CN108311126A - A kind of preparation and application thereof of polyethylene glycol functional bonded silica gel - Google Patents
A kind of preparation and application thereof of polyethylene glycol functional bonded silica gel Download PDFInfo
- Publication number
- CN108311126A CN108311126A CN201810146473.0A CN201810146473A CN108311126A CN 108311126 A CN108311126 A CN 108311126A CN 201810146473 A CN201810146473 A CN 201810146473A CN 108311126 A CN108311126 A CN 108311126A
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- silica gel
- bonded silica
- preparation
- functional bonded
- 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.)
- Pending
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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to functional material synthesis technical fields, and more particularly, to a kind of preparation and application thereof of polyethylene glycol functional bonded silica gel, preparation method includes the following steps:Step 1:Silica gel is activated, hydroxy functionalized silica gel is obtained;Step 2:In hydroxy functionalized Silica Surface grafted silane coupling agent;Step 3:Polyethylene glycol is dissolved in organic solvent; sodium hydride is added thereto; it is stirred at room temperature to no longer aerogenesis, is filtered to remove unreacted sodium hydride, the product in step 2 is added to filtrate; catalyst is added; it is stirred at reflux under inert gas protection, product is filtered and washed, dry; obtain polyethylene glycol functional bonded silica gel, the mass ratio of polyethylene glycol and product in step 2 is (0.5~2):(1.0~1.8), the polyethylene glycol of macromolecule can be grafted to Silica Surface by this method, and method is simple, and obtained polyethylene glycol functional bonded silica gel has α cyclodextrin the effect of good selection separation.
Description
Technical field
The present invention relates to functional material synthesis technical fields, more particularly, to a kind of suitable for the poly- of column chromatography chromatogram separation
Ethylene glycol functionality bonded silica gel, the invention further relates to the preparation method of the bonded silica gel and purposes.
Background technology
Supramolecular chemistry is to study the complexity combined with non-covalent bond weak interaction force orderly and have specific work(
The chemistry of the molecular aggregate of energy, supermolecule (being mostly cyclic structure) can utilize intermolecular interaction and three-dimensional size to imitate
It answers, is selectively identified with target molecule, the self assembly behavior of supermolecule occurs.Cyclodextrin (cyclodextrin, CD) be by
D- glucopyranose units are by a kind of cyclic oligomer maltose made of α-(1 → 4)-glucosides key connection, since it has
Hydrophobic cavity and water-wetted surface can be combined with inorganic, organic and biomolecule as host compound and generate host-guest inclusion
Object becomes a kind of main body chemical combination important in supramolecular chemistry field to embody the Molecular Recognization of cyclodextrin
Object.Cyclodextrin can be self-assembly of supramolecular hydrogel with hydrophilic polyethylene glycol (PEG), be formed by gel and generally have
There are good degradability and thixotropy, be easy to respond the stimulation of external environment, makes it in control release, tissue training
It supports, mildly separation, gel propellant preparation, information storage and perception etc. show huge application potential.It there is no at present
People's concern using self assembly to cyclodextrin progress Selective Separation, and due to the characteristic of hydrogel itself shear shinning and right
The sensibility of external environment stimulation so that gel cannot be used directly for the separation of alpha-cyclodextrin (α-CD).
A large amount of preparative separations of α-CD generally use control technique, i.e., decyl alcohol appropriate is added in enzyme reaction system, makes
α-the CD of synthesis form compound not soluble in water and precipitate therewith, and this precipitation can mitigate inhibition of the α-CD to reaction,
Achieve the purpose that increase yield.However there is also some unfavorable factors in use for decyl alcohol, such as its boils up till 229
DEG C, it is difficult to removed from aqueous solution, and that there are energy consumptions is excessively high, danger coefficient is big, time-consuming, diluting reaction mother liquor for steam distillation
The shortcomings of.Although can be detached by thin-layer chromatography, high performance anion exchange chromatography, high performance liquid chromatography and Capillary Electrophoresis
To the α-CD of higher degree, but its fractional dose is very limited, cannot meet the needs of growing to α-CD.
