CN109092276A - A kind of preparation of the spherical gel chromatographic media of multi-layer pore size distribution - Google Patents
A kind of preparation of the spherical gel chromatographic media of multi-layer pore size distribution Download PDFInfo
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- CN109092276A CN109092276A CN201811064311.9A CN201811064311A CN109092276A CN 109092276 A CN109092276 A CN 109092276A CN 201811064311 A CN201811064311 A CN 201811064311A CN 109092276 A CN109092276 A CN 109092276A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/291—Gel sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—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
- B01J20/28047—Gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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Abstract
The present invention relates to a kind of preparation of the spherical gel chromatographic media of multi-layer pore size distribution, the preparation of the chromatographic media can form the multi-level structure being made of kernel and wrapping layer due to using multiple suspension emulsion process.The chromatographic media has the characteristic that multi-layer medium is same substance or similar substance, is tightly combined between each level, it is ensured that adsorption capacity will not shell；And there is diplopore characteristic, it is the nano grade pore being made of gel itself grid hole and the micron order hole as made from pore-foaming agent respectively；In addition, the porosity and aperture size ecto-entad gradient distribution of different levels, can strengthen solutes accumulation rate in medium, chromatography overall separation efficiency is improved, while medium is also able to maintain good mechanical strength.
Description
Technical field
The present invention relates to technical field of chromatography, and in particular to a kind of porosity being made of kernel and wrapping layer and aperture ruler
The preparation method of the spherical gel chromatographic media of the multi-layer pore size distribution of very little ecto-entad gradient distribution.
Background technique
Liquid chromatography technology is a kind of efficient separating and purifying technology, is the modern main means isolated and purified, in life
The numerous areas such as object, chemical industry, which suffer from, to be widely applied.Core in chromatographic technique is exactly chromatographic media, the performance of chromatographic media
Quality determines the separating effect of chromatography separating method, therefore, as the requirement to bio-separation is continuously improved, high-performance chromatography
Medium is prepared into the key problem for studying chromatographic technique for many years.High performance chromatographic media should have adsorbance it is high,
Convenient for elution, high mechanical strength, the features such as, while the modification density of the partial size of medium, aperture and aglucon should also meet centainly
Condition adapt to related separation field.
Currently, common chromatographic media has core-shell type chromatographic media, interval wall-shaped chromatographic media and diplopore chromatographic media.Shell
Caryogram chromatographic media can be divided into kernel and shell two parts with its unique advantage, that is, same medium, this two parts can be by characteristic
Different material is constituted so that the medium have the characteristics that it is different.Common core-shell type medium is using natural polysaccharide as matrix.Between
Septal type chromatographic media mainly passes through the effective of the length and dielectric surface for increasing spacerarm (short spacerarm and long spacer arm)
Group carrys out the adsorption effect of amplified medium.So that the space enlargement of media interior, while reducing separate substance and being spread in medium
Suffered steric hindrance increases the rate that separate substance is spread in media interior to a certain extent in this way, is convenient for target
Separate substance diffuses into media interior, realizes the absorption of object.Diplopore chromatographic media is mainly characterized by, in same medium
There are two distinct types of aperture, one kind is biggish recirculation hole for inside, and another kind of is small diffusion hole, due to double-pore structure
Presence, greatly accelerate separate substance in the mass transfer of media interior, separate substance preferably expanded in media interior
Dissipate, which increases the exchange opportunity of target substance and dielectric surface group, enable target protein more with medium
Internal group swaps, and achievees the effect that be adsorbed and separate, improves the adsorption capacity of medium to a certain extent.It
This exclusive double-pore structure, so as to preferably meet application of the medium in separation field.
Chromatographic media can be divided into natural macromolecular material, artificial synthesized high molecular material according to the difference of its framework material
With inorganic material etc..Protein chromatography field is common at present and widely used medium is using agarose as skeleton.Agarose
Strand on there are many active hydroxyls, the presence of hydroxyl makes agarose have stronger hydrophily.Meanwhile agarose is solidifying
Glue has stronger resistance to pressure and mechanical strength, and has relatively stable physics and chemical property.After aglucon is modified
Agarose, not only with hydrophily and itself porous structure, also make it with special absorption and separation function.It is common
Chromatographic media be all spherical, different separation situation, reach separating effect using the chromatographic media of different-grain diameter.At present
There are many method for preparing microballoon, mainly there are emulsion polymerization, suspension polymerisation, dispersin polymerization and seed swelling polymerization etc..It is micro-
The partial size of ball medium be mainly by adjusting in reaction solid-liquid ratio or other adjustable parameters control.
