CN104437442A - Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof - Google Patents
Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof Download PDFInfo
- Publication number
- CN104437442A CN104437442A CN201410837801.3A CN201410837801A CN104437442A CN 104437442 A CN104437442 A CN 104437442A CN 201410837801 A CN201410837801 A CN 201410837801A CN 104437442 A CN104437442 A CN 104437442A
- Authority
- CN
- China
- Prior art keywords
- beta
- silica gel
- schardinger dextrin
- nanometer particle
- golden nanometer
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—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
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3833—Chiral chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
Abstract
The invention discloses a beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and a preparation method thereof. The stationary phase is prepared by the following steps: synthesizing a beta-cyclodextrin derivative with a sulfhydryl group, forming a gold nanoparticle shell on the surface of silica gel by using a sol-gel method, and connecting the beta-cyclodextrin derivative with the sulfhydryl group to the gold nanoparticle surface through an S-H key to form the chiral stationary phase, wherein the silica gel serves as a core, and the beta-cyclodextrin bonded gold nanoparticles are taken as the shell. The process is simple, the prepared separation material is novel in structure, the separation efficiency is high due to the gold nanoparticles, and the method is applied to separation of a chiral compound.
Description
Technical field
The present invention relates to a kind of liquid chromatogram chiral stationary phase and preparation method thereof, specifically, be to provide a kind of golden nanometer particle/silica gel chiral fixed phase preparing beta-schardinger dextrin-modification and preparation method thereof.
Background technology
Liquid chromatography is the effective means splitting enantiomer, and existing market has developed polytype chiral stationary phase.According to the textural classification of Stationary liquid, roughly can be divided into Pirkle type chiral stationary phase, oversubscription subclass chiral stationary phase, Polysaccharides Type Chiral Stationary Phases, Antibiotic stationary phase, protein-based chiral stationary phase, ligand exchange type chiral stationary phase, molecular engram chiral stationary phase, polymer-type chiral stationary phase etc.These Stationary liquid are all that various chiral selector is fixed on stromal surface by the method for coating or bonding.
The development developing into chromatographic stationary phases of nanometer technology brings new opportunity.Because nano material specific area is large, mass-transfer efficiency is high, shows excellent separation selectivity and separative efficiency in separation science field.At present, large quantities of nano material (comprising fullerene, CNT, polymer drops, metal oxide and Nano silver grain etc.) is as a kind of separating medium, be successfully used in the fields such as chromatography of ions, Capillary Electrophoresis, capillary electric chromatogram, gas-chromatography, minor effect genes, and shown excellent separation selectivity and separative efficiency.(the H.J.Duan such as Dun, et al, Analytical Chemistry, 76 (2004) 5016-5023) nano zircite LBL self-assembly is made Stationary Phase for HPLC at Silica Surface, obtain the filler pattern of rule, be separated for normal-phase chromatography.This Stationary liquid specific area is large, can acid and alkali-resistance, and chemical stability is good, and good penetrability, separating effect and the separation selectivity of analyzing thing are greatly improved.Bovine serum albumin(BSA) bonding is made chip capillary electrochromatography Stationary liquid by Weng etc. (X.X.Weng, et al, Electrophoresis, 27 (2006) 3129-3135) on the carbon nanotubes, rapidly and efficiently be separated Tryptophan enantiomer.Moliner-Martinez (Y.M.Martinez, et al, Electrophoresis, 28 (2007) 2573-2579) be used as pseudo-stationary phase with chiral selector to after carbon nano-tube modification, the special and ephedrine enantiomer of baseline separation clo human relations.As can be seen here, due to the dimensional effect of nano particle, nano material be incorporated in Stationary liquid, the chiral resolution ability of Stationary liquid can be significantly improved.
However, the kind at present nano material being introduced Stationary Phase for HPLC is also very limited, therefore, to the preparation of this type of chiral stationary phase and and application study have great importance, open up new path by for the new chiral stationary phase of exploitation.
Summary of the invention
In view of above-mentioned, object of the present invention aims to provide golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-modification be separated for liquid chromatogram and preparation method thereof.This is a kind of novel parting material, and this material structure is novel, and separative efficiency is high, and separation selectivity is good, and its preparation method is simple and reliable, may be used for chiral separation.
