CN114752373B - Application of dysprosium metal organic framework material in fluorescence detection of iodide ions in water body - Google Patents
Application of dysprosium metal organic framework material in fluorescence detection of iodide ions in water body Download PDFInfo
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000001917 fluorescence detection Methods 0.000 title claims description 7
- -1 iodide ions Chemical class 0.000 title description 13
- 238000001514 detection method Methods 0.000 claims abstract description 34
- 238000000295 emission spectrum Methods 0.000 claims abstract description 16
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 10
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000007850 fluorescent dye Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000005284 excitation Effects 0.000 claims description 11
- RMILQYNYQUIGTM-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1OC1=CC(C(O)=O)=CC(C(O)=O)=C1 Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC(C(O)=O)=CC(C(O)=O)=C1 RMILQYNYQUIGTM-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000000914 Dysprosium Chemical class 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229940006461 iodide ion Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 claims description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical group C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000013354 porous framework Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 abstract description 29
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000009897 systematic effect Effects 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010058314 Dysplasia Diseases 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 206010018498 Goitre Diseases 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 208000036626 Mental retardation Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001605 fetal effect Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 201000003872 goiter Diseases 0.000 description 1
- 231100000001 growth retardation Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The invention discloses a Dy-MOF (dysprosium metal organic framework) material for detecting I in a water body ‑ Application of aspects, the application being: dy-MOF and Dy-MOF-containing I ‑ After mixing the water to be detected, carrying out ultraviolet irradiation, recording fluorescence emission spectrum, obtaining fluorescence intensity I at 464nm and 574nm from the emission spectrum 464 、I 574 Find I 464 /I 574 Ratio according to I 464 /I 574 Calculating I in the water body to be detected ‑ . The invention utilizes Dy-MOF of dysprosium metal organic frame to detect I in water body ‑ The self-reference characteristic is provided, the data distortion caused by external environment and instrument condition change and other factors is reduced, the obvious high-selectivity and sensitivity response are provided, the detection limit is as low as 0.0242 mu M, and the interference of other common anions is effectively avoided; meanwhile, the device has simple instrument and equipment, convenient operation, low cost and speedFast, has potential application prospect.
Description
Technical Field
The invention belongs to the technical field of detection of anions in water bodies, and particularly relates to a ratio type fluorescent probe for detecting trace I in water bodies by taking dysprosium metal organic framework material as a ratio type fluorescent probe - Is contained in the composition.
Background
Anionic contamination has become one of the major environmental concerns of global concern today. On the one hand, nonmetallic pollutants which are harmful to public health are mostly in the form of anions, complex anions or polymeric anions, such as F - 、I - 、NO 3 - 、SO 3 2- 、Cr 2 O 7 2- And H 2 AsO 3 - Etc.; on the other hand, the pollution caused by anions is difficult to be purified in the environment by natural action, and thus has a longer lasting hazard. After the anions enter the environment, the anions can quickly enter the biosphere and the water circle due to weak adsorption capability of surface soil, rock and the like, and serious threat is caused to the health and safety of organisms, ecosystems and human bodies.
Among the various important anions, iodide is a very important trace element, and plays a very important role in physiological activities and metabolism of the human body. The physiological functions of iodine include: maintain the decomposition and metabolism of energy and other substances in the living body, accelerate the absorption and utilization of vitamins in human body, regulate the growth and development of human body, promote the development of brain, etc. In regional environments (water, soil, atmosphere, food), too low or too high an iodine content can cause a endemic disease: local goiter, commonly known as "big neck disease", may cause growth retardation and mental retardation for children; it may cause fetal dysplasia and even life-long mental disability in pregnant women. In addition, iodine is a common radioactive element. The uranium fissions can produce 12 different radioisotopes, most of which have a short half-life. When nuclear leakage accident occurs, iodine element diffuses to environment, and IO is contained in water 3 - 、I - Equal morphology, especially 129 I, extremely long half-life, is treatmentThe main object of the waste is shot. Therefore, it is particularly necessary to develop efficient, compact, sensitive and rapid iodide ion detection techniques.
