CN1456387A - Sequential porous silica gel whole column and its preparation and use - Google Patents
Sequential porous silica gel whole column and its preparation and use Download PDFInfo
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- CN1456387A CN1456387A CN 03119094 CN03119094A CN1456387A CN 1456387 A CN1456387 A CN 1456387A CN 03119094 CN03119094 CN 03119094 CN 03119094 A CN03119094 A CN 03119094A CN 1456387 A CN1456387 A CN 1456387A
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Abstract
An integral column of ordered porous silica gel is composed of the cross-linked silica gel skeleton with pores on its surface and the mutually communicated arteries. It is prepared by sol-gel method, that is, under the existance of the additive able to form ordered structure, the ordered structure of additive plays the role of pore template during the dewatering and polycondensation of silicon sol and then is removed in post-treatment to form the ordered skeleton pores while the system phases are separated into silicon oxide enriched phase and solvent enriched phase under the induction of said additive, which are then treated to form said mutually communicated arteries.
Description
Technical field
The present invention relates to a kind of ordered mesoporous silica gel integral post and method for making and purposes.
Background technology
High performance liquid chromatography (High-performance liquid-chromatography, HPLC) compartment analysis means with fastest developing speed since the seventies in 20th century have been, it is mainly different and separated based on acting force between different samples and moving phase and the stationary phase, and these effects can be distribution, absorption, ion-exchange or the like.According to the difference of these effects, liquid chromatography is broadly divided into following a few class; Distribution chromatography, adsorption chromatography, ion-exchange chromatography, affinity chromatography or the like, different chromatogram modes can be used for different sample systems, can characteristic per sample select different chromatogram type and operator scheme, has extensive applicability, be applied to the separation of multiple material, as the separation of higher boiling, strong polarity, ionic, thermal instability compound, the separation of biologically active material, macromolecular separation or the like.According to estimates, the involatile compound more than 70%, all usable highly effective liquid chromatography compartment analysis.In view of its extensive applicability, good selectivity, high post is imitated, and is widely used in fields such as biochemistry, medical science, pharmacy, chemical, food hygiene, environmental protection tests, commodity inspection and method inspection at present.
In liquid chromatographic system, the core component of decision analysis result and separation degree quality is a chromatographic column, and chromatographic column stationary phase commonly used can be divided into organic substrate and inorganic matrix two big classes at present.The organic substrate stationary phase mainly contains: poly-hydroxymethyl propyl acrylate (PHAM), polyvinyl alcohol (PVA) hydrophilic polymers such as (PVA); Hydrophobic polymers such as polystyrene-divinylbenzene cross-linked copolymer (PS-DVB), polymethacrylate or the ligand-modified PS-DVB of alkyl, PHAM, HEMA, PVA etc.; Glucosan, agarose, cellulose, etc. flexible glue.Inorganic matrix mainly contains: inorganic oxide such as monox, aluminium oxide, zirconia, titanium dioxide, cerium oxide, thoria, magnesium oxide and composite inorganic oxide, molecular sieve, hydroxyapatite, carbon etc.
The preparation of organic substrate stationary phase is simple, chemical stability is good, and surface nature is even, has excellent biological compatibility, be usually used in protein, amino acid whose separation and purification, yet such stationary phase physical strength is not high, and solvent resistance is poor, and resistance to elevated temperatures is relatively poor, when existing, microorganism easily degrades, swelling, distortion easily take place in the use, cause post to imitate decline, post voltage rise height, column life is lower.Compare with the organic substrate stationary phase, inorganic matrix stationary phase compact structure, the physical strength height, high pressure resistant, swellability is little, solvent resistance good, and good stability is used more extensive.
In the inorganic matrix stationary phase, different host materials has different surface propertys, is applicable to different separate object, is usually used in the separation of basic sample solution as zirconia, and titanium dioxide is used for the separation of protein, and graphitic carbon is used for the separation of isomeride.These materials do not have general adaptability because its special surface nature is often better to specific separating substances effect, and comparatively speaking, monox (silica gel) is used more extensive.
