CN1943848A - Hydrophilic forward chromatographic column, filler and separating method - Google Patents
Hydrophilic forward chromatographic column, filler and separating method Download PDFInfo
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- CN1943848A CN1943848A CNA2006100155845A CN200610015584A CN1943848A CN 1943848 A CN1943848 A CN 1943848A CN A2006100155845 A CNA2006100155845 A CN A2006100155845A CN 200610015584 A CN200610015584 A CN 200610015584A CN 1943848 A CN1943848 A CN 1943848A
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- chromatographic column
- hydrophilic
- filler
- silica gel
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- 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
- B01D15/30—Partition chromatography
- B01D15/305—Hydrophilic interaction chromatography [HILIC]
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Abstract
The present invention relates to hydrophilic forward chromatographic column, filler and separation method. The hydrophilic forward chromatographic column is silica gel material with bonded amido radical or carbamido radical, and is filled with filler in its inside pipe communicated with pipeline for liquid to pass through. Compared with traditional Hilic chromatographic column, the present invention has the advantages of high stability, high reproductivity and single separating mechanism. The present invention is used in separating mixture with organic compound and possesses powerful adsorption and separation on polar compound.
Description
Technical field
The invention belongs to technical field of analytical chemistry, particularly hydrophilic forward chromatographic column, filler and separation method.
Background technology
At Pharmaceutical Analysis and purifying, in the analysis of environmental analysis and part pesticide residue, the chromatography of the compound that hydrophily is stronger is a difficult problem in the analytical test field always.Particularly at drug metabolism study, in nucleic acid and the polypeptide drugs research, this problem is more apparent outstanding.
Wherein, use the methods of ion pairs traditionally for easier Ionized organic acid or organic base more.Promptly in flowing mutually, add a large amount of ion-pairing agents, to realize the required separation that obtains.There are many shortcomings that self can't overcome in this conventional method.Mainly be the system complexity, the method poor reproducibility, equilibration time is long etc.The more important thing is that present liquid chromatogram and mass spectrometry have become the popular tendency of liquid chromatogram development, the ion pair method then is difficult to use on liquid chromatogram and mass spectrometry equipment.Therefore, some producers forward chromatographic column of beginning to develop the reverse-phase chromatographic column that can be complementary with 100% aqueous solution and can flowing and be complementary mutually with high water-based in the world in recent years, the scope of application of corresponding positive and reverse-phase chromatographic column is obviously expanded, thereby do not used the ion-pairing agent condition also can carry out liquid-phase chromatographic analysis the stronger compound of hydrophily.
Relevant chromatographic material and the chromatographic column reported mainly can be divided into two classes: a class be can with the reverse-phase chromatographic column of 100% aqueous solution coupling, claim the AQ chromatographic column again; Another kind of be can with the moisture higher forward chromatographic column that flows and be complementary mutually, claim the Hilic chromatographic column again.So far the HILIC post of having reported comprises the silicagel column of no bonding, aminopropyl bonded silica gel post, ion exchange column and γ hydroxyl bonding silicagel column.But first three is planted chromatographic column and has stability and poor reproducibility, separating mechanism complexity problems such as (ion-exchange and polarity absorption mixing mechanisms); A little less than then a kind of effect of and polar compound, thereby centrifugation is relatively poor.So the finishing of development of new functional group, reappearance and stability are preferably arranged, the HILIC chromatographic column that separating mechanism is single is highly significant.
Summary of the invention
According to the deficiencies in the prior art, the invention provides hydrophilic forward chromatographic column, filler and separation method.Novel positive (Hilic) chromatographic column of the mobile phase of the born high water content of this hydrophilic functional groups finishing.This invention is modified to reach the traditional silicagel column of solution the low activity silica gel surface of treated mistake near neutral, strong polarity hydrophilic radical with one, and nh 2 column is unstable in high aqueous medium, poor reproducibility, separating mechanism complicated problems.Its characteristics comprise: in high water-based flows mutually stability and separating property are preferably arranged; Unique selectivity; Single separation mechanism.
Concrete technology is as follows:
Hydrophilic forward chromatographic column filler of the present invention is that bonding has amide groups or urea groups class functional group on silica gel material.
Used silica gel material is for adopting spherical porous silica gel usually, and the particle diameter of spherical porous silica gel is the 1-50 micron, and average pore size is the 5-30 nanometer.
