CN110297057A - A kind of novel on-line solid phase extraction column and preparation method thereof - Google Patents
A kind of novel on-line solid phase extraction column and preparation method thereof Download PDFInfo
- Publication number
- CN110297057A CN110297057A CN201910676858.2A CN201910676858A CN110297057A CN 110297057 A CN110297057 A CN 110297057A CN 201910676858 A CN201910676858 A CN 201910676858A CN 110297057 A CN110297057 A CN 110297057A
- Authority
- CN
- China
- Prior art keywords
- phase extraction
- extraction column
- solution
- solid
- solid phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- HYTUQENVFPSZBW-UHFFFAOYSA-N O.O.O.O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O.O.O.O=C1N[ClH](=O)NC2=C1NC(=O)N2 HYTUQENVFPSZBW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical class O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 claims 2
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 238000004108 freeze drying Methods 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 13
- 238000004458 analytical method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004587 chromatography analysis Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 210000004369 blood Anatomy 0.000 description 6
- 239000008280 blood Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- HWXIGFIVGWUZAO-UHFFFAOYSA-N doxofylline Chemical compound C1=2C(=O)N(C)C(=O)N(C)C=2N=CN1CC1OCCO1 HWXIGFIVGWUZAO-UHFFFAOYSA-N 0.000 description 3
- 229960004483 doxofylline Drugs 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 1
- 229960000623 carbamazepine Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The present invention relates to Solid Phase Extraction fields, and in particular to a kind of novel on-line solid phase extraction column and preparation method thereof.A kind of novel on-line solid phase extraction column, including solid-phase extraction column ontology, the extraction column ontology includes packed column, and the packed column both ends rigid connection has siphunculus, and the outside rigid connection of the siphunculus has connector.Extraction stuffing is graphene alloy composite materials.Solid Phase Extraction column polarity, structure obtained by of the invention can easily be accommodated, and are suitable for residual object sample purification and are enriched with, good separating effect can apply to liquid-phase chromatographic analysis field, greatly improve the degree of automation of analysis.
Description
Technical field
The present invention relates to Solid Phase Extraction fields, and in particular to a kind of novel on-line solid phase extraction column and preparation method thereof.
Background technique
Purification, enrichment and the separation of complex sample (such as blood sample) are the key that analysis one rings of work, it is in workload
With the very big specific gravity for all accounting for entire analysis work in terms of technical requirements, the selection of method for purifying and enriching also will affect entire
Detect the accuracy and repeatability of program.Why solid-phase extraction column can separate target compound from sample substrate,
Functional group mainly on solid-phase adsorbent and the active force between the functional group of target compound retain target compound
On solid-phase adsorbent, then flowed away by solid-phase extraction column without retained sample substrate.This active force is broadly divided into
Nonpolar action power, polarity active force, ionization power, covalent effect power and multi-acting force.Solid Phase Extraction is relative to other
Purification enrichment isolation technics, have the advantage that can batch processing, save the time, reduce solvent use and waste generate, it is a variety of
The alternative of bonded stationary phase, can concentration and separation trace analysis object, it is easy to accomplish automation, the rate of recovery is high, favorable reproducibility etc..
Solid phase extraction method has been increasingly becoming the main method of sample pretreatment at present.According to the difference of operating method, and
Offline Solid Phase Extraction and on-line solid phase extraction can be divided into.On-line solid phase extraction technology is also known as in-line purification and beneficiation technologies, mainly
For efficient liquid phase chromatographic analysis, extraction is synchronously completed with chromatography, and by various Vavle switchings, by Solid Phase Extraction, treated
Sample is pushed into analysis system, realizes and completes detection work in a system.It is online solid as the sample treatment technology of automation
Phase abstraction technique can realize sample in-line purification and enrichment, avoid cumbersome Artificial sample pretreatment process, greatly save sample
Usage amount and time, reproducibility is high, and the rate of recovery is good, and with the exploitation of various solid-phase extraction columns, this method future applies model
Enclosing can more extensively.But when specifically used, the existing solid-phase extraction column based on amorphous silica gel filler be cannot achieve online
High pressure extraction, and have that extraction functional group is single, sample capacity is lower, strength retention is weak, purification and enrichment can not a step it is complete
At etc. technical problems.
Summary of the invention
The purpose of the present invention is being directed to the status of the prior art, a kind of preparation of novel on-line solid phase extraction column packing is provided
Method simultaneously loads online solid-phase extraction column, which be suitable for wider using graphene alloy composite materials as filler
The wide spectrum Solid Phase Extraction of polar compound.