Silicon oxide surface character is simple, no lattice imperfection, and energy even distributes, and can effectively avoid the non-specific action of stationary phase and sample and the post that causes is imitated lowly.In addition, there is abundant silicon hydroxyl in the silica gel surface, easily participate in bonding reaction, be beneficial to surface modification, to adapt to different separate object, be used for the separating hydrophobicity compound as the bonding chain alkyl, the bonding short-chain alkyl is used for isolated protein, and the bonding polyol then can be realized the separation of glucide.In a word, with regard to present liquid chromatography, silica gel and modified silica-gel are most widely used stationary phase, also are the most ripe stationary phase.
Silica gel is used as the liquid chromatography stationary phase, and its shape, physical dimension, pore structure and pore size are the key factors that influences chromatogram column efficiency.It is stationary phase that early stage liquid chromatography often adopts amorphous silica gel.Amorphous silica gel is subjected to its shape limitation, can't closely fill, and simultaneously the irregularity of particle causes the disorderly and unsystematic of slit between particle, causes the eddy current diffusion serious, and is low thereby post is imitated, the sample separation difficulty.Along with progress of science and technology, spherical silica gel is extensively synthesized, and is applied to liquid chromatography.Spherical silica gel is that evenly closely filling of chromatographic column laid a good foundation, and provides assurance for increasing the post effect.The early stage spherical silica gel particle diameter that uses is greatly about 30～50 μ m, because it is oversize, the space is darker, and dark excessively hole causes the long of sample mass transfer path, and mass transfer rate is slow, chromatographic peak width, and post is imitated low; The reduction of particle size can effectively reduce the hole degree of depth, reduces the resistance to mass tranfer between moving phase and the stationary phase, imitate thereby increase substantially post, so the chromatograph packing material grain size is tending towards the miniaturization development.Yet grain graininess can not infinitely dwindle, and little grain graininess often causes high post pressure drop, and chromatographic apparatus is had higher requirement.The present liquid chromatography of generally using, its pump pressure upper limit can't satisfy the pressure demand of low particle size chromatographic column mostly at 50MPa.Press with chromatogram column length in view of post to be inversely proportional to, when adopting the small grain size chromatograph packing material, often adopt short chromatographic column remedying the deficiency of pump pressure, yet so, single chromatographic column post is imitated and do not significantly improved.Therefore, present its size of widely used chromatographic column filler is mostly between 5～10 μ m.
Except that shape, the size of filler influences the chromatogram column efficiency, structure, the size in filling surface hole also have profound influence to it.The existence of surface holes can effectively increase the specific surface of stationary phase, provides and the more action site of sample, increase separation selectivity, so chromatograph packing material often is a porous structure.Suitable its pore structure of chromatograph packing material should be that pore size is moderate, narrowly distributing, hole depth as shallow.Different separate object requires different to the aperture, often select filler about the 10nm of aperture for use as micromolecular separation, and the separation of macro-molecular protein then requires aperture size more than 30nm.Pore size should be complementary with the diffusion mass transfer speed of sample, though help mass transfer too greatly, causes that specific surface descends, and causes separation selectivity to reduce; The too little mass transfer that then is unfavorable for, it is lower to cause post to be imitated.Except that aperture size, pore diameter distribution is also most important to chromatogram column efficiency, and pore diameter distribution is narrow, the mass transfer rate unanimity of sample in each hole then, and the chromatographic peak symmetry, post is imitated higher; Pore diameter distribution is wide, and sample is the mass transfer rate difference in different holes, has lag-effect in aperture, the chromatographic peak hangover, and post is imitated lower, so pore diameter distribution is narrow more good more.