The functionalized silane of amide groups or urea groups class functional group's amide groups or urea groups;
Spendable functionalized silane comprises:
ROSi(CH
3)
2CH
2CH
2NHCONH
2，ROSi(CH
3)
2CH
2CH
2CONH
2，ROSi(CH
3)
2CH
2CH
2CH
2NHCONH
2，
ROSi(CH
3)
2CH
2CH
2CH
2CONH
2，ROSi(CH
3)
2CH
2CH
2CH
2OCONHR’，
(RO)
2Si(CH
3)CH
2CH
2CH
2NHCONH
2，(RO)
3SiCH
2CH
2CH
2NHCONH
2，(RO)3SiCH2CH2CONH2，
(RO)
2Si(CH
3)CH
2CH
2CONH
2，(RO)
3SiCH
2CH
2CH
2OCONHR’；
Wherein: R can be common alkyl such as methyl, ethyl, propyl group, or simple aromatic group such as phenyl; R ' is generally methyl or ethyl.Also can use the similar functionalized silane that reaches 6 methylene carbochains.
Filler of the present invention is directly to react with the functionalized silane that comprises specific amide groups or urea groups by spherical porous silica gel to make.
The functionalized silane of amide groups of the present invention or urea groups is as (RO)
3SiCH
2CH
2CONH
2Silica gel is preferably high-purity silica gel, and metals content impurity＜100ppm is with non-characteristic suction-operated and the raising bonding coverage rate that reduces the surface.Bonding coverage rate＞1.5mol/m
2, preferably be higher than 2mol/m
2Can use hydrofluoric acid or hydrochloric acid to surface treatment, reduce tenor and increase the silicon hydroxy radical content; Or use orthosilicic acid fat that hydrolysis is again handled on the surface, reach similar purpose.The bonding coverage rate is at 1.5mol/m
2To 3.5mol/m
2, preferably be higher than 2mol/m.The bonding degree is 0.1-3mmol/g.
The universal architecture of silica gel material as shown in Figure 1 behind its bonding: can see clearly that from Fig. 1 the bore area 5 of bonding, separated material are resolved balance by absorption in the above and realized separating; Silica gel skeleton 6 guarantees whole stability; Hole path 7, make separated object can reach functionalized inner surface. utilize filler of the present invention to prepare hydrophilic forward chromatographic column of the present invention, the structural representation of chromatographic column is as shown in Figure 2: filler 3 is filled cylindrical metal or plastics column jeckets in the column jeckets 2, the outside, two ends has interior rib-loop to link to each other with pipeline, the inboard, two ends has sieve plate 4 to prevent that solid packing from leaking outside, but liquid is passed through; Be filled with filler of the present invention in the column jecket, resulting filler after homogenate, under high pressure pours into column jecket, puts sieve plate then, tightens column cap.Just obtain novel hydrophilic positive (HILIC) chromatographic column among the present invention.Gc column tube can be general all kinds of liquid chromatogram column jeckets, and the column jecket internal diameter is usually at the 1-100 millimeter, pipe range 20-300 millimeter
Adopt hydrophilic forward chromatographic column of the present invention, can be used for positive or reversed-phase liquid chromatography and separate.But its normal-phase chromatography that is applied as under the aqueous mobile phase condition separates.Concrete grammar is as follows: as shown in Figure 3: 1) with the constant current liquid phase pump, sampling valve, chromatographic column and detector are cascaded with stainless steel tube or plastic tube, 2) sample inlet opening (1) to be separated is injected the sample cell that sampling valve links to each other, 3) starting sampling valve makes sample cell be connected with chromatographic column with infusion pump, 4) flow bring sample into chromatographic column and separate 5) each component of separating is detected and shows by detector the time.
Chromatographic column of the present invention is applicable to degree such as grade or gradient separations, and the component ratio of the phase that promptly flows can keep the constant degree such as grades or the gradient of change according to certain rules in whole separation process.Can contain 0-100% water in flowing mutually.When moisture, other composition should can dissolve each other with water.Organic solvent commonly used has (but being not limited to) methyl alcohol, acetonitrile, isopropyl alcohol, ethanol, tetrahydrochysene skin sirloin; Can add the acid of a spot of 0-100mmol/l solubility, alkali or other buffer salt in flowing mutually.The phase pH scope that flows should be preferably between the 2-8 to guarantee certain chromatographic column stability between 1-10.The serviceability temperature scope is preferably in 20-50 ℃ greatly about 5-80 ℃.Separated characterization compound is generally (but being not limited to) water-soluble stronger organic compound.As: organic base, organic acid, acid amides, semi-annular jade pendant acid amides, organic urea, semi-annular jade pendant uride, carbohydrate, nucleic acid, polypeptide, polyphenol compound etc.Can contain the acid that dissolves in mobile phase of 1-100mmol in flowing mutually, alkali or salt are as compound; The pH scope is 1-10, is preferably in 2-8.The liquid chromatograph of chromatographic column; 2) use and to contain water and the organic solvent that can dissolve each other with water for flowing mutually.
