CN113402646B - Method for detecting silver ions - Google Patents
Method for detecting silver ions Download PDFInfo
- Publication number
- CN113402646B CN113402646B CN202110558449.XA CN202110558449A CN113402646B CN 113402646 B CN113402646 B CN 113402646B CN 202110558449 A CN202110558449 A CN 202110558449A CN 113402646 B CN113402646 B CN 113402646B
- Authority
- CN
- China
- Prior art keywords
- suspension
- silver ions
- vesicle suspension
- ethylene diamine
- vesicle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 silver ions Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 80
- 239000000243 solution Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 25
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- ZPUDRBWHCWYMQS-UHFFFAOYSA-N pentacosa-10,12-diynoic acid Chemical compound CCCCCCCCCCCCC#CC#CCCCCCCCCC(O)=O ZPUDRBWHCWYMQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000002189 fluorescence spectrum Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 12
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007995 HEPES buffer Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000000862 absorption spectrum Methods 0.000 claims description 10
- 238000004445 quantitative analysis Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229920000015 polydiacetylene Polymers 0.000 abstract description 53
- 238000001514 detection method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000000007 visual effect Effects 0.000 abstract description 3
- 238000010223 real-time analysis Methods 0.000 abstract description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 45
- 229910021645 metal ion Inorganic materials 0.000 description 17
- 239000000523 sample Substances 0.000 description 11
- 230000004044 response Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000004451 qualitative analysis Methods 0.000 description 7
- 230000003993 interaction Effects 0.000 description 6
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 5
- 229960001484 edetic acid Drugs 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000003473 lipid group Chemical group 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HUSJNUJNBGHUOQ-UHFFFAOYSA-N pentacosa-10,12-dienoic acid Chemical compound CCCCCCCCCCCCC=CC=CCCCCCCCCC(O)=O HUSJNUJNBGHUOQ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F138/00—Homopolymers of compounds having one or more carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N2021/755—Comparing readings with/without reagents, or before/after reaction
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a method for detecting silver ions, which specifically comprises the steps of dropwise adding an ethanol solution of 10, 12-pentacosadiynoic acid into an aqueous solution of disodium ethylene diamine tetraacetate by adopting a vesicle suspension under the condition of stirring at room temperature in a dark place, and then standing the suspension overnight at a low temperature to enable the suspension to be self-assembled to obtain a colorless supramolecular suspension; and then polymerizing the colorless supramolecular suspension under ultraviolet irradiation to obtain a blue polydiacetylene vesicle suspension. Compared with other detection methods, the polydiacetylene vesicle suspension designed by the invention can be used for Ag in water environment+The visual detection of (2) does not need complicated biochemical modification, does not need large-scale instrument and equipment and a fussy sample pretreatment process, has low detection cost, and can realize quick real-time analysis.
Description
Technical Field
The invention belongs to the field of chemical detection, and particularly relates to a method for detecting silver ions.
Background
Silver and its compounds are widely used in production and life, and excessive silver can seriously harm ecological environment and human health, so it can be used for Ag in environment+The rapid and accurate detection has very important significance. Existing Ag+Detection methods such as spectroscopy, fluorescent probe methods, and electrochemical sensors, etc., often require expensive instruments, specialist operations, time-consuming sample pre-treatment processes, or complex design synthesis processes, and are difficult to implement in-situ detection.
The Polydiacetylene (PDA) is a conjugated polymer with special optical properties, and can generate color conversion from blue to red and change from non-fluorescence to fluorescence under the external stimulation, so that the PDA in the blue state is considered as an ideal metal ion sensor material, and the optical change can be conveniently detected in three modes of naked eye identification, ultraviolet visible absorption spectrum and fluorescence spectrum.
In the research field of PDA-based metal ion sensors, most of them are used for the purpose of experimental selective detectionThe researchers used the chemical modification method: a functional molecule (or group) capable of selectively recognizing certain metal ions is connected to the terminal carboxyl of a commercial monomer PCDA (10, 12-pentacosadiynoic acid monomer for short) commonly used in the detection field. When metal ions are added into the system, specific metal ions can be subjected to coordination combination or chemical combination with the terminal group of the PDA side chain, so that the conjugated structure of the PDA is disturbed, and finally the optical property of the PDA is changed, thereby realizing the purpose of metal ion detection. Such as: chinese patent CN110501316A discloses' a polydiacetylene liposome in water environment with Pb2+The visual detection method of (1), reference "Pham, t.c.; kim, y.k.et al.a Selective Colorimetric and Fluorometric chemosensors Based on Conjugated polydiacetates for Cadmium Ion detection 2019,3(11), 1133-.
