CN109336898B - Iron ion probe and application thereof - Google Patents
Iron ion probe and application thereof Download PDFInfo
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- CN109336898B CN109336898B CN201811484506.9A CN201811484506A CN109336898B CN 109336898 B CN109336898 B CN 109336898B CN 201811484506 A CN201811484506 A CN 201811484506A CN 109336898 B CN109336898 B CN 109336898B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000523 sample Substances 0.000 title claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 50
- -1 iron ion Chemical class 0.000 claims abstract description 43
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 238000010668 complexation reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
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- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 13
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- 239000001257 hydrogen Substances 0.000 description 5
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- 238000005481 NMR spectroscopy Methods 0.000 description 4
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- 235000002597 Solanum melongena Nutrition 0.000 description 3
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
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- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
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- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
The invention relates to the technical field of fluorescent probes, in particular to a high-sensitivity iron ion probe and application thereof. The specific scheme is as follows: the invention discloses a structural formula of a high-sensitivity iron ion probe and also discloses a method for detecting Fe3+Application of (2) in Fe3+At a concentration of 3mmol/L, Fe3+Has a minimum detection limit of 0.32 mu M and is associated with Fe3+And carrying out a complexation reaction. The iron ion probe synthesized by the method has the advantages of simple synthesis process, easily obtained raw materials, simple reaction conditions, simple operation and high yield, and can be used for treating Fe in various common metal ions3+Has high selectivity and is not subject to other common conditionsSee interference of ions on Fe3+The combination of (A) and (B) belongs to reaction type recognition and has irreversibility; fe can be detected by the target probe3+And the naked eye detection is carried out without any equipment. And, for Fe3+The detection time is short, and the sensitivity is higher.
Description
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to an iron ion probe and application thereof.
Background
Iron is one of essential trace elements of human body, accounts for about 0.006% of human body weight, is also the most important transition metal ion in organisms, is a cofactor of many enzymatic reactions, provides oxygen carrying capacity for heme, and plays a vital role in various physiological processes such as cellular metabolism. Meanwhile, Fe is the most main component of various enzymes such as myoglobin, hemoglobin and the like. The source of iron in the human body is on the one hand the intake from food and on the other hand the release of red blood cells. If the body is lack of iron, the synthesis of myoglobin and the like is influenced and corresponding case characteristics such as reduced immunity and anti-infection capacity, weakened body temperature regulation capacity, nervous disorder and the like are shown. In addition, iron deficiency symptoms frequently occurring in life are iron deficiency anemia. Therefore, the detection of iron ions is very important.
The traditional detection method of the iron ions at present comprises the following steps: atomic Absorption Spectrophotometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES), electrochemical analysis, and the like. However, the above method requires expensive instruments and specialized inspection personnel, and is not suitable for mass detection and real-time detection. The fluorescent probe detection method technology becomes a research hotspot due to the advantages of good sensitivity, low cost, easy operation and the like. Therefore, the present invention provides a novel probe having iron ions capable of detecting Fe3+。
Disclosure of Invention
The invention aims to provide a ferric ion probe and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides an iron ion probe, which has the following structural formula:
preferably, the iron ion probe is prepared by the following steps:
(1) dissolving 2-5G of rhodamine 6G in 100-200 mL of absolute ethanol to obtain a rhodamine 6G solution; uniformly mixing ethylenediamine and absolute ethyl alcohol to obtain an ethylenediamine solution, dripping the ethylenediamine solution into the rhodamine 6G solution, and stirring at room temperature for 18-22 min;
(2) heating and refluxing the mixed solution obtained in the step (1) at the reflux temperature of 110-130 ℃, the reflux time of 10-15 h and the reflux speed of 1 drop/second, determining a reaction end point by using a spreading agent point plate, and stopping refluxing when the reaction reaches the end point;
(3) after refluxing, controlling the temperature to be 79-81 ℃, and distilling and recovering ethanol; stirring the solution at normal temperature for 2-4 h until a light yellow solid is separated out, and then carrying out suction filtration, washing and drying to obtain a light yellow product LDMO;
(4) dissolving the LDMO in 10-50 mL of absolute ethyl alcohol, adding o-vanillin, heating and refluxing at the reflux temperature of 100-120 ℃ for 6-10 h, dotting the solution with a developing agent to determine whether the reaction is finished, stopping refluxing after the reaction is finished, cooling the solution to room temperature, separating out yellow solid in the solution, and washing and recrystallizing the yellow solid to obtain the target product.
