CN105968145A - Metal organic frame fluorescent probe and application thereof in hydrogen sulfide detection - Google Patents
Metal organic frame fluorescent probe and application thereof in hydrogen sulfide detection Download PDFInfo
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- CN105968145A CN105968145A CN201610381094.0A CN201610381094A CN105968145A CN 105968145 A CN105968145 A CN 105968145A CN 201610381094 A CN201610381094 A CN 201610381094A CN 105968145 A CN105968145 A CN 105968145A
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 49
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 150000000918 Europium Chemical class 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- -1 carboxyl Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 3
- 229910016644 EuCl3 Inorganic materials 0.000 claims description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- 229910020489 SiO3 Inorganic materials 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 description 2
- 239000007995 HEPES buffer Substances 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 210000001156 gastric mucosa Anatomy 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003914 insulin secretion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000002107 myocardial effect Effects 0.000 description 1
- 230000007830 nerve conduction Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 208000002815 pulmonary hypertension Diseases 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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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
-
- 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"
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- 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
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- 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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a metal organic frame fluorescent probe and application thereof in hydrogen sulfide detection. A preparation method of the metal organic frame fluorescent probe comprises the steps that 1, UiO-66-(COOH)2 containing non-coordinate carboxyl is prepared and synthesized; 2, stirring and heating are utilized, metal ions Eu3+ and Cu2+ are successfully coordinate with the non-coordinate carboxyl of UiO-66-(COOH)2, and the fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2 is obtained. The metal organic frame fluorescent probe is good in stability, and the probe can be used for rapid recognition and quantitative detection of hydrogen sulfide, and has the high selectivity and good anti-jamming capability; ratio fluorescent analysis can be achieved, influences of detection condition differences on results are greatly eliminated, and the detection sensitivity is improved. The metal organic frame fluorescent probe can be used for detecting hydrogen sulfide in environmental, biological, chemical and other samples.
Description
Technical field
The present invention relates to a kind of metal organic frame fluorescent probe and application, the especially application in sulfurated hydrogen detection.
Background technology
For centuries, hydrogen sulfide (H2S) toxic pollutant of environment has been obtained people's in-depth study.But, recently about physiology endogenous H2The research work of S is devoted to its regulation and control to some physiological functions. H2S, this has the gas of special odor, is proved to be the 3rd endogenous gas signaling molecule after nitric oxide and carbon monoxide.Under physiological concentration level, H2S participates in a series of physiological regulating control process, such as, regulate antiotasis, myocardial contraction, nerve conduction and insulin secretion etc..Cell once can not maintain its normal H2S concentration, will cause the disease such as tremulous pulse and pulmonary hypertension, Alzheimer's disease, gastric mucosa injury and liver cirrhosis.Answer H in living things system2The requirement of S concentration level detection, design choice is good, highly sensitive, have the H in detecting living cells and tissue of low cytotoxicity2The fluorescent probe of S level change, it has also become one of challenging advanced subject in biomedical advancement.
In recent years, luminescent metal-organic framework materials (luminescent metal-organic
Frameworks, luminous MOFs) owing to having, luminescence sites is abundant, emission wavelength range is wide, be prone to the advantages such as multi-functional modification, thus illuminating, show, communicate, imaging, the field such as fluorescence detection and sensing are with a wide range of applications and are paid attention to by material and chemical research person more and more.Although the small-molecule fluorescent probe being currently used for detecting environmental and biological materials common metal ion and chemical substance has a lot, but, the working environment complexity of small-molecule fluorescent probe, synthesis very complicated, many fluorescent probes can be combined with many kinds of substance and produce identical fluorescence response, and selectivity is poor.Thus be necessary to study MOFs application in terms of fluorescence detection.
Summary of the invention
It is an object of the present invention to provide a kind of metal organic frame fluorescent probe.
Another object of the present invention is that described metal organic frame fluorescent probe is applied to sulfurated hydrogen detection.