However, the above method inevitably involves a large amount of organic synthesis, and the reason for analyzing the organic synthesis is mainly as follows:
1) since organic synthesis generally acts on the terminal carboxyl group of the PCDA monomer (structural formula shown below), the functional molecule for recognizing the metal ion should have the ability to selectively bind to the metal ion first and then have reactivity with the terminal carboxyl group of the PCDA monomer. This requires a higher demand for functional molecules, while there are fewer commercial monomers to choose from to meet the above requirements. Therefore, it is common to chemically modify the functional molecule before chemically modifying the PCDA monomer. A large number of organic synthesis processes not only cause harm to human bodies and the environment, but also complicate the method and improve the preparation cost.
2) The procedure for obtaining the polymer PDA from the monomers is as follows, only if the self-assembly of the diacetylene monomers satisfies certain structural parameters (d is about
About 45 deg.C), polymerization can be initiated by conditions such as light; the polymerization reaction has very strict structural parameters for the self-assembled arrangement of monomers. Therefore, even if a functional group is successfully introduced into the PCDA monomer through organic synthesis, the modified monomer may not be self-assembled due to steric hindrance, non-covalent interaction, or the like, or the structural parameters of self-assembly may not meet the requirements of solid-phase polymerization, and if the system cannot be polymerized to obtain stable blue-color PDA, the capability of metal ion detection is lost.
In summary, the development of PDA-based sensors is limited to some extent by the complex organic synthesis.
Disclosure of Invention
The invention aims to provide a method for detecting silver ions, which can avoid a complex organic synthesis process and realize the detection of Ag+The method has the advantages of rapid, sensitive and accurate identification and low cost.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
a preparation method of vesicle suspension for detecting silver ions is characterized by comprising the following steps:
1) dropwise adding an ethanol solution of 10, 12-pentacosadienoic acid (PCDA) into an aqueous solution of disodium ethylene diamine tetraacetate (EDTA-2Na) under the condition of stirring at room temperature in a dark place to obtain a colorless supramolecular suspension (PCDA/EDTA for short);
2) placing the colorless supramolecular suspension obtained in the step 1) at a low temperature in a dark place to enable the colorless supramolecular suspension to be fully self-assembled; the reason why the suspension obtained in step 1) is placed in the dark at a low temperature is to allow sufficient self-assembly, and it is considered to be an annealing treatment;
3) and (3) polymerizing the colorless suspension obtained in the step 2) under ultraviolet irradiation to obtain blue vesicle suspension for detecting silver ions, namely polydiacetylene vesicle suspension (PDA/EDTA vesicle suspension).
Further, in the step 1), the concentration of the 10, 12-pentacosadiynoic acid monomer in the ethanol solution is 1.8-2.2 mmol/L;
the disodium ethylene diamine tetraacetate water solution is prepared by dissolving disodium ethylene diamine tetraacetate solid powder in HEPES buffer solution under the condition of heating and stirring;
wherein the concentration of the ethylene diamine tetraacetic acid disodium is 1-2 mmol/L; the concentration of HEPES buffer solution is 15-20mM, and the pH value is 7.2-7.6.
Further, in the step 1), the volume ratio of the ethanol solution of the 10, 12-pentacosadiynoic acid to the aqueous solution of the disodium ethylene diamine tetraacetate is 0.5-1.5: 10.
Further, in the step 2), the low-temperature dark placement refers to keeping for 8-12 hours at a temperature of 4 +/-0.5 ℃ in the dark, such as placing in a refrigerator.
Further, in the step 3), the ultraviolet irradiation conditions are as follows: irradiating for 5-10min with 254nm ultraviolet light with power of 6W and distance of 10cm from the sample to be measured.
Further, in the step 1), the concentration of the 10, 12-pentacosadiynoic acid monomer in the ethanol solution is preferably 2 mmol/L;
wherein, the concentration of the ethylene diamine tetraacetic acid disodium is preferably 2 mmol/L; the concentration of the HEPES buffer solution is preferably 20mM, pH 7.4.
