CN103721567B - A kind of sample solution purifier based on hollow fiber nanofiltration membrane material - Google Patents
A kind of sample solution purifier based on hollow fiber nanofiltration membrane material Download PDFInfo
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- CN103721567B CN103721567B CN201310729940.XA CN201310729940A CN103721567B CN 103721567 B CN103721567 B CN 103721567B CN 201310729940 A CN201310729940 A CN 201310729940A CN 103721567 B CN103721567 B CN 103721567B
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Abstract
The invention discloses a kind of sample solution purifier based on hollow fiber nanofiltration membrane material, this device comprises a detachable plastic sleeve pipe be made up of two plastic tubes varied in size and is fixed on hollow fiber nanofiltration membrane on interior pipe.This hollow fiber nanofiltration membrane has the physical filtering effect of Nano grade and the fenestra of chemisorption, the analysans of small-molecular-weight is made to pass through fenestra with the driving force of centrifugal force or syringe, pump, the sample pretreatment during analysis detection in the fields such as biology, chemistry, food can be widely used in, it is swift and convenient to operate, simple, treated sample has impurity and disturbs few feature.This device, as standalone module unit, can realize the combination of multiple modular unit, purified treatment while can be applicable to multiple sample solution.
Description
Technical field
The present invention relates to a kind of sample solution purifier based on hollow fiber nanofiltration membrane material, for analyzing sample pretreatment during detection.
Background technology
The analytic process of a sample, from original sample to final analysis result, generally comprises sample pretreatment and Instrumental Analysis process.Modern Instrumental Analysis is often through adopting the accurate instrument such as chromatogram, spectrum, mass spectrum, and to realize highly sensitive analysis result, this just proposes higher requirement to the clean-up effect of sample.Impurity in sample often disturbs the response of object to be analyzed in analytical instrument, and when especially adopting mass spectral analysis, the impurity in sample can produce matrix effect to instrument, causes suppression or the increase of mass spectrum response signal, causes the deviation of analysis result.
Sample pretreatment in sample analysis testing process be one not only consuming time but also very easily introduce the step of error, the accuracy and precision of the final result of the direct impact analysis of quality of sample treatment, simultaneously also can service life of impact analysis instrument and sensitivity.And, in some cases, because sample size is numerous, if adopt the mode of processing sample one by one, then the problem of inefficiency can be brought.
For traditional solid phase extraction method based on chemisorbed and analytic function, when purified blood slurry samples, the phosphatide with hydrophobic effect site has amphiprotic group especially: choline and phosphoric acid, they have alkalescence and acidity simultaneously, this just means the chemical property that target substance to be analyzed in sample solution has, and can appear in the structure of phospholipid moiety simultaneously; And protein has similar character equally.When which results in sample solution purification, be difficult to be removed as the phosphatide of impurity and protein, and then the matrix effect produced because they and object to be analyzed bring the competition of instrument signal, cause the analysis result of the detectors such as such as mass spectrum to occur the larger problem that makes a variation.And in the mode of hollow fiber ultrafiltration membrane ultrafiltration, although be compared to solid phase extraction method, can the larger protein of removal unit fractionated molecule amount, but it effectively can not remove the protein of molecular weight between 2000-20000 dalton, for the phosphatide of molecular weight less than 1000, it still also can not be removed.
Summary of the invention
The object of the invention is to realize the Sample Pretreatment Technique Used that a kind of sample to analyzing when detecting has clean-up effect more thoroughly.
Based on a sample solution purifier for hollow fiber nanofiltration membrane material, comprise detachable plastic sleeve pipe (1), the outer tube varied in size by two and interior pipe form, and interior pipe is fixed wtih hollow fiber nanofiltration membrane (2).
The outer tube of detachable plastic sleeve pipe is threaded connection and is connected with pipe cap (3) and is sealed, and interior pipe (4) has the edge of corner angle (6) to be fixed on outer tube by one, and the volume of outer tube is 1-100mL.
