CN106492506A - Polymer-modified integral post of a kind of nanometer gold and its preparation method and application - Google Patents
Polymer-modified integral post of a kind of nanometer gold and its preparation method and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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Abstract
The invention discloses the method that a kind of polymer-modified integral column capillary tube micro-extraction of the nanometer gold of dimercaptosuccinic acid modification analyzes sea water and people's whole blood rare earth elements with ICP MS on-line couplings.With glycidyl methacrylate as monomer, ethylene glycol dimethacrylate is as cross-linking agent, polyalcohol integral pole is obtained by the way of in-situ polymerization, then carrying out series of chemical by the epoxide surface in integral post makes which be rich in sulfydryl, so as to modified upper nanometer gold by the way of chemical bonding, finally with nanometer gold as middle part, there is to rare earth element in its surface modification the dimercaptosuccinic acid of affinity interaction.The separation and concentration that the integral post is used for complex sample rare earth elements, it is possible to achieve the on-line analyses of sea water and people's whole blood rare earth elements, and significantly improve adsorption capacity of the integral post to rare earth element(3 6.5 times), have the advantages that high sensitivity, high sample throughput, low sample consumption and the wider pH scope of applications and stronger anti-matrix interference ability.
Description
Technical field
The invention belongs to separating and technical field of analysis and detection, and in particular to a kind of nanometer gold of dimercaptosuccinic acid modification changes
Property polyalcohol integral pole and preparation method thereof, and its be combined to multiple with inductivity coupled plasma mass spectrometry for capillary tube micro-extraction
Rare earth element in miscellaneous sample carries out on-line analyses detection.
Background technology
Rare earth element is widely used in industrial (magnetic material, catalysis material), agriculture due to having some special properties
The field such as industry (RE microbial fertilizer) and biomedical (mri contrast agent), a large amount of uses of rare earth element can be such which keeps away
It is discharged into exempting from environment, material impact is produced to organism by accumulating in food chain.Research shows, takes in low dose for a long time
The rare earth element of amount can cause brain accumulate, induce poisonous effect, make nerve baffle, IQ reduce;Rare earth element can also affect
The metabolic pathway of life entity and the activity of multiple enzyme, especially lanthanum and gadolinium can block the ion channel of calcium in cell;In addition,
Rare earth element can also invade sexual cell, destroy the reproductive performance of people.Therefore, the detection of environment and human body rare earth elements has
Significance.
Inductivity coupled plasma mass spectrometry (ICP-M S) due to sensitivity is high, range of linearity width and can multielement with
When the features such as detect, it is considered to be the powerful technological means of rare earth elemental analysis.But, when ICP-MS is used in actual sample
During the direct analysis of rare earth element, too low (the sub- ng L of sample rare earth elements concentration can be run into-1Level) and sample substrate is again
Miscellaneous the problems such as, so that affect the accuracy of testing result.Therefore, usually need to be aided with suitable sample pre-treatments skill before determining
Art, with the purpose for reaching decontamination substrate, eliminating interference, separation and concentration target analytes.It is rich that rare earths separation is had been used at present
The Sample Pretreatment Technique of collection has liquid-phase extraction, Solid-Phase Extraction and capillary tube micro-extraction etc..Wherein, liquid-phase extraction has usually been used
Machine reagent, complex operation, although Solid-Phase Extraction is easy to be quick, it is to avoid using organic reagent, there is also consumption sample size greatly, no
The shortcomings of beneficial to automatization, and capillary tube micro-extraction has that adsorption capacity is big, sample consumption is few, mass transfer velocity is fast and is easy to automatic
The advantages of change.
Nanoparticle is as particle diameter is little, specific surface area is big, with many special natures such as quantum effect and skin effect,
The modified aspect of capillary monolithic column has very big application potential.Its machinery can be increased using nanometer particle-modified integral post strong
Degree, improves the selectivity to target analytes, increases adsorption capacity, expands use range of integral post etc..The kind of nanoparticle
Class includes:Carbon nanomaterial, SiO2Nano material, metal and metal oxide nano-material, polymer nano material etc..Its
In, therefore nanometer gold can firmly be tied by sulfydryl or amino by nanometer gold due to forming covalent bond with sulfydryl and amino
Integral post surface is closed, different function base modifications is then carried out again to nanometer gold, is realized the extraction to different target analyte.
