CN114920894A - Cu 2+ And Al 3+ Difunctional fluorescent covalent organic framework material and preparation method and application thereof - Google Patents
Cu 2+ And Al 3+ Difunctional fluorescent covalent organic framework material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114920894A CN114920894A CN202210740307.XA CN202210740307A CN114920894A CN 114920894 A CN114920894 A CN 114920894A CN 202210740307 A CN202210740307 A CN 202210740307A CN 114920894 A CN114920894 A CN 114920894A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- framework material
- covalent organic
- sample
- solution
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
-
- 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"
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
Cu 2+ And Al 3+ A double-function fluorescent covalent organic framework material and a preparation method and application thereof relate to a fluorescent covalent organic framework material and a preparation method and application thereof. The method aims to solve the technical problems of few types, single identification performance and poor selectivity of the existing fluorescent covalent organic framework material. Cu of the invention 2+ And Al 3+ The periodic structure fragment of the bifunctional fluorescent covalent organic framework material is as follows:
it adopts 2- (4-fluorophenyl) -1H-phenanthro [9,10-d]Imidazole-5, 10-diamine and 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 "-triphenyl]-4,4 "-dicarboxaldehydeObtained by reaction. Cu of the invention 2+ And Al 3+ The difunctional fluorescent covalent organic framework material serving as a fluorescent material can be applied to Cu in environments and biological systems 2+ And Al 3+ And (6) detecting.
Description
Technical Field
The invention relates to a fluorescent covalent organic framework material and a preparation method and application thereof.
Background
Copper is a very important transition metal element. Plays an important role in regulating physiological mechanisms and maintaining physiological balance in life bodies; however, Cu present in excess 2+ Has adverse effects on both living body and environment, for example, neurodegenerative diseases and excessive Cu in human body 2+ (ii) related; if Cu is contained in drinking water 2+ Excess will cause gastrointestinal dysfunction in humans. Aluminum is the most abundant metal in the earth's crust. Aluminum and its alloys are widely used in various industries due to their advantages of corrosion resistance, low density, good thermal and electrical conductivity, good ductility, etc. Small amount of Al 3+ No harm to human body, but excessive Al 3+ Can be combined with protein to directly damage central nervous system, and cause hypomnesis and mental retardation, which will result in early aging. The world health organization (WTO) reports that Al in purified water 3+ The standard content should be less than 0.2 mg/L. Thus, accurate, quantitative and quantitativeMeasurement of Property Al 3+ And Cu 2+ The content of (A) has very important significance. At present, trace amount of Cu is detected 2+ And Al 3+ The method of (3) is selected from atomic absorption emission spectrometry, atomic fluorescence spectrometry, electrochemical method, and inductive coupling method. However, the method depends on a large instrument, is high in cost and complex in operation, and cannot meet the requirement of rapid and convenient detection. In recent years, more and more researchers have started Cu 2+ And Al 3+ Research work on fluorescent probes. Mixiaolong et al reported two rhodamine derivatives Cu 1784-1791 on volume 37, 10 th of 2016 (proceedings of chemistry in higher school) 2+ Fluorescent probe of (2), in sunlight, Cu 2+ The two rhodamine derivatives can be changed from colorless to orange or pink; lakshman Patra et Al synthesized a Schiff base double bond-based compound and published in New chemistry, volume 42, pages 19076-19082, article ESIPT and CHEF characteristics-based novel efficient Al detection 3+ And Zn 2+ Ion multi-analyte fluorescence sensor for detecting Al by using Schiff base double bond compound through fluorescence method 3+ The detection limit reaches 0.0224 mu mol/L, but the compound detects Al 3+ Poor selectivity, resulting in limited application thereof; in 2020, Cui et al, microporous and hollow materials, Vol.299, 19076-19082, report that a Cu-recognizable material is designed based on an aldehyde-amine condensation reaction 2+ COFs materials of (1), but some transition metal ions such as Cr 3+ 、Fe 3+ And Fe 2+ Has certain quenching capability on the fluorescence of COFs-DT and can not realize the effect on Cu 2+ High selectivity of the process. At present, the literature does not report Cu 2+ And Al 3+ A preparation method and application of a bifunctional fluorescent covalent organic framework material.
Disclosure of Invention
The invention provides Cu for solving the technical problems of few types, single identification performance and poor selectivity of the existing fluorescent covalent organic framework material 2+ And Al 3+ The fluorescent covalent organic framework material has novel structure, high stability, sensitive recognition,Good selectivity, can realize the Cu in the actual water sample 2+ And Al 3+ And (4) carrying out quantitative detection.
Cu of the invention 2+ And Al 3+ The periodic structural fragments of the bifunctional fluorescent covalent organic framework material are as follows:
cu as described above 2+ And Al 3+ The bifunctional fluorescent covalent organic framework material adopts 2- (4-fluorophenyl) -1H-phenanthro [9,10-d]Imidazole-5, 10-diamine and 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 "-triphenyl]-4,4 "-diformaldehyde, of the formula:
cu as described above 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, according to the ratio of the amount of the 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine to the amount of the 5 '- (4-formylphenyl) - [1, 1': 3 ', 1' -triphenyl ] -4,4 '-dicarboxaldehyde being (1-5), 1, adding the 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and the 5' - (4-formylphenyl) - [1,1 ': 3', 1 '-triphenyl ] -4, 4' -dicarboxaldehyde into the mixed solvent, then according to the formula of the 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, the mass ratio of the 10-diamine to the acid is 1 (0.01-0.1), adding the acid into the mixed solvent as a catalyst, and uniformly mixing to obtain a mixed solution;
secondly, putting the mixed solution into a schlenk tube, and performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating the schlenk tube to 100-200 ℃ and reacting for 1-7 days;
fourthly, cooling to room temperature after the reaction is finished, filtering, repeatedly washing a filter cake by using an organic solvent, and drying in vacuum to obtain Cu 2+ And Al 3+ Double workA fluorescent covalent organic framework material.