The present invention is that technical solution used by solving its technical problem is:
A kind of novel on-line solid phase extraction column, including solid-phase extraction column ontology, the extraction column ontology includes packed column, institute
Stating the rigid connection of packed column both ends has siphunculus, and the outside rigid connection of the siphunculus has connector.
Further, the packed column is cylinder, and the axle center of the packed column offers the stuffing hole of both ends connection,
Extraction stuffing is filled in the stuffing hole.
Further, the extraction stuffing is graphene alloy composite materials.
Further, the siphunculus is cylindrical tube.
Further, the connector is hex nut shape.
Further, the preparation method of the graphene alloy composite materials includes the following steps:
S1: weighing 20~30mg graphene oxide, is dissolved in 50mL water and is added NaOH adjusting pH to 8~10, L- is added
Ascorbic acid, stirs 4~8 hours under the conditions of 70~90 DEG C, then by obtained dispersion liquid at 10000~12000rpm from
8~12min of the heart, residue redissolve to obtain graphene dispersing solution with 30mL water；
S2: the tetra chlorauric acid trihydrate solution and 2~5 times of tetra chlorauric acids three that 1.0~2.0mL concentration is 10g/L are measured
Hydrate soln amount, concentration are the L-AA solution of 0.5g/L, and two kinds of solution are mixed into the deionized water of 100mL, room
The lower sufficiently reaction of temperature；Then be added 1~3% sodium citrate aqueous solution of 1mL, sufficiently react, at 10000~12000rpm from
10~15min of the heart；Last 30mL water redissolves residue, and solution of gold nanoparticles is prepared in sonic oscillation；
S3: it in the case of stirring, sequentially adds the graphene dispersing solution obtained in step S1 and is obtained in step S2
Solution of gold nanoparticles is reacted 40~60min, is repeated 3 times；Described solution after reaction is placed at -50 DEG C saves overnight, freezing
Graphene alloy composite materials are obtained after drying.
Further, the mass ratio of graphene oxide and L-AA is 1:0.25~2 in the step S1.
Further, the volume ratio of graphene dispersing solution and solution of gold nanoparticles is 1~3:1 in the step S3.
A kind of preparation method of novel on-line solid phase extraction column, includes the following steps:
S1: weighing 10mg graphene alloy composite materials and be scattered in 3~5mL deionized water, sufficiently obtains ink after ultrasound
Black alkene alloy composite materials dispersion liquid is adjusted to isodensity using the equal slurry processes of isodensity by alkene alloy composite materials dispersion liquid；
S2: the alkene alloy composite materials dispersion liquid that S1 is obtained inserts online solid phase extraction under 20~30MPa pressure condition
Take column, use isopropanol as displacement fluid, stop pressurization after flowing out certain volume, after pressure balance with concentration be 0.2%~
0.5% aqueous formic acid, 0.2%~0.5% ammonium hydroxide, methanol are respectively washed.
The present invention has the advantages that
1. using packing material of the graphene alloy composite materials as on-line solid phase extraction column for the first time, graphene alloy is multiple
Condensation material has good absorption property to object, can significantly remove interference impurity；
2. the preparation method of solid phase extraction filler of the present invention is simple, quick, can be used for covering simultaneously from polarity to nonpolarity
Purification, enrichment, extraction and the detection of polymorphic type compound；
3. filling online solid-phase extraction column using isodensity homogenate method, the small column polarity of gained, structure be can easily be accommodated, sample size
It is small, concentration and separation effect is good, can apply to liquid-phase chromatographic analysis field, greatly improve the degree of automation of analysis.
Detailed description of the invention
Fig. 1 is on-line solid phase extraction column prepared by embodiment 1；
Fig. 2 is the mark-on serum matrix chromatogram of on-line solid phase extraction in embodiment 1；
Fig. 3 is the mark-on serum matrix chromatogram of offline Solid Phase Extraction in embodiment 1.
Fig. 4 is doxofylline drug chromatogram in blood sample in embodiment 1.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Diagram and specific embodiment are closed, the present invention is further explained.
Embodiment 1
As shown in Figure 1, a kind of novel on-line solid phase extraction column, including solid-phase extraction column ontology, the extraction column ontology packet
Packed column 1 is included, the packed column both ends rigid connection has siphunculus 3, and the outside rigid connection of the siphunculus 3 has connector 4.
The packed column 1 is cylinder, and the axle center of the packed column 1 offers the stuffing hole 2 of both ends connection, described to fill out
Expect to be filled with extraction stuffing in hole 2.
The extraction stuffing is graphene alloy composite materials.