Silicagel column partition method is a kind of now widely used separating and purifying technology, silica gel have good mechanical stability,
Chemical stability and thermal stability, will not cooperating microorganisms, surface have a large amount of silicone hydroxyl have good plasticity, have
The frame structure of rigidity, cheap easy acquisition.Chemical modification is carried out to Silica Surface, forms the chemical bond with specific function
Close silica gel, it has also become the common method in chromatograph packing material field.Currently, it has been reported that the polyethylene glycol that the degree of polymerization is 2-10 is connect
On branch to silica gel, for the Selective Separation to organic compound, still, preparation method is complicated, and small-molecular-weight is poly-
Ethylene glycol is not high to the Selective Separation degree of α-CD, and the polyethylene glycol steric hindrance of macromolecule is big, leads to its reaction
Activity is low, it is difficult to be grafted onto Silica Surface.Therefore, a kind of simple and effective preparation method is developed, it can be by the poly- second of macromolecule
Glycol is grafted to Silica Surface, is just particularly important.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of polyethylene glycol functional bonded silica gels, together
When the present invention also provides the preparation method of the bonded silica gel and purposes, this method to be grafted the polyethylene glycol of macromolecule
To Silica Surface, and method is simple, and obtained polyethylene glycol functional bonded silica gel has good selection point to alpha-cyclodextrin
From effect.
A kind of polyethylene glycol functional bonded silica gel proposed by the present invention, structural formula are:
N=10-97.
The preparation method of polyethylene glycol functional bonded silica gel proposed by the present invention, includes the following steps:
Step 1:Silica gel is activated, hydroxy functionalized silica gel is obtained;
Step 2:In hydroxy functionalized Silica Surface grafted silane coupling agent;
Step 3:The preparation of polyethylene glycol functional bonded silica gel:
Polyethylene glycol is dissolved in organic solvent, sodium hydride is added thereto, is stirred at room temperature to no longer aerogenesis, filtering with
Unreacted sodium hydride is removed, the product in step 2 is added to filtrate, catalyst is added, in N2Protection is stirred at reflux, product mistake
It filters and washs, it is dry, obtain polyethylene glycol functional bonded silica gel, the mass ratio of polyethylene glycol and product in step 2 is (0.5
~2):(1.0~1.8).
Further, in step 1, HCl/H is used2O solution activates silica gel, and washing obtains hydroxyl work(after dry
The silica gel of energyization;
Further, in step 1, the average particle size of silica gel is 200-300 mesh.
Further, in step 1, the activation step of silica gel is as follows, first in HCl/H26h is impregnated in O solution, then 85
It is stirred at reflux 10~12h at~95 DEG C.
Further, in step 1, washing step is as follows, first filters, and is then washed with deionized water to neutrality, then uses ethyl alcohol
It washes primary.
Further, in step 1, drying temperature is 100 DEG C, dry 12h.
Further, step 2 includes:Silane coupling agent is dissolved in organic solvent, the hydroxyl of step 1 preparation is added with stirring
The silica gel of base functionalization, in N2The lower back flow reaction of protection, reacts postcooling, washs until no thick substances, drying for standby;
Further, in step 2, silane coupling agent is γ-[(2,3- the third oxygen of epoxy)] propyl trimethoxy silicane.
Further, in step 2, the volume ratio of silane coupling agent and organic solvent is 1:10~1:15.
Further, in step 2, the volume ratio of silane coupling agent and organic solvent is 1:10.
Further, in step 2, organic solvent is dry toluene.
Further, in step 2, reflux time is 10~12h.
Further, in step 2, the step of washing, is as follows, is washed successively to no thick substances with toluene, methanol, acetone
Until.
