CN113960004B - Method for detecting Ni (II) based on up-conversion fluorescence internal filtering effect - Google Patents
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Abstract
The invention discloses a method for detecting Ni (II) based on up-conversion fluorescence internal filtering effect, when Ni (II) exists, dimethylglyoxime and dimethylglyoxime undergo complex reaction, and a reaction product DMG-Ni (II) complex can be doped with rare earth up-conversion nano material NaYF 4 : an effective fluorescence internal filtration effect occurs between Yb and Tm, and the coupling of a labeling material is not needed, so that the quantitative analysis of Ni (II) is directly carried out through the quenching degree of a fluorescence signal. The method has the advantages that: 1. the operation is simple and convenient, and expensive and complex equipment and instruments are not needed; 2. the method has good selectivity and high sensitivity; 3. the method has high specificity and anti-interference capability to Ni (II), and is expected to be used for detecting complex samples; 4. the raw materials required in the use process cannot cause secondary pollution to the environment, are clean and environment-friendly, are favorable for further development and utilization of the method, and have potential practical application values in the pollution early warning analysis of the heavy metal ions in the future environment.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry and nano technology, and particularly relates to a method for detecting Ni (II) based on an up-conversion fluorescence internal filtering effect.
Background
Nickel is an essential trace element in biological systems such as respiratory systems, biosynthesis and metabolism. Metallic nickel and its compounds have been widely used in the modern industry. Nickel compounds are useful in electroplating and in the production of nickel cadmium batteries and electronic devices, and nickel alloys (e.g., stainless steel) are useful in the production of tools, instruments, and the like. However, the high use rate of nickel inevitably leads to environmental pollution, and 250mg of soluble nickel per day causes poisoning, and accumulation in the body causes pulmonary fibrosis and kidney diseases. Therefore, ni (II) detection in the environment is important.
To date, most Ni (II) sensors are potentiometric based, and these sensors have the general problem of poor selectivity. Currently, rare earth up-conversion nanomaterials (UCNPs) have been successfully used widely for detection of heavy metal ions due to their unique optical properties.
The Internal Filtering Effect (IFE) is a non-radiative energy conversion model in fluorescence spectroscopy, and is a phenomenon that is generated by absorption of laser light or visible light, or both, by an absorbent in the detection system. The IFE has the advantages that: (1) Covalent connection between the energy acceptor and the donor is not needed, so that the synthesis of the fluorescent material is simplified, and the preparation of a complex probe is avoided; (2) Since the absorbance conversion of the sensor is converted into conversion of the fluorescent intensity in an exponential form, the sensitivity of the analysis is higher than that of the absorption method. However, IFE occurs only when the absorption spectrum of the absorber overlaps with the excitation spectrum or the emission spectrum of the fluorescent agent, or both, with simultaneous spectral bands. Furthermore, the two materials should not spontaneously react chemically and not interfere with the fluorescent properties.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for detecting Ni (II) based on an up-conversion fluorescence internal filtering effect. The invention uses UCNPs as fluorescent probes and utilizes the change of up-conversion fluorescence intensity to realize high-sensitivity detection and high-selectivity detection of Ni (II). The dimethylglyoxime and Ni (II) form a wine red soluble complex, the complex and UCNPs generate an inner filtering effect so as to quench the fluorescence of the UCNPs, and the quantitative detection of Ni (II) can be realized through the change of fluorescence intensity caused by the complexation of the dimethylglyoxime and Ni (II).
In order to achieve the above purpose, the present invention provides the following technical solutions:
method for detecting Ni (II) based on up-conversion fluorescence internal filtering effect, and establishing Ni (II) standard curve by using PAA-UCNPs@NaGdF 4 And adding the fluorescent probe, iodine solution and a dimethylglyoxime alkaline solution into a liquid to be detected as a fluorescent probe, mixing and reacting, measuring the fluorescent intensity of a reaction liquid, and qualitatively detecting Ni (II) in the liquid to be detected according to the measured fluorescent intensity.