The modified integral post of nanometer gold has been used for the separation of polypeptide and protein and other in biological sample at present, but
Application in terms of the separation detection of inorganic metal ion is considerably less.
Content of the invention
The purpose of the present invention is to prepare a kind of modified polymer entirety of nanometer gold that can be used for rare earths separation enrichment
Post, sets up polymer integral column capillary tube micro-extraction (monolithic CME) and inductivity coupled plasma mass spectrometry (ICP-MS)
On-line coupling analyzes the new method of complex sample rare earth elements.The method can realize sea water and people's whole blood rare earth elements
On-line analyses, and adsorption capacity of the integral post to rare earth element is considerably improved, there is the method high sensitivity, high sample to lead to
The advantages of amount, low sample consumption and the wider pH scope of applications and stronger anti-matrix interference ability, it is suitable for micro complexity
The analysis of trace/ultra trace rare earth element in matrix sample.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of the polymer-modified integral post of the nanometer gold of dimercaptosuccinic acid modification, comprises the following steps:
(1) capillary tube is activated using water, NaOH, water, HCl, water and WD-70 successively;
(2) by glycidyl methacrylate, ethylene glycol dimethacrylate, Hexalin, lauryl alcohol and azo two
Ultrasound after isopropyl cyanide mixing, is then injected in the capillary tube that step (1) has been activated, and seals capillary tube two ends with silicagel pad, so
React at 60 DEG C afterwards, after question response terminates, with the unreacted monomer of alcohol flushing and porogen, obtain polyalcohol integral pole;
(3) polyalcohol integral pole for step (2) being prepared using 2-aminoethyl disulfide dihydrochloride, propylamine and dithiothreitol, DTT successively
It is modified;
(4) be passed through nano-Au solution in the modified good polyalcohol integral pole of step (3) until whole pillar become red,
Till effluent assumes pink;
(5) integral post obtained with dimercaptosuccinic acid solution rinsing step (4) to be to obtain the rich carboxylic integral post in surface,
Then rinsed with high purity water, that is, obtain the polymer-modified integral post of nanometer gold of dimercaptosuccinic acid modification, i.e. poly (GMA-
EDMA-AuNPs-MSA) integral post.
Step (1) is specially:Ultra-pure water, 1.0mol L are used successively-1NaOH solution, ultra-pure water, 1.0mol L-1's
HCl solution, ultra-pure water are rinsed to capillary tube, are then dried up with argon;It is 1 by volume ratio:1 WD-70 is mixed with ethanol
Close solution to rush to capillary tube, two ends are sealed with silica gel, be placed in reaction in 70 DEG C of baking ovens, then will be not anti-in capillary tube with ethanol
The reagent that answers is developed, then is dried up capillary tube with argon standby.
In step (1), the capillary tube is the vitreous silica capillary tube of 20cm × 530 μm, uses ultrapure water successively
10min、1.0mol·L-1NaOH solution rinse 2h, ultrapure water 30min, 1.0mol L-1HCl solution rinse 2h,
In ultrapure water 30min, baking oven, the time of reaction is 12h.
Step (3) is specially:The polymer being prepared into 2-aminoethyl disulfide dihydrochloride solution rinsing step (2) of pH=9 first
Then pillar two ends are sealed by integral post with silicagel pad, are placed in 50 DEG C of water-bath and are reacted;Repeat above operation twice;So
Integral post being rinsed with high purity water afterwards, then integral post being rinsed with the propylamine solution of pH=11, silicagel pad is placed in after sealing pillar two ends
React in 50 DEG C of water-bath;Finally integral post is rinsed with the dithiothreitol, DTT solution of pH=9, make disulfide bonds, obtain mercapto
The integral post of base derivatization.
In the polymer-modified integral post of the nanometer gold of described dimercaptosuccinic acid modification, the particle diameter of nanometer gold is 13nm.
A kind of polymer-modified integral post of the nanometer gold of dimercaptosuccinic acid modification, is prepared by above-mentioned preparation method.
The polymer-modified integral post of the nanometer gold of above-mentioned dimercaptosuccinic acid modification is used for the enrichment and detection of rare earth element.