Preferably, in the step (1), the volume ratio of the ethylenediamine to the absolute ethyl alcohol is 1: 5.
Preferably, in the step (2) and the step (4), the developing solvent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 1: 1.
Preferably, in the step (4), the molar ratio of the LDMO to the o-vanillin is 1: 1.
The invention also provides a Fe ion probe for detecting Fe3+The application of (1).
Preferably, the iron ion probe is in Fe3+At a concentration of 3mmol/L, for Fe3+The lowest detection limit of (2) was 0.32. mu.M.
Preferably, the iron ion probe is mixed with Fe3+And (4) carrying out complexation reaction according to the ratio of 1: 1.
The synthetic route of the rhodamine 6G is as follows:
the synthesis route of the intermediate LDMO in the invention is as follows:
the synthetic route of the target probe of the invention is as follows:
the invention has the following beneficial effects:
the iron ion probe is synthesized by using rhodamine 6G, ethylenediamine and o-vanillin as raw materials, the synthesis process is simple, the raw materials are easy to obtain, the reaction condition is simple, the operation is simple, the yield is high, and Fe is detected in various common metal ions3+Has high selectivity, is not interfered by other common ions, and can be used for treating Fe3+The combination of (A) and (B) belongs to reaction type recognition and has irreversibility; fe can be detected by the target probe3+And the naked eye detection is carried out without any equipment. And, for Fe3+Short detection time, higher sensitivity and capability of detecting Fe3+Water with concentration of 3mmol/L, for Fe3+The lowest detection limit was 0.32. mu.M.
Drawings
FIG. 1 is a structural formula of an iron ion probe according to the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of an iron ion probe according to the present invention;
FIG. 3 is a graph of the UV absorption spectrum of a ferric ion probe with different metal ions added;
FIG. 4 is Fe3+Ultraviolet absorption spectrum with other metal ions；
FIG. 5 shows Fe in the presence of iron ion probe3+Ultraviolet absorption spectrograms before and after EDTA is added into the solution;
FIG. 6 is Fe3+Job's-plot against iron ion probe;
FIG. 7 is Fe3+Ultraviolet absorption spectrogram of concentration change and iron ion probe action;
FIG. 8 is Fe3+Linear regression equation for maximum absorption at 530 nm;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise indicated, the technical means used in the examples are conventional means well known to those skilled in the art.
EXAMPLE 1 preparation of iron ion Probe
(1) And (3) synthesizing rhodamine 6G:
a. 5.0000g of 3-ethylamino-4-methylphenol, 15.0000g of phthalic anhydride and 4.8000g of zinc chloride are placed in a mortar for grinding, the ground materials are poured into an eggplant-shaped flask (the size of the eggplant-shaped flask is conventionally selected according to the use requirement), the flask is heated, the temperature is kept at 165 ℃, the mixture is slowly stirred for reaction for 1 hour, the mixture is gradually melted and the color is deepened, the mixture is carefully stirred at the time, the consistency is gradually reduced along with the reaction, and then the mixture is gradually enlarged, and the reactant presents a metallic lustrous brownish purple red color; then, vacuum pumping is carried out under reduced pressure, the bottle stopper is removed after 5-10 min, and the bottle is not sublimated until no phthalic anhydride exists in the bottle;
b. dissolving the mixture obtained in the step a in 120mL of N, N-Dimethylformamide (DMF), slowly dropping 1200mL of 5% sodium chloride aqueous solution, violently stirring at 60 ℃ for 30min, carrying out suction filtration while hot, washing the filter cake with water for 1-2 times, wherein the filter cake is purple red, and carrying out vacuum drying at 60 ℃ to obtain eggplant purple powder;
c. subjecting the purple eggplant powder obtained in step b to column chromatography, eluting with ethyl acetate and then with dichloromethane to obtain a purple powder having 10.5226g of yield of 77%. 10.0000G of the mauve powder is subjected to esterification reaction with 300mL of absolute ethyl alcohol and 10mL of concentrated sulfuric acid, the solution after the reaction is poured into 600mL of 5% sodium chloride aqueous solution, the mixture is fully stirred for 0.5h at the temperature of 40 ℃, then is subjected to suction filtration and is recrystallized by using ethanol, and the final product rhodamine 6G, namely 10.2556G of purple crystals, is obtained, wherein the yield is 85%.