Present widely used liquid chromatography stuffing has carried out effective control to particle size, pore size, pore diameter distribution, can provide the post of 80000-100000plate/m to imitate as the silica gel about 5 μ m, can satisfy the demand that common sample is separated, and along with other subject development such as biological chemistry, combination synthetic chemistries, liquid chromatographic system is had higher requirement, and liquid chromatographic system must provide Gao Zhuxiao and the penetrating amount of high sample to adapt to it simultaneously.Traditional liquid chromatography stuffing is because the mass transfer between moving phase and the stationary phase is a diffusion mass transfer, mass transfer rate is slower, the flow velocity of moving phase must be complementary with it, just can provide high post to imitate, if flow rate of mobile phase is higher, and mass transfer rate is slower, chromatographic peak width then, post is imitated low, and the raising of flow rate of mobile phase simultaneously can increase post and press the serviceable life of lowering apparatus and chromatographic column.Though thereby traditional chromatographic column can provide higher post to imitate, and the high penetrating amount of sample can't be provided, separation efficiency is lower.The liquid chromatography stationary phase of a new generation---integral post stationary phase can be realized the Gao Zhuxiao high flow rate under because its unique column structure, for biological chemistry, the development of making up synthetic chemistry etc. provide opportunity.
The nineties in 20th century, Nakanishi etc. took the lead in adopting sol-gel technique to synthesize monolithic silica column, and was used for liquid chromatography.Its synthetic route is as follows: esters of silicon acis, catalyzer, water, polyglycol (or polyvinyl alcohol (PVA)) are mixed, under catalyst action, esters of silicon acis hydrolysis, polycondensation, form the crosslinked back bone network of silicon dioxide, and other components in the system are filled between the network gap, handle the penetrating duct of formation through follow-up oven dry, calcination, continuous silica gel skeleton and the penetrating duct of running through are monolithic silica column.Adopt the synthetic integral post material of this kind method, the hole on its skeleton surface is generally less, is unfavorable for mass transfer when being applied to chromatogram, thereby needs to handle through reaming.Variable concentrations ammoniacal liquor corrosion silica gel skeleton certain hour, dissolve-sedimentation chemistry variation again on the skeleton surface, and the aperture increases, for quick mass transfer provides the basis.The big I of penetrating hole and silicon dioxide skeleton is regulated by selecting suitable reactant to form in the integral post; And the big I of the central hole structure of integral post and specific surface is by to the control of ammonia concn and controlled; Thereby the whole post bed structure of integral post can be regulated and control separately to satisfy different practical applications.
The special construction that this diplopore of integral post distributes has determined the chromatographic performance that it is remarkable.The existence in penetrating hole makes the porosity of integral post increase greatly, thereby the high flow rate of moving phase can't cause high post pressure drop, means that chromatographic resolution can finish under high flow rate of mobile phase; The existence in penetrating hole simultaneously also allows the moving phase integral post inside of directly flowing through, and has realized convective mass transfer.Compare with plain particles filler diffusion mass transfer, the speed of convective mass transfer improves greatly, sample can be between moving phase and stationary phase partition equilibrium fast, no lag-effect, thereby the raising of flow rate of mobile phase, the decline that can't cause post to imitate has promptly realized Gao Zhuxiao under the high flow rate.Traditional compartment analysis speed has been accelerated in the appearance of integral post, and the processing power of sample is greatly improved in the unit interval, for the development of life science, combination synthetic chemistry etc. is laid a good foundation.
Integral post is self-evident with respect to the advantage of filled column, and how simple, convenient and rapid preparation integral post just becomes problem demanding prompt solution.Though it is effective that Nakanishi etc. prepare the method for integral post, its step is too loaded down with trivial details, and the post bed must could obtain suitable mesopore through alkali liquid corrosion, and alkali liquid corrosion can cause pore structure mixed and disorderly, pore diameter distribution broadens, and then causes the inhomogeneity of mass transfer, and the infringement post is imitated.
Summary of the invention
The present invention is exactly at above-mentioned deficiency, and the monolithic silica column that has proposed a kind of brand new is ordered mesoporous silica gel integral post and method for making and purposes, and the gained integral post can avoid alkali liquid corrosion and the pore size distribution that causes broadens, and helps improving chromatogram column efficiency.
Technical scheme provided by the invention is: a kind of ordered mesoporous silica gel integral post, this integral post is made of through hole and monox skeleton, on monox skeleton surface and/or inside the skeleton hole is arranged, arrange in order in the skeleton hole.