Hollow fiber nanofiltration membrane (2) is connected by bottom seal member (5) and interior pipe, and the quantity of hollow fiber nanofiltration membrane is 1-100 bundle.The two kinds of modes that have hollow fiber nanofiltration membrane are fixed in interior pipe (4): first kind of way is hollow fiber nanofiltration membrane upper end open, and and seal member (5) upper surface flush, seal member (5) 0.01-5cm is exposed in film lower end, and lower end sealing; Another kind of mode is the sealing of hollow fiber nanofiltration membrane upper end, and fixed by the inwall of fixed part (7) and interior pipe (4), fixed part (7) distance seal member (5) 0.01-5cm, film lower ending opening, and with seal member (5) lower surface flushes, fixed part (7) has multiple through hole, allows sample liquids to pass therethrough and arrives seal member (5) upper surface.
Hollow fiber nanofiltration membrane material is one or more the mixed materials in polysulfones, polypropylene, Kynoar or polytetrafluoroethylene (PTFE).
One or more the mixing in grafting process or carboxyl grafting, amino, amide groups, sulfonic group, quaternary amine base, C12 Zhi HuoC18Zhi functional group is not done on hollow fiber nanofiltration membrane fenestra surface.
Sample solution purifier uses the one in centrifugation, syringe or infusion pump, makes sample liquids pass through hollow fiber nanofiltration membrane.Sample liquids contains the aqueous solution or the water-based homogenate of one or more organic solvents in the methyl alcohol of 0.0001-99.9% arbitrary proportion, ethanol, acetonitrile, acetone or isopropyl alcohol.Sample liquids is containing the aqueous solution of one or more materials in the ammoniacal liquor of 0.0001-99.9% arbitrary proportion, triethylamine, formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, phosphoric acid or sulfuric acid or water-based homogenate.
2 to 384 unit parallel connections, as a unit, use, for processing while multiple sample by a sample solution purifier.
The present invention utilizes hollow fiber nanofiltration membrane, with the pore size filter less than hollow fiber ultrafiltration membrane, Physical entrapment is realized to the impurity of molecular weight more than 2000, in some cases again in conjunction with reverse phase absorption effect or ion exchange, realize retaining more impurity with chemical action, thus more thoroughly clean-up effect is realized to sample.
Hollow fiber nanofiltration membrane has the fenestra less than hollow fiber ultrafiltration membrane, can retain the impurity of more small-molecular-weight.The more important thing is, by radiation grafting technology, functional group that can be different in grafting in the fenestra of hollow-fibre membrane, such as has C12 and the C18 ester of inverting function, there are the carboxyl of ion exchange, amino, sulfonic group, quaternary amine base etc., there is the functional groups such as the acrylamide of polarity effect.Self tool of these functional groups has the dimensions, and when being received in a large number in the fenestra of hollow fiber nanofiltration membrane, can reduce the aperture of fenestra.By regulating the quantity of grafted functional group, the aperture that a series of size presents linear change can be adjusted in theory, thus meet the demand of the removal of the material of different molecular weight, which provides more than hollow fiber ultrafiltration membrane filter capacity much bigger by force.Hollow fiber nanofiltration membrane after grafting not only can the filtration MW material that is greater than 20000, and also has the filter effect more much better than milipore filter for the material of molecular weight between 2000-20000.In addition, the fenestra of grafting particular functional group, also there is certain specific chemisorption, thus more catharsis is provided on the basis of physical filtering, the hollow fiber nanofiltration membrane that such as can be grafted with carboxyl functional group the mode of cation exchange can be removed and have cationic phosphatide and positively charged protein.
By the hollow fiber nanofiltration membrane after hollow fiber nanofiltration membrane or grafting, be fixed on plastic containers by the mode of thermoplastic or resin-cast, construct inside and outside two independently spaces on the both sides of hollow fiber nanofiltration membrane tube wall, form a special sample solution purifier.In the mode that centrifugal mode or syringe, pump drive, sample solution is arrived space outerpace from inner space by fenestra hollow fiber nanofiltration membrane tube wall.At sample in hollow fiber nanofiltration membrane fenestra, there occurs physical filtering the impurity of macromolecule is retained, simultaneous chemisorption can adsorb more impurity, and this just provides possibility for a kind of simple, efficient sample solution purification style of exploitation.
