CN107126941B - Solid-phase micro-extraction coating, preparation and application based on metalloporphyrin microporous polymer - Google Patents
Solid-phase micro-extraction coating, preparation and application based on metalloporphyrin microporous polymer Download PDFInfo
- Publication number
- CN107126941B CN107126941B CN201710421756.7A CN201710421756A CN107126941B CN 107126941 B CN107126941 B CN 107126941B CN 201710421756 A CN201710421756 A CN 201710421756A CN 107126941 B CN107126941 B CN 107126941B
- Authority
- CN
- China
- Prior art keywords
- metalloporphyrin
- solid
- phase micro
- extraction
- porphyrin
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 238000002470 solid-phase micro-extraction Methods 0.000 title claims abstract description 66
- 229920000642 polymer Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920000620 organic polymer Polymers 0.000 claims abstract description 40
- 239000000835 fiber Substances 0.000 claims abstract description 33
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 230000021615 conjugation Effects 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000001465 metallisation Methods 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000004186 food analysis Methods 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000010453 quartz Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000002444 silanisation Methods 0.000 claims description 2
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009825 accumulation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 150000007524 organic acids Chemical class 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 235000005985 organic acids Nutrition 0.000 description 9
- IGIDLTISMCAULB-UHFFFAOYSA-N 3-methylvaleric acid Chemical compound CCC(C)CC(O)=O IGIDLTISMCAULB-UHFFFAOYSA-N 0.000 description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
- 244000089698 Zanthoxylum simulans Species 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 239000013317 conjugated microporous polymer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 241000208125 Nicotiana Species 0.000 description 5
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 5
- NDVASEGYNIMXJL-UHFFFAOYSA-N beta-sabinene Natural products C=C1CCC2(C(C)C)C1C2 NDVASEGYNIMXJL-UHFFFAOYSA-N 0.000 description 5
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 4
- IBVJWOMJGCHRRW-UHFFFAOYSA-N 3,7,7-Trimethylbicyclo[4.1.0]hept-2-ene Chemical compound C1CC(C)=CC2C(C)(C)C12 IBVJWOMJGCHRRW-UHFFFAOYSA-N 0.000 description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- 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 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- 229940005605 valeric acid Drugs 0.000 description 4
- KQAZVFVOEIRWHN-UHFFFAOYSA-N α-thujene Chemical compound CC1=CCC2(C(C)C)C1C2 KQAZVFVOEIRWHN-UHFFFAOYSA-N 0.000 description 4
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 3
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- NDVASEGYNIMXJL-NXEZZACHSA-N (+)-sabinene Natural products C=C1CC[C@@]2(C(C)C)[C@@H]1C2 NDVASEGYNIMXJL-NXEZZACHSA-N 0.000 description 2
- OPFTUNCRGUEPRZ-QLFBSQMISA-N (-)-beta-elemene Chemical compound CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 2
- VLXDPFLIRFYIME-QRTUWBSPSA-N (1S,2R,6R,7R,8S)-1,3-dimethyl-8-propan-2-yltricyclo[4.4.0.02,7]dec-3-ene Chemical compound C1C=C(C)[C@@H]2[C@@]3(C)CC[C@@H](C(C)C)[C@@H]2[C@H]31 VLXDPFLIRFYIME-QRTUWBSPSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 2
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- IBVJWOMJGCHRRW-DTWKUNHWSA-N 2-Carene Natural products C1CC(C)=C[C@H]2C(C)(C)[C@@H]12 IBVJWOMJGCHRRW-DTWKUNHWSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- SCCDQYPEOIRVGX-UHFFFAOYSA-N Acetyleugenol Chemical compound COC1=CC(CC=C)=CC=C1OC(C)=O SCCDQYPEOIRVGX-UHFFFAOYSA-N 0.000 description 2
- IERHLVCPSMICTF-XVFCMESISA-N CMP group Chemical group P(=O)(O)(O)OC[C@@H]1[C@H]([C@H]([C@@H](O1)N1C(=O)N=C(N)C=C1)O)O IERHLVCPSMICTF-XVFCMESISA-N 0.000 description 2
- NPNUFJAVOOONJE-FLFDDASRSA-N Isocaryophyllene Chemical compound C1CC(/C)=C\CCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-FLFDDASRSA-N 0.000 description 2
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N O-methyleugenol Chemical compound COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 2
- 229940088601 alpha-terpineol Drugs 0.000 description 2
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 2
- 229930006722 beta-pinene Natural products 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 229930007927 cymene Natural products 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003891 environmental analysis Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 210000003643 myeloid progenitor cell Anatomy 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 229930006696 sabinene Natural products 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229930006978 terpinene Natural products 0.000 description 2
- 150000003507 terpinene derivatives Chemical class 0.000 description 2
- NPNUFJAVOOONJE-ZIAGYGMSSA-N trans-caryophyllene Natural products C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OGLDWXZKYODSOB-UHFFFAOYSA-N α-phellandrene Chemical compound CC(C)C1CC=C(C)C=C1 OGLDWXZKYODSOB-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- OPFTUNCRGUEPRZ-UHFFFAOYSA-N (+)-beta-Elemen Natural products CC(=C)C1CCC(C)(C=C)C(C(C)=C)C1 OPFTUNCRGUEPRZ-UHFFFAOYSA-N 0.000 description 1