Further, the preparation method of the PAA-UCNPs comprises the following steps:
(1) Synthesis of OA-UCNPs: mixing rare earth stearate, naF, oleic acid and octadecene, placing in argon atmosphere, refluxing and heating to 140 ℃, and maintaining for 30min for dehydration and degassing; then rapidly heating to 312-314 ℃, keeping the reaction for 45min, cooling to room temperature, centrifuging the obtained product at 11000rpm, discarding supernatant, centrifuging and washing precipitate with ethanol, cyclohexane and distilled water until no NaF component exists, and vacuum drying at 70 ℃ to obtain OA-UCNPs (OA is oleic acid);
(2)UCNPs@NaGdF 4 is prepared from the following steps: reflux-heating oleic acid, octadecene, naF, gd stearate and the obtained OA-UCNPs to 140 ℃ under argon atmosphere, and dehydrating and degassing for 30 min; then rapidly heating to 312-314 ℃, keeping the reaction for 50min, cooling to room temperature, centrifuging the obtained product at 11000rpm for 3min, discarding supernatant, adding ethanol to precipitate the product, washing with cyclohexane and distilled water, centrifuging, and vacuum drying at 70deg.C to obtain UCNPs@NaGdF 4 ；
(3)PAA-UCNPs@NaGdF 4 Is prepared from the following steps: the UCNPs@NaGdF is obtained 4 Mixing with chloroform solution, ultrasonic dispersing, adding polyacrylic acid solution, sealing, stirring, washing, centrifuging at 11000rpm, and removingVacuum drying the clear solution and precipitate at 70deg.C for 2 hr to obtain PAA-UCNPs@NaGdF 4 。
Further, the rare earth stearate in the step (1) is a mixture of Y stearate, yb stearate and Tm stearate in a molar ratio (Y: yb: tm=79.5:20:0.5).
Further, the molar ratio of the rare earth stearate to NaF in the step (1) is 0.8:28, and the molar ratio of oleic acid to octadecene is 12:8. The molar ratio of oleic acid to octadecene in the step (2) is 1:1, and the molar ratio of NaF to Gd stearate and OA-UCNPs is 1:1:1.
Further, step (3) the UCNPs@NaGdF 4 The mass volume ratio of the aqueous solution to the chloroform solution is 50mg to 1mL.
Further, the PAA-UCNPs@NaGdF 4 The volume ratio of the solution, iodine solution, the dimethylglyoxime alkaline solution and the Ni (II) solution is 25:2:5:10.
Further, the final concentration of Ni (II) in the mixture is 2. Mu.M-55. Mu.M.
Further, the alkaline solution of dimethylglyoxime is prepared by mixing dimethylglyoxime with ammonia water.
Further, the quantitative detection conditions are: excitation power 2W/cm 2 The voltage is 500V.
The principle of the invention is as follows:
in alkaline solution with iodine as oxidant, dimethylglyoxime (DMG) can form a wine red soluble complex with Ni (II), the absorption spectrum of the complex overlaps with the emission spectrum of UCNPs to form effective IFE so as to quench the fluorescence of UCNPs, and the change of fluorescence intensity caused by complexing between DMG and Ni (II) realizes the detection of Ni (II) with high sensitivity and high selectivity.
The product prepared by the invention belongs to a core-shell structure, OA-UCNPs with a core structure are prepared by rare earth stearate, naF, oleic acid and octadecene, and UCNPs@NaGdF with a core-shell structure are prepared by oleic acid, octadecene, naF and Gd stearate 4 Finally, the final product PAA-UCNPs@NaGdF is formed by coating polyacrylic acid (PAA) 4 . PAA addition improves PAA-UCNPs@NaGdF 4 And the carboxyl of PAA is easily dissociated into carboxylate anions to be negatively charged, thereby being better applied to the detection of heavy metal ions in aqueous solution.
Compared with the prior art, the invention has the beneficial effects that:
(1) The rare earth doped up-conversion luminescent nano material is used as a fluorescent probe, and near infrared light is adopted for excitation, so that no background fluorescence exists;
(2) The operation is simple and convenient, and expensive and complex equipment and instruments are not needed; the method has good selectivity and high sensitivity;
(3) Has high specificity to Ni (II) and can be used for complex sample detection. The raw materials required in the use process can not cause secondary pollution to the environment, so that the probe is clean and environment-friendly, and is beneficial to further development and utilization of the probe; the simple and sensitive method has potential practical application value in the pollution early warning analysis of the heavy metal ions in the future environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron microscope image of OA-UCNPs;
FIG. 2 is an X-ray diffraction pattern of OA-UCNPs;
FIG. 3 is UCNPs@NaGdF 4 Is a transmission electron microscope image;
FIG. 4 shows PAA-UCNPs@NaGdF 4 And fourier transform infrared spectrograms of OA-UCNPs;
FIG. 5 is a schematic diagram of PAA-UCNPs@NaGdF 4 A characterization of fluorescence versus uv-visible absorption of DMG-Ni (II) complexes;
FIG. 6 is a graph showing the change in fluorescence intensity of OA-UCNPs by Ni (II) at various concentrations;
FIG. 7 is a graph of a fitted linear relationship of Ni (II) detection;
FIG. 8 is a schematic diagram of fluorescence Internal Filtration Effect (IFE) based on UCNPs and DMG-Ni (II) complexes;
fig. 9 is a diagram of a selective analysis.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The liquid raw materials used in the invention are all directly purchased reagents.