The metal organic frame fluorescent probe of the present invention, its preparation method comprises the steps:
(1) by zirconates, organic ligand, deionized water and glacial acetic acid, zirconates in molar ratio: organic ligand: deionized water: glacial acetic acid=1:0.5～2:250～400:0.4～1 is at room temperature sufficiently mixed, it is then placed in condensing reflux reaction 20 ~ 36 h in the oil bath pan of 70 DEG C ~ 130 DEG C, it is centrifuged after being cooled to room temperature, precipitate is used deionized water cyclic washing, centrifugation, obtains containing the UiO-66-(COOH) not being coordinated carboxyl2；
(2) UiO-66-(COOH) that step (1) synthesizes is taken2Dispersed in deionized water, add trivalent europium salt and cupric salt, condensing reflux 12 ~ 50 h is stirred at 50 DEG C ~ 90 DEG C, it is centrifuged after being cooled to room temperature, precipitate is used deionized water cyclic washing, after centrifugation, by acetone-exchanged 3 ~ 5 days, change an acetone, described UiO-66-(COOH) every day2It is 1:50 ~ 150 with the mass ratio of deionized water, UiO-66-(COOH)2Being 1:1 ~ 10 with the mass ratio of trivalent europium salt, trivalent europium salt is 1:0.5 ~ 3 with the ratio of the mole of cupric salt；
(3) room temperature will be cooled to through the product after step (2) acetone-exchanged in 90 DEG C ~ 120 DEG C freeze-day with constant temperature, obtains metal organic frame fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2。
In the present invention, described zirconates is Zr (NO3)4·5H2O、ZrCl4And ZrOCl2·8H2One or several in O.
In the present invention, described organic ligand can be Pyromellitic Acid.
In the present invention, described trivalent europium salt can be Eu (NO3)3·6H2O、Eu2(SO4)3·8H2O、Eu2(SO4)3·10H2O and EuCl3·6H2One or several in O.
In the present invention, described cupric salt can be CuCl2、Cu(NO3)2·2.5H2O、Cu(NO3)2·3H2O and CuSO4·5H2One or several in O.
Metal organic frame fluorescent probe Eu prepared by the inventive method3+/Cu2+@UiO-66-(COOH)2Hydrogen sulfide there is is specific recognition, can be by fluorescence spectrum detection means to sulfurated hydrogen detection.
Metal organic frame fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2Application in sulfurated hydrogen detection, its application process is as follows:
Take respectively 1 mL concentration be 5 mM containing F-,
Cl-, Br-, I-, HS-, HCOO-,
CH3COO-, NO2 -, SiO3 2-,
NO3 -, HPO4 2-, PO4 3-,
P3O9 3-, S2O3 2-,
SO4 2-, HCO3 -, and N3 -The sodium salt solution of anion is placed in cuvette, each fluorescent probe Eu adding 1 mg in each cuvette3+/Cu2+@UiO-66-(COOH)2, shaking up, under the excitation wavelength of 305 nm, after 30 seconds, measure its fluorescence emission spectrum, result display adds these aniones: F-,
Cl-, Br-, I-, HCOO-, CH3COO-,
NO2 -, SiO3 2-, NO3 -,
HPO4 2-, PO4 3-, P3O9 3-,
S2O3 2-, SO4 2-, HCO3 -,
And N3 -Sodium salt solution all to fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2At 615 nm peaks by force with 393 nm peaks by force than (I615/I393) have little to no effect, only HS-Sodium salt solution to fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2At 615 nm peaks by force with 393 nm peaks by force than (I615/I393) there is significantly impact, this has indicated that fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2Hydrogen sulfide is had preferable selectivity.
(2) NaHS (NaHS is as the donor of hydrogen sulfide) is dissolved in HEPES buffer, it is made into the solution of variable concentrations, concentration range a of solution is in 0≤a≤5000 μM, each 1 mL of sodium hydrosulfide taking variable concentrations is placed in cuvette, and the sodium hydrosulfide in each cuvette is separately added into 1 mg fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2, with 305 nmWavelengthExcite, monitor the change of fluorescence intensity at 615 nm and 393 nm, with the increase of concentration of hydrogen sulfide, 615 nm peaks by force with 393 nm peaks by force than (I615/I393) increase, in the range of finite concentration, I615/I393Linear with the concentration of hydrogen sulfide, the concentration calculating hydrogen sulfide that accordingly can be quantitative.
The mechanism of detection is: in addition to this broadband emission at 393 nm of part, by the Eu of metal ion functionalization3+/Cu2+@UiO-66-(COOH)2, introduce Eu at another 615 nm3+Transmitting, have also been introduced reaction site Cu of hydrogen sulfide simultaneously2+, due to S2-With Cu2+There is the strongest affinity interaction, with the increase of concentration of hydrogen sulfide, Cu2+With S2-Generate CuS to decrease Eu3+Luminous quenching effect, part passes can increase to europium, 615 nm peaks by force with 393 nm peak ratio increases by force, linear with concentration of hydrogen sulfide within the specific limits, such that it is able to the quantitative concentration calculating hydrogen sulfide.
Synthetic route of the present invention is simple, reaction condition is gentle, post processing is simple and convenient and productivity is higher, it is simple to application；Fluorescent probe stability prepared by the present invention is preferable, this probe can be used for hydrogen sulfide quickly identify, detection by quantitative, and there is higher selectivity and preferable capacity of resisting disturbance；Ratio fluorescent analysis can be realized, significantly eliminate the impact on result of the testing conditions difference, improve the sensitivity of detection, advance metal organic frame fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2Application in context of detection.Can be used for the detection of hydrogen sulfide in the samples such as environment, biology, chemistry.