The present invention is that one kind is prepared using multistep suspension emulsion process using hydrophilic high mols such as Ago-Gels as matrix
The spherical gel of the multi-layer pore size distribution of the porosity and aperture sizes ecto-entad gradient distribution that be made of kernel and wrapping layer
Medium.
Summary of the invention
The present invention relates to a kind of preparation of the spherical gel chromatographic media of multi-layer pore size distribution, the preparation of the chromatographic media by
In using multiple suspension emulsion process, the multi-level structure being made of kernel and wrapping layer can be formed, the structure of similar onion.
The chromatographic media has the characteristic that multi-layer medium is same substance or similar substance, is tightly combined between each level, can be with
Guarantee adsorption capacity, will not shell；And there is diplopore characteristic, be respectively the nano grade pore that is made of gel itself grid hole and
The micron order hole as made from pore-foaming agent；In addition, the porosity and aperture size ecto-entad gradient distribution of different levels, Ke Yiqiang
Change solutes accumulation rate in medium, improves chromatography overall separation efficiency, while medium is also able to maintain good mechanical strength.
The preparation of the spherical gel chromatographic media of multi-layer pore size distribution passes through first using multiple suspension emulsion process
After secondary suspension emulsification, the lesser medium of partial size is made as kernel by hydrophilic high mol matrix and pore-foaming agent, then using the
Secondary suspension, which emulsifies and removes pore-foaming agent, is prepared the double-deck grade pore size distribution spherical medium being made of kernel and one layer of wrapping layer,
And so on, it suspends and emulsifies by n times, finally remove pore-foaming agent, so that it may N level pore size distribution spherical medium be prepared.When
Right multi-layer is embodied in number of plies N more than or equal to 2, can adjust the number of plies according to actual needs.Although Jie of multi-layer pore size distribution
Matter has multilayered structure, but since each layer of matrix is same or similar, can combine closely between each level, will not be because of each layer
The phenomenon that performance of grade matrix differs larger and shells.Due in the preparation of medium in addition to there is hydrophilic high mol as matrix
Outside, it is also added into solid pore-foaming agent, therefore the spherical medium of multi-layer pore size distribution has the characteristic of double porosity media, double-pore structure packet
It includes the small nano-size pores structure being made of the grid hole of hydrophilic high mol gel itself and is formed in matrix by pore-foaming agent
The size of micron order macroporous structure, aperture is related with substrate performance and concentration, and the size of macropore and the size of pore-foaming agent particle have
It closes.But the spherical medium of multi-layer pore size distribution overcomes the limited disadvantage of traditional double porosity media pore rate, can guarantee by force
Pore rate is improved under the premise of degree.
In addition, the important feature that the spherical medium of multi-layer pore size distribution has is exactly porosity and aperture size ecto-entad
Gradient distribution, the reason of distribution occur are that the size of solid pore-foaming agent particle is different in different layers, solid pore-foaming agent particle
Size ecto-entad gradient distribution, therefore their aperture sizes of macropore for being formed in matrix also ecto-entad gradient distribution,
And the gel strength of different layers mesostroma is different, the concentration ecto-entad gradient distribution of gel, the network hole ruler of gel itself
It is very little to increase with the reduction of its concentration, therefore the aperture size of the aperture in medium also ecto-entad gradient distribution, in addition, not
The dosage of solid pore-foaming agent is different in same layer, the dosage ecto-entad gradient distribution of solid pore-foaming agent particle, and porosity is with solid
The increase of body particle pore-foaming agent dosage and increase, therefore porosity also ecto-entad gradient distribution, so that different layers be made to have not
Same pore size distribution.In the spherical medium of multi-layer pore size distribution, the thickness of different levels is related with media size, and ratio can be certain
It is adjusted in range.