(2) Synthesis of rhodamine 6G derivative intermediate LDMO
a. 2.0038G of rhodamine 6G is weighed into a 250mL eggplant type flask, 150mL of absolute ethyl alcohol is added, and the mixture is stirred at normal temperature for 10min to be completely dissolved, so that the solution is brown. Uniformly mixing 4mL of ethylenediamine and 20mL of absolute ethyl alcohol in a conical flask, dripping into a solution containing rhodamine 6G, and stirring at room temperature for 20 min;
b. b, carrying out oil bath heating reflux on the mixed solution obtained in the step a, wherein the reflux temperature is 120 ℃, the reflux time is 12 hours, the reflux speed is 1 drop/second, and the color of the solution gradually becomes light and yellow; then petroleum ether/ethyl acetate 1:1 is used as a developing agent, a plate is dotted to determine the reaction end point, and when the reaction reaches the end point, the reflux is stopped;
c. after the reflux is finished, controlling the temperature to be 80 ℃, and distilling and recovering 100mL of ethanol, wherein the solution is dark in color and is yellow-orange; and then stirring the solution at normal temperature for 3 hours until a light yellow solid is separated out, performing suction filtration by using a circulating water type vacuum pump, collecting a filter cake, washing the filter cake for 2-3 times by using absolute ethyl alcohol, and drying the washed solid in a vacuum drying oven to obtain 1.5514g of light yellow product LDMO, wherein the yield is 81%.
(3) Intermediate LDMO synthesized target probe
a. 0.5010g of intermediate LDMO is put into a 50mL eggplant-shaped flask, added into 20mL absolute ethyl alcohol and stirred for 20min at normal temperature to be completely dissolved, and the solution is yellow; then 0.1510g of o-vanillin (yellow solid with milk fragrance) is added, the solution color is deepened, and the molar ratio of the intermediate LDMO to the o-vanillin is 1: 1;
b. b, carrying out oil bath heating reflux on the mixed solution obtained in the step a, wherein the reflux temperature is 110 ℃, the reflux time is 8 hours, and the color of the solution is further deepened along with the reaction and is in yellow brown; then using petroleum ether/ethyl acetate 1:1 as a developing agent, spotting a plate to determine that the reaction is finished, stopping refluxing after the reaction is finished, cooling the solution to room temperature, wherein yellow solid is precipitated in the solution, sucking the residual solution by using a rubber head dropper, washing the solid by using absolute ethyl alcohol for 1-2 times, and then performing recrystallization by using the absolute ethyl alcohol, wherein the recrystallization step is as follows: adding the solid into absolute ethyl alcohol, heating and refluxing the solution at 70 ℃ to enable the solid to be completely dissolved in a short time (if the solid cannot be completely dissolved, natural filtration is carried out through filter paper to obtain a clear and transparent solution), transferring the solution into a 100mL small beaker after dissolution, sealing the beaker with a preservative film, reserving a plurality of small holes (the number of the small holes is not required and can be set as required) on the preservative film, and placing the beaker in a fume hood for crystal precipitation to obtain 0.3959g of target product yellow needle-shaped solid with the yield of 61%.
It should be noted that: the rhodamine 6G in the invention can directly adopt the commercial rhodamine 6G, and also can be prepared by adopting the method of the invention, and the rhodamine 6G can be prepared for use.