Furthermore, the mixed solvent in the step one is any two of mesitylene, p-dichlorobenzene, N-dimethylformamide, dioxane and N-butanol.
Further, the acid in the step one is any one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, concentrated hydrochloric acid with a mass percent concentration of 30% -37% or concentrated sulfuric acid with a mass percent concentration of 95% -98%.
Further, the organic solvent in the fourth step is one or two of tetrahydrofuran, methanol, ethanol, ethyl acetate, acetone, dichloromethane or 1, 2-dichloroethane.
Cu as described above 2+ And Al 3+ The application of the bifunctional fluorescent covalent organic framework material is to use the bifunctional fluorescent covalent organic framework material as a fluorescent material for Cu 2+ And Al 3+ Qualitative and quantitative detection.
Using the above-mentioned Cu 2+ And Al 3+ Cu preparation by using bifunctional fluorescent covalent organic framework material 2+ And Al 3+ The qualitative detection method comprises the following steps:
firstly, mixing Cu 2+ And Al 3+ Uniformly dispersing the difunctional fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) to obtain a probe solution A; the mixed solution is prepared from acetonitrile and 4-hydroxypiperazine ethanesulfonic acid according to the volume ratio of 8 (1-5), and the Cu in the probe solution A 2+ And Al 3+ The concentration of the difunctional fluorescent covalent organic framework material is 0.1-0.5 g/L;
secondly, adding a sample I to be detected containing metal ions into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, recording the emission intensity when the emission wavelength is 470nm as T A ；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, and recording the emission when the emission wavelength is 470nmIntensity, noted as T B ；
Fifth, compare T A And T B If T is A /12≤T B ＜T A And 8, judging that the sample to be detected contains Cu 2+ (ii) a If T A /8≤T B ＜T A Then the Cu content in the sample to be tested is determined 2+ Or Al 3+ Or Cu 2+ And Al 3+ 。
Using the above-mentioned Cu 2+ And Al 3+ Quantitative detection of Cu in actual water sample by using bifunctional fluorescent covalent organic framework material 2+ And Al 3+ The method is a standard curve method and specifically comprises the following steps:
firstly, mixing Cu 2+ And Al 3+ Uniformly dispersing the difunctional fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) to obtain a probe solution A; the mixed solution is prepared from acetonitrile and 4-hydroxypiperazine ethanesulfonic acid according to the volume ratio of 8 (1-5), and the Cu in the probe solution A 2+ And Al 3+ The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
II, gradually adding C into the probe solution A 1 、C 2 、C 3 ……C n Cu of (2) 2+ Respectively obtaining sample solutions B 1 、B 2 、B 3 ……B n ；
Thirdly, gradually adding the probe solution A with the concentration of C respectively 1 、C 2 、C 3 ……C n Al of (2) 3+ Respectively obtaining sample solutions D 1 、D 2 、D 3 ……D n ；
Fourthly, with 330nm as the excitation wavelength, the sample solution B is measured 1 ～B n Respectively recording the emission intensity at an emission wavelength of 470nm, and recording as T B1 ～T Bn ；
Fifthly, with 330nm as the excitation wavelength, the sample solution D is measured 1 ～D n Respectively recording the emission intensity at an emission wavelength of 470nm, and recording as T D1 ～T Dn ；
Sixthly, using Cu 2+ Concentration C 1 ～C n Abscissa, in emission intensity T of sample solution B1 ～T Bn For ordinate, Cu is plotted 2+ A standard curve;
seventhly, with Al 3+ Concentration C 1 ～C n Abscissa, in emission intensity T of sample solution D1 ～T Dn To the ordinate, Al is plotted 3+ A standard curve;
eighthly, adding an actual water sample into the probe solution A, and uniformly mixing to prepare a sample solution B x ；
Nine, adding 2.0 μ M Cu to the sample solution Bx 2+ Measuring the fluorescence emission spectrum of the sample solution Bx with 330nm as excitation wavelength, recording the emission intensity at 470nm as T Bx-Cu ；
Ten, will T Bx-Cu And C, comparing the ordinate of the standard curve in the step six, and searching T Bx-Cu Cu in standard curve corresponding to strength 2+ Determining the concentration of Cu in the actual water sample according to the recovery rate and the average deviation after 3 times of measurement 2+ Concentration;
eleven, adding 2.0 mu M Al into the sample solution Bx 3+ Measuring the fluorescence emission spectrum of the sample solution Bx with 330nm as excitation wavelength, recording the emission intensity at 470nm as T Bx-Al ；
Twelve, reducing T Bx-Al And C, comparing the ordinate of the standard curve in the step seven, and searching T Bx-Al Al in standard curve corresponding to strength 3+ Determining the concentration of Al in the actual water sample according to the recovery rate and the average deviation after 3 times of measurement 3+ And (4) concentration.
Furthermore, the actual water sample in the step eight is tap water, bottled water, canned drinks, river water or lake water.