For realizing goal of the invention of the present invention, technical scheme provided by the invention is a kind of golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-modification, and its general structure is:
Wherein, ●-represent gold nano grain,
-represent beta-schardinger dextrin-.
Another technical scheme provided by the invention is the preparation method of the golden nanometer particle/silica gel chiral fixed phase preparing beta-schardinger dextrin-modification, comprises the steps:
1) preparation of beta-schardinger dextrin-that derives of mercapto groups
Be that 2 ~ 4mol/L sodium hydrate aqueous solution fully mixes by beta-schardinger dextrin-and concentration, sodium hydroxide concentration is 35 ~ 45% of beta-schardinger dextrin-quality, then paratoluensulfonyl chloride is dropwise added mixed liquor, paratoluensulfonyl chloride and beta-schardinger dextrin-mass ratio are 1:4 ~ 8, react 4-8 hour, then filter under ice bath, regulate pH to neutral, recrystallization, dry, obtain benzoylated beta-schardinger dextrin-;
Be that benzoylated beta-schardinger dextrin-and the derivative reagent of 1:1 ~ 1.5 is dissolved in the mixed liquor of methanol/water by mass ratio, the volume ratio of methanol/water is 4:1, needed for every gram of benzoylated beta-schardinger dextrin-, methanol/water solution is 50 ~ 80mL, react 40 ~ 60 hours, suction filtration, with gained solid after the sodium hydrate aqueous solution dissolving suction filtration of 10%, stirs 5 ~ 7 hours at 50 DEG C, regulate about pH to 2, finally add trichloro-ethylene; The amount that every gram of derivative reagent adds trichloro-ethylene is 2 ~ 5mL, stirs 24 ~ 36 hours, suction filtration, recrystallization, obtains the beta-schardinger dextrin-that mercapto groups is derivative.
2) preparation of alkylamino silica gel
By diameter 3 ~ 10 μm of colloidal silica dispersion in dry toluene, add amino silane, under nitrogen protection, stirring and refluxing 12-24 hour, then filters, and uses carrene successively, acetone, methanol wash, dry, obtains alkylamino silica gel; Wherein, dry toluene dosage needed for every gram of silica gel is 10 ~ 50mL, and amino silane dosage needed for every gram of silica gel is 0.5 ~ 1.5mL.
3) golden nanometer particle is in the formation of Silica Surface
Alkylamino silica gel is dispersed in the aqueous solution of chloraurate of 0.01 ~ 0.05%, is heated to boiling, then add the reducing agent aqueous solution of 0.5 ~ 2% fast, cool to room temperature after reaction 10 ~ 40min; This process repeats namely to obtain the coated silica gel of golden nanometer particle for 2 ~ 3 times; Wherein, aqueous solution of chloraurate dosage needed for every gram of alkylamino silica gel is 20 ~ 50mL, and reducing agent dosage needed for every gram of gold chloride is 2 ~ 5g.
4) golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification
By colloidal silica dispersion coated for golden nanometer particle in N, in dinethylformamide, then the N that mass concentration is the beta-schardinger dextrin-that 0.2-1.0% mercapto groups derives is added, dinethylformamide solution, reaction 24-48 hour, filters, use N successively, dinethylformamide, ultra-pure water clean, dry, obtain the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification; Needed for the silica gel that wherein every gram of golden nanometer particle is coated, DMF dosage is 10-30mL, and the beta-schardinger dextrin-dosage that needed for the silica gel that every gram of golden nanometer particle is coated, mercapto groups is derivative is 0.5-1.0g.
The consumption of 10% sodium hydrate aqueous solution that every gram of derivative reagent is corresponding is 20-40mL.Described derivative reagent is thiocarbamide.
Described amino silane is aminopropyl trimethoxysilane or aminopropyl triethoxysilane.
Described silica gel is spherical silica gel, and aperture is 10 ~ 50nm, and specific area is 300-500m
2/ g.
Described reducing agent is trisodium citrate.Described golden nanometer particle is spherical, and particle diameter is 10-50nm.
Tool of the present invention has the following advantages:
1. novel structure.The Stationary liquid of the present invention's synthesis take silica gel as core, and golden nanometer particle is shell, and beta-schardinger dextrin-is functional group.Due to the dimensional effect of nano particle, the chiral resolution ability of Stationary liquid therefore significantly can be strengthened.