- 229930004051 (+)-delta-cadinene Natural products 0.000 description 1
- FUCYIEXQVQJBKY-ZFWWWQNUSA-N (+)-δ-Cadinene Chemical compound C1CC(C)=C[C@H]2[C@H](C(C)C)CCC(C)=C21 FUCYIEXQVQJBKY-ZFWWWQNUSA-N 0.000 description 1
- KXSDPILWMGFJMM-AEJSXWLSSA-N (1s,4r,5r)-4-methyl-1-propan-2-ylbicyclo[3.1.0]hexan-4-ol Chemical compound C([C@]1(O)C)C[C@]2(C(C)C)[C@H]1C2 KXSDPILWMGFJMM-AEJSXWLSSA-N 0.000 description 1
- KXSDPILWMGFJMM-GUBZILKMSA-N (1s,4s,5r)-4-methyl-1-propan-2-ylbicyclo[3.1.0]hexan-4-ol Chemical compound C([C@@]1(O)C)C[C@]2(C(C)C)[C@H]1C2 KXSDPILWMGFJMM-GUBZILKMSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- YSTPAHQEHQSRJD-UHFFFAOYSA-N 3-Carvomenthenone Chemical compound CC(C)C1CCC(C)=CC1=O YSTPAHQEHQSRJD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LLKXNMNOHBQSJW-UHFFFAOYSA-N Elemol Natural products CCC(=C)C1CC(C=CC1(C)C)C(C)(C)O LLKXNMNOHBQSJW-UHFFFAOYSA-N 0.000 description 1
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 1
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 240000003243 Thuja occidentalis Species 0.000 description 1
- 235000008109 Thuja occidentalis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- QMAYBMKBYCGXDH-RRFJBIMHSA-N alpha-Muurolene Natural products C1CC(C)=C[C@@H]2[C@H](C(C)C)CC=C(C)[C@H]21 QMAYBMKBYCGXDH-RRFJBIMHSA-N 0.000 description 1
- QMAYBMKBYCGXDH-UHFFFAOYSA-N alpha-amorphene Natural products C1CC(C)=CC2C(C(C)C)CC=C(C)C21 QMAYBMKBYCGXDH-UHFFFAOYSA-N 0.000 description 1
- IPZIYGAXCZTOMH-UHFFFAOYSA-N alpha-eudesmol Natural products CC1=CCCC2CCC(CC12)C(C)(C)O IPZIYGAXCZTOMH-UHFFFAOYSA-N 0.000 description 1
- QMAYBMKBYCGXDH-ZNMIVQPWSA-N alpha-muurolene Chemical compound C1CC(C)=C[C@H]2[C@H](C(C)C)CC=C(C)[C@H]21 QMAYBMKBYCGXDH-ZNMIVQPWSA-N 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- OGLDWXZKYODSOB-SNVBAGLBSA-N alpha-phellandrene Natural products CC(C)[C@H]1CC=C(C)C=C1 OGLDWXZKYODSOB-SNVBAGLBSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- HMTAHNDPLDKYJT-UHFFFAOYSA-N amorphadiene Natural products C1=C(C)CCC2C(C)CCC(C(C)=C)C21 HMTAHNDPLDKYJT-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- 229960005233 cineole Drugs 0.000 description 1
- RFFOTVCVTJUTAD-UHFFFAOYSA-N cineole Natural products C1CC2(C)CCC1(C(C)C)O2 RFFOTVCVTJUTAD-UHFFFAOYSA-N 0.000 description 1
- GFJIQNADMLPFOW-UHFFFAOYSA-N cis-Elemol Natural products CC(=C)C1CC(C(C)(C)O)CCC1(C)C=C GFJIQNADMLPFOW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GFJIQNADMLPFOW-VNHYZAJKSA-N elemol Chemical compound CC(=C)[C@@H]1C[C@H](C(C)(C)O)CC[C@@]1(C)C=C GFJIQNADMLPFOW-VNHYZAJKSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- WWULHQLTPGKDAM-UHFFFAOYSA-N gamma-eudesmol Natural products CC(C)C1CC(O)C2(C)CCCC(=C2C1)C WWULHQLTPGKDAM-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930001612 germacrene Natural products 0.000 description 1
- YDLBHMSVYMFOMI-SDFJSLCBSA-N germacrene Chemical compound CC(C)[C@H]1CC\C(C)=C\CC\C(C)=C\C1 YDLBHMSVYMFOMI-SDFJSLCBSA-N 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940116837 methyleugenol Drugs 0.000 description 1
- PRHTXAOWJQTLBO-UHFFFAOYSA-N methyleugenol Natural products COC1=CC=C(C(C)=C)C=C1OC PRHTXAOWJQTLBO-UHFFFAOYSA-N 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229930006968 piperitone Natural products 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012857 repacking Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- KXSDPILWMGFJMM-UHFFFAOYSA-N trans-sabinene hydrate Natural products CC1(O)CCC2(C(C)C)C1C2 KXSDPILWMGFJMM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/592—Stability against heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/96—Applications coating of particles
- C08G2261/962—Applications coating of particles coating of organic particles
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to the solid-phase micro-extraction coatings based on metalloporphyrin microporous polymer, preparation method and application.The preparation method of solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, it include: the preparation of metalloporphyrin suspension and the pretreatment of solid-phase micro-extraction fibre, then the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer is obtained in the surface metallization porphyrin suspension of solid-phase micro-extraction fibre, the preparation of the metalloporphyrin suspension is the following steps are included: S11: prepares porphyrin conjugation micropore organic polymer under microwave synthesis condition；S12: micropore organic polymer is conjugated by porphyrin and synthesizes metalloporphyrin conjugation micropore organic polymer with metal salt action；S13: metalloporphyrin suspension is prepared by metalloporphyrin conjugation micropore organic polymer.Coating prepared by the present invention has many advantages, such as that thermal stability is good, accumulation ability is strong, can be applied to the extracting head of solid phase microextraction, food analysis, in terms of effectively applied.
Description
Technical field
The present invention relates to analytical chemistry and environmental analysis field, more particularly to consolidating based on metalloporphyrin microporous polymer
Phase extraction coating and its preparation method and application.
