CN102527355A - Method for preparing bipyridine bonding silica gel filler - Google Patents
Method for preparing bipyridine bonding silica gel filler Download PDFInfo
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- CN102527355A CN102527355A CN2010105952008A CN201010595200A CN102527355A CN 102527355 A CN102527355 A CN 102527355A CN 2010105952008 A CN2010105952008 A CN 2010105952008A CN 201010595200 A CN201010595200 A CN 201010595200A CN 102527355 A CN102527355 A CN 102527355A
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- silica gel
- bipyridyl
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Abstract
The invention discloses a method for preparing a bipyridine bonding silica gel filler. The method comprises the following steps of: performing silanized modification on the surface of totally-porous spherical silica gel to prepare chloropropyl silica gel, performing quaterisation reaction of chloropropyl and bipyridine to obtain alkyl bipyridine single salt bonding silica gel, and performing further quaterisation of an alkyl bipyridine single salt to generate alkyl bipyridine double salt bonding silica gel, and thus, obtaining a bipyridine bonding silica gel liquid chromatogram filler. The filler has the advantages of multiple action mechanisms and the like, can be subjected to chromatographic separation in modes of phase reversal and ion chromatography and can separate neutral organic compounds, inorganic negative ion and organic negative ions simultaneously, and has high selectivity and stability.
Description
Technical field
The invention belongs to the preparation method of efficient liquid phase chromatographic stuffing, particularly utilize the quaterisation of bipyridyl, prepare the method for bipyridyl bonded silica gel as efficient liquid phase chromatographic stuffing.Under different chromatographic isolation patterns, use this chromatograph packing material and carry out compartment analysis, can be respectively as anti-phase, chromatography of ions applying filler in chromatographic isolation, and can under suitable flowing phase condition, separate simultaneously different classes of analyte.
Background technology
Along with developing rapidly of life science, environmental science etc., modern separation science faces the compartment analysis difficult problem of complex sample, and liquid chromatogram plays a part very important for the compartment analysis of complex system.The complicated component of complex sample, acidity, alkalescence, neutral compound and nonionic and ionic compound coexistence often need loaded down with trivial details sample pre-treatments just can carry out effective chromatographic isolation.Separation detection compound of different nature under the same high-efficient liquid phase color spectral model, and the chromatographic applications under the same chromatographic column multi-mode all are the research contents that the chromatogram worker pays close attention to all the time.And traditional efficient liquid phase chromatographic stuffing has selectivity, and separating mechanism is comparatively single, is difficult under same chromatogram mode, separate form complicated sample, and can not realizes the chromatographic applications under the same chromatographic column multi-mode.The chromatograph packing material that preparation has the multiple mechanism of action is to realize complex separations and with the key of post multi-mode chromatographic applications.
Bipyridyl is a kind of weak base, and intramolecule has two nitrogen-atoms that can form quaternary ammonium salt respectively, can selectively modify it, and can be bonded on the silica gel easily through quaterisation.Alkyl bipyridine salt molecule on the bipyridyl bonded silica gel can provide the multiple mechanism of action, and for example: the carbochain in the molecule has certain hydrophobicity, can be through the strong and weak fixedly hydrophobicity of phase of regulating of carbochain hydrophobicity; Bipyridyl has two six atom conjugated systems, and conjugated system has the pi-electron cloud, can have π-π effect with having between the molecule of pi-electron, and have induced dipole-dipole, n-π effect between the same polarity compound, and the nitrogen on the heterocycle can form hydrogen bond; Bipyridine salt has certain hydrophily and anion exchange characteristic, with there being ion exchange between the anion, with there being Coulomb repulsion effect etc. between the cation.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing bipyridyl bonded silica gel efficient liquid phase chromatographic stuffing.The chromatographic column of this filler has multiple action mechanism, can be used for post multi-mode chromatographic isolation, can be respectively applied for reverse-phase chromatography, ion chromatographic separation detection, and can separate the multiclass compound simultaneously.