2. preparation is simple, applied range.Products material wide material sources of the present invention, reaction condition are gentle, cost is lower; Stationary phase preparation process is simple and reliable, is widely used in the separation of various chiral material, has certain practical value.
Accompanying drawing explanation
Fig. 1, gold nano grain transmission electron microscope picture.
Fig. 2, the transmission electron microscope picture of silica gel.
Fig. 3, the transmission electron microscope picture of the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification.
Fig. 4, the Stationary liquid that application obtains is separated the chromatographic fractionation figure of a pair flavanones enantiomer.
Fig. 5, the Stationary liquid that application obtains is separated the chromatographic fractionation figure of a pair Bupivacaine enantiomer.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
The method preparing the golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-modification of the present invention, comprises the steps: 1) preparation of beta-schardinger dextrin-that derives of mercapto groups
Be that 2 ~ 4mol/L sodium hydrate aqueous solution fully mixes by beta-schardinger dextrin-and concentration, sodium hydrate aqueous solution consumption is 35 ~ 45% of beta-schardinger dextrin-quality, then paratoluensulfonyl chloride is dropwise added mixed liquor, paratoluensulfonyl chloride and beta-schardinger dextrin-mass ratio are 1:4 ~ 8, react 4-8 hour, then filter under ice bath, regulate pH to neutral, recrystallization, dry, obtain benzoylated beta-schardinger dextrin-;
Be that benzoylated beta-schardinger dextrin-and the derivative reagent of 1:1 ~ 1.5 is dissolved in the mixed liquor of methanol/water by mass ratio, the volume ratio of methanol/water is 4:1, needed for every gram of benzoylated beta-schardinger dextrin-, methanol/water solution is 50 ~ 80mL, react 40 ~ 60 hours, suction filtration, with gained solid after the sodium hydrate aqueous solution dissolving suction filtration of 10%, stirs 5 ~ 7 hours at 50 DEG C, regulate about pH to 2, finally add trichloro-ethylene; The amount that every gram of derivative reagent adds trichloro-ethylene is 2 ~ 5mL, stirs 24 ~ 36 hours, suction filtration, recrystallization, obtains the beta-schardinger dextrin-that mercapto groups is derivative.Described derivative reagent is thiocarbamide; Every gram of derivative reagent corresponding 10% sodium hydroxide concentration be 20-40mL.
2) preparation of alkylamino silica gel
By diameter 3 ~ 10 μm of colloidal silica dispersion in dry toluene, add amino silane, under nitrogen protection, stirring and refluxing 12-24 hour, then filters, and uses carrene successively, acetone, methanol wash, dry, obtains alkylamino silica gel; Wherein, dry toluene dosage needed for every gram of silica gel is 10 ~ 50mL, and amino silane dosage needed for every gram of silica gel is 0.5 ~ 1.5mL.
3) golden nanometer particle is in the formation of Silica Surface
Alkylamino silica gel is dispersed in the aqueous solution of chloraurate of 0.01 ~ 0.05%, is heated to boiling, then add the reducing agent aqueous solution of 0.5 ~ 2% fast, cool to room temperature after reaction 10 ~ 40min; This process repeats namely to obtain the coated silica gel of golden nanometer particle for 2 ~ 3 times; Wherein, aqueous solution of chloraurate dosage needed for every gram of alkylamino silica gel is 20 ~ 50mL, and reducing agent dosage needed for every gram of gold chloride is 2 ~ 5g; Described reducing agent is trisodium citrate.
4) golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification
By colloidal silica dispersion coated for golden nanometer particle in N, in dinethylformamide, then the N that mass concentration is the beta-schardinger dextrin-that 0.2-1.0% mercapto groups derives is added, dinethylformamide solution, reaction 24-48 hour, filters, use N successively, dinethylformamide, ultra-pure water clean, dry, obtain the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification; Needed for the silica gel that wherein every gram of golden nanometer particle is coated, DMF dosage is 10-30mL, and the beta-schardinger dextrin-dosage that needed for the silica gel that every gram of golden nanometer particle is coated, mercapto groups is derivative is 0.5-1.0g.
For above-mentioned preparation method, enumerate embodiment below and be specifically described.