The invention also provides a vesicle suspension for detecting silver ions, which is characterized by being prepared by the preparation method.
The method for detecting silver ions by using the vesicle suspension prepared by the preparation method is characterized in that a sample to be detected is added into the vesicle suspension, and after incubation for 20-25min, the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the vesicle suspension are measured: the preferred incubation time is 20min, depending on the time required to achieve maximum colorimetric response in the experiment;
and if the absorption peak at 636-644nm and the absorption peak at 535-545nm in the ultraviolet visible absorption spectrum are obviously reduced, and the fluorescence intensity at 558-562nm and 625-632nm in the fluorescence emission spectrum is obviously increased, determining that the sample to be detected contains silver ions. Different instruments or different operating environments may cause the peak to float within the above-described range.
Further, the sample to be tested is added to the vesicle suspension, and the vesicle suspension changes from blue to red.
Furthermore, when the content of the silver ions in the solution to be detected is within the range of 30-400 mu M, the method can also be used for carrying out quantitative analysis on the silver ions in the solution to be detected.
The invention has the advantages that:
1. compared with the traditional method for detecting silver ions, the polydiacetylene vesicle suspension designed by the invention can be used for Ag in water environment+The visual detection of (2) does not need complicated biochemical modification, does not need large-scale instrument and equipment and a fussy sample pretreatment process, has low detection cost, can realize quick real-time analysis, and is simpler, more convenient, quicker and more economic.
2. Disodium ethylene diamine tetraacetate is introduced into the vesicle suspension, and the disodium ethylene diamine tetraacetate in the vesicle suspension is free from Ag under the environment of specific concentration and pH value+Other metal ions have strong complexation (the other metal ions are masked), and carboxyl groups exist at the tail end of the PDA vesicle obtained by self-assembly polymerization of 10, 12-pentacosadiynoic acid for complexation of Ag+The characteristics of (A) realize the control of Ag+Selective detection of (2).
3. The preparation of the vesicle suspension avoids complex chemical synthesis, and can prepare the PDA vesicle suspension without large-scale instruments and equipment, thereby realizing the aim of Ag in a water system+Colorimetric and fluorometric dual detection and analysis.
Drawings
FIG. 1 is a scanning electron microscope and a Transmission Electron Microscope (TEM) of the PDA vesicle suspension in example 1 of the present invention, wherein (a) is a SEM (scanning Electron microscope) and (b) is a TEM of different sizes;
FIG. 2 is a DSC curve of pure PCDA and PCDA/EDTA;
FIG. 3 is a FT-IR spectrum of PCDA, EDTA-2Na, and PDA/EDTA;
FIG. 4 shows the UV-Vis spectrum, fluorescence emission spectrum and color change of the PDA vesicle suspension in example 1 before and after response to 16 metal ions (250 μ M); (a) is ultraviolet visible absorption spectrum, (b) is fluorescence emission spectrum, (c) is color change diagram;
FIG. 5 is a schematic diagram of selective recognition of Ag + ions by PDA/EDTA suspensions;
FIG. 6 is the color response of PDA vesicle suspensions to different concentrations of Ag + in example 1 of the present invention;
FIG. 7 shows the UV-VIS absorption spectra of the PDA vesicle suspension of example 1 in response to different concentrations of Ag + and the calibration curves prepared therefrom, wherein (a) shows the UV-VIS absorption spectra, and (b) shows the calibration curves;
FIG. 8 shows the fluorescence emission spectra of the PDA vesicle suspension of the present invention in example 1 after response to different concentrations of Ag +, and the standard curves prepared therefrom, wherein (a) shows the fluorescence emission spectra, and (b) shows the standard curves.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
example 1
(1) Preparation of PDA vesicle suspension:
weighing 7.5mg of 10, 12-pentacosadiynoic acid, dissolving in 10ml of ethanol to prepare 2mmol/L of 10, 12-pentacosadiynoic acid ethanol solution, and storing for later use; weighing 50mg of disodium ethylene diamine tetraacetate powder, dissolving the disodium ethylene diamine tetraacetate powder in 100mL of HEPES (20mM, pH 7.4) buffer solution under the condition of heating and stirring, preparing into 1.5mmol/L disodium ethylene diamine tetraacetate aqueous solution, and preserving for later use; slowly and dropwise adding 0.5mL of 10, 12-pentacosadiynoic acid ethanol solution into 10mL of ethylene diamine tetraacetic acid aqueous solution at the room temperature of 1000rpm, then placing the obtained colorless suspension in a refrigerator at 4 ℃ for storing in a dark place for 8h, taking out, and irradiating for 5min by using 254nm ultraviolet light (6W, 10cm away from a sample) to obtain blue PDA vesicle suspension; through the scanning electron microscope and transmission electron microscope photographs in fig. 1, it can be confirmed that the PDA vesicle suspension has a spherical vesicle structure.