The present invention realizes through following measure:
In view of the characteristics of alkyl bipyridine salt, the present invention is through the quaterisation of bipyridyl, with 4; 4 '-bipyridyl or 2; The chloropropyl silica gel reaction that 2 '-bipyridyl and modified silica-gel obtain generates alkyl bipyridyl list salt bonding silica gel, can proceed quaterisation to it with halogenated hydrocarbons; Generate alkyl bipyridyl double salt bonded silica gel, make efficient liquid phase chromatographic stuffing.This filler has that multiple action mechanism, hydrophobicity and ion exchangeable are adjustable, separating property good, with post multi-mode chromatographic applications, separate advantages such as multiclass material simultaneously.Through utilizing the chromatographic column of this type filler; Under the reverse-phase chromatography pattern; Neutral organic compound (fused ring compound, ditridecyl phthalate), acidic organic compound (phenol, p-hydroxybenzoate), alkaline organic compound (phenyl amines) etc. have been separated effectively; The mechanism of action is heterogeneous mutual effect, mainly comprises interactions such as π-π, hydrophobic, static, hydrogen bond; Under the chromatography of ions pattern, separated inorganic anion, organic anion etc. effectively, the mechanism of action is mainly interactions such as anion exchange, π-π; Utilize suitable flowing phase, separated phenol, phenyl amines, condensed ring class, inorganic and organic anion simultaneously.The bipyridyl bonded silica gel chromatograph packing material of the quaterisation preparation through bipyridyl has the special selectivity of heterogeneous mutual effect, aspect the liquid chromatogram compartment analysis good application prospects is being arranged.
Full porous spherical silica gel is carried out modification with the chloropropyl silylating reagent obtain chloropropyl silica gel, again bipyridyl and its are generated alkyl bipyridyl list salt bonding silica gel through quaterisation; On this filler basis, can continue it is carried out quaternized generation alkyl bipyridyl double salt bonded silica gel through halogenated hydrocarbons, make heterogeneous mutual effect liquid chromatography stuffing.
A kind of preparation method of bipyridyl bonded silica gel filler is characterized in that this method has A, two steps of B:
Synthesizing of A chloropropyl silica gel
The silica gel of activation is added in the reaction vessel, make reaction dissolvent, stir, add chloropropyl silane with toluene; Carry out the stirring and refluxing reaction, reaction finishes back cooling, vacuum filtration; Use toluene, ethanol, water, methanol wash successively, vacuum drying obtains chloropropyl silica gel;
Synthesizing of B bipyridyl bonded silica gel
Chloropropyl silica gel is added in the reaction vessel, add N, N '-dimethyl formamide is made reaction dissolvent, stirs; Add bipyridyl, carry out stirring reaction, reaction finishes back cooling, suction filtration; Use ethanol, water, methanol wash successively, vacuum drying obtains alkyl bipyridyl list salt bonding silica gel;
Alkyl bipyridyl list salt bonding silica gel is proceeded quaterisation, and alkyl bipyridyl list salt bonding silica gel and halogenated hydrocarbons are reacted, and preparation alkyl bipyridyl double salt bonded silica gel obtains chromatograph packing material, i.e. bipyridyl bonded silica gel liquid chromatography stuffing.
The present invention is the quaterisation that utilizes bipyridyl, and bipyridyl is bonded on the full porous spherical silica gel.
In the A step, chloropropyl silane is 3-chloropropyl trichlorine (front three/ethyoxyl) silane, and the mass ratio of silica gel and chloropropyl silane is 1: 0.3-1: 2, and the silica gel quality is 1 with the volume of toluene ratio: 5-1: 10, the reaction time is 12-48 hour.
In the B step, bipyridyl is 4,4 '-bipyridyl or 2, and 2 '-bipyridyl, the mass ratio of chloropropyl silica gel and bipyridyl are 1: 0.3-1: 2.
In the B step, the reaction temperature of preparation alkyl bipyridyl list salt bonding silica gel is 60-145 ℃, and the reaction time is 12-72 hour.
In the B step, the halogenated hydrocarbons that preparation alkyl bipyridyl double salt bonded silica gel adopts is bromo-hydrocarbons or idohydrocarbon, and both mass ratioes are 1: 0.5-1: 10, and reaction temperature is 40-110 ℃, the reaction time is 6-72 hour.
The present invention is in the clastotype of reverse-phase chromatography condition; With methanol-water, acetonitrile-water etc. as chromatogram flow phase; Flow rate of mobile phase 0.5-2.0ml/min; Ultraviolet detects wavelength 254 or 230nm, and separated object is fused ring compound, phenol, phenyl amines, parabens, phthalate esters etc.
