CN114436817B - Porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite and application thereof - Google Patents
Porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite and application thereof Download PDFInfo
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- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 66
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- 239000013384 organic framework Substances 0.000 title claims abstract description 12
- -1 4-carboxyphenyl Chemical group 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 239000004305 biphenyl Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 1
- 238000012113 quantitative test Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 12
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 7
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- 239000000872 buffer Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000002091 cationic group Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
- C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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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- 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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Abstract
The invention provides a porous hydrogen bond organic skeleton-based fluorescent probe capable of quantitatively detecting hypochlorite and application thereof, wherein the novel porous hydrogen bond organic skeleton is named HOF-FAFU-1, and the chemical formula is C 40 H 24 O 8 R 2 It is constructed from 3,3'5,5' -tetra (4-carboxyphenyl) -4,4 '-di-R-biphenyl (named 4,4' -R-BPTC) ligand, wherein R group can be hydroxyl, amino, alkoxy, etc. The structure of HOF-FAFU-1 is that 4,4' -R-BPTC is connected into a two-dimensional hydrogen bond network of 4,4 grids through double hydrogen bond action of carboxyl-carboxyl, and then the two-dimensional hydrogen bond network is connected through pi-pi action between layers to form a three-dimensional open framework. The porous hydrogen bond organic framework-based fluorescent probe has the characteristics of good linear relation for hypochlorite sensing, good selectivity, wide linear range, low detection lower limit and the like. The fluorescent probe used by the invention also has the advantages of low use amount, simple synthesis process and strong operability, thus having wide application prospect.
Description
Technical Field
The invention belongs to the technical field of synthesis and chemical analysis detection of porous crystalline materials, and particularly relates to a porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite and application thereof.
Background
Hypochlorite (ClO) - ) Is an important active oxygen small molecule. In daily life, hypochlorite (ClO - ) Is widely applied to drinking water disinfection, paper bleaching, living and industrial wastewater purification, and is a strong bactericide and disinfectant. Hypochlorite in tap water (ClO) - ) The residual concentration is usually controlled within the range of 0.01 to 10mM, and the content thereof is detectedIs very important. Excessive hypochlorite can produce a plurality of toxic substances to cause tissue injury and different diseases, such as Alzheimer disease, cardiovascular diseases and the like, and hypochlorite can not play a role in sterilization and disinfection when insufficient. It is therefore highly desirable to develop a highly sensitive, highly selective hypochlorite detector.
Disclosure of Invention
In order to solve the problems, the invention synthesizes a novel porous hydrogen bond organic framework as a fluorescent probe (named HOF-FAFU-1) which aims at chlorate (ClO) - ) The detection of the method has the advantages of quick response, high selectivity, wide detection linear range, low detection lower limit and the like. The first aim of the invention is to prepare a novel porous hydrogen bond organic framework material (HOF-FAFU-1) by a simple synthesis method; the second purpose of the invention is to provide a fluorescent probe with the characteristics of simple operation, high sensitivity and selectivity, high response speed, low detection limit and the like, so as to realize quantitative detection of hypochlorite in water body including tap water.
The specific technical scheme of the invention is as follows:
a porous hydrogen bond organic skeleton-based fluorescent probe capable of quantitatively detecting hypochlorite, which is named HOF-FAFU-1 and has a chemical formula of C 40 H 24 O 8 R 2 Is constructed from 3,3', 5' -tetra (4-carboxyphenyl) -4,4 '-di-R-biphenyl (named 4,4' -R-BPTC) ligand. Wherein, R group can be hydroxyl, amino, alkoxy, etc. That is, the ligand constituting the fluorescent probe may be 3,3', 5' -tetrakis (4-carboxyphenyl) -4,4 '-dihydroxybiphenyl (4, 4' -OH-BPTC), 3', 5' -tetrakis (4-carboxyphenyl) -4,4 '-diaminobiphenyl (4, 4' -NH) 2 -BPTC), 3', 5' -tetrakis (4-carboxyphenyl) -4,4 '-dialkoxybiphenyl (4, 4' -RO-BPTC), and the like, and may also be 4,4'-OH-BPTC, 4' -NH 2 -a mixed ligand in which a plurality of BPTC and 4,4' -RO-BPTC are mixed together in any ratio.