Tube wall due to hollow fiber nanofiltration membrane has the structure of fenestra and supporting layer, when fenestra is positioned at tube wall outside time, be called outer press mold, when fenestra is positioned at tube wall inside time, be called press mold.Sample solution is flow to supporting layer from fenestra by the direction of hollow fiber nanofiltration membrane tube wall, so when sample solution purifier use in press mold time, sample solution is introduced into hollow fiber nanofiltration membrane inside, then flowed out in outside plastic tube by tube wall, be collected; And when the outer press mold of use, sample solution flows to hollow fiber nanofiltration membrane inside from hollow-fibre membrane outside by tube wall, then entering in outside plastic tube, be collected.
The present invention adopts the hollow fiber nanofiltration membrane after hollow fiber nanofiltration membrane or grafting, is processed into specific device, and it can adopt the driving force of mode sampling solution by film of centrifugal, syringe, pump.It may be used for the process of the biological fluid such as blood sample, urine sample, also may be used for the solid sample process of the biological tissue such as muscle, feed, can also be used for the process of the environmental samples such as sewage.In use, the solvent composition of sample solution also can affect filter effect.Because hollow fiber nanofiltration membrane all exists certain hydrophobic effect before and after grafting, the dead absorption that evaluating objects produce are raw certain can be treated, so be necessary to add a certain proportion of organic solvent in sample solution, any one in such as methyl alcohol, ethanol, acetonitrile, acetone and isopropyl alcohol equal solvent, also these solvents can be mixed, obtain the effect of specific desorption.When after hollow fiber nanofiltration membrane grafting ion cation exchange groups, be necessary to add one or more materials in ammoniacal liquor, triethylamine, formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, phosphoric acid and sulfuric acid, suppress the ion-exchange group of grafting to treat the absorption of evaluating objects thing.
The device that the present invention relates to can used aloned, also can combinationally use while realizing multiple sample and process.Along with the development of modern analytical technique, the demand analyzed while a large amount of sample also usually occurs, 96 orifice plates such as, often used in biological sample analysis or 384 orifice plates, just can analyze 96 samples or 384 samples simultaneously.96 unit or 384 unit, as a unit, when needs process multiple sample, are connected in parallel by hollow fiber nanofiltration membrane device of the present invention, for analyzing while 96 or 384 samples.For some bulky sample solutions, larger plastic tube can be adopted, as 100mL, many hollow fiber nanofiltration membranes are fixed on the slightly little plastic inner pipe of volume simultaneously, improve the flux of processing sample solution, realize the process of bulk sample solution.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation, but it does not carry out any restriction to the present invention.
Fig. 1 is the plane of the first fixed form of the present invention, be characterized in that hollow fiber nanofiltration membrane is exposed to the bottom of seal member, during use, sample solution is from the flowing of film interior, finally collects in the outer tube based on the sample solution purifier of hollow fiber nanofiltration membrane material.
In figure, 1 is detachable plastic sleeve pipe, and 2 is hollow fiber nanofiltration membrane, and 3 is pipe cap, and 4 is interior pipe, and 5 is seal member, and 6 is edge.
Fig. 2 is the plane of the second fixed form of the present invention, be characterized in that hollow fiber nanofiltration membrane is exposed to the top of seal member, during use during sample solution from film externally to internal flow, finally collect in the outer tube of sample solution purifier of hollow fiber nanofiltration membrane material.
In figure, 7 is fixed part, and 5 is seal member.
Fig. 3 is without the LC-MS/MS analysis chart based on the Clenbuterol in the sample solution purifier blood plasma before treatment of hollow fiber nanofiltration membrane material.