The siphunculus 3 is cylindrical tube.
The connector 4 is hex nut shape.
(1) preparation of graphene alloy composite materials:
The first step prepares graphene solution: precision weighs the graphene oxide of 25mg, is dissolved in 50mL water and NaOH is added
PH to 9 is adjusted, 25mg L-AA is then added, stirs 5 hours under the conditions of 80 DEG C, then obtained dispersion liquid exists
10min is centrifuged under 10000rpm, residue redissolves to obtain graphene dispersing solution with 30mL water；
Second step prepare nano-particle solution: precision measure 1.0mL tetra chlorauric acid trihydrate (10g/L) solution and
The L-AA solution (0.5g/L) of 3.0mL, two kinds of solution are mixed into the deionized water of 100mL, react 5min at room temperature.
Then 1.5% sodium citrate aqueous solution of 1mL is added, stops reaction after 10min, is centrifuged 10min at 10000rpm.Finally
30mL water redissolves residue, and solution of gold nanoparticles is prepared in sonic oscillation；
Third step synthetic composite material: in the case of stirring, sequentially add 2mL reduced form graphene oxide dispersion and
1mL solution of gold nanoparticles, reacts 45min, this process is repeated 3 times.Mixed liquor is finally placed -50 DEG C to save overnight, freezing
Graphene alloy composite materials are obtained after drying.
(2) prepared by on-line solid phase extraction column
Precision weighs 10mg graphene alloy composite materials and is scattered in 5mL aqueous solution, and ultrasonic 30min prepares dispersion liquid,
Method is homogenized using isodensity, isodensity is adjusted to, inserts online solid-phase extraction column under high pressure.Use isopropanol as replacement
Liquid stops pressurization after flowing out certain volume, removes after pressure balance spare.With aqueous formic acid, ammonium hydroxide, methanol point after filling
It does not clean.
(3) enrichment purification of carbamazepine medicine concentration extracts in blood sample
The first step, sample process: taking sample treatment solution, quantitatively pipettes 0.5ml and is added in empty sample bottle；Take sample to be tested
At least 4mL is centrifuged 10min in the case where centrifugal speed is 4000rpm, quantitatively pipettes supernatant 0.5ml and be added in above-mentioned sample bottle, whirlpool
Stream mixes, and is put into sample introduction 100ul in autosampler and carries out liquid chromatogram quantitative detection；
Pattern detection: second step uses fully automatic therapy drug surveillance analysis system (SLC, Suzhou Ai Dimai medical science and technology
Co., Ltd) sample is detected.
Chromatographic condition: on-line extraction column: above-mentioned on-line solid phase extraction column；On-line analysis column: C18 column (150 × 4.6mm, 5 μ
M partial size)；Mobile phase: extract liquor H1 and extract liquor H2, eluent A, eluent B and eluent C；Column temperature: 35 DEG C；Sample volume:
100μL；Wavelength: 239nm.
1 condition of gradient elution of table
Testing result is as in Figure 2-4:
(1) matrix effect: under the pitch-based sphere of 20ng/mL, the on-line solid phase extraction through graphene alloy compounded mix
Column enrichment purification is compared with the directly upper machine of the sample through common offline solid phase extraction column (C18 filler) enrichment purification, purification effect
Fruit is obvious, and matrix effect is obviously improved.
(2) method sensitivity is investigated: main includes the measurement of detection limit (LOD) and quantitative limit (LOQ).Wherein LOD is blood
The concentration of the object of signal-to-noise ratio S/N=3 in clear matrix, LOQ are the dense of the object of signal-to-noise ratio S/N=10 in serum matrix
Degree.The LOD of doxofylline is 0.15-0.5ug/mL, LOQ 0.7-2ug/mL.
(3) it the rate of recovery verifying of method: is investigated using the rate of recovery of the matrix mark-on method to method, respectively in serum
Add the doxofylline standard of basic, normal, high three concentration levels (respectively 1.5ug/mL, 15.0ug/mL and 30.0ug/mL)
Product, using original sample as control group, each parallel three parts of experiments.Sample detects after purifying according to above-mentioned steps, rate of recovery 95.0-
103.5%；
(4) the precision verifying of method: on the same day, parallel 6 parts of samples are tested, and are obtained in a few days after purification assays
Precision: 1.9-10.5%；For three days on end, parallel 5 parts of samples are tested daily, and detection obtains day to day precision after calculating:
4.9-13.2%.
(5) sample detection: 60 blood samples of random collecting are detected using the method for the present embodiment.Testing number
According to showing: in 60 samples, detection normal specimens are 51, and abnormal sample is 9.