Through hole is cross-linked with each other in the above-mentioned integral post, forms permeable structures, and the through hole aperture is between 0.1 μ m～20 μ m.
The monox skeleton is cross-linked with each other in the above-mentioned integral post, forms continuous skeleton structure, and its structure can be sheet, sphere or bar-shaped, and its size is 0.5 μ m～20 μ m.
In the above-mentioned integral post arrangement in silica gel surface and/or inner skeleton hole be six sides or cube etc. orderly ordered structure, skeleton hole pore size is between 2nm～500nm.
The invention allows for the synthetic method of above-mentioned ordered mesoporous silica gel integral post: at 20～80 ℃, the pH value is under 1～12 the condition, contain in the system of the adjuvant that can form ordered structure, silicasol is template with the adjuvant, polycondensation reaction takes place around it, carrying out along with polycondensation reaction, the adjuvant system of inducing be separated and form the silica gel enrichment mutually with the solvent enrichment mutually, the two runs through the logical structure of formation doubly-linked each other, through overaging, washing, dry, subsequent treatment such as calcination can obtain crosslinked silica gel skeleton and the penetrating duct of running through, and orderly adjuvant template is also in washing, be removed in the processes such as calcination, thereby stay orderly meso-hole structure, promptly get the ordered mesoporous silica gel integral post.
Above-mentioned adjuvant is the material that can form ordered structure in solution system, can be single material, polyoxyethylene-PPOX-polyethylene oxide block copolymer such as Pluronic F127 (EO of planting
106PO
70EO
106), Pluronic P123 (EO
20-PO
70-EO
20) etc., also can be multiple material, as the potpourri of polyglycol and quaternary ammonium salt cationic.
Above-mentioned silicasol is by positive esters of silicon acis, chlorosilane hydrolysis, partial hydrolysis, polycondensation, part polycondensation gained.
Above-mentioned baking temperature is 30～80 ℃, and calcination temperature is 280～600 ℃.
Integral post of the present invention can be used as liquid chromatography stationary phase, capillary electric chromatogram stationary phase, catalyzer or catalyst support.
The present invention can form ordered structure with silicasol, in solution adjuvant, water, catalyzer are raw material, adopt sol-gel (sol-gel) technology, and make full use of adjuvant and can form ordered structure and simultaneously can induce the dual-use function that is separated again, synthesized the ordered mesoporous silica gel integral post.The ordered structure that adjuvant forms is served as the mesopore template, just obtain central hole structure after removing in subsequent treatment, can obtain difform central hole structure by selecting different adjuvants, can obtain the mesopore of cubic structure as adopting F127.By adjusting the amount of adjuvant, be allowed to condition at the formwork structure that forms different size in the system, then can obtain the intermediate pore size of modest size.The mesopore that adopts this mode to obtain, the aperture is orderly, and big or small homogeneous has been avoided alkali liquid corrosion and the pore size distribution that causes broadens, and more helps improving chromatogram column efficiency, and step is also more simple simultaneously.The present invention is because its special one-piece construction and orderly central hole structure show great application potential at separation field, catalytic field.By at surface bond or apply different reactive groups, be applied to different separate object,, be used for the separation of the separation of hydrophobic compound as the bonding octadecyl, bonding calixarenes, cyclodextrin are used for the fractionation of chipal compounds, and surface-coated carbon is used for the separation of position isomer etc.