Fig. 4 is through the LC-MS/MS analysis chart of the Clenbuterol in the blood plasma after based on the sample solution purifier process of hollow fiber nanofiltration membrane material.
Fig. 5 is through the protein removal design sketch of human serum sample after the sample solution purifier process based on hollow fiber nanofiltration membrane material.
Fig. 6 is through the protein removal design sketch of human serum sample after 0.22 μm of syringe filter process.
Detailed description of the invention
Embodiment 1
The purifier purifying sample solution in nanofiltration mode of the present invention, its structure with reference to figure 1, can comprise detachable plastic sleeve pipe (1), pipe cap (3), and the hollow fiber nanofiltration membrane (2) be connected with interior pipe.Plastic tube is the tubular container adopting polyethylene (PE) or the material such as Merlon (PC) or polypropylene (PP) to make, and centrifuge tube gag can adopt the material consistent with centrifuge tube.Can intercept the hollow fiber nanofiltration membrane of appropriate length in actual applications in right amount, hollow fiber nanofiltration membrane arrival end is fixed on interior pipe (4) lower end, and film arrival end flushes with the upper interface of fixed part (7) or slightly exceeds; The hollow fiber nanofiltration membrane port of export is connected with bottom interior pipe by seal member (5).Interior pipe has the edge of corner angle (6) to be fixed on outer tube by one, fluid sample to be processed can be placed in interior pipe, pressure is applied by centrifuge, syringe or pump, the molecule of relatively small molecular weight and solvent is made to enter the internal gutter of hollow fiber nanofiltration membrane, and then it is inner to arrive plastic outer tube by fenestra, and the material of macromolecule can be trapped in film pipe.Sample after the filtration of being collected by outer tube just can enter into all kinds of detecting instruments such as mass spectrum, spectrum, chromatogram after taking out and detect.
Embodiment 2
Of the present invention with the purifier of filter type purification sample solution, its structure can with reference to figure 2, the hollow fiber nanofiltration membrane port of export is fixed on interior pipe lower end, and the port of export flushes with interface under fixed part (7) or slightly exceeds, and the port of export is communicated with the inner space of plastic outer tube.Hollow fiber nanofiltration membrane arrival end is closed, and is connected with the middle part of plastic inner pipe by fixed part.Fluid sample to be processed can be placed in interior pipe, rotated by centrifuge, the molecule of small-molecular-weight and solvent are by the fenestra of hollow fiber nanofiltration membrane under the influence of centrifugal force, enter the internal gutter of film, and then enter into plastic outer tube by the port of export, the sample solution after being purified.
The purifier purifying sample solution in nanofiltration mode of the present invention, also by reaching the object of filtration, purification sample with syringe or pump engagement fluid sample.
Embodiment 3
Sample solution purifier based on hollow fiber nanofiltration membrane material is applied to the sample pre-treatments during Clenbuterol detected in Swine plasma:
1 length should be used to be grafted with acrylic acid groups for 1cm hollow fiber nanofiltration membrane based on sample solution purifier of hollow fiber nanofiltration membrane material, acrylic acid carboxylic group can adsorb phosphatide, but does not adsorb Clenbuterol.The volume of outer tube is 1mL.
Get the Swine plasma of 100 μ L in the sample bottle of 1.5mL, then the Clenbuterol standard items of 100 μ L40ppb are added, add the methanol extraction albumen of 200 μ L again, after vortex concussion 2min, this sample centrifugal under 8000rpm, after obtaining supernatant, transfers to whole supernatant in hollow fiber nanofiltration membrane assembly, again with the centrifugal 10min of 4000rpm, the sample solution collected in 100 μ L plastic outer tubes prepares to carry out LC-MS/MS detection.
Comparative experimental example:
Get the supernatant in above-mentioned treatment step, as the control sample of the sample of the sample solution purifier process based on hollow fiber nanofiltration membrane material, directly carry out the detection of LC-MS/MS.
