JPH01199155A - Filler for liquid chromatography - Google Patents
Filler for liquid chromatographyInfo
- Publication number
- JPH01199155A JPH01199155A JP63152119A JP15211988A JPH01199155A JP H01199155 A JPH01199155 A JP H01199155A JP 63152119 A JP63152119 A JP 63152119A JP 15211988 A JP15211988 A JP 15211988A JP H01199155 A JPH01199155 A JP H01199155A
- Authority
- JP
- Japan
- Prior art keywords
- clay mineral
- cations
- water
- filler
- spherical
- 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.)
- Granted
Links
- 239000000945 filler Substances 0.000 title claims abstract description 25
- 238000004811 liquid chromatography Methods 0.000 title claims description 15
- 239000002734 clay mineral Substances 0.000 claims abstract description 57
- 150000001768 cations Chemical group 0.000 claims abstract description 29
- 239000011229 interlayer Substances 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 150000002892 organic cations Chemical class 0.000 claims abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 35
- 238000012856 packing Methods 0.000 claims description 34
- 238000010304 firing Methods 0.000 claims description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000843 powder Substances 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000010410 layer Substances 0.000 abstract description 8
- 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 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910021647 smectite Inorganic materials 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052792 caesium Inorganic materials 0.000 abstract description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 2
- 229910052604 silicate mineral Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 abstract description 2
- 206010000060 Abdominal distension Diseases 0.000 abstract 3
- 208000024330 bloating Diseases 0.000 abstract 3
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 239000004927 clay Substances 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 21
- 239000000741 silica gel Substances 0.000 description 19
- 229910002027 silica gel Inorganic materials 0.000 description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 12
- 238000004810 partition chromatography Methods 0.000 description 11
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 125000005372 silanol group Chemical group 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000499 gel Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229940095102 methyl benzoate Drugs 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000004494 ethyl ester group Chemical group 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229940094522 laponite Drugs 0.000 description 4
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229930024421 Adenine Natural products 0.000 description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 3
- 229960000643 adenine Drugs 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- -1 and in this sense Chemical compound 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005377 adsorption chromatography Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 1
- DBKNGKYVNBJWHL-UHFFFAOYSA-N chloro-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)Cl DBKNGKYVNBJWHL-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010332 dry classification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940035289 tobi Drugs 0.000 description 1
- NLVFBUXFDBBNBW-PBSUHMDJSA-N tobramycin Chemical compound N[C@@H]1C[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N NLVFBUXFDBBNBW-PBSUHMDJSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000006227 trimethylsilylation reaction Methods 0.000 description 1
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は液体クロマトグラフィー用充填剤に関する。更
に詳しくは、特定の層間カチオンを有する球状の粘土鉱
物及びそれらを焼成して得られる新規な液体り０マドグ
ラフイー用充填剤である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a packing material for liquid chromatography. More specifically, the present invention relates to spherical clay minerals having specific interlayer cations and a novel filler for liquid lithography obtained by firing them.
そしてこれを用いることにより従来の充填剤では分離が
困難であった各種物質が効率良く分離、分析で鎗、ざら
に短時間で効率よく分取精製可能な新規な液体クロマト
グラフィー用充填剤を提供するものである。By using this material, we provide a new packing material for liquid chromatography that can efficiently separate various substances that are difficult to separate using conventional packing materials, and can be used for analysis in a very short time. It is something to do.
［従来の技術］
液体クロマトグラフィーは、その分離機構により、大き
くは吸着クロマトグラフィーと分配クロマトグラフィー
に分類される。分配クロマトグラフィーは更に、溶離液
と充填剤の極性の関係から順相分配クロマトグラフィー
と逆相分配クロマトグラフィーとに分けられる。[Prior Art] Liquid chromatography is broadly classified into adsorption chromatography and partition chromatography depending on its separation mechanism. Partition chromatography is further divided into normal phase partition chromatography and reverse phase partition chromatography based on the polarity relationship between the eluent and the packing material.
吸着及び順相分配クロマトグラフィーにおける充填剤と
しては、いずれも巨大孔と微細孔が綱目状に分布した全
多孔性シリカ系がほとんどであり、その他アルミナ系及
びスチレンジビニルベンゼン、ヒドロキシメタクリレー
トなどのポーラスポリマー系、また特殊な用途として水
酸化カルシウム粉末、リン酸カルシウムゲルなどが用い
られている。Most of the packing materials used in adsorption and normal phase partition chromatography are completely porous silica-based materials in which macropores and micropores are distributed in a grid pattern, and other materials include alumina-based materials and porous polymers such as styrene divinylbenzene and hydroxymethacrylate. Calcium hydroxide powder, calcium phosphate gel, etc. are used for special purposes.
逆相分配クロマトグラフィー用充填剤としては、ＯＤＳ
に代表されるように、前記充填剤（例えばシリカ）を担
体とし、これにオクタデシル基等のアルキル基等を化学
結合させたものが多く用いられている。As a packing material for reverse phase partition chromatography, ODS
As typified by , those in which the filler (for example, silica) is used as a carrier and an alkyl group such as an octadecyl group is chemically bonded to the carrier are often used.
一方、充填剤の粒子の形状には、球形と不定形があるが
、一般に、球形充填剤は高密度に再現性よく充填するこ
とができることから、カラム効率が良い。On the other hand, the shape of the particles of the filler includes spherical and amorphous shapes, but in general, spherical fillers can be packed with high density and good reproducibility, and therefore have good column efficiency.
［発明が解決しようとする課題］
吸着及び順相分配クロマトグラフィーでは、孔径６０人
ないし１００人、比表面積約３００〜５００ｍ２／ｇの
シリカゲルが最も広く普及している。シリカゲル表面の
活性点はシラノール基（５ｉ−ＯＨ）で、このシラノー
ル基に対する溶質分子の官能基の吸着エネルギーが重要
な要因となっている。従って、その適用は酸素、窒素原
子を含む官能基（カルボニル基、水酸基、アミノ基など
）を少数個もつ非イオン性分子に限られ、このような意
味からシリカゲル充填剤は中間極性をもつ、中位の分子
量の溶質に良好に適用される。このようなことからイオ
ン性物質や極性の強い物質には自ずとその適用範囲に限
界がある。[Problems to be Solved by the Invention] In adsorption and normal phase partition chromatography, silica gel with a pore size of 60 to 100 pores and a specific surface area of about 300 to 500 m2/g is most widely used. The active sites on the silica gel surface are silanol groups (5i-OH), and the adsorption energy of the functional groups of solute molecules to these silanol groups is an important factor. Therefore, its application is limited to nonionic molecules that have a small number of functional groups (carbonyl groups, hydroxyl groups, amino groups, etc.) containing oxygen and nitrogen atoms, and in this sense, silica gel fillers have intermediate polarity. It is well applied to solutes with a molecular weight of about For this reason, ionic substances and highly polar substances naturally have a limited range of application.