The HOF-FAFU-1 fluorescent probe provided by the invention is a novel porous hydrogen bond organic framework material. The single crystal structure can be monoclinic system, C2/m space group, different R groupsThe unit cell parameters may vary slightly, for example, when the R group is hydroxyl, the unit cell parameters are: α＝γ＝90.00°,β＝94.89,/>and when the R group is amino, the unit cell parameters are: />α＝γ＝90.00°,β＝97.59,/> HOF-FAFU-1 may also belong to the triclinic system, < >>The space group may be slightly different from the R-based unit cell parameters, such as when R is hydroxy, the unit cell parameters are: /> α＝100.17°,β＝90.84,γ＝93.07°,/>
Further, the structure of HOF-FAFU-1 is that carboxyl groups in 4,4' -R-BPTC molecules, namely 3,3'5,5' -tetra (4-carboxyphenyl) -4,4' -di-R-biphenyl such as 3,3'5,5' -tetra (4-carboxyphenyl) -4,4' -dihydroxybiphenyl are connected through intermolecular hydrogen bonds, namely carboxylic acid-carboxylic acid double hydrogen bonds, so that a two-dimensional network with 4,4 lattices is formed. In the structure of HOF-FAFU-1, the biphenyl in the 4,4' -R-BPTC molecule is basically coplanar (can deviate from the coplanar slightly), and the 4,4 lattices form three-dimensional porous hydrogen bond organic framework materials through pi-pi action between layers.
Furthermore, the HOF-FAFU-1 fluorescent probe is a brand new crystalline porous material, which contains one-dimensional diamond-shaped pore canal with the size ofThe porosity is 45-50%, and the pore canal and the porosity can slightly change according to the difference of R groups.
The synthesis of the HOF-FAFU-1 fluorescent probe mainly comprises two methods, namely slow single crystal synthesis and fast microcrystalline synthesis, and the specific synthesis steps are as follows:
the slow monocrystalline synthesis method comprises the following steps:
the ligand 3,3', 5' -tetra (4-carboxyphenyl) -4,4' -di R biphenyl is ultrasonically dissolved in a solvent to prepare a solution, then under the condition of a certain temperature and standing, steam of a reagent is added into the solution in a steam natural diffusion mode, and the standing diffusion is carried out to obtain the bulk crystal of HOF-FAFU-1.
Further, the mass of the 4,4' -R-BPTC ligand is 0.01-100g; the solvent is one or more of solvents such as DMF, DMSO, DMA, DEF, DME capable of dissolving 4,4' -R-BPTC ligand, and the volume of the solvent is 0.01-4mL; wherein the reagent is a common solvent, and the solvent is one or more of acetonitrile, acetic acid, methanol, ethanol, propanol, diethyl ether, dichloromethane, chloroform, acetone, n-hexane, tetrahydrofuran, toluene and the like; the reaction temperature is-50-150 ℃; standing for 0-360 days. Wherein, the amounts of the solvent, the reagent and the ligand can be synchronously amplified and synthesized.
The rapid microcrystalline synthesis method is specifically as follows:
3,3', 5' -tetra (4-carboxyphenyl) -4,4' -di-R biphenyl is dispersed in a solvent by ultrasonic to prepare a solution, then a reagent is added at a certain temperature, and the solution is stirred, kept stand, and finally filtered or centrifuged to obtain HOF-FAFU-1 powder crystal.
Further, the mass of the 4,4' -R-BPTC ligand is 0.01-100g; the solvent is one or more of solvents such as DMF, DMSO, DMA, DEF, DME capable of dissolving 4,4' -R-BPTC ligand, and the volume of the solvent is 0.01-4mL; wherein the reagent is a common solvent, and the solvent is one or more of acetonitrile, acetic acid, methanol, ethanol, propanol, diethyl ether, dichloromethane, chloroform, acetone, n-hexane, tetrahydrofuran, toluene and the like; the reaction temperature is-50-150 ℃; the stirring speed is 0-15000r/min; stirring and reacting for 0-360 days; standing for 0-360 days. Wherein, the amounts of the solvent, the reagent and the ligand can be synchronously amplified and synthesized.
The HOF-FAFU-1 fluorescent probe can be applied to qualitative and quantitative detection of hypochlorite in water.
Compared with the background technology, the technical proposal has the following advantages:
1) The invention adopts a slow diffusion method and a rapid synthesis method to prepare the porous hydrogen bond organic framework HOF-FAFU-1 fluorescent probe capable of detecting hypochlorite.
2) The HOF-FAFU-1 fluorescent probe has simple synthesis steps, good material stability, strong operability and wide application prospect
3) The hypochlorite fluorescent probe provided by the invention has the advantages of extremely short response time, wide linear range, low detection limit and good selectivity, and can be used as a candidate object with potential for detecting hypochlorite in real time.
4) The hypochlorite fluorescent probe can qualitatively and quantitatively detect the content of residual chlorine in tap water, and has practical application value in the fields of chemistry, biology and the like.
Drawings
FIG. 1 is a block diagram of a HOF-FAFU-1 fluorescent probe according to the present invention;
FIG. 2 is a graph showing fluorescence spectra of fluorescent probe suspensions of the present invention after storage for a period of time; wherein the abscissa represents the wavelength and the ordinate represents the fluorescence intensity value.
FIG. 3 is a graph showing the change of fluorescence intensity ratio of fluorescent probe in Tris-HCl buffer with different pH values; wherein the abscissa represents the wavelength and the ordinate represents the fluorescence intensity value.
FIG. 4 is a graph showing the change in fluorescence intensity of fluorescent probe suspensions of the present invention at different concentrations; wherein the abscissa represents the wavelength and the ordinate represents the fluorescence intensity.
FIG. 5 is a graph showing response time of fluorescent probe of the present invention to hypochlorite in Tris-HCl buffer (10 mM) at pH 4.0; wherein the abscissa represents wavelength and the ordinate represents fluorescence intensity ratio (I 422 /I 0 )。
FIG. 6 is a graph showing the change in fluorescence spectrum of a fluorescent probe of the present invention in response to hypochlorite at various concentrations in Tris-HCl buffer (10 mM) at pH 4.0; wherein the abscissa represents the wavelength and the ordinate represents the fluorescence intensity.
FIG. 7 shows the ratio of the amount of hypochlorite added to the fluorescence intensity (I) of the fluorescent probe of the present invention in Tris-HCl buffer (10 mM) at pH 4.0 422 ) A varying linear relationship; wherein the abscissa represents the concentration of hypochlorite and the ordinate represents the fluorescence intensity ratio (I 422 /I 0 )。
FIG. 8 shows a series of cationic Li ions in the presence and absence of hypochlorite in Tris-HCl buffer (10 mM) at pH 4.0 with the fluorescent probe of the present invention + ,Na + ,K + ,NH 4 + ,Ca 2+ , Ba 2+ ,Mg 2+ ,Eu 3+ Effect on fluorescence ratio bar graph; wherein the abscissa represents the cation species, and the ordinate represents the fluorescence intensity ratio (I 422 /I 0 )。
FIG. 9 shows the anion F of the fluorescent probe of the present invention in the presence and absence of hypochlorite in Tris-HCl buffer (10 mM) at pH 4.0 without any treatment - ,Cl - ,Br - , SO 4 2- ,HCO 3- ,CO 3- ,PO 4 3- ,HPO 4 2- ,H 2 PO 4- ,NO 3 - ,CH 3 COO - And H 2 O 2 Effect bar graph on fluorescence ratio; wherein the abscissa represents the cation species, and the ordinate represents the fluorescence intensity ratio (I 422 /I 0 )。
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: low-speed monocrystalline synthesis of fluorescent probe HOF-FAFU-1
4,4' -OH-BPTC (10 mg) was ultrasonically dispersed in DMF (1 mL), then placed in a vial, the vial was placed in a large bottle, acetonitrile was placed in the large bottle and covered with a cap, and left standing at room temperature for one week to obtain the fluorescent probe in the present invention.
Example 2: low-speed monocrystalline synthesis of fluorescent probe HOF-FAFU-1
4,4' -NH 2 BPTC (10 mg) was sonicated in DMF (1 mL) and then placed in a vial, the vial was placed in a large vial, acetonitrile was placed in the large vial and capped with a cap, and left to stand for one week at ambient temperature to give the fluorescent probe in the present invention.
Example 3: low-speed monocrystalline synthesis of fluorescent probe HOF-FAFU-1
4,4' -RO-BPTC (10 mg) was ultrasonically dispersed in DMF (1 mL), followed by placing in a vial, placing the vial in a large bottle, placing acetonitrile in the large bottle and covering with a cap, and standing at room temperature for one week to obtain the fluorescent probe in the present invention.
Example 4: low-speed monocrystalline synthesis of fluorescent probe HOF-FAFU-1
Selection of 4,4' -NH 2 -BPTC, 4'-OH-BPTC or 4,4' -OCH 3 One or two or three ligands of BPTC are mixed in any ratio to obtain a ligand (total 10 mg), ultrasonically dispersed in DMF (1 mL), then placed in a vial, the vial is placed in a large bottle, acetonitrile is placed in the large bottle and covered with a cover, and the fluorescent probe in the invention is obtained after standing for one week at normal temperature.