A kind of polymer-modified integral post of nanometer gold that is modified using above-mentioned dimercaptosuccinic acid is analyzed to rare earth element
The method of detection, comprises the following steps:
(1) by the sample solution pH regulator containing rare earth element to be measured to 5, the nanometer gold for being passed through dimercaptosuccinic acid modification changes
Property polyalcohol integral pole, then passes to HNO3Solution carries out desorbing, and stripping liquid pumps into ICP-MS online by flow injection instruments and enters
Row is determined;
(2) high purity water for not adding element to be measured is operated by step (1), and is measured with ICP-MS, gained signal
Value is used as blank value.
Described sample solution is sea water or people's whole blood digestion solution.
The present invention is prepared for poly (GMA-EDMA) integral post of decorated by nano-gold using chemical modification, and with nanometer gold is
Middle part, in the dimercaptosuccinic acid that its surface modification has affinity to rare earth element, as nanometer gold has larger ratio
Surface area, can dramatically increase the functional group content on integral post surface, so as to improve the adsorption capacity of integral post, the integral post tool
Have the advantages that to prepare that good, the resistance to matrix interference ability of repeatability is strong, long service life.By the micro- extraction of polymer capillary integral post
Take and be combined with ICP-MS, can achieve seawater sample rare earth elements is directly separated enrichment detection, and after people's whole blood is cleared up
Detection.
The present invention is had the advantage that relative to prior art and effect:
Good dispersiveness of the polymer integral column capillary tube of the decorated by nano-gold prepared based on the present invention to rare earth element
Can, it is proposed that poly (GMA-EDMA-Au NPs-MSA) integral column capillary tube micro-extraction is joined with inductivity coupled plasma mass spectrometry
With the new method of analysis complex matrices sample rare earth elements, the method can achieve sea water (need not clear up) and people's whole blood (is cleared up
The on-line analyses of rare earth elements afterwards), compared with without the modified integral post of nanometer gold, adsorption capacity improves 3-6.5 times,
The advantages of pH scope of applications that anti-matrix interference ability is strong, sensitivity is high and wider, it is suitable for trace in micro complicated substrate sample
The analysis of amount/ultra trace rare earth element.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1
(500μm).
Fig. 2 is scanning electron microscope (SEM) figure of poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1
(200μm).
Fig. 3 is scanning electron microscope (SEM) figure of poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1
(100nm).
Fig. 4 is scanning electron microscope (SEM) figure of poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1
(100nm).
Fig. 5 is the X-ray energy spectrum (EDS) of poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1
Figure.
Fig. 6-Fig. 9 is that poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1 is used for the micro- extraction of capillary tube
The condition optimizing figure for taking;Wherein, optimization figures of the Fig. 6 for sample solution pH value, optimization figures of the Fig. 7 for sample solution flow velocity, Fig. 8 is
The optimization figure of concentration of nitric acid in eluent, optimization figures of the Fig. 9 for sampling volume.
Figure 10 is that poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1 is used for capillary tube micro-extraction
When the figure of resistance to disturbed condition to humic acid.
Specific embodiment
The present invention is expanded on further with reference to the accompanying drawings and examples, but these embodiments are only limitted to the explanation present invention, and
The scope of the present invention can not be limited.
Embodiment 1:The preparation of the modified capillary monolithic column of nanometer gold of dimercaptosuccinic acid modification
(1) the pre-activate process of capillary tube:From vitreous silica capillary tube (20cm × 530 μm), rushed with ultra-pure water successively
Wash 10min, 1.0mol L-1NaOH solution rinse 2h, ultrapure water 30min, 1.0mol L-1HCl solution flushing 2h,
Then ultrapure water 30min is dried up with nitrogen to neutrality.By the mixed solution of WD-70 and ethanol, (volume ratio is 1:1) pour
In capillary tube, two ends are sealed with silicagel pad, are placed in reaction 12h in 70 DEG C of baking ovens, then will be unreacted in capillary tube with ethanol
Reagent is rushed out, then will be dried up inside capillary tube with argon standby.