In the spherical medium of multi-layer pore size distribution, the alternative range of hydrophilic high mol matrix is very wide, can be natural
Hydrophilic high mol or synthesis hydrophilic macromolecule, Natural hydrophilic macromolecule can be agarose, cellulose, alginic acid, hyaluronic acid,
Chitosan, collagen, polylysine, poly- L- Glutamic Acid etc., synthesis hydrophilic macromolecule can be polyvinyl alcohol, acrylic acid, poly- third
Olefin(e) acid, polymethylacrylic acid, polyacrylamide, poly- N- are poly- for acrylamide etc..In addition, can be in the different layers of medium identical
Homogenous material, be also possible to material not of the same race, can according to need and be adjusted.The spherical medium of multi-layer pore size distribution
In, it is not soluble in water but be dissolved in the solid matter of diluted acid, dissolved matter that the material of solid pore-foaming agent can be calcium carbonate, calcium phosphate etc.
Nontoxic, there is no safety issues.
The spherical gel chromatographic media schematic diagram of multi-layer pore size distribution is as shown in Fig. 1.
Detailed description of the invention
The spherical gel chromatographic media schematic diagram of Fig. 1 multi-layer pore size distribution
Specific embodiment
The present invention is prepared using multiple suspension emulsion process by interior using hydrophilic high mols such as Ago-Gels as matrix
Core and wrapping layer constitute the spherical gel chromatographic media of multi-layer, porosity and aperture size ecto-entad gradient distribution.Pass through
The spherical medium for preparing different levels, has studied the influence that chromatographic media structure treats the absorption of separate substance.Example is specifically
It is bright as follows:
Example 1:
The preparation flow of the spherical medium of two level pore size distributions is as follows:
(1) 50ml the preparation of kernel: is contained into 1g agarose and 12gCaCO3And the aqueous solution of sufficiently colloidal sol is added to and contains
Have in the reactor of certain volume oil phase (soybean oil and Span 80) and stir 20min at 90 DEG C, continues after being rapidly cooled to 15 DEG C
20min is stirred, collects after standing and is cleaned with deionized water, is crosslinked with epoxychloropropane, sodium borohydride reduction, and use sieve
It is sieved, obtains 5-30 μm of spherical inner core.
(2) additional wrapping layer: the kernel for taking 10ml to sieve is added to 50ml and contains 2g agarose and 8gCaCO3And it fills
Divide in the aqueous solution of colloidal sol, stir evenly and continue heating a period of time, mixture is quickly poured into containing certain volume oil phase
20min is stirred at 90 DEG C in the reactor of (soybean oil and Span 80), continues to stir 20min after being rapidly cooled to 15 DEG C, stand
It collects and is cleaned with deionized water afterwards, be crosslinked with epoxychloropropane, sodium borohydride reduction, and sieved with sieve, obtain 10-
60 μm of two level pore size distribution spherical mediums.
(3) removal of calcium carbonate: a certain amount of two level pore size distribution spherical mediums for sieving and obtaining are taken, certain volume is added
Dilute HCL aqueous solution of 0.1mol/L is impregnated, while ceaselessly being shaken, until bubble-free generates, is then rinsed with deionized water dry
Only.
(4) DEAE aglucon is modified: the spherical medium prepared is added to the DEAE hydrochloric acid solution of certain volume and concentration
In, it is sealed in 60 DEG C of water-baths and preheats 10min, then mixed with isometric certain density NaOH solution, sealing concussion
1h is reacted, it is cooling, it is rinsed with deionized water to neutrality, is finally stored in the ethyl alcohol that volume fraction is 20%.
Example 2:
The preparation flow of the spherical medium of three level pore size distributions is as follows:
Firstly, the preparation of kernel and additional first layer wrapping layer are same as above.
Then, additional second layer wrapping layer: the two level spherical mediums for taking 10ml to sieve are added to 50ml and contain 3g
Agarose and 4gCaCO3And in the aqueous solution of sufficiently colloidal sol, stirs evenly and continue heating a period of time, mixture is quickly fallen
Enter in the reactor containing certain volume oil phase (soybean oil and Span 80) and stir 20min at 90 DEG C, after being rapidly cooled to 15 DEG C
Continue to stir 20min, collect after standing and cleaned with deionized water, with epoxychloropropane crosslinking, sodium borohydride reduction, and with sieving
Net is sieved, and 30-180 μm of three level pore size distribution spherical mediums are obtained.