The structural formula of the iron ion probe prepared in this example is:
and (3) performing structure detection on the prepared target product yellow acicular solid, and characterizing the yellow acicular solid by using a nuclear magnetic resonance apparatus, wherein a nuclear magnetic resonance hydrogen spectrogram of the yellow acicular solid is shown in figure 2, and the nuclear magnetic resonance hydrogen spectrogram of the target product can be known as follows:1H NMR(60MHz，CDCl3) Δ 8.07(s, 1H), 7.94(m, 1H), 7.47(m, 2H),7.17(m, 1H), 6.84(d, 3H), 6.42(s, 2H), 6.28(d, 2H), 3.92(s, 3H), 3.27(m, 9H), 1.92(d, 6H), 1.37(t, 6H), it was found that the kind of hydrogen in the target product was determined18 species, peak area indicates the number of hydrogen of each species.
The results show that: the structure of the prepared target product yellow needle-shaped solid is consistent with the designed structure.
Example 2 ion response and selectivity of iron ion Probe
Adding 2940 mu L of acetonitrile aqueous solution (the volume ratio of water to acetonitrile is 1:4) and 30 mu L of iron ion probe solution (88 mg of the target product prepared in example 1 is weighed and added into a 50mL volumetric flask, dissolved by acetonitrile and subjected to volume measurement by acetonitrile) into 15-piece 7mL centrifuge tubes respectively by using a pipette gun, then adding 60 mu L of prepared 3mmol/L of metal ion solution into 14-piece centrifuge tubes respectively, wherein each metal ion solution corresponds to one centrifuge tube, one acetonitrile aqueous solution without probe solution is used as a blank sample and is marked by label paper; wherein the 14 kinds of metal ions are respectively Ag+、Al3+、Ba2+、Ca2+、Co2+、Cu2+、Fe3+、Hg+、K+、Mn+、Na+、Ni+、Pb+、Zn2+。
When Fe is added3+When the solution is in solution, the color of the solution in the centrifugal tube is changed from light yellow to colorless and gradually changed to red, and after a period of time, Al is added3+Also appeared light red, added with Fe3+Color ratio of acetonitrile aqueous solution of (A) to (B) of Al3+The addition of other metal ion solution does not cause the probe solution in the centrifuge tube to change obviously, which indicates that the iron ion probe is used for Fe3+And Al3 +All with varying degrees of response.
Then, an ultraviolet spectrophotometer is used for detecting the ultraviolet absorption condition of the solution in the 14 centrifugal tubes except the blank sample, the set wavelength is 300-600 nm, and the result is shown in figure 3, and only added Fe is found3+The solution had a very pronounced UV absorption at 530 nm.
The results show that: in FIG. 3, only Fe3+And Al3+Has obvious ultraviolet absorption at 530nm and Fe3+Absorbance of (2) is higher than that of Al3+Without other ions being significantAnd (4) absorbing. Therefore, it is considered that an aqueous acetonitrile solution containing an iron ion probe and Fe3+The chemical reaction is generated, and other metal ions do not react with the iron ion probe, which shows that the iron ion probe of the invention is used for Fe3+Has good selectivity.
Due to Fe3+Fast response time to probe, Al3+Slow response time to the probe, therefore, with Fe3+As the primary ion detected.
EXAMPLE 3 interference of iron ion probes
This example is for Fe3+Whether the interference is generated to the response of other metal ions or not is detected, 60 mu L of Fe is added into 14 centrifugal tubes except the blank sample in example 2 by using a pipette gun3+The solution was then shaken up. Adding Fe3+After the solution, the color of the 14 centrifugal tubes is changed into red, which indicates that other metal ion solutions do not affect the iron ion probe of the invention.
Then, an ultraviolet spectrophotometer is used for detecting the ultraviolet absorption condition of the solution in the 14 centrifugal tubes, the wavelength is set to be 300-600 nm, and the result is shown in figure 4. The results show that: when Fe is added3+After the solution, all solutions in 14 centrifugal tubes have obvious ultraviolet absorption peaks at 530nm, and the absorbance changes, wherein Fe3+The absorbance of the solution is obviously higher than that of other metal ions and Fe3+The absorbance of (b) indicates that other metal ions are responsible for Fe3+Does not interfere with the response of the iron ion probe to acetonitrile in water.
Example 4 analysis of complexation mechanism
Aqueous acetonitrile containing iron ion Probe considered according to example 2 with Fe3+A chemical reaction takes place, for which purpose the chemical reaction is further investigated. Adding 3mmol/L EDTA solution into the solution containing iron ion probe which turns red in example 2, wherein the color of the solution changes from red to light yellow, carrying out ultraviolet and visible light analysis on the solution before and after adding EDTA, the ultraviolet absorption spectrogram is shown in figure 5, and the solution before adding EDTA has obvious peak at 530nm,the solution is red in color and has obvious fluorescence; when 3mmol/L EDTA solution is added, the solution turns into light yellow, and then the ultraviolet absorption is detected, and it is obvious that no absorption occurs at the wavelength of 530 nm. This yields: the iron ion probe and Fe of the invention3+Is a color change that occurs through a complexation reaction, the reaction mechanism being as follows:
example 5Job's-Plot assay
Taking 12 centrifuge tubes, of which 1 tube was filled with 3mL of acetonitrile in water (water to acetonitrile ratio 1:4 by volume) using a pipette as a reference, 2900. mu.L of acetonitrile in water was added to the remaining 11 tubes using a pipette, followed by addition of the iron ion probe solution (which was pipetted from the solution prepared in example 2) and Fe3+Solution, and keeping the iron ion probe solution and Fe3+The sum of the volumes of the solutions was 100. mu.L, where Fe3+The volume of the solution is gradually increased from 0 μ L to 100 μ L with 10 μ L as a gradient, that is, the volume of the iron ion probe solution is gradually decreased from 100 μ L to 0 μ L, and finally the solution in the 12 centrifuge tubes is detected by an ultraviolet spectrophotometer, and the detection result is shown in FIG. 6. As can be seen from the figure, the iron ion probe of the present invention is combined with Fe3+Is carried out according to a 1:1 complexation reaction.
Example 6 sensitivity analysis
Taking 14 centrifuge tubes, 1 of which was inserted into 3mL of acetonitrile aqueous solution (volume ratio of water to acetonitrile 1:4) using a pipette gun as a reference, and 13 of which were added 30. mu.L of each iron ion probe solution (which was pipetted from the solution prepared in example 2) using a pipette gun, and then Fe was added with a gradient of 10. mu.L3+Solution of Fe3+The volume of the solution is increased from 0 to 120 mu L, in order to ensure that the total volume of the solution in the centrifuge tube is 3mL, the volume of the acetonitrile water solution is decreased from 2970 mu L to 2850 mu L, the label is attached to the acetonitrile water solution for labeling, finally, the solution in the 14 centrifuge tubes is detected by an ultraviolet spectrophotometer, and Fe is detected at 530nm3+The results of the linear regression equation analysis are shown in FIGS. 7 and 8, and it can be seen from FIG. 7 that the following equation varies with Fe3+The solution concentration is increased, the absorbance is increased, and the ultraviolet absorption at the wavelength of 530nm is stronger and stronger. As can be seen from FIG. 8, absorbance and Fe were observed in the wavelength range of 40 to 120nm3+The concentration of the solution is linear, and the linear equation is: y0.00474 x-0.17524 and r 0.9864. According to the lowest detection formula: LOD is 3 sigma/k, wherein k is the slope, sigma is the standard deviation of the measured value and a blank sample, and finally the calculation shows that the acetonitrile water solution of the iron ion probe is opposite to Fe3+The minimum detection limit of (2) is 0.32 mu M, namely 0.01792mg/L, and the value is less than the minimum limit specified by national drinking water (GB5749-2006, sanitary standard of domestic drinking water, Fe3+Minimum 0.3mg/L) for detecting Fe in ecological environment3+The content has a great practical significance.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (3)
1. An iron ion probe, characterized in that: the iron ion probe has the following structural formula:
2. use of a ferric ion probe according to claim 1, wherein: the iron ion probe is used for detecting Fe3+The application of the iron ion probe in Fe3+At a concentration of 3mmol/L, for Fe3+The lowest detection limit of (2) was 0.32. mu.M.
3. Use of a ferric ion probe according to claim 2, wherein: the iron ion probe and Fe3+And (4) carrying out complexation reaction according to the ratio of 1: 1.
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