecular-mass inorganic and organic anions by ion chromatography–atmospheric pressure ionization mass spectrometry | |
| CN110066314A (en) | A kind of efficient affinity purification technique for improving polymer separation resolution ratio | |
| CN107941928A (en) | A kind of method of antibiotic in liquid chromatography mass Simultaneous Determination environment water | |
| Cirilli et al. | Retention behavior of proton pump inhibitors using immobilized polysaccharide-derived chiral stationary phases with organic-aqueous mobile phases | |
| Peldszus et al. | Determination of short-chain aliphathic, oxo-and hydroxy-acids in drinking water at low microgram per liter concentrations | |
| CN102757516B (en) | Decoloration method of enoxaparin sodium | |
| Butler et al. | Liquid chromatography—electrochemistry procedure for the determination of chlorophenolic compounds in pulp mill effluents and receiving waters | |
| CN111122715B (en) | Method for simultaneously determining contents of various trace anions in sodium carboxymethylcellulose by using ion chromatography | |
| Lazarus | Purification of plant extracts for ion-exchange chromatography of free amino acids | |
| CN210604524U (en) | Detection system for trace bromide ions in sodium persulfate | |
| Chico et al. | Ion suppression study for tetracyclines in feed | |
| Buslig et al. | High-performance liquid chromatographic separation of carboxylic acids with anion-exchange and reverse-phase columns | |
| Perfetti | Determination of heterocyclic aromatic amines in process flavors by a modified liquid chromatographic method | |
| CN112110830B (en) | Material pretreatment method for preparing tea theanine | |
| Chen et al. | Performance Liquid Chromatography/Tandem Mass Spectrometry | |
| Wong | Analyses of vitamin B6 in extractives of food materials by high-performance liquid chromatography | |
| Kerth et al. | Determinations of trace anions in hydrogen peroxide | |
| CN113433233A (en) | Centrifugal ultrafiltration-ion chromatography-triple quadrupole mass spectrometry detection method for ethephon in fruits and vegetables |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210528 |