Meanwhile, the present invention also uses Differential Scanning Calorimetry (DSC) to measure the major phase transition temperature (Tm) of PCDA/EDTA, where Tm represents the transition of lipid chains from a tightly packed phase to a disordered phase. It is known that pure PCDA crystals have a melting point of about 62 ℃ and pure EDTA has a melting point of 248 ℃, and that the addition of EDTA causes a shoulder peak to appear at around 68 ℃ in the endothermic peak of PCDA/EDTA, as shown in FIG. 2. The existence of 68 ℃ shoulder indicates that the introduction of EDTA slightly improves the alignment stability and regularity of PCDA, and also indicates that certain interaction necessarily exists between EDTA and PCDA. The EDTA is mainly present in the form of H in aqueous solutions having a pH of 5 to 92Y2-And HY3-In the molecule, protonated carboxyl (-COOH) exists, so theoretically, in the PCDA/EDTA suspension, hydrogen bond interaction is possibly formed between EDTA and PCDA molecules, and the PCDA and the EDTA molecules are connected through the hydrogen bond interaction, so that the arrangement regularity of the PCDA vesicles is improved.
The interaction between PDA and EDTA present in the suspension can also be demonstrated by FT-IR spectroscopy, as shown in figure 3. The characteristic absorption peak in the spectrum of EDTA-2Na is 1640cm-1And 1400cm-1. The characteristic absorption peak of the spectrum of the PCDA is 1698cm-1To (3). Whereas, after addition of EDTA, the spectrum of PDA/EDTA was 1647cm-1New characteristic peaks appear. The protonated carboxyl group of EDTA forms hydrogen bond interaction with the carboxyl group at the end of PDA, resulting in the shift of carbonyl absorption peak, and the result of DSC study also laterally confirms the inference. Meanwhile, the spectrum of the PDA/EDTA still has a characteristic absorption peak of EDTA-2Na, which indicates that part of EDTA-2Na still exists in a free form in the system.
(2) Blue PDA vesicles were used for qualitative and quantitative analysis of Ag +:
respectively preparing Hg in deionized water2+、Pb2+、Ag+、Zn2+、Al3+、Ca2+、Cu2+、Co2+、Ni2+、Mg2+、Cr3+、Fe3+、Sn2+、Na+、K+、Li+Sample solutions of sixteen metal ions; respectively taking 2 at room temperatureMu L of the sixteen metal ion sample solutions are added into 200 mu L of PDA vesicle suspension (the final concentration of metal ions is 250 mu M), after incubation for 20min, the ultraviolet visible absorption spectrum and the fluorescence emission spectrum of the PDA vesicle suspension added with different metal ion solutions are measured, and the specific color response condition is observed by naked eyes for recording, see figure 4; according to FIG. 4, Ag+The existence of the (B) causes the absorption peak at about 640nm in the ultraviolet-visible spectrum of the PDA to be obviously reduced, the absorption peak at about 540nm to be obviously improved, and the fluorescence intensity at 560nm and 628nm in the fluorescence spectrum to be obviously improved; blue PDA vesicle suspensions were also accompanied by Ag+Becomes red, thereby can be added to Ag+Qualitative analysis was performed, and the schematic is shown in FIG. 5.