Background technique
((solid-phase microextraction, SPME) technology is 1989 by Canada to solid phase microextraction
The it is proposeds such as Waterloo university Pawlinszyn and its partner Arthur.Solid phase microextraction overcomes traditional sample pre-treatments
The defect of technology integrates sampling, extraction, concentration, sample introduction, reduces cumbersome sample handling processes and reduces analysis inspection
Survey the time.Its common concern of significant technical advantage just by environment, food, medical industry analysts personnel, and widely popularize
Using.In the development of solid phase microextraction, a restraining factors are exactly the exploitation of solid-phase micro-extraction coating.
Commercial solid-phase micro-extraction coating has dimethyl silicone polymer, polyacrylate, dimethyl silicone polymer/bis- at present
Vinyl benzene, dimethyl silicone polymer/carboxyethyl, divinylbenzene/carboxyethyl, polyethylene glycol/divinylbenzene, divinyl
Benzene etc. is several.The coating of commercialization is all broad spectrum activity mostly, weaker to the selectivity of certain or the specific analyte of certain class.
Which has limited further applying for the technology.In addition, some disadvantages existing for the coating of commercialization, such as thermal instability, machinery
Intensity difference, selectivity are low, low to the extraction efficiency of polar compound in polarity matrix (such as aqueous solution) also to become limitation SPME skill
The factor of art application.Some homemade coatings have also been developed now, are all improved in terms of selectivity and sensitivity, but coating
The type of material is still to be developed.The development of material is so that solid-phase micro-extraction coating shines new vitality, newly
The efficient adsorbent material of type.Therefore, developing efficient, highly selective, stable in physicochemical property, low cost, durable coating becomes
The emphasis of SPME technical research and application.
Conjugation micropore organic polymer (Conjugated Microporous Polymers, CMPs) is a kind of by altogether
The capillary copolymer material containing lightweight elements such as carbon, hydrogen, oxygen, nitrogen, boron of valence link link.This kind of material can have by different
Machine ligand forms the polymer with different topology structure.It can also be synthesized by the allotment of monomer and its variation of reaction condition
Microporous polymer with different pore size size.It is extremely stable that strong covalent bond and intrinsic microcellular structure assign such material
Physical property.Different topological structures and aperture structure makes such material have good answer in terms of specific selection and absorption
Use potentiality.
CMPs is in gas absorption especially to CO at present2Storage in terms of have a brilliant effect, and passed in catalysis, fluorescence
Sense, light capture aspect all have been reported that application, but in terms of separate analysis apply it is less, therefore by such material applied to separate
Analysis aspect has to be developed.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of, and the solid phase microextraction based on metalloporphyrin microporous polymer is applied
Layer and preparation method thereof, which has many advantages, such as that large specific surface area, aperture are uniform, thermal stability is good, is a kind of suction well
Attached property material, can be by porous suction-operated and the metallic site complex coordination of material the effects of, carry out target molecule rich
Collection, simultaneously because the coating material structure containing conjugated pi, therefore compound containing double bonds in structure can be carried out effectively rich
Collection.The coating has many advantages, such as that thermal stability is good, accumulation ability is strong, can be applied to the extracting head of solid phase microextraction, in food point
Analysis, environmental analysis etc. are effectively applied.
The present invention is achieved by the following technical solutions:
A kind of preparation method of the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, characterized by comprising:
Then the preparation of metalloporphyrin suspension and the pretreatment of solid-phase micro-extraction fibre coat gold on the surface of solid-phase micro-extraction fibre
Belong to porphyrin suspension and obtain the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer,
The preparation of the metalloporphyrin suspension the following steps are included:
S11: porphyrin conjugation micropore organic polymer is prepared under microwave synthesis condition；
S12: micropore organic polymer is conjugated by porphyrin and synthesize with metal salt action that metalloporphyrin conjugation micropore is organic to be gathered
Close object；
S13: metalloporphyrin suspension is prepared by metalloporphyrin conjugation micropore organic polymer.
As an implementation, the preparation method of the step S11 porphyrin conjugation micropore organic polymer is: in inertia
Under atmosphere and microwave synthesis condition, porphyrin monomer and to benzene hypoboric acid by Suzuki coupling reaction synthesize porphyrin be conjugated micropore have
Machine polymer, microwave synthesis condition are mixing speed 800rpm, reaction power 100w, 90 DEG C of reaction temperature, the reaction time
90min。
Further, under inert atmosphere and microwave synthesis condition, the Suzuki coupling reaction synthesis porphyrin is conjugated micropore
The specific method of organic polymer is: by porphyrin monomer, is scattered in solvent Isosorbide-5-Nitrae-dioxane to benzene hypoboric acid, ultrasonic mixing
Uniformly, freeze-be evacuated-thaw cycles three times, be added K2CO3Solution and catalyst Pd (PPh3)4, freeze again-be evacuated-it thaws
Three times, the porphyrin monomer is 10:20:80:1 to the ratio between amount of substance of benzene hypoboric acid, potassium carbonate and catalyst to circulation；Institute
It states between step S11 and step S12 further include: after Suzuki coupling reaction, filtering, residue tetrahydrofuran, methanol, third
Successively then wash products in order to further clean up the porous interior complete substance of unreacted use tetrahydro to ketone respectively again
For 24 hours, 90 DEG C of vacuum drying 12h, the porphyrin after being dried is conjugated micropore organic polymer for furans, methanol, the cleaning of acetone Soxhlet.
As an implementation, the preparation method of the step S12 metalloporphyrin conjugation micropore organic polymer is: will
Porphyrin conjugation micropore organic polymer and Zinc diacetate dihydrate after drying are scattered in the ratio between amount of substance for 1:1.3 simultaneously
DMF, ultrasonic mixing is uniform, is heated to 120 DEG C, is stirred to react 12h, and filtering is successively cleaned with methanol, ethyl alcohol, water, 90 DEG C of vacuum
Dry 12h, the metalloporphyrin after being dried are conjugated micropore organic polymer.