Conventional methods for detecting iodide ions include electrochemical methods, gas chromatography, high performance liquid chromatography, capillary electrophoresis, and the like. Although these methods can achieve sensitive and selective detection of iodide ions, they generally require complicated pretreatment processes and expensive large-scale instruments, are time-consuming and labor-consuming, have many interference factors, and are difficult to achieve rapid detection of iodide ions. Therefore, it is urgent to find a simple, rapid, sensitive and stable method for detecting iodide ions.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a dysprosium metal organic framework material (Dy-MOF) for detecting I in a water body - The application in the aspect is the ratio type fluorescence sensing detection, has simple instrument and equipment and is suitable for I - Has the advantages of obvious high selectivity, sensitivity response and the like; in addition, in the detection process, other common anions have very little interference on the detection, so that data distortion caused by factors such as external environment and instrument condition change is avoided to a great extent, and the accuracy and stability of the detection are improved.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
provides a Dy-MOF (dysprosium metal organic framework) material for detecting I in a water body - Application of the aspect.
According to the scheme, the application is as follows: dy-MOF and Dy-MOF-containing I - After mixing the water to be detected, carrying out ultraviolet irradiation, recording fluorescence emission spectrum, obtaining fluorescence intensity I at 464nm and 574nm from the emission spectrum 464 、I 574 Find I 464 /I 574 Ratio according to I 464 /I 574 Calculating I in the water body to be detected - 。
Preferably, the wavelength of ultraviolet excitation light used in ultraviolet irradiation is 220nm to 250nm, more preferably 230nm.
According to the scheme, the specific steps of the application are as follows:
1) Weighing a certain amount of Dy-MOF, and ultrasonically dispersing in deionized water to obtain a uniformly dispersed suspension; wherein the proportion of the fluorescent probe Dy-MOF and deionized water is as follows: 1mg:10-30mL;
2) Taking the suspension V obtained in the step 1) 1 mL and water V to be detected 2 mL, mixing uniformly; excitation by means of a fluorescence spectrometer and recording of the emission spectrum, from which the fluorescence intensities I at 464nm and 574nm are obtained 464 、I 574 Calculated to obtain I 464 /I 574 Ratio of; the obtained I 464 /I 574 Substituting the ratio into the working curve to obtain I - The concentration N mu M of the water body to be detected can be calculated by further utilizing the formula (1) - Content of (2) C μm; wherein the working curve is based on the iodine ion concentration as the abscissa, and I is 464 /I 574 The ratio is drawn by an ordinate;
C＝(V 1 +V 2 )*N/V 2 (1)。
according to the above scheme, in the step 2), V 1 The mL is 1-5mL.
According to the scheme, the working curve drawing steps are as follows:
1) Preparing a liquid to be detected: preparing I with concentration of 1mM by using deionized water as solvent - An aqueous solution;
2) Preparing fluorescent probe suspension: dispersing Dy-MOF in deionized water by ultrasonic to obtain uniformly dispersed suspension; the ratio of fluorescent probe to deionized water is: 1mg:10-30mL;
3) Fluorescence detection: taking 2mL of Dy-MOF suspension in a cuvette, opening a fluorescence spectrometer, and recording an emission spectrum under ultraviolet excitation; gradually and sequentially adding I - (1 mM) 20. Mu.L each time, mixed well, and the emission spectrum of the suspension was measured and recorded;
4) Drawing a working curve: analysis of the data gave fluorescence intensities I at 464nm and 574nm from the emission spectrum 464 、I 574 Find I 464 /I 574 Ratio of; on the abscissa of iodide ion concentration, I 464 /I 574 The ratio is taken as the ordinate, I is made 464 /I 574 The relation curve of the ratio and the iodine ion content is linearly fitted to obtain the trace I in the ratio type fluorescence detection water body - Is a working curve of (a).
According to the above scheme, the Dy-MOF is prepared by reacting 5- (4-carboxyphenoxy) isophthalic acid (H 3 cpia) as ligand, dy 3+ Metal organic framework materials that are porous frameworks of coordination centers.