In conclusion solid-phase extraction column of the invention is, it can be achieved that sample in-line purification and enrichment, avoid cumbersome artificial sample
Product pretreatment process greatlys save sample usage amount and time, and reproducibility is high, and the rate of recovery is good, can be each in quantitative analysis blood
Kind drug concentration provides a kind of quick, accurate and effective detection method.
This is the basic principles, main features and advantages of the present invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent defines.
Claims (9)
1. a kind of novel on-line solid phase extraction column, including solid-phase extraction column ontology, it is characterised in that: the extraction column ontology includes
Packed column, the packed column both ends rigid connection have siphunculus, and the outside rigid connection of the siphunculus has connector.
2. extraction column according to claim 1, it is characterised in that: the packed column is cylinder, the packed column
Axle center offers the stuffing hole of both ends connection, is filled with extraction stuffing in the stuffing hole.
3. solid-phase extraction column according to claim 2, it is characterised in that: the extraction stuffing is that graphene alloy is compound
Material.
4. solid-phase extraction column according to claim 1, it is characterised in that: the siphunculus is cylindrical tube.
5. solid-phase extraction column according to claim 1, it is characterised in that: the connector is hex nut shape.
6. solid-phase extraction column according to claim 3, it is characterised in that: the preparation of the graphene alloy composite materials
Method includes the following steps:
S1: weighing 20~30mg graphene oxide, is dissolved in 50mL water and is added NaOH adjusting pH to 8~10, it is anti-bad that L- is added
Hematic acid stirs 4~8 hours under the conditions of 70~90 DEG C, obtained dispersion liquid is then centrifuged 8 at 10000~12000rpm
~12min, residue redissolve to obtain graphene dispersing solution with 30mL water；
S2: the tetra chlorauric acid trihydrate solution and 2~5 times of hydrations of tetra chlorauric acids three that 1.0~2.0mL concentration is 10g/L are measured
Object amount of solution, concentration are the L-AA solution of 0.5g/L, and two kinds of solution are mixed into the deionized water of 100mL, at room temperature
Sufficiently reaction；Then be added the sodium citrate aqueous solution of 1mL1~3%, sufficiently react, at 10000~12000rpm be centrifuged 10~
15min；Last 30mL water redissolves residue, and solution of gold nanoparticles is prepared in sonic oscillation；
S3: in the case of stirring, the Jenner for sequentially adding the graphene dispersing solution obtained in step S1 and being obtained in step S2
Rice corpuscles solution reacts 40~60min, is repeated 3 times；Described solution after reaction is placed at -50 DEG C saves overnight, freeze-drying
Graphene alloy composite materials are obtained afterwards.
7. solid-phase extraction column according to claim 6, it is characterised in that: graphene oxide and L- are anti-bad in the step S1
The mass ratio of hematic acid is 1:0.25~2.
8. solid-phase extraction column according to claim 6, it is characterised in that: graphene dispersing solution and Jenner in the step S3
The volume ratio of rice corpuscles solution is 1~3:1.
9. a kind of Solid Phase Extraction column preparation method described in claim 1, includes the following steps:
S1: weighing 10mg graphene alloy composite materials and be scattered in 3~5mL deionized water, and black alkene is sufficiently obtained after ultrasound and is closed
Black alkene alloy composite materials dispersion liquid is adjusted to isodensity using the equal slurry processes of isodensity by metal/composite material dispersion liquid；
S2: the alkene alloy composite materials dispersion liquid that S1 is obtained inserts on-line solid phase extraction under 20~30MPa pressure condition
Column uses isopropanol as displacement fluid, stops pressurization after flowing out certain volume, after pressure balance with concentration be 0.2%~
0.5% aqueous formic acid, 0.2%~0.5% ammonium hydroxide, methanol are respectively washed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910676858.2A CN110297057A (en) | 2019-07-25 | 2019-07-25 | A kind of novel on-line solid phase extraction column and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910676858.2A CN110297057A (en) | 2019-07-25 | 2019-07-25 | A kind of novel on-line solid phase extraction column and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110297057A true CN110297057A (en) | 2019-10-01 |
Family