Preparing Ag with different concentrations in deionized water+The solution of (1); respectively taking 2 mu L of Ag with a series of concentration gradients at room temperature+The solution was added to 200. mu.L of PDA vesicle suspension (Ag)+The final concentration of the solution is 0-400 mu M), after incubation for 20min, measuring the ultraviolet visible absorption spectrum and the fluorescence emission spectrum of the PDA vesicle suspension, observing the specific color response condition by naked eyes, and recording (figures 6-8). According to FIG. 6, with Ag+The concentration increased, which caused the color response of the PDA vesicle suspension from blue to red to become increasingly apparent. According to FIG. 7, when Ag+Ag in the range of 30-400 mu M+The higher the concentration, the more it causes the decrease in the absorbance of the PDA vesicle suspension uv-visible absorbance spectrum at 640nm and the increase in the absorbance at 540 nm. According to the formula
Calculating different concentrations of Ag+CR (colorimetric response) value of PDA after addition, wherein PB is0Initial ratio before stimulation, PB1For the final ratio after stimulation, PB (percent blue) is calculated as follows: PB ═ Ablue/(Ablue+Ared) Wherein A isblueAnd AredAbsorbance at 640nm and 540nm in the ultraviolet-visible absorption spectrum respectively; with Ag+Concentration is in the abscissa, CR (colorimetric response) The values are plotted on the ordinate against the standard curve in FIG. 7. According to FIG. 8, when Ag is+Ag in the range of 30-400 mu M+The higher the concentration, the more it causes an increase in fluorescence intensity at 560nm of the fluorescence spectrum of the PDA vesicle suspension; with Ag+The concentration is plotted on the abscissa and the fluorescence intensity at 560nm is plotted on the ordinate, and the standard curve of FIG. 8 is plotted. According to the standard curve in FIG. 7 or FIG. 8, Ag in the concentration range of 30-400. mu.M can be measured+Quantitative analysis was performed.
Example 2:
(1) preparation of PDA vesicle suspension:
weighing 7.5mg of 10, 12-pentacosadiynoic acid, dissolving in 10ml of ethanol to prepare 2mmol/L of 10, 12-pentacosadiynoic acid ethanol solution, and storing for later use; weighing 33.6mg of disodium ethylene diamine tetraacetate powder, dissolving in 100mL of HEPES (20mM, pH 7.4) buffer solution under the condition of heating and stirring, preparing into 1mmol/L disodium ethylene diamine tetraacetate aqueous solution, and storing for later use; under the condition of the rotation speed of 1000rpm at room temperature, 1.0mL of 10, 12-pentacosadiynoic acid ethanol solution is slowly dripped into 10mL of ethylene diamine tetraacetic acid aqueous solution dropwise, the obtained colorless suspension is placed in a refrigerator at 4 ℃ and kept in a dark place for 8h, and the colorless suspension is taken out and irradiated for 10min by 254nm ultraviolet light (6W, 10cm away from a sample) to obtain blue PDA vesicle suspension.
(2) Blue PDA vesicles for Ag+Qualitative and quantitative analysis of (2):
the analytical procedure was as in example 1. Of the 16 metal ions to be measured, only Ag+The existence of the (B) causes the absorption peak at about 640nm in the ultraviolet-visible spectrum of the PDA to be obviously reduced, the absorption peak at about 540nm to be obviously improved, and the fluorescence intensity at 560nm and 628nm in the fluorescence spectrum to be obviously improved; blue PDA vesicle suspensions were also accompanied by Ag+Becomes red, thereby can be added to Ag+Qualitative analysis was performed. Determination of addition of different concentrations of Ag+UV-VIS absorption spectrum and fluorescence emission spectrum of PDA vesicle suspension in solution, in Ag+The concentration is abscissa, the CR value and the fluorescence intensity at 560nm are ordinate respectively, a standard curve is drawn, and Ag is plotted according to the standard curve+Performing quantitative analysis。
Example 3:
(1) preparation of PDA vesicle suspension:
weighing 7.5mg of 10, 12-pentacosadiynoic acid, dissolving in 10ml of ethanol to prepare 2mmol/L of 10, 12-pentacosadiynoic acid ethanol solution, and storing for later use; weighing 67.2mg of disodium ethylene diamine tetraacetate powder, dissolving the disodium ethylene diamine tetraacetate powder in 100mL of HEPES (20mM, pH 7.4) buffer solution under the condition of heating and stirring, preparing into 2mmol/L disodium ethylene diamine tetraacetate aqueous solution, and storing for later use; under the condition of the rotation speed of 1000rpm at room temperature, 1.5mL of 10, 12-pentacosadiynoic acid ethanol solution is slowly dripped into 10mL of ethylene diamine tetraacetic acid aqueous solution dropwise, the obtained colorless suspension is placed in a refrigerator at 4 ℃ and kept in a dark place for 12 hours, and the colorless suspension is taken out and irradiated for 5 minutes by 254nm ultraviolet light (6W, 10cm away from a sample) to obtain blue PDA vesicle suspension.