Embodiment embodiment 1: ordered mesoporous silica gel integral post synthetic
1.08g F127 is dissolved in 10ml pH2.0 acetate solution, to Dropwise 5 ml trimethoxy chlorosilane wherein, and vigorous stirring under the ice bath, treat that solution is mixed into an even phase, put into 40 ℃ of reactions of baking oven 36h, aged at room temperature 72h is taken out in the cooling back, treat its air dry and have certain physical strength, water washes out organic template F127, and carefully oven dry is thereafter placed in the muffle furnace, from 40 ℃ with 2 ℃/min temperature programme to 500 ℃ and be incubated 3h, take out and promptly get the ordered mesoporous silica gel integral post.Scanning electron microscope shows the about 2 μ m of silicon skeleton size, the about 5 μ m of through hole size, and pore size determination instrument shark bone frame hole pore size average out to 9.34nm, the transmission electron microscope display aperture is cubic structure, arranges in order.Embodiment 2: ordered mesoporous silica gel integral post synthetic
1.00g polyglycol and 0.24g hexadecyl trimethyl ammonium bromide are dissolved in 10ml pH10.5 ammoniacal liquor, to wherein dripping the 4.5ml methyl silicate, vigorous stirring under the ice bath, treat that solution is mixed into an even phase, put into 25 ℃ of reactions of baking oven 36h, take out the cooling back, aged at room temperature 96h, treat its air dry and have certain physical strength, water washes out organic template polyglycol and hexadecyl trimethyl ammonium bromide, and carefully oven dry is thereafter placed in the muffle furnace, from 40 ℃ with 2 ℃/min temperature programme to 350 ℃ and be incubated 3h, take out and promptly get the ordered mesoporous silica gel integral post.Scanning electron microscope shows the about 4 μ m of silicon skeleton size, the about 3 μ m of through hole size, and pore size determination instrument shark bone frame hole pore size average out to 13.30nm, the transmission electron microscope display aperture is sexangle and arranges in order.Embodiment 3: the ordered mesoporous silica gel integral post is used for the separation of hydrophobic compound
Integral post surface bond octadecyl group: after 5mol/L hydrochloric acid cleans integral post post bed 2h of the present invention, secondary water cleans to neutral, fully after the drying, be immersed in the mixed liquor of 5.0ml octadecyltriethoxy silane and 50ml toluene, backflow 10h under the nitrogen atmosphere then uses toluene, methanol wash successively.With this integral post is stationary phase, with methanol (85/15, v/v) be moving phase, flow velocity 5ml/min reaches baseline separation in benzene, toluene, ethylbenzene, the propyl benzene 3min; With methanol (60/40, v/v) be moving phase, when flow velocity is 3ml/min,, reach baseline separation in naphthylamines and the biphenylamine 2min to methylaniline.Embodiment 4: the ordered mesoporous silica gel integral post is used for chiral resolution
Integral post surface bond beta-schardinger dextrin-group: after 5mol/L hydrochloric acid cleaned integral post post bed 2h of the present invention, secondary water cleaned to neutral, and fully dry back is standby.The beta-schardinger dextrin-5g of vacuum drying learns from else's experience, with anhydrous dimethyl formamide (DMF) is solvent, and NaH is a catalyzer, at room temperature stirring reaction 1h, the unreacted solid of elimination adds KH-560 (γ-(glycidoxy) propyl trimethoxy silicane) 10ml in filtrate.Integral post is immersed in this solution, behind 110 ℃ of reaction 10h, uses DMF, methyl alcohol, washing successively.With this integral post is stationary phase, with 0.5%TEAA/ alcohol (98/2, v/v) be moving phase, the fine styrax raceme that split when flow velocity is 2ml/min.Embodiment 5: the ordered mesoporous silica gel integral post is used for the separation of position isomer
With F127 is that the synthetic ordered mesoporous silica gel integral post of template is a matrix, behind its surface and inside deposition carbon, obtain the mesoporous silica gel integral post that carbon applies, with this integral post with suitable external bobbin seal and insert in the liquid chromatographic system, with acetonitrile: water (50: 50) is moving phase, flow velocity 3ml/min, with adjacent,, para-nitrotoluene is probe, the detection wavelength is 254nm, investigated carbon and applied the separation case of mesoporous silica gel integral post position isomer, adjacent in the 5min,, para-nitrotoluene obtained baseline separation.
Claims (9)
1. ordered mesoporous silica gel integral post, it is characterized in that: this integral post is made of through hole and monox skeleton, on monox skeleton surface and/or inside the skeleton hole is arranged, arrange in order in the skeleton hole.