As an implementation, the preparation method of the step S13 metalloporphyrin suspension is: by the metal after drying
Porphyrin conjugation micropore organic polymer is ground, and PEG-400 is added as disperse additive, ultrasound as decentralized medium in isopropanol
Disperse 30min, obtains metalloporphyrin suspension.
As an implementation, the preprocess method of the solid-phase micro-extraction fibre are as follows:
S21: one end 2cm is immersed in acetone solvent and impregnates 10min, peels off appearance by the quartz fibre of interception 17cm long
Then the polyimide coating in face makes its surface active with HCl solution and NaOH solution, distilled water is cleaned, naturally dry.
As an implementation, the method for the surface metallization porphyrin suspension of solid-phase micro-extraction fibre includes following
Step:
S31: by quartz fibre silanization: three ethoxy of 3- aminopropyl is immersed in the processed quartz fibre one end step S21
In base silane (APTES), continuous 10 liftings are put into 70 DEG C of vacuum oven dry 5min (since quartz fiber surface is exposed
Hydroxyl reacts to form Si-O-Si key with silylating reagent, makes fiber surface with amido functional group)；
S32: the quartz fibre of step S31 modified is immersed in metalloporphyrin suspension, is lifted 10 times, 105 DEG C back and forth
Dry 2min, is then immersed in 3- aminopropyl triethoxysilane (APTES), lifts 10 times back and forth, is dried in vacuo 5min；
S33: back and forth using S31 and S32 as one, repetitive operation 10 times, obtain coating (can scrape off extra painting with blade
Layer, reservation coated length are 2cm)；
S34: coating obtained is subjected to aging in gas chromatographic sample introduction mouth, aging condition is 250 DEG C of aging 1h, finally
Obtain the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer.As shown in figure 3, SPME coating i.e. under this condition, applies
Loose and porous structure is presented in layer, so that loading capacity is relatively high.
Solid-phase micro-extraction coating provided by the invention based on metalloporphyrin microporous polymer, is obtained by above-mentioned preparation method
It arrives.
The present invention also provides a kind of solid phase micro-extracting heads, which is characterized in that including quartz fibre and is coated on quartz fibre
The above-mentioned solid-phase micro-extraction coating based on metalloporphyrin microporous polymer on surface.
The present invention also provides a kind of solid-phase micro-extraction coatings based on metalloporphyrin microporous polymer in food analysis, environment
Analyze the application of aspect.
Solid-phase micro-extraction coating based on metalloporphyrin microporous polymer of the invention, has the advantages that
(1) solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, uniform pore diameter, large specific surface area, absorption are held
Amount is high；
(2) due to having choosing to substance under the collective effect of silylating reagent APTES and metalloporphyrin micropore organic polymer
Select suction-operated；
(3) metalloporphyrin micropore organic polymer coating thermal stability is very high, and the production method of coating is relatively simple
It is single, it is easy to operate and control.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Detailed description of the invention
Fig. 1 is the reaction schematic diagram for preparing metalloporphyrin conjugation micropore organic polymer；
Fig. 2 is the thermal multigraph based on metalloporphyrin microporous polymer.
Fig. 3 is the scanning electron microscope (SEM) photograph of the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer；
Fig. 4 is preparation and the enrichment process schematic diagram of the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer；
Fig. 5 is 2 Chinese prickly ash volatile component chromatogram of embodiment,
Wherein: 1: α-thujene；2:(1R)-(+)-α firpene；3: sabinene；4: laurene；5: α-phellandrene；6:2- carene；
7:p- cymene；8: dipentene；9: cineole；10:(E) ocimenum；11:(Z) -3,7- dimethyl -1,3,6- octadecane triolefin；
12: terpinenes；13: trans- -4- thujanol；14: terpinolene；15: linalool；16:4- terpenol；17: alpha-terpineol；18:
Terpinenes；19: nopinene；20: piperitone；21: trans-cinnamic aldehyde；22: estragole；23:4- thujanol；24:1- methyl-
4- (1- methyl ethylene) adnoral acetate；25:2- carene；26: beta-elemene；27:(-)-isocaryophyllene；28: big root is fragrant
Leaf alkene；29: α-muurolene；30:4,9- amorphadiene；31:(+)-δ-cadinene；
Fig. 6 is 3 spiceleaf volatile component chromatogram of embodiment,
Wherein: 1: firpene；2: sabinene；3: nopinene；4:P- cymene；5: eudesmol；6: trans- -4- arbor-vitae；7: suitable
Formula -4- thujanol；8:4- terpenol；9: alpha-terpineol；10: trans-cinnamic aldehyde；11: chavicol methyl ether；12: γ-limonene；13:1-
Methyl -4- (1- methyl ethylene) adnoral acetate；14: Acetyl eugenol；15: ocimenum；16: Ylangene；17: β-olive
Fragrant alkene；18: methyl eugenol；19:(-)-isocaryophyllene；20:(E) germacrene；21:(-) α-eudesmene；22: elemol；
Fig. 7 is volatile organic acids chromatogram in 4 tobacco leaf of embodiment,
Wherein: 1: acetic acid；2: propionic acid；3: butyric acid；4: isovaleric acid；5: valeric acid；6: crotonic acid；7:3- methylvaleric acid；8: oneself
Acid；9: enanthic acid；10: octanoic acid；
Fig. 8 is enrichment times of the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer to volatile organic acids
Figure；
Fig. 9 is the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer compared with the absorption property of commercial coat
Figure.
Specific embodiment
Embodiment 1
The preparation of solid-phase micro-extraction coating based on metalloporphyrin micropore organic polymer the following steps are included:
(1) preparation of metalloporphyrin suspension
S11: the synthesis (as shown in Figure 1) of porphyrin conjugation micropore organic polymer:
Tetrabromo phenyl porphyrin (186.10mg, 0.1mmol), to benzene hypoboric acid (33.15mg, 0.2mmol), 8ml Isosorbide-5-Nitrae-two
Six ring of oxygen, be added flask in, ultrasound makes to be uniformly mixed, freeze-be evacuated-thaw cycles three times, remove oxygen, be added K2CO3Solution
2.0ml (110.4mg, 0.8mmol) and catalyst Pd (PPh3)4(11.6mg, 10 μm of ol), are put into micro-wave oven, freeze-be evacuated-
Three times, mixing speed 800rpm under nitrogen protection, under optimum condition, selects microwave power 100w, reaction temperature to thaw cycles
90 DEG C, reaction time 90min, after reaction, reaction solution is filtered, and successively clean production with water, methanol, tetrahydrofuran and acetone
Object.It is further purified with Soxhlet extraction, is cleaned for 24 hours with tetrahydrofuran, methanol, acetone reflux respectively, 90 DEG C of vacuum drying
12h obtains porphyrin conjugation micropore organic polymer；
S12: the synthesis (as shown in Figure 1) of metalloporphyrin conjugation micropore organic polymer:
Porphyrin is taken to be conjugated micropore organic polymer (0.08764mmol), (CH3COO)2Zn·2H2O (0.1139mmol) is equal
It is even to be scattered in 23ml n,N-Dimethylformamide, heating reaction 12h at 120 DEG C.Filtering, is successively cleaned with methanol, ethyl alcohol, water,
90 DEG C of vacuum drying 12h obtain metalloporphyrin conjugation micropore organic polymer (Zn-CMP), indicate the heat of the material as shown in Figure 2
Phenogram is weighed, knows the material better heat stability in figure；
S13: Zn-CMP material obtained is ground, and weighs 10mg, and 1ml isopropanol is added, and 0.1ml PEG-400 is added,
Ultrasonic disperse 30min guarantees that material is evenly dispersed, obtains metalloporphyrin suspension.
(2) pretreatment of quartz fibre
S21: taking the quartz fibre of 17cm long, and one end about 2cm is immersed in acetone solvent and impregnates 10min, peels off outer
Then the polyimide coating in face impregnates 1h with 1mol/L HCl solution, distilled water cleans drying, then molten with 1mol/L NaOH
Liquid impregnates 1h, and distilled water is cleaned, naturally dry drying.
(3) preparation of the solid-phase micro-extraction coating based on metalloporphyrin micropore organic polymer
S31: above-mentioned pretreated quartz fibre is immersed into silylating reagent 3- aminopropyl triethoxysilane (APTES)
In lift 10 times back and forth, 5min are dried in 70 DEG C of vacuum drying；
S32: the quartz fibre of modified is immersed in metalloporphyrin suspension, is lifted back and forth 10 times, 105 DEG C of drying
2min；
S33: repeating S31 to S32 and operate 10 times, obtain Zn-CMP solid-phase micro-extraction coating, scrape off extra coating with blade,
Reservation coated length is 2cm；
S34: SPME coating is fitted into self-control 5 μ l sample injectors of repacking, preceding 250 DEG C of agings of insertion chromatography column feed materials mouth are used
1h is to get the solid-phase micro-extraction coating based on metalloporphyrin micropore organic polymer.It quartz fibre after processing and is covered in
The solid-phase micro-extraction coating based on metalloporphyrin micropore organic polymer on its surface forms solid phase micro-extracting head.As shown in figure 3,
SPME coating under this condition, loose and porous structure is presented in coating, so that loading capacity is relatively high.
Volatile flavor compounds are identified in 2 Chinese prickly ash of embodiment
(1) sample treatment: Chinese prickly ash sample is ground, and sieving weighs 200mg sample in 20ml solid phase microextraction head space
In product, 30min is balanced in 60 DEG C of water-baths, in the solid phase micro-extracting head insertion ml headspace bottle that embodiment 1 is prepared, extraction
30min, it is solid-phase micro-extraction coating preparation and extraction process that last quartz fibre, which keeps 3min, Fig. 4 in gas chromatographic sample introduction mouth,
Schematic diagram.
(2) Chinese prickly ash GC conditions: carrier gas: He gas, column flow, 1mL/min；Input mode: it shunts；Split ratio: 5:
1；Chromatographic column: Agilent DB-5MS (30m × 0.25mm × 0.25 μm)；Injector temperature: 200 DEG C；Temperature programming: 60 DEG C are not
It keeps, 2 DEG C/min rises to 85 DEG C and do not keep, and 8 DEG C/min rises to 200 DEG C and do not keep, and 10 DEG C/min rises to 220 DEG C of holding 2min；
250 DEG C of transmission line temperature.
Chinese prickly ash sample Mass Spectrometry Conditions: level four bars；Scanning mode: SCAN；Scanning range: 45~550u；Ion source: electronics bangs
It hits ion source (EI), temperature: 250 DEG C；Electron energy: 70ev.
(3) Qualitative Identification is analyzed: qualitative analysis is using NIST library searching and combines bibliography progress qualitative, specifically
As a result as shown in Figure 5.
As a result, it has been found that the coating can effectively extract the volatile materials in Chinese prickly ash sample, and combine document
The volatile materials in Chinese prickly ash is identified with Relational database.
Volatile flavor compounds are identified in 3 spiceleaf of embodiment
(1) sample treatment: spiceleaf sample is ground, and sieving weighs 200mg sample in 20ml solid phase microextraction head space
In product, 30min is balanced in 60 DEG C of water-baths, in the solid phase micro-extracting head insertion ml headspace bottle that embodiment 1 is prepared, extraction
30min, last fiber keep 3min in gas chromatographic sample introduction mouth.