According to the scheme, the Dy-MOF preparation steps are as follows:
with an inorganic dysprosium salt and 5- (4-carboxyphenoxy) isophthalic acid (H 3 cpia) is used as a raw material, a proper amount of distilled water is used as a solvent, diethylamine is added after uniform mixing, hydrothermal reaction is carried out at 110-130 ℃, after the reaction is completed, cooling is carried out to room temperature, filtering is carried out, distilled water is used for washing, filtering is carried out, and airing is carried out, thus obtaining the dysprosium metal organic frame material Dy-MOF.
Preferably, the inorganic dysprosium salt is dysprosium nitrate or dysprosium chloride.
Preferably, the inorganic dysprosium salt and 5- (4-carboxyphenoxy) isophthalic acid (H 3 The molar ratio of the cpia) is 1:0.5-1; diethylamine and 5- (4-carboxyphenoxy) isophthalic acid (H 3 cpia) is greater than 5.
Preferably, the hydrothermal reaction time is 12-96 hours.
The invention has the beneficial effects that:
1. the invention utilizes Dy-MOF of dysprosium metal organic frame to detect I in water body - For I - Has obvious high selectivity and sensitivity response; the ratio type fluorescent probe is of an MOF structure, so that the contact area between the fluorescent probe and a substrate is increased, the fluorescent detection is fully exerted, the detection sensitivity of a system is improved, and the detection limit is as low as 0.0242 mu M; meanwhile, the method has the advantages of simple instrument and equipment, convenient operation, low cost and high speed, overcomes the defects of high detection cost, low detection speed and the like of the traditional method, and has potential application prospect.
2. In the invention, the ratio-type fluorescent probe Dy-MOF takes the ratio of the fluorescent intensity of two emission wavelengths as an output signal, and the characteristic green light emission (with the wavelength of 574 nm) of dysprosium ions is controlled by I - Quenching, while yellow light emission (with the wavelength of 464 nm) is little disturbed by external conditions, and the luminous intensity is stable. The two emission bands have different quenching degrees, the ratio type fluorescent probe is constructed, the self-reference characteristic is realized, the systematic error and the human error can be reduced to a great extent, the selectivity is good, the interference from other common anions in the environment is effectively avoided, and the higher stability is provided.
Drawings
Fig. 1 is a schematic structural diagram of Dy-MOF material in example 1 of the present invention.
FIG. 2 is a diagram showing the performance of Dy-MOF fluorescent probes in example 2 of the present invention - Fluorescence emission spectra of concentration gradient titration experiments.
FIG. 3 is a diagram of example 2 of the present invention 464 /I 574 Ratio and I - Is a graph of concentration.
FIG. 4 is a fluorescence emission spectrum of the Dy-MOF fluorescent probe of example 3 of the present invention for the anion selective detection experiment.
FIG. 5 shows various anion pairs I in an experiment for selectively detecting anions by Dy-MOF fluorescent probes in example 3 of the present invention 464 /I 574 Influence of the ratio.
FIG. 6 shows a Dy-MOF fluorescent probe assay I in example 4 of the present invention - Fluorescence spectrum diagram of anti-interference experiment.
FIG. 7 shows a Dy-MOF fluorescent probe assay I in example 4 of the present invention - I of anti-interference experiment 464 /I 574 Ratio bar graph.
Detailed Description
The technical scheme of the invention will be further described with reference to the accompanying drawings and specific embodiments. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention.
The reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
The preparation method of the provided ratio-type fluorescent probe Dy-MOF comprises the following steps:
taking 0.5mmol of nitric acid hexahydrateDysprosium [ Dy (NO) 3 ) 3 ]·(H 2 O) 6 And 0.3mmol of 5- (4-carboxyphenoxy) isophthalic acid (H 3 cpia), put into a beaker, add 10mL distilled water, mix well and add 3 drops of diethylamine (diethylamine and H) 3 The molar ratio of cpia was greater than 5) and then transferred to a 23mL Teflon lined stainless steel reactor. Sealed and reacted hydrothermally at 120℃for 72 hours. After the reaction was completed, the autoclave was cooled to room temperature. Filtering, washing the product with distilled water for 3 times, filtering, and airing to obtain the Dy-MOF.