Characteristics of the present invention are: key has been to use novel amide groups or urea groups class functional group as silica gel surface bond phase, thereby obtain desired, based on traditional Hilic chromatographic column of nonbonding silica gel or nh 2 column more advantages of excellent stability, reappearance and single separation mechanism.Be characterized in containing CONH
2Or CONHR (R is an alkyl) functional group, have the ability of very strong polarity and formation hydrogen bond.And be the group of neutrality or utmost point weak acid alkalescence.Be used on liquid chromatogram, separating the mixture of organic compound.Polar compound there are very strong absorption affinity and separating power; Can with contain O, N, P, the organic matter of S forms hydrogen bond.
Description of drawings
Fig. 1: filler schematic diagram;
Fig. 2: chromatographic column schematic diagram;
Fig. 3: chromatographic column separation method schematic diagram;
The separating effect schematic diagram of Fig. 4: embodiment 13;
The separating effect schematic diagram of Fig. 5: embodiment 14;
The separating effect schematic diagram of Fig. 6: embodiment 15.
The specific embodiment
Embodiment 1: preparation of silica gel
1240ml pure water, 26g red fuming nitric acid (RFNA), 840g Ludox (7.1%) and 37g urea are added in the 6000ml beaker successively, be stirred to the urea dissolving.
Under stirring fast, add 100g formaldehyde, continued to stir soon 25 ℃ of room temperatures 15 seconds.
Leave standstill.10-15min separates out white precipitate.
Placed 5-8 hour, and skimmed liquid, add pure water and stir, left standstill 30 minutes, skim liquid.
With the acetone washing, 3 times, filter.100 ℃ in vacuum, oven dry in 12 hours.Microscopy is 4-5 μ m, sphere, evenly.
High-temperature firing, 300 ℃, 3-4h; 500 ℃, 2-3h; 800 ℃, 2h; 1000 ℃, 3h.
Get white solid 53 grams after the burning-out; 400 milliliters of 0.5M HF heated in water solution to 90 ℃ 4 hours; Filter, 200 ml pure waters washing 2 times, 200 milliliters of acetone wash 3 times; Vacuum drying 8 hours.Microscopy is 5 μ m spheries.Aperture 8nm, specific surface: 198m
2/ g
Embodiment 2:
Silica gel 50 grams that prepare among the embodiment 1 add tetraethoxysilane 4 grams, triethylamine 1 gram, 200 milliliters of toluene; Electronic stirring heating down refluxed 16 hours for 110 ℃; Filter, use 100 milliliters of toluene wash 3 times at every turn, at every turn with 100 milliliters of washings of methyl alcohol 3 times, the volume ratio of methyl alcohol and water is stirring in 1: 1, uses toluene wash 3 times more again, and each 150 milliliters, methanol wash 3 times, each 100 milliliters; 100 ℃ of vacuum drying 12 hours; Get white spherical solid powder 52 grams.C％＝0.2.
Embodiment 3:
Silica gel 50 grams that prepare among the embodiment 1 add tetraethoxysilane 2 grams, methyl three second methoxy silane 2 grams, triethylamine 1 gram, 200 milliliters of toluene; Electronic stirring heating down refluxed 16 hours for 110 ℃; Filter, use 100 milliliters of toluene wash 3 times at every turn, at every turn with 100 milliliters of washings of methyl alcohol 3 times, the volume ratio of methyl alcohol and water is stirring in 1: 1, uses toluene wash 3 times more again, and each 150 milliliters, methanol wash 3 times, each 100 milliliters; 100 ℃ of vacuum drying 12 hours; Get white spherical solid powder 51 grams.C％＝1.1.
Embodiment 4:
White solid 20 grams that prepare among the embodiment 2 add EtOSi (CH
3)
2CH
2CH
2CONH
210 grams, triethylamine 1 gram, 100 milliliters of toluene; Electronic stirring heating down refluxed 18 hours for 110 ℃; Filter, use 100 milliliters of toluene wash 3 times at every turn, at every turn with 100 milliliters of washings of methyl alcohol 3 times, the volume ratio of methyl alcohol and water is stirring in 1: 1, uses toluene wash 3 times more again, and each 150 milliliters, methanol wash 3 times, each 100 milliliters; 100 ℃ of vacuum drying 10 hours; Get white spherical solid powder 22 grams.C％＝3.2，N％＝0.8。(0.5mmol/g)。
Embodiment 5:
White solid 20 grams that prepare among the embodiment 3 add EtOSi (CH
3)
2CH
2CH
2NHCONH
210 grams, triethylamine 1 gram, 100 milliliters of toluene; Later stage technology is identical with embodiment 4; Get white spherical solid powder 20 grams.C％＝4.8，N％＝1.8。(0.6mmol/g)
Embodiment 6:
White solid 20 grams that prepare among the embodiment 2 add (EtO)
3SiCH
2CH
2CH
2NHCONH
220 grams, triethylamine 1 gram, 100 milliliters of toluene; Later stage technology is identical with embodiment 1; Get white spherical solid powder 21 grams.C％＝3.8，N％＝1.9。(0.8mmol/g)
Embodiment 7:
White solid 20 grams that prepare among the embodiment 1 add (PhO)
3SiCH
2CH
2CONH
220 grams, triethylamine 1 gram, 100 milliliters of toluene; Later stage technology is identical with embodiment 4; Get white spherical solid powder 22 grams.C％＝1.8，N％＝0.6。(0.4mmol/g)
Embodiment 8:
Ball-type silica gel 30 grams (30nm average pore size, 5 μ m average grain diameters) add EtOSi (CH
3)
2CH
2CH
2CONH
28 grams, triethylamine 1 gram, 200 milliliters of toluene; Electronic stirring heating down refluxed 18 hours for 110 ℃; Later stage technology is identical with embodiment 4; Get white spherical solid powder 29 grams.C％＝1.4，N％＝0.4。(0.2mmol/g)
Embodiment 9:
Unformed silica gel 600 grams (6nm average pore size, 50 μ m average grain diameters) add 500 grams (EtO)
3SiCH
2CH
2CH
2NHCONH
2, triethylamine 50 grams, 2000 milliliters of toluene; Electronic stirring heating down refluxed 18 hours for 110 ℃; Filter, 1000 milliliters of washings of toluene 3 times, 1000 milliliters of washings of methyl alcohol 3 times, the volume ratio of methyl alcohol and water is stirring in 1: 1,1500 milliliters of washings of toluene 3 times, 1000 milliliters of washings of methyl alcohol 3 times; 100 ℃ of vacuum drying, 10 hours; Get white spherical solid powder 630 grams.C％＝7.8，N％＝4.3。(1.5mmol/g)
Embodiment 10:
Resulting white solid 3 grams among the embodiment 5,30 milliliters of methyl alcohol stir and make slurries.Under 500 kg/cm pressure, use the methyl alcohol can to advance 1 4.6 millimeters (internal diameter) * 250 millimeter (length) chromatographic column.
Embodiment 11:
Resulting white solid 340 grams among the embodiment 9,1000 milliliters of methyl alcohol stir and make slurries.Under 100 kg/cm pressure, use the methyl alcohol can to advance 1 50 millimeters (internal diameter) * 250 millimeter (length) chromatographic column.
Resulting white solid 0.5 gram among the embodiment 5,10 milliliters of methyl alcohol stir and make slurries.Under 300 kg/cm pressure, use the methyl alcohol can to advance 1 2.1 millimeters (internal diameter) * 50 millimeter (length) chromatographic column.
Embodiment 13:
Resulting chromatographic column among the embodiment 10 is used Tianjin, island 10A liquid chromatographic system, under following condition, a series of nitroaniline compounds are separated 4 chromatographic peaks that obtain as shown in Figure 4, be respectively: nitrobenzene 8, ortho-nitraniline 9, meta nitro aniline 10 and paranitroanilinum 11.Imitating the number of plates with the paranitroanilinum test pole is 21225, and tailing factor is 1.10.
Test condition
Sample nitroaniline compounds
91.8% chlorobutane mutually flows; 8% methyl alcohol; 0.2% water
Flow velocity 1.0mL/min
35 ℃ of temperature
Detect UV 254nm
Result's (paranitroanilinum):
| Retention time (branch) | 7.015 |
| Theoretical cam curve | 21225 |
| Tailing factor (5%) | 1.10 |
| Pressure (MPa) | 6.6 |
Embodiment 14:
With Tianjin, island 10A liquid chromatograph, prepared chromatographic column in the example 10, the urea pyrimidine is separated with acetyl group urea pyrimidine mixture.Obtain separating resulting in following condition: acetylcytosine 12 as Fig. 5; Cytimidine 13; With the cytimidine theory of testing number of plates is 12030; Retention index K '=1.2; And separating degree α between the acetylcytosine (cytimidine/N-acetylcytosine) is 1.5.
Chromatographic column: HILIC, 5um, 4.6 * 150mm
Phase flows: 10mmol sodium dihydrogen phosphate (pH7.0)/acetonitrile=35/65
Temperature: 45 ℃
Detect: UV 254nm
Sample: cytimidine/acetylcytosine
Embodiment 15
With Tianjin, island 10A liquid chromatograph, prepared chromatographic column in the example 10, analyze jinggangmycin purity.Used condition is: chromatographic column: 4.6 * 250mm, 5um; Phase flows: acetonitrile/water gradient 85/15-40/60%, 30 minutes; Temperature: 25 ℃; Detect: UV 210nm.Effectively separated between measured matter jinggangmycin and impurity.Carry out normalization with peak area and calculate jinggangmycin purity: 76%, chromatogram is seen Fig. 6, visible peak is a jinggangmycin 14.
The present invention open and proposition and hydrophilic forward chromatographic column, filler and separation method, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, technological parameter realize.The present invention and hydrophilic forward chromatographic column, filler and separation method are described by preferred embodiment, person skilled obviously can be changed or suitably change and combination as herein described and hydrophilic forward chromatographic column, filler and separation method in not breaking away from content of the present invention, spirit and scope, realizes the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (10)
1. a hydrophilic forward chromatographic column filler is characterized in that bonding has amide groups or urea groups class functional group on silica gel material.
2. hydrophilic forward chromatographic column filler as claimed in claim 1 is characterized in that described silica gel material for adopting spherical porous silica gel usually, and the particle diameter of spherical porous silica gel is the 1-50 micron, and average pore size is the 5-30 nanometer.
3. hydrophilic forward chromatographic column filler as claimed in claim 1 is characterized in that the functionalized silane of described amide groups or urea groups class functional group's amide groups or urea groups.
4. hydrophilic forward chromatographic column filler as claimed in claim 3 is characterized in that described functionalized silane comprises:
ROSi(CH
3)
2CH
2CH
2NHCONH
2，ROSi(CH
3)
2CH
2CH
2CONH
2，ROSi(CH
3)
2CH
2CH
2CH
2NHCONH
2，
ROSi(CH
3)
2CH
2CH
2CH
2CONH
2，ROSi(CH
3)
2CH
2CH
2CH
2OCONHR’，
(RO)
2Si(CH
3)CH
2CH
2CH
2NHCONH
2，(RO)
3SiCH
2CH
2CH
2NHCONH
2，(RO)
3SiCH
2CH
2CONH
2，
(RO)
2Si(CH
3)CH
2CH
2CONH
2，(RO)
3SiCH
2CH
2CH
2OCONHR’；
Wherein: R can be common alkyl such as methyl, ethyl, propyl group, or simple aromatic group such as phenyl; R ' is generally methyl or ethyl.
Also can use the similar functionalized silane that reaches 6 methylene carbochains.
5. hydrophilic forward chromatographic column filler as claimed in claim 2 is characterized in that described silica gel is high-purity silica gel, and metals content impurity＜100ppm is with non-characteristic suction-operated and the raising bonding coverage rate that reduces the surface.Bonding coverage rate 1.5mol/m
2To 3.5mol/m
2
6. the prepared hydrophilic forward chromatographic column of filler as claimed in claim 1 is characterized in that filling filler 3 in column jecket 2, the outside, column jecket two ends has interior rib-loop to link to each other with pipeline, and the inboard, two ends has sieve plate 4 to prevent that solid packing from leaking outside.
7. the prepared hydrophilic forward chromatographic column of filler as claimed in claim 6 is characterized in that described chromatographic column column jecket internal diameter usually at the 1-100 millimeter, pipe range 20-300 millimeter.
8. adopt the chromatography separating method of the described hydrophilic forward chromatographic column of claim 6, its feature makes step as follows: 1) constant current liquid phase pump, sampling valve, chromatographic column and detector are cascaded with stainless steel tube or plastic tube, 2) sample to be separated is injected the sample cell that links to each other with sampling valve through inlet opening (1), 3) starting sampling valve makes sample cell be connected with chromatographic column with infusion pump, 4) flow bring sample into chromatographic column and separate 5) each component of separating is detected and shows by detector the time.
9. the chromatography separating method of hydrophilic forward chromatographic column as claimed in claim 9 is characterized in that describedly containing 0-100% water, the acid of 0-100mmol/l solubility, alkali or other buffer salt in flowing mutually; When moisture, other composition should can dissolve each other with water; The pH scope is 1-10, and temperature range is at 5-80 ℃.
10. the chromatography separating method of hydrophilic forward chromatographic column as claimed in claim 9 is characterized in that described mobile phase pH scope is 2-8, and temperature range is at 20-50 ℃, can contain the flow acid of phase of dissolving in of 1-100mmol in flowing mutually, and alkali or salt are as compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100155845A CN100496705C (en) | 2006-09-05 | 2006-09-05 | Hydrophilic NPLC, filler and separating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100155845A CN100496705C (en) | 2006-09-05 | 2006-09-05 | Hydrophilic NPLC, filler and separating method |
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| Publication Number | Publication Date |
|---|---|
| CN1943848A true CN1943848A (en) | 2007-04-11 |
| CN100496705C CN100496705C (en) | 2009-06-10 |
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ID=38043631
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721980B (en) * | 2009-11-13 | 2012-04-18 | 天津博纳艾杰尔科技有限公司 | Mixed fillers of liquid-phase chromatographic column and chromatographic column |
| CN103055827A (en) * | 2013-01-24 | 2013-04-24 | 重庆理工大学 | Chromatographic sheet with self-repairing function and preparation method thereof |
| CN113976187A (en) * | 2021-11-08 | 2022-01-28 | 天津中科博蕴生物技术有限公司 | Method for separating nucleic acid by adopting silica gel bonded matrix |
-
2006
- 2006-09-05 CN CNB2006100155845A patent/CN100496705C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721980B (en) * | 2009-11-13 | 2012-04-18 | 天津博纳艾杰尔科技有限公司 | Mixed fillers of liquid-phase chromatographic column and chromatographic column |
| CN103055827A (en) * | 2013-01-24 | 2013-04-24 | 重庆理工大学 | Chromatographic sheet with self-repairing function and preparation method thereof |
| CN113976187A (en) * | 2021-11-08 | 2022-01-28 | 天津中科博蕴生物技术有限公司 | Method for separating nucleic acid by adopting silica gel bonded matrix |
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| Publication number | Publication date |
|---|---|
| CN100496705C (en) | 2009-06-10 |
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Denomination of invention: Hydrophilic forward chromatographic column, filler and separating method Effective date of registration: 20101109 Granted publication date: 20090610 Pledgee: Tianjin TEDA Small Enterprise Credit Guarantee Center Pledgor: Tianjin Bonna-Agela Technologies Co., Ltd. Registration number: 2010990000955 |
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Denomination of invention: Hydrophilic forward chromatographic column, filler and separating method Effective date of registration: 20120305 Granted publication date: 20090610 Pledgee: Tianjin TEDA Small Enterprise Credit Guarantee Center Pledgor: Tianjin Bonna-Agela Technologies Co., Ltd. Registration number: 2012990000075 |
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Denomination of invention: Hydrophilic forward chromatographic column, filler and separating method Effective date of registration: 20130315 Granted publication date: 20090610 Pledgee: Tianjin TEDA Small Enterprise Credit Guarantee Center Pledgor: Tianjin Bonna-Agela Technologies Co., Ltd. Registration number: 2013990000149 |
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Denomination of invention: Hydrophilic forward chromatographic column, filler and separating method Effective date of registration: 20140321 Granted publication date: 20090610 Pledgee: Tianjin TEDA Small Enterprise Credit Guarantee Center Pledgor: Tianjin Bonna-Agela Technologies Co., Ltd. Registration number: 2014990000185 |
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