一方、ポーラスポリマーはポリマーの種類により溶質分
子と特殊な相互作用をして、シリカゲル充填剤とは異な
った分離様式を示し、シリカゲル充填剤では分離が困難
であった溶質分子の分離も可能となる場合も多い。しか
しながら、ポリマーの溶解や膨潤などにより、分離効率
が低下するといった欠点をもっている。また、耐圧性も
シリカゲル充填剤には劣る。On the other hand, porous polymers have special interactions with solute molecules depending on the type of polymer, and exhibit a different separation mode than silica gel packings, making it possible to separate solute molecules that are difficult to separate using silica gel packings. There are many cases. However, it has the disadvantage that the separation efficiency decreases due to dissolution and swelling of the polymer. In addition, pressure resistance is inferior to silica gel fillers.
また、シリカ表面にアルキル基を導入した従来の逆相分
配液体クロマトグラフィー用充填剤においては、シラノ
ール基とアルキルクロルシランとの反応が完結せずシラ
ノール基が１０〜２０％残存して逆相分配液体クロマト
グラフィーにおいて太きな問題点となっている。すなわ
ち、残存シラノール基が存在すると、極性物質との相互
作用が強く起こり、このため、分析や分取において極性
化合物のピークは輻尋となり、ざらにテーリング現象が
起きる。ざらに、残存シラノール基は、極性の大きい化
合物と非可逆的な吸着を起こすので、このために充填カ
ラム６劣化が早（なる。ざらに、残存シラノール基の存
在およびシリカ質の存在により、耐酸性および耐アルカ
リ性が弱く、使用できる移動相溶媒のＰＨ領領域、従来
の充填カラムの場合、ｐＨ２〜７に制限される等の数多
くの問題点が存在している。このため、従来の充填カラ
ムの一部には、ジメチルオクタデシルクロルシランある
いはジメチルオクチルクロルシランとの反応の後で、残
存シラノール基を封鎖するために、再度トリメチルクロ
ルシラン（ＴＭＳ）等で処理したものもある。しかしな
がら、トリメチルシリル化処理によっても、残存シラノ
ール基を完全になくすことはできない。In addition, in conventional packing materials for reversed-phase partition liquid chromatography in which alkyl groups are introduced onto the silica surface, the reaction between the silanol groups and the alkylchlorosilane is not completed, and 10 to 20% of the silanol groups remain, resulting in reversed-phase partitioning. This is a major problem in liquid chromatography. That is, the presence of residual silanol groups causes strong interaction with polar substances, and therefore, in analysis and preparative separation, the peaks of polar compounds become narrow, and a tailing phenomenon occurs. In general, residual silanol groups cause irreversible adsorption with highly polar compounds, which causes the packed column 6 to deteriorate quickly. There are many problems such as poor pH and alkali resistance, and the pH range of mobile phase solvents that can be used is limited to pH 2 to 7 in the case of conventional packed columns.For this reason, conventional packed columns have In some cases, after the reaction with dimethyloctadecylchlorosilane or dimethyloctylchlorosilane, some are treated again with trimethylchlorosilane (TMS) etc. to block the remaining silanol groups.However, trimethylsilylation Even with treatment, residual silanol groups cannot be completely eliminated.
本発明者らは、このような事情に鑑み鋭意研究を重ねた
結果、水膨潤性粘土鉱物の層間イオンをナトリウム以外
の他の金属または有機イオンに実質的に交換した球状の
粘土鉱物を充填剤として用いることにより、吸着及び順
相分配クロマトグラフィーにおいては従来のシリカゲル
充填剤やポーラスポリマーでは分離が困難であった物質
も効率良（分離できることを、また逆相分配クロマトグ
ラフィーにおいてはシラノール基の影響が無いため、塩
基性物質や強い極性の物質のピークがシャープで、長期
にわたって使用可能であることを見出し、この知見に基
づいて本発明を完成するに到った。In view of these circumstances, the present inventors have conducted extensive research, and as a result, we have developed a filler using spherical clay minerals in which the interlayer ions of water-swellable clay minerals have been substantially exchanged with metals or organic ions other than sodium. In adsorption and normal phase partition chromatography, it is possible to efficiently separate substances that are difficult to separate with conventional silica gel packings and porous polymers. It was discovered that the peaks of basic substances and strongly polar substances are sharp and can be used for a long period of time because of the lack of oxidation, and based on this knowledge, the present invention was completed.
［課題を解決するための手段］
すなわち本発明は、水Ｗ潤性粘土鉱物の層間イオンがナ
トリウムイオン以外の他のカチオンで実質的に置換され
てなる球状の粘土鉱物からなる液体クロマトグラフィー
用充填剤、および該粘土鉱物を焼成して得られる焼成粘
土鉱物からなる液体クロマトグラフィー用充填剤を提供
するものである。[Means for Solving the Problems] That is, the present invention provides a packing for liquid chromatography consisting of a spherical clay mineral in which the interlayer ions of the water-wettable clay mineral are substantially replaced with cations other than sodium ions. The present invention provides a filler for liquid chromatography comprising a fired clay mineral obtained by firing the clay mineral, and a fired clay mineral obtained by firing the clay mineral.
以下、本発明の構成について詳述する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明に用いる水膨潤性粘土鉱物は、スメクタイト属に
属する層状ケイ酸塩鉱物であり、モンモリロナイト、バ
イデライト、ノントロナイト、サボナイト及びヘクトラ
イト等であり、天然又は合成品のいずれでもよい。具体
的には、クニビア、スメクトン（クニミネ工業）、ビー
ガム（パンダービルト社）、ラポナイト（ラボルテ社）
、フッ累日ケイ素雲母（トビ−工業）等が利用できる。The water-swellable clay mineral used in the present invention is a layered silicate mineral belonging to the genus smectite, such as montmorillonite, beidellite, nontronite, savonite, and hectorite, and may be either natural or synthetic. Specifically, Knivia, Smectone (Kunimine Industries), Veegum (Panderbilt), Laponite (Laborte)
, fluorinated disilicic mica (Tobi Industries), etc. can be used.