Cu of the invention 2+ And Al 3+ Cu as fluorescent probe pair by using bifunctional fluorescent covalent organic framework material 2+ And Al 3+ Has strong sensitivity and anti-interference capability, and can simultaneously carry out treatment on Cu 2+ And Al 3+ Realizes double recognition and is not affected by other metal ions in the environmentAnd the environment is not affected by acid-base environment. Compared with other fluorescent probes, the Cu of the invention 2+ And Al 3+ The difunctional fluorescent covalent organic framework material serving as a fluorescent probe can be applied to Cu in environments and biological systems 2+ And Al 3+ Detection expands the application range and application field of the covalent organic framework. Cu using the present invention 2+ And Al 3+ Detection of Cu by using bifunctional fluorescent covalent organic framework material 2+ And Al 3+ The method is simple, the response is rapid, and Cu is in the test process 2+ And Al 3+ The difunctional fluorescent covalent organic framework material can keep stable fluorescence intensity, shows that the difunctional fluorescent covalent organic framework material has good chemical stability, is not influenced by external environment in recognition, and can realize the effect of Cu in an actual water sample 2+ And Al 3+ And (4) carrying out quantitative detection.
Drawings
FIG. 1 is Cu prepared in example 1 2+ And Al 3+ Infrared spectrogram of the bifunctional fluorescent covalent organic framework material;
FIG. 2 is Cu prepared in example 1 2+ And Al 3+ Scanning electron microscope images of the bifunctional fluorescent covalent organic framework material;
FIG. 3 is Cu prepared in example 1 2+ And Al 3+ Transmission electron microscope image of the difunctional fluorescent covalent organic framework material;
FIG. 4 is Cu prepared in example 1 2+ And Al 3+ Bifunctional fluorescent covalent organic framework materials (0.3g/L, V) Acetonitrile :V HEPES 8:2, pH 7.4) with 0.2 μmol/L Cu 2+ And Al 3+ Fluorescence spectra when coexisting, the abscissa is wavelength, and the ordinate is fluorescence intensity;
FIG. 5 is Cu prepared in example 1 2+ And Al 3+ Bifunctional fluorescent covalent organic framework materials (0.3g/L, V) Acetonitrile :V HEPES 8:2, pH 7.4) with 0.2 μmol/L Cu 2+ In the coexistence, the horizontal coordinate of the bar graph of the fluorescence intensity in the presence of other metal ions is the metal ions, and the vertical coordinate is the fluorescence intensity;
FIG. 6 is Cu prepared in example 1 2+ And Al 3+ Dual function fluorescenceFluorescent covalent organic framework materials (0.3g/L, V) Acetonitrile :V HEPES 8:2, pH 7.4) with 0.2 μmol/L Al 3+ In the coexistence, the horizontal coordinate of the bar graph of the fluorescence intensity in the presence of other metal ions is the metal ions, and the vertical coordinate is the fluorescence intensity;
FIG. 7 is Cu 2+ Concentration and Cu prepared in example 1 2+ And Al 3+ Fluorescence intensity (V) of double-function fluorescent covalent organic framework material Acetonitrile ::V HEPES 8:2, pH 7.4) with concentration on the abscissa and fluorescence intensity on the ordinate.
FIG. 8 shows Al 3+ Concentration and Cu prepared in example 1 2+ And Al 3+ Fluorescence intensity (V) of double-function fluorescent covalent organic framework material Acetonitrile ::V HEPES 8:2, pH 7.4) with concentration on the abscissa and fluorescence intensity on the ordinate.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: cu of the present example 2+ And Al 3+ The preparation method of the bifunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.15mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 0.5mL of dioxane and 0.5mL of mesitylene, and then adding 0.012mol of glacial acetic acid as a catalyst to uniformly mix to obtain a mixed solution;
secondly, adding the mixed solution into a schlenk tube, and performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the schlenk tube in a nitrogen environment;
thirdly, heating the schlenk tube to 110 ℃, and reacting for 3 days;
fourthly, cooling to room temperature after the reaction is finished, filtering, repeatedly washing a filter cake by using a mixed solvent of acetone and tetrahydrofuran, and drying in vacuum to obtain Cu 2+ And Al 3+ Bifunctional fluorescent covalent organic framework materials. Yield 75%, melting point>320℃。
Cu prepared in example 1 by Fourier Infrared Spectroscopy 2+ And Al 3+ The bifunctional fluorescent covalent organic framework material is subjected to structural characterization, and the obtained infrared spectrum is shown in figure 1. At 1620cm -1 The characteristic absorption peak of C ═ N appears, which indicates that Cu 2+ And Al 3+ The preparation of the difunctional fluorescent covalent organic framework material is successful.
For Cu prepared in example 1 2+ And Al 3+ XPS test of the bifunctional fluorescent covalent organic framework material shows that the 1s orbital binding energy of N is 399.28eV, which indicates that Cu 2+ And Al 3+ The successful preparation of the bifunctional fluorescent covalent organic framework material is mutually verified with infrared spectrum.
Cu prepared in example 1 2+ And Al 3+ The scanning electron micrograph of the bifunctional fluorescent covalent organic framework material is shown in FIG. 2, and the transmission electron micrograph is shown in FIG. 3. It can be seen that Cu 2+ And Al 3+ The bifunctional fluorescent covalent organic framework material is in a nano microsphere structure. As can be seen from the above characterization results, the Cu prepared in this example 2+ And Al 3+ The periodic structure fragment of the bifunctional fluorescent covalent organic framework material is as follows:
cu in example 1 2+ And Al 3+ The spectral performance test of the bifunctional fluorescent covalent organic framework material comprises the following steps:
first, spectral test
Cu prepared by carrying out example 1 2+ And Al 3+ The method for measuring the fluorescence spectra of the bifunctional fluorescent covalent organic framework material and different metal ions comprises the following steps:
weigh 1.0mmol of metal salt: NaNO 3 、KNO 3 、Ba(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Ca(NO 3 ) 2 ·4H 2 O、Cr(NO 3 ) 3 ·9H 2 O、Fe(NO 3 ) 3 ·9H 2 O、Al(NO 3 ) 3 ·9H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、Zn(NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·4H 2 O、AgNO 3 、Cd(NO 3 ) 2 ·4H 2 O、Hg(NO 3 ) 2 And Pb (NO) 3 ) 2 The solution was put into a 10mL volumetric flask, and the volume was fixed with 0.01mol/L HEPES buffer solution having pH of 7.4, and the solution was uniformly shaken with ultrasound to completely dissolve the metal salt, thereby obtaining a metal cation stock solution having a concentration of 0.1 mol/L.
Acetonitrile and a HEPES buffer solution having a pH of 7.4 were mixed at a volume ratio of 8:2 to obtain a mixed solution, and the Cu prepared in example 1 was added to the mixed solution 2+ And Al 3+ And obtaining 0.3g/L probe test solution by using the difunctional fluorescent covalent organic framework material.
And respectively adding 0.2 mu mol/L of metal cation stock solution into the probe test solution, and performing ultrasonic oscillation for 5min to obtain a mixed solution.
Separately measure Cu with 330nm as excitation wavelength 2+ And Al 3+ The fluorescence emission spectra of the bifunctional fluorescent covalent organic framework material and the mixed solution with different metal ions added are shown in FIG. 4. As can be seen from FIG. 4, Cu was produced in this example 2+ And Al 3+ The fluorescence emission wavelength of the bifunctional fluorescent covalent organic framework material is 470nm, and the fluorescence intensity is 812a.u. After addition of different metal cations (Zn) 2+ 、Ca 2+ 、Mg 2+ 、Fe 3+ 、Hg 2+ 、Pb 2+ 、Na + 、Ba 2+ 、Ni 3+ 、K + 、Co 2+ 、Cd 2+ 、Ag + 、Cr 3 + )，Cu 2+ And Al 3+ The fluorescent intensity of the bifunctional fluorescent covalent organic framework material is not changed greatly, and the intensity is about 812a.u. While adding Cu 2+ And Al 3+ The fluorescence intensity was significantly reduced to 65a.u. and 107a.u. respectively, and the degree of quenching was about 12-fold and 8-fold, respectively. Therefore, it can be preliminarily deduced from the fluorescence emission spectrum,cu prepared in this example 2+ And Al 3+ Bifunctional fluorescent covalent organic framework material pair Cu 2+ And Al 3+ Has selective recognition capability.
Cu prepared in example 1 2+ And Al 3+ Bifunctional fluorescent covalent organic framework material in Cu 2+ And Al 3+ The method for testing the metal ion interference resistance during detection comprises the following steps: acetonitrile and a HEPES buffer solution having a pH of 7.4 were mixed at a volume ratio of 8:2 to obtain a mixed solution, and the Cu prepared in example 1 was added to the mixed solution 2+ And Al 3+ Obtaining a probe solution with the concentration of 0.3mg/mL by using the double-function fluorescent covalent organic framework material; then, various ion solutions (Zn) were added to the probe solution at a concentration of 0.2. mu. mol/L 2+ 、Ca 2+ 、Mg 2+ 、Fe 3+ 、Hg 2+ 、Pb 2+ 、Na + 、Ba 2+ 、Ni 3+ 、K + 、Co 2+ 、Cd 2+ 、Ag + 、Cr 3+ ) Shaking up, then adding 0.2 mu mol/L Cu respectively 2+ Or Al 3+ And ions are prepared into a mixed test solution of a probe, identification ions and interference ions. After shaking sufficiently, the fluorescence test was immediately performed after 5min of ultrasonic oscillation, and the results are shown in FIGS. 5 and 6. It can be seen from the figure that Cu in the presence of other metal cations 2+ Or Al 3+ In the presence of other ions, Cu 2+ And Al 3+ The fluorescence intensity of the bifunctional fluorescent covalent organic framework material is not changed, namely Cu 2+ And Al 3+ Bifunctional fluorescent covalent organic framework material pair Cu 2+ And Al 3+ The fluorescence detection of (2) is not interfered by other metal ions.
Cu prepared by example 1 2+ And Al 3+ Use of bifunctional fluorescent covalent organic framework materials for Cu 2+ And Al 3+ The qualitative detection method comprises the following steps:
firstly, mixing Cu 2+ And Al 3+ Uniformly dispersing the difunctional fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with the volume ratio of 2:1 to obtain a probeSolution A, Probe solution A Cu 2+ And Al 3+ The concentration of the difunctional fluorescent covalent organic framework material is 0.3 g/L;
secondly, respectively adding a sample I to be detected and a sample II to be detected, which contain metal ions, into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, recording the emission intensity when the emission wavelength is 470nm, and recording as T A ，T A ＝812a.u.；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, recording the emission intensity when the emission wavelength is 470nm, and recording as T B (ii) a Wherein the emission intensity of the sample solution B added with the sample I to be detected is T BⅠ 68a.u. and the emission intensity of the sample solution B added with the sample II to be tested is T BⅡ ＝105a.u.；
Fifth, compare T A And T B And (3) finding that:
T BⅠ ＝68a.u.＝T A 12, judging that the sample II to be tested contains Cu 2+ ；
T BⅡ ＝105a.u.，101.5＝T A /8＜T BⅡ If TA is 812, the sample to be tested is judged to contain Cu 2+ Or Al 3+ Or Cu 2+ And Al 3+ 。
Cu prepared by use of example 1 2+ And Al 3+ Quantitative detection of Cu in actual water sample by using bifunctional fluorescent covalent organic framework material 2+ And Al 3+ The concentration method comprises the following steps:
first, mixing Cu 2+ And Al 3+ Uniformly dispersing the difunctional fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with a volume ratio of 8:2 to obtain a probe solution A, wherein Cu in the probe solution A 2+ And Al 3+ The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, the probe solution A is gradually added with the concentrations of 0.1. mu.M, 0.3. mu.M, 0.5. mu.M, 0.7. mu.M, 1.0. mu.M, 1.2. mu.M, 1.4. mu.M, 1.6. mu.M, 1.8. mu.M, 2.0. mu.M, 2.3. mu.M, 2.5. mu.Mmu.M, 2.8. mu.M, 3.0. mu.M Cu 2+ Respectively obtaining sample solutions B 1 、B 2 、B 3 ……B n ；
Thirdly, Al is gradually added to the probe solution A at concentrations of 0.1. mu.M, 0.3. mu.M, 0.5. mu.M, 0.7. mu.M, 1.0. mu.M, 1.2. mu.M, 1.4. mu.M, 1.6. mu.M, 1.8. mu.M, 2.0. mu.M, 2.3. mu.M, 2.5. mu.M, 2.8. mu.M, 3.0. mu.M, respectively 3+ Respectively obtaining sample solutions D 1 、D 2 、D 3 ……D n ；
Fourthly, with 330nm as the excitation wavelength, the sample solution B is measured 1 ～B n Respectively recording the emission intensity at an emission wavelength of 470nm, and recording as T B1 ～T Bn ；
Fifthly, with 330nm as the excitation wavelength, the sample solution D is measured 1 ～D n Respectively recording the emission intensity at an emission wavelength of 470nm, and recording as T D1 ～T Dn ；
Sixthly, using Cu 2+ Concentration C 1 ～C n Abscissa, in emission intensity T of sample solution B1 ～T Bn To the ordinate, draw Cu 2+ A standard curve;
seventhly, with Al 3+ Concentration C 1 ～C n Abscissa, in emission intensity T of sample solution D1 ～T Dn To the ordinate, Al is plotted 3+ A standard curve;
eighthly, adding an actual water sample into the probe solution A, and uniformly mixing to prepare a sample solution B x ；
Nine, adding 2.0. mu.M Cu to the sample solution Bx 2+ Measuring the fluorescence emission spectrum of the sample solution Bx with 330nm as excitation wavelength, recording the emission intensity at 470nm as T Bx-Cu ；
Ten, will T Bx-Cu And (5) searching T by contrasting the ordinate of the standard curve in the sixth step Bx-Cu Cu in standard curve corresponding to strength 2+ Determining the concentration of Cu in the actual water sample according to the recovery rate and the average deviation after 3 times of measurement 2+ Concentration;
eleven, adding 2.0 mu M Al into the sample solution Bx 3+ Measuring the fluorescence emission spectrum of the sample solution Bx with 330nm as excitation wavelength, recording the emission intensity at 470nm as T Bx-Al ；
Twelve, will T Bx-Al Comparing the ordinate of the standard curve in the seventh step, and searching T Bx-Al Al in standard curve corresponding to strength 3+ Determining the concentration of Al in the actual water sample according to the recovery rate and the average deviation after 3 times of measurement 3+ And (4) concentration.
The test was repeated 2 times using the above method using a spiking recovery experiment, and the results are shown in tables 1 and 2. As seen from tables 1 and 2, the measured recovery rates and standard deviations both satisfied the measurement requirements, confirming that the Cu prepared in this example 2+ And Al 3+ The difunctional fluorescent covalent organic framework material can be used for Cu in an actual water sample 2+ And Al 3+ And (4) quantitatively detecting the concentration.
TABLE 1 sample recovery method Cu 2+ Results of concentration measurement
TABLE 2 sample application recovery method Al 3+ Results of concentration measurement
Example 2: cu of the present example 2+ And Al 3+ The preparation method of the bifunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.225mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 1mL of dioxane and 0.5mL of mesitylene, and uniformly mixing;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating the schlenk tube to 160 ℃, and reacting for 3 days;
fourthly, cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using a mixed solvent of acetone and methanol, and drying in vacuum to obtain Cu 2+ And Al 3+ Bifunctional fluorescent covalent organic framework materials. Yield 71%, melting point>320℃。
Example 3: cu of the present example 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.15mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 0.5mL of p-dichlorobenzene and 1mL of mesitylene, and then adding 0.012mol of benzoic acid as a catalyst to uniformly mix;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating a schlenk tube to 120 ℃ and reacting for 4 days;
fourthly, cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using a mixed solvent of acetone and tetrahydrofuran, and drying in vacuum to obtain Cu 2+ And Al 3+ A bifunctional fluorescent covalent organic framework material. Yield 70%, melting point>320℃。
Example 4: cu of the present example 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.3mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 0.5mL of dioxane and 0.5mL of p-dichlorobenzene, and then adding 0.03mol of glacial acetic acid as a catalyst to mix uniformly;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating a schlenk tube to 120 ℃ and reacting for 3 days;
fourthly, cooling to room temperature after the reaction is finished, filtering, repeatedly washing a filter cake by using a mixed solvent of acetone and tetrahydrofuran, and drying in vacuum to obtain Cu 2+ And Al 3+ A bifunctional fluorescent covalent organic framework material. Yield 65%, melting point>320℃。
Example 5: cu of the present example 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, respectively adding 0.3mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 1mL of n-butyl alcohol and 0.5mL of dioxane, and then adding 0.015mol of p-toluenesulfonic acid as a catalyst to uniformly mix;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the schlenk tube in a nitrogen environment;
thirdly, heating a schlenk tube to 150 ℃ and reacting for 5 days;
fourthly, cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using a mixed solvent of ethyl acetate and tetrahydrofuran, and drying in vacuum to obtain Cu 2+ And Al 3+ A bifunctional fluorescent covalent organic framework material. Yield 70%, melting point>320℃。
Example 6: cu of the present example 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.3mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into 1.5mL of dioxane according to the mass ratio of 4:1, and then adding 0.024mL of concentrated hydrochloric acid with the mass percentage concentration of 35% as a catalyst to uniformly mix;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the schlenk tube in a nitrogen environment;
thirdly, heating the schlenk tube to 180 ℃ and reacting for 2 days;
fourthly, cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using a mixed solvent of ethyl acetate and methanol, and drying in vacuum to obtain Cu 2+ And Al 3+ Bifunctional fluorescent covalent organic framework materials. Yield 71%, melting point>320℃。
Example 7: cu of the present example 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.225mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 1.2mL of n-butanol and 0.8mL of p-dichlorobenzene respectively, and uniformly mixing the mixture by taking 0.013mL of concentrated sulfuric acid with the mass percentage concentration of 98% as a catalyst;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating the schlenk tube to 130 ℃, and reacting for 7 days;
fourthly, cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using a mixed solvent of acetone and dichloromethane, and drying in vacuum to obtain Cu 2+ And Al 3+ Bifunctional fluorescent covalent organic framework materials. Yield 68%, melting point>320℃。
Example 8: cu of the present example 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material comprises the following steps:
firstly, adding 0.375mol of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.05mol of 5 ' - (4-formylphenyl) - [1,1 ': 3 ', 1 ' -triphenyl ] -4,4 ' -dicarboxaldehyde into a mixed solvent of 1mL of N-butanol and 0.5mL of N, N-dimethylformamide respectively, and then adding 0.034mol of benzenesulfonic acid as a catalyst to uniformly mix;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating the schlenk tube to 140 ℃ and reacting for 6 days;
fourthly, descending after the reaction is finishedCooling to room temperature, carrying out suction filtration, repeatedly washing a filter cake by using a mixed solvent of ethanol and tetrahydrofuran, and carrying out vacuum drying to obtain Cu 2+ And Al 3+ A bifunctional fluorescent covalent organic framework material. Yield 66%, melting point>320℃。
Claims (10)
1. Cu 2+ And Al 3+ The bifunctional fluorescent covalent organic framework material is characterized in that the periodic structure segment of the covalent organic framework material is as follows:
2. preparation of a Cu as claimed in claim 1 2+ And Al 3+ The method for preparing the difunctional fluorescent covalent organic framework material is characterized by comprising the following steps:
firstly, according to the mass ratio of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 5 '- (4-formylphenyl) - [1, 1': 3 ', 1' -triphenyl ] -4,4 '-dicarboxaldehyde being (1-5), 1, adding 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 5' - (4-formylphenyl) - [1,1 ': 3', 1 '-triphenyl ] -4, 4' -dicarboxaldehyde into the mixed solvent, then according to the mass ratio of 2- (4-fluorophenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine, the mass ratio of the 10-diamine to the acid is 1 (0.01-0.1), adding the acid into the mixed solvent as a catalyst, and uniformly mixing to obtain a mixed solution;
secondly, putting the mixed solution into a schlenk tube, and performing cycle operation of vacuumizing and filling nitrogen into the schlenk tube to keep the nitrogen environment in the schlenk tube;
thirdly, heating the schlenk tube to 100-200 ℃ and reacting for 1-7 days;
fourthly, cooling to room temperature after the reaction is finished, filtering, repeatedly washing a filter cake by using an organic solvent, and drying in vacuum to obtain Cu 2+ And Al 3+ A bifunctional fluorescent covalent organic framework material.
3. According to claim 2One kind of Cu 2+ And Al 3+ The preparation method of the bifunctional fluorescent covalent organic framework material is characterized in that the mixed solvent in the step one is any two of mesitylene, p-dichlorobenzene, N-dimethylformamide, dioxane and N-butyl alcohol.
4. Cu according to claim 2 or 3 2+ And Al 3+ The preparation method of the difunctional fluorescent covalent organic framework material is characterized in that the acid in the step one is any one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, concentrated hydrochloric acid with the mass percentage concentration of 30-37% or concentrated sulfuric acid with the mass percentage concentration of 95-98%.
5. Cu according to claim 2 or 3 2+ And Al 3+ The preparation method of the bifunctional fluorescent covalent organic framework material is characterized in that the organic solvent in the step four is one or two of tetrahydrofuran, methanol, ethanol, ethyl acetate, acetone, dichloromethane or 1, 2-dichloroethane.
6. A Cu as claimed in claim 1 2+ And Al 3+ The application of the difunctional fluorescent covalent organic framework material is characterized in that the application is to mix Cu 2+ And Al 3+ Difunctional fluorescent covalent organic framework material used as fluorescent material for Cu 2+ And Al 3+ Qualitative and quantitative detection.
7. Cu according to claim 6 2+ And Al 3+ The application of the bifunctional fluorescent covalent organic framework material is characterized in that Cu is utilized 2+ And Al 3+ Cu preparation by using bifunctional fluorescent covalent organic framework material 2+ And Al 3+ The qualitative detection method comprises the following steps:
first, mixing Cu 2+ And Al 3+ The difunctional fluorescent covalent organic framework material is uniformly dispersed in acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES)Obtaining a probe solution A in the mixed solution; the mixed solution is prepared from acetonitrile and 4-hydroxypiperazine ethanesulfonic acid according to the volume ratio of 8 (1-5), and the Cu in the probe solution A 2+ And Al 3+ The concentration of the difunctional fluorescent covalent organic framework material is 0.1-0.5 g/L;
secondly, adding a sample I to be detected containing metal ions into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, recording the emission intensity when the emission wavelength is 470nm, and recording as T A ；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, recording the emission intensity when the emission wavelength is 470nm, and recording as T B ；
Fifth, compare T A And T B If T is A /12≤TB＜T A And 8, judging that the sample to be detected contains Cu 2+ (ii) a If T is A /8≤T B ＜T A Then the Cu content in the sample to be tested is determined 2+ Or Al 3+ Or of Cu 2+ And Al 3+ 。
8. Cu according to claim 7 2+ And Al 3+ The application of the difunctional fluorescent covalent organic framework material is characterized in that a sample I to be detected is tap water, bottled water, canned drink, river water or lake water.
9. Cu according to claim 6 2+ And Al 3+ The application of the bifunctional fluorescent covalent organic framework material is characterized in that Cu is utilized 2+ And Al 3+ Quantitative detection of Cu in actual water sample by using dual-function fluorescent covalent organic framework material 2+ And Al 3+ The method is a standard curve method and specifically comprises the following steps:
firstly, mixing Cu 2+ And Al 3+ Uniformly dispersing the difunctional fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) to obtain a probe solution A; wherein the mixed solution is prepared by mixing acetonitrile and 4-hydroxypiperazine ethanesulfonic acidThe volume ratio of the acid is 8 (1-5), and the probe solution A contains Cu 2+ And Al 3+ The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, gradually adding the probe solution A into the probe solution A to obtain the probe solution C 1 、C 2 、C 3 ……C n Of Cu 2+ Respectively obtaining sample solutions B 1 、B 2 、B 3 ……B n ；
Thirdly, gradually adding the probe solution A with the concentration of C respectively 1 、C 2 、C 3 ……C n Al of (2) 3+ Respectively obtaining sample solutions D 1 、D 2 、D 3 ……D n ；
Fourthly, with 330nm as the excitation wavelength, the sample solution B is measured 1 ～B n Respectively recording the emission intensity at an emission wavelength of 470nm, and recording as T B1 ～T Bn ；
Fifthly, with 330nm as the excitation wavelength, the sample solution D is measured 1 ～D n Respectively recording the emission intensity at an emission wavelength of 470nm, and recording as T D1 ～T Dn ；
Sixthly, using Cu 2+ Concentration C 1 ～C n Abscissa, in emission intensity T of sample solution B1 ～T Bn To the ordinate, draw Cu 2+ A standard curve;
seventhly, with Al 3+ Concentration C 1 ～C n Abscissa, in emission intensity T of sample solution D1 ～T Dn To the ordinate, Al is plotted 3+ A standard curve;
eighthly, adding an actual water sample into the probe solution A, uniformly mixing the actual water sample and the probe solution A to prepare a sample solution B x ；
Nine, adding 2.0 μ M Cu to the sample solution Bx 2+ Measuring the fluorescence emission spectrum of the sample solution Bx with 330nm as excitation wavelength, recording the emission intensity at 470nm as T Bx-Cu ；
Ten, will T Bx-Cu And (5) searching T by contrasting the ordinate of the standard curve in the sixth step Bx-Cu Cu in standard curve corresponding to strength 2+ Determining the concentration of Cu in the actual water sample according to the recovery rate and the average deviation after 3 times of measurement 2+ Concentration;
eleven, adding 2.0 mu M Al into the sample solution Bx 3+ Measuring the fluorescence emission spectrum of the sample solution Bx with 330nm as excitation wavelength, recording the emission intensity at 470nm as T Bx-Al ；
Twelve, reducing T Bx-Al And C, comparing the ordinate of the standard curve in the step seven, and searching T Bx-Al Al in standard curve corresponding to strength 3 + Determining the concentration of Al in the actual water sample according to the recovery rate and the average deviation after 3 times of measurement 3+ And (4) concentration.
10. Cu according to claim 9 2+ And Al 3+ The application of the double-function fluorescent covalent organic framework material is characterized in that the actual water sample in the step eight is tap water, bottled water, canned beverage, river water or lake water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210740307.XA CN114920894B (en) | 2022-06-27 | 2022-06-27 | Cu (copper) alloy 2+ And Al 3+ Double-functional fluorescent covalent organic framework material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210740307.XA CN114920894B (en) | 2022-06-27 | 2022-06-27 | Cu (copper) alloy 2+ And Al 3+ Double-functional fluorescent covalent organic framework material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114920894A true CN114920894A (en) | 2022-08-19 |
| CN114920894B CN114920894B (en) | 2023-07-07 |
Family
ID=82815153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210740307.XA Active CN114920894B (en) | 2022-06-27 | 2022-06-27 | Cu (copper) alloy 2+ And Al 3+ Double-functional fluorescent covalent organic framework material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114920894B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020094632A1 (en) * | 2018-11-05 | 2020-05-14 | Cowatech Aps | Catalytic desalination using co2-responsive organic compounds |
| CN112940718A (en) * | 2021-02-08 | 2021-06-11 | 齐齐哈尔大学 | Cu2+Fluorescent covalent organic framework material and preparation method and application thereof |
| CN113024835A (en) * | 2021-04-14 | 2021-06-25 | 华南师范大学 | Preparation of covalent organic framework containing bipyridyl group and application of covalent organic framework in mercury ion recognition |
| WO2021153689A1 (en) * | 2020-01-29 | 2021-08-05 | 国立研究開発法人科学技術振興機構 | Composite material containing cof, heat dissipation/storage member, and production method for said composite material, and cof monocrystal and production method therefor |
| CN114085387A (en) * | 2021-12-13 | 2022-02-25 | 齐齐哈尔大学 | Covalent organic framework material for hydroquinone adsorption and preparation method and application thereof |
-
2022
- 2022-06-27 CN CN202210740307.XA patent/CN114920894B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020094632A1 (en) * | 2018-11-05 | 2020-05-14 | Cowatech Aps | Catalytic desalination using co2-responsive organic compounds |