Embodiment 1
1). the preparation of the beta-schardinger dextrin-that mercapto groups derives
30.0g beta-schardinger dextrin-is added the sodium hydrate aqueous solution of 150mL 2.0mol/L, abundant stirring, then 6.0g paratoluensulfonyl chloride is dropwise added mixed liquor, react 6 hours under ice bath, then filter, with salt acid for adjusting pH to neutral, be recrystallized with water, drying, obtains benzoylated beta-schardinger dextrin-;
Benzoylated for 5.0g beta-schardinger dextrin-and 6.0g thiocarbamide are dissolved in the mixed liquor of 250mL methanol/water (volume ratio is 4:1); react 50 hours; suction filtration, dissolves suction filtration gained solid with the sodium hydrate aqueous solution of 180mL 10%, stirs 6 hours at 50 DEG C; with about salt acid for adjusting pH to 2; finally add 18mL trichloro-ethylene, stir 30 hours, suction filtration; with pure water recrystallization, obtain the beta-schardinger dextrin-that mercapto groups is derivative.
2). the preparation of alkylamino silica gel
Silica gel is spherical silica gel, and diameter is 5 μm, and aperture is 10nm, specific area 380m
2/ g.By 3g colloidal silica dispersion in 30mL dry toluene, add 2.5mL aminopropyl trimethoxysilane, under nitrogen protection, stirring and refluxing 24 hours.Then filter with sintered filter funnel, use carrene successively, acetone, methanol wash, to be placed in vacuum drying chamber in 60 DEG C of dryings 12 hours, to obtain alkylamino silica gel.
3). golden nanometer particle is in the formation of Silica Surface
3g alkylamino silica gel is dispersed in the aqueous solution of chloraurate of 100mL 0.03%, is heated to boiling, then add the trisodium citrate aqueous solution 6mL of 1.5% fast, cool to room temperature after reaction 20min.This process repeats namely to obtain the coated silica gel of golden nanometer particle for 3 times.
4). the synthesis of the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification
By colloidal silica dispersion coated for 3g golden nanometer particle in 50mL N, in dinethylformamide, then the N that mass concentration is the beta-schardinger dextrin-that 1.0% mercapto groups derives is added, dinethylformamide solution 200mL, reacts 36 hours, filters, with N, dinethylformamide, ultra-pure water clean, dry, obtain the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification.
Embodiment 2
1). the preparation of the beta-schardinger dextrin-that mercapto groups derives
72g beta-schardinger dextrin-is added the sodium hydrate aqueous solution of 200mL 4.0mol/L, abundant stirring, then 9.0g paratoluensulfonyl chloride is dropwise added mixed liquor, react 8 hours under ice bath, then filter, with salt acid for adjusting pH to neutral, be recrystallized with water, drying, obtains benzoylated beta-schardinger dextrin-;
Benzoylated for 8.0g beta-schardinger dextrin-and 12.0g thiocarbamide are dissolved in the mixed liquor of 640mL methanol/water (volume ratio is 4:1); react 60 hours; suction filtration, dissolves suction filtration gained solid with the sodium hydrate aqueous solution of 480mL 10%, stirs 7 hours at 50 DEG C; with about salt acid for adjusting pH to 2; finally add 60mL trichloro-ethylene, stir 36 hours, suction filtration; with pure water recrystallization, obtain the beta-schardinger dextrin-that mercapto groups is derivative.
2). the preparation of alkylamino silica gel
Silica gel is spherical silica gel, and diameter is 10 μm, and aperture is 50nm, specific area 300m
2/ g.By 4g colloidal silica dispersion in 200mL dry toluene, add 6mL aminopropyl trimethoxysilane, under nitrogen protection, stirring and refluxing 24 hours.Then filter with sintered filter funnel, use carrene successively, acetone, methanol wash, to be placed in vacuum drying chamber in 60 DEG C of dryings 12 hours, to obtain alkylamino silica gel.
3). golden nanometer particle is in the formation of Silica Surface
4g alkylamino silica gel is dispersed in the aqueous solution of chloraurate of 200mL 0.05%, is heated to boiling, then add the trisodium citrate aqueous solution 25mL of 2% fast, cool to room temperature after reaction 40min.This process repeats namely to obtain the coated silica gel of golden nanometer particle for 3 times.