(2) preparation of poly (GMA-EDMA) integral post:Integral post is synthesized using thermal initiation situ aggregation method, by 140mg
The Hexalin of EDMA, 0.66mL of GMA, 120mg, the lauryl alcohol of 0.09mL and 1% AIBN mixing, after ultrasonic 10min, note
Entering in the capillary tube that step (1) has been activated, then capillary tube two ends being sealed with silicagel pad, 12h is reacted at 60 DEG C, question response is tied
Shu Hou, falls unreacted monomer and porogen with alcohol flushing;
(3) integral post surface finish nano gold:Compound concentration is 1.0mol L-12-aminoethyl disulfide dihydrochloride solution be used in combination
NaOH aqueous solutions adjust pH to 9, at room temperature by the solution with 5 μ L min-1Flow velocity rinsing step (2) in prepare
Then pillar two ends are sealed by poly (GMA-EDMA) integral post 1h with silicagel pad, are placed in 50 DEG C of water-bath reaction 1h.Above-mentioned
Modification will be repeated twice to obtain the conversion ratio of maximum, rinse integral post to neutrality with high purity water afterwards.Compound concentration again
For 1.0mol L-1Propylamine solution and with aqueous hydrochloric acid solution adjust pH to 11, with 5 μ L min-1Flow velocity rinse integral post 1h,
After silica gel seals two ends, 50 DEG C of water-bath reaction 1h are still placed in, to be reacted with remaining epoxy radicals in integral post.Then match somebody with somebody
0.2mol L processed-1DTT simultaneously adjusts pH to 9 with sodium hydrate aqueous solution, at room temperature with 3 μ L min-1Flow velocity rinses integral post
2h so that disulfide bonds, obtains the capillary monolithic column of sulfydryl derivatization, is rinsed integral post into high purity water afterwards
Property, then by nano-Au solution by the Monolithic Columns rich in sulfydryl, till effluent becomes pink.
(4) preparation of the nanometer gold modification integral post of dimercaptosuccinic acid modification:It is 50mmol L by concentration-1Sulfydryl fourth
Diacid solution is with 0.1mL min-1Speed slowly flow across the integral post that obtains in embodiment 3 to obtain poly (GMA-co-
EDMA-AuNPs-MSA), the integral post two ends for preparing respectively are clipped and is about 2-3cm and has the part of larger dead volume, then will
Which is uniformly cut into the integral post of 2cm length, standby.
The scanning electron microscope (SEM) photograph of prepared poly (GMA-co-EDMA-Au NPs-MSA) integral post as Figure 1-4, by
It is uniform that Fig. 1 and Fig. 2 can be seen that post bed structure, is tightly combined with capillary wall, takes off wall phenomenon, capillary monolithic column by
Microsphere of uniform size and the through hole composition for mutually running through, it is ensured that good permeability;Amplify 80000 times when (such as Fig. 3 institutes
Show), it can be seen that nanogold particle is evenly dispersed in integral post surface, without agglomeration, the modified success of nanometer gold is described;
Fig. 4 is nanometer gold integral post surface before modified, above without particulate material.
Prepared prepared poly (GMA-co-EDMA-Au NPs-MSA) integral post Au content is using EDS elements point
It is 29.61% (as shown in Figure 5) that analysis method measures the mass percent of Au, further illustrates nanometer gold and is successfully bonded to integral post
On.
Embodiment 2:Application of poly (GMA-EDMA-Au NPs-MSA) integral post on rare earth element is detected
Poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1 is used for capillary tube micro-extraction and ICP-
The method that monolithic CME-ICP-MS detect rare earth element is set up in MS combinations
1) first the condition of capillary tube micro-extraction is optimized, as shown in Fig. 6-Fig. 9, excellent one by one using unitary variant method
Change the condition of capillary tube micro-extraction, it is 5 that the optimal conditionss for finally determining are sample solution pH value, loading flow velocity is 0.1mL
min-1, sample volume is 0.5mL, and eluant is HNO3, eluant strength and volume are respectively 0.5mol L-1、0.02mL.
2) in optimal conditions common interference ion (such as table 1) and humic acid (Figure 10) are enriched with to rare earth element and are detected
Impact investigated, as a result show, the method carry out actual sample analyze when there are preferable selectivity and un-mixing bases
The ability of body, the analysis of the people's whole blood after can be used for the direct analysis of sea water and clearing up.
