CN110411812A - A kind of carboxyl magnetic bead is used for the application of heavy metal in enrichment purification grain - Google Patents
A kind of carboxyl magnetic bead is used for the application of heavy metal in enrichment purification grain Download PDFInfo
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Abstract
A kind of application the present invention provides carboxyl magnetic bead for heavy metal in enrichment purification grain, the present invention utilizes the heavy metal in carboxyl magnetic bead quick adsorption grain leaching liquor, significantly reduce the impurity content in prepare liquid, compared with traditional heavy metal pre-treating method, this method used time is short, cost is lower, strong corrosive reagent dosage is few, step is simple and can realize full automatic treatment, can be widely applied in grain the enrichment of heavy metal with separate, simplify pre-treatment operation, improve detection sensitivity.
Description
Technical field
The invention belongs to Chemical Decomposition field, it is related to a kind of carboxyl magnetic bead and is answered for heavy metal in enrichment purification grain
With more particularly to a kind of application using lead or cadmium heavy metal in carboxyl enrichment with magnetic bead purifying foodstuff.
Background technique
Heavy metal pollution is related to the various aspects in life, including food-safety problem.Lead, cadmium in heavy metal mainly lead to
It crosses food and breathing enters human body, although heavy metal not will cause people's acute poisoning under normal circumstances in agricultural product, a huge sum of money
Belong to and being accumulated in human body by food chain, and then influences human health.Currently, the detection method of heavy metal is quickly sent out in grain
Exhibition not only has the atomic absorption spectrography (AAS) precisely detected suitable for laboratory, atomic fluorescence light splitting light method meter, ICP-OES, ICP-
MS etc., there are also immunoassay, test strips method, colorimetric method, XRF, the electrochemical analysis methods etc. that are suitable for quickly detecting.So
And the above method will realize Accurate Determining, must just rely on reliable pre-treating method, in particular for complicated grain matrix
Body.Traditional sample-pretreating method common are dry ashing, wet digestion, micro-wave digestion, high-pressure digestion etc., be required to
It is longer processing the time, a large amount of high concentrated acid reagent, high temperature and pressure treatment conditions and large-scale instrument and equipment, be unfavorable for weight
Metal quickly detects, the realization of on-site test and the full-automatic pre-treatment of sample.How to improve pre-treatment efficiency, simplify operation even
It is full automatic working, the quick processing detection for realizing heavy metal in grain, just becomes what heavy metal analysis technology further developed
Critical issue.
CN103575593B discloses one kind and quickly mildly extracts heavy metal method from cereal, the steps include: cereal
Sample comminution is mixed with diluted acid, extracts heavy metal ion；By carrying out standing or centrifugal treating, grain sample after shaking, being vortexed
In the heavy metal elements such as cadmium, lead be transferred in supernatant substantially, the supernatant of acquisition is for detecting.This method has time-consuming
It is short, without a large amount of corrosive reagents, without high temperature and specific instrument, at normal temperature can be completed, easy to operate, Fast Practical
The advantages that.But in practice process, there is high dissolubility organic matter only by the supernatant of dilute acid pretreatment, such as protein, carbon
The characteristics of hydrate, there is certain influence to detection process, largely detects such sample for a long time and instrument has been caused in various degree
Damage, it is maximum for the instrumental effects of high precision.
Therefore it provides a kind of impurity content is low, accuracy is high, the method for heavy metal has suitable for fast enriching grain
Significance.
Summary of the invention
In view of the deficiencies of the prior art and actual demand, the present invention provides a kind of carboxyl magnetic bead for enrichment purification grain
The application of middle heavy metal.The present invention significantly reduces prepare liquid using the heavy metal in carboxyl magnetic bead quick adsorption grain leaching liquor
In impurity content, testing result is more accurate, be suitable for various instruments, it is environmentally friendly, have a vast market foreground.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the application the present invention provides a kind of carboxyl magnetic bead for heavy metal in enrichment purification grain.
In the present invention, the heavy metal ion in grain leaching liquor is adsorbed by carboxyl magnetic bead, is further enriched with prepare liquid, is shown
The period for shortening grain detection pretreatment process is write, accuracy in detection is improved, meets the needs of on-site test, quickly detect grain
In heavy metal.
Preferably, the mass concentration of the carboxyl magnetic bead is 5~20%, for example, can be 5%, 6%, 7%, 8%, 9%,
10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
Second aspect, the present invention provides a kind of kit of heavy metal in enrichment purification grain, including carboxyl magnetic bead, described
The mass concentration of carboxyl magnetic bead is 5~20%.
Preferably, the kit further includes dilute acid soln.
Preferably, the dilute acid soln includes dust technology, dilute hydrochloric acid, oxalic acid, citric acid, lactic acid, malic acid, acetic acid or sulphur
In acid any one or at least two combination, preferably dust technology and/or dilute hydrochloric acid.
Preferably, the mass fraction of the dilute acid soln is 0.1-15%, for example, can be 0.1%, 0.5%, 1%,
2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, preferably 5-8%.
The third aspect, the present invention provides a kind of method of heavy metal in the enrichment purification grain based on carboxyl magnetic bead, described
Method the following steps are included:
(1) using the heavy metal ion in dilute acid soln extraction grain, oscillation centrifugation obtains sample leaching liquor；
(2) using the heavy metal ion in carboxyl magnetic bead adsorption sample leaching liquor, Magneto separate after elution, supernatant is enriched with
The purified treatment fluid containing heavy metal ion.
Magnetic separation technique is relatively conventional in biochemical immunity analysis field at present, by means of immunomagnetic beads be used to purifying protein or
Macromolecular object is separated, the preparation of immunomagnetic beads is also more classical.And in Analysis of Heavy Metal field, immunomagnetic beads are difficult to extensively
Using because the heavy metal antibody being integrated on magnetic bead can not heavy metal ion in Direct Recognition solution, can only identify weight
The chelate that metal ion and chelating agent are formed, so chelating agent must be added in advance in the solution, and part instrument can not
The heavy metal of Chelating state is directly detected, it is limited in the application of heavy metal field that this results in immunomagnetic beads.And the principle of carboxyl magnetic bead
Different from immunomagnetic beads, carboxyl magnetic bead is able to based on the electrostatic force between carboxyl and heavy metal ion by heavy metal adsorption to magnetic
Bead surface, through elution, heavy metal ion is present in dilute acid soln in the form of ionic state again, can be used for various instruments
The detection at end, and through this treatment process, can effectively remove other impurities ingredient in grain leaching liquor, as inorganic salts, albumen,
Pigment etc. is easy the substance impacted to detection.In the present invention, by heavy metal ion through dilute acid soln from grain matrix
It extracts, adjustment pH to OK range, then passes through the carboxyl magnetic bead Static Adsorption heavy metal ion of facile syntheesis, be adsorbed
The magnetic bead of heavy metal ion is eluted by acidic effluent liquid, and eluent can be used for the further detection of instrument side.
Preferably, step (1) described dilute acid soln include dust technology, dilute hydrochloric acid, oxalic acid, citric acid, lactic acid, malic acid,
In acetic acid or sulfuric acid any one or at least two combination, preferably dust technology and/or dilute hydrochloric acid.
Preferably, the solid-to-liquid ratio of the grain and dilute acid soln is 1:(5~15) g/mL, such as can be 1:5g/mL, 1:
6g/mL, 1:7g/mL, 1:8g/mL, 1:9g/mL, 1:10g/mL, 1:11g/mL, 1:12g/mL, 1:13g/mL, 1:14g/mL or
1:15g/mL, preferably 1:(8~10) g/mL.
Preferably, the mass fraction of the dilute acid soln is 0.1~15%, for example, can be 0.1%, 0.5%, 1%,
2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, preferably 5~8%.
In the present invention, the mass fraction of dilute acid soln is controlled in the range of 0.1~15%, is on the one hand to guarantee
Lead cadmium in grain sufficiently extracts, because only that meeting the requirement of acidity in solution, lead cadmium could be extracted adequately, this
It is also one step of key for guaranteeing extraction effect；On the other hand, acid concentration is not to be the bigger the better, when acidity is excessively high, sample it is dilute
Acid extract, which can turn yellow, becomes viscous (result that partial organic substances matter is oxidized), while acidity is too high, adjusts required when pH
The amount of alkali will definitely increase, and introducing excessive cation will affect the adsorption effect of magnetic bead.
Preferably, step (1) described heavy metal includes lead and/or cadmium.
Preferably, the time of step (1) described oscillation be 3~20min, such as can be 3min, 4min, 5min, 6min,
7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or
20min, preferably 10~12min.
Preferably, the revolving speed of step (1) described centrifugation be 4000~10000rpm, such as can be 4000rpm,
4500rpm、5000rpm、5500rpm、6000rpm、6500rpm、7000rpm、7500rpm、8000rpm、8500rpm、
9000rpm, 9500rpm or 10000rpm, preferably 7500~8000rpm.
Preferably, the time of step (1) described centrifugation be 3~10min, such as can be 3min, 4min, 5min, 6min,
7min, 8min, 9min or 10min, preferably 8~10min.
Preferably, further including the steps that adjusting sample leaching liquor pH value after step (1), the pH value is 6~12, such as
It can be 6,7,8,9,10,11 or 12, preferably 6.5.
In the present invention, the pH value for needing to adjust sample leaching liquor before the absorption of carboxyl magnetic bead is neutral to approaching, pH used
Adjusting liquid includes sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or ammonium acetate buffer solution.
Preferably, the carboxyl magnetic bead preparation method the following steps are included:
On the basis of the magnetic microsphere of coated with silica, reaction is stirred at room temperature to modify ammonia using silane coupling agent
Base adds the succinic anhydride being dissolved in dimethyl sulfoxide and/or glutaric anhydride solution, be stirred to react at room temperature 4~8h with
Carboxyl is modified, after reaction, successively cleans 3~5 times with second alcohol and water to get carboxyl magnetic bead is arrived.
The present invention is based on the huge specific surface areas of carboxyl magnetic bead and carboxyl and the electrostatic adsorption force of heavy metal ion to play
Enrichment purification effect provides a kind of pre-treatment side that heavy metal rapidly extracting purification in the grain of magnetic bead is modified based on carboxylated
Method, the rate of recovery is up to 80% or more.The modification of magnetic bead can carry out at normal temperatures and pressures, and synthetic method is simple.With traditional resolution,
The methods of ashing is compared, and this method is more mild, easy, quick, compared with traditional heavy metal pre-treating method, this method used time
It is short, cost is lower, strong corrosive reagent dosage is few, step is simple and can realize full automatic treatment, can be widely applied in grain
The enrichment of heavy metal with separate, simplify pre-treatment operation, improve detection sensitivity.
Preferably, the coupling agent is silane coupling agent, preferably 3- ammonia second (third) ethyl triethoxy silicane alkane.
Preferably, it is described be stirred to react with modify the mixing time of amino be 4~20h, such as can be 4h, 5h, 6h,
7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, preferably 15~16h.
Preferably, the volume ratio of the magnetic microsphere and silane coupling agent is 1:(0.7~1.1), such as can be 1:
0.7,1:0.8,1:0.9,1:1,1:1.1, preferably 1:(0.75~0.8).
In the present invention, the volume ratio of magnetic microsphere and silane coupling agent is in 1:(0.7~1.1) in the range of, it can make anti-
More completely and autohemagglutination between group should not will cause.Magnetic bead surfaces modified effect can be made undesirable beyond prescribed limit.
Preferably, the concentration of the succinic anhydride solution be 0.15~0.2g/mL, such as can be 0.15g/mL,
0.16g/mL, 0.17g/mL, 0.18g/mL, 0.19g/mL or 0.2g/mL, preferably 0.18g/mL.
In the present invention, succinic anhydride mainly reacted with the amino of modified magnetic bead surfaces, reaction process mainly with
The amount of the substance of two kinds of groups is related, and the concentration for limiting succinic anhydride mainly considers final reaction volume, guarantees synthesis
The controllability of process.
Preferably, the volume ratio of the amino magnetic bead and succinic anhydride solution is 1:(0.35~0.4), such as can be 1:
0.35,1:0.36,1:0.37,1:0.38,1:0.39 or 1:0.4, preferably 1:0.38.
Preferably, the additive amount of the carboxyl magnetic bead is the carboxyl magnetic bead solution that 5~6 μ L mass fractions are 10%.
Preferably, the eluent of step (2) described elution includes dilute hydrochloric acid and/or dust technology.
Preferably, the pH value of the eluent is 1~3, such as can be 1,2 or 3, preferably 2.
Preferably, the time of the elution be 40s~5min, such as can be 40s, 50s, 1min, 2min, 3min,
4min or 5min, preferably 2~3min.
Preferably, the time of step (2) described absorption be 1~5min, such as can be 1min, 2min, 3min, 4min or
5min, preferably 2~3min.
Preferably, further include the steps that heavy metal ion in detection processing liquid after step (2).
Preferably, the method for the detection includes sampling Graphite Furnace Atomic Absorption detection, ICP-MS detection or portable electrochemical
Any one of detector or at least two combination.
As optimal technical scheme of the present invention, the method tool of heavy metal in the enrichment purification grain based on carboxyl magnetic bead
Body the following steps are included:
(1) using the heavy metal ion in dilute acid soln extraction grain, the solid-to-liquid ratio of the grain and dilute acid soln is 1:
(5~15), the mass concentration of the dilute acid soln are 3~15%, and 3~20min of shaken at room temperature connects solution sufficiently with grain
Mixed liquor is centrifuged 3~10min by touching at 4000~10000rpm, and separation of solid and liquid obtains sample leaching liquor, adjusts sample extraction
The pH value of liquid is to 6~6.5；
(2) heavy metal ion in the carboxyl magnetic bead adsorption sample leaching liquor of 4-8mg is added, 1~5min is adsorbed, to magnetic bead
After capturing the heavy metal ion in sample leaching liquor, magnetic analysis separation redissolves magnetic bead with the eluent of pH value 1~3, shaken at room temperature or
Ultrasound 1~5min of elution, magnetic analysis separate, the treatment fluid containing heavy metal ion after supernatant, that is, enrichment purification, detection processing liquid.
Compared with prior art, the invention has the following beneficial effects:
The present invention provides a kind of magnetic beads of carboxylated to provide a kind of economically viable preceding place for the heavy metal in grain
The preparation of reason method, magnetic bead can carry out at room temperature, and reaction is simple controllable.When entire method has low cost-effectiveness, consumption
Between short, magnetic response ability is strong, the advantage that can easily separate from solution in the presence of external magnetic field, effectively keep away
Exempt from using strong acid and large-scale instrument, and the solution after eluting is applicable to quick detection device and precision instrument.Therefore base
Have in terms of grain Analysis of Heavy Metal in the pre-treating method of the heavy metal rapidly extracting purification of carboxylated modification magnetic bead wide
Application prospect.
Detailed description of the invention
Fig. 1 is testing result of the treatment fluid to be measured of embodiment 1 on Electrochemical detector；
Fig. 2 is testing result of the treatment fluid to be measured of comparative example 1 on Electrochemical detector；
Fig. 3 is testing result of the treatment fluid to be measured of comparative example 2 on Electrochemical detector；
Fig. 4 is testing result of the treatment fluid to be measured of comparative example 3 on Electrochemical detector.
Specific embodiment
The technological means and its effect taken for the present invention is further explained, with reference to embodiments with attached drawing to this hair
It is bright to be further described.It is understood that the specific embodiments described herein are used only for explaining the present invention, rather than
Limitation of the invention.
In the examples where no specific technique or condition is specified, described technology or conditions according to the literature in the art,
Or it is carried out according to product description.Reagents or instruments used without specified manufacturer, be can be by regular channel commercially available from
The conventional products of acquisition.
Embodiment 1
Lead cadmium pre-treating method in rice based on magnetic bead absorption, the steps include:
(1) preparation of sample leaching liquor:
It weighs 0.2g rice sample and is dispersed in 5%HNO3In solution, make solid-to-liquid ratio 1:10, after vibrating 10min, centrifugation
Supernatant is taken after 8000rpm, 5min, is 6.5 with sodium hydroxide solution adjustment pH, is obtained sample leaching liquor.
(2) preparation of carboxyl magnetic bead:
On the basis of the magnetic microsphere of coated with silica, silane coupling agent 3- ammonia second (third) ethyl triethoxy silicane alkane is used
Reaction 16h is stirred at room temperature to modify amino, the volume ratio of the magnetic microsphere and silane coupling agent is 1:0.75, obtains ammonia
Base magnetic bead；Above-mentioned amino magnetic bead is added in the succinic anhydride solution for being dissolved in dimethyl sulfoxide, succinic anhydride solution it is dense
Degree is 0.18g/mL, and the volume ratio of amino magnetic bead and succinic anhydride solution is 1:0.38, is stirred to react 4h at room temperature to modify carboxylic
Base successively cleans 3~5 times with second alcohol and water to get carboxyl magnetic bead is arrived after reaction.
(3) method that carboxyl magnetic bead handles heavy metal ion in grain:
The pH of sample treatment liquid is transferred to 6.5, the carboxyl magnetic for the carboxyl magnetic bead solution that 5 μ L mass fractions are 10% is added
Pearl, after mixing, standing adsorption 3min, to the heavy metal ion in magnetic capture sample leaching liquor, magnetic analysis separation；
The dust technology of pH3 is redissolved into magnetic bead, oscillation elution 3min, magnetic analysis separation, supernatant is containing after enrichment purification
The treatment fluid to be measured of heavy metal ion.
Embodiment 2
Lead cadmium pre-treating method in rice based on magnetic bead absorption, the steps include:
(1) preparation of sample leaching liquor:
It weighs 0.2g rice sample to be dispersed in 8%HCl solution, makes solid-to-liquid ratio 1:5, after vibrating 3min, centrifugation
Supernatant is taken after 4000rpm, 3min, is 6.5 with sodium hydroxide solution adjustment pH, is obtained sample leaching liquor.
(2) preparation of carboxyl magnetic bead:
On the basis of the magnetic microsphere of coated with silica, silane coupling agent 3- ammonia second (third) ethyl triethoxy silicane alkane is used
Reaction 4h is stirred at room temperature to modify amino, the volume ratio of the magnetic microsphere and silane coupling agent is 1:0.7, obtains amino
Magnetic bead；Above-mentioned amino magnetic bead is added in the succinic anhydride solution for being dissolved in dimethyl sulfoxide, the concentration of succinic anhydride solution
For 0.15g/mL, the volume ratio of amino magnetic bead and succinic anhydride solution is 1:0.35, is stirred to react 6h at room temperature to modify carboxyl,
After reaction, 3 times successively are cleaned to get carboxyl magnetic bead is arrived with second alcohol and water.
(3) method that carboxyl magnetic bead handles heavy metal ion in grain:
The pH of sample treatment liquid is transferred to 6.5, the carboxyl magnetic for the carboxyl magnetic bead solution that 5 μ L mass fractions are 10% is added
Pearl, after mixing, standing adsorption 3min, to the heavy metal ion in magnetic capture sample leaching liquor, magnetic analysis separation；
The dilute hydrochloric acid of pH2 is redissolved into magnetic bead, shaken at room temperature 3min, magnetic analysis separation, supernatant is containing after enrichment purification
The treatment fluid to be measured of heavy metal ion.
Embodiment 3
Lead cadmium pre-treating method in rice based on magnetic bead absorption, the steps include:
(1) preparation of sample leaching liquor:
It weighs 0.2g rice sample and is dispersed in 15%HNO3In solution, make solid-to-liquid ratio 1:15, after vibrating 20min, centrifugation
Supernatant is taken after 10000rpm, 10min, is 6.5 with sodium hydroxide solution adjustment pH, is obtained sample leaching liquor.
(2) preparation of carboxyl magnetic bead:
On the basis of the magnetic microsphere of coated with silica, silane coupling agent 3- ammonia second (third) ethyl triethoxy silicane alkane is used
Reaction 20h is stirred at room temperature to modify amino, the volume ratio of the magnetic microsphere and silane coupling agent is 1:0.8, obtains ammonia
Base magnetic bead；Above-mentioned amino magnetic bead is added in the succinic anhydride solution for being dissolved in dimethyl sulfoxide, succinic anhydride solution it is dense
Degree is 0.2g/mL, and the volume ratio of amino magnetic bead and succinic anhydride solution is 1:0.4, is stirred to react 8h at room temperature to modify carboxyl,
After reaction, 5 times successively are cleaned to get carboxyl magnetic bead is arrived with second alcohol and water.
(3) method that carboxyl magnetic bead handles heavy metal ion in grain:
The pH of sample treatment liquid is transferred to 6.5, the carboxyl magnetic for the carboxyl magnetic bead solution that 5 μ L mass fractions are 10% is added
Pearl, after mixing, standing adsorption 3min, to the heavy metal ion in magnetic capture sample leaching liquor, magnetic analysis separation；
The dust technology of pH3 is redissolved into magnetic bead, oscillation elution 5min, magnetic analysis separation, supernatant is containing after enrichment purification
The treatment fluid to be measured of heavy metal ion.
Comparative example 1
Rice sample is handled using Microwave Digestion, is specifically included:
0.2g rice sample is weighed into micro-wave digestion pipe, the excellent pure grade nitric acid of 5mL is added, micro-wave digestion program is set, is pressed
Cleared up according to the temperature program of table 1, after take out digestion tube, be placed in catch up with acid cover in 160 DEG C catch up with acid to close dry.
A small amount of distilled water is transferred to centrifuge tube, and adjusts pH to 6.5, and constant volume to 5mL is to be measured.
1 micro-wave digestion temperature program of table
| Temperature (DEG C) | Retention time (min) |
| 80 | 3 |
| 100 | 3 |
| 120 | 3 |
| 150 | 10 |
| 180 | 20 |
Comparative example 2
It weighs 0.2g rice sample and is dispersed in 5%HNO3In solution, make solid-to-liquid ratio 1:10, after vibrating 10min, centrifugation
Supernatant is taken after 8000rpm, 5min, is 6.5 with sodium hydroxide solution adjustment pH, it is to be measured to obtain sample leaching liquor.
Comparative example 3
Compared with Example 1, other than carboxyl magnetic bead is replaced with amino magnetic bead, other conditions are with embodiment 1, wherein ammonia
Base magnetic bead the preparation method comprises the following steps:
On the basis of the magnetic microsphere of coated with silica, silane coupling agent 3- ammonia second (third) ethyl triethoxy silicane alkane is used
Reaction 16h is stirred at room temperature to modify amino, the volume ratio of the magnetic microsphere and silane coupling agent is 1:0.75, obtains ammonia
Base magnetic bead.
Sampling Graphite Furnace Atomic Absorption detection
According to the setting parameter of table 2 and table 3, embodiment 1 and comparative example 1-3 are detected, from the point of view of testing result, warp
The measured value of magnetic bead processing is crossed closer to micro-wave digestion as a result, accuracy is higher (being shown in Table 4).
2 sampling Graphite Furnace Atomic Absorption temperature program (cadmium) of table
| Step | Function | Temperature (DEG C) | Rate (DEG C/S) | Retention time (s) | Argon gas | Assist gas | AZ* | Run |
| 1 | It is dry | 70 | 3 | 10 | Max | Stop | ||
| 2 | It is dry | 90 | 1 | 10 | Max | Stop | ||
| 3 | It is dry | 110 | 2 | 2 | Max | Stop | ||
| 4 | Ashing | 350 | 250 | 35 | Max | Max | ||
| 5 | AZ* | 350 | 0 | 4 | Stop | Stop | 0 | 3.7 |
| 6 | Atomization | 1200 | 1500 | 3 | Stop | Stop | ||
| 7 | Except residual | 2300 | 500 | 4 | Max | Max |
3 sampling Graphite Furnace Atomic Absorption temperature program (lead) of table
| Step | Function | Temperature (DEG C) | Rate (DEG C/S) | Retention time (s) | Argon gas | Assist gas | AZ* | Run |
| 1 | It is dry | 90 | 5 | 20 | Max | Stop | ||
| 2 | It is dry | 105 | 3 | 20 | Max | Stop | ||
| 3 | It is dry | 110 | 2 | 10 | Max | Stop | ||
| 4 | Ashing | 800 | 250 | 20 | Max | Max | ||
| 5 | AZ* | 800 | 0 | 4 | Stop | Stop | 0 | 3.7 |
| 6 | Atomization | 1500 | 1400 | 4 | Stop | Stop | ||
| 7 | Except residual | 2300 | 500 | 4 | Max | Max |
The comparison of table 4 this method testing result and comparative example result
Portable electrochemical detector test
Parameter setting electrochemical operation parameter according to table 5 is sweep time, scanning voltage, electrolyte solution.To implementation
Example 1 and comparative example 1-3 are detected, as a result as shown in Figs 1-4.
5 electrochemical operation parameter of table
| Parameter | Sweep time (s) | Quiescent time (s) | Initial potential (v) | It terminates current potential (v) | Electrolyte solution |
| Setting | 200s | 10s | -1.3v | -0.6v | 0.5M ammonium acetate |
By Fig. 1-4 it is found that in terms of Electrochemical detector testing result, the detection liquid handled through carboxyl magnetic bead, lead cadmium
Dissolution peak peak type it is round and smooth, spike potential is normal, close with the peak type of micro-wave digestion liquid without impurity peaks, but in practical applications,
Handy and safe more than micro-wave digestion step is quick；And its peak type has apparent do without the diluted acid leaching liquor of carboxyl magnetic bead processing
Disturb peak；The detection liquid handled using amino magnetic bead, signal concentration are low with normal recovery levels.
As shown in Table 6, magnetic bead treated result that sample solution tests through electrochemical instrument is compared with national standard ICP-MS method,
There is no significant difference.
The comparison of table 6 electrochemical instrument testing result and ICP-MS methods and results
In conclusion the present invention extracts the heavy metal in grain using carboxylated magnetic bead, it is a kind of economically viable preceding place
The preparation of reason method, magnetic bead can carry out at room temperature, and reaction is simple controllable, when entire method has low cost-effectiveness, consumption
Between short, magnetic response ability is strong, the advantage that can easily separate from solution in the presence of external magnetic field, effectively keep away
Exempt from using strong acid and large-scale instrument, and the solution after eluting is applicable to quick detection device and precision instrument, therefore base
Have in terms of grain Analysis of Heavy Metal in the pre-treating method of the heavy metal rapidly extracting purification of carboxylated modification magnetic bead wide
Application prospect.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of application of carboxyl magnetic bead for heavy metal in enrichment purification grain.
2. application according to claim 1, which is characterized in that the mass concentration of the carboxyl magnetic bead is 5~20%.
3. the kit of heavy metal in a kind of enrichment purification grain, which is characterized in that including carboxyl magnetic bead, the carboxyl magnetic bead
Mass concentration is 5~20%；
Preferably, the kit further includes dilute acid soln；
Preferably, the dilute acid soln includes in dust technology, dilute hydrochloric acid, oxalic acid, citric acid, lactic acid, malic acid, acetic acid or sulfuric acid
Any one or at least two combination, preferably dust technology and/or dilute hydrochloric acid；
Preferably, the mass concentration score of the dilute acid soln is 0.1~15%, preferably 5~8%.
4. a kind of method of heavy metal in enrichment purification grain based on carboxyl magnetic bead, which is characterized in that the method includes with
Lower step:
(1) using the heavy metal ion in dilute acid soln extraction grain, oscillation centrifugation obtains sample leaching liquor；
(2) using the heavy metal ion in carboxyl magnetic bead adsorption sample leaching liquor, Magneto separate after elution, supernatant, that is, enrichment purification
The treatment fluid containing heavy metal ion afterwards.
5. according to the method described in claim 4, it is characterized in that, step (1) described dilute acid soln includes dust technology, dilute salt
In acid, oxalic acid, citric acid, lactic acid, malic acid, acetic acid or sulfuric acid any one or at least two combination, preferably dilute nitre
Acid and/or dilute hydrochloric acid；
Preferably, the solid-to-liquid ratio of the grain and dilute acid soln is 1:(5~15) g/mL, preferably 1:(8~10) g/mL；
Preferably, the mass fraction of the dilute acid soln is 0.1~15%, preferably 5~8%；
Preferably, step (1) described heavy metal includes lead and/or cadmium；
Preferably, the time of step (1) described oscillation is 3~20min, preferably 10~12min；
Preferably, the revolving speed of step (1) described centrifugation is 4000~10000rpm, preferably 7500~8000rpm；
Preferably, the time of step (1) described centrifugation is 3~10min, preferably 8~10min.
6. method according to claim 4 or 5, which is characterized in that further include adjusting sample leaching liquor pH after step (1)
The step of value, the pH value are 6~6.5, preferably 6.5.
7. according to the described in any item methods of claim 4-6, which is characterized in that the preparation method of the carboxyl magnetic bead include with
Lower step:
On the basis of the magnetic microsphere of coated with silica, it is stirred at room temperature and is reacted to modify amino using silane coupling agent,
The succinic anhydride being dissolved in dimethyl sulfoxide and/or glutaric anhydride solution are added, is stirred to react 4~8h at room temperature to modify
Carboxyl successively cleans 3~5 times with second alcohol and water to get carboxyl magnetic bead is arrived after reaction；
Preferably, the coupling agent is silane coupling agent, preferably 3- ammonia second (third) ethyl triethoxy silicane alkane；
Preferably, described to be stirred to react to modify the mixing time of amino as 4~20h, preferably 15~16h；
Preferably, the volume ratio of the magnetic microsphere and silane coupling agent is 1:(0.7~1.1), preferably 1:(0.75~
0.8)；
Preferably, the concentration of the succinic anhydride solution is 0.15~0.2g/mL, preferably 0.18g/mL；
Preferably, the volume ratio of the amino magnetic bead and succinic anhydride solution is 1:(0.35~0.4), preferably 1:0.38.
8. according to the described in any item methods of claim 4-7, which is characterized in that the additive amount of the carboxyl magnetic bead is 5~6 μ L
The carboxyl magnetic bead solution that mass fraction is 10%；
Preferably, the eluent of step (2) described elution includes dilute hydrochloric acid and/or dust technology；
Preferably, the pH value of the eluent is 1~3, preferably 2；
Preferably, the time of the elution is 1~5min, preferably 2~3min；
Preferably, the time of step (2) described absorption is 1~5min, preferably 2~3min.
9. according to the described in any item methods of claim 4-8, which is characterized in that further include in detection processing liquid after step (2)
The step of heavy metal ion；
Preferably, the method for the detection includes sampling Graphite Furnace Atomic Absorption detection, ICP-MS detection or portable electrochemical detection
Any one of instrument or at least two combination.
10. according to the described in any item methods of claim 4-9, which is characterized in that specifically includes the following steps:
(1) using the heavy metal ion in dilute acid soln extraction grain, the solid-to-liquid ratio of the grain and dilute acid soln be 1:(5~
15), the mass concentration of the dilute acid soln is 3~15%, and 3~20min of shaken at room temperature comes into full contact with solution with grain, will
Mixed liquor is centrifuged 3~10min at 4000~10000rpm, and separation of solid and liquid obtains sample leaching liquor, adjusts sample leaching liquor
PH value is to 6~12；
(2) heavy metal ion in the carboxyl magnetic bead adsorption sample leaching liquor of 4-8mg is added, 1~5min is adsorbed, to magnetic capture
After heavy metal ion in sample leaching liquor, magnetic analysis separation redissolves magnetic bead, shaken at room temperature or ultrasound with the eluent of pH value 1~3
40s~5min is eluted, magnetic analysis separates, the treatment fluid containing heavy metal ion after supernatant, that is, enrichment purification, detection processing liquid.
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