| WO2021153689A1 (en) * | 2020-01-29 | 2021-08-05 | 国立研究開発法人科学技術振興機構 | Composite material containing cof, heat dissipation/storage member, and production method for said composite material, and cof monocrystal and production method therefor |
| CN112940718A (en) * | 2021-02-08 | 2021-06-11 | 齐齐哈尔大学 | Cu2+Fluorescent covalent organic framework material and preparation method and application thereof |
| CN113024835A (en) * | 2021-04-14 | 2021-06-25 | 华南师范大学 | Preparation of covalent organic framework containing bipyridyl group and application of covalent organic framework in mercury ion recognition |
| CN114085387A (en) * | 2021-12-13 | 2022-02-25 | 齐齐哈尔大学 | Covalent organic framework material for hydroquinone adsorption and preparation method and application thereof |
Non-Patent Citations (7)
| Title |
|---|
| CUI, C，等: "Covalent organic framework with bidentate ligand sites as reliable fluorescent sensor for Cu2+", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 299, pages 1 - 8 * |
| CUI, WR，等: "Covalent Organic Framework Nanosheets for Fluorescence Sensing via Metal Coordination", ACS APPLIED NANO MATERIALS, vol. 2, no. 8, pages 5342 - 5349 * |
| PATRA, L，等: "A new multi-analyte fluorogenic sensor for efficient detection of Al3+ and Zn2+ ions based on ESIPT and CHEF features", NEW JOURNAL OF CHEMISTRY, vol. 42, no. 23, pages 19076 - 19082 * |
| WANG, LY,等: "A thiadiazole-functionalized covalent organic framework for efficient CO2 capture and separation", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 224, pages 95 - 99, XP029438323, DOI: 10.1016/j.micromeso.2015.11.030 * |
| 林春花: "功能化荧光框架材料在有机小分子和重金属离子检测中的应用", 中国博士学位论文全文数据库 (工程科技Ⅰ辑), no. 03, pages 014 - 213 * |
| 米小龙，等: "基于罗丹明荧光信号报告基团的细胞通透性铜离子荧光探针", 高等学校化学学报, vol. 37, no. 10, pages 1784 - 1791 * |
| 谭冰: "共价有机骨架及其复合材料的制备及荧光传感和催化性能", 中国博士学位论文全文数据库 (工程科技Ⅰ辑), no. 01, pages 027 - 206 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114920894B (en) | 2023-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112940718B (en) | Cu2+Fluorescent covalent organic framework material and preparation method and application thereof | |
| CN110156806A (en) | It is a kind of based on the copper ion Ratiometric fluorescent probe and preparation method of rhodamine derivative and application | |
| CN108359444B (en) | Detecting Fe3+And can utilize Fe3+Detection of Ca2+Fluorescent probes and methods of making and using the same | |
| CN107573258B (en) | A kind of fluorescence probe and preparation method and application detecting aluminium ion and zinc ion | |
| CN107652309B (en) | A kind of fluorescein for open hole detection-ultraviolet molecular probe of rhodamine B copper ion and its synthesis and application method | |
| CN109206351A (en) | A kind of near infrared fluorescent probe, preparation method and application for surveying palladium ion based on flower cyanines structure | |
| CN114920894B (en) | Cu (copper) alloy 2+ And Al 3+ Double-functional fluorescent covalent organic framework material and preparation method and application thereof | |
| CN117347336A (en) | Fluorescent aptamer biosensor for detecting kanamycin and preparation method and application thereof | |
| CN108931505A (en) | The detection method of nitrite ion based on rare-earth metals organic framework material | |
| CN108864159A (en) | A kind of pyrroles can be used for detecting Fe3+ under acidic environment-benzene boron fluorine fluorescent chemicals and preparation method thereof | |
| CN109283163B (en) | Method for detecting L-cysteine based on calcium-metal organic framework material as fluorescent probe | |
| CN115181068B (en) | TPI derivative fluorescent probe and application thereof in preparation of copper ion detection reagent | |
| CN109053626A (en) | A kind of fluorescence probe and preparation method thereof and its application in divalent palladium detection | |
| CN111808607B (en) | Fluorescent probe for detecting peroxynitrosyl anions, preparation method and application | |
| CN110658167B (en) | Method for applying silver-metal organic framework material as fluorescent probe to folic acid detection | |
| Yang et al. | A simple ‘turn-on’fluorescence chemosensor for Al (iii) detection in aqueous solution and solid matrix | |
| CN114031532A (en) | Thiourea-modified pyrene derivative fluorescent probe and preparation method and application thereof | |
| CN111440201B (en) | Preparation method and application of organic compound | |
| CN111592532A (en) | Near-infrared fluorescent probe for detecting hydrazine and preparation and application thereof | |
| CN106496255B (en) | A kind of acylhydrazone Zn complex fluorescence probe and its preparation method and application | |
| CN112375230B (en) | Three-rare earth fluorescent sensor capable of being used for identifying metabolites of human body | |
| CN116444396B (en) | Asymmetric double Schiff alkali aluminum ion fluorescent probe, synthesis method and application | |
| CN102533254A (en) | Selenium nano-sensing material and preparation method thereof | |
| CN115356318B (en) | Fluorescence detection method of tobacco pesticide residue bud inhibition pellet | |
| CN112480152B (en) | Rare earth fluorescent probe and preparation method and application thereof |
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 |