Example 1
1) Preparation of NaYF by thermal decomposition 4 : yb, tm nanocrystals (OA-UCNPs): 0.8mmol of rare earth stearate (wherein the Y: yb: tm molar ratio is 79.5:20:0.5), 28 mmole of NaF, 12 mmole of Oleic Acid (OA), 8 mmole of Octadecene (ODE) were charged into a 100mL three-necked flask;
the system was heated to 140 ℃ under argon atmosphere for 30min to obtain anhydrous and anaerobic reaction conditions. Then heating rapidly, keeping the temperature between 312 and 314 ℃, continuously reacting for 45min, naturally cooling to room temperature, centrifuging the reaction product at 11000rpm for 3min, removing supernatant, adding ethanol to precipitate the product, washing and centrifuging with cyclohexane and distilled water for many times until no organic oil and NaF component exist, transferring to an oven, and vacuum drying at 70 ℃ for standby to obtain beta-phase NaYF 4 : yb, tm nanocrystals (OA-UCNPs, OA is oleic acid).
TEM and XRD characterization patterns of OA-UCNPs are shown in FIG. 1 and FIG. 2. FIG. 1 shows that the synthesized OA-UCNPs nano particles are spherical, have good dispersibility and have the particle size of about 30nm. The XRD data of FIG. 2 shows NaYF in hexagonal phase 4 Is completely identical, indicating that the synthesized OA-UCNPs (NaYF) 4 : yb, tm) is hexagonal phase (beta phase), and has better fluorescence performance.
2)UCNPs@NaGdF 4 Is prepared from the following steps: into a 100ml three-necked flask, 6.4mmol of Oleic Acid (OA), 6.4mmol of Octadecene (ODE) and beta-phase NaYF were charged 4 : yb, tm 0.2mmol, naF0.2mmol, gd stearate 0.2mmol, and under argon atmosphere, were heated under reflux to 140℃for 30min to obtain anhydrous and anaerobic reaction conditions. Then rapidly heating to 312-314 ℃, keeping the reaction for 50min, cooling to room temperature, centrifuging the obtained product at 11000rpm for 3min, discarding supernatant, adding ethanol to precipitate the product, washing and centrifuging with cyclohexane and distilled water for multiple times, and vacuum drying at 70 ℃ to obtain UCNPs@NaGdF 4 。
UCNPs@NaGdF 4 A TEM characterization of (a) is shown in figure 3. FIG. 3 shows that the synthesized core-shell structure nanoparticle is spherical, has good dispersibility and has a particle size of about 35nm.
3)PAA-UCNPs@NaGdF 4 Is prepared from the following steps: 50mg UCNPs@NaGdF 4 d dispersing in 1mL chloroform solution (small amount of ethanol is added if the solution cannot be completely dispersed) for ultrasonic dispersion, then weighing 1g polyacrylic acid (PAA) and dissolving in 15mL deionized water, mixing with the solution, sealing, continuously stirring for 24h, washing with water-alcohol (volume ratio of 1:1) three times after the reaction is finished, centrifuging at 11000rpm for 5min, removing supernatant, and vacuum drying at 60 ℃ for 2h to obtain PAA-UCNPs@NaGdF 4 d。
PAA-UCNPs@NaGdF 4 And OA-UCNPs are shown in FIG. 4. FT-IR spectrum shows that OA-UCNPs and PAA-UCNPs@NaGdF 4 At 3458cm -1 A very broad peak exists at 1550 and 1460cm, mainly due to the stretching vibration peak of-OH -1 Asymmetric and symmetric stretching vibration peaks of carboxyl (COO-) of oleic acid/polyacrylic acid, 2851cm -1 And 2937cm -1 Then respectively belonging to methylene (-CH) on long alkyl chain of oleic acid/polyacrylic acid molecule 2 (-) symmetrical and asymmetrical stretching vibration peaks; UCNPs are at 1725cm after polyacrylic acid is modified -1 At which is the stretching vibration peak of c=o of the carboxyl group. It can be seen that the PAA has been successfully modified to UCNPs@NaGdF 4 The surface of the fluorescent dye has water solubility and carries negative charge, and is better applied to detection of heavy metal ions in aqueous solution.