Analysis result refers to Fig. 3 and Fig. 4.Fig. 4 adopts based on the rate of recovery of the clenobuterol hydrochloride in the sample of the sample solution purifier process of hollow fiber nanofiltration membrane material close to 100%, and the rate of recovery of clenobuterol hydrochloride in the sample of Fig. 3 contrast test only about 50%.To analyze reason be the former phosphatide removal efficiency is 3 times of the latter, decreases substrate inhibition effect on LC-MS/MS.
Embodiment 4
The albumen in serum removed by sample solution purifier based on hollow fiber nanofiltration membrane material:
3 length should be adopted to be the hollow fiber nanofiltration membrane being grafted with amide group of 2cm based on sample solution purifier of hollow fiber nanofiltration membrane material.Outer tube volume is 5mL.
In the sample solution purifier of hollow fiber nanofiltration membrane material, add 0.5mL human serum, with 4000rpm centrifugal filtration, collect filtered fluid to be measured as test liquid.
Comparative experimental example:
Get the 0.5mL human serum of the sample solution purifier not crossing hollow fiber nanofiltration membrane material, filter by 0.22 μm of syringe filter, collect filtered fluid solution as a comparison sample.
Analysis result is shown in Fig. 5 and Fig. 6.Fig. 5 is the protein chromatography analysis chart of the human serum sample of the sample solution purifier process adopting hollow fiber nanofiltration membrane material, the protein chromatography analysis chart that the 0.22 μm of syringe filter being compared to Fig. 6 is filtered, the protein of most macromolecule is all removed by the former.Tracing it to its cause is that hollow fiber nanofiltration membrane has less aperture, better can filter out the protein in human serum.
Embodiment 5
Based on the sample solution purifier of hollow fiber nanofiltration membrane material, the pre-treatment for sewage sample:
Based on the sample solution purifier of hollow fiber nanofiltration membrane material, the outer tube of 100mL should be had, and adopt 30 length to be the hollow fiber nanofiltration membrane not having grafting process of 5cm.
50mL sewage is positioned in the sample solution purifier of hollow fiber nanofiltration membrane material, then under 4000rpm rotating speed from 10min, collect filtered fluid.
Comparative experimental example:
0.22 μm of syringe filter is adopted to dispose of sewage sample.Use syringe that 50mL sewage is pushed through syringe filter.
Result 50mL sewage sample can conveniently by the sample solution purifier of hollow fiber nanofiltration membrane material, but when using 0.22 μm of syringe filter, only the sewage sample of 5mL just makes plugged filter.
Embodiment 6
Based on the sample solution purifier of hollow fiber nanofiltration membrane material, sample pre-treatments during detection for Ribavirin in chicken:
3 length should be adopted to be the hollow fiber nanofiltration membrane being grafted with carboxyl and C12 ester group of 3cm based on sample solution purifier of hollow fiber nanofiltration membrane material, outer tube volume 12mL.
Chicken meat sample containing 10ppb Ribavirin cleaned and shreds, getting 2g sample, being placed in 50mL centrifuge tube.Add 4mL water, vortex sample 1min, often in pipe, add the acetonitrile solution of 10mL containing 1% acetic acid.Cover centrifuge tube and vortex 1min.Under normal temperature, the centrifugation 5min of 5000rpm, obtains supernatant.2mL supernatant is placed in the sample solution purifier of Hollow-fibre membranes material, centrifugal 5min under the rotating speed of 4000rpm, the liquid after being purified.Preparation is carried out detection and is analyzed.
Testing result shows, and in chicken, Ribavirin has the rate of recovery of more than 90%.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to technical scheme of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical scheme of the present invention.
Claims (8)
1. based on a sample solution purifier for hollow fiber nanofiltration membrane material, comprise detachable plastic sleeve pipe (1), the outer tube varied in size by two and interior pipe form, and interior pipe is fixed wtih hollow fiber nanofiltration membrane (2);
Hollow fiber nanofiltration membrane (2) is connected by bottom seal member (5) and interior pipe, and the quantity of hollow fiber nanofiltration membrane is 1-100 bundle;
The two kinds of modes that have hollow fiber nanofiltration membrane are fixed in interior pipe (4): first kind of way is hollow fiber nanofiltration membrane upper end open, and with seal member (5) upper surface flush, seal member (5) 0.01-5cm is exposed in film lower end, and lower end sealing; Another kind of mode is the sealing of hollow fiber nanofiltration membrane upper end, and fixed by the inwall of fixed part (7) and interior pipe (4), fixed part (7) distance seal member (5) 0.01-5cm, film lower ending opening, and with seal member (5) lower surface flushes, fixed part (7) has multiple through hole, allows sample liquids to pass therethrough and arrives seal member (5) upper surface.
2. sample solution purifier according to claim 1, it is characterized in that the outer tube of detachable plastic sleeve pipe is threaded connection to be connected with pipe cap (3) and to be sealed, interior pipe (4) has the edge of corner angle (6) to be fixed on outer tube by one, and the volume of outer tube is 1-100mL.
3. sample solution purifier according to claim 1, is characterized in that hollow fiber nanofiltration membrane material is one or more the mixed materials in polysulfones, polypropylene, Kynoar or polytetrafluoroethylene (PTFE).
4. sample solution purifier according to claim 1, is characterized in that one or more the mixing in grafting process or carboxyl grafting, amino, amide groups, sulfonic group, quaternary amine base, C12 Zhi HuoC18Zhi functional group is not done on hollow fiber nanofiltration membrane fenestra surface.
5. sample solution purifier according to claim 1, is characterized in that sample solution purifier uses the one in centrifugation, syringe or infusion pump, makes sample liquids pass through hollow fiber nanofiltration membrane.
6. sample solution purifier according to claim 5, is characterized in that sample liquids contains the aqueous solution or the water-based homogenate of one or more organic solvents in the methyl alcohol of 0.0001-99.9% arbitrary proportion, ethanol, acetonitrile, acetone or isopropyl alcohol.
7. sample solution purifier according to claim 5, is characterized in that sample liquids contains a kind of in the ammoniacal liquor of 0.0001-99.9% arbitrary proportion, triethylamine, formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, phosphoric acid or the sulfuric acid aqueous solution or water-based homogenate of or two or more material.
8. sample solution purifier according to claim 1, is characterized in that sample solution purifier is as a unit, uses, 2 to 384 unit parallel connections for processing while multiple sample.
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| CN105928731A (en) * | 2016-04-29 | 2016-09-07 | 北京倍肯恒业科技发展股份有限公司 | Aseptic multi-point sampling apparatus |
| CN107684774B (en) * | 2017-09-29 | 2023-09-22 | 广州市雷德生物科技有限公司 | Filtering device |
| CN110938139A (en) * | 2020-01-20 | 2020-03-31 | 中国医科大学 | Hollow fiber ultrafiltration method for total IgE detection of forensic hemolytic sample |
| TWI802273B (en) * | 2022-02-16 | 2023-05-11 | 列特博生技股份有限公司 | Device and method for extracting biomolecules |
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| CA1259870A (en) * | 1984-10-01 | 1989-09-26 | Eiichi Hamada | Heat exchanger and blood oxygenating device furnished therewith |
| CN2611021Y (en) * | 2003-04-10 | 2004-04-14 | 浙江欧美环境工程有限公司 | Channel-like water collection and water distribution type hollow fiber membrane assembly |
| CN201082383Y (en) * | 2007-05-18 | 2008-07-09 | 上海立昇净水设备有限公司 | Shaft type immersion hollow fiber film component |
| CN101898088B (en) * | 2009-05-25 | 2012-12-26 | 河北医科大学 | Centrifugal ultrafiltration device suitable to be used in preprocessing of micro sample |
| JP2011224026A (en) * | 2010-04-15 | 2011-11-10 | Toray Ind Inc | Blood purification device and method of manufacturing the same |
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