The present invention is in the clastotype of chromatography of ions condition; With the Klorvess Liquid of 5-100mmol/L or sodium dihydrogen phosphate as chromatogram flow phase; Flowing phase pH is 3.0-7.0; Flow rate of mobile phase 0.5-2.0ml/min, ultraviolet detects wavelength 200nm, and separated object is common inorganic anion (IO
3 -, BrO
3 -, Br
-, NO
3 -, I
-, SCN
-); With the potassium chloride of 5-100mmol/L or sodium dihydrogen phosphate and methyl alcohol (55: 45, v/v) as chromatogram flow phase, ultraviolet detects wavelength 200nm, separated object is organic anion (benzoate anion class, benzene sulfonic acid root class, phthalic acid root class) etc.
The present invention compares with the chromatograph packing material of routine and has the following advantages:
1. through the filler of this invention preparation, ion-exchange base density, the hydrophilic and hydrophobic on silica gel surface are adjustable, and chromatographic performance is stable.
2. filler possesses a post multi-mode chromatographic isolation and to the heterogeneity analyte outstanding advantage of chromatographic isolation simultaneously.
3. filler is a kind of filler with multiple action mechanism, not only can separate neutrality, acidity and alkaline organic compound etc., and can separate with organic anion etc. inorganic.
4. filler can comprise that phenol, phenyl amines, fused ring compound and anion separate simultaneously to multiclass analyte of different nature through adopting suitable flowing phase.
5. the chromatographic performance of filler is superior, column capacity is big.
The present invention is by means of the quaterisation of bipyridyl, on the surface of the full porous silicon ball of micron-scale, modified bipyridyl, prepared heterogeneous mutual effect chromatograph packing material, has a post multi-mode separating application and the special benefits that the heterogeneity analyte is separated simultaneously.Under the reverse-phase chromatography pattern, separating neutrality, acidity, alkali compounds etc. respectively, and separate inorganic, organic anion etc. under the chromatography of ions pattern respectively, and can above-mentioned multiclass analyte be separated simultaneously, is a kind of chromatographic column filler with application potential.
Description of drawings
Fig. 1 is the synthetic sketch map of bipyridyl bonded silica gel chromatograph packing material.
Fig. 2 is the effect sketch map of embodiment 3 bipyridyl bonded silica gel filler reversed phase chromatography separation fused ring compounds.Abscissa is that retention time unit is min, and ordinate is that detection signal response unit is mAU, (1 benzene, 2 naphthalenes, 3 fluorenes, 4 anthracenes, 5 fluoranthene 6 bend 73, the 4-BaP).
Fig. 3 is the effect sketch map of embodiment 3 bipyridyl bonded silica gel filler reversed phase chromatography separation phthalate esters compounds.Abscissa is that retention time unit is min; Ordinate is that detection signal response unit is mAU, (1 repefral, 2 diallyl phthalates, 3 dibutyl phthalates, 4 dicyclohexyl phthalates, 5 dioctyl phthalates, 6 diisooctyl phthalates).
Fig. 4 is the effect sketch map of embodiment 4 bipyridyl bonded silica gel filler ion chromatographic separation inorganic anions.Abscissa is that retention time unit is min, and ordinate is that detection signal response unit is mAU, (1IO
3 -2BrO
3 -3Br
-4NO
3 -5I
-6SCN
-).
Fig. 5 is the effect sketch map of embodiment 4 bipyridyl bonded silica gel filler ion chromatographic separation organic anions.Abscissa is that retention time unit is min, and ordinate is that detection signal response unit is mAU, (1 p-aminobenzoic acid, 2 Sodium Benzoates, 3 sulfanilic acid, 4 Potassium Hydrogen Phthalates, 5 sodium salicylates).
Fig. 6 is the separating effect sketch map when to be embodiment 5 bipyridyl bonded silica gel fillers to the multiclass analyte comprise phenol, condensed ring class, inorganic, organic anion.Abscissa is that retention time unit is min, and ordinate is that detection signal response unit is mAU, (1 phenol, 2 naphthalenes, 3 alpha naphthols, 4 fluorenes 5IO
3 -6I
-7 Potassium Hydrogen Phthalates, 8 sodium salicylates).