Further, dry to be dried in vacuo in step 2, drying temperature is 50~80 DEG C, and drying time is 8~12h.
Further, in step 3, the molecular weight of polyethylene glycol is 600~6000.
Further, in step 3, the molecular weight of polyethylene glycol is 1000.
Further, in step 3, organic solvent is toluene or n,N-Dimethylformamide.
Further, in step 3, catalyst is boron trifluoride ether, tetrabutylammonium bromide or HClO4。
Further, in step 3, the mass ratio of polyethylene glycol and catalyst is 1~2:4~10.
Further, in step 3, reflux temperature is 80~110 DEG C, and return time is for 24 hours.
Further, in step 3, product washing step is as follows, and product is washed repeatedly successively with DMF, methanol, acetone.
Further, in step 3, drying temperature is 100 DEG C, and drying time is 8~12h.
Beneficial effects of the present invention are embodied in:
Self assembly effect can occur with solute for polyethylene glycol bonded silica gel prepared by the present invention, be used for cyclic annular carbohydrate for the first time
Separation, the substance of difficult separation provide the possibility of separation.
Polyethylene glycol bonded silica gel preparation method of the present invention, flow are simple, and yield is higher, favorable reproducibility, are applicable to often
Normal temperature and pressure has good application prospect.
Description of the drawings
Fig. 1 is the infrared spectrogram of 1 activated silica gel of embodiment, KH-560 bonded silica gels and PEG bonded silica gels.
Fig. 2 is the TG collection of illustrative plates of 1 activated silica gel of embodiment, KH-560 bonded silica gels and PEG bonded silica gels.
Fig. 3 is the DGT collection of illustrative plates of 1 activated silica gel of embodiment, KH-560 bonded silica gels and PEG bonded silica gels.
Fig. 4 is the elution curve of α-CD in embodiment 2.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
Polyethylene glycol functional bonded silica gel is prepared, steps are as follows:
(1) activation of silica gel:
The column chromatography silica gel for weighing 20g 200-300 mesh immerses the HCl/H of 120mL 10%2In O solution, after impregnating 6h,
It is stirred at reflux 12h at 95 DEG C and removes metal ion, through filtering and being washed with deionized water to neutrality, ethyl alcohol is washed once, is done at 100 DEG C
Dry 12h is obtained to surface and is uniformly distributed the activated silica gel of hydroxyl, is stored in spare in drier;
(2) preparation of γ-[(the third oxygen of 2,3- epoxies)] propyl trimethoxy silica gel:
It weighs 5g activated silica gels and reaction vessel is added, then add 100mL dry toluene solvents, be added with stirring 10mLKH-560
With the new steamed triethylamine of 5 drops.Use N2It protects, it is cooling after heating stirring back flow reaction 12h, it is washed repeatedly with acetone and methanol
It washs until no thick substances, 8h, γ-[(2,3- the third oxygen of epoxy)] propyl trimethoxy silicon is finally dried in vacuo at 80 DEG C
Glue, product are white solid particle, are stored in spare in drier.
(3) preparation of polyethylene glycol functional bonded silica gel
10g cetomacrogol 1000s are weighed to be dissolved in 150mLDMF, thereto be added 0.48g sodium hydrides, stir at room temperature to
No longer aerogenesis is filtered to remove unreacted sodium hydride.16g γ-[(the third oxygen of 2,3- epoxies)] propyl three is added to above-mentioned filtrate
Five drop HClO are added in methoxyl group silica gel4As catalyst, heating stirring flows back for 24 hours at 80 DEG C, and product filters and use DMF, first
Alcohol, acetone wash repeatedly successively.Polyethylene glycol bonded silica gel is obtained after 100 DEG C of oven drying 12h, is stored in spare in drier.
Chemical equation is as follows:
The analysis and characterization of polyethylene glycol functional bonded silica gel prepared by embodiment 1
1. infrared analysis result
As shown in Figure 1, investigating the structure of polyethylene glycol bonded silica gel of the present invention, 2876cm using infrared spectrum-1,
2945cm-1The absorption peak at place should correspond to the absorption of methylene on coupling agent, 911cm-1The absorption peak at place is the spy of epoxy group
Peak is levied, the appearance of epoxy group absorption peak disappears again, it may be said that bright polyethylene glycol has successfully been bonded to Silica Surface.
2. elemental analysis result
It can prove that each step is all successfully realized reaction using elemental analysis, as shown in table 1 below:Activated silica gel itself C,
H content is seldom, and the C of KH-560 bonded silica gels and polyethylene glycol bonded silica gel, H content obviously increase, and illustrates to have obtained target production
Object.
The elemental analysis result of 1 activated silica gel of table, KH-560 bonded silica gels and polyethylene glycol bonded silica gel
3. thermogravimetric analysis
As shown in Figures 2 and 3, thermogravimetric analysis is carried out by the polyethylene glycol bonded silica gel prepared to the present invention, can seen
To its weightless temperature about at 250 DEG C, polyethylene glycol bonded silica gel is weightless seldom when temperature is less than 250 DEG C, and temperature influences it
Less, illustrate that PEG bonded silica gels have good thermal stability.
Embodiment 2
The Selective Separation of polyethylene glycol functional bonded silica gel prepared by the present invention to α-CD
Polyethylene glycol bonded silica gel filler prepared by embodiment 1 is filled in tool piston chromatography void column (20*300mm), and
It is balanced with water, prepares four kinds of solution of glucose, maltose, α-CD, β-CD of equimolar concentration and is filled to self-control chromatography
It in column, is eluted with the water of 5 times of column volumes, measured after column remaining glucose in liquid, maltose, α-CD, β-CD
Content, the results are shown in Table 2.
Retention rate of the 2 polyethylene glycol bonded silica gel column of table to each carbohydrate
As can be seen from Table 2, the polyethylene glycol bonded silica gel material of preparation is significantly higher than to grape the retention rate of α-CD
The retention rate of sugar, maltose and β-CD, shows good selectivity.
Take appropriate PEG bonded silica gels in beaker, mobile phase and silica gel be added and is sufficiently stirred mixing, use later ultrasonic wave into
Row 10min degassing process is simultaneously stirred continuously, and the silica gel suspension being disposed is carried out wet method dress post with natural sedimentation.It is derived from
Glucose processed, α-CD mixed liquor loadings, the mixed liquor with n-butanol, glacial acetic acid, water is mobile phase, is eluted at room temperature,
A pipe is collected per 5min using fraction collector, collection liquid point silica gel plate is developed the color, determines the starting point collected and terminal.It collects
Terminate to use high-efficient liquid phase analysis separating resulting.It was found that linear carbohydrate is first eluted, cyclic annular carbohydrate is then eluted, α-
The elution curve of CD is shown in Fig. 4.
Comparative example 1
The use of molecular weight is respectively 200,400,600,1000,2000 and according to experiment condition same as Example 1
4000,6000 polyethylene glycol is grafted to Silica Surface, reservation of the polyethylene glycol bonded silica gel column tested to each carbohydrate
Rate the results are shown in Table 3.
Retention rate/% of the 3 polyethylene glycol bonded silica gel column of table to each carbohydrate
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (10)
1. a kind of polyethylene glycol functional bonded silica gel, it is characterised in that:Its structural formula is as follows:
N=10~97.
2. a kind of preparation method of polyethylene glycol functional bonded silica gel, it is characterised in that:Include the following steps:
Step 1:Silica gel is activated, hydroxy functionalized silica gel is obtained;
Step 2:In hydroxy functionalized Silica Surface grafted silane coupling agent;
Step 3:Polyethylene glycol is dissolved in organic solvent, sodium hydride is added thereto, is stirred at room temperature to no longer aerogenesis, filtering
To remove unreacted sodium hydride, the product in step 2 is added to filtrate, catalyst is added, stirs under inert gas protection
Reflux, product are filtered and are washed, dry, obtain polyethylene glycol functional bonded silica gel, the matter of polyethylene glycol and product in step 2
Amount is than being (0.5~2):(1.0~1.8).
3. the preparation method of polyethylene glycol functional bonded silica gel according to claim 2, it is characterised in that:The step
In 3, the molecular weight of polyethylene glycol is 600~6000.
4. the preparation method of polyethylene glycol functional bonded silica gel according to claim 2, it is characterised in that:The step
In 3, the mass ratio of polyethylene glycol and sodium hydride is 1:0.048.
5. the preparation method of polyethylene glycol functional bonded silica gel according to claim 2, it is characterised in that:The step
In 3, organic solvent is toluene or n,N-Dimethylformamide, and the mass volume ratio of polyethylene glycol and organic solvent is 1g:15mL,
Catalyst is boron trifluoride ether, tetrabutylammonium bromide or HClO4, the mass ratio of polyethylene glycol and catalyst is 1~2:4~
10。
6. the preparation method of polyethylene glycol functional bonded silica gel according to claim 2, it is characterised in that:The step
In 3, the reaction condition of reflux is:In N2Under protection, for 24 hours, washing, dry condition are 80~110 DEG C of return stirrings:Product is used
DMF, methanol, acetone wash repeatedly successively, 100 DEG C of 8~12h of oven drying.
7. the preparation method of polyethylene glycol functional bonded silica gel according to claim 2, it is characterised in that:Step 1 is wrapped
Include following steps:The column chromatography silica gel for weighing 200-300 mesh immerses HCl/H2In O solution, after impregnating 6h, stirred at 85~95 DEG C
10~the 12h that flows back removes metal ion, and through filtering and being washed with deionized water to neutrality, ethyl alcohol is washed once, dry 12h at 100 DEG C,
Obtain the activated silica gel that hydroxyl is uniformly distributed to surface.
8. the preparation method of polyethylene glycol functional bonded silica gel according to claim 2, it is characterised in that:Step 2 is wrapped
Include following steps:By volume 1:10~1:15 by γ-[(the third oxygen of 2,3- epoxies)] propyl trimethoxy silicanes and dry toluene
It is placed in container, hydroxy functionalized silica gel prepared by step 1 is added under mechanical agitation, in N2The lower reflux of protection, reaction 10~
Stop after 12h, it is cooling, it is washed until no thick substances with toluene, methanol acetone successively, finally vacuum is dry at 50~80 DEG C
Dry 8~12h.
9. polyethylene glycol functional bonded silica gel made from claim 2-8 any one of them preparation methods.
10. purposes of the polyethylene glycol functional bonded silica gel as column chromatography chromatogram column packing described in claim 1 or 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810146473.0A CN108311126A (en) | 2018-02-12 | 2018-02-12 | A kind of preparation and application thereof of polyethylene glycol functional bonded silica gel |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810146473.0A CN108311126A (en) | 2018-02-12 | 2018-02-12 | A kind of preparation and application thereof of polyethylene glycol functional bonded silica gel |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108311126A true CN108311126A (en) | 2018-07-24 |
Family
ID=62903031
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810146473.0A Pending CN108311126A (en) | 2018-02-12 | 2018-02-12 | A kind of preparation and application thereof of polyethylene glycol functional bonded silica gel |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108311126A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118184991A (en) * | 2024-05-16 | 2024-06-14 | 浙江月旭材料科技有限公司 | Size exclusion chromatographic packing and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101829551A (en) * | 2010-05-12 | 2010-09-15 | 武汉大学 | Silica gel fixed phase of mixed model as well as preparation method and application thereof |
CN103212386A (en) * | 2012-12-20 | 2013-07-24 | 北京化工大学 | High purity full porous silica gel-bonded chromatography immobile phase preparation method |
CN107597070A (en) * | 2017-10-30 | 2018-01-19 | 江南大学 | It is a kind of using hybrid silicon cyclodextrin as novel hybride sorbing material of core shell structure and preparation method thereof |
-
2018
- 2018-02-12 CN CN201810146473.0A patent/CN108311126A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101829551A (en) * | 2010-05-12 | 2010-09-15 | 武汉大学 | Silica gel fixed phase of mixed model as well as preparation method and application thereof |
CN103212386A (en) * | 2012-12-20 | 2013-07-24 | 北京化工大学 | High purity full porous silica gel-bonded chromatography immobile phase preparation method |
CN107597070A (en) * | 2017-10-30 | 2018-01-19 | 江南大学 | It is a kind of using hybrid silicon cyclodextrin as novel hybride sorbing material of core shell structure and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
孟小兵等: ""聚乙二醇功能性键合硅胶的制备及其性质研究"", 《中国科技论文在线》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN118184991A (en) * | 2024-05-16 | 2024-06-14 | 浙江月旭材料科技有限公司 | Size exclusion chromatographic packing and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109395698A (en) | A kind of preparation method using mixed ligand synthesis metal organic framework UiO-66 adsorbent | |
CN102423699B (en) | Preparation method of coating-type polysaccharide chiral stationary phase | |
CN109092354A (en) | A kind of immobilized acidic ionic liquid catalysts of silanization chitosan and preparation method thereof | |
CN101775152B (en) | Preparation method of surface imprinted material for matrine substance separation and purification | |
CN102068965A (en) | Method for preparing chitosan separation medium suitable for protein purification | |
CN101298042A (en) | Spherical ordered mesoporous silicon oxide substrate chromatograph stationary phase and preparation | |
CN102079795A (en) | Preparation of water-soluble crosslinked chitosan and application thereof | |
CN106749922A (en) | A kind of preparation method and applications of beta cyclodextrin hybridized polymer Microcolumn | |
CN108311126A (en) | A kind of preparation and application thereof of polyethylene glycol functional bonded silica gel | |
CN111001188B (en) | Reversed phase separation medium and preparation method and application thereof | |
CN105289558B (en) | The preparation and application of multicomponent block hydrophile copolymers silica gel hybridization chromatograph packing material | |
CN106632529B (en) | A kind of shell tetrose monomer separation extracting method based on molecular imprinting technology | |
CN103193898B (en) | L-Phe derives the synthesis of beta-cyclodextrin bonded silica gel and applies the separation of Alanine enantiomers | |
CN101497035B (en) | Preparation method of solid-phase extraction small column for molecular imprinting of substituted carbamide pesticide | |
CN105457503A (en) | Preparation and application of chlorogenic acid molecular imprinting chitosan membrane | |
CN106866900A (en) | A kind of photoresponse molecularly imprinted material on surface and its preparation method and application | |
CN101851318B (en) | Preparation method of punicalagin molecular imprinted polymer microspheres | |
CN102381713A (en) | Hydrophobic silica gel for oil vapor recovery | |
CN106268712B (en) | A kind of method of preparation and use of the micro-extraction carbon-point based on surface molecule print | |
CN104263717B (en) | β glucuroides magnetic molecularly imprinted material and its application in timosaponin BII conversions | |
CN107096509A (en) | The sephadex and preparation method of a kind of succinic acid of amido containing α function base | |
CN105170098A (en) | Method for preparing hydrophobic silica gel through microwave-esterification modification | |
CN102993389A (en) | Optical intelligent silicagel surface molecularly imprinted microsphere and preparation method thereof | |
CN110404584A (en) | A kind of 4-methyl umbelliferone molecular engram nanofiber, preparation method and application | |
CN106422410B (en) | A kind of preparation method and application of antenna type amino acid pattern immobilization ionic liquid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180724 |