(2) spiceleaf GC conditions: carrier gas: He；Column flow, 1mL/min；Input mode: it shunts；Split ratio: 5:1；
Chromatographic column: Agilent DB-5MS (30m × 0.25mm × 0.25 μm)；Injector temperature: 200 DEG C；Temperature programming: 60 DEG C are not protected
It holds, 2 DEG C/min rises to 90 DEG C, and 5 DEG C/min rises to 200 DEG C, and 10 DEG C/min rises to 220 DEG C of holding 2min；Transmission line temperature, 250
℃。
Mass Spectrometry Conditions: level four bars；Scanning mode: SCAN；Scanning range: 45~550u；Ion source: electron impact ion source
(EI), temperature: 250 DEG C；Electron energy: 70ev.
(3) Qualitative Identification is analyzed: qualitative analysis is using NIST library searching and combines bibliography progress qualitative, specifically
As a result as shown in Figure 6.
As a result, it has been found that the coating can effectively extract the volatile materials in spiceleaf sample, and combine document
Its volatile materials is identified with Relational database, provides related foundation for the analysis of volatile materials in fragrance.
Volatile organic acids quantitative analysis in 4 tobacco leaf of embodiment
(1) tobacco leaf pre-treatment: weighing 20mg offal in 20mL ml headspace bottle, the micro- extraction of the solid phase that embodiment 1 is prepared
It takes in head insertion ml headspace bottle, under preferred extraction conditions, slective extraction time 20min, 70 DEG C of extraction temperature, desorption time
2min。
(2) gas chromatography-mass spectrum condition:
Gas-chromatography: carrier gas: He gas, column flow, 1.7ml/min；Input mode: it shunts；Chromatographic column: DB-WAX (30m ×
0.25mm×0.25μm)；Injector temperature: 200 DEG C；It does not shunt；Temperature programming: 60 DEG C do not keep, and 20 DEG C/min rises to 90 DEG C
It does not keep, 7 DEG C/min rises to 105 DEG C and do not keep, and 1 DEG C/min rises to 140 DEG C and do not keep；10 DEG C/min rises to 147 DEG C and does not keep 4
DEG C/min rises to 152 DEG C and do not keep；10 DEG C/min rises to 180 DEG C of holding 1min；Sample injection time, 2min；
Mass Spectrometry Conditions: level four bars；Interface temperature, 250 DEG C；230 DEG C of ion source temperature.Acquisition mode: SIM；Solvent delay
Time: 2min；Various volatility have the fragment ion of organic acid, acetic acid: 45,60；Propionic acid: 45,55,57,73,74；Butyric acid:
45,55,60,73；Isovaleric acid: 45,60,87；Valeric acid: 45,55,60,73；Crotonic acid: 45,68,69,86；3 methylvaleric acid:
45,57,60,87；Caproic acid: 55,60,73,87；Enanthic acid: 55,60,73,87；2- methyl enanthic acid: 57,74,87,73；Octanoic acid: 55,
60,73,85,101,115。
(3) quantitative analysis of volatile organic acids.External standard method carries out quantitative correction to 11 kinds of volatile organic acids, to tobacco leaf
In volatile organic acids analyzed.It is analyzed under optimal conditions, obtains chromatogram as shown in Figure 7, will be obtained
The peak area of chromatogram bring into quantitative correction curve, obtain the content of corresponding volatile organic acids.Acetic acid: 131 μ g/g；
Propionic acid: 0.873 μ g/g；Butyric acid: 0.052 μ g/g；Isovaleric acid: 0.105 μ g/g；Valeric acid: 0.173 μ g/g；Crotonic acid: 0.481 μ g/
g；3 methylvaleric acid: it is not detected；Caproic acid: 0.195 μ g/g；Enanthic acid: 0.153 μ g/g；2- methyl enanthic acid: it is not detected；Octanoic acid:
0.184μg/g。
(4) effect of extracting of the solid-phase micro-extraction coating based on metalloporphyrin micropore organic polymer
Solvent is prepared as the mixed mark solution of methanol: 30mg/L acetic acid, propionic acid, crotonic acid, 15mg/L butyric acid, isovaleric acid, valeric acid,
3 methylvaleric acid, caproic acid, enanthic acid, octanoic acid, 7.5mg/L 2- methyl enanthic acid.The mixed mark of 1 μ L is taken to be put into the Headspace Gas Chromatography of 20mL
In bottle, it is set to volatilize completely under air-proof condition.It will be based on the exposure of the solid-phase micro-extraction coating of metalloporphyrin micropore organic polymer
In ml headspace bottle, 20min, 200 DEG C of desorption 2min of gas chromatographic sample introduction mouth are extracted at 70 DEG C, then carry out GC-MS analysis.Such as figure
8 indicate fiber to the enrichment times of various volatile organic acids.It can be seen that fiber compares the enrichment times of organic acid
Height, extraction selectivity are preferable.
Common having centainly is compared under same extraction conditions, and polar commercial extracting head and the present invention are homemade
Based on metalloporphyrin micropore organic polymeric solid phase micro-extracting head, as shown in figure 9, by finding out in figure, relative to other extracting heads,
The effect of extracting of solid phase micro-extracting head of the present invention is generally preferable.