ID=68031865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910676858.2A Pending CN110297057A (en) | 2019-07-25 | 2019-07-25 | A kind of novel on-line solid phase extraction column and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110297057A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203564815U (en) * | 2013-11-25 | 2014-04-30 | 河南科技学院 | Centrifugal solid-phase extraction column |
| CN105392557A (en) * | 2013-06-14 | 2016-03-09 | 株式会社日立高新技术 | Pressure increasing system, and method for increasing pressure of gaseous body |
| CN106442903A (en) * | 2016-11-28 | 2017-02-22 | 无锡艾科瑞思产品设计与研究有限公司 | Solid phase extraction column used for food detection |
| CN106841480A (en) * | 2017-03-06 | 2017-06-13 | 上海市农业科学院 | A kind of enrichment purification method of aflatoxin |
| CN108888998A (en) * | 2018-05-11 | 2018-11-27 | 上海市农业科学院 | A kind of solid-phase extraction column and preparation method thereof for enrichment purification mycotoxin |
-
2019
- 2019-07-25 CN CN201910676858.2A patent/CN110297057A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105392557A (en) * | 2013-06-14 | 2016-03-09 | 株式会社日立高新技术 | Pressure increasing system, and method for increasing pressure of gaseous body |
| CN203564815U (en) * | 2013-11-25 | 2014-04-30 | 河南科技学院 | Centrifugal solid-phase extraction column |
| CN106442903A (en) * | 2016-11-28 | 2017-02-22 | 无锡艾科瑞思产品设计与研究有限公司 | Solid phase extraction column used for food detection |
| CN106841480A (en) * | 2017-03-06 | 2017-06-13 | 上海市农业科学院 | A kind of enrichment purification method of aflatoxin |
| CN108888998A (en) * | 2018-05-11 | 2018-11-27 | 上海市农业科学院 | A kind of solid-phase extraction column and preparation method thereof for enrichment purification mycotoxin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102262163B (en) | Rapid and automatic determination method and device for tripolycyanamide content in dairy products | |
| CN102119961A (en) | Detection method of compound danshen dripping pills | |
| CN110455943A (en) | A kind of on-line mixing filler solid-phase extraction column and preparation method thereof | |
| CN105403631A (en) | Method for rapidly detecting content of vitamin D3 in health foods | |
| Jiang et al. | Miniaturized solid-phase extraction using a mesoporous molecular sieve SBA-15 as sorbent for the determination of triterpenoid saponins from Pulsatilla chinensis by ultrahigh-performance liquid chromatography-charged aerosol detection | |
| CN104111291B (en) | A kind of soil poisoning dead Ticks pesticide and the detection method of three kinds of metabolite thereof | |
| CN113533548B (en) | Method for detecting 1-vinyl imidazole in chemical product | |
| CN108693288A (en) | A method of quinolone drugs is extracted and analyzed using DPX pipette tips formula dispersed solid phase microextraction columns | |
| CN110297057A (en) | A kind of novel on-line solid phase extraction column and preparation method thereof | |
| CN102866226B (en) | Method for using pyrazosulfuron-ethyl molecularly imprinted polymer for analyzing sulfonylurea herbicide and application thereof | |
| CN1847843A (en) | Method of measuring ginsenoside Rb1 content in Chinese medicine | |
| CN111912920A (en) | Method for detecting mycophenolic acid and metabolites thereof in plasma by ultra-high performance liquid chromatography tandem mass spectrometry technology | |
| CN104634911B (en) | A kind of 4 kinds of flavonoids effective constituent detection methods of CHUANKEZHI ZHUSHEYE | |
| CN114878708B (en) | Method for detecting 5 amanita peptides, dephosphorized nupharin and bufadienolide | |
| CN113406241B (en) | Detection method of Xintong granules | |
| CN112710797B (en) | Quality detection method for cough and asthma relieving pharmaceutical composition | |
| CN112051343B (en) | Method for determining antibiotic residues | |
| Chu et al. | A sensitive dispersive micro solid‐phase extraction coupled with high performance liquid chromatography for determination of three flavonoids in complex matrics by using crab shell as a sorbent | |
| CN114910583A (en) | Detection method of orange-shell mixture | |
| CN112098551A (en) | Method for detecting ginsenoside in health food | |
| CN115541773A (en) | Detection method for 5 rhubarb anthraquinone components in traditional Chinese medicine composition for treating nephropathy | |
| CN110687224A (en) | Method for measuring triptolide A in tripterygium wilfordii medicinal material and tripterygium wilfordii multi-glycoside tablet prepared from tripterygium wilfordii medicinal material | |
| CN108169390A (en) | The remaining detection method of avermectin in a kind of bacteria residue | |
| CN108519454A (en) | The remaining pre-treating method of Multiple Pesticides and its detection method in a kind of measurement tealeaves | |
| CN117110491B (en) | Method for detecting ginsenoside in traditional Chinese medicine preparation containing American ginseng |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191001 |