本発明の実施にあたっては、これらの水膨潤性粘土鉱物
のうちから、一種または二種以上が任意に選択される。In carrying out the present invention, one or more types of water-swellable clay minerals are arbitrarily selected from among these water-swellable clay minerals.
クロマトグラフィー用充填剤としては、比表面積の大き
い粉末である程、吸着容量が太き（、溶質分子を強く保
持することができ充填剤として適している。このような
意味から、合成品である水ｌ！ｌｉ潤性粘土鉱物が適し
ており、たとえば合成サボナイトであるスメクントや合
成ヘクトライトであるラポナイトが特に好ましい。As a packing material for chromatography, the larger the specific surface area of the powder, the larger the adsorption capacity (the more strongly it can hold solute molecules, making it suitable as a packing material.In this sense, it is preferable to use synthetic powders. Water-wettable clay minerals are suitable, such as the synthetic sabonite smectite and the synthetic hectorite laponite, which are particularly preferred.
水膨潤性粘土鉱物は粉末表面やその層間マ各種極性分子
と特殊な相互作用をする性質があり、そのため溶質分子
に対する選択性が吸着及び順相分配クロマトグラフィー
におけるシリカゲル充填剤や逆相分配クロマトグラフィ
ーにおけるアルキル基を化学結合きせた従来の充填剤と
は異なっており、新しいタイプの充填剤となっている。Water-swellable clay minerals have the property of having special interactions with various polar molecules on the powder surface and between the layers, and therefore, the selectivity for solute molecules is enhanced by adsorption and silica gel packing in normal phase partition chromatography, and in reverse phase partition chromatography. This is a new type of filler, which is different from conventional fillers in which alkyl groups are chemically bonded.
また−般にシリカ表面は酸性であるため、塩基性物質と
特異的な吸着をし、このような物質ではピークはテーリ
ングしてくる。これに対して、粘土鉱物表面は塩基性で
あるため、塩基性物質に対しシャープなピークを得るこ
とができる。Furthermore, since the silica surface is generally acidic, it specifically adsorbs basic substances, and such substances cause peak tailing. On the other hand, since the clay mineral surface is basic, a sharp peak can be obtained for basic substances.
液体クロマトグラフィー用充填剤としては、球形である
程カラム効率が良くなる。本発明に係る充填剤も球形で
あることを特徴とする。As a packing material for liquid chromatography, the more spherical the packing material, the better the column efficiency. The filler according to the present invention is also characterized by being spherical.
本発明に係る充填剤を得る簡便な方法としてはまず、球
形の水膨潤性粘土鉱物を得、その後、層間の交換可能な
カチオンをナトリウム以外のカチオンで置換する方法が
あげられる。球形の水膨潤性粘土鉱物を、得るには噴霧
乾燥法によるのが良い。A simple method for obtaining the filler according to the present invention is to first obtain a spherical water-swellable clay mineral, and then replace the exchangeable cation between the layers with a cation other than sodium. Spray drying is preferably used to obtain spherical water-swellable clay minerals.
これを用いることにより、簡便で比較的粒径の整つた球
形の粘土鉱物が得られる。By using this, it is possible to obtain a simple spherical clay mineral with a relatively uniform particle size.
すなわち、水膨潤性粘土鉱物を水性溶媒中に分散してゲ
ル化し、しかる後に該分散液を噴！乾燥する方法である
。That is, a water-swellable clay mineral is dispersed in an aqueous solvent to form a gel, and then the dispersion is sprayed! This is a drying method.
上記ゲルを調製するにあたっては水膨潤性粘土鉱物の濃
度が２０重量％以下になるようにすることが望ましく、
特に望ましくは１〜１０重量％である。When preparing the above gel, it is desirable that the concentration of the water-swellable clay mineral is 20% by weight or less,
Particularly preferably, it is 1 to 10% by weight.
２０重量％を越える濃度ではゲル粘度が２高く、噴霧乾
燥時の噴霧ノズルへの液の送りが難しく、またノズルの
目づまり等が生じてしまう。If the concentration exceeds 20% by weight, the gel viscosity is 2 times higher, making it difficult to feed the liquid to the spray nozzle during spray drying, and clogging the nozzle.
また上記ゲルの調製に際しては、水膨＆Ｉ憔粘土鉱物が
十分に分散、膨潤するように十分撹拌することが好まし
い。分散、膨潤が不十分な場合は噴霧乾燥時にノズルの
目づまりや、得られた球状粘土鉱物がふぞろいとなる場
合があり好ましくない＝噴霧乾燥に際しては、ディスク
タイプや加圧ノズル式、２流体ノズル式などの一般的噴
霧乾燥法が適用できる。Further, when preparing the above gel, it is preferable to stir sufficiently so that the water-swollen clay mineral is sufficiently dispersed and swollen. If dispersion and swelling are insufficient, the nozzle may become clogged during spray drying, and the resulting spherical clay minerals may become uneven, which is undesirable. For spray drying, use a disc type, pressure nozzle type, or two-fluid nozzle. General spray drying methods such as the formula can be applied.
いずれの場合も噴霧時の入口空気温度は、粘土鉱物が３
００℃位までは熱的に十分安定であることから、１５０
〜３００℃程度の広い温度範囲が設定できる。In either case, the inlet air temperature during spraying is 3.
Since it is thermally stable enough up to about 00℃, 150℃
A wide temperature range of ~300°C can be set.
また排気温度はノズルからの噴霧流量などによって規定
されるが、大旨１００℃前後で良い。こうして得られる
球状粘土鉱物の粒子径は２〜２０μｍである。Further, the exhaust temperature is determined by the flow rate of the spray from the nozzle, etc., but generally speaking, it may be around 100°C. The particle size of the spherical clay mineral thus obtained is 2 to 20 μm.
これらの、水膨潤性粘土鉱物の層間には、通常ナトリウ
ムイオンやリチウムイオンなどのカチオンが存在し、水
膨潤性粘土鉱物全体を電気的に中和しているが、これら
のカチオンは交換性であり、容易に他のカチオンと置き
換わることができる。Cations such as sodium ions and lithium ions usually exist between the layers of these water-swellable clay minerals, and electrically neutralize the entire water-swellable clay mineral, but these cations are not exchangeable. and can be easily replaced with other cations.
こ、のカチオン交換容量は水［ｉ性粘土鉱物の！類によ
っても異なるが、粘土鉱物１００ｇ当り大兄６゜から１
５０ミリ当量であ払。さらにこのように他の金属カチオ
ンや有機カチオンに置き換わった粘土鉱物は水膨潤性が
無くなり、水と接してもゲルとはならず粉末として存在
している。前記のようにして得られた球状の粘土鉱物そ
のままでは、水に接すると膨潤し充填剤として適当でな
い。本発明の充填剤は、この粘土鉱物の層間イオンを他
の金属カチオンや有機カチオンに換え、水膨潤性を無く
して充填剤として用いるものである。本発明の充填剤は
、吸着、順相分配、又は逆相分配クロマトグラフィーの
いずれにおいても用いることができるが、層間が有機カ
チオンの場合、より疎水的な充填剤となり逆相分配クロ
マトグラフィーに特に適している。The cation exchange capacity of this is water [i-type clay mineral! Although it varies depending on the type, it is 6° to 1° per 100g of clay mineral.
Payment is made in 50 mm equivalent. Furthermore, clay minerals that have been replaced with other metal cations or organic cations lose their water-swelling properties, and do not form a gel even when in contact with water, but instead exist as a powder. If the spherical clay mineral obtained as described above swells when it comes into contact with water, it is not suitable as a filler. The filler of the present invention is used as a filler by replacing the interlayer ions of this clay mineral with other metal cations or organic cations to eliminate water swelling properties. The packing material of the present invention can be used in any of adsorption, normal phase partitioning, or reversed phase partition chromatography, but when the interlayer is an organic cation, the packing material becomes more hydrophobic and is particularly suitable for reversed phase partitioning chromatography. Are suitable.
ナトリウム以外の金属カチオンとしては、銀、ルビジウ
ム、セシウムなどの一層カチオン、カルシウム、銅、亜
鉛、コバルト、カドミウム、ニッケルなどの二価カチオ
ンやアルミニウム、鉄、ルテニウムなどの三価カチオン
などが用いられる。Examples of metal cations other than sodium include monovalent cations such as silver, rubidium, and cesium, divalent cations such as calcium, copper, zinc, cobalt, cadmium, and nickel, and trivalent cations such as aluminum, iron, and ruthenium.
有機カチオンとしては、ベンジルジメチルステアリルア
ンモニウムクロライド、ジメチルジステアリルアンモニ
ウムクロライド、トリメチルステアリルアンモニウムク
ロライド等の四級アンモニウム塩などを用いることがで
きる。As the organic cation, quaternary ammonium salts such as benzyldimethylstearylammonium chloride, dimethyldistearylammonium chloride, and trimethylstearylammonium chloride can be used.
層間カチオンの交換方法としては、水や有機溶媒に金属
イオンや有機カチオンの塩を溶解し、そこに球状の水膨
潤性粘土鉱物を分散し、撹拌する。As a method for exchanging interlayer cations, metal ions and salts of organic cations are dissolved in water or an organic solvent, spherical water-swellable clay minerals are dispersed therein, and the mixture is stirred.
その後、粘土鉱物を分離し、洗浄し、しかる後に乾燥す
ればよい。Thereafter, the clay minerals may be separated, washed, and then dried.
ここで用いる金属イオンや有機カチオンの塩としては、
これらの塩化物、硝酸塩、硫酸塩など溶解性のものであ
ればいずれでもよい。有機溶媒としては、エタノール、
メタノール又はアセトンなど一般的なものが用いられる
。The metal ion and organic cation salts used here are:
Any soluble chloride, nitrate, sulfate, etc. may be used. As the organic solvent, ethanol,
Common materials such as methanol or acetone are used.
製造時の水膨潤性粘土鉱物の濃度は、特に制限はないが
２０重量％以上になると、撹拌が困難となり、イオン交
換が行なわれ難くなる。分散液中の金属イオンや有機カ
チオンの量は、水膨潤性粘土鉱物のカチオン交換容量以
上であることが望ましい。イオン交換反応を行なう際の
分散液の温度は、何度でもよ（、通常室温で充分である
。乾燥温度は、有機カチオン及び粘土鉱物の分解温度以
下であれば何度でもよい。The concentration of the water-swellable clay mineral during production is not particularly limited, but if it exceeds 20% by weight, stirring becomes difficult and ion exchange becomes difficult. It is desirable that the amount of metal ions and organic cations in the dispersion is equal to or greater than the cation exchange capacity of the water-swellable clay mineral. The temperature of the dispersion during the ion exchange reaction may be any temperature (usually room temperature is sufficient).The drying temperature may be any temperature as long as it is below the decomposition temperature of the organic cation and clay mineral.
１ざらに、これらの粉末を焼成して用いても良い。These powders may be fired and used.
焼成温度、焼成時間は用いた粘土鉱物や分離しようとす
る溶質分子に応じて選択されるが、球状粉末が互いに焼
結を起こす温度以下であることが必要である。層間イオ
ンが金属イオンの場合、焼成により耐溶剤性は増す。The firing temperature and firing time are selected depending on the clay mineral used and the solute molecules to be separated, but it is necessary that the temperature is below the temperature at which the spherical powders mutually sinter. When the interlayer ions are metal ions, the solvent resistance increases by firing.
このようにして得られた球状粘土鉱物の層間イオンがナ
トリウム以外の他のカチオンで実質的に置換されている
ことは、次のようにして確認できる。即ち層間イオンが
金属カチオンの場合には、原子吸光等を用いて元素分析
すれば容易に交換したカチオンの量を確認できる。同様
に層間イオンが有機カチオンの場合には、層間隔をＸ線
回折測定から求めることにより層間隔の拡大をもって置
換されたことが確認できる。It can be confirmed as follows that the interlayer ions of the spherical clay mineral thus obtained are substantially replaced with cations other than sodium. That is, when the interlayer ions are metal cations, the amount of exchanged cations can be easily confirmed by elemental analysis using atomic absorption or the like. Similarly, when the interlayer ions are organic cations, substitution can be confirmed by increasing the interlayer spacing by determining the interlayer spacing from X-ray diffraction measurements.
本発明の充填剤は必要に応じて通常の乾式分級法により
分級して液体クロマトグラフィー用充填剤として利用さ
れる。The packing material of the present invention is used as a packing material for liquid chromatography after being classified by a conventional dry classification method, if necessary.