Solid-phase micro-extraction coating based on metalloporphyrin micropore organic polymer of the invention can be to volatility in fragrance
Substance is effectively enriched with, especially terpenoid substance, is composed library in conjunction with NIST, is identified fragrance material.The coating simultaneously
Volatile organic acids in tobacco leaf can be effectively enriched with, it is detected in conjunction with GC-MS, the study found that the coating is to waving
Hair property organic acid enrichment times are high, better than commercial several frequently seen coating.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (9)
1. a kind of preparation method of the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, characterized by comprising: gold
Belong to the preparation of porphyrin suspension and the pretreatment of solid-phase micro-extraction fibre, then in the surface metallization of solid-phase micro-extraction fibre
Porphyrin suspension obtains the solid-phase micro-extraction coating based on metalloporphyrin microporous polymer,
The preparation of the metalloporphyrin suspension the following steps are included:
S11: porphyrin conjugation micropore organic polymer is prepared under microwave synthesis condition: in inert atmosphere and microwave synthesis condition
Under, porphyrin monomer and to benzene hypoboric acid by Suzuki coupling reaction synthesize porphyrin be conjugated micropore organic polymer；
S12: micropore organic polymer is conjugated by porphyrin and synthesizes metalloporphyrin conjugation micropore organic polymer with metal salt action:
It is that 1:1.3 is scattered in simultaneously that porphyrin after drying, which is conjugated micropore organic polymer and Zinc diacetate dihydrate with the ratio between amount of substance,
DMF, ultrasonic mixing is uniform, is heated to 120 DEG C, is stirred to react 12h, and filtering is successively cleaned with methanol, ethyl alcohol, water, 90 DEG C of vacuum
Dry 12h, the metalloporphyrin after being dried are conjugated micropore organic polymer；
S13: metalloporphyrin suspension is prepared by metalloporphyrin conjugation micropore organic polymer.
2. the preparation method of the solid-phase micro-extraction coating according to claim 1 based on metalloporphyrin microporous polymer,
Be characterized in that: in the step S11, microwave synthesis condition is mixing speed 800rpm, reaction power 100w, reaction temperature 90
DEG C, reaction time 90min.
3. the preparation method of the solid-phase micro-extraction coating according to claim 2 based on metalloporphyrin microporous polymer,
Be characterized in that: under inert atmosphere and microwave synthesis condition, the Suzuki coupling reaction synthesis porphyrin is conjugated micropore organic polymer
The specific method of object is: by porphyrin monomer, is scattered in solvent Isosorbide-5-Nitrae-dioxane to benzene hypoboric acid, ultrasonic mixing is uniform, freezes
Three times, K is added in knot-pumping-thaw cycles2CO3Solution and catalyst Pd (PPh3)4, freeze-be evacuated-thaw cycles three again
Secondary, the porphyrin monomer is 10:20:80:1 to the ratio between amount of substance of benzene hypoboric acid, potassium carbonate, catalyst；The step
Between S11 and step S12 further include: after Suzuki coupling reaction, filtering, residue tetrahydrofuran, methanol, acetone are successively
Then wash products are cleaned for 24 hours with tetrahydrofuran, methanol, acetone Soxhlet respectively again, 90 DEG C of vacuum drying 12h, after being dried
Porphyrin be conjugated micropore organic polymer.
4. the preparation method of the solid-phase micro-extraction coating according to claim 3 based on metalloporphyrin microporous polymer,
Be characterized in that: the preparation method of the step S13 metalloporphyrin suspension is: the metalloporphyrin conjugation micropore after drying is organic
Polymer is ground, and as decentralized medium PEG-400 is added as disperse additive, ultrasonic disperse 30min obtains gold in isopropanol
Belong to porphyrin suspension.
5. the preparation method of the solid-phase micro-extraction coating according to claim 1 based on metalloporphyrin microporous polymer,
It is characterized in that: the preprocess method of the solid-phase micro-extraction fibre are as follows:
S21: one end 2cm is immersed in acetone solvent and impregnates 10min, peels off outer surface by the quartz fibre of interception 17cm long
Then polyimide coating makes its surface active with HCl solution and NaOH solution, distilled water is cleaned, naturally dry.
6. the preparation method of the solid-phase micro-extraction coating according to claim 5 based on metalloporphyrin microporous polymer,
Be characterized in that: the method for the surface metallization porphyrin suspension of solid-phase micro-extraction fibre the following steps are included:
S31: by quartz fibre silanization: 3- aminopropyl-triethoxy silicon is immersed in the processed quartz fibre one end step S21
In alkane, continuous 10 liftings are put into 70 DEG C of vacuum oven dry 5min；
S32: the quartz fibre of step S31 modified is immersed in metalloporphyrin suspension, is lifted 10 times back and forth, 105 DEG C of dryings
2min is then immersed in 3- aminopropyl triethoxysilane, is lifted 10 times back and forth, and 5min is dried in vacuo；
S33: it repeats S31 and S32 and operates 10 times, obtain coating；
S34: coating obtained is subjected to aging in gas chromatographic sample introduction mouth, aging condition is 250 DEG C of aging 1h, is finally obtained
Solid-phase micro-extraction coating based on metalloporphyrin microporous polymer.
7. a kind of solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, which is characterized in that according to claim 1~6
The preparation method of any solid-phase micro-extraction coating based on metalloporphyrin microporous polymer obtains.
8. a kind of solid phase micro-extracting head, which is characterized in that the claim 7 including quartz fibre and coated on quartz fiber surface
The solid-phase micro-extraction coating based on metalloporphyrin microporous polymer.