(2) Blue PDA vesicles for Ag+Qualitative and quantitative analysis of (2):
the analytical procedure was as in example 1. Thus can be applied to Ag+Qualitative and quantitative analyses were performed.
Example 4:
(1) preparation of PDA vesicle suspension:
weighing 6.7mg of 10, 12-pentacosadiynoic acid, dissolving in 10ml of ethanol to prepare 1.8mmol/L of 10, 12-pentacosadiynoic acid ethanol solution, and storing for later use; weighing 67.2mg of disodium ethylene diamine tetraacetate powder, dissolving the disodium ethylene diamine tetraacetate powder in 100mL of HEPES (15mM, pH 7.6) buffer solution under the condition of heating and stirring, preparing into 2mmol/L disodium ethylene diamine tetraacetate aqueous solution, and storing for later use; under the condition of the rotation speed of 1000rpm at room temperature, 1.0mL of 10, 12-pentacosadiynoic acid ethanol solution is slowly dripped into 10mL of ethylene diamine tetraacetic acid aqueous solution dropwise, the obtained colorless suspension is placed in a refrigerator at 4 ℃ and kept in a dark place for 12 hours, and the colorless suspension is taken out and irradiated for 5 minutes by 254nm ultraviolet light (6W, 10cm away from a sample) to obtain blue PDA vesicle suspension.
(2) Blue PDA vesicles for Ag+Qualitative and quantitative analysis of (2):
the analytical procedure was as in example 1. Thus can be applied to Ag+Qualitative and quantitative analyses were performed.
Example 5:
(1) preparation of PDA vesicle suspension:
weighing 8.2mg of 10, 12-pentacosadiynoic acid, dissolving in 10ml of ethanol to prepare 2.2mmol/L of 10, 12-pentacosadiynoic acid ethanol solution, and storing for later use; weighing 67.2mg of disodium ethylene diamine tetraacetate powder, dissolving the disodium ethylene diamine tetraacetate powder in 100mL of HEPES (20mM, pH 7.2) buffer solution under the condition of heating and stirring, preparing into 2mmol/L disodium ethylene diamine tetraacetate aqueous solution, and storing for later use; under the condition of the rotation speed of 1000rpm at room temperature, 1.0mL of 10, 12-pentacosadiynoic acid ethanol solution is slowly dripped into 10mL of ethylene diamine tetraacetic acid aqueous solution dropwise, the obtained colorless suspension is placed in a refrigerator at 4 ℃ and kept in a dark place for 12 hours, and the colorless suspension is taken out and irradiated for 10 minutes by 254nm ultraviolet light (6W, 10cm away from a sample) to obtain blue PDA vesicle suspension.
(2) Blue PDA vesicles for Ag+Qualitative and quantitative analysis of (2):
the analytical procedure was as in example 1. Thus can be applied to Ag+Qualitative and quantitative analyses were performed.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.
Claims (9)
1. A preparation method of vesicle suspension for detecting silver ions is characterized by comprising the following steps:
1) dropwise adding an ethanol solution of 10, 12-pentacosadiynoic acid into an aqueous solution of disodium ethylene diamine tetraacetate under the condition of stirring at room temperature in a dark place to obtain a suspension;
in the ethanol solution, the concentration of the 10, 12-pentacosadiynoic acid monomer is 1.8-2.2 mmol/L;
the disodium ethylene diamine tetraacetate water solution is prepared by dissolving disodium ethylene diamine tetraacetate solid powder in HEPES buffer solution under the condition of heating and stirring;
wherein the concentration of the ethylene diamine tetraacetic acid disodium is 1-2 mmol/L; the concentration of the HEPES buffer solution is 15-20mM, and the pH value is 7.2-7.6;
2) placing the suspension obtained in the step 1) at low temperature in a dark place to ensure that the suspension is fully self-assembled;
3) and (3) polymerizing the fully self-assembled suspension obtained in the step 2) under the irradiation of ultraviolet light to obtain the vesicle suspension for detecting silver ions.
