CN108889276A - A kind of exclusive separation silica gel solid phase of ginsenoside and preparation method - Google Patents
A kind of exclusive separation silica gel solid phase of ginsenoside and preparation method Download PDFInfo
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- CN108889276A CN108889276A CN201810724108.3A CN201810724108A CN108889276A CN 108889276 A CN108889276 A CN 108889276A CN 201810724108 A CN201810724108 A CN 201810724108A CN 108889276 A CN108889276 A CN 108889276A
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- China
- Prior art keywords
- silica gel
- ginsenoside
- anthraquinone
- phase
- dihydroxy anthraquinone
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000741 silica gel Substances 0.000 title claims abstract description 74
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007790 solid phase Substances 0.000 title claims abstract description 10
- 238000000926 separation method Methods 0.000 title abstract description 14
- 229930182494 ginsenoside Natural products 0.000 title abstract description 8
- 229940089161 ginsenoside Drugs 0.000 title abstract description 7
- NJUXRKMKOFXMRX-UHFFFAOYSA-N ginsenoside Rz1 Natural products CC(C)=CCC=C(C)C1CCC(C2(CCC3C4(C)C)C)(C)C1C(O)CC2C3(C)CCC4OC1OC(CO)C(O)C(O)C1OC1OC(CO)C(O)C(O)C1O NJUXRKMKOFXMRX-UHFFFAOYSA-N 0.000 claims abstract description 51
- KWDWBAISZWOAHD-UHFFFAOYSA-N Ginsenoside Rk1 Natural products CC(C)=CCCC(=C)C1CCC(C2(CCC3C4(C)C)C)(C)C1C(O)CC2C3(C)CCC4OC1OC(CO)C(O)C(O)C1OC1OC(CO)C(O)C(O)C1O KWDWBAISZWOAHD-UHFFFAOYSA-N 0.000 claims abstract description 42
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 15
- 229960001156 mitoxantrone Drugs 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 41
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 38
- 150000004056 anthraquinones Chemical class 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 230000005526 G1 to G0 transition Effects 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- QBPFLULOKWLNNW-UHFFFAOYSA-N chrysazin Chemical compound O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O QBPFLULOKWLNNW-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 229960001577 dantron Drugs 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000006210 lotion Substances 0.000 claims description 5
- 238000003303 reheating Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- APAJFZPFBHMFQR-UHFFFAOYSA-N anthraflavic acid Chemical compound OC1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 APAJFZPFBHMFQR-UHFFFAOYSA-N 0.000 abstract description 18
- KQSBZNJFKWOQQK-UHFFFAOYSA-N hystazarin Natural products O=C1C2=CC=CC=C2C(=O)C2=C1C=C(O)C(O)=C2 KQSBZNJFKWOQQK-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 abstract description 4
- LWFDUMPGOAKHKC-UHFFFAOYSA-N C1=CC=C2C=C(C(=O)C(C(O)=C3O)=O)C3=CC2=C1 Chemical group C1=CC=C2C=C(C(=O)C(C(O)=C3O)=O)C3=CC2=C1 LWFDUMPGOAKHKC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013558 reference substance Substances 0.000 description 25
- KWDWBAISZWOAHD-MHOSXIPRSA-N (2s,3r,4s,5s,6r)-2-[(2r,3r,4s,5s,6r)-4,5-dihydroxy-6-(hydroxymethyl)-2-[[(3s,5r,8r,9r,10r,12r,13r,14r,17s)-12-hydroxy-4,4,8,10,14-pentamethyl-17-(6-methylhepta-1,5-dien-2-yl)-2,3,5,6,7,9,11,12,13,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]o Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1CC[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4C(=C)CCC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O KWDWBAISZWOAHD-MHOSXIPRSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 235000003140 Panax quinquefolius Nutrition 0.000 description 6
- 241000208340 Araliaceae Species 0.000 description 5
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 235000008434 ginseng Nutrition 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000004780 2D liquid chromatography Methods 0.000 description 3
- NJUXRKMKOFXMRX-AXUZFSSLSA-N ginsenoside Rg5 Natural products CC(=CCC=C(C)[C@H]1CC[C@]2(C)[C@@H]1[C@H](O)C[C@@H]3[C@@]4(C)CC[C@@H](O[C@H]5O[C@H](CO)[C@@H](O)[C@H](O)[C@H]5O[C@H]6O[C@H](CO)[C@@H](O)[C@H](O)[C@H]6O)C(C)(C)[C@@H]4CC[C@@]23C)C NJUXRKMKOFXMRX-AXUZFSSLSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RWXIFXNRCLMQCD-JBVRGBGGSA-N (20S)-ginsenoside Rg3 Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1CC[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4[C@@](C)(O)CCC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RWXIFXNRCLMQCD-JBVRGBGGSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XIRZPICFRDZXPF-UHFFFAOYSA-N Ginsenoside Rg3 Natural products CC(C)=CCCC(C)(O)C1CCC(C2(CC(O)C3C4(C)C)C)(C)C1C(O)CC2C3(C)CCC4OC1OC(CO)C(O)C(O)C1OC1OC(CO)C(O)C(O)C1O XIRZPICFRDZXPF-UHFFFAOYSA-N 0.000 description 2
- NJUXRKMKOFXMRX-RNCAKNGISA-N Ginsenoside Rg5 Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@H]1CC[C@]2(C)[C@H]3C[C@@H](O)[C@H]4[C@@]([C@@]3(CC[C@H]2C1(C)C)C)(C)CC[C@@H]4C(/C)=C/CC=C(C)C)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O NJUXRKMKOFXMRX-RNCAKNGISA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 150000002338 glycosides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000208343 Panax Species 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WUDFEXSJURUGSD-UHFFFAOYSA-N anthracene-1,8-diol Chemical compound C1=CC(O)=C2C=C3C(O)=CC=CC3=CC2=C1 WUDFEXSJURUGSD-UHFFFAOYSA-N 0.000 description 1
- INKAUXVRBIUCSL-UHFFFAOYSA-N anthracene-9,10-dione;methanol Chemical class OC.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 INKAUXVRBIUCSL-UHFFFAOYSA-N 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/52—Sorbents specially adapted for preparative chromatography
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of exclusive separation silica gel solid phase of ginsenoside and preparation methods.It is a discovery of the invention that being bonded 1,2- dihydroxy anthraquinone, 2,6- dihydroxy anthraquinone or 1 in Silica Surface, 8- dihydroxy anthraquinone can significantly improve silica gel to the separating effect of ginsenoside RZ1 and RK1.1,2- dihydroxy anthraquinone, 2,6- dihydroxy anthraquinone, 1,4- dihydroxy anthraquinone or 1, although 8- dihydroxy anthraquinone is all dihydroxy-anthracene quinone structure, 1, the bonding of 4- dihydroxy anthraquinone can not enhance silica gel to the separating capacity of ginsenoside RZ1 and RK1, this may be related with hydroxy position.Thus it is possible to produce preparation 1,2- dihydroxy anthraquinone, 2,6- dihydroxy anthraquinone or 1, exclusive analysis chromatographic column of the chromatographic column of 8- dihydroxy anthraquinone bonded silica gel filler as ginsenoside RZ1 and RK1, low in cost, application method is simple.
Description
Technical field
The invention belongs to analysis detection fields, are related to the separation of isomeric compound, and in particular to a kind of ginsenoside is special
Belong to separation silica gel solid phase and preparation method.
Background technique
Ginsenoside is the principle active component of the panax species such as rare medicinal herbs ginseng and American Ginseng, is had preferable anti-
The pharmacological activity such as tumour, anti-inflammatory, anti-oxidant and inhibition Apoptosis.
Ginsenoside broad categories, wherein there are also multipair or multiple groups isomers.Some isomer chemical polarities
Closely similar, causing the separation of these isomers to be analyzed, there are larger difficulties.By taking ginsenoside RZ1, RK1 and RG5 as an example,
Three's isomer each other, from biological relations, the C20 hydroxyl and C21 hydrogen of ginsenoside RG3 occurs elimination reaction and obtains people
Join saponin(e RK1, the C20 hydroxyl and C22 hydrogen of ginsenoside RG3 occurs elimination reaction and obtain ginsenoside RG5 and RZ1, ginseng soap
Glycosides RK1 and RG5, RZ1 are double-bond positional isomerization, and ginsenoside RG5 and RZ1 are double bond cis-trans isomerism.Wherein, ginsenoside RZ1
It is closely similar in the retention behavior of liquid chromatogram with ginsenoside RK1, it is extremely difficult to separate.With the earliest finder of ginsenoside RZ1
(bibliography for Sang Myung LEE：Ginsenosides from Heat Processed Ginseng,Chem
Pharm Bull, 2009), researcher uses two-dimensional liquid chromatography and just separates ginsenoside RZ1 and ginsenoside RK1.But
It is, one skilled in the art will appreciate that two-dimensional liquid chromatography develops very immature, poor reproducibility, not to be able to satisfy drug quality control
The strict demand of system.Pharmacopoeia of each country is all very prudent to two-dimensional liquid chromatography, and only United States Pharmacopeia has recorded individually extremely at present
It is difficult to isolated kind.Chinese patent CN107505409A discloses a kind of side for separating ginsenoside RZ1 and ginsenoside RK1
Method, this method is using a kind of Chiral Mobile Phase additive process based on reversed-phase silica gel column chromatography, although separating degree is good, hand
Property mobile phase prepare relatively complicated, and must face with now matching, it is poor to flow phase stability.
Therefore, it is necessary to develop a kind of stationary phase, using common mobile phase can efficiently separate ginsenoside RZ1 with
RK1。
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, the first purpose is to provide a kind of anthraquinone derivative bonded silica
Glue stationary phase, the second purpose are to provide the preparation method of the stationary phase, and third purpose is to provide the ginsenoside inspection of the stationary phase
Survey application.
Above-mentioned purpose of the invention is achieved by following technical solution：
Technical solution one：
A kind of anthraquinone derivative bonded silica gel stationary phase is obtained in Silica Surface bonding 1,2- dihydroxy anthraquinone.
The preparation method of above-mentioned anthraquinone derivative bonded silica gel stationary phase, includes the following steps：
Step S1, first uses 3mol/L salt acid soak silica gel 12h, and reheating flows back 10h, is then washed with water repeatedly to neutrality, most
It is washed 2 times with acetone afterwards, baking water removal activation 6h, is stored in spare in drier after cooling at 160 DEG C；
Step S2 takes the dry silica gel that 6.0g is activated, and 80mL dry toluene is added, is added with stirring 4.0mLKH-560
With 3 drop Triethylamine catalysts, it is heated to reflux under nitrogen protection for 24 hours, it is cooling, for 24 hours with toluene extracting, successively use acetone, methanol
And acetone washing, 8h is dried in vacuo at 80 DEG C, obtains coupling agent bonded silica gel GBS；
Step S3, under heating stirring, 1, the 2- dihydroxy anthraquinone for keeping 1.0g sufficiently dry is dissolved into the anhydrous new steaming first of 80mL
In benzene, 4.0g GBS is subsequently added under stirring, 2 drop perchloric acid are heated to reflux for 24 hours under nitrogen protection, and it is cooling, with methanol Soxhlet
Extract remaining 1,2- dihydroxy anthraquinone, until washing lotion be it is colorless and transparent, be dried in vacuo 8h at 80 DEG C, obtain 1,2- dihydroxy anthraquinone
Bonded silica gel stationary phase, kept dry after vacuum dried 10h.
Preferably, the silica gel be spherical silica gel, 5 μm of partial size, apertureSpecific surface area is 450m2/g。
A kind of exclusive for separating the chromatographic column of ginsenoside RZ1 and RK1, stationary phase is above-mentioned anthraquinone derivative key
Close silica gel solid phase.
A kind of chromatographic process separating ginsenoside RZ1 and RK1, chromatographic parameter are as follows：
Chromatographic column：Above-mentioned chromatographic column；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B.
Preferably, flow velocity 1.0mL/min.
Preferably, column temperature is 35 DEG C.
Preferably, Detection wavelength 203nm.
Technical solution two：
A kind of anthraquinone derivative bonded silica gel stationary phase is obtained in Silica Surface bonding 2,6- dihydroxy anthraquinone.
The preparation method of above-mentioned anthraquinone derivative bonded silica gel stationary phase, includes the following steps：
Step S1, first uses 3mol/L salt acid soak silica gel 12h, and reheating flows back 10h, is then washed with water repeatedly to neutrality, most
It is washed 2 times with acetone afterwards, baking water removal activation 6h, is stored in spare in drier after cooling at 160 DEG C；
Step S2 takes the dry silica gel that 6.0g is activated, and 80mL dry toluene is added, is added with stirring 4.0mLKH-560
With 3 drop Triethylamine catalysts, it is heated to reflux under nitrogen protection for 24 hours, it is cooling, for 24 hours with toluene extracting, successively use acetone, methanol
And acetone washing, 8h is dried in vacuo at 80 DEG C, obtains coupling agent bonded silica gel GBS；
Step S3, under heating stirring, 2, the 6- dihydroxy anthraquinone for keeping 1.0g sufficiently dry is dissolved into the anhydrous new steaming first of 80mL
In benzene, 4.0g GBS is subsequently added under stirring, 2 drop perchloric acid are heated to reflux for 24 hours under nitrogen protection, and it is cooling, with methanol Soxhlet
Extract remaining 2,6- dihydroxy anthraquinone, until washing lotion be it is colorless and transparent, be dried in vacuo 8h at 80 DEG C, obtain 2,6- dihydroxy anthraquinone
Bonded silica gel stationary phase, kept dry after vacuum dried 10h.
Preferably, the silica gel be spherical silica gel, 5 μm of partial size, apertureSpecific surface area is 450m2/g。
A kind of exclusive for separating the chromatographic column of ginsenoside RZ1 and RK1, stationary phase is above-mentioned anthraquinone derivative key
Close silica gel solid phase.
A kind of chromatographic process separating ginsenoside RZ1 and RK1, chromatographic parameter are as follows：
Chromatographic column：Above-mentioned chromatographic column；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B.
Preferably, flow velocity 1.0mL/min.
Preferably, column temperature is 35 DEG C.
Preferably, Detection wavelength 203nm.
Technical solution three：
A kind of anthraquinone derivative bonded silica gel stationary phase is obtained in Silica Surface bonding 1,8- dihydroxy anthraquinone.
The preparation method of above-mentioned anthraquinone derivative bonded silica gel stationary phase, includes the following steps：
Step S1, first uses 3mol/L salt acid soak silica gel 12h, and reheating flows back 10h, is then washed with water repeatedly to neutrality, most
It is washed 2 times with acetone afterwards, baking water removal activation 6h, is stored in spare in drier after cooling at 160 DEG C；
Step S2 takes the dry silica gel that 6.0g is activated, and 80mL dry toluene is added, is added with stirring 4.0mLKH-560
With 3 drop Triethylamine catalysts, it is heated to reflux under nitrogen protection for 24 hours, it is cooling, for 24 hours with toluene extracting, successively use acetone, methanol
And acetone washing, 8h is dried in vacuo at 80 DEG C, obtains coupling agent bonded silica gel GBS；
Step S3, under heating stirring, 1, the 8- dihydroxy anthraquinone for keeping 1.0g sufficiently dry is dissolved into the anhydrous new steaming first of 80mL
In benzene, 4.0g GBS is subsequently added under stirring, 2 drop perchloric acid are heated to reflux for 24 hours under nitrogen protection, and it is cooling, with methanol Soxhlet
Extract remaining 1,8- dihydroxy anthraquinone, until washing lotion be it is colorless and transparent, be dried in vacuo 8h at 80 DEG C, obtain 1,8- dihydroxy anthraquinone
Bonded silica gel stationary phase, kept dry after vacuum dried 10h.
Preferably, the silica gel be spherical silica gel, 5 μm of partial size, apertureSpecific surface area is 450m2/g。
A kind of exclusive for separating the chromatographic column of ginsenoside RZ1 and RK1, stationary phase is above-mentioned anthraquinone derivative key
Close silica gel solid phase.
A kind of chromatographic process separating ginsenoside RZ1 and RK1, chromatographic parameter are as follows：
Chromatographic column：Above-mentioned chromatographic column；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B.
Preferably, flow velocity 1.0mL/min.
Preferably, column temperature is 35 DEG C.
Preferably, Detection wavelength 203nm.