9. the solid-phase micro-extraction coating according to claim 7 based on metalloporphyrin microporous polymer is in food analysis, ring
The application of border analysis aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710421756.7A CN107126941B (en) | 2017-06-07 | 2017-06-07 | Solid-phase micro-extraction coating, preparation and application based on metalloporphyrin microporous polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710421756.7A CN107126941B (en) | 2017-06-07 | 2017-06-07 | Solid-phase micro-extraction coating, preparation and application based on metalloporphyrin microporous polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107126941A CN107126941A (en) | 2017-09-05 |
| CN107126941B true CN107126941B (en) | 2019-07-16 |
Family
ID=59734408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710421756.7A Active CN107126941B (en) | 2017-06-07 | 2017-06-07 | Solid-phase micro-extraction coating, preparation and application based on metalloporphyrin microporous polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107126941B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273481B (en) * | 2018-01-12 | 2019-04-05 | 山东省分析测试中心 | Polyphenylene-conjugation microporous polymer solid-phase micro-extraction coating preparation and its application |
| CN110681365A (en) * | 2018-07-06 | 2020-01-14 | 中国科学院大连化学物理研究所 | Conjugated microporous polymers, method for the production thereof and use thereof |
| CN109096456B (en) * | 2018-08-20 | 2020-11-10 | 吉林师范大学 | Porphyrin-based conjugated microporous polymer and preparation method thereof |
| CN109589937B (en) * | 2019-01-25 | 2021-09-14 | 河南科技学院 | Preparation method and application of solid-phase micro-extraction fiber of self-assembled multilayer porphyrin organic framework compound |
| CN109867770B (en) * | 2019-03-11 | 2021-11-30 | 吉林大学 | Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof |
| CN110294838B (en) * | 2019-07-03 | 2021-11-02 | 江南大学 | Polyhydroxy porphyrin polymer and preparation method thereof |
| CN111504994B (en) * | 2020-05-07 | 2022-02-18 | 山东省地质矿产勘查开发局第一地质大队 | Porphyrin-based porous organic polymer and application thereof in colorimetric detection of sulfur ions |
| CN115012063A (en) * | 2022-06-28 | 2022-09-06 | 徐永海 | Mould-proof quick-drying towel fabric and preparation method thereof |
| CN115672396B (en) * | 2022-10-26 | 2024-03-08 | 西安工程大学 | Preparation method of glass-based porphyrin film photocatalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310733A (en) * | 1986-03-03 | 1988-01-18 | Kotobuki Seiyaku Kk | Cancerous cytotoxic active substance and production thereof |
| JP2007039588A (en) * | 2005-08-04 | 2007-02-15 | Kyoto Univ | Subporphyrin compound, process for its production and its application |
| CN103755928A (en) * | 2013-09-17 | 2014-04-30 | 华南理工大学 | Water-soluble porphyrin conjugated polymer as well as preparation method and application thereof |
-
2017
- 2017-06-07 CN CN201710421756.7A patent/CN107126941B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6310733A (en) * | 1986-03-03 | 1988-01-18 | Kotobuki Seiyaku Kk | Cancerous cytotoxic active substance and production thereof |
| JP2007039588A (en) * | 2005-08-04 | 2007-02-15 | Kyoto Univ | Subporphyrin compound, process for its production and its application |
| CN103755928A (en) * | 2013-09-17 | 2014-04-30 | 华南理工大学 | Water-soluble porphyrin conjugated polymer as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Fe3O4@SiO2@porphrin 纳米颗粒的制备及其对环境水样中多环芳烃的磁固相萃取;余静等;《第21 届全国色谱学术报告会及仪器展览会》;20170519;第561页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107126941A (en) | 2017-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107126941B (en) | Solid-phase micro-extraction coating, preparation and application based on metalloporphyrin microporous polymer | |
| Zhang et al. | Fabrication of novel nanoporous array anodic alumina solid-phase microextraction fiber coating and its potential application for headspace sampling of biological volatile organic compounds | |
| RU2012141952A (en) | SILICON OXIDE FIBER NANOPARTICLES WITH DEVELOPED SURFACE | |
| CN102489272B (en) | Solid-phase micro-extraction coating prepared on basis of polydopamine modified stainless steel wires and preparation method and application thereof | |
| CN108543527A (en) | A kind of covalent organic framework compound solid-phase micro-extraction fibre head and preparation method thereof | |
| Zhang et al. | Preparation of novel alumina nanowire solid-phase microextraction fiber coating for ultra-selective determination of volatile esters and alcohols from complicated food samples | |
| CN106442464A (en) | Preparing method of silicon wafer/reduced graphene/gold nanocomposite material | |
| CN102416313A (en) | Bisphenol A dummy template molecularly imprinted stir bar and preparation method thereof | |
| Lopes et al. | Preparation and characterization of polydimethylsiloxane/poly (vinylalcohol) coated solid phase microextraction fibers using sol–gel technology | |
| CN104492491B (en) | A kind of big ball Pd/Al of the films of ZIF 8 cladding grade2O3Egg-shell catalyst and preparation method thereof | |
| Guo et al. | In situ fabrication of nitrogen doped graphitic carbon networks coating for high-performance extraction of pyrethroid pesticides | |
| CN101059480A (en) | Glassy carbon electrode modified electrochemical detection method for diethylstilbestrol | |
| CN109248700B (en) | Preparation method and application of nitrogen-doped carbon material catalyst | |
| CN103880721B (en) | A kind of method of the Jin Ping Mei separating chiral medicine Trolovol enantiomorph based on functionalization | |
| CN109589937A (en) | A kind of preparation method and applications of the solid-phase micro-extraction fibre of self assembling multilayer porphyrin organic frame compound | |
| CN106450358A (en) | N-doped carbon nano-tube/carbon compound oxygen reduction catalyst and preparation method thereof | |
| CN103399099A (en) | Method for detecting nine organophosphorus pesticides simultaneously | |
| CN110479222B (en) | Preparation method of Zr (IV) -2-amino terephthalic acid complex hybrid polymer monolithic column and application thereof in solid phase micro-extraction | |
| Zhang et al. | Reaction mechanism of in-situ vaporization catalytic reforming of aqueous bio-oil for hydrogen production | |
| CN107118793A (en) | A kind of application of metal carrying catalyst in grease and biomass copyrolysis prepare aromatic hydrocarbons | |
| CN102500422A (en) | Functionalized graphene and preparation method as well as application thereof | |
| Hegde et al. | C− H Activation of Benzamides Using Biogenically Synthesized Pd@ CNTs Catalyst under External Ligand Free Condition: Access to Isoquinolones and A DFT Study of Phytochemicals | |
| CN102702565A (en) | Preparation method and application of indole acetic acid (IAA) molecularly imprinted polymer (MIP) | |
| CN116854911A (en) | Porous covalent triazine framework material, porous covalent triazine framework material solid-phase microextraction probe, preparation method and application thereof | |
| CN109745953B (en) | Environment-friendly modified shaddock peel cigarette holder adsorbent and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |