CN111778015B - Zr 4+ Induced metal organic gel fluorescent switch sensing material and preparation method and application thereof - Google Patents
Zr 4+ Induced metal organic gel fluorescent switch sensing material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111778015B CN111778015B CN202010545592.0A CN202010545592A CN111778015B CN 111778015 B CN111778015 B CN 111778015B CN 202010545592 A CN202010545592 A CN 202010545592A CN 111778015 B CN111778015 B CN 111778015B
- Authority
- CN
- China
- Prior art keywords
- mog
- btc
- cro
- reaction vessel
- switch sensing
- 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.)
- Expired - Fee Related
Links
- 239000011540 sensing material Substances 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 229910007926 ZrCl Inorganic materials 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 47
- 239000004475 Arginine Substances 0.000 claims description 27
- 239000000017 hydrogel Substances 0.000 claims description 27
- 239000000499 gel Substances 0.000 claims description 26
- 230000000171 quenching effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 238000010791 quenching Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000638 stimulation Effects 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 101710093617 Dihydroxyacetone synthase Proteins 0.000 description 1
- 208000000857 Hepatic Insufficiency Diseases 0.000 description 1
- 206010019663 Hepatic failure Diseases 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- -1 XLT Substances 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 230000009395 genetic defect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- PVFDPMYXCZLHKY-MLLWLMKGSA-M sodium [(1R,2R,4aR,8aS)-2-hydroxy-5-[(2E)-2-[(4S)-4-hydroxy-2-oxooxolan-3-ylidene]ethyl]-1,4a,6-trimethyl-2,3,4,7,8,8a-hexahydronaphthalen-1-yl]methyl sulfate Chemical compound [Na+].C([C@@H]1[C@](C)(COS([O-])(=O)=O)[C@H](O)CC[C@]11C)CC(C)=C1C\C=C1/[C@H](O)COC1=O PVFDPMYXCZLHKY-MLLWLMKGSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
-
- 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"
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C09K2211/183—Metal complexes of the refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta or W
-
- 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"
- G01N2021/6432—Quenching
-
- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses Zr 4+ The induced metal organic gel fluorescent switch sensing material and the preparation method and the application thereof, wherein the method comprises the following steps: a1, mixing DMF and H 2 Transferring O into a reaction vessel, then shaking thoroughly until mixed completely, DMF: H 2 The volume ratio of O is 7; a2, adding BTC into the reaction vessel, carrying out ultrasonic treatment on the reaction vessel for 20 seconds until the ligand BTC in the system is completely dissolved, and then carrying out ZrCl 4 Adding into mixed solvent; zrCl 4 The molar ratio of BTC is 1; and A3, putting the reaction system into an ultrasonic instrument, and performing ultrasonic treatment at 80 ℃ for 30 minutes to form white columnar gel. The novel fluorescent switch sensing platform constructed by the invention can selectively detect ARG through charge transfer effect and rapidly detect and remove CrO in water through energy resonance transfer and chemical adsorption effect 4 2‑ 。
Description
Technical Field
The invention belongs to the field of analytical chemistry, and relates to a method for preparing a high-purity potassium permanganate solution by using trimesic acid, arginine and zirconium chloride as main raw materials and using DMF (dimethyl formamide) and H 2 O as solvent to construct a Zr 4+ An induced metal-organic hydrogel fluorescent switch sensing platform for stably and selectively detecting ARG and rapidly detecting and removing CrO in water 4 2- 。
Background
Arginine (ARG) is a semi-essential basic amino acid containing multiple N binding sites in the human body and plays an important role in wound healing, promoting urea synthesis and excretion, and maintaining acid-base balance and sperm activity. ARG is commonly used in food productsCan be used as flavoring agent or nutritional supplement, and added into edible product. Although ARG has many benefits for the human body, it is not suitable for people with different constitutions or levels of health due to its specific requirements for food. For example, people with allergic constitution, diabetes or hepatic insufficiency are not suitable for consumption. Therefore, there is a need to find a sensor that can detect arginine in food. Serious ionic contamination of wastewater is considered one of the most disturbing environmental problems, especially the impact on human health. In particular Cr (VI), e.g. CrO 4 2- It is very harmful because of its strong toxicity. It accumulates in the human body even at low concentrations, resulting in genetic defects, corrosiveness and strong carcinogenicity, and there is therefore an urgent need to find a method or material which can simultaneously detect and remove toxic ions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Zr 4+ Induced metal organic gel fluorescent switch sensing material, preparation method and application thereof, and application thereof in stable and selective detection of ARG and rapid detection and removal of CrO in water 4 2- . The novel fluorescent switch induction platform shows good selectivity and stability to arginine in the linear range of 0-2.5. Mu.M, with a limit of detection (LOD) of 2.99ppb. Zr-MOG' hydrogel after ARG detection is directly applied to CrO 4 2- The stimulus response in the aqueous phase shows excellent selectivity and high efficiency in the linear range of 0.5-10.2 μ M, with a detection limit as low as 5.2ppb.
Zr 4+ The preparation method of the induced metal organic gel fluorescent switch sensing material is characterized by comprising the following steps:
a1, mixing DMF and H 2 O into the reaction vessel and then shaken thoroughly until complete mixing, DMF: H 2 The volume ratio of O is 7;
a2, adding BTC into the reaction vessel, carrying out ultrasonic treatment on the reaction vessel for 20 seconds until the ligand BTC in the system is completely dissolved, and then carrying out ZrCl 4 Adding into the mixed solvent; zrCl 4 The molar ratio of BTC is 1;
and A3, putting the reaction system into an ultrasonic instrument, and carrying out ultrasonic treatment at 80 ℃ for 30 minutes to form white columnar gel.
Zr prepared by the preparation method 4+ The induced metal organic gel fluorescence switch sensing material captures Zr-MOG' hydrogel of ARG, and the fluorescence efficiency of the material is obviously amplified; at the same time, crO 4 2- The fluorescent efficiency of the Zr-MOG' hydrogel with the trapped ARG is obviously quenched.
The application of the metal organic gel fluorescent switch sensing material is used as the fluorescent switch sensing material.
The application of the metal organic gel fluorescent switch sensing material is used as an Arginine (ARG) detection sensor.
The application of the metal organic gel fluorescent switch sensing material as CrO 4 2- Detecting sensors or in removing CrO 4 2- The use of (1).
The invention has the following advantages:
1. the analyte can be detected in water;
2. novel fluorescent switch sensing platform for selectively detecting ARG through charge transfer and rapidly detecting and removing CrO in water through energy resonance transfer and chemical adsorption 4 2- ；
3. Lower detection limit compared to other reported methods;
4. under the interference of other amino acids, metal ions and other substances, the detection effect is still not influenced.
Drawings
FIG. 1 is a pictorial representation of a gel;
FIG. 2 scanning electron microscope and transmission electron microscope pictures of a gel;
FIG. 3 (a) XPS summary profile of gel; (b) infrared absorption spectrum of the gel; (C) C1s orbital spectrum of Zr-MOG gel; (d) C1s orbital spectrum of Zr-MOG' gel;
FIG. 4 (a) a spectrum of Zr-MOG selective trapping food additive; (b) fluorescence enhancement efficiency of the Zr-MOG gel; (c) and (d) concentration titration spectra of the Zr-MOG gel; (e) a line fit plot of the Zr-MOG gel; (f) non-linear fit plot of Zr-MOG gel.
FIG. 5 (a) stimulus response experiment of different heavy metal ions to Zr-MOG' hydrogel; (b) Quenching efficiency of the heavy metal ions on Zr-MOG' hydrogel fluorescence quenching; (c) a chart of a concentration titration experiment spectrum of Cr (VI) to the gel; (d) Linear fit curve of Cr (VI) to gel stimulus response
FIG. 6 (a) absorption spectra of Zr-MOG' xerogel adsorbing Cr (VI) at different concentrations; (b) Langmuir adsorption isotherm fit curve of Zr-MOG' xerogel adsorbing Cr (VI); (c) Absorption spectrum diagram of adsorption kinetics of Zr-MOG' xerogel adsorbing Cr (VI); (d) A line graph of adsorption kinetics of Cr (VI) adsorbed by the Zr-MOG' xerogel; (e) interference experiment of Zr-MOG' xerogel adsorbing Cr (VI); (f) Optical photographs before and after the Zr-MOG' xerogel adsorbs Cr (VI).
Detailed Description
The present invention will be described in detail with reference to specific examples.
The present invention selects the following food additives as target analytes for conducting selectivity experiments: ARG, SRL, XLT, AA, LAC, CA, TAR, GLY, ALA, FRU, DHAS.
The synthesized Zr-MOG is selectively detected for ARG.
The specific implementation steps for preparing the Zr-MOG are as follows:
1. DMF (7 mL) and H 2 O (3 mL) was transferred into a glass vial and then shaken thoroughly until mixed completely.
2. BTC (0.051g, 0.025mmol) was added to a small glass bottle. The vial was sonicated for 20 seconds until the ligand in the system was completely dissolved. Then ZrCl is added 4 (0.023g, 0.1mmol) was added to the mixed solvent.
3. Finally, the reaction system was placed in an ultrasonic apparatus and ultrasonically heated (80 ℃) for 30 minutes to form a white columnar gel (FIG. 1). The hydrogel yield is
Detection of Zr-MOG as fluorescent Probe for ARG:
various food additives were added to the reaction system prior to gel formation (between steps 1-2 above) to explore their ability to respond to Zr-MOG stimulation. Interestingly, no other target analytes produced a significant fluorescence enhancement effect on Zr-MOG except ARG (FIG. 4 a). Furthermore, the fluorescence amplification efficiency of ARG is as high as 87.9% with other variables fixed (fig. 4 b), indicating its excellent ability to turn "on" in a fluorescent switch.
To further explore the ability of the Zr-MOG hydrogel to detect trace ARG, fluorescence emission spectra of the Zr-MOG hydrogel were obtained after mixing AGR with different concentrations of hydrogel precursor solutions. As shown in FIGS. 4c and 4d, the fluorescence intensity of the hydrogel gradually increased with increasing ARG concentration. Concentration and fluorescence intensity of 0-2.5. Mu.M (R) 2 Range of = 0.993) shows a good linear fit curve. They show a good non-linear fit trend (R) over a wide concentration range (0-25.6 mM) 2 = 0.982). This may be due to limited Zr 4+ The binding sites caused a restriction of the Zr-MOG hydrogel to capture ARG. LOD =3 σ/K sv (σ is the standard deviation of the lowest signal, K sv Representing the approximate slope of the linearly fitted curve) was used to calculate the hydrogel detection limit of the ARG. Hydrogels have certain advantages over other reports in synthesis and modification time, synthesis cost, detection range and detection limit (2.99 ppb in the 0-2.5 μ M range).
Ion fluorescence detection
Since the hydrogel after trapping ARG has many naked N element binding sites, the ARG-trapped Zr-MOG 'hydrogel can be directly used for the experiment of response to ion stimulation, and the hydrogel containing 0.03mM arginine (Zr-MOG') can be directly used for the subsequent ion measurement. Zr-MOG' (2.5 mL) was dispersed in 5mL of H 2 O, then stirred vigorously for 30 minutes. The obtained dispersion was finally used for fluorescence sensing experiments.
Zr-MOG' (500. Mu.L) was transferred to a centrifuge tube containing a solution of various ions (2.5 mL) and the tube was shaken for 30 minutes. After the hydrogel and the ions are completely mixed, the hydrogel can be used for subsequent stimulation response experiments of the ions to the gel.
CrO 4 2- And (3) analysis: the target analyte was (0.1 mM) several ionic solutions. The method comprises the following steps: cd (cadmium-doped cadmium) 2+ ，Na + ，Ce 3+ ， Nd 3+ ，Er 3+ ，Tb 3+ ，F - ，Ac - ，SO 4 2- ，HSO 4 - ，CO 3 2- ，HCO 3 - ，H 2 PO 4 - ，HPO 4 2- ，PO 4 3- And CrO 4 2- . Fluorescence spectra were recorded by excitation at 370 nm.
According to FIGS. 5a and 5b, except CrO 4 2- Almost completely quenches the fluorescence of the Zr-MOG' hydrogel, other ions are weakened to different degrees, crO 4 2- The quenching efficiency is highest and can reach 98.5 percent (figure 5 b). Thus, the Zr-MOG' hydrogel is comparable to CrO 4 2- And is more sensitive.
To understand CrO further 4 2- The stimulation response to the Zr-MOG 'hydrogel is studied according to the CrO fluorescence intensity of the Zr-MOG' hydrogel 4 2- The concentration varied from 0-500. Mu.M increase (FIG. 5 c). The quenching effect can be quantified by using the Stern-Volmer (SV) equation: i is 0 /I＝1+K SV [M]In which I 0 And I is the luminous intensity of the Zr-MOG' hydrogel and added with CrO with different concentrations 4 2- Luminescence intensity of Zr-MOG' hydrogel of solution, [ M]Is CrO 4 2- In a molar ratio of SV Is the quenching constant. Clearly, in the low concentration range, the SV plot is almost linear (fig. 5 d). Zr-MOG' hydrogel vs CrO 4 2- Highest K of SV The value was 0.06429X 106M -1 For CrO 4 2- The detection limit of (a) was 5.2ppb. Compared with the MOF and other related materials and sensors, the material has excellent quenching capacity. Illustrating its excellent ability to turn "off" in a fluorescent switch.
It will be appreciated that modifications and variations are possible to those skilled in the art in light of the above teachings, and it is intended to cover all such modifications and variations as fall within the scope of the appended claims.
Claims (1)
1. Metal organic gel fluorescent switch sensing material used as CrO 4 2- Detecting sensors or in removing CrO 4 2- Application of (1), crO 4 2- The fluorescent efficiency of the Zr-MOG hydrogel containing 0.03mM arginine has a remarkable quenching effect; the preparation method of the metal organic gel fluorescent switch sensing material Zr-MOG comprises the following steps:
a1, adding DMF and H 2 O into the reaction vessel and then shaken thoroughly until complete mixing, DMF: H 2 The volume ratio of O is 7;
a2, adding BTC into the reaction vessel, carrying out ultrasonic treatment on the reaction vessel for 20 seconds until the ligand BTC in the system is completely dissolved, and then adding ZrCl 4 Adding into the mixed solvent; zrCl 4 The molar ratio of BTC is 1;
and A3, putting the reaction system into an ultrasonic instrument, and performing ultrasonic treatment at 80 ℃ for 30 minutes to form white columnar Zr-MOG gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010545592.0A CN111778015B (en) | 2020-06-16 | 2020-06-16 | Zr 4+ Induced metal organic gel fluorescent switch sensing material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010545592.0A CN111778015B (en) | 2020-06-16 | 2020-06-16 | Zr 4+ Induced metal organic gel fluorescent switch sensing material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111778015A CN111778015A (en) | 2020-10-16 |
| CN111778015B true CN111778015B (en) | 2022-11-29 |
Family
ID=73598246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010545592.0A Expired - Fee Related CN111778015B (en) | 2020-06-16 | 2020-06-16 | Zr 4+ Induced metal organic gel fluorescent switch sensing material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111778015B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004315B (en) * | 2021-02-09 | 2023-05-26 | 安徽大学 | Histidine-triggered organic hydrogel fluorescent probe and preparation method and application thereof |
| CN112940277B (en) * | 2021-02-19 | 2022-05-24 | 安徽大学 | Formic acid rare earth metal organic framework complex and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008092628A1 (en) * | 2007-01-30 | 2008-08-07 | Universität Zu Köln | Method for the production of biocompatible hybrimers for optical applications |
| CN110358109A (en) * | 2019-08-14 | 2019-10-22 | 安徽大学 | A kind of luminous Zr-MOG metal organogel and its synthetic method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10064960B2 (en) * | 2011-11-25 | 2018-09-04 | Danmarks Tekniske Universitet | Formulation of solid nano-sized particles in a gel-forming system |
-
2020
- 2020-06-16 CN CN202010545592.0A patent/CN111778015B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008092628A1 (en) * | 2007-01-30 | 2008-08-07 | Universität Zu Köln | Method for the production of biocompatible hybrimers for optical applications |
| CN110358109A (en) * | 2019-08-14 | 2019-10-22 | 安徽大学 | A kind of luminous Zr-MOG metal organogel and its synthetic method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111778015A (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tsai et al. | Removal of basic dye (methylene blue) from wastewaters utilizing beer brewery waste | |
| CN111778015B (en) | Zr 4+ Induced metal organic gel fluorescent switch sensing material and preparation method and application thereof | |
| Cesarino et al. | Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions | |
| CN109342385B (en) | Carbon quantum dot for rapidly detecting nitrite content in food and environment and application method thereof | |
| Wu et al. | A novel Zn/Eu-MOF for the highly sensitive, reversible and visualized sensing of ofloxacin residues in pork, beef and fish | |
| Kim et al. | Colorimetric detection and removal of radioactive Co ions using sodium alginate-based composite beads | |
| CN113390846A (en) | Application of sulfur quantum dots as fluorescent probe in tetracycline detection | |
| Duan et al. | SERS-based chip for discrimination of formaldehyde and acetaldehyde in aqueous solution using silver reduction | |
| CN100514043C (en) | Urine iodine test reagent kit | |
| CN113563879A (en) | Preparation method of graphene quantum dot fluorescent probe for paraquat detection | |
| CN114958361A (en) | Blue carbon dot/gold nanocluster-based ratiometric fluorescence sensor and application thereof in glyphosate detection | |
| CN114229827A (en) | Carbon nanodot, dual-mode probe prepared based on carbon nanodot and application of dual-mode probe | |
| Chen et al. | Fast and Effective Turn‐on Paper‐based Phosphorescence Biosensor for Detection of Glucose in Serum | |
| LU502866B1 (en) | Iodine-doped Carbon Quantum Dots and Preparation Method and Application Thereof | |
| CN104132920A (en) | Method for measuring Ag<+> or F<-> through fluorescence quenching | |
| Zaporozhets et al. | Determination of fluoride and oxalate using the indicator reaction of Zr (IV) with methylthymol blue adsorbed on silica gel | |
| Zhao et al. | An intelligent smartphone-test strip detection platform for rapid and on-site sensing of benzoyl peroxide in flour samples | |
| Zhang et al. | An enhanced-stability metal–organic framework of NH2-MIL-101 as an improved fluorescent and colorimetric sensor for nitrite detection based on diazotization reaction | |
| Toribara et al. | Analytical chemistry of micro quantities of beryllium | |
| CN113429960A (en) | Can be used for trace Cu2+Carbon quantum dot composite UiO-66 derivative for ion detection | |
| CN115404074B (en) | Fluorescent detection nano probe, preparation method and application | |
| Saadati et al. | Optical dِِِِiscrimination of histamine and ethylenediamine in meat samples using a colorimetric affordable test strip (CATS): introducing a novel lab-on paper sensing strategy for low-cost ensuring food safety by rapid and accurate monitoring of biogenic amines | |
| CN115975641A (en) | Tb/CdTe ratio fluorescent probe, preparation method and application thereof in norfloxacin detection | |
| CN103735271A (en) | Method for conducting fingerprint identification and analyzed object detection simultaneously through dark-field microscope | |
| CN110044862B (en) | Method for detecting acetamiprid based on ferroferric oxide polypyrrole and fluorescent material |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20221129 |