2. The method for preparing a vesicle suspension for detecting silver ions according to claim 1, wherein:
in the step 1), the volume ratio of the ethanol solution of the 10, 12-pentacosadiynoic acid to the aqueous solution of the disodium ethylene diamine tetraacetate is 0.5-1.5: 10.
3. The method for preparing a vesicle suspension for detecting silver ions according to claim 2, characterized in that:
in the step 2), the low-temperature dark placement means that the mixture is stored at the temperature of 4 +/-0.5 ℃ for 8-12h in the dark.
4. The method for preparing a vesicle suspension for detecting silver ions according to claim 3, wherein:
in the step 3), the ultraviolet irradiation conditions are as follows: irradiating for 5-10min with 254nm ultraviolet light with power of 6W and distance of 10cm from the sample to be measured.
5. The method for preparing a vesicle suspension for detecting silver ions according to claim 4, wherein:
in the step 1), the concentration of a 10, 12-pentacosadiynoic acid monomer in the ethanol solution is 2 mmol/L;
wherein the concentration of the ethylene diamine tetraacetic acid disodium is 2 mmol/L; the concentration of HEPES buffer solution was 20mM, pH 7.4.
6. A vesicle suspension for detecting silver ions, comprising: the preparation method is adopted to prepare the compound of the formula I as shown in any one of claims 1 to 5.
7. A method for detecting silver ions by using the vesicle suspension prepared by the preparation method of any one of claims 1-5, which is characterized by comprising the following steps:
adding a sample to be detected into the vesicle suspension, incubating for 20-25min, and determining the ultraviolet visible absorption spectrum and the fluorescence emission spectrum of the vesicle suspension:
and if the absorption peak at 636-644nm and the absorption peak at 535-545nm in the ultraviolet visible absorption spectrum are obviously reduced, and the fluorescence intensity at 558-562nm and 625-632nm in the fluorescence emission spectrum is obviously increased, determining that the sample to be detected contains silver ions.
8. The method for detecting silver ions according to claim 7, wherein:
the sample to be tested is added to the vesicle suspension, which changes from blue to red.
9. The method for detecting silver ions according to claim 7, wherein:
when the content of the silver ions in the solution to be detected is within the range of 30-400 mu M, the method can also carry out quantitative analysis on the silver ions in the solution to be detected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110558449.XA CN113402646B (en) | 2021-05-21 | 2021-05-21 | Method for detecting silver ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110558449.XA CN113402646B (en) | 2021-05-21 | 2021-05-21 | Method for detecting silver ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113402646A CN113402646A (en) | 2021-09-17 |
| CN113402646B true CN113402646B (en) | 2022-04-15 |
Family
ID=77679228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110558449.XA Active CN113402646B (en) | 2021-05-21 | 2021-05-21 | Method for detecting silver ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113402646B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114018892B (en) * | 2021-11-19 | 2024-01-30 | 江苏科技大学 | Method for detecting GST by combining magnetic single-drop microextraction fluorescent switch with PDA coating vesicle |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910828A (en) * | 2014-03-25 | 2014-07-09 | 西北农林科技大学 | Polydiacetylene color-changing vesicle and application thereof in activity analysis of beta-glucuronidase |
| CN108467449A (en) * | 2018-05-04 | 2018-08-31 | 西北师范大学 | A kind of polydiacetylene base Thermoreversibly color-changing composite material and preparation method thereof |
| WO2018220644A1 (en) * | 2017-05-29 | 2018-12-06 | Adhikary Rishi | Method of preparation and use of polydiacetylene-based nanoparticles for the sensing of analytes |
| CN110501316A (en) * | 2019-08-20 | 2019-11-26 | 西北农林科技大学 | A kind of poly- diacetylene liposome Pb in water environment2+Visible detection method |
| CN110615868A (en) * | 2019-09-27 | 2019-12-27 | 东北林业大学 | Preparation method of fluorescein functionalized polydiacetylene vesicle capable of regulating and controlling multicolor fluorescence emission and construction of molecular logic gate of fluorescein functionalized polydiacetylene vesicle |
-
2021