The structure of the obtained dysprosium (III) -metal organic framework Dy-MOF is a low-symmetry triclinic space group. Two adjacent Dy (III) atoms are connected by two carboxylate groups to form a bimetallic unit [ Dy ] 2 (COO) 2 (COO) 2 (H 2 O) 4 ]Then pass through another four mu 2 the-COO groups are linked to form a one-dimensional chain of bimetallic units. Each cpia anion and five Dys 3+ And (5) cation coordination. This connectivity pattern produced 3D channels of Dy-MOF with 1D channels parallel to the b-axis, see fig. 1.
Example 2
Detection experiments providing iodide ions: working curve drawing
1) Preparation of sample suspension: dysprosium (III) -metal organic frameworks Dy-MOF (1 mg) prepared in example 1 were ultrasonically dispersed in 10mL of deionized water to obtain a uniformly dispersed Dy-MOF suspension.
2) Configuration of I at a concentration of 1mM - A solution.
3) Detection experiment: taking 2.5mL of Dy-MOF suspension prepared in the step 1) in a cuvette, opening a fluorescence spectrometer, and recording an emission spectrum under the excitation of ultraviolet light with the wavelength of 230nm. Then add 20. Mu.L of I in sequence - Aqueous solution (1 mM), to I - The concentration was 320. Mu.M, mixed well, and the luminescence emission spectrum was excited and recorded, see FIG. 2.
The measurement result shows that: fluorescence intensity I of the ratio-type fluorescent probe at 464nm 464 A weak decrease occurs, whereas the fluorescence intensity I at 574nm 574 And the concentration of iodine ions is obviously reduced along with the gradual increase of the concentration of iodine ions. Furthermore, by calculationThe fluorescence spectrum at the luminous intensity ratio of 464nm to 574nm (I 464 /I 574 ) The data indicate I 464 /I 574 Has good linear relation with the iodine ion concentration in the range of 0-200 mu M, and the linear equation is (2):
y＝2.008+0.0148C (2)
wherein y: fluorescence emission intensity I 464 /I 574 Ratio of; [ C]:I - Is a concentration of (3).
Correlation coefficient (R) 2 ) 0.999, see FIG. 3.
Meanwhile, the fitting straight line is Dy-MOF as a fluorescent probe to carry out fluorescent detection I - The working curve of the (B) can be used for obtaining the I in the target detection liquid - The content is as follows. From the working curve, the calculated limit of detection was 0.0242 μm.
Example 3
Selective detection of other anions with iodide:
1) Dy-MOF suspension preparation: the same as in example 2.
2) Respectively preparing aqueous solutions of different anions with concentration of 0.01M, wherein the anions are F - 、Cl - 、Br - 、I - 、HCO 3 - 、CO 3 2- 、SO 4 2- 、SO 3 2- 、HPO 4 2- 、PO 4 3- 、NO 3 - 。
3) Selectivity detection experiment: 2.5mL of Dy-MOF suspension prepared in 1) are respectively taken and placed in a cuvette, the aqueous solutions (0.01M, 20 mu L) of different anions obtained in the step 2) are respectively added, a fluorescence spectrometer is opened, and fluorescence emission spectra are recorded under the excitation of ultraviolet light with the wavelength of 230nm, and the spectra are shown in figure 4 according to the Blank and Br - 、HCO 3 - 、CO 3 2- 、SO 4 2- 、SO 3 2- 、HPO 4 2- 、PO 4 3- 、NO 3 - 、I - And (5) arrangement. Analysis of the spectral data gave fluorescence intensities I at 464nm and 574nm from the emission spectrum 464 、I 574 Find I 464 /I 574 The ratio is shown in FIG. 5.
The measurement result shows that: i only after the addition of iodide ions 464 /I 574 The ratio is significantly increased, exhibiting a pronounced quenching response. Adding other anions I 464 /I 574 The ratio remained almost unchanged and no response was made to the ratio-type fluorescent probe. The fluorescent probe provided by the invention is described in the specification of I - The invention has extremely high selectivity, adopts the ratio type fluorescent probe to have self-reference characteristic, greatly reduces the systematic error, has high detection precision, and can be used as a fluorescent sensor to efficiently detect I - 。
Example 4
Anti-interference detection experiment of other anions on iodide:
1) Dy-MOF suspension preparation: the same as in example 2.
2) Preparing aqueous solutions of different anions with concentration of 0.01M, wherein the anions are F respectively - 、Cl - 、Br - 、I - 、HCO 3 - 、CO 3 2- 、SO 4 2- 、SO 3 2- 、HPO 4 2- 、PO 4 3- 、NO 3 - The method comprises the steps of carrying out a first treatment on the surface of the Preparing aqueous solutions of different anions with concentration of 5mM, wherein the anions are F respectively - 、Cl - 、Br - 、I - 。
3) Anti-interference detection experiment: separately, 2.5mL of Dy-MOF suspension prepared in 1) was placed in a cuvette, and 20. Mu.L of I was added - Solution (0.01M) then other anions (0.01M, 20. Mu.L, excluding I) - ) Adding into the suspension, and under 230nm ultraviolet light excitation, respectively recording suspension blank, adding I - The luminescence emission spectrum after the solution and after the addition of interfering ions is shown in fig. 6.
The measurement result shows that: the fluorescent detection of iodide ions is not affected by various interfering anions. Description of Dy-MOF fluorescent Probe for carrying out I - The selective detection of (C) is not interfered by other anions in the environment, and the system can be effectively reducedAnd the system error and the human error are high in selectivity and sensitivity.
4) Further selecting F with concentration of 5mM - 、Cl - 、Br - 、I - And performing anti-interference detection. 5mM KI and 5mM NaF (or NaCl, naBr) solutions were alternately introduced into the suspension in the following order: naF (20. Mu.L), KI (20. Mu.L), naF (20. Mu.L), KI (20. Mu.L) and the total volume of analyte added was 120. Mu.L. Fluorescence emission spectra of the resulting suspensions were recorded after each addition using an excitation wavelength of 230nm. NaF is replaced by NaBr and NaCl respectively, and the anti-interference experiment is repeated. Recording the fluorescence intensity I of the ratio-type fluorescent probe at 464nm and 574nm 464 、I 574 And calculating the fluorescence spectrum luminous intensity ratio (I) 464 /I 574 ) The results are shown in FIG. 7.
The results show that: the ratio of luminous intensity after the addition of the iodide ion solution only at a time (I 464 /I 574 ) Change obviously, and F - 、Cl - 、Br - Ratio of addition to luminous intensity (I) 464 /I 574 ) The effect of (2) is almost negligible. Further elucidation of Dy-MOF fluorescent probes for I - The selective detection of the ion-exchange membrane is not interfered by other anions, the selectivity is good, the systematic error and the human error can be reduced to a great extent, and higher accuracy and stability are provided.
Example 5
Provides a composition containing I - Detection of an aqueous sample of ions, comprising the steps of:
1) Dy-MOF suspension preparation: the same as in example 2.
2) 2mL of the suspension obtained in the step 1 is placed in a cuvette, and 50 mu L I is added - Aqueous ion solution (ICP-MS detection result, I - 4.919 mM), and uniformly mixed. The fluorescence spectrometer is turned on, and the addition I is recorded under the excitation of ultraviolet light with the wavelength of 230nm - The fluorescence intensity of 464nm and 574nm is obtained by the emission spectrum after the ion, and I is obtained by calculation 464 /I 574 The ratio is 3.779, and the formula (2) is further utilized to calculate I in the detection system - Is 119.66. Mu.M. Further utilize the formula%1) The added 50 mu L I can be calculated - I in aqueous solution - Ion content 4.906mM. Within the error range, the test method provided by the invention is consistent with the test result of ICP-MS, and the test result of the method is proved to be reliable, real and effective.
In conclusion, the embodiment proves that the ratio type fluorescence detection method provided by the invention is used for detecting I in water body - The application of (2) has the following advantages: the device has the advantages of simple equipment, high selectivity and sensitivity, excellent environment interference resistance and reliable detection result.
Claims (8)
1. Dy-MOF (dysprosium metal organic framework) material I in detection water body - In terms of application, the Dy-MOF is characterized in that 5- (4-carboxyphenoxy) isophthalic acid is used as ligand and Dy 3+ A metal organic framework material that is a porous framework of coordination centers;
the Dy-MOF preparation steps are as follows:
inorganic dysprosium salt and 5- (4-carboxyphenoxy) isophthalic acid are taken as raw materials, a proper amount of distilled water is added as a solvent, diethylamine is added after uniform mixing, hydrothermal reaction is carried out at 110-130 ℃, after the reaction is completed, cooling to room temperature, filtering, washing with distilled water, filtering and airing are carried out, thus obtaining the dysprosium metal organic frame material Dy-MOF; wherein, the feeding mole ratio of the inorganic dysprosium salt and the 5- (4-carboxyphenoxy) isophthalic acid in the reaction is 1:0.5-1.
2. The use according to claim 1, characterized in that the use is: dy-MOF and Dy-MOF-containing I - After mixing the water to be detected, carrying out ultraviolet irradiation, recording fluorescence emission spectrum, obtaining 464nm and 574nm fluorescence intensity I from the emission spectrum 464 、I 574 Find I 464 /I 574 Ratio according to I 464 /I 574 Calculating I in the water body to be detected - 。
3. The use according to claim 2, wherein the ultraviolet excitation light used for the ultraviolet irradiation has a wavelength of 220nm-250 nm.
4. The use according to claim 1 or 2, characterized in that the specific steps used are:
1) Weighing a certain amount of Dy-MOF, and ultrasonically dispersing in deionized water to obtain a uniformly dispersed suspension; wherein the proportion of the fluorescent probe Dy-MOF and deionized water is as follows: 1mg:10-30mL;
2) Taking the suspension V obtained in the step 1) 1 mL and water V to be detected 2 mL, mixing uniformly; excitation by means of a fluorescence spectrometer and recording of the emission spectrum thereof, from which the fluorescence intensities I at 464nm and 574nm are obtained 464 、I 574 Calculated to obtain I 464 /I 574 Ratio of; the obtained I 464 /I 574 Substituting the ratio into the working curve to obtain I - The concentration N mu M of the water body to be detected can be calculated by further utilizing the formula (1) - Content of (2) C μm; wherein the working curve is based on the iodine ion concentration as the abscissa, and I is 464 /I 574 The ratio is drawn by an ordinate;
C=( V 1 +V 2 )N/V 2 (1)。
5. the use according to claim 4, wherein in step 2), V 1 The mL is 1-5mL.
6. The use according to claim 4, wherein the working curve is drawn by:
1) Preparing a liquid to be detected: deionized water is used as solvent to prepare I with concentration of 1mM - An aqueous solution;
2) Preparing fluorescent probe suspension: dispersing Dy-MOF in deionized water by ultrasonic to obtain uniformly dispersed suspension; the ratio of fluorescent probe to deionized water is: 1mg:10-30mL;
3) Fluorescence detection: colorimetric Dy-MOF suspension 2mLOpening a fluorescence spectrometer in the dish, and recording an emission spectrum under ultraviolet excitation; i of 1mM is added gradually and sequentially - The aqueous solution, 20 mu L each time, is mixed evenly, and the emission spectrum of the suspension system is measured and recorded;
4) Drawing a working curve: analysis of the data gave a fluorescence intensity I at 464nm and 574nm from the emission spectrum 464 、I 574 Find I 464 /I 574 Ratio of; on the abscissa of iodide ion concentration, I 464 /I 574 The ratio is taken as the ordinate, I is made 464 /I 574 The relation curve of the ratio and the iodine ion content is linearly fitted to obtain the trace I in the ratio type fluorescence detection water body - Is a working curve of (a).
7. The use of claim 1, wherein in the Dy-MOF preparation, the inorganic dysprosium salt is dysprosium nitrate or dysprosium chloride; the molar ratio of diethylamine to 5- (4-carboxyphenoxy) isophthalic acid is greater than 5.
8. The use of claim 1, wherein the Dy-MOF preparation has a hydrothermal reaction time period of 12-96 hours.
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