4). the synthesis of the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification
By colloidal silica dispersion coated for 2g golden nanometer particle in 60mL N, in dinethylformamide, then the N that mass concentration is the beta-schardinger dextrin-that 0.6% mercapto groups derives is added, dinethylformamide solution 180mL, reacts 24 hours, filters, use N successively, dinethylformamide, ultra-pure water clean one time, dry, obtain the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification.
Embodiment 3
1). the preparation of the beta-schardinger dextrin-that mercapto groups derives
30.0g beta-schardinger dextrin-is added the sodium hydrate aqueous solution of 90mL 3.0mol/L, abundant stirring, then 7.5g paratoluensulfonyl chloride is dropwise added mixed liquor, react 4 hours under ice bath, then filter, with salt acid for adjusting pH to neutral, be recrystallized with water, drying, obtains benzoylated beta-schardinger dextrin-;
Benzoylated for 4.0g beta-schardinger dextrin-and 4.0g thiocarbamide are dissolved in the mixed liquor of 260mL methanol/water (volume ratio is 4:1); react 40 hours; suction filtration, dissolves suction filtration gained solid with the sodium hydrate aqueous solution of 80mL 10%, stirs 5 hours at 50 DEG C; with about salt acid for adjusting pH to 2; finally add 8mL trichloro-ethylene, stir 24 hours, suction filtration; with pure water recrystallization, obtain the beta-schardinger dextrin-that mercapto groups is derivative.
2). the preparation of alkylamino silica gel
Silica gel is spherical silica gel, and diameter is 3 μm, and aperture is 30nm, specific area 500m
2/ g.By 4g colloidal silica dispersion in 100mL dry toluene, add 2mL aminopropyl triethoxysilane, under nitrogen protection, stirring and refluxing 24 hours.Then filter with sintered filter funnel, use carrene successively, acetone, methanol wash one time, to be placed in vacuum drying chamber in 60 DEG C of dryings 12 hours, to obtain alkylamino silica gel.
3). golden nanometer particle is in the formation of Silica Surface
4g alkylamino silica gel is dispersed in the aqueous solution of chloraurate of 80mL 0.01%, is heated to boiling, then add the trisodium citrate aqueous solution 3.2mL of 0.5% fast, cool to room temperature after reaction 15min.This process repeats namely to obtain the coated silica gel of golden nanometer particle for 3 times.
4). the synthesis of the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification
By colloidal silica dispersion coated for 2g golden nanometer particle in 40mL N, in dinethylformamide, then the N that mass concentration is the beta-schardinger dextrin-that 0.5% mercapto groups derives is added, dinethylformamide solution 200mL, reacts 24 hours, filters, use N successively, dinethylformamide, ultra-pure water clean one time, dry, obtain the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification.
The structural confirmation result of the golden nanometer particle/silica gel solid phase of this beta-schardinger dextrin-modification of above-mentioned preparation is as follows: Fig. 1 clearly show overall pattern and the particle size of gold nano grain.Gold nano grain is elliposoidal, and size distribution is relatively more even, greatly about about 8 ~ 15nm, dispersed relatively good, does not occur agglomeration.Fig. 2 and Fig. 3 indicates the surface topography after silica gel and trapping gold nano particle, as seen from Figure 2, and Silica Surface smoother; But after having wrapped up gold nano grain, many nano particles have obviously been piled up at the silica gel edge in Fig. 3, show that the gold nano grain layer of Silica Surface is formed.
Table 1 is the elementary analysis table of the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification, from table 1, results of elemental analyses also can see that aminopropyl trimethoxysilane modifies the carbon content increase of rear silica gel, shows that aminopropyl trimethoxysilane is successfully modified in Silica Surface.And the Stationary liquid of bonding beta-schardinger dextrin-finds that the content of sulphur grows out of nothing, this should be the result after introducing thiocarbamide, and therefore these all clearly show that the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification is successfully produced;
Table 1, the elementary analysis table of the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification.
Embodiment 4
With the golden nanometer particle/silica gel solid phase of obtained beta-schardinger dextrin-modification, homogenate method is filled in long 150mm, and internal diameter is that in the stainless steel pillar of 4.6mm, the chromatographic column obtained is for Analyze & separate sample.
Application examples 1
By the chromatographic column prepared by embodiment 4, be separated a pair flavanones enantiomer.Fig. 4 is its chromatographic isolation result.Chromatographic condition is: acetonitrile/acetic acid-triethylamine (1%) solution (it is 5.04 that the triethylamine aqueous solution of 1% drips vinegar acid for adjusting pH) (30/70, v/v), isocratic elution; Flow velocity is 1.0mL/min; Determined wavelength 254nm.