2. integral post according to claim 1, it is characterized in that: through hole is cross-linked with each other, and forms permeable structures, and the through hole aperture is between 0.1 μ m～20 μ m.
3. integral post according to claim 1 and 2 is characterized in that: the monox skeleton is cross-linked with each other, and forms continuous skeleton structure, and its structure is sheet, sphere or bar-shaped, and its size is 0.5 μ m～20 μ m.
4. integral post according to claim 1 and 2 is characterized in that: the arrangement in skeleton hole is six sides or cubic structure, and skeleton hole pore size is between 2nm～500nm.
5. the method for making of the described integral post of claim 1, it is characterized in that: at 20～80 ℃, the pH value is under 1～12 the condition, with the adjuvant that can form ordered structure is template, silicasol is added in the adjuvant around adjuvant dehydration polycondensation, form cross-linked structure, handle the ordered mesoporous silica gel integral post material that obtains through overaging, washing, drying, calcination then.
6. method for making according to claim 5 is characterized in that: the adjuvant that can form ordered structure is polyoxyethylene-PPOX-polyethylene oxide block copolymer, or the potpourri of polyglycol and quaternary ammonium salt cationic.
7. according to claim 5 or 6 described method for makings, it is characterized in that: above-mentioned baking temperature is 30～80 ℃, and calcination temperature is 280～600 ℃.
8. according to claim 5 or 6 described method for makings, it is characterized in that: used silicasol is the hydrolysate or the partial hydrolysate of positive esters of silicon acis, chlorosilane.
9. the described integral post of claim 1 is as liquid chromatography stationary phase, capillary electric chromatogram stationary phase, catalyzer or catalyst support.
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Cited By (17)
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| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN100529754C (en) * | 2006-11-10 | 2009-08-19 | 中国科学院山西煤炭化学研究所 | A method for separating benzene and homologen |
| CN101975835A (en) * | 2010-10-13 | 2011-02-16 | 天津大学 | Ordered pore-structured silica gel monolithic column and preparation method thereof |
| CN101525137B (en) * | 2008-03-06 | 2011-07-13 | 中国石油化工股份有限公司 | Method for preparing mesoporous/macroporous composite pore structural silicone monolith |
| CN101804336B (en) * | 2009-02-16 | 2012-08-08 | 索尼公司 | Biomicromolecule-separating, monolithic silica column and its production process, and separation method of biomicromolecules |
| CN102883806A (en) * | 2010-03-15 | 2013-01-16 | F·帕尔芒捷 | Multicapillary monolith |
| CN103170161A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybridized monolithic column |
| CN103387238A (en) * | 2013-06-25 | 2013-11-13 | 上海师范大学 | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO |
| CN103721669A (en) * | 2013-12-10 | 2014-04-16 | 天津大学 | Preparation method of silica gel hybridization capillary tube monolithic column |
| CN104028007A (en) * | 2013-03-05 | 2014-09-10 | 中国科学院大连化学物理研究所 | Imidazole ionic liquid capillary monolithic column, and making method and application thereof |
| CN105699559A (en) * | 2016-03-30 | 2016-06-22 | 中国科学院兰州化学物理研究所 | Preparation method of chiral gas chromatographic column taking nano-cellulose or nano-starch derivatives as stationary phase |
| CN105944682A (en) * | 2016-07-04 | 2016-09-21 | 北京理工大学 | Preparation method of organic gas mesoporous adsorbent |
| CN110575683A (en) * | 2019-08-29 | 2019-12-17 | 福州佳宸生物科技有限公司 | hydroxyapatite functionalized monolithic column prepared by in-situ mineralization method |
| CN111617516A (en) * | 2020-07-10 | 2020-09-04 | 安徽师范大学 | Silica gel integral open-tube capillary column with metal wire as template and preparation method thereof |