Example 5: rapid microcrystalline synthesis of fluorescent probe HOF-FAFU-1
4,4' -OH-BPTC (10 mg) was ultrasonically dispersed in DMF (0.1 mL), followed by addition of acetonitrile (0.9 mL), stirring at room temperature for 2h, and centrifugation to obtain the fluorescent probe in the present invention.
Example 6: rapid microcrystalline synthesis of fluorescent probe HOF-FAFU-1
4,4' -NH 2 BPTC (10 mg) was ultrasonically dispersed in DMF (0.1 mL), followed by addition of acetonitrile (0.9 mL), stirring at room temperature for 2h, and centrifugation to give the fluorescent probe of the present invention.
Example 7: rapid microcrystalline synthesis of fluorescent probe HOF-FAFU-1
4,4' -RO-BPTC (10 mg) was ultrasonically dispersed in DMF (0.1 mL), followed by addition of acetonitrile (0.9 mL), stirring at room temperature for 2h, and centrifugation to obtain the fluorescent probe in the present invention.
Example 8: rapid microcrystalline synthesis of fluorescent probe HOF-FAFU-1
Selection of 4,4' -NH 2 -BPTC, 4'-OH-BPTC or 4,4' -OCH 3 One or two or three ligands of BPTC are mixed in any ratio to obtain a ligand (total 10 mg), the ligand is ultrasonically dispersed in DMF (0.1 mL), acetonitrile (0.9 mL) is added, stirring is carried out for 2h at room temperature, and the fluorescent probe in the invention is obtained after centrifugation.
Example 9: application of fluorescent probe in the invention
HOF-FAFU-1 fluorescent probe and water are firstly prepared into 50.00mg/L suspension, 1.900mL of probe suspension is added into 0.1000mL of Tris-HCl buffer solution with pH value of 4.0, and sodium hypochlorite (NaClO) solution with different concentrations prepared by tap water is added. Experimental results show that the fluorescent probe material is specific to ClO - The detection limit of the fluorescent probe is 0.005mM, and the fluorescent probe has good detection performance on sodium hypochlorite within the concentration range of 0.005-0.5 mM, so that the content of residual chlorine in tap water can be quantitatively detected. Therefore, the fluorescent probe has important application value for quantitative detection of hypochlorite in tap water.
Referring to fig. 2 and 3, it can be seen from the figures that the long-time preservation and the pH change have no obvious effect on the performance of the HOF-FAFU-1 fluorescent probe, so that the HOF-FAFU-1 fluorescent probe provided by the invention has better stability.
Referring to FIG. 4, it can be seen that the HOF-FAFU-1 fluorescent probe provided by the invention has the advantage of low usage.
Referring to FIG. 5, it can be seen that the HOF-FAFU-1 fluorescent probe provided by the invention has extremely high response speed to hypochlorite.
Referring to fig. 6 and 7, it can be seen from the figures that the HOF-FAFU-1 fluorescent probe provided by the invention has the advantages of high sensitivity, wide detection linear range and low detection lower limit, and has a good linear relationship for hypochlorite sensing.
Referring to FIGS. 8 and 9, it can be seen that the HOF-FAFU-1 fluorescent probe provided by the invention has the advantage of high selectivity.
In conclusion, after HOF-FAFU-1 adopted by the invention acts as a fluorescent probe and hypochlorite, the intensity of a blue luminescence center (about 420-450 nm) is gradually reduced, so that quantitative detection of hypochlorite in water including tap water is realized. The porous hydrogen bond organic frame-based fluorescent probe provided by the invention has the characteristics of good linear relation to hypochlorite sensing, good selectivity, wide linear range, low detection lower limit and the like. The fluorescent probe used by the invention also has the advantages of low use amount, simple synthesis process and strong operability, thus having wide application prospect.
While the foregoing is directed to embodiments, embodiments and methods of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A porous hydrogen bond organic skeleton-based fluorescent probe capable of quantitatively detecting hypochlorite is characterized in that the fluorescent probe is named HOF-FAFU-1, is a porous hydrogen bond organic skeleton material, and has a chemical formula of C 40 H 24 O 8 R 2 Is constructed by 3,3', 5' -tetra (4-carboxyphenyl) -4,4' -di R biphenyl ligand; wherein R is hydroxy, amino or alkoxy;
the single crystal structure of the HOF-FAFU-1 is monoclinic system, C2/m space group or triclinic system,a space group; the unit cell parameters of the catalyst slightly change with the difference of R groups;
the HOF-FAFU-1 is formed by connecting four carboxyl groups in 3,3', 5' -tetra (4-carboxyphenyl) -4,4' -di-R-biphenyl through intermolecular hydrogen bonds, so as to form a two-dimensional hydrogen bond network with 4,4 lattices;
in the HOF-FAFU-1 structure, biphenyl in 3,3', 5' -tetra (4-carboxyphenyl) -4,4' -di-R-base biphenyl molecules is in coplanar or slightly deviates from the coplanar, and 4,4 grids are subjected to pi-pi action between layers, so that a three-dimensional porous hydrogen bond organic framework material is formed.
2. The porous hydrogen bond organic skeleton-based fluorescent probe capable of quantitatively detecting hypochlorite ions according to claim 1, wherein the ligand constituting the fluorescent probe is any one or more of 3,3'5,5' -tetrakis (4-carboxyphenyl) -4,4' -dihydroxybiphenyl, 3'5,5' -tetrakis (4-carboxyphenyl) -4,4' -diaminobiphenyl, 3'5,5' -tetrakis (4-carboxyphenyl) -4,4' -dialkoxybiphenyl.
3. The porous hydrogen bond organic skeleton-based fluorescent probe for quantitatively detecting hypochlorite ions according to claim 1, wherein the HOF-FAFU-1 is a porous material containing one-dimensional diamond-shaped pore channels with the size of(15.4±1.0)×(15.4±1.0) Å 2 The porosity is 45-50%; the pore canal and the porosity change with the difference of R groups.
4. The porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite ions according to claim 1, wherein the rapid microcrystalline synthesis method of HOF-FAFU-1 is specifically as follows:
3,3', 5' -tetra (4-carboxyphenyl) -4,4' -di-R biphenyl is dispersed in a solvent by ultrasonic to prepare a solution, then a reagent is added at a certain temperature, and the solution is stirred, kept stand, and finally filtered or centrifuged to obtain HOF-FAFU-1 powder crystal.
5. The porous hydrogen-bonded organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite ions according to claim 4, wherein the solvent in the rapid microcrystalline synthesis method is any one or more of DMF, DMSO, DMA, DEF, DME; the reagent is a common solvent, and the solvent at least comprises one or more of acetonitrile, acetic acid, methanol, propanol, ethanol, diethyl ether, dichloromethane, chloroform, acetone, n-hexane, tetrahydrofuran/toluene/water; the concentration of the solution is between zero and saturated solution, and comprises saturated solution; the reaction temperature is-50 ℃ to 150 ℃; stirring speed is 0-15000r/min, and stirring reaction time is 0-360 days; standing for 0-360 days.
6. Use of a fluorescent probe according to any one of claims 1-5 for hypochlorite detection in a body of water.
7. The use according to claim 6, wherein the hypochlorite test comprises a qualitative test and a quantitative test.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007039368A (en) * | 2005-08-02 | 2007-02-15 | Kyoto Univ | Organic acid and method for producing the same |
| CN106749364A (en) * | 2016-12-29 | 2017-05-31 | 江苏大学 | A kind of preparation and application of the fluorescent molecular probe for detecting hypochlorite ion |
| JP2020054801A (en) * | 2018-09-07 | 2020-04-09 | 旭化成株式会社 | Sorption material, specific substance capture system, and specific substance capture method |
| CN112345505A (en) * | 2020-11-04 | 2021-02-09 | 南京信息工程大学 | Method for detecting hypochlorite by using tetra (4-aminobiphenyl) ethylene and application |
| JP2021041314A (en) * | 2019-09-06 | 2021-03-18 | 旭化成株式会社 | Adsorption material, production method of adsorption material, and specific substance capturing system |
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| US7858598B2 (en) * | 2007-03-12 | 2010-12-28 | Morningside Ventures Limited & Versitech Limited | Reagents for detection of hypochlorous acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007039368A (en) * | 2005-08-02 | 2007-02-15 | Kyoto Univ | Organic acid and method for producing the same |
| CN106749364A (en) * | 2016-12-29 | 2017-05-31 | 江苏大学 | A kind of preparation and application of the fluorescent molecular probe for detecting hypochlorite ion |
| JP2020054801A (en) * | 2018-09-07 | 2020-04-09 | 旭化成株式会社 | Sorption material, specific substance capture system, and specific substance capture method |
| JP2021041314A (en) * | 2019-09-06 | 2021-03-18 | 旭化成株式会社 | Adsorption material, production method of adsorption material, and specific substance capturing system |
| CN112345505A (en) * | 2020-11-04 | 2021-02-09 | 南京信息工程大学 | Method for detecting hypochlorite by using tetra (4-aminobiphenyl) ethylene and application |
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