1 nanometer gold of table modification integral post is used for the tolerable concentration of coexisting ion when capillary tube micro-extraction is tested
3) the preparation repeatability and service life of poly (GMA-EDMA-Au NPs-MSA) integral post are investigated.
The preparation repeatability of integral post is investigated, and same batch (n=7) and different batches have been investigated under optimum experiment condition
(n=7) recovery of extraction of the integral post for preparing to target rare earth element, and calculate its relative standard deviation.In same batch
RSD (n=7) between 3.4% (Nd) -5.2% (Lu), the RSD (n=7) of different batches 2.7% (Ho) -6.0% (Sm) it
Between.Additionally, with 0.04mL 0.5mol L-1Nitric acid with 0.1mL min-1Flow velocity rinse post bed, you can realize integral post
Regeneration.In optimal conditions, the integral post reusable more than 165 times and extraction efficiency is not decreased obviously.
4) whether the adsorption capacity of rare earth element is significantly carried for investigation poly (GMA-EDMA-Au NPs-MSA) integral post
Height, compared for modified whole without modified integral post poly of nanometer gold (GMA-EDMA-IDA) and nanometer gold in optimal conditions
Adsorption capacities of the scapus poly (GMA-EDMA-AuNPs-MSA) to rare earth element, comparing result as shown in table 2, by can be with table
Find out, the modified integral post adsorption capacity of nanometer gold increased 3-6.5 times, it was demonstrated that nanometer gold serves increasing multifunctional groups really
Effect.
Rear integral post is contrasted 2 nanometer gold of table to the adsorption capacity of rare earth element before modified
5) this method is used for the analysis of sea water and Whole Blood of Healthy, the meansigma methodss of three measurement results to be listed in table 3 and table 4
In.The recovery testu of basic, normal, high three concentration levels has been carried out to sample respectively, and its recovery of standard addition is in 80-116%
Between, show that this method can be used for the analysis of trace in seawater sample and complex biological sample/ultra trace rare earth element.
The testing result and mark-on reclaims result of 3 sea water rare earth elements of table
The testing result and mark-on reclaims result of 4 people's whole blood rare earth elements of table
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement that is made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. the preparation method of the polymer-modified integral post of the nanometer gold of a kind of dimercaptosuccinic acid modification, it is characterised in that include with
Lower step:
(1) capillary tube is activated using water, NaOH, water, HCl, water and WD-70 successively;
(2) by glycidyl methacrylate, ethylene glycol dimethacrylate, Hexalin, two isobutyl of lauryl alcohol and azo
Ultrasound after nitrile mixing, is then injected in the capillary tube that step (1) has been activated, and seals capillary tube two ends with silicagel pad, Ran Hou
60 DEG C of reactions, after question response terminates, with the unreacted monomer of alcohol flushing and porogen, obtain polyalcohol integral pole;
(3) polyalcohol integral pole that step (2) is prepared is carried out using 2-aminoethyl disulfide dihydrochloride, propylamine and dithiothreitol, DTT successively
Modified;
(4) nano-Au solution is passed through in the modified good polyalcohol integral pole of step (3) until whole pillar becomes red, flows out
Till liquid assumes pink;
(5) integral post obtained with dimercaptosuccinic acid solution rinsing step (4) to be to obtain the rich carboxylic integral post in surface, then
Rinsed with high purity water, that is, obtain the polymer-modified integral post of nanometer gold of dimercaptosuccinic acid modification.
2. preparation method according to claim 1, it is characterised in that:Step (1) is specially:Successively with ultra-pure water,
1.0mol·L-1NaOH solution, ultra-pure water, 1.0mol L-1HCl solution, ultra-pure water capillary tube is rinsed, then
Dried up with argon;It is 1 by volume ratio:1 WD-70 is rushed to capillary tube with the mixed solution of ethanol, and two ends are sealed with silica gel, are put
React in 70 DEG C of baking ovens, then unreacted reagent in capillary tube is developed with ethanol, then capillary tube is blown with argon
Dry standby.
3. preparation method according to claim 2, it is characterised in that:In step (1), the capillary tube is 20cm × 530 μ
The vitreous silica capillary tube of m, uses ultrapure water 10min, 1.0mol L successively-1NaOH solution rinse 2h, ultrapure water
30min、1.0mol·L-1HCl solution rinse 2h, ultrapure water 30min, the time of reaction is 12h in baking oven.
4. preparation method according to claim 1, it is characterised in that:Step (3) is specially:First with the cystamine of pH=9
Then pillar two ends are sealed with silicagel pad, are placed in 50 by the polyalcohol integral pole that dihydrochloride solution rinsing step (2) is prepared
DEG C water-bath in react;Repeat above operation twice;Then integral post, then the propylamine solution with pH=11 are rinsed with high purity water
Integral post is rinsed, silicagel pad is placed in after sealing pillar two ends in 50 DEG C of water-bath reacts;Finally with the dithiothreitol, DTT of pH=9
Solution rinses integral post, makes disulfide bonds, obtains the integral post of sulfydryl derivatization.
5. preparation method according to claim 1, it is characterised in that:The nanometer gold of described dimercaptosuccinic acid modification is modified
In polyalcohol integral pole, the particle diameter of nanometer gold is 13nm.
6. the polymer-modified integral post of the nanometer gold of a kind of dimercaptosuccinic acid modification, it is characterised in that:Arbitrary by claim 1-5
Preparation method described in is prepared.
7. the polymer-modified integral post of the nanometer gold of the dimercaptosuccinic acid modification described in claim 6 is used for the enrichment of rare earth element
And detection.
8. a kind of polymer-modified integral post of the nanometer gold of the dimercaptosuccinic acid modification described in utilization claim 6 is to rare earth element
It is analyzed the method for detection, it is characterised in that comprise the following steps:
(1) by the sample solution pH regulator containing rare earth element to be measured to 5, the nanometer gold for being passed through dimercaptosuccinic acid modification is modified poly-
Compound integral post, then passes to HNO3Solution carries out desorbing, and stripping liquid pumps into ICP-MS online by flow injection instruments and surveyed
Fixed;
(2) high purity water for not adding element to be measured is operated by step (1), and is measured with ICP-MS, gained signal value is made
For blank value.
9. method according to claim 8, it is characterised in that:Described sample solution is sea water or people's whole blood digestion solution.
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CN109225171A (en) * | 2018-09-29 | 2019-01-18 | 武汉大学 | A kind of preparation method and application of the modified organic inorganic hybridization integral post of surface ion imprinted polymer |
RU2696011C1 (en) * | 2019-05-06 | 2019-07-30 | Федеральное бюджетное учреждение науки "Федеральный научный центр медико-профилактических технологий управления рисками здоровью населения" Федеральной службы по надзору в сфере защиты прав потребителей и благополучия человека (ФБУН "ФНЦ медико-профилактических технологий управления рисками здоровью | Method of determining blood content of rare-earth elements: yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium by mass spectrometry with inductively coupled plasma |
CN115301216A (en) * | 2022-08-04 | 2022-11-08 | 武汉大学 | High internal phase emulsion polymerization grading porous capillary monolithic column and preparation method and application thereof |
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CN109225171A (en) * | 2018-09-29 | 2019-01-18 | 武汉大学 | A kind of preparation method and application of the modified organic inorganic hybridization integral post of surface ion imprinted polymer |
CN109225171B (en) * | 2018-09-29 | 2020-06-09 | 武汉大学 | Preparation method and application of surface ion imprinted polymer modified organic-inorganic hybrid monolithic column |
RU2696011C1 (en) * | 2019-05-06 | 2019-07-30 | Федеральное бюджетное учреждение науки "Федеральный научный центр медико-профилактических технологий управления рисками здоровью населения" Федеральной службы по надзору в сфере защиты прав потребителей и благополучия человека (ФБУН "ФНЦ медико-профилактических технологий управления рисками здоровью | Method of determining blood content of rare-earth elements: yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium by mass spectrometry with inductively coupled plasma |
CN115301216A (en) * | 2022-08-04 | 2022-11-08 | 武汉大学 | High internal phase emulsion polymerization grading porous capillary monolithic column and preparation method and application thereof |
CN115301216B (en) * | 2022-08-04 | 2024-04-05 | 武汉大学 | High internal phase emulsion polymerization grading porous capillary monolithic column and preparation method and application thereof |
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