- 2021-05-21 CN CN202110558449.XA patent/CN113402646B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910828A (en) * | 2014-03-25 | 2014-07-09 | 西北农林科技大学 | Polydiacetylene color-changing vesicle and application thereof in activity analysis of beta-glucuronidase |
| WO2018220644A1 (en) * | 2017-05-29 | 2018-12-06 | Adhikary Rishi | Method of preparation and use of polydiacetylene-based nanoparticles for the sensing of analytes |
| CN108467449A (en) * | 2018-05-04 | 2018-08-31 | 西北师范大学 | A kind of polydiacetylene base Thermoreversibly color-changing composite material and preparation method thereof |
| CN110501316A (en) * | 2019-08-20 | 2019-11-26 | 西北农林科技大学 | A kind of poly- diacetylene liposome Pb in water environment2+Visible detection method |
| CN110615868A (en) * | 2019-09-27 | 2019-12-27 | 东北林业大学 | Preparation method of fluorescein functionalized polydiacetylene vesicle capable of regulating and controlling multicolor fluorescence emission and construction of molecular logic gate of fluorescein functionalized polydiacetylene vesicle |
Non-Patent Citations (1)
| Title |
|---|
| 聚二乙炔囊泡的制备及其在医疗检测领域的应用;郝瑜佳等;《分析化学( FENXI HUAXUE) 评述与进展》;20200229;第48卷(第2期);164-173 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113402646A (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yi et al. | Smartphone-based ratiometric fluorescent definable system for phosphate by merged metal− organic frameworks | |
| CN108863922B (en) | AIE-based polymer ratio fluorescence sensor capable of rapidly detecting hypochlorous acid and preparation method and application thereof | |
| Wang et al. | Nitrogen and boron-incorporated carbon dots for the sequential sensing of ferric ions and ascorbic acid sensitively and selectively | |
| Luo et al. | Dual-modes of ratiometric fluorescent and smartphone-integrated colorimetric detection of glyphosate by carbon dots encapsulated porphyrin metal–organic frameworks | |
| CN113402646B (en) | Method for detecting silver ions | |
| Chen et al. | A ratiometric fluorescence nanosensor for highly selective and sensitive detection of selenite | |
| Yang et al. | Carbon dots-embedded zinc-based metal-organic framework as a dual-emitting platform for metal cation detection | |
| Yu et al. | Pyridinaldehyde modified luminescence metal-organic framework for highly sensitive and selective fluorescence detection of pyrophosphate | |
| He et al. | Ratiometric determination of copper (II) using dually emitting Mn (II)-doped ZnS quantum dots as a fluorescent probe | |
| CN108250133B (en) | fluorescence-Raman dual-probe material for detecting zinc ions and preparation method thereof | |
| CN107643271B (en) | Salicylic acid-Mn doped ZnS quantum dot composite nanoparticle ratio type fluorescent probe and preparation method and application thereof | |
| CN109705111A (en) | A kind of mercury ion detecting probe and its preparation method and application | |
| CN113376129B (en) | Preparation method and application of carbon dot-based nano composite for detecting iron ions | |
| CN111795958B (en) | Specific detection of Ag + Preparation of CdSe quantum dot, detection method and application thereof | |
| Yan et al. | Fluorescent filter paper with pH-responsive carbon dots for the on-site detection of biogenic amines in food | |
| CN109705029B (en) | Carbon quantum dot modified by hydroxypyridone compound and preparation and application thereof | |
| CN114369255B (en) | Fe in water 3+ Detected rare earth metal organic framework material | |
| CN106520126A (en) | Mercury ion probe based on doping ion light-emitting mechanism as well as synthetic method for mercury ion probe and application | |
| CN106317096B (en) | A kind of Phen and imidazole type rare earth coordination molecule base probe and its preparation method and application | |
| Wang et al. | Ratiometric fluorescence nanoprobe based on carbon dots and terephthalic acid for determining Fe2+ in environmental samples | |
| CN113621362B (en) | Preparation method and application of ZIF-8 coated luminescent polyacid composite material | |
| CN105418941A (en) | Nanometer composite material, preparing method and application | |
| Yu et al. | Catalytic dynamic spectrofluorimetry determination of trace antimony using new type arsenoxylphenylazo rhodanine | |
| CN115960607B (en) | Tetracycline detection material, preparation method thereof and tetracycline detection method | |
| CN113960004B (en) | Method for detecting Ni (II) based on up-conversion fluorescence internal filtering effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |