CN114436817A - Porous hydrogen bond organic skeleton-based fluorescent probe capable of quantitatively detecting hypochlorite and application thereof - Google Patents
Porous hydrogen bond organic skeleton-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 78
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 69
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 18
- -1 4-carboxyphenyl Chemical group 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 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 36
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- 239000013384 organic framework Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000013081 microcrystal Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001308 synthesis method Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims 4
- 238000002360 preparation method Methods 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 3
- 230000008569 process Effects 0.000 abstract description 2
- 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
- 230000004044 response Effects 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 239000000872 buffer Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 230000035945 sensitivity 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
- 239000007853 buffer solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 125000002091 cationic group Chemical class 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 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
- 239000010840 domestic wastewater Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 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
- 238000000746 purification Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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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
- C07C65/01—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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- 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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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 as HOF-FAFU-1, and the chemical formula of the novel porous hydrogen bond organic skeleton is C40H24O8R2Consisting of a 3,3 ', 5 ' -tetrakis (4-carboxyphenyl) -4,4 ' -di R groupBiphenyl (named as 4, 4' -R-BPTC) ligand, wherein, the R group can be hydroxyl, amino, alkoxy, etc. The structure of HOF-FAFU-1 is that 4, 4' -R-BPTC is firstly connected into a two-dimensional hydrogen bond network with 4,4 lattices 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 skeleton-based fluorescent probe has the characteristics of good linear relation on the sensing of hypochlorite, good selectivity, wide linear range, low detection lower limit and the like. The fluorescent probe used in the invention also has the advantages of low usage amount, simple synthesis process and strong operability, thereby 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 skeleton-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)-) It is widely used for drinking water disinfection, paper bleaching, domestic and industrial waste water purification, and is a strong bactericide and disinfectant. Hypochlorite (ClO) in tap water-) The residual concentration is usually controlled within the range of 0.01-10 mM, and is very important for detecting the content of the residual concentration. Excessive hypochlorite produces many toxic substances to cause tissue damage and various diseases such as alzheimer's disease, cardiovascular disease, etc., while insufficient hypochlorite cannot sterilize. Therefore, it is very necessary to develop a hypochlorite detector with high sensitivity and high selectivity.
Disclosure of Invention
In order to solve the problems, the invention synthesizes a novel porous hydrogen bond organic framework as a fluorescent probe (named as HOF-FAFU-1) which is p-chlorate (ClO)-) The detection has the advantages of fast response, high selectivity, wide detection linear range, low detection lower limit and the like. The first purpose of the invention is to prepare a novel porous hydrogen bond organic framework material (HOF-FAFU-1) by a simple synthetic method; the second purpose of the invention is to provide a fluorescent probe which has the characteristics of simple operation, high sensitivity and selectivity, high response speed, low detection limit and the like, thereby realizing the quantitative detection of hypochlorite in water bodies 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 is named as HOF-FAFU-1, and the chemical formula of the fluorescent probe is C40H24O8R2Is composed of 3,3 '5, 5' -tetraThe (4-carboxyl phenyl) -4,4 '-di R biphenyl (named as 4, 4' -R-BPTC) ligand. Wherein, the 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) and 3,3 ', 5' -tetrakis (4-carboxyphenyl) -4,4 '-dialkoxybiphenyl (4, 4' -RO-BPTC), and the like, and may also be 4,4 '-OH-BPTC, 4, 4' -NH2-BPTC and 4, 4' -RO-BPTC in any ratio of mixed ligands.
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, and the unit cell parameters of different R groups have slight changes, for example, when the R group is hydroxyl, the unit cell parameters are as follows:
α＝γ＝90.00°,β＝94.89,
and when the R group is amino, the unit cell parameters are as follows:
α＝γ＝90.00°,β＝97.59,
HOF-FAFU-1 may also belong to the triclinic system,
space group, the unit cell parameters of different R groups are the same with minor differences, such as when the R group is hydroxyl, the unit cell parameters are:
α＝100.17°,β＝90.84,γ＝93.07°,
further, the structure of HOF-FAFU-1 is such that carboxyl groups in 4,4 ' -R-BPTC molecules, i.e., 3 ', 5 ' -tetrakis (4-carboxyphenyl) -4,4 ' -diradicals of biphenyl such as 3,3 ', 5 ' -tetrakis (4-carboxyphenyl) -4,4 ' -dihydroxybiphenyl, are connected by intermolecular hydrogen bonds, i.e., carboxylic acid-carboxylic acid double hydrogen bonds, to form a two-dimensional network having a 4,4 lattice. In the structure of HOF-FAFU-1, biphenyl in the molecule of 4, 4' -R-BPTC is basically in a coplanar state (can be slightly deviated from the coplanar state), and the 4,4 lattices form a three-dimensional porous hydrogen-bonding organic framework material through pi-pi action between layers.
Furthermore, the HOF-FAFU-1 fluorescent probe is a brand new crystalline porous material, which contains one-dimensional rhombic pore canals with the pore canal size
The porosity is 45-50%, and the pore canal and porosity can slightly change with 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 microcrystal synthesis, and the specific synthesis steps are as follows:
the slow single crystal synthesis method is specifically as follows:
ultrasonically dissolving a ligand 3,3 ', 5 ' -tetra (4-carboxyphenyl) -4,4 ' -biriphenyl in a solvent to prepare a solution, then adding steam of a reagent into the solution in a steam natural diffusion mode at a certain temperature and standing, and standing for diffusion to obtain a bulk crystal of HOF-FAFU-1.
Further, the mass of the 4, 4' -R-BPTC ligand is 0.01-100 g; the solvent is one or more of DMF, DMSO, DMA, DEF, DME and the like which can dissolve 4, 4' -R-BPTC ligand, and the volume of the solvent is 0.01-4 mL; wherein, the reagent is 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, etc.; 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 microcrystal synthesis method is concretely as follows:
ultrasonically dispersing 3,3 ', 5 ' -tetra (4-carboxyphenyl) -4,4 ' -biriphenyl in a solvent to prepare a solution, then adding a reagent at a certain temperature, stirring, standing, and finally filtering or centrifuging to obtain HOF-FAFU-1 powder crystals.
Further, the mass of the 4, 4' -R-BPTC ligand is 0.01-100 g; the solvent is one or more of DMF, DMSO, DMA, DEF, DME and the like which can dissolve 4, 4' -R-BPTC ligand, and the volume of the solvent is 0.01-4 mL; wherein, the reagent is 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, etc.; the reaction temperature is-50-150 ℃; the stirring speed is 0-15000 r/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 scheme has the following advantages:
1) the invention adopts a slow diffusion method and a rapid synthesis method to prepare a porous hydrogen bond organic framework HOF-FAFU-1 fluorescent probe capable of detecting hypochlorite.
2) The HOF-FAFU-1 fluorescent probe has the advantages of simple synthesis steps, good material stability, strong operability and wide application prospect
3) The hypochlorite fluorescent probe provided by the invention has extremely short response time, wide linear range, low detection limit and good selectivity, and can be used as a very potential candidate 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 structural diagram of a HOF-FAFU-1 fluorescent probe according to the present invention;
FIG. 2 is a graph of fluorescence spectra of a fluorescent probe suspension 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 the fluorescent probe in Tris-HCl buffer solutions of 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 the fluorescent probe suspension 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 the response time of the fluorescent probe of the present invention to hypochlorite in Tris-HCl buffer (10mM) at pH 4.0; wherein the abscissa represents the wavelength and the ordinate represents the fluorescence intensity ratio (I)422/I0)。
FIG. 6 is a graph showing the change of fluorescence spectra of the fluorescent probe of the present invention in response to different concentrations of hypochlorite in Tris-HCl buffer (10mM) 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 of the fluorescent probe of the present invention in Tris-HCl buffer (10mM) at pH 4.0 (I)422) A linear relationship of change; wherein the abscissa represents the concentration of hypochlorite and the ordinate represents the fluorescence intensity ratio (I)422/I0)。
FIG. 8 shows a series of cationic Li ions in Tris-HCl buffer (10mM) at pH 4.0 in the presence and absence of hypochlorite+,Na+,K+,NH4 +,Ca2+, Ba2+,Mg2+,Eu3+Bar graph of the effect on fluorescence ratio; wherein the abscissa represents the cation species and the ordinate represents the fluorescence intensity ratio (I)422/I0)。
FIG. 9 shows an anion F of a fluorescent probe of the present invention without any treatment in a Tris-HCl buffer (10mM) at pH 4.0 in the presence and absence of hypochlorite-,Cl-,Br-, SO4 2-,HCO3-,CO3-,PO4 3-,HPO4 2-,H2PO4-,NO3 -,CH3COO-And H2O2Bar graph of the effect on fluorescence ratio; wherein the abscissa represents the cation species and the ordinate represents the fluorescence intensity ratio (I)422/I0)。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: slow single crystal synthesis of fluorescent probe HOF-FAFU-1
4, 4' -OH-BPTC (10mg) was ultrasonically dispersed in DMF (1mL) and then placed in a small bottle, and the small bottle was placed in a large bottle, which was covered with acetonitrile and a lid, and allowed to stand at normal temperature for one week to obtain the fluorescent probe of the present invention.
Example 2: slow single crystal synthesis of fluorescent probe HOF-FAFU-1
Reacting 4, 4' -NH2BPTC (10mg) was ultrasonically dispersed in DMF (1mL) and then placed in a small vial, and the small vial was placed in a large vial, which was covered with acetonitrile and a lid, and allowed to stand at normal temperature for one week to obtain the fluorescent probe of the present invention.
Example 3: slow single crystal synthesis of fluorescent probe HOF-FAFU-1
4, 4' -RO-BPTC (10mg) was ultrasonically dispersed in DMF (1mL) and then placed in a small bottle, and the small bottle was placed in a large bottle, which was covered with acetonitrile and a lid, and allowed to stand at normal temperature for one week to obtain the fluorescent probe of the present invention.
Example 4: slow single crystal synthesis of fluorescent probe HOF-FAFU-1
Selection of 4, 4' -NH2-BPTC, 4,4 '-OH-BPTC or 4, 4' -OCH3One or two or three ligands of-BPTC were mixed in an arbitrary ratio to give a complex ligand (total 10mg), ultrasonically dispersed in DMF (1mL), followed by placing in a small bottle, placing in a large bottle, placing acetonitrile in the large bottle and covering with a lid, and standing at normal temperature for one week to obtain the fluorescent probe of the present invention.
Example 5: rapid microcrystal synthesis of fluorescent probe HOF-FAFU-1
4, 4' -OH-BPTC (10mg) was ultrasonically dispersed in DMF (0.1mL), followed by addition of acetonitrile (0.9mL), stirring at room temperature for 2h, and centrifugation to give the fluorescent probe of the present invention.
Example 6: rapid microcrystal synthesis of fluorescent probe HOF-FAFU-1
Reacting 4, 4' -NH2BPTC (10mg) was ultrasonically dispersed in DMF (0.1mL), followed by addition of acetonitrile (0.9mL), stirring at room temperature for 2h, and centrifugation to give the fluorescent probe of the present invention.
Example 7: rapid microcrystal synthesis of fluorescent probe HOF-FAFU-1
4, 4' -RO-BPTC (10mg) was ultrasonically dispersed in DMF (0.1mL), followed by addition of acetonitrile (0.9mL), stirring at room temperature for 2h, and centrifugation to give the fluorescent probe of the present invention.
Example 8: rapid microcrystal synthesis of fluorescent probe HOF-FAFU-1
Selection of 4, 4' -NH2-BPTC, 4,4 '-OH-BPTC or 4, 4' -OCH3One or two or three ligands of-BPTC are mixed in any ratio to give a complex ligand (total 10mg), ultrasonically dispersed in DMF (0.1mL), followed by addition of acetonitrile (0.9mL), stirring at room temperature for 2h, and centrifugation to give the fluorescent probe of the present invention.
Example 9: application of fluorescent probe in the invention
Firstly, preparing 50.00mg/L suspension of HOF-FAFU-1 fluorescent probe and water, adding 1.900mL of probe suspension into 0.1000mL of Tris-HCl buffer solution with the pH value of 4.0, and then adding sodium hypochlorite (NaClO) solutions with different concentrations prepared by tap water. The experimental result shows that the fluorescent probe material is used for ClO-The detection limit of (3) is 0.005mM, and the detection performance of the fluorescent probe on sodium hypochlorite within the concentration range of 0.005-0.5 mM is good, which shows that the fluorescent probe can quantitatively detect the content of residual chlorine in tap water. Therefore, the fluorescent probe has important application value for quantitative detection of hypochlorite in tap water.
Referring to the attached figures 2 and 3, it can be seen that the long-term storage and pH change have no obvious influence 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 present invention has the advantage of low usage amount.
Referring to FIG. 5, it can be seen that the HOF-FAFU-1 fluorescent probe provided by the present invention has an extremely fast response speed to hypochlorite.
Referring to FIGS. 6 and 7, it can be seen 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 the HOF-FAFU-1 fluorescent probe has good linear relation for sensing hypochlorite.
Referring to FIGS. 8 and 9, it can be seen that the HOF-FAFU-1 fluorescent probe provided by the present invention has the advantage of high selectivity.
In conclusion, after the HOF-FAFU-1 adopted by the invention is used as a fluorescent probe to act with hypochlorite, the intensity of a blue luminescence center (about 420-450nm) is gradually reduced, thereby realizing the quantitative detection of hypochlorite in tap water in a water body. The porous hydrogen bond organic frame-based fluorescent probe provided by the invention has the characteristics of good linear relation, good selectivity, wide linear range, low detection lower limit and the like on the sensing of hypochlorite. The fluorescent probe used in the invention also has the advantages of low usage amount, simple synthesis process and strong operability, thereby having wide application prospect.
The above-mentioned embodiments are further described in detail for the purpose of illustrating the invention, and it should be understood that the above-mentioned embodiments are only illustrative of the preferred embodiments of the present invention, and are not to be construed as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The porous hydrogen bond organic skeleton-based fluorescent probe capable of quantitatively detecting hypochlorite is characterized by being a porous hydrogen bond organic skeleton material with a chemical formula of C40H24O8R2Is constructed by 3,3 ', 5 ' -tetra (4-carboxyphenyl) -4,4 ' -di R biphenyl ligand; wherein, the R group is hydroxyl, amino or alkoxy.
2. The porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 1, characterized in that the ligand for constructing 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, and 3,3 ' 5,5 ' -tetrakis (4-carboxyphenyl) -4,4 ' -dialkoxybiphenyl.
3. The porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 1, characterized in thatWherein the single crystal structure of the HOF-FAFU-1 is monoclinic, C2/m space group, or triclinic,
a space group; the unit cell parameters vary slightly with the R group.
4. The porous hydrogen-bonding organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 1, characterized in that HOF-FAFU-1 is formed by connecting four carboxyl groups in 3,3 ' 5,5 ' -tetra (4-carboxyphenyl) -4,4 ' -di R-biphenyl through intermolecular hydrogen bonding, so as to form a two-dimensional hydrogen bonding network with 4,4 lattices;
in the HOF-FAFU-1 structure, biphenyl in 3,3 ', 5 ' -tetra (4-carboxyphenyl) -4,4 ' -di R biphenyl molecules is in a coplanar state or slightly deviates from a coplanar state, and a 4,4 lattice forms a three-dimensional porous hydrogen bond organic framework material through pi-pi action between layers.
5. The porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 1, wherein the HOF-FAFU-1 is a porous material containing one-dimensional rhombic pores with the pore size of
The porosity is 45-50%; the pore channel and porosity change with the difference of R groups.
6. The porous hydrogen bonding organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 1, wherein the preparation method of the HOF-FAFU-1 comprises a slow single crystal synthesis method and a fast microcrystal synthesis method;
the slow single crystal synthesis method is specifically as follows:
ultrasonically dissolving a ligand 3,3 ', 5 ' -tetra (4-carboxyphenyl) -4,4 ' -birphenyl in a solvent to prepare a solution, and diffusing steam generated by a reagent into the solution at a certain temperature to obtain a bulk crystal of HOF-FAFU-1;
the rapid microcrystal synthesis method is concretely as follows:
ultrasonically dispersing 3,3 ', 5 ' -tetra (4-carboxyphenyl) -4,4 ' -biriphenyl in a solvent to prepare a solution, then adding a reagent at a certain temperature, stirring, standing, and finally filtering or centrifuging to obtain HOF-FAFU-1 powder crystals.
7. The porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 6, wherein the solvent in the slow single crystal synthesis method is any one or more of DMF, DMSO, DMA, DEF and 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 the solution comprises saturated solution; the reaction temperature is-50 ℃ to 150 ℃; standing for 0-360 days.
8. The porous hydrogen bond organic framework-based fluorescent probe capable of quantitatively detecting hypochlorite according to claim 6, wherein the solvent in the rapid microcrystal synthesis method is any one or more of DMF, DMSO, DMA, DEF and 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 the solution comprises saturated solution; the reaction temperature is-50 ℃ to 150 ℃; stirring at 0-15000r/min for 0-360 days; standing for 0-360 days.
9. Use of a fluorescent probe according to any one of claims 1 to 8 in the detection of hypochlorite in a body of water.
10. The use of claim 9, wherein the hypochlorite detection comprises qualitative detection and quantitative detection.
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| JP2007039368A (en) * | 2005-08-02 | 2007-02-15 | Kyoto Univ | Organic acid and method for producing the same |
| US20080274560A1 (en) * | 2007-03-12 | 2008-11-06 | Versitech Limited | Reagents for detection of hypochlorous acid |
| 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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| JP2007039368A (en) * | 2005-08-02 | 2007-02-15 | Kyoto Univ | Organic acid and method for producing the same |
| US20080274560A1 (en) * | 2007-03-12 | 2008-11-06 | Versitech Limited | Reagents for detection of hypochlorous acid |
| 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 |
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