The specific embodiment
In order to understand the present invention better, describe through instance:
Embodiment 1: the preparation of bipyridyl bonded silica gel filler
Comprise following A, two steps of B successively:
A. chloropropyl silica gel is synthetic
5.0g silica gel is added in the reaction vessel, add 50ml toluene, mechanical agitation is even, adds the 5.0ml3-r-chloropropyl trimethoxyl silane, stirring and refluxing 24 hours.After reaction finished, vacuum filtration was used 200ml toluene, 200ml ethanol, 100ml water, 200ml methanol wash successively, and 65 ℃ of following vacuum drying are 12 hours then, obtain chloropropyl silica gel.
B. the bipyridyl bonded silica gel is synthetic
3.0g chloropropyl silica gel is added in the reaction vessel, add 30mlN, N '-dimethyl formamide, mechanical agitation is even, adds 3.0g 4, and 4 '-bipyridyl makes to be reflected at 140 ℃ and to carry out 72 hours.Then, suction filtration is used 200ml ethanol, 200ml water, 200ml methanol wash successively, and 65 ℃ of following vacuum drying are 12 hours then, obtain bipyridyl bonded silica gel chromatograph packing material.
Embodiment 2: the preparation of bipyridyl bonded silica gel filler
Comprise following A, two steps of B successively:
A. chloropropyl silica gel is synthetic
5.0g silica gel is added in the reaction vessel, add 50ml toluene, mechanical agitation is even, adds the 5.0ml3-r-chloropropyl trimethoxyl silane, stirring and refluxing 24 hours.Then, vacuum filtration is used 200ml toluene, 200ml ethanol, 100ml water, 200ml methanol wash successively, and 65 ℃ of following vacuum drying are 12 hours then, obtain chloropropyl silica gel.
B. the bipyridyl bonded silica gel is synthetic
5.0g chloropropyl silica gel is added in the reaction vessel, adds 50ml N, N '-dimethyl formamide, mechanical agitation evenly after, add 5.0g 4,4 '-bipyridyl makes to be reflected at 130 ℃ and to carry out 72 hours.Then, suction filtration is used 300ml ethanol, 300ml water, 300ml methanol wash successively, and 65 ℃ of following vacuum drying are 12 hours then, obtain alkyl bipyridyl list salt bonding silica gel.3.0g alkyl bipyridyl list salt bonding silica gel is added in the reaction vessel, add 30ml N, N '-dimethyl formamide after mechanical agitation is even, adds the 10ml1-n-octane bromide, carries out stirring reaction 12 hours at 100 ℃.After reaction finished, suction filtration was used 300ml ethanol, 300ml methanol wash successively, and 65 ℃ of following vacuum drying are 12 hours then, obtain bipyridyl bonded silica gel filler.
Embodiment 3: bipyridyl bonded silica gel filled column reversed phase chromatography separation
The bipyridyl bonded silica gel filler of embodiment 1 is adorned post, column length 150mm, column internal diameter 4.6mm.With methanol-water (90: 10, v/v) as flowing phase, flow velocity 1ml/min, ultraviolet detects wavelength 254nm, separate fused ring compound (benzene, naphthalene, fluorenes, anthracene, fluoranthene, bend, 3, the 4-BaP); With methanol-water (60: 40; V/v) as flowing phase; Flow velocity 1.0ml/min; Ultraviolet detects wavelength 230nm, separates phthalate esters compound (repefral, diallyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, diisooctyl phthalate).
Embodiment 4: bipyridyl bonded silica gel filled column ion chromatographic separation
The bipyridyl bonded silica gel filler of embodiment 1 is adorned post, column length 150mm, column internal diameter 4.6mm.With Klorvess Liquid (50mmol/L, pH=5.5) as flowing phase, flow velocity 1.0ml/min, ultraviolet detects wavelength 200nm, separates inorganic anion (IO
3 -, BrO
3 -, Br
-, NO
3 -, I
-, SCN
-); With sodium dihydrogen phosphate (30mmol/L; PH=4.5)-and methyl alcohol (55: 45, v/v) as flowing phase, flow velocity 1.0ml/min; Ultraviolet detects wavelength 200nm, separates organic anion (p-aminobenzoic acid, Sodium Benzoate, sulfanilic acid, Potassium Hydrogen Phthalate, sodium salicylate).
Embodiment 5: bipyridyl bonded silica gel filled column separates to multiclass heterogeneity analyte the time
The bipyridyl bonded silica gel filler of embodiment 1 is adorned post, column length 150mm, column internal diameter 4.6mm.With sodium dihydrogen phosphate (30mmol/L; PH=4.5)-and methyl alcohol (45: 55, v/v) as flowing phase, flow velocity 1.0ml/min; Ultraviolet detects wavelength 200nm, simultaneously analyte (phenol, naphthalene, alpha naphthol, fluorenes, the IO of multiclass character such as separating phenols, fused ring compound, inorganic and organic anion
3 -, I
-, Potassium Hydrogen Phthalate, sodium salicylate).
Claims (5)
1. the preparation method of a bipyridyl bonded silica gel filler is characterized in that this method has A, two steps of B:
Synthesizing of A chloropropyl silica gel
The silica gel of activation is added in the reaction vessel, make reaction dissolvent, stir, add chloropropyl silane with toluene; Carry out the stirring and refluxing reaction, reaction finishes back cooling, vacuum filtration; Use toluene, ethanol, water, methanol wash successively, vacuum drying obtains chloropropyl silica gel;
Synthesizing of B bipyridyl bonded silica gel
Chloropropyl silica gel is added in the reaction vessel, add N, N '-dimethyl formamide is made reaction dissolvent, stirs; Add bipyridyl, carry out stirring reaction, reaction finishes back cooling, suction filtration; Use ethanol, water, methanol wash successively, vacuum drying obtains alkyl bipyridyl list salt bonding silica gel;
Alkyl bipyridyl list salt bonding silica gel is proceeded quaterisation, and alkyl bipyridyl list salt bonding silica gel and halogenated hydrocarbons are reacted, and preparation alkyl bipyridyl double salt bonded silica gel obtains chromatograph packing material, i.e. bipyridyl bonded silica gel liquid chromatography stuffing.
2. the method for claim 1; It is characterized in that in the A step that chloropropyl silane is 3-chloropropyl trichlorine (front three/ethyoxyl) silane, the mass ratio of silica gel and chloropropyl silane is 1: 0.3-1: 2; The silica gel quality is 1 with the volume of toluene ratio: 5-1: 10, and the reaction time is 12-48 hour.
3. the method for claim 1 is characterized in that in the B step, and bipyridyl is 4,4 '-bipyridyl or 2, and 2 '-bipyridyl, the mass ratio of chloropropyl silica gel and bipyridyl are 1: 0.3-1: 2.
4. the method for claim 1 is characterized in that in the B step, and the reaction temperature of preparation alkyl bipyridyl list salt bonding silica gel is 60-145 ℃, and the reaction time is 12-72 hour.
5. the method for claim 1; It is characterized in that in the B step that the halogenated hydrocarbons that preparation alkyl bipyridyl double salt bonded silica gel adopts is bromo-hydrocarbons or idohydrocarbon, both mass ratioes are 1: 0.5-1: 10; Reaction temperature is 40-110 ℃, and the reaction time is 6-72 hour.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101566567A (en) * | 2009-05-31 | 2009-10-28 | 武汉理工大学 | Thin-film material for optical fiber biosensor probe and preparation method thereof |
| JP2010116512A (en) * | 2008-11-14 | 2010-05-27 | Toyota Central R&D Labs Inc | Organic silane compound and mesoporous organic silica |
| CN101864291A (en) * | 2010-05-26 | 2010-10-20 | 上海大学 | Fluorescent nanoparticles Ru(bpy)3/SiO2, preparation method and application thereof |
-
2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010116512A (en) * | 2008-11-14 | 2010-05-27 | Toyota Central R&D Labs Inc | Organic silane compound and mesoporous organic silica |
| CN101566567A (en) * | 2009-05-31 | 2009-10-28 | 武汉理工大学 | Thin-film material for optical fiber biosensor probe and preparation method thereof |
| CN101864291A (en) * | 2010-05-26 | 2010-10-20 | 上海大学 | Fluorescent nanoparticles Ru(bpy)3/SiO2, preparation method and application thereof |
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Application publication date: 20120704 |