Beneficial effect：
It is a discovery of the invention that being bonded 1,2- dihydroxy anthraquinone, 2,6- dihydroxy anthraquinone or 1,8- dihydroxy-anthracene in Silica Surface
Quinone can significantly improve silica gel to the separating effect of ginsenoside RZ1 and RK1.1,2- dihydroxy anthraquinone, 2,6- dihydroxy anthraquinone,
Isosorbide-5-Nitrae-dihydroxy anthraquinone or 1, although 8- dihydroxy anthraquinone is all dihydroxy-anthracene quinone structure, the bonding of Isosorbide-5-Nitrae-dihydroxy anthraquinone
Silica gel can not be enhanced to the separating capacity of ginsenoside RZ1 and RK1, this may be related with hydroxy position.Thus it is possible to produce
The chromatographic column of 1,2- dihydroxy anthraquinone, 2,6- dihydroxy anthraquinone or 1,8- dihydroxy anthraquinone bonded silica gel filler is prepared as ginseng
The exclusive analysis chromatographic column of saponin(e RZ1 and RK1, low in cost, application method is simple.
Detailed description of the invention
Fig. 1 is the chemical structural formula of anthraquinone derivative A~D；
Fig. 2 is separation chromatogram of the anthraquinone derivative A bonded silica gel stationary phase to ginsenoside RZ1 and RK1；
Fig. 3 is separation chromatogram of the anthraquinone derivative B bonded silica gel stationary phase to ginsenoside RZ1 and RK1；
Fig. 4 is separation chromatogram of the anthraquinone derivative C bonded silica gel stationary phase to ginsenoside RZ1 and RK1；
Fig. 5 is separation chromatogram of the anthraquinone derivative D bonded silica gel stationary phase to ginsenoside RZ1 and RK1；
Fig. 6 is separation chromatogram of the nonbonding silica gel solid phase to ginsenoside RZ1 and RK1.
Specific embodiment
It is specific with reference to the accompanying drawings and examples to introduce essentiality content of the present invention, but guarantor of the invention is not limited with this
Protect range.
Embodiment 1：The preparation of anthraquinone derivative bonded silica gel stationary phase and dress column
One, the chemical structural formula of anthraquinone derivative A~D is as shown in Figure 1, respectively 1,2- dihydroxy anthraquinone, 2,6- dihydroxy
Base anthraquinone, 1,4- dihydroxy anthraquinone, 1,8- dihydroxy anthraquinone.
Two, the preparation step of anthraquinone derivative A~D bonded silica gel stationary phase is as follows：
Step S1, first with 3mol/L salt acid soak silica gel (spherical silica gel, 5 μm of partial size, apertureSpecific surface area is
450m2/ g, purchased from match branch skill) 12h, reheating flow back 10h, be then washed with water to neutrality, finally washed 2 times with acetone repeatedly,
Baking water removal activation 6h, is stored in spare in drier after cooling at 160 DEG C；
Step S2 takes the dry silica gel that 6.0g is activated, and 80mL dry toluene is added, is added with stirring 4.0mLKH-560
With 3 drop Triethylamine catalysts, it is heated to reflux under nitrogen protection for 24 hours, it is cooling, for 24 hours with toluene extracting, successively use acetone, methanol
And acetone washing, 8h is dried in vacuo at 80 DEG C, obtains coupling agent bonded silica gel (GBS)；
Step S3, under heating stirring, it is anhydrous new that anthraquinone derivative A, B, C or the D for keeping 1.0g sufficiently dry are dissolved into 80mL
It steaming in toluene, 4.0g GBS is subsequently added under stirring, 2 drop perchloric acid are heated to reflux for 24 hours under nitrogen protection, and it is cooling, use methanol
Anthraquinone derivative A, B, C or D of Soxhlet extraction remnants, until washing lotion be it is colorless and transparent, be dried in vacuo 8h at 80 DEG C, obtain anthraquinone and spread out
Biological A~D bonded silica gel stationary phase, kept dry after vacuum dried 10h.
Three, the filling of anthraquinone derivative A~D bonded silica gel chromatographic column
Make homogenate agent with isopropanol, anthraquinone derivative A~D bonded silica gel is inserted into stainless steel chromatographic column (4.6mm i.d.
× 150mm) in be used as stationary phase, it is spare with water and methanol repeated flushing.
Embodiment 2：Separating effect of the anthraquinone derivative A bonded silica gel stationary phase to ginsenoside RZ1 and RK1
Ginsenoside RZ1 and ginsenoside RK1 reference substance purity are not less than 98%.
The preparation of mixed reference substance solution：Precision weighs ginsenoside RZ1 respectively and ginsenoside RK1 reference substance is each
10mg is set in 20ml measuring bottle, with acetonitrile dissolution and constant volume, is shaken up, is obtained mixed reference substance solution.
HPLC chromatogram parameter：
Chromatograph：2695 type high performance liquid chromatograph of Waters；
Chromatographic column：Anthraquinone derivative A bonded silica gel chromatographic column (150 × 4.6mm, preparation method are shown in embodiment 1)；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B；
Flow velocity：1.0mL/min；
Column temperature：35℃；
Detection wavelength：203nm.
Precision measures 10 μ L mixed reference substance solutions and injects liquid chromatograph, records chromatogram, as shown in Figure 2.
As it is clear from fig. 2 that ginsenoside RZ1 and RK1 separating degree is good, reach baseline separation.
Embodiment 3：Separating effect of the anthraquinone derivative B bonded silica gel stationary phase to ginsenoside RZ1 and RK1
Ginsenoside RZ1 and ginsenoside RK1 reference substance purity are not less than 98%.
The preparation of mixed reference substance solution：Precision weighs ginsenoside RZ1 respectively and ginsenoside RK1 reference substance is each
10mg is set in 20ml measuring bottle, with acetonitrile dissolution and constant volume, is shaken up, is obtained mixed reference substance solution.
HPLC chromatogram parameter：
Chromatograph：2695 type high performance liquid chromatograph of Waters；
Chromatographic column：Anthraquinone derivative B bonded silica gel chromatographic column (150 × 4.6mm, preparation method are shown in embodiment 1)；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B；
Flow velocity：1.0mL/min；
Column temperature：35℃；
Detection wavelength：203nm.
Precision measures 10 μ L mixed reference substance solutions and injects liquid chromatograph, records chromatogram, as shown in Figure 3.
It can be seen from figure 3 that ginsenoside RZ1 and RK1 separating degree is good, reach baseline separation.
Embodiment 4：Separating effect of the anthraquinone derivative C bonded silica gel stationary phase to ginsenoside RZ1 and RK1
Ginsenoside RZ1 and ginsenoside RK1 reference substance purity are not less than 98%.
The preparation of mixed reference substance solution：Precision weighs ginsenoside RZ1 respectively and ginsenoside RK1 reference substance is each
10mg is set in 20ml measuring bottle, with acetonitrile dissolution and constant volume, is shaken up, is obtained mixed reference substance solution.
HPLC chromatogram parameter：
Chromatograph：2695 type high performance liquid chromatograph of Waters；
Chromatographic column：Anthraquinone derivative C bonded silica gel chromatographic column (150 × 4.6mm, preparation method are shown in embodiment 1)；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B；
Flow velocity：1.0mL/min；
Column temperature：35℃；
Detection wavelength：203nm.
Precision measures 10 μ L mixed reference substance solutions and injects liquid chromatograph, records chromatogram, as shown in Figure 4.
As seen from Figure 4, ginsenoside RZ1 and RK1 co-elute, can not separate.
Embodiment 5：Separating effect of the anthraquinone derivative D bonded silica gel stationary phase to ginsenoside RZ1 and RK1
Ginsenoside RZ1 and ginsenoside RK1 reference substance purity are not less than 98%.
The preparation of mixed reference substance solution：Precision weighs ginsenoside RZ1 respectively and ginsenoside RK1 reference substance is each
10mg is set in 20ml measuring bottle, with acetonitrile dissolution and constant volume, is shaken up, is obtained mixed reference substance solution.
HPLC chromatogram parameter：
Chromatograph：2695 type high performance liquid chromatograph of Waters；
Chromatographic column：Anthraquinone derivative D bonded silica gel chromatographic column (150 × 4.6mm, preparation method are shown in embodiment 1)；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B；
Flow velocity：1.0mL/min；
Column temperature：35℃；
Detection wavelength：203nm.
Precision measures 10 μ L mixed reference substance solutions and injects liquid chromatograph, records chromatogram, as shown in Figure 5.
From figure 5 it can be seen that ginsenoside RZ1 and RK1 separating degree is good, reach baseline separation.
Embodiment 6：Separating effect of the nonbonding silica gel solid phase to ginsenoside RZ1 and RK1
Ginsenoside RZ1 and ginsenoside RK1 reference substance purity are not less than 98%.
The preparation of mixed reference substance solution：Precision weighs ginsenoside RZ1 respectively and ginsenoside RK1 reference substance is each
10mg is set in 20ml measuring bottle, with acetonitrile dissolution and constant volume, is shaken up, is obtained mixed reference substance solution.
HPLC chromatogram parameter：
Chromatograph：2695 type high performance liquid chromatograph of Waters；
Chromatographic column：(150 × 4.6mm is directly filled using spherical silica gel according to 1 method of embodiment nonbonding silica gel chromatographic column
Column)；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B；
Flow velocity：1.0mL/min；
Column temperature：35℃；
Detection wavelength：203nm.
Precision measures 10 μ L mixed reference substance solutions and injects liquid chromatograph, records chromatogram, as shown in Figure 6.
As seen from Figure 6, ginsenoside RZ1 and RK1 co-elute, can not separate.
Above-described embodiment shows that silica gel can be significantly improved to ginseng soap by being bonded anthraquinone derivative A, B or D in Silica Surface
The separating effect of glycosides RZ1 and RK1.Although anthraquinone derivative A~D is dihydroxy-anthracene quinone structure, the key of anthraquinone derivative C
Merging cannot enhance silica gel to the separating capacity of ginsenoside RZ1 and RK1, this may be related with hydroxy position.Therefore, Ke Yisheng
Production prepares exclusive analysis chromatography of the chromatographic column as ginsenoside RZ1 and RK1 of anthraquinone derivative A, B or D bonded silica gel filler
Column, low in cost, application method is simple.
The effect of above-described embodiment is specifically to introduce essentiality content of the invention, but those skilled in the art should know
Protection scope of the present invention should not be confined to the specific embodiment by road.
Claims (8)
1. a kind of anthraquinone derivative bonded silica gel stationary phase, it is characterised in that：It is obtained in Silica Surface bonding 1,8- dihydroxy anthraquinone
It arrives.
2. the preparation method of anthraquinone derivative bonded silica gel stationary phase described in claim 1, which is characterized in that including walking as follows
Suddenly：
Step S1 first uses 3mol/L salt acid soak silica gel 12h, reheating reflux 10h to be then washed with water repeatedly to neutrality, finally used
Acetone is washed 2 times, and baking water removal activation 6h, is stored in spare in drier after cooling at 160 DEG C；
Step S2 takes the dry silica gel that 6.0g is activated, and 80mL dry toluene is added, and is added with stirring the drop of 4.0mLKH-560 and 3
Triethylamine catalyst is heated to reflux for 24 hours under nitrogen protection, cooling, for 24 hours with toluene extracting, successively uses acetone, methanol and acetone
It washs, is dried in vacuo 8h at 80 DEG C, obtains coupling agent bonded silica gel GBS；
Step S3, under heating stirring, 1, the 8- dihydroxy anthraquinone for keeping 1.0g sufficiently dry is dissolved into the anhydrous new steaming toluene of 80mL,
4.0g GBS is subsequently added under stirring, 2 drop perchloric acid are heated to reflux for 24 hours under nitrogen protection, and it is cooling, with methanol Soxhlet extraction
Remaining 1,8- dihydroxy anthraquinone, until washing lotion be it is colorless and transparent, be dried in vacuo 8h at 80 DEG C, obtain the bonding of 1,8- dihydroxy anthraquinone
Silica gel solid phase, kept dry after vacuum dried 10h.
3. preparation method according to claim 2, it is characterised in that：The silica gel be spherical silica gel, 5 μm of partial size, apertureSpecific surface area is 450m2/g。
4. a kind of exclusive for separating the chromatographic column of ginsenoside RZ1 and RK1, it is characterised in that：Its stationary phase is claim 1
The anthraquinone derivative bonded silica gel stationary phase.
5. a kind of chromatographic process for separating ginsenoside RZ1 and RK1, which is characterized in that chromatographic parameter is as follows：
Chromatographic column：Chromatographic column as claimed in claim 4；
Mobile phase A phase：Water；
Mobile phase B phase：Acetonitrile；
Elution program：0-5min, 35%B；5-20min, 35% → 85%B.
6. chromatographic process according to claim 5, it is characterised in that：Flow velocity is 1.0mL/min.
7. chromatographic process according to claim 5, it is characterised in that：Column temperature is 35 DEG C.
8. chromatographic process according to claim 5, it is characterised in that：Detection wavelength is 203nm.
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