| CN112571817A (en) * | 2020-11-24 | 2021-03-30 | 浙江清华柔性电子技术研究院 | Ordered controllable porous silica gel and preparation method thereof |
| CN113522256A (en) * | 2021-07-19 | 2021-10-22 | 中国科学院兰州化学物理研究所 | Preparation and application of hydrogel @ silicon dioxide liquid chromatography filler |
| CN115254074A (en) * | 2022-09-26 | 2022-11-01 | 晋江精纯科技有限公司 | Preparation method of monodisperse pore passage controllable through-flow type chromatographic microspheres |
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2003
- 2003-05-19 CN CN 03119094 patent/CN1213799C/en not_active Expired - Fee Related
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| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN100529754C (en) * | 2006-11-10 | 2009-08-19 | 中国科学院山西煤炭化学研究所 | A method for separating benzene and homologen |
| CN101525137B (en) * | 2008-03-06 | 2011-07-13 | 中国石油化工股份有限公司 | Method for preparing mesoporous/macroporous composite pore structural silicone monolith |
| CN101804336B (en) * | 2009-02-16 | 2012-08-08 | 索尼公司 | Biomicromolecule-separating, monolithic silica column and its production process, and separation method of biomicromolecules |
| CN102883806A (en) * | 2010-03-15 | 2013-01-16 | F·帕尔芒捷 | Multicapillary monolith |
| CN102883806B (en) * | 2010-03-15 | 2016-05-04 | F·帕尔芒捷 | Multiple capillary entirety |
| CN101975835A (en) * | 2010-10-13 | 2011-02-16 | 天津大学 | Ordered pore-structured silica gel monolithic column and preparation method thereof |
| CN101975835B (en) * | 2010-10-13 | 2013-04-10 | 天津大学 | Ordered pore-structured silica gel monolithic column and preparation method thereof |
| CN103170161A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybridized monolithic column |
| CN103170161B (en) * | 2011-12-22 | 2014-09-24 | 中国科学院大连化学物理研究所 | Preparation method of organic-inorganic hybridized monolithic column |
| CN104028007A (en) * | 2013-03-05 | 2014-09-10 | 中国科学院大连化学物理研究所 | Imidazole ionic liquid capillary monolithic column, and making method and application thereof |
| CN103387238B (en) * | 2013-06-25 | 2015-04-08 | 上海师范大学 | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO |
| CN103387238A (en) * | 2013-06-25 | 2013-11-13 | 上海师范大学 | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO |
| CN103721669A (en) * | 2013-12-10 | 2014-04-16 | 天津大学 | Preparation method of silica gel hybridization capillary tube monolithic column |
| CN105699559A (en) * | 2016-03-30 | 2016-06-22 | 中国科学院兰州化学物理研究所 | Preparation method of chiral gas chromatographic column taking nano-cellulose or nano-starch derivatives as stationary phase |
| CN105944682A (en) * | 2016-07-04 | 2016-09-21 | 北京理工大学 | Preparation method of organic gas mesoporous adsorbent |
| CN110575683A (en) * | 2019-08-29 | 2019-12-17 | 福州佳宸生物科技有限公司 | hydroxyapatite functionalized monolithic column prepared by in-situ mineralization method |
| CN111617516A (en) * | 2020-07-10 | 2020-09-04 | 安徽师范大学 | Silica gel integral open-tube capillary column with metal wire as template and preparation method thereof |
| CN112571817A (en) * | 2020-11-24 | 2021-03-30 | 浙江清华柔性电子技术研究院 | Ordered controllable porous silica gel and preparation method thereof |
| CN113522256A (en) * | 2021-07-19 | 2021-10-22 | 中国科学院兰州化学物理研究所 | Preparation and application of hydrogel @ silicon dioxide liquid chromatography filler |
| CN113522256B (en) * | 2021-07-19 | 2022-06-21 | 中国科学院兰州化学物理研究所 | Preparation and application of hydrogel @ silicon dioxide liquid chromatography filler |
| CN115254074A (en) * | 2022-09-26 | 2022-11-01 | 晋江精纯科技有限公司 | Preparation method of monodisperse pore passage controllable through-flow type chromatographic microspheres |
| CN115254074B (en) * | 2022-09-26 | 2023-02-03 | 晋江精纯科技有限公司 | Preparation method of monodisperse pore controllable through-flow type chromatographic microsphere |
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