Accompanying drawing explanation
Fig. 1 is X-ray collection of illustrative plates, respectively illustrates the UiO-66 of simulation, synthesized fluorescent probe Eu in figure3+/Cu2+@UiO-66-(COOH)2X-ray collection of illustrative plates.
Fig. 2 is the fluorescent probe Eu of embodiment 1 synthesis3+/Cu2+@UiO-66-(COOH)2Scanning electron microscopic picture.
Fig. 3 is the fluorescent probe Eu of embodiment 3 synthesis3+/Cu2+@UiO-66-(COOH)2Selectivity to sulfurated hydrogen detection.
Fig. 4 is the fluorescent probe Eu of embodiment 3 synthesis3+/Cu2+@UiO-66-(COOH)2Luminous intensity (I615/I393) with the change of concentration (0-625 μM) of hydrogen sulfide.
Fig. 5 is the fluorescent probe Eu of embodiment 3 synthesis3+/Cu2+@UiO-66-(COOH)2Luminous intensity (I615/I393) with the relation of the response time of sulfurated hydrogen detection.
Detailed description of the invention
It is further elucidated with present disclosure below in conjunction with embodiment; but these examples are not limiting as protection scope of the present invention; on the basis of technical scheme, those skilled in the art need not to pay various amendments or deformation that creative work can make still within protection scope of the present invention.
Embodiment 1
(1) in round-bottomed flask, ZrCl is added4(2.43 g, 10.4 mmol), Pyromellitic Acid (2.54 g, 10 mmol), deionized water (60 mL) and glacial acetic acid (40 mL), stir 30 min under room temperature, put into condensing reflux in the oil bath pan of 100 DEG C and react 24 h；
Being centrifuged after being cooled to room temperature, be scattered in deionized water by precipitate, be centrifuged repeatedly washing 3 times, after centrifugation, the precipitate obtained is containing the UiO-66-(COOH) not being coordinated carboxyl2；
(2) UiO-66-(COOH) of above-mentioned synthesis is taken2
(0.1 g) is dispersed in deionized water (10 mL), adds Eu (NO3)3·6H2O (0.446 g, 1 mmol) and Cu (NO3)2·2.5H2O (0.465 g, 1 mmol), 60 DEG C of stirring condensing reflux 24 h；It is cooled to after room temperature centrifugal, precipitate is scattered in deionized water, be centrifuged repeatedly washing 3 times, after centrifugation, by acetone-exchanged 3 days, change an acetone every day；
(3) product after step shadow (2) acetone-exchanged is put in 90 DEG C of freeze-day with constant temperature in drying baker, after being cooled to room temperature, obtain metal organic frame fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2。
This metal organic frame fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2X-ray collection of illustrative plates be shown in Fig. 1, and the X-ray trace analysis of the UiO-66 of simulation, Eu is described3+/Cu2+@UiO-66-(COOH)2Crystal structure intact.Its scanning electron microscopic picture is as shown in Figure 2.
Embodiment 2
(1) in round-bottomed flask, Zr (NO is added3)4·5H2O (4.46 g, 10.4 mmol), Pyromellitic Acid (2.10 g, 10 mmol), deionized water (60 mL) and glacial acetic acid (40 mL), stir 30 min under room temperature, put into condensing reflux in the oil bath pan of 100 DEG C and react 24 h；Being centrifuged after being cooled to room temperature, be scattered in deionized water by precipitate, be centrifuged repeatedly washing 3 times, after centrifugation, the precipitate obtained is containing the UiO-66-(COOH) not being coordinated carboxyl2；
(2) UiO-66-(COOH) of above-mentioned synthesis is taken2
(0.1 g) is dispersed in deionized water (10 mL), adds EuCl3·6H2O (0.366 g, 1 mmol) and Cu (NO3)2·2.5H2O (0.465 g, 1 mmol), 90 DEG C of stirring condensing reflux 12h；It is cooled to after room temperature centrifugal, precipitate is scattered in deionized water, be centrifuged repeatedly washing 3 times, after centrifugation, by acetone-exchanged 3 days, change an acetone every day；
(3) product after step (2) acetone-exchanged is put in 120 DEG C of freeze-day with constant temperature in drying baker, after being cooled to room temperature, obtain the metal organic frame fluorescent probe Eu for sulfurated hydrogen detection3+/Cu2+@UiO-66-(COOH)2。
Embodiment 3 metal organic frame fluorescent probe is for the selectivity of sulfurated hydrogen detection, response time and sensitivity
(1) take respectively 1 mL concentration be 5 mM containing F-,
Cl-, Br-, I-, HS-, HCOO-,
CH3COO-, NO2 -, SiO3 2-,
NO3 -, HPO4 2-, PO4 3-,
P3O9 3-, S2O3 2-,
SO4 2-, HCO3 -, and N3 -The sodium salt solution of anion is placed in cuvette, each fluorescent probe Eu adding 1 mg in each cuvette3+/Cu2+@UiO-66-(COOH)2, shaking up, under the excitation wavelength of 305 nm, after 30 seconds, measure its fluorescence emission spectrum (as shown in Figure 3), result display adds these aniones: F-,
Cl-, Br-, I-, HCOO-, CH3COO-,
NO2 -, SiO3 2-, NO3 -,
HPO4 2-, PO4 3-, P3O9 3-,
S2O3 2-, SO4 2-, HCO3 -,
And N3 -Sodium salt solution all to fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2Fluorescence intensity have little to no effect, only HS-Sodium salt solution to fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2At 615 nm peaks by force with 393 nm peaks by force than (I615/I393) there is significantly impact, this has indicated that fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2Hydrogen sulfide is had preferable selectivity.
(2) NaHS (NaHS is as the donor of hydrogen sulfide) is dissolved in HEPES buffer, it is made into the solution of variable concentrations (0 ~ 5000 μM), each 1 mL of sodium hydrosulfide taking variable concentrations is placed in cuvette, and the sodium hydrosulfide in each cuvette is separately added into 1 mg fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2, excite with 305 nm, monitor the change of fluorescence intensity at 615 nm and 393 nm, with the increase of concentration of hydrogen sulfide, 615 nm peaks by force with 393 nm peaks by force than (I615/I393) increase, in the range of 0 ~ 625 μM, I615/I393Linear with the concentration of hydrogen sulfide (as shown in Figure 4), the concentration limit calculating hydrogen sulfide is 5.454 μMs.Fig. 5 is the fluorescence response spectrogram that Zr-MOFs fluorescent probe adds hydrogen sulfide.As seen from the figure, fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2The response time of hydrogen sulfide is less than 30 seconds, test result indicate that fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2Can be used in the real time on-line monitoring to hydrogen sulfide.
Claims (6)
1. a metal organic frame fluorescent probe, it is characterised in that its preparation method comprises the steps:
(1) by zirconates, organic ligand, deionized water and glacial acetic acid, zirconates in molar ratio: organic ligand: deionized water: glacial acetic acid=1:0.5～2:250～400:0.4～1 is at room temperature sufficiently mixed, it is then placed in condensing reflux reaction 20 ~ 36 h in the oil bath pan of 70 DEG C ~ 130 DEG C, it is centrifuged after being cooled to room temperature, precipitate is used deionized water cyclic washing, centrifugation, obtains containing the UiO-66-(COOH) not being coordinated carboxyl2；
(2) UiO-66-(COOH) that step (1) synthesizes is taken2Dispersed in deionized water, add trivalent europium salt and cupric salt, condensing reflux 12 ~ 50 h is stirred at 50 DEG C ~ 90 DEG C, it is centrifuged after being cooled to room temperature, precipitate is used deionized water cyclic washing, after centrifugation, by acetone-exchanged 3 ~ 5 days, change an acetone, described UiO-66-(COOH) every day2It is 1:50 ~ 150 with the mass ratio of deionized water, UiO-66-(COOH)2Being 1:1 ~ 10 with the mass ratio of trivalent europium salt, trivalent europium salt is 1:0.5 ~ 3 with the ratio of the mole of cupric salt；
(3) room temperature will be cooled to through the product after step (2) acetone-exchanged in 90 DEG C ~ 120 DEG C freeze-day with constant temperature, obtains metal organic frame fluorescent probe Eu3+/Cu2+@UiO-66-(COOH)2。
2. the metal organic frame fluorescent probe as described in claim 1, it is characterised in that described zirconates is Zr (NO3)4·5H2O、ZrCl4And ZrOCl2·8H2One or several in O.
3. the metal organic frame fluorescent probe as described in claim 1, it is characterised in that described organic ligand is Pyromellitic Acid.
4. the metal organic frame fluorescent probe as described in claim 1, it is characterised in that described trivalent europium salt is Eu (NO3)3·6H2O、Eu2(SO4)3·8H2O、Eu2(SO4)3·10H2O and EuCl3·6H2One or several in O.
5. the metal organic frame fluorescent probe as described in claim 1, it is characterised in that described cupric salt is CuCl2、Cu(NO3)2·2.5H2O、Cu(NO3)2·3H2O and CuSO4·5H2One or several in O.
6. the application in sulfurated hydrogen detection of the metal organic frame fluorescent probe as described in claim 1.
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