4) 250 mu L of 2mg/mL of PAA-UCNPs@NaGdF is taken 4 The aqueous solution was mixed with 100. Mu.L of Ni (II) aqueous solutions of different concentrations, followed by adding 20. Mu.L of iodine solution and 580. Mu.L of ultra pure water, shaking, followed by adding 50. Mu.L of DMG solution containing aqueous ammonia (0.5 g of dimethylglyoxime was dissolved in 50mL of aqueous ammonia, transferring to a 100mL volumetric flask after the dissolution was completed, and metering the volume to scale mark with ultra pure water), shaking, and the final volume of the mixed system was 1mL, so that the final concentration of Ni (II) was 2. Mu.M to 55. Mu.M. Reacting at room temperature for 20min, detecting with fluorescence spectrophotometer, and exciting power 2W/cm 2 The voltage is 500V.
FIG. 5 is a schematic diagram of PAA-UCNPs@NaGdF 4 Characterization of fluorescence versus UV-visible absorption of DMG-Ni (II) complexes. FIG. 5 is a good demonstration of UV-visible absorption of DMG-Ni (II) complex with PAA-UCNPs@NaGdF 4 Fluorescent light of (2)The spectra have good overlap, providing feasibility for fluorescence Internal Filtration Effects (IFE) between the two.
FIG. 6 is a graph showing the change of the fluorescence intensity of UCNPs at different concentrations of Ni (II), and it can be seen that the fluorescence intensity of UCNPs gradually decreases with the increase of the concentration of Ni (II) at 478 nm.
FIG. 7 is a graph showing a linear relationship between Ni (II) concentration and fluorescence quenching degree of UCNPs at 478nm, wherein the linear relationship is shown by the equation F 0 /F＝0.04293C+0.94942(F 0 /F，F 0 The initial fluorescence intensity of the solution without Ni (II) was represented by F, the fluorescence intensity of the solution after Ni (II) was added, and the concentration of Ni (II) was represented by C, and the detection Limit (LOD) was calculated to be 0.32. Mu.M by the 3 sigma method.
FIG. 8 is a schematic diagram of fluorescence Internal Filtration Effect (IFE) based on UCNPs and DMG-Ni (II) complexes. UCNPs@NaGdF 4 The surface-modified polyacrylic acid (PAA) has water solubility and carries negative charges. In alkaline solution in the presence of the oxidant iodine, dimethylglyoxime (DMG) forms a reddish soluble complex with Ni (II). The ultraviolet absorption of the complex is a broadband absorption at 440 nm. UCNPs@NaGdF 4 Emits blue fluorescence with a wavelength of 478nm visible to naked eyes under the irradiation of 980nm excitation light, and the absorption spectrum of the DMG-Ni (II) complex and UCNPs@NaGdF 4 The emission spectra of (2) overlap to form an effective fluorescence Internal Filter Effect (IFE) to quench the up-converted fluorescence, thereby realizing high sensitivity and high selectivity detection of Ni (II).
Example 2
The difference from example 1 is that the Ni (II) aqueous solution of different concentrations in step 4) is replaced so that the final concentrations of this component in the mixture are respectively: the selectivity test was performed for 35. Mu.M Ni (II), 350. Mu.M Fe (III), 350. Mu.M Cd (II), 350. Mu.M Cr (III), 350. Mu.M Cu (II), 350. Mu.M Ag (I), 350. Mu.M Mg (II), 350. Mu.M Zn (II), 350. Mu.M Ca (II), 350. Mu.M Na (I), 350. Mu. M K (I), and the results are shown in FIG. 9.
As can be seen from FIG. 9, ni (II) greatly quenches the fluorescence of UCNPs as compared with other metal ions, F 0 /F(F 0 Represents the initial solution without Ni (II)Initial fluorescence intensity, F represents the fluorescence intensity of the solution after Ni (II) addition) ratio is maximum. The method for detecting Ni (II) based on the up-conversion fluorescence internal filtering effect has better selectivity (shown by a black column). As is apparent from FIG. 9, when examining the anti-interference ability of the probe in the presence of Ni (II) together with other heavy metal ions, F is found under the condition that the concentration of other metal ions is ten times that of Ni (II) 0 The value of/F still approaches that of Ni (II) alone, and thus it can be seen that high concentration of interfering ions does not cause insufficient amount of the developer DMG, which indicates that the detection of Ni (II) in this experiment has excellent anti-interference ability (shown by gray bars).
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (4)
1. A method for detecting Ni (II) based on up-conversion fluorescence internal filtering effect is characterized in that a Ni (II) standard curve is established by using PAA-UCNPs@NaGdF 4 Adding the fluorescent probe, iodine solution and a dimethylglyoxime alkaline solution into a liquid to be detected as a fluorescent probe, mixing and reacting, measuring the fluorescent intensity of a reaction liquid, and quantitatively detecting Ni (II) in the liquid to be detected according to the measured fluorescent intensity;
the PAA-UCNPs@NaGdF 4 The preparation method of (2) comprises the following steps:
(1) Synthesis of OA-UCNPs: mixing rare earth stearate, naF, oleic acid and octadecene, placing in argon atmosphere, refluxing and heating to 140 ℃, and maintaining for 30min for dehydration and degassing; then rapidly heating to 312-314 ℃, keeping the reaction for 45min, cooling to room temperature, centrifuging the obtained product at 11000rpm, discarding supernatant, centrifuging and washing precipitate with ethanol, cyclohexane and distilled water until no NaF component exists, and vacuum drying at 70 ℃ to obtain OA-UCNPs;
(2)UCNPs@NaGdF 4 is prepared from the following steps: reflux-heating oleic acid, octadecene, naF, gd stearate and the obtained OA-UCNPs to 140 ℃ under argon atmosphere, and dehydrating and degassing for 30 min; then rapidly heating to 312-314 ℃ and keepingCooling to room temperature after 50min of reaction, centrifuging the obtained product at 11000rpm for 3min, discarding supernatant, adding ethanol to settle the product, washing with cyclohexane and distilled water, centrifuging, and vacuum drying at 70deg.C to obtain UCNPs@NaGdF 4 ；
(3)PAA-UCNPs@NaGdF 4 Is prepared from the following steps: the UCNPs@NaGdF is obtained 4 Mixing with chloroform solution, ultrasonic dispersing, adding polyacrylic acid solution, sealing, stirring, washing, centrifuging at 11000rpm, removing supernatant, and vacuum drying at 70deg.C for 2 hr to obtain PAA-UCNPs@NaGdF 4 ；
250 mu L of 2mg/mL of PAA-UCNPs@NaGdF is taken 4 Mixing the aqueous solution with 100 mu L of Ni (II) aqueous solution with different concentrations, adding 20 mu L of iodine solution and 580 mu L of ultrapure water, shaking uniformly, adding 50 mu L of DMG solution containing ammonia water, shaking uniformly, and enabling the final volume of the mixed system to be 1mL so that the final concentration of Ni (II) is 2 mu M-55 mu M; reacting at room temperature for 20min, detecting with fluorescence spectrophotometer, and exciting power 2W/cm 2 A voltage of 500V;
the preparation method of 50 mu L of DMG solution containing ammonia water comprises the following steps: dissolving 0.5g of dimethylglyoxime in 50mL of ammonia water, transferring into a 100mL volumetric flask after the dimethylglyoxime is completely dissolved, and fixing the volume to a scale mark by using ultrapure water;
the concentration of Ni (II) and the fluorescence quenching degree of UCNPs at 478nm show good linear relation, and the linear equation is F 0 /F＝0.04293C+0.94942，F 0 /F，F 0 The initial fluorescence intensity of the solution without Ni (II) is represented by F, the fluorescence intensity of the solution after Ni (II) is added, and C is the concentration of Ni (II).
2. The method of claim 1, wherein the rare earth stearate in step (1) is Y stearate, yb stearate, tm stearate, wherein the molar ratio of rare earth elements is: y: yb: tm=79.5:20:0.5.
3. The process of claim 1, wherein the rare earth stearate to NaF molar ratio of step (1) is 0.8:28 and the oleic acid to octadecene molar ratio is 12:8; the molar ratio of oleic acid to octadecene in the step (2) is 1:1, and the molar ratio of NaF to Gd stearate and OA-UCNPs is 1:1:1.
4. The method of claim 1, wherein the ucnps@nagdf of step (3) 4 The mass-volume ratio of the aqueous solution to the chloroform solution is 50 mg/1 mL.
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| CN106806906A (en) * | 2017-01-03 | 2017-06-09 | 浙江大学 | A kind of preparation method for collecting the fluorescence imaging rare earth upconversion nano pharmaceutical carrier integrated with medicine is carried |
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