CN106492506B - A kind of polymer-modified integral post of nanogold and its preparation method and application - Google Patents
A kind of polymer-modified integral post of nanogold and its preparation method and application Download PDFInfo
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- B01D15/08—Selective adsorption, e.g. chromatography
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Abstract
The invention discloses the methods of rare earth element in a kind of polymer-modified integral column capillary tube micro-extraction of nanogold of dimercaptosuccinic acid modification and ICP-MS on-line coupling analysis seawater and people's whole blood.It is crosslinking agent by monomer, ethylene glycol dimethacrylate of glycidyl methacrylate, 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 it rich in sulfydryl, to upper nanogold modified by the way of chemical bonding, finally with nanogold for intermediate ligand, there is the dimercaptosuccinic acid of affinity interaction in its surface modification to rare earth element.The integral post is used for the separation and concentration of rare earth element in complex sample, the on-line analysis of rare earth element in seawater and people's whole blood may be implemented, and integral post is significantly improved to the adsorption capacity (3-6.5 times) of rare earth element, have many advantages, such as highly sensitive, high sample throughput, low sample consumption and the wider pH scope of application and stronger anti-Matrix effects ability.
Description
Technical field
The invention belongs to separate and technical field of analysis and detection, and in particular to a kind of nanogold of dimercaptosuccinic acid modification changes
Property polyalcohol integral pole and preparation method thereof, and its be combined for capillary micro-extraction and inductivity coupled plasma mass spectrometry to multiple
Rare earth element in miscellaneous sample carries out on-line analysis detection.
Background technique
Rare earth element is due to being widely used in industrial (magnetic material, catalysis material), agriculture with some special properties
Fields, a large amount of uses of rare earth element such as industry (RE microbial fertilizer) and biomedical (mri contrast agent) can make it that can not keep away
It can be discharged into environment with exempting from, organism had an important influence on by being accumulated in food chain.Studies have shown that taking in low dose for a long time
The rare earth element of amount can cause brain to be accumulated, and induce poisonous effect, so that nerve is baffled, IQ reduces；Rare earth element also will affect
The activity of the metabolic pathway of life entity and a variety of biological enzyme, especially lanthanum and gadolinium can block the ion channel of calcium in cell；In addition,
Rare earth element can also invade reproduction cell, destroy the fecundity of people.Therefore, the detection of rare earth element has in environment and human body
Significance.
Inductivity coupled plasma mass spectrometry (ICP-M S) due to high sensitivity, the range of linearity it is wide and can multielement it is same
When the features such as detecting, it is considered to be the powerful technological means of rare earth elemental analysis.But when ICP-MS is used in actual sample
When the direct analysis of rare earth element, too low (the sub- ng L of rare earth element concentration in sample can be encountered-1It is horizontal) and sample substrate it is multiple
The problems such as miscellaneous, to will affect the accuracy of testing result.Therefore, usually need to be aided with suitable sample pre-treatments skill before measurement
Art, to achieve the purpose that decontamination substrate, eliminate interference, separation and concentration target analytes.Rare earths separation richness is had been used at present
The Sample Pretreatment Technique of collection has liquid-phase extraction, Solid Phase Extraction and capillary micro-extraction etc..Wherein, liquid-phase extraction has usually been used
Machine reagent, it is complicated for operation, although Solid Phase Extraction is easy quickly, avoid using organic reagent, there is also consumption sample sizes greatly, no
The disadvantages of conducive to automation, and capillary micro-extraction is with adsorption capacity is big, sample consumption is few, mass transfer velocity is fast and is easy to automatic
The advantages that change.
Nanoparticle has many special natures such as quantum effect and skin effect since partial size is small, large specific surface area,
The modified aspect of capillary monolithic column has very big application potential.It is mechanical strong that it can be increased using nanometer particle-modified integral post
Degree improves the selectivity to target analytes, increases adsorption capacity, expands the use scope etc. of integral post.The kind of nanoparticle
Class includes: carbon nanomaterial, SiO2Nano material, metal and metal oxide nano-material, polymer nano material etc..Its
In, nanogold can firmly be tied nanogold by sulfydryl or amino due to that can form covalent bond with sulfydryl and amino
Integral post surface is closed, different function bases then is carried out to nanogold again and is modified, realizes the extraction to different target analyte.
The modified integral post of nanogold has been used for the separation of polypeptide and protein and other in biological sample at present, still
In terms of the separation detection of inorganic metal ion using considerably less.
Summary of the invention
It is whole the purpose of the present invention is preparing a kind of polymer that the nanogold that can be used for rare earths separation enrichment is modified
Column establishes 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 rare earth element in complex sample.Rare earth element in seawater and people's whole blood may be implemented in this method
On-line analysis, and significant the integral post that improves, to the adsorption capacity of rare earth element, this method has highly sensitive, high sample logical
The advantages that amount, low sample consumption and wider pH scope of application and stronger anti-Matrix effects ability, it is suitable for micro complexity
Trace/ultra trace rare earth element analysis in matrix sample.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of the polymer-modified integral post of nanogold of dimercaptosuccinic acid modification, comprising the following steps:
(1) successively capillary is activated using water, NaOH, water, HCl, water and WD-70；
(2) by glycidyl methacrylate, ethylene glycol dimethacrylate, cyclohexanol, lauryl alcohol and azo two
Ultrasound after isobutyronitrile mixing, is then injected into step (1) activated capillary, is sealed capillary both ends with silicagel pad, so
It is reacted afterwards at 60 DEG C, to after reaction, rinse unreacted monomer and pore-foaming agent with ethyl alcohol, obtain polyalcohol integral pole；
(3) polyalcohol integral pole that successively step (2) is prepared using 2-aminoethyl disulfide dihydrochloride, propylamine and dithiothreitol (DTT)
It is modified；
(4) nano-Au solution is passed through in the polyalcohol integral pole being modified to step (3) until whole pillar become it is red,
Until pink is presented in efflux；
(5) with the integral post that dimercaptosuccinic acid solution rinsing step (4) obtains to obtain the rich carboxylic integral post in surface,
Then it is rinsed with high purity water to get the polymer-modified integral post of nanogold modified to dimercaptosuccinic acid, i.e. poly (GMA-
EDMA-AuNPs-MSA) integral post.
Step (1) specifically: successively use ultrapure water, 1.0molL-1NaOH solution, ultrapure water, 1.0molL-1's
HCl solution, ultrapure water are rinsed capillary, are then dried up with argon gas；It is the WD-70 of 1:1 and mixing for ethyl alcohol by volume ratio
It closes solution to rush to capillary, both ends are sealed with silica gel, are placed in reaction in 70 DEG C of baking ovens, then will be not anti-in capillary with ethyl alcohol
The reagent answered develops, then with argon gas is dried up capillary spare.
In step (1), the capillary is the vitreous silica capillary of 20cm × 530 μm, successively uses ultrapure water
10min、1.0mol·L-1NaOH solution rinse 2h, ultrapure water 30min, 1.0molL-1HCl solution rinse 2h,
Ultrapure water 30min, the baking oven interior time reacted is 12h.
Step (3) specifically: the polymer being prepared into first with the 2-aminoethyl disulfide dihydrochloride solution rinsing step (2) of pH=9
Then pillar both ends are sealed with silicagel pad, are placed in 50 DEG C of water-bath and react by integral post；It repeats above operation twice；So
Integral post is rinsed with high purity water afterwards, then rinses integral post with the propylamine solution of pH=11, silicagel pad seals pillar both ends and is placed on
It is reacted in 50 DEG C of water-bath；Integral post finally is rinsed with the dithiothreitol (DTT) solution of pH=9, makes disulfide bonds, obtains mercapto
The integral post of base derivatization.
The partial size of nanogold is 13nm in the polymer-modified integral post of nanogold of the dimercaptosuccinic acid modification.
A kind of polymer-modified integral post of nanogold of dimercaptosuccinic acid modification, is prepared by above-mentioned preparation method.
The polymer-modified integral post of nanogold of above-mentioned dimercaptosuccinic acid modification is used for the enrichment and detection of rare earth element.
It is a kind of using above-mentioned dimercaptosuccinic acid modification nanogold polymer-modified integral post rare earth element is analyzed
The method of detection, comprising the following steps:
(1) the sample solution pH containing rare earth element to be measured is adjusted to 5, the nanogold for being passed through dimercaptosuccinic acid modification changes
Property polyalcohol integral pole, then passes to HNO3Solution is desorbed, stripping liquid by flow injection instruments be pumped into online ICP-MS into
Row measurement；
(2) high purity water that element to be measured is not added is operated by step (1), and is measured with ICP-MS, gained signal
Value is used as blank value.
The sample solution is seawater 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 is with nanogold
Intermediate ligand, in the dimercaptosuccinic acid that its surface modification is affinity to rare earth element, since nanogold has biggish ratio
Surface area, can dramatically increase the functional group content on integral post surface, so that the adsorption capacity of integral post is improved, integral post tool
Have the advantages that preparation reproducibility is good, resistance to matrix interference ability is strong, long service life.By the micro- extraction of polymer capillary integral post
It takes and is combined with ICP-MS, it can be achieved that being directly separated for rare earth element is enriched with after detection and the resolution of people's whole blood in seawater sample
Detection.
The present invention has the following advantages compared with the prior art and effect:
Good dispersiveness of the polymer integral column capillary tube based on decorated by nano-gold prepared by the present invention to rare earth element
Can, it proposes poly (GMA-EDMA-Au NPs-MSA) integral column capillary tube micro-extraction and inductivity coupled plasma mass spectrometry joins
With the new method of rare earth element in analysis complex matrices sample, this method can realize seawater (without resolution) and (resolution of people's whole blood
The on-line analysis of rare earth element in later), compared with without the modified integral post of nanogold, adsorption capacity improves 3-6.5 times,
Anti- Matrix effects ability is strong, high sensitivity and the advantages that the wider pH scope of application, is suitable for trace in micro complicated substrate sample
The analysis of amount/ultra trace rare earth element.
Detailed description of the invention
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
The condition optimizing figure taken；Wherein, Fig. 6 is the optimization figure of sample solution pH value, and Fig. 7 is the optimization figure of sample solution flow velocity, and Fig. 8 is
The optimization figure of concentration of nitric acid in eluent, Fig. 9 are the optimization figure of sampling volume.
Figure 10 is that poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1 is used for capillary micro-extraction
When to the figure of resistance to disturbed condition of humic acid.
Specific embodiment
The present invention is further explained with reference to the accompanying drawings and examples, but these embodiments are only limitted to illustrate the present invention, and
It cannot limit the scope of the invention.
Embodiment 1: the preparation of the modified capillary monolithic column of the nanogold of dimercaptosuccinic acid modification
(1) it the pre-activate process of capillary: selects vitreous silica capillary (20cm × 530 μm), is successively rushed with ultrapure water
Wash 10min, 1.0molL-1NaOH solution rinse 2h, ultrapure water 30min, 1.0molL-1HCl solution flushing 2h,
Ultrapure water 30min is to neutrality, then with being dried with nitrogen.The mixed solution (volume ratio 1:1) of WD-70 and ethyl alcohol is poured
In capillary, both ends are sealed with silicagel pad, are placed in 70 DEG C of baking ovens and are reacted 12h, then will be unreacted in capillary with ethyl alcohol
Reagent is rushed out, then with argon gas that drying inside capillary is spare.
(2) preparation of poly (GMA-EDMA) integral post: situ aggregation method is caused using heat and synthesizes integral post, by 140mg
The cyclohexanol of EDMA, 0.66mL of GMA, 120mg, the lauryl alcohol of 0.09mL and 1% AIBN mixing, after ultrasonic 10min, note
Enter in step (1) activated capillary, then sealed capillary both ends with silicagel pad, in 60 DEG C of reaction 12h, wait react knot
Shu Hou rinses out unreacted monomer and pore-foaming agent with ethyl alcohol；
(3) integral post surface finish nano gold: compound concentration 1.0molL-12-aminoethyl disulfide dihydrochloride solution be used in combination
NaOH aqueous solution adjusts pH to 9, at room temperature by the solution with 5 μ Lmin-1Flow velocity rinsing step (2) in prepare
Poly (GMA-EDMA) integral post 1h, is then sealed pillar both ends with silicagel pad, is placed in 50 DEG C of water-bath reaction 1h.It is above-mentioned
Modification will be repeated twice to obtain maximum conversion ratio, rinse integral post to neutrality with high purity water later.Compound concentration again
For 1.0molL-1Propylamine solution and with aqueous hydrochloric acid solution tune pH to 11, with 5 μ Lmin-1Flow velocity rinse integral post 1h,
After silica gel seals both ends, 50 DEG C of water-bath reaction 1h are placed in, still to be reacted with epoxy group remaining in integral post.Then match
0.2molL processed-1DTT and with sodium hydrate aqueous solution tune pH to 9, at room temperature with 3 μ Lmin-1Flow velocity rinses integral post
2h, so that disulfide bonds, obtain the capillary monolithic column of sulfydryl derivatization, later rinsed integral post into high purity water
Property, then by nano-Au solution by the Monolithic Columns rich in sulfydryl, until efflux becomes pink.
(4) preparation of the modified integral post of the nanogold of dimercaptosuccinic acid modification: being 50mmolL by concentration-1Sulfydryl fourth
Diacid solution is with 0.1mLmin-1Speed slowly flow across integral post obtained in embodiment 3 to obtain poly (GMA-co-
EDMA-AuNPs-MSA), the integral post both ends prepared are respectively clipped to the part for being about 2-3cm and having larger dead volume, then will
Its integral post for being uniformly cut into 2cm long, it is spare.
The scanning electron microscope (SEM) photograph of prepared poly (GMA-co-EDMA-Au NPs-MSA) integral post is as shown in Figs 1-4, by
It is uniform that Fig. 1 and Fig. 2 can be seen that column bed structure, is tightly combined with capillary wall, does not take off wall phenomenon, capillary monolithic column by
Microballoon of uniform size and the through-hole being intertwined composition, ensure that good permeability；(such as Fig. 3 institute when amplifying 80000 times
Show), it can be seen that nanogold particle is evenly dispersed in integral post surface, without agglomeration, illustrates that nanogold is modified successfully；
Fig. 4 is the integral post surface of nanogold before modified, does not have particulate material above.
Prepared prepared poly (GMA-co-EDMA-Au NPs-MSA) integral post Au content is using EDS element point
The mass percent that analysis method measures Au is 29.61% (as shown in Figure 5), further illustrates that nanogold is successfully bonded to integral post
On.
Application of embodiment 2:poly (GMA-EDMA-Au NPs-MSA) integral post in rare earth element detection
Poly (GMA-EDMA-Au NPs-MSA) integral post prepared by embodiment 1 is used for capillary micro-extraction and ICP-
The method that monolithic CME-ICP-MS detection rare earth element is established in MS combination
1) condition of capillary micro-extraction is optimized first, it is excellent one by one using unitary variant method as shown in Fig. 6-Fig. 9
Change the condition of capillary micro-extraction, it is 5 that finally determining optimal conditions, which is sample solution pH value, and loading flow velocity is 0.1mL
min-1, sample volume 0.5mL, eluant, eluent HNO3, eluant strength and volume are respectively 0.5molL-1、0.02mL。
2) common interference ion (such as table 1) and humic acid (Figure 10) are enriched with and are detected to rare earth element in optimal conditions
Influence investigated, the results showed that, this method when carrying out actual sample analysis have preferable selectivity and un-mixing bases
The ability of body can be used for the direct analysis of seawater and the analysis of people's whole blood after resolution.
The tolerable concentration of coexisting ion when the modified integral post of 1 nanogold of table is tested for capillary micro-extraction
3) the preparation reproducibility and service life of poly (GMA-EDMA-Au NPs-MSA) integral post are investigated.
The preparation reproducibility of integral post is investigated, same batch (n=7) and different batches have been investigated under optimal experiment condition
(n=7) integral post prepared is to the recovery of extraction of target rare earth element, and calculates 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.In addition, with 0.04mL 0.5molL-1Nitric acid with 0.1mLmin-1Flow velocity rinse column bed, integral post can be realized
Regeneration.In optimal conditions, the integral post reusable 165 times or more and extraction efficiency is not decreased obviously.
4) whether the adsorption capacity of rare earth element is significantly mentioned for investigation poly (GMA-EDMA-Au NPs-MSA) integral post
Height, the integral post poly (GMA-EDMA-IDA) and nanogold that compared no nanogold modification in optimal conditions are modified whole
For scapus poly (GMA-EDMA-AuNPs-MSA) to the adsorption capacity of rare earth element, comparing result is as shown in table 2, by can be in table
Find out, the modified integral post adsorption capacity of nanogold increases 3-6.5 times, it was demonstrated that nanogold plays increasing multifunctional groups really
Effect.
Rear integral post compares the adsorption capacity of rare earth element to 2 nanogold of table before modified
5) this method is used for the analysis of seawater and Whole Blood of Healthy, the average value of measurement result to be listed in table 3 and table 4 three times
In.The recovery testu of basic, normal, high three concentration levels is carried out to sample respectively, 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 rare earth element in 3 seawater of table
The testing result and mark-on reclaims result of rare earth element in 4 people's whole blood of table
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of the polymer-modified integral post of nanogold of dimercaptosuccinic acid modification, which is characterized in that including with
Lower step:
(1) successively capillary is activated using water, NaOH, water, HCl, water and WD-70；
(2) by glycidyl methacrylate, ethylene glycol dimethacrylate, two isobutyl of cyclohexanol, lauryl alcohol and azo
Ultrasound after nitrile mixing, is then injected into step (1) activated capillary, seals capillary both ends with silicagel pad, then exist
60 DEG C of reactions, to after reaction, rinse unreacted monomer and pore-foaming agent with ethyl alcohol, obtain polyalcohol integral pole；
(3) successively the polyalcohol integral pole that step (2) prepares is carried out using 2-aminoethyl disulfide dihydrochloride, propylamine and dithiothreitol (DTT)
It is modified；
(4) nano-Au solution is passed through in the polyalcohol integral pole being modified to step (3) until whole pillar becomes red, outflow
Until pink is presented in liquid；
(5) with the integral post that dimercaptosuccinic acid solution rinsing step (4) obtains to obtain the rich carboxylic integral post in surface, then
It is rinsed with high purity water to get the polymer-modified integral post of nanogold modified to dimercaptosuccinic acid.
2. preparation method according to claim 1, it is characterised in that: step (1) specifically: successively with ultrapure water,
1.0mol·L-1NaOH solution, ultrapure water, 1.0molL-1HCl solution, ultrapure water capillary is rinsed, then
It is dried up with argon gas；The mixed solution of WD-70 and ethyl alcohol that volume ratio is 1:1 are rushed to capillary, both ends are sealed with silica gel, are set
It reacts, is then developed reagent unreacted in capillary with ethyl alcohol, then blown capillary with argon gas in 70 DEG C of baking ovens
It does spare.
3. preparation method according to claim 2, it is characterised in that: in step (1), the capillary is the μ of 20cm × 530
The vitreous silica capillary of m successively uses ultrapure water 10min, 1.0molL-1NaOH solution rinse 2h, ultrapure water
30min、1.0mol·L-1HCl solution rinse 2h, ultrapure water 30min, the time reacted in baking oven is 12h.
4. preparation method according to claim 1, it is characterised in that: step (3) specifically: use the cystamine of pH=9 first
Then pillar both ends are sealed with silicagel pad, are placed in 50 by the polyalcohol integral pole that dihydrochloride solution rinsing step (2) prepares
DEG C water-bath in react；It repeats 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, which seals pillar both ends and is placed in 50 DEG C of water-bath, reacts；Finally use 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 nanogold of the dimercaptosuccinic acid modification is modified
The partial size of nanogold is 13nm in polyalcohol integral pole.
6. a kind of polymer-modified integral post of nanogold of dimercaptosuccinic acid modification, it is characterised in that: any by claim 1-5
Preparation method described in is prepared.
7. the enrichment that the polymer-modified integral post of nanogold of dimercaptosuccinic acid modification as claimed in claim 6 is used for rare earth element
And detection.
8. a kind of polymer-modified integral post of nanogold modified using dimercaptosuccinic acid as claimed in claim 6 is to rare earth element
The method for carrying out analysis detection, which comprises the following steps:
(1) the sample solution pH containing rare earth element to be measured is adjusted to 5, the nanogold for being passed through dimercaptosuccinic acid modification is modified poly-
Object integral post is closed, HNO is then passed to3Solution is desorbed, and stripping liquid is pumped into ICP-MS by flow injection instruments online and is surveyed
It is fixed；
(2) high purity water that element to be measured is not added is operated by step (1), and is measured with ICP-MS, gained signal value is made
For blank value.
9. according to the method described in claim 8, it is characterized by: the sample solution is seawater or people's whole blood digestion solution.
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| 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 |
| 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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| CN102391947A (en) * | 2011-11-03 | 2012-03-28 | 广西师范大学 | Preparation method for porous monolithic column immobilized enzyme micro-reactor |
| CN103994991A (en) * | 2014-05-21 | 2014-08-20 | 华东理工大学 | Preparation method of surface-enhanced raman spectrum (SERS) substrate based on capillary monolithic column |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391947A (en) * | 2011-11-03 | 2012-03-28 | 广西师范大学 | Preparation method for porous monolithic column immobilized enzyme micro-reactor |
| CN103994991A (en) * | 2014-05-21 | 2014-08-20 | 华东理工大学 | Preparation method of surface-enhanced raman spectrum (SERS) substrate based on capillary monolithic column |
Non-Patent Citations (3)
| Title |
|---|
| "Polymer monolithic capillary microextraction on-line coupled with inductively coupled plasma-mass spectrometry for the determination of trace Au and Pd in biological samples";Xiaolan Liu et al;《Spectrochimica Acta Part B》;20140916;第254-260页 |
| "毛细管整体柱微萃取在衡量元素分析中的应用";张琳;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20151115;第63-66，104页 |
| "纳米金修饰的聚合物整体柱制备及其表面增强拉曼光谱研究";刘丽娜等;《光谱学与光谱分析》;20121031;第32卷(第10期);第213-214页 |
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