［発明の効果］
本発明の球状の粘土鉱物からなる充填剤は、−般に用い
られるシリカを担体とした充填剤に比べて、表面シラノ
ール基の影響が無いため、特に塩基性分子や極性分子に
対してラヤープなピークが得られ、また層間に交換した
カチオンにより、各々独特の分離特性をもたせることが
できる。またこれらの分子に対し幅広い溶離液で溶出可
能であり、加えて球状であることがらカラム効率が格段
に良い新規な液体クロマトグラフィー用充填剤である。[Effects of the Invention] The filler made of the spherical clay mineral of the present invention is less affected by surface silanol groups than the commonly used filler using silica as a carrier, so it is particularly sensitive to basic molecules and polar molecules. A broad peak can be obtained for each layer, and each layer can have unique separation characteristics due to the cations exchanged between the layers. Furthermore, these molecules can be eluted with a wide range of eluents, and in addition, because of its spherical shape, it is a novel packing material for liquid chromatography that has extremely high column efficiency.
〔実施例］
次に本発明の一層の理解のために、実施例をあげて更に
詳細に説明する。本発明はこれらによって限定されるも
のではない。[Example] Next, in order to further understand the present invention, the present invention will be described in further detail by giving examples. The present invention is not limited to these.
実施例１
ラポナイトＸＬＧ３００ｇをイオン交換水１０Ｌに撹拌
しながら分散させる。得られたゲルをディスク式噴霧乾
燥実験器によりディスク回転数２０．ＯＯＯｒｐｍ。Example 1 300 g of Laponite XLG is dispersed in 10 L of ion-exchanged water with stirring. The obtained gel was dried in a disk-type spray dryer at a disk rotation speed of 20. OOOrpm.
入口空気温度約２００℃、排気温度約１１０℃で噴霧乾
燥したところ、２〜２０μｍの球状粉末が２４０ｇ得ら
れた。このものの走査型電子顕微鏡写真を図１に示す。When spray-dried at an inlet air temperature of about 200°C and an exhaust temperature of about 110°C, 240 g of spherical powder with a diameter of 2 to 20 μm was obtained. A scanning electron micrograph of this product is shown in FIG.
この球状粘土鉱物を乾式分級機ＴＡＲＢＯＣＬＡＳＳＩ
ＦＩＨＥＲＴＣ−１５８（日清エンジニアリング社製）
を用いて分級し、５〜１０ｕＩ１１の粒径の粉末を６０
ｇを得た。This spherical clay mineral is processed using the dry classifier TARBOCLASSI.
FIHERTC-158 (manufactured by Nisshin Engineering Co., Ltd.)
The powder with a particle size of 5 to 10 uI was classified using 60
I got g.
実施例２
エタノール５００ｄに塩化カルシウム（２水和物）２．
２１ ｇを溶解し、実施例１で得られた分級した球状粘
土鉱物１０ｇを分散し、４時間攪拌する。その後、濾過
し水で洗浄し、８０℃で乾燥して球状粉末を得た。この
もののカルシウム量を原子吸光を用いて求めたところ２
．２重量％であり、はぼ１００％カチオン交換が行なわ
れたことが確認された。次いで該粉末５ｇをパッカーと
ポンプを用いて、内径４．６１および長き２５ｃｍのス
テンレススチール製カラムに平衡スラリー法で充填し、
充填カラムを作成した。Example 2 Calcium chloride (dihydrate) in 500 d of ethanol2.
10 g of the classified spherical clay mineral obtained in Example 1 was dispersed therein, and the mixture was stirred for 4 hours. Thereafter, it was filtered, washed with water, and dried at 80°C to obtain a spherical powder. The amount of calcium in this substance was determined using atomic absorption.2
．． 2% by weight, confirming that almost 100% cation exchange was performed. Then, 5 g of the powder was packed into a stainless steel column with an inner diameter of 4.61 and a length of 25 cm using an equilibrium slurry method using a packer and a pump.
A packed column was created.
本カラムを高速液体クロマトグラフに接続し、移動相と
して、ｎ−ヘキサン：エタノール（９０： １０）を毎
分１１１ｔで流し、炭化水素、エステル、ニトロ化合物
およびアミ′ノ化合物の代表として、トルエン、安息香
酸メチル、ニトロベンゼンおよびアニリンを選び、これ
らの標準混合物を注入し、Ｕｖ検出器を用いて２８０ｎ
ｍで検出し、クロマトグラムを得た。これを第２図に示
す。この図のように、これらの物質が良好に分離されて
いる。This column was connected to a high-performance liquid chromatograph, and n-hexane:ethanol (90:10) was flowed at 111 tons per minute as the mobile phase. Select methyl benzoate, nitrobenzene and aniline, inject a standard mixture of these and test at 280nm using a UV detector.
Detection was performed using m, and a chromatogram was obtained. This is shown in FIG. As shown in this figure, these substances are well separated.
比較例１
市販シリカゲル充填カラム（細孔６０人、粒径５μ論）
を用いて、実施例２と同じ条件で同じ物質を分析した。Comparative Example 1 Commercially available silica gel packed column (60 pores, 5μ particle size)
The same substance was analyzed using the same conditions as in Example 2.
このクロマトグラムを第３図に示す。This chromatogram is shown in FIG.
トルエン、安息香酸メチル、ニトロベンゼンはシリカ表
面との水素結合がほとんど無い事より同じような小さな
保持時間をもち、一方アニリンはシリカ表面との強い吸
着により、これらの分子より大きな保持時間をもってい
る。Toluene, methyl benzoate, and nitrobenzene have similar small retention times due to almost no hydrogen bonding with the silica surface, while aniline has a longer retention time than these molecules due to strong adsorption with the silica surface.
このように、本発明の充填剤は塩基性であるアニリンに
対し、シリカゲル充填剤のように特異的な吸着をしない
ため、これらの分子の分離が極めてよい。As described above, since the packing material of the present invention does not specifically adsorb basic aniline unlike the silica gel packing material, separation of these molecules is extremely good.
実施例３
エタノール５００ ｄに塩化第二鉄（無水）４．８７ｇ
を溶解し、実施例１で得られた球状粘土鉱物１０ｇを分
散し、４時間攪拌する。その後、濾過水洗し、８０℃で
乾燥した後、５００℃で４時間焼成し、実施例２と同様
にカラムに充填し、充填カラムを作成した。Example 3 4.87 g of ferric chloride (anhydrous) in 500 d of ethanol
and dispersed therein 10 g of the spherical clay mineral obtained in Example 1, followed by stirring for 4 hours. Thereafter, the mixture was filtered, washed with water, dried at 80°C, and then calcined at 500°C for 4 hours, and packed into a column in the same manner as in Example 2 to produce a packed column.
本カラムを高速液体クロマトグラフに接続し、移動相と
して、水：メタノール（２０：８０）を毎分１ｄで流し
、ナフタレンとアントラセンを注入し、Ｕ■検出器を用
いて２５４ｎｍで検出し、クロマトグラムを得た。これ
を第４図に示す。この図のように、これらの物質が良好
に分離されている。This column was connected to a high-performance liquid chromatograph, water:methanol (20:80) was flowed at a rate of 1 d/min as the mobile phase, naphthalene and anthracene were injected, and detection was performed at 254 nm using a U detector. Got a gram. This is shown in FIG. As shown in this figure, these substances are well separated.
実施例４
エタノール５００＋ｄにトリメチルモノステアリルアン
モニウムクロライド１０．４４ｇを溶解し、実施例１で
得られた分級した球状粘土鉱物１０ｇを分散し、４時間
攪拌した。その後、濾過し水で洗浄し、８０℃で乾燥し
て、球状粉末を得た。このものの層間隔をＸ線回折測定
により求めたところ、実施例１の分級した球状粘土鉱物
に比べて約３人拡がっており、層間のイオンがトリメチ
ルモノステアリルアンモニウムクロライドで置換された
ことが確認きれた。このようにして得られた粉末を実施
例２と同様にカラムに充填し、充填カラムを作成した。Example 4 10.44 g of trimethylmonostearyl ammonium chloride was dissolved in ethanol 500+d, and 10 g of the classified spherical clay mineral obtained in Example 1 was dispersed therein, followed by stirring for 4 hours. Thereafter, it was filtered, washed with water, and dried at 80°C to obtain a spherical powder. When the interlayer spacing of this material was determined by X-ray diffraction measurement, it was found to be about 3 times wider than the classified spherical clay mineral of Example 1, confirming that the ions between the layers were replaced with trimethylmonostearyl ammonium chloride. Ta. The thus obtained powder was packed into a column in the same manner as in Example 2 to create a packed column.
本カラムを高速液体クロマトグラフに接続し、移動相と
して、メタノールを毎分１ｍｌで流し、ナフタレンとア
ントラセンを注入し、Ｕ■検出器を用いて２５４ｎｍで
検出し、クロマトグラムを得た。This column was connected to a high-performance liquid chromatograph, methanol was flowed at 1 ml per minute as a mobile phase, naphthalene and anthracene were injected, and detection was performed at 254 nm using a U2 detector to obtain a chromatogram.
これを第５図に示す。この図のように、これらの物質が
良好に分離されている。This is shown in FIG. As shown in this figure, these substances are well separated.
比較例２
市販の０ＤＳ−シリカゲル充填カラムを用いて、実施例
４と同じ条件で同じ物質を分析した。このクロマトグラ
ムを第６図に示す。Comparative Example 2 The same substance was analyzed under the same conditions as in Example 4 using a commercially available 0DS-silica gel packed column. This chromatogram is shown in FIG.
第５図と第６図の比較より、本発明の充填剤がこれらの
分離に従来のシリカゲル充填剤より優れていることがわ
かる。A comparison between FIG. 5 and FIG. 6 shows that the packing material of the present invention is superior to the conventional silica gel packing material in these separations.
実施例５
エタノール５００ｄにジメチルジステアリルアンモニウ
ムクロライド１７．６０ ｇを溶解し、実施例１で得ら
れた分級した球状粘土鉱物１０ｇを分散し、４時間攪拌
する。その後、濾過し水で洗浄し、８０℃で乾燥する。Example 5 17.60 g of dimethyl distearyl ammonium chloride is dissolved in 500 d of ethanol, 10 g of the classified spherical clay mineral obtained in Example 1 is dispersed, and the mixture is stirred for 4 hours. Thereafter, it is filtered, washed with water, and dried at 80°C.
そのようにして得られた粉末を実施例２と同様にカラム
に充填し、充填カラムを作成した。The powder thus obtained was packed into a column in the same manner as in Example 2 to create a packed column.
本カラムを高速液体クロマトグラフに接続し、移動相と
して、水を毎分１ ｍｌで流し、核酸のアデニンを注入
し、ＵＶ検出器を用いて２６０ｎｍで検出し、クロマト
グラムを得た。これを第７図に示す。This column was connected to a high performance liquid chromatograph, water was flowed as a mobile phase at a rate of 1 ml per minute, the nucleic acid adenine was injected, and the column was detected at 260 nm using a UV detector to obtain a chromatogram. This is shown in FIG.
この図のように、この物質がシャープに検出されている
。As shown in this figure, this substance is clearly detected.
比較例３
市販の０ＤＳ−シリカゲル充填カラムを用いて、実施例
５と同じ条件で同じ物質を分析した。このクロマトグラ
ムを第８図に示す。このような塩基性物質は０ＤＳ−シ
リカゲル充填剤表面に残存しているシラノール基との相
互作用によりピークはテーリングしている。Comparative Example 3 The same substance was analyzed under the same conditions as in Example 5 using a commercially available 0DS-silica gel packed column. This chromatogram is shown in FIG. The peak of such a basic substance is tailed due to interaction with the silanol groups remaining on the surface of the 0DS-silica gel filler.
第７図と第８図の比較より、本発明の充填剤がこのよう
な塩基性物質に対し従来の０ＤＳ−シリカゲル充填剤よ
り優れていることがわかる。A comparison between FIG. 7 and FIG. 8 shows that the filler of the present invention is superior to the conventional 0DS-silica gel filler with respect to such basic substances.
実施例６
エタノールＩＬに硝酸銀１．７ｇを溶解し、実施例１で
得られた分級した球状粘土鉱物１０ｇを分散し、４時間
撹拌する。その後濾過、水で洗浄し、８０℃で乾燥し、
実施例２と同様にカラムに充填し、充填カラムを作成し
た。Example 6 1.7 g of silver nitrate is dissolved in ethanol IL, 10 g of the classified spherical clay mineral obtained in Example 1 is dispersed, and the mixture is stirred for 4 hours. After that, it was filtered, washed with water, and dried at 80°C.
A column was filled in the same manner as in Example 2 to create a packed column.
本カラムを高速液体クロマトグラフに接続し、移動相と
してアセトンを毎分１ｍｌで流し、各種の脂肪酸（パル
ミチン酸、オレイン酸、リノール酸、γ−リルイン酸）
のエチルエステルの混合物を注入し、ＲＩ検出器を用い
て検出しクロマトグラムを得た。これを第９図に示す。This column was connected to a high-performance liquid chromatograph, and acetone was flowed at a rate of 1 ml per minute as the mobile phase.
A mixture of ethyl esters was injected and detected using an RI detector to obtain a chromatogram. This is shown in FIG.
０ＤＳ−シリカゲルのような逆相系の充填剤を用いて分
析を行った場合は溶出順序が逆になり、パルミチン酸と
オレイン酸のピークが完全に重なってしまい、分離が不
可能であるが、本カラムを用いた場合は図から明らかな
ようにきれいに分離している。また本カラムを用いた場
合は、試料負荷量が約５倍大きく、分取に適していると
言える。このように本カラムは不飽和度の違う物質の分
離に適していることがわかる。When analysis is performed using a reversed-phase packing material such as 0DS-silica gel, the elution order is reversed and the palmitic acid and oleic acid peaks completely overlap, making separation impossible. As is clear from the figure, when this column was used, the separation was clear. Furthermore, when this column is used, the sample load is about 5 times larger, making it suitable for preparative separation. This shows that this column is suitable for separating substances with different degrees of unsaturation.
第１図は本発明で用いる球状のラポナイトの粒子構造を
示す走査型電子顕微鏡写真である。
第２図は実施例２の充填剤を用いて、トルエン、安息香
酸メチル、ニトロベンゼンおよびアニリンを分析した場
合のクロマトグラムである。
第３図は市販シリカゲル充填カラム（細孔６０人、粒径
５μｍ）を用いて、トルエン、安息香酸メチル、ニトロ
ベンゼンおよびアニリンを分析した場合のクロマトグラ
ムである。
第２図と第３図において、１はトルエン、２は安息香酸
メチル、３はニトロベンゼン、４はアニリンを示してい
る。
第４図は実施例３の充填剤を用いて、ナフタレンとアン
トラセンを分析した場合のクロマトグラムである。
第５図は実施例４の充填剤を用いて、ナフタレンとアン
トラセンを分析した場合のクロマトグラムである。
第６図は市販０ＤＳ−シリカゲル充填カラムを用いて、
ナフタレンとアントラセンを分析した場合のクロマトグ
ラムである。
第４図、第５図及び第６図において、１はナフタレン、
２はアントラセンを示している。
第７図は実施例５の充填剤を用いて、アデニンを分析し
た場合のクロマトグラムである。
第８図は市販０ＤＳ−シリカゲル充填カラムを用いて、
アデニンを分析した場合のクロマトグラムである。
第９図は実施例６の充填剤を用いて、各種の脂肪酸（バ
ルミチン酸、オレイン酸、リノール酸、γ−リルイン酸
）のエチルエステルの混合物を分析した場合のクロマト
グラムである。
第９図において、１はバルミチン酸エチルエステル、２
はオレイン酸エチルエステル、３はリノール酸エチルエ
ステル、４は７−リルイン酸エチルエステルを示してい
る。
特許出願人 株式会社 資生堂
蓼 １ ■
ｉｎ
竿 ２ 回
ｉｎ
￥ ３−
０ ５ ＩＱ １５ ２０ｍ１
ｎ
蓼 ４ 田
ｉｎ
某 ５１！７
ｉｎ
￥６ 困
ｉｎ
寥７ 回
ｍｉｎ
第８ 口
ｉｎ
竿９ｒｇＪFIG. 1 is a scanning electron micrograph showing the grain structure of spherical laponite used in the present invention. FIG. 2 is a chromatogram obtained when toluene, methyl benzoate, nitrobenzene, and aniline were analyzed using the packing material of Example 2. FIG. 3 is a chromatogram obtained when toluene, methyl benzoate, nitrobenzene and aniline were analyzed using a commercially available silica gel packed column (60 pores, particle size 5 μm). In Figures 2 and 3, 1 represents toluene, 2 represents methyl benzoate, 3 represents nitrobenzene, and 4 represents aniline. FIG. 4 is a chromatogram when naphthalene and anthracene were analyzed using the packing material of Example 3. FIG. 5 is a chromatogram when naphthalene and anthracene were analyzed using the packing material of Example 4. Figure 6 shows the results using a commercially available 0DS-silica gel packed column.
This is a chromatogram when analyzing naphthalene and anthracene. In Figures 4, 5 and 6, 1 is naphthalene;
2 indicates anthracene. FIG. 7 is a chromatogram when adenine was analyzed using the packing material of Example 5. Figure 8 shows the results using a commercially available 0DS-silica gel packed column.
This is a chromatogram when analyzing adenine. FIG. 9 is a chromatogram obtained by analyzing a mixture of ethyl esters of various fatty acids (valmitic acid, oleic acid, linoleic acid, and γ-liluic acid) using the packing material of Example 6. In Figure 9, 1 is valmitic acid ethyl ester, 2
indicates oleic acid ethyl ester, 3 indicates linoleic acid ethyl ester, and 4 indicates 7-liluic acid ethyl ester. Patent Applicant Shiseido Tate Co., Ltd. 1 ■ in rod 2 times in ￥ 3-0 5 IQ 15 20m1
n 蓼 4 田 in certain 51!7 in ￥6 trouble in 寥 7 times min 8th mouth in rod 9rgJ
Claims (4)
ン以外の他のカチオンで実質的に置換されてなる球状の
粘土鉱物からなる液体クロマトグラフィー用充填剤。(1) A packing material for liquid chromatography consisting of a spherical clay mineral in which the interlayer ions of the water-swellable clay mineral are substantially replaced with cations other than sodium ions.
ン以外の他のカチオンで実質的に置換されてなる球状の
粘土鉱物を焼成して得られる焼成粘土鉱物からなる液体
クロマトグラフィー用充填剤。(2) A filler for liquid chromatography comprising a fired clay mineral obtained by firing a spherical clay mineral in which the interlayer ions of the water-swellable clay mineral are substantially replaced with cations other than sodium ions.
三価の金属カチオンである請求項１又は２に記載の液体
クロマトグラフィー用充填剤。(3) The packing material for liquid chromatography according to claim 1 or 2, wherein the cation other than the sodium ion is a monovalent or trivalent metal cation.
オンである請求項１又は２に記載の液体クロマトグラフ
ィー用充填剤。(4) The packing material for liquid chromatography according to claim 1 or 2, wherein the cation other than the sodium ion is an organic cation.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63152119A JP2692862B2 (en) | 1987-10-31 | 1988-06-22 | Packing material for liquid chromatography |
| CA000570892A CA1321188C (en) | 1987-07-03 | 1988-06-30 | Packing material for liquid chromatography |
| EP19880306015 EP0297901B1 (en) | 1987-07-03 | 1988-07-01 | Packaging material for liquid chromatography |
| DE8888306015T DE3870727D1 (en) | 1987-07-03 | 1988-07-01 | PACKING MATERIAL FOR LIQUID CHROMATOGRAPHY. |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-276668 | 1987-10-31 | ||
| JP27666887 | 1987-10-31 | ||
| JP63152119A JP2692862B2 (en) | 1987-10-31 | 1988-06-22 | Packing material for liquid chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01199155A true JPH01199155A (en) | 1989-08-10 |
| JP2692862B2 JP2692862B2 (en) | 1997-12-17 |
Family
ID=26481133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63152119A Expired - Lifetime JP2692862B2 (en) | 1987-07-03 | 1988-06-22 | Packing material for liquid chromatography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2692862B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03167294A (en) * | 1989-11-27 | 1991-07-19 | Shiseido Co Ltd | Method for separating and purifying eicosapentaenoic acid compound |
| JPH0495048A (en) * | 1990-08-10 | 1992-03-27 | Shiseido Co Ltd | Separation and purification of docosahexaenoic acid compound |
| WO1994019278A1 (en) * | 1993-02-26 | 1994-09-01 | Shiseido Co., Ltd. | Cation-substituted clay mineral, process for producing the same, and chromatographic packing comprising the same |
| JP2012121790A (en) * | 2010-11-15 | 2012-06-28 | Shiseido Co Ltd | Spherical porous diamond particle and method for manufacturing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442378A (en) * | 1977-09-09 | 1979-04-04 | Nippon Saafuakutanto Kougiyou | Manufacture of organic denatured clay mineral |
| JPS5855332A (en) * | 1981-09-28 | 1983-04-01 | Kunimine Kogyo Kk | Thermally stable clay derivative having structure with large surface area |
| JPS6163521A (en) * | 1984-09-05 | 1986-04-01 | Topy Ind Ltd | Freely swelling synthetic mica |
| JPS61204138A (en) * | 1985-03-07 | 1986-09-10 | Asahi Chem Ind Co Ltd | Method of resolving optical isomer |
-
1988
- 1988-06-22 JP JP63152119A patent/JP2692862B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5442378A (en) * | 1977-09-09 | 1979-04-04 | Nippon Saafuakutanto Kougiyou | Manufacture of organic denatured clay mineral |
| JPS5855332A (en) * | 1981-09-28 | 1983-04-01 | Kunimine Kogyo Kk | Thermally stable clay derivative having structure with large surface area |
| JPS6163521A (en) * | 1984-09-05 | 1986-04-01 | Topy Ind Ltd | Freely swelling synthetic mica |
| JPS61204138A (en) * | 1985-03-07 | 1986-09-10 | Asahi Chem Ind Co Ltd | Method of resolving optical isomer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03167294A (en) * | 1989-11-27 | 1991-07-19 | Shiseido Co Ltd | Method for separating and purifying eicosapentaenoic acid compound |
| JPH0495048A (en) * | 1990-08-10 | 1992-03-27 | Shiseido Co Ltd | Separation and purification of docosahexaenoic acid compound |
| JPH0813776B2 (en) * | 1990-08-10 | 1996-02-14 | 株式会社資生堂 | Method for separating and purifying docosahexaenoic acid compound |
| WO1994019278A1 (en) * | 1993-02-26 | 1994-09-01 | Shiseido Co., Ltd. | Cation-substituted clay mineral, process for producing the same, and chromatographic packing comprising the same |
| JP2012121790A (en) * | 2010-11-15 | 2012-06-28 | Shiseido Co Ltd | Spherical porous diamond particle and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2692862B2 (en) | 1997-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Trüdinger et al. | Porous zirconia and titania as packing materials for high-performance liquid chromatography | |
| US4101460A (en) | High performance ion exchange composition | |
| US4874518A (en) | Porous silica microspheres having a silanol enriched surface | |
| Peristyy et al. | Diamond based adsorbents and their application in chromatography | |
| US3782075A (en) | Completely porous microspheres for chromatographic uses | |
| Yilmaz et al. | A facile method for preparing molecularly imprinted polymer spheres using spherical silica templates | |
| EP0123293B1 (en) | Process for preparing superficially porous supports for chromatography and catalysts | |
| Clausen et al. | Chromatographic characterization of phosphonate analog EDTA-modified zirconia support for biochromatographic applications | |
| US5108595A (en) | Porous silica microspheres having silanol-enriched and silanized surfaces | |
| Janzen et al. | Adsorption of proteins on porous and non-porous poly (ethyleneimine) and tentacle-type anion exchangers | |
| Ahmed et al. | Investigation on synthesis of spheres-on-sphere silica particles and their assessment for high performance liquid chromatography applications | |
| Jadhav et al. | Packed hybrid silica nanoparticles as sorbents with thermo-switchable surface chemistry and pore size for fast extraction of environmental pollutants | |
| US5145578A (en) | Packing material for liquid chromatography | |
| JPH01199155A (en) | Filler for liquid chromatography | |
| Ge et al. | Titanium-coated silica spheres prepared by self-assembly technique for use as HPLC packing | |
| EP0297901B1 (en) | Packaging material for liquid chromatography | |
| Barrett et al. | Characterization of a range of alkyl-bonded silica HPLC stationary phases: chromatographic behavior of neutral, acidic, and basic test solutes | |
| US3676366A (en) | Process for the production of highly porous bead-form silica catalyst supports | |
| dos Santos et al. | Quantification of Hydroxyl Groups from Alumina in Aluminosilicate Materials by Adsorption Isotherms | |
| EP0221780A2 (en) | Porous silica microspheres having silanol-enriched and silanized surfaces | |
| US6316647B1 (en) | Cation-exchanged clay mineral, packing material for chromatography using the same and method of producing the same | |
| Filbert et al. | Pore-Size Effects on Column Performance in Gas-Liquid Chromatography | |
| JP2548874B2 (en) | Chromatographic separation packing material | |
| Kaneko et al. | Silica-containing mixed-oxide gels prepared by a coprecipitation method as novel packing materials for liquid chromatography | |
| JP3664746B2 (en) | Chromatographic packing material using cation-substituted clay mineral, method for separating fish oil and fat using the same, and method for producing cation-substituted clay mineral |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080905 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term |