Then, the removal and the modification of DEAE aglucon of calcium carbonate are carried out, ibid.
Example 3:
The preparation of the spherical medium of two level pore size distribution of unlike material:
(1) 50ml the preparation of kernel: is contained into 1g agarose and 12gCaCO3And the aqueous solution of sufficiently colloidal sol is added to and contains
Have in the reactor of certain volume oil phase (soybean oil and Span 80) and stir 20min at 90 DEG C, continues after being rapidly cooled to 15 DEG C
20min is stirred, collects after standing and is cleaned with deionized water, is crosslinked with epoxychloropropane, sodium borohydride reduction, and use sieve
It is sieved, obtains 5-30 μm of spherical inner core.
(2) additional wrapping layer: the kernel for taking 10ml to sieve is added to 50ml and contains 2g chitosan and 8CaCO3And it fills
Divide in the aqueous solution of colloidal sol, stir evenly and continue heating a period of time, mixture is quickly poured into containing certain volume oil phase
20min is stirred at 90 DEG C in the reactor of (soybean oil and Span 80), continues to stir 20min after being rapidly cooled to 15 DEG C, stand
It collects and is cleaned with deionized water afterwards, be crosslinked with epoxychloropropane, sodium borohydride reduction, and sieved with sieve, obtain 10-
60 μm of two level pore size distribution spherical mediums.
The removal and the modification of DEAE aglucon of calcium carbonate are then carried out, ibid.
The absorption property and homogenieity porous media of the spherical gel medium for the multi-layer pore size distribution that the present invention is prepared
Compared to more preferable, to the adsorption capacity of BSA up to 140mg or more, and it meets Langmuir etc. to the absorption behavior of protein
Warm equation.
Though the present invention is only described by aforementioned three examples, but still can change parameter therein, of the invention not departing from
The lower design of spirit is implemented.
Claims (7)
1. main method is as follows the present invention relates to a kind of preparation method of the spherical gel chromatographic media of multi-layer pore size distribution:
It is the agarose of 1%-4% (mass ratio) first with the concentration that suspension method will contain solid pore-foaming agent 8%-40% (mass ratio)
Aqueous solution is prepared into 5-30 microns of agarose gel microsphere, crosslinking and screening；Using the microballoon sieved as kernel, make its with
Concentration containing solid pore-foaming agent 4%-30% (mass ratio) is that the agarose solution of 2%-6% (mass ratio) is prepared by mixing into
10-60 microns of agarose gel microsphere, crosslinking and screening, can be made into the ball of two level pore size distributions if removing pore-foaming agent at this time
Shape Ago-Gel medium；Again using the microballoon containing pore-foaming agent sieved as kernel, makes it and contain solid pore-foaming agent 1%-
The concentration of 20% (mass ratio) is prepared by mixing into 30-180 micron agarose for the agarose solution of 4%-8% (mass ratio) and coagulates
Glue microballoon, crosslinking and screening, and so on, finally remove the spherical agarose that pore-foaming agent can be prepared into multi-layer pore size distribution
Gel media.The different ladders distribution of medium internal porosity and aperture ecto-entad may be implemented in the type medium, strengthens medium
Interior solutes accumulation rate improves chromatography overall separation efficiency.
2. the spherical gel medium of multi-layer pore size distribution according to claim 1, it is characterized in that multi-layer be by kernel and
Wrapping layer is constituted, and the number of plies is more than or equal to 2, and the number of plies is adjustable according to demand.
3. the spherical gel medium of multi-layer pore size distribution according to claim 1, it is characterized in that there is diplopore in the medium
Characteristic, aperture are mainly made of the network hole of gel itself, and attribute Nano grade, macropore is generated by pore-foaming agent, belongs to micron
Rank；The size of aperture is related with gel material performance and concentration, and the size of macropore is related with the size of pore-foaming agent particle, hole
Rate is related with dosage.
4. the spherical gel medium of multi-layer pore size distribution according to claim 1, it is characterized in that porosity in medium and
Aperture size ecto-entad gradient distribution, can become larger, and can also gradually become smaller, adjustable in a certain range.
5. the spherical gel medium of multi-layer pore size distribution according to claim 1, it is characterized in that in each level of the medium
Thickness is related with medium overall size, and ratio is adjustable in a certain range.
6. the spherical gel medium of multi-layer pore size distribution according to claim 1, it is characterized in that the material for preparing gel can
To be homogenous material such as agarose；It is also possible to different materials, such as: cellulose, alginic acid, hyaluronic acid, chitosan, glue
Original, polylysine, poly- L- Glutamic Acid etc.；It can also be hydrophilic high mol such as polyvinyl alcohol, acrylic acid, the polyacrylic acid of synthesis,
Polymethylacrylic acid, polyacrylamide, poly- N- is poly- for acrylamide etc., can adjust as needed.
7. the spherical gel medium of multi-layer pore size distribution according to claim 1, it is characterized in that solid pore-foaming agent used
Particle size range can be different, and the pore-foaming agent particle size of internal layer is big than outer layer, and material therefor is calcium carbonate, calcium phosphate
Etc. not soluble in water but be dissolved in the solid matter of diluted acid, dissolved matter is nontoxic.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040234A (en) * | 2019-12-16 | 2020-04-21 | 四川大学 | Novel preparation method of hierarchical pore chitin material |
| CN113853520A (en) * | 2019-05-24 | 2021-12-28 | 赛多利斯司特蒂姆生物工艺公司 | Chromatographic method, method for determining the concentration of at least one compound in a chromatographic method and method for obtaining at least one chromatographic parameter |
| WO2023236487A1 (en) * | 2022-06-07 | 2023-12-14 | 江苏集萃智能液晶科技有限公司 | Polymeric microparticle having pore channels of two sizes and preparation method therefor |
| CN117624483A (en) * | 2024-01-26 | 2024-03-01 | 凯莱英医药集团（天津）股份有限公司 | Core-shell porous polymer microsphere and preparation method and application thereof |
| US12092621B2 (en) | 2019-05-24 | 2024-09-17 | Sartorius Stedim Biotech Gmbh | Method of determining the concentration of at least one compound in a chromatography device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418357A (en) * | 2012-05-15 | 2013-12-04 | 北京化工大学 | Porous media with different porosity distribution |
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2018
- 2018-09-12 CN CN201811064311.9A patent/CN109092276A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418357A (en) * | 2012-05-15 | 2013-12-04 | 北京化工大学 | Porous media with different porosity distribution |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113853520A (en) * | 2019-05-24 | 2021-12-28 | 赛多利斯司特蒂姆生物工艺公司 | Chromatographic method, method for determining the concentration of at least one compound in a chromatographic method and method for obtaining at least one chromatographic parameter |
| CN113853520B (en) * | 2019-05-24 | 2024-02-09 | 赛多利斯司特蒂姆生物工艺公司 | Chromatographic method, method for determining the concentration of at least one compound in a chromatographic method and method for obtaining at least one chromatographic method parameter |
| US12092621B2 (en) | 2019-05-24 | 2024-09-17 | Sartorius Stedim Biotech Gmbh | Method of determining the concentration of at least one compound in a chromatography device |
| CN111040234A (en) * | 2019-12-16 | 2020-04-21 | 四川大学 | Novel preparation method of hierarchical pore chitin material |
| CN111040234B (en) * | 2019-12-16 | 2021-09-14 | 四川大学 | Preparation method of hierarchical pore chitin material |
| WO2023236487A1 (en) * | 2022-06-07 | 2023-12-14 | 江苏集萃智能液晶科技有限公司 | Polymeric microparticle having pore channels of two sizes and preparation method therefor |
| CN117624483A (en) * | 2024-01-26 | 2024-03-01 | 凯莱英医药集团（天津）股份有限公司 | Core-shell porous polymer microsphere and preparation method and application thereof |
| CN117624483B (en) * | 2024-01-26 | 2024-04-19 | 凯莱英医药集团（天津）股份有限公司 | Core-shell porous polymer microsphere and preparation method and application thereof |
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