Application examples 2
By the chromatographic column prepared by embodiment 4, be separated a pair Bupivacaine enantiomer.Fig. 5 is its chromatographic isolation result.Chromatographic condition is: methyl alcohol/acetic acid-triethylamine (1%) aqueous solution (it is 4.98 that the triethylamine aqueous solution of 1% drips vinegar acid for adjusting pH), (25/75, v/v), isocratic elution; Flow velocity is 1.0mL/min; Determined wavelength 215nm.
Fig. 4 and Fig. 5 illustrates, the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification provided by the invention, for the separation of chiral material, has very strong fractionation ability.
Above-mentioned fact Example is only in order to example of the present invention is clearly described, and is not the restriction to embodiments of the present invention, cannot be illustrated here to all embodiments.Every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (8)
1. golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-modification, its general structure is:
Wherein, ●-represent gold nano grain,
-represent beta-schardinger dextrin-.
2. a preparation method for the golden nanometer particle/silica gel chiral fixed phase of beta-schardinger dextrin-modification, comprises the steps:
1) preparation of beta-schardinger dextrin-that derives of mercapto groups
Be that 2 ~ 4mol/L sodium hydrate aqueous solution fully mixes by beta-schardinger dextrin-and concentration, described sodium hydroxide concentration is 35 ~ 45% of beta-schardinger dextrin-quality, then paratoluensulfonyl chloride is dropwise added mixed liquor, paratoluensulfonyl chloride and beta-schardinger dextrin-mass ratio are 1:4 ~ 8, react 4-8 hour, then filter under ice bath, regulate pH to neutral, recrystallization, dry, obtain benzoylated beta-schardinger dextrin-;
Be that benzoylated beta-schardinger dextrin-and the derivative reagent of 1:1 ~ 1.5 is dissolved in the mixed liquor of methanol/water by mass ratio, the volume ratio of methanol/water is 4:1, needed for every gram of benzoylated beta-schardinger dextrin-, methanol/water solution is 50 ~ 80mL, react 40 ~ 60 hours, suction filtration, with gained solid after the sodium hydrate aqueous solution dissolving suction filtration of 10%, stirs 5 ~ 7 hours at 50 DEG C, regulate about pH to 2, finally add trichloro-ethylene; The amount that every gram of derivative reagent adds trichloro-ethylene is 2 ~ 5mL, stirs 24 ~ 36 hours, suction filtration, recrystallization, obtains the beta-schardinger dextrin-that mercapto groups is derivative;
2) preparation of alkylamino silica gel
By diameter 3 ~ 10 μm of colloidal silica dispersion in dry toluene, add amino silane, under nitrogen protection, stirring and refluxing 12-24 hour, then filters, and uses carrene successively, acetone, methanol wash, dry, obtains alkylamino silica gel; Wherein, dry toluene dosage needed for every gram of silica gel is 10 ~ 50mL, and amino silane dosage needed for every gram of silica gel is 0.5 ~ 1.5mL;
3) golden nanometer particle is in the formation of Silica Surface
Alkylamino silica gel is dispersed in the aqueous solution of chloraurate of 0.01 ~ 0.05%, is heated to boiling, then add the reducing agent aqueous solution of 0.5 ~ 2% fast, cool to room temperature after reaction 10 ~ 40min; This process repeats namely to obtain the coated silica gel of golden nanometer particle for 2 ~ 3 times; Wherein, aqueous solution of chloraurate dosage needed for every gram of alkylamino silica gel is 20 ~ 50mL, and reducing agent dosage needed for every gram of gold chloride is 2 ~ 5g;
4) golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification
By colloidal silica dispersion coated for golden nanometer particle in N, in dinethylformamide, then the N that mass concentration is the beta-schardinger dextrin-that 0.2-1.0% mercapto groups derives is added, dinethylformamide solution, reaction 24-48 hour, filters, use N successively, dinethylformamide, ultra-pure water clean, dry, obtain the golden nanometer particle/silica gel solid phase of beta-schardinger dextrin-modification; Needed for the silica gel that wherein every gram of golden nanometer particle is coated, DMF dosage is 10-30mL, and the beta-schardinger dextrin-dosage that needed for the silica gel that every gram of golden nanometer particle is coated, mercapto groups is derivative is 0.5-1.0g.
3. the preparation method of the golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-modification according to claim 2, is characterized in that: step 1) derivative reagent used is thiocarbamide.
4. the preparation method of the golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-modification according to claim 2, is characterized in that described step 1) in every gram of derivative reagent corresponding 10% sodium hydrate aqueous solution consumption be 20-40mL.
5. the preparation method of the golden nanometer particle/silica gel chiral fixed phase of a kind of beta-schardinger dextrin-modification according to claim 2, is characterized in that described step 2) amino silane is aminopropyl trimethoxysilane or aminopropyl triethoxysilane.
6. the preparation method of the golden nanometer particle/silica gel solid phase of a kind of beta-schardinger dextrin-modification according to claim 2, is characterized in that described step 2) silica gel used is spherical silica gel, aperture is 10-50nm, and specific area is 300-500m
2/ g.
7. the preparation method of the golden nanometer particle/silica gel solid phase of a kind of beta-schardinger dextrin-modification according to claim 2, is characterized in that described step 3) described reducing agent is trisodium citrate.
8. the preparation method of the golden nanometer particle/silica gel solid phase of a kind of beta-schardinger dextrin-modification according to claim 2, is characterized in that described step 3) in described golden nanometer particle be spherical, particle diameter is 10-50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410837801.3A CN104437442B (en) | 2014-12-29 | 2014-12-29 | Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410837801.3A CN104437442B (en) | 2014-12-29 | 2014-12-29 | Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437442A true CN104437442A (en) | 2015-03-25 |
| CN104437442B CN104437442B (en) | 2017-04-26 |
Family
ID=52884651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410837801.3A Expired - Fee Related CN104437442B (en) | 2014-12-29 | 2014-12-29 | Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437442B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362714A (en) * | 2016-10-14 | 2017-02-01 | 宁夏大学 | Chiral chromatography stationary phase with silver functionalized silicon base and preparation method thereof |
| CN108276589A (en) * | 2018-01-11 | 2018-07-13 | 浙江农林大学 | A kind of preparation method of modified cyclodextrin polyalcohol hydrogel and application |
| CN108295817A (en) * | 2018-03-16 | 2018-07-20 | 嘉兴学院 | A kind of surface sulfhydrylation carbon fiber and preparation method thereof |
| CN111229188A (en) * | 2018-11-28 | 2020-06-05 | 天津大学 | Glycopeptide antibiotic functionalized magnetic composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306354A (en) * | 2007-05-17 | 2008-11-19 | 华东理工大学 | Cyclodextrin chiral chromatogram fixed phase and preparation method thereof |
| CN102776536A (en) * | 2011-05-12 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Mercapto-beta-cyclodextrin modified silver nano-rode array, its preparation method and its use |
| CN103837519A (en) * | 2014-04-10 | 2014-06-04 | 中国科学院合肥物质科学研究院 | A method of measuring a plurality of polychlorinated biphenyls by surface enhanced Raman spectroscopy |
| CN104028253A (en) * | 2014-06-23 | 2014-09-10 | 镇江出入境检验检疫局检验检疫综合技术中心 | Gold nanoparticle-polysaccharide bonded silica gel fixed phase and preparation method thereof |
-
2014
- 2014-12-29 CN CN201410837801.3A patent/CN104437442B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306354A (en) * | 2007-05-17 | 2008-11-19 | 华东理工大学 | Cyclodextrin chiral chromatogram fixed phase and preparation method thereof |
| CN102776536A (en) * | 2011-05-12 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Mercapto-beta-cyclodextrin modified silver nano-rode array, its preparation method and its use |
| CN103837519A (en) * | 2014-04-10 | 2014-06-04 | 中国科学院合肥物质科学研究院 | A method of measuring a plurality of polychlorinated biphenyls by surface enhanced Raman spectroscopy |
| CN104028253A (en) * | 2014-06-23 | 2014-09-10 | 镇江出入境检验检疫局检验检疫综合技术中心 | Gold nanoparticle-polysaccharide bonded silica gel fixed phase and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LONG YANG,ET AL: "Dual β-cyclodextrin functionalized Au@SiC nanohybrids for the electrochemical determination of tadalafil in the presence of acetonitrile", 《BIOSENSORS AND BIOELECTRONICS》 * |
| MIN LI,ET AL: "Application of cyclodextrin-modified gold nanoparticles in enantioselective monolith capillary electrochromatography", 《TALANTA》 * |
| 胡佳等: "巯基环糊精的合成", 《化工技术与开发》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362714A (en) * | 2016-10-14 | 2017-02-01 | 宁夏大学 | Chiral chromatography stationary phase with silver functionalized silicon base and preparation method thereof |
| CN106362714B (en) * | 2016-10-14 | 2019-03-22 | 宁夏大学 | Silver-colored functionalization silicon substrate chiral chromatogram stationary phase and preparation method thereof |
| CN108276589A (en) * | 2018-01-11 | 2018-07-13 | 浙江农林大学 | A kind of preparation method of modified cyclodextrin polyalcohol hydrogel and application |
| CN108295817A (en) * | 2018-03-16 | 2018-07-20 | 嘉兴学院 | A kind of surface sulfhydrylation carbon fiber and preparation method thereof |
| CN111229188A (en) * | 2018-11-28 | 2020-06-05 | 天津大学 | Glycopeptide antibiotic functionalized magnetic composite material and preparation method and application thereof |
| CN111229188B (en) * | 2018-11-28 | 2022-03-29 | 天津大学 | Glycopeptide antibiotic functionalized magnetic composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437442B (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Applications of metal-organic frameworks as advanced sorbents in biomacromolecules sample preparation | |
| Cao et al. | Magnetic AuNP@ Fe3O4 nanoparticles as reusable carriers for reversible enzyme immobilization | |
| Chen et al. | Graphene/graphene oxide and their derivatives in the separation/isolation and preconcentration of protein species: A review | |
| CN102974314B (en) | Magnetic gold nanoparticle composite material, and preparation method and application thereof | |
| CN105203380B (en) | A kind of preparation method and applications of the composites of magnetic MIL 100 | |
| Zhao et al. | Recent advances of mesoporous materials in sample preparation | |
| Zheng et al. | Click synthesis of glucose-functionalized hydrophilic magnetic mesoporous nanoparticles for highly selective enrichment of glycopeptides and glycans | |
| CN104437442A (en) | Beta-cyclodextrin-modified gold nanoparticle/silica gel chiral stationary phase and preparation method thereof | |
| Connolly et al. | Polymeric monolithic materials modified with nanoparticles for separation and detection of biomolecules: a review | |
| Duan et al. | Nanoparticles as stationary and pseudo-station+ ary phases in chromatographic and electrochromatographic separations | |
| Saeed et al. | Metal–organic framework-based affinity materials in proteomics | |
| Tang et al. | Nanoparticle-based monoliths for chromatographic separations | |
| Kip et al. | Ni (II)-decorated porous titania microspheres as a stationary phase for column chromatography applications: Highly selective purification of hemoglobin from human blood | |
| CN106492770A (en) | A kind of histidine-tagged protein affinity purification material and its application | |
| CN106276925A (en) | A kind of method preparing meso-porous silica core-shell microspheres | |
| CN101990475A (en) | A process for the preparation of silver nano particles | |
| CN103736433A (en) | Hydrophobic magnetic mesoporous microsphere as well as preparation method and application thereof | |
| Dastafkan et al. | Silver nanoparticles for separation and preconcentration processes | |
| Najam-ul-Haq et al. | Versatile nanocomposites in phosphoproteomics: a review | |
| CN105597713B (en) | Magnetic solid-phase extraction material and preparation method and application thereof | |
| Kitte et al. | Recent advances in nanomaterial‐based capillary electrophoresis | |
| Aboul‐Enein et al. | Application of nanoparticles in chiral analysis and chiral separation | |
| Li et al. | Polyethyleneimine-functionalized Fe 3 O 4/attapulgite particles for hydrophilic interaction-based magnetic dispersive solid-phase extraction of fluoroquinolones in chicken muscle | |
| CN104010970A (en) | Porous particles for liquid chromatography and processes for the preparation thereof | |
| Chen et al. | A new ionic liquid bridged periodic mesoporous organosilicas stationary phase for per aqueous liquid chromatography and its application in the detection of biogenic amines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170426 Termination date: 20171229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |