CN101788492A - Method for detecting trace iron ions at high sensitivity - Google Patents
Method for detecting trace iron ions at high sensitivity Download PDFInfo
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- CN101788492A CN101788492A CN201010131708A CN201010131708A CN101788492A CN 101788492 A CN101788492 A CN 101788492A CN 201010131708 A CN201010131708 A CN 201010131708A CN 201010131708 A CN201010131708 A CN 201010131708A CN 101788492 A CN101788492 A CN 101788492A
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- ferric ion
- high sensitivity
- iron ions
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Abstract
The invention discloses a method for detecting trace iron ions at high sensitivity, which comprises the steps of: searching a proper medium condition of diaminomaleonitrile (DAMN); measuring fluorescence intensities of a coordination compound, the coordination compound and a medium, and the coordination compound and the medium and metal ions; determining hypersensitivity or quenching effect generated by metal ions to the fluorescence of the coordination compound; measuring a linear relation between the concentration of the metal ions and a quenching value; and measuring the content of the metal ions in food. By using characteristic of quenching generated by the iron ions to the fluorescence of the DAMN and the linear relation formed between the fluorescence quenching value (delta F) and the concentration of the iron ions, the method is further used for measuring the content of iron in foods of infant rice flour, milk powder and the like, wherein the detection limit of the iron is 1.5 mu g.L<-1>, and the relative standard deviation is 0.17 percent. Compared with the prior art, the method has the advantages of good selectivity, high sensitivity, simple and convenient use, and the like.
Description
Technical field
The present invention relates to a kind of method of highly sensitive detection trace metal ion, belong to technical field of analysis and detection, relate in particular to a kind of method that detects trace iron ions.
Background technology
Metallic ion iron is the trace element of needed by human, plays an important role in human biochemistry's process, and human body Excessive Intake or deficiency all can affect greatly health.Therefore, the content of the metallic ion of needed by human in the food is carried out the accurate mensuration of iron-holder in the highly sensitive detection, particularly infant food, have very significant meaning.Traditional detection method, as colourimetry, atomic absorption method, chemoluminescence method etc., the means of testing complexity, sensitivity is also not high enough.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method with detection trace iron ions that selectivity is good, highly sensitive and method is easy, especially can be used for the mensuration of infant's ground rice, milk powder iron content.
For solving the problems of the technologies described above, through years of researches work, following technical scheme now is provided: a kind of method of detecting trace iron ions at high sensitivity is characterized in that may further comprise the steps:
A, get two parts of the diaminomaleonitrile solution of same concentration, be respectively solution A and solution B, add the ferric ion standard solution of an amount of concentration known in the solution B;
B, with the pH value 4～5 H respectively
2SO
4Solution carries out constant volume to two parts of solution of A, B, shakes up to place 40～120 minutes;
C, measure the fluorescence intensity F of solution A and two kinds of systems of solution B respectively
0And F;
D, two parts of solution fluorescence intensity quenching value Δ F=F of calculating
0-F, and with Δ F to iron concentration drawing curve, measure the linear relationship between ferric ion concentration and the Δ F;
E, ferric ion solutions to be measured is carried out constant volume according to above-mentioned steps, shake up and placed 40～120 minutes, measure its fluorescence intensity, and calculate fluorescence intensity quenching value Δ F, the concentration that ferric ion concentration of knowing according to abovementioned steps and the linear relationship between the Δ F calculate ferric ion solutions to be measured.
As a kind of preferred version of the method for detecting trace iron ions at high sensitivity of the present invention, wherein said excitation wavelength is 226nm, and emission wavelength is that 406nm measures wavelength.
As a kind of preferred version of the method for detecting trace iron ions at high sensitivity of the present invention, H among the wherein said step b
2SO
4The pH value of solution is 4.5.
As a kind of preferred version of the method for detecting trace iron ions at high sensitivity of the present invention, the mass concentration of the diaminomaleonitrile among the wherein said step a is 0.40gL
-1
As a kind of preferred version of the method for detecting trace iron ions at high sensitivity of the present invention, among the wherein said step b behind the constant volume solution be 10ml, wherein the consumption of diaminomaleonitrile is at 1.20～1.40mL.
As a kind of preferred version of the method for detecting trace iron ions at high sensitivity of the present invention, the ferric ion solution among the wherein said step a is 10.0mgL
-1The ferric ion standard solution.
As a kind of preferred version of the method for detecting trace iron ions at high sensitivity of the present invention, the reaction time of ferric ion and diaminomaleonitrile is 50 minutes among the wherein said step b.
A kind of preferred version as the method for detecting trace iron ions at high sensitivity of the present invention wherein under described experiment condition, only changes the addition of ferric ion, records the ferric ion amount at 0.01～0.48mgL
-1Scope in Δ F be good linear relationship, its equation of linear regression is Δ F=183.1C-0.1046, wherein C is the concentration of ferric ion, unit is mgL
-1, relative coefficient is 0.9962.
A kind of preferred version as the method for detecting trace iron ions at high sensitivity of the present invention takes by weighing 1.000g baby ground rice and places the 100mL conical flask, adds 25.00mL H
2O
2With 3.75mL nitric acid, add 5% AEO 25.00mL behind 100 ℃ of water-bath heating 65min, continue heating 40min, change constant volume in the 100mL volumetric flask after the cooling over to, pipette an amount of sample liquid by its ferric ion content of described determination of experimental method.
Detection method of the present invention, mainly be to utilize diaminomaleonitrile (DAMN) to have strong and the stable fluorescence characteristic, utilize it very easily to form the complex compound characteristic with metallic ion, the fluorescence intensity that causes DAMN significantly changes, thereby reach highly sensitive detection, specifically may further comprise the steps: seek the suitable ambient condition of DAMN trace metal ion; Measure the fluorescence intensity of complex, complex+medium, complex+medium+metallic ion; Determine that metallic ion produces the effect of enhanced sensitivity or quencher to the fluorescence of complex; Measure the concentration of metallic ion and the linear relationship between the quenching value; Measure the content of metallic ion in the food.This method utilizes ferric ion the fluorescence of diaminomaleonitrile (DAMN) to be produced the characteristic of quencher, and its fluorescent quenching value (Δ F) constitutes linear relationship with iron concentration, and then being used for the mensuration of food iron contents such as infant's ground rice, milk powder, detecting of iron is limited to 1.5 μ gL
-1, relative standard deviation is 0.17%, this method compared with prior art has advantages such as good, the highly sensitive and method of selectivity is easy.
Description of drawings
The present invention will be further described in detail below in conjunction with the drawings and specific embodiments.
Fig. 1 is the fluorescence spectrum figure of the invention process gained.
Embodiment
The following stated embodiment understands the present invention in detail.
1 instrument and reagent
LS-50B type fluorospectrophotometer (U.S. Perkin-E1mer company); The accurate pH meter (Shanghai Precision Scientific Apparatus Co., Ltd) of pHS-3C type; Quartzy automatic dual pure water distiller (Changzhou Guohua Electric Appliance Co., Ltd.); FA1004N type electronic analytical balance (Minqiao Precision Scientific Instruments Co., Ltd., Shanghai).
Iron standard solution: accurately take by weighing 0.08634gNH
4Fe (SO
4)
212H
2O, with a small amount of redistilled water dissolving, and constant volume is made into 0.1gL in the 100mL volumetric flask
-1Iron (III) ion standard solution, be diluted to 10.0mgL during use
-1Working fluid.Diaminomaleonitrile (DAMN) solution (10.0gL
-1): accurately take by weighing 1.000g DAMN, use a small amount of anhydrous alcohol solution, redistilled water is settled to 100mL, is made into 10.0gL
-1Storing solution, stepwise dilution becomes the working fluid of desired concn during use.Mutritive infant rice flour is chosen Shantou City Sanlu Food Co., Ltd and is produced.Agents useful for same is pure for analyzing, and experimental water is redistilled water.
2 experimental techniques
Adding an amount of concentration in the 10mL volumetric flask successively is 10.0mgL
-1Iron standard solution, 1.3mL 0.4gL
-1DAMN solution, be 4.5 H with pH
2SO
4Solution is settled to scale, shake up place 50min after, with 1cm fluorescence ware, with the excitation wavelength of 226nm, the emission wavelength of 406nm is measured the fluorescence intensity F of system, measures the fluorescence intensity F of reagent blank simultaneously on LS-50B type fluorospectrophotometer
0, calculate Δ F=F
0-F, and with Δ F to Fe (III) concentration drawing curve.
3 results and discussion
3.1 the selection of excitation wavelength and emission wavelength
By determination of experimental method pH be 4.5 H
2SO
4Solution, H
2SO
4+ DAMN solution, H
2SO
4The fluorescence spectrum of+DAMN solution+Fe systems such as (III), as shown in Figure 1.Wherein curve 1 is the H of pH=4.5
2SO
4Solution (end liquid), curve 2 are end liquid+DAMN solution (0.052gL
-1), curve 3 is end liquid+DAMN solution+Fe (III) (0.44mgL
-1).The result shows: pH is 4.5 H
2SO
4Solution is 406nm place fluorescence intensity very low (curve 1) at emission wavelength, and is noiseless to measuring; H
2SO
4The excitation peak of+DAMN solution and emission peak are respectively 226nm and 406nm (curve 2); After adding metal cations Fe (III), peak height obviously descends, and marked change (curve 3) does not take place for peak shape and peak position.Show that Fe (III) has quenching effect to the fluorescence intensity of DAMN, and the concentration of quenching value Δ F and Fe (III) is good linear relationship within the specific limits.Therefore, present embodiment selective excitation wavelength is 226nm, and emission wavelength is that 406nm measures wavelength.
3.2 selection of experiment conditions
3.2.1 the influence of medium
The fluorescence intensity of system is subjected to the influence of medium bigger, has tested different types of buffer solution respectively, as boric acid-KCl-NaOH, KH
2PO
4-NaOH, HAc-NaAc etc. find that the fluorescence intensity of system is very unstable, show that these buffer solution are not suitable for doing the medium of DAMN.Tested the H of different pH values simultaneously
2SO
4Solution is made medium, finds when the pH of solution value is between 4.0～5.0, and the fluorescence intensity of system is big and stable.Therefore experimental selection pH is 4.5 H
2SO
4Solution is made medium.
3.2.2DAMN the influence of consumption
Having investigated mass concentration is 0.40gL
-1The consumption of DAMN solution is to the influence of fluorescence intensity, and the result shows: the fluorescence intensity of the consumption of DAMN when 1.20～1.40mL is constant substantially, and the consumption influence is minimum, is 0.40gL so mass concentration is got in experiment
-1The consumption of DAMN be 1.30mL.
3.2.3 the influence in reaction time
During room temperature, to Fe(III)+the time dependent situation of fluorescence intensity of DAMN complex investigates.Every the fluorescence intensity of 5min mensuration system, experimental result shows: fluorescence intensity reaches stable behind the reaction 50min, and can stablize 1h, so the experimental selection reaction time is 50min.
3.3 the influence of coexisting ion
Under selected experiment condition, studied the disturbed condition when common ion coexists with Fe (III) in the ground rice, to test for 1.0 μ gFe (III), the relative error of mensuration is ± 5%, each coexisting ion allowance is (μ g): Na
+, K
+(6000); Mn
2+(1200); Zn
2+(800); Cu
2+, Ca
2+, Ni
2+(700); Mg
2+(400); Cr
2+, Ag
2+, Pb
2+(300); Cd
2+(100).Experimental result shows that this method has selectivity preferably to measuring Fe (III), and ground rice liquid can directly be measured without separation.
3.4 working curve
Under selected experiment condition, only change the addition of Fe (III), record Fe (III) amount at 0.01～0.48mgL
-1Scope in Δ F be good linear relationship, its equation of linear regression is Δ F=183.1C (mgL
-1)-0.1046 (C:Fe (the concentration mgL of III
-1), relative coefficient is 0.9962.
3.5 the detectability of method and precision
10 blank solutions of replicate determination, its relative standard deviation RSD=0.11% draws detecting of this method with 3 times standard deviations divided by the slope of working curve and is limited to 1.5 μ gL
-1To Fe
3+Mass concentration be 0.16mgL
-1Standard solution carry out 10 replicate determinations, its relative standard deviation is 0.17%.
4 sample analysis and mark-on reclaim experiment
Accurately take by weighing 1.000g ground rice and place the 100mL conical flask, add 25.00mL H
2O
2With 3.75mL nitric acid, add 5% AEO 25.00mL behind 100 ℃ of water-bath heating 65min, continue heating 40min, change constant volume in the 100mL volumetric flask after the cooling over to
[8]Pipette an amount of sample liquid by its Fe of determination of experimental method (III) content and carry out mark-on and reclaim experiment, it the results are shown in Table 1, table 2.
Table 1 sample analysis result (n=6)
It should be noted that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1. the method for a detecting trace iron ions at high sensitivity is characterized in that may further comprise the steps:
A, get two parts of the diaminomaleonitrile solution of same concentration, be respectively solution A and solution B, add the ferric ion standard solution of an amount of concentration known in the solution B;
B, with the pH value 4～5 H respectively
2SO
4Solution carries out constant volume to two parts of solution of A, B, shakes up to place 40～120 minutes;
C, measure the fluorescence intensity F of solution A and two kinds of systems of solution B respectively
0And F;
D, two parts of solution fluorescence intensity quenching value Δ F=F of calculating
0-F, and with Δ F to ferric ion concentration drawing curve, measure the linear relationship between ferric ion concentration and the Δ F;
E, ferric ion solutions to be measured is carried out constant volume according to above-mentioned steps, shake up and placed 40～120 minutes, measure its fluorescence intensity, and calculate fluorescence intensity quenching value Δ F, the concentration that ferric ion concentration of knowing according to abovementioned steps and the linear relationship between the Δ F calculate ferric ion solution to be measured.
2. the method for detecting trace iron ions at high sensitivity according to claim 1, it is characterized in that: described excitation wavelength is 226nm, emission wavelength is that 406nm measures wavelength.
3. the method for detecting trace iron ions at high sensitivity according to claim 1 is characterized in that: H among the described step b
2SO
4The pH value of solution is 4.5.
4. the method for detecting trace iron ions at high sensitivity according to claim 1, it is characterized in that: the mass concentration of the diaminomaleonitrile among the described step a is 0.40gL
-1
5. the method for detecting trace iron ions at high sensitivity according to claim 4 is characterized in that: among the described step b behind the constant volume solution be 10ml, wherein the consumption of diaminomaleonitrile is at 1.20～1.40mL.
6. the method for detecting trace iron ions at high sensitivity according to claim 1, it is characterized in that: the ferric ion solution among the described step a is 10.0mgL
-1The ferric ion standard solution.
7. the method for detecting trace iron ions at high sensitivity according to claim 1, it is characterized in that: the reaction time of ferric ion and diaminomaleonitrile is 50 minutes among the described step b.
8. the method for detecting trace iron ions at high sensitivity according to claim 1 is characterized in that: under described experiment condition, only change the addition of ferric ion, record the ferric ion amount at 0.01～0.48mgL
-1Scope in Δ F be good linear relationship, its equation of linear regression is Δ F=183.1C-0.1046, wherein C is the concentration of ferric ion, unit is mgL
-1
9. the method for detecting trace iron ions at high sensitivity according to claim 1 is characterized in that: take by weighing 1.000g baby ground rice and place the 100mL conical flask, add 25.00mL H
2O
2With 3.75mL nitric acid, add 5% AEO 25.00mL behind 100 ℃ of water-bath heating 65min, continue heating 40min, change constant volume in the 100mL volumetric flask after the cooling over to, pipette an amount of sample liquid by its ferric ion content of described determination of experimental method.
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|---|---|---|---|
| CN201010131708A CN101788492A (en) | 2010-03-25 | 2010-03-25 | Method for detecting trace iron ions at high sensitivity |
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ID=42531787
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108593616A (en) * | 2018-05-03 | 2018-09-28 | 哈尔滨理工大学 | A kind of UIO-66-NH of fluoroscopic examination iron ion2Preparation method |
| CN112098353A (en) * | 2020-09-29 | 2020-12-18 | 中南大学 | Method for detecting total iron content in high-concentration interfering ion solution |
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|---|---|---|---|---|
| JPH06186163A (en) * | 1992-05-11 | 1994-07-08 | Nec Corp | Chemically analyzing method |
| JPH102862A (en) * | 1996-06-13 | 1998-01-06 | Bunshi Bio Photonics Kenkyusho:Kk | Immobilizing reagent for detecting fluorescence of catechol compound and vanillyl compound, and detecting method therefor |
| CN101657921A (en) * | 2007-04-12 | 2010-02-24 | 3M创新有限公司 | High-performance, high durability non-precious metal fuel cell catalysts |
-
2010
- 2010-03-25 CN CN201010131708A patent/CN101788492A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06186163A (en) * | 1992-05-11 | 1994-07-08 | Nec Corp | Chemically analyzing method |
| JPH102862A (en) * | 1996-06-13 | 1998-01-06 | Bunshi Bio Photonics Kenkyusho:Kk | Immobilizing reagent for detecting fluorescence of catechol compound and vanillyl compound, and detecting method therefor |
| CN101657921A (en) * | 2007-04-12 | 2010-02-24 | 3M创新有限公司 | High-performance, high durability non-precious metal fuel cell catalysts |
Non-Patent Citations (1)
| Title |
|---|
| 乔善宝等: "荧光焠灭法测定婴幼儿米粉中的铁", 《化学世界》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108593616A (en) * | 2018-05-03 | 2018-09-28 | 哈尔滨理工大学 | A kind of UIO-66-NH of fluoroscopic examination iron ion2Preparation method |
| CN112098353A (en) * | 2020-09-29 | 2020-12-18 | 中南大学 | Method for detecting total iron content in high-concentration interfering ion solution |
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Application publication date: 20100728 |