CN111848664A - Receptor compound for colorimetric detection of fluoride ions, and preparation method and application thereof - Google Patents
Receptor compound for colorimetric detection of fluoride ions, and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 94
- -1 fluoride ions Chemical class 0.000 title claims abstract description 59
- 238000001514 detection method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001450 anions Chemical class 0.000 claims abstract description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- DOPJTDJKZNWLRB-UHFFFAOYSA-N 2-Amino-5-nitrophenol Chemical compound NC1=CC=C([N+]([O-])=O)C=C1O DOPJTDJKZNWLRB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000003814 drug Substances 0.000 claims abstract description 9
- 239000005457 ice water Substances 0.000 claims abstract description 9
- 239000012429 reaction media Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- MMNLHUHQFDVPSQ-UHFFFAOYSA-N N=C=O.CCO[Si](OCC)(OCC)C(C)C Chemical compound N=C=O.CCO[Si](OCC)(OCC)C(C)C MMNLHUHQFDVPSQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 116
- 238000012360 testing method Methods 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 206010016818 Fluorosis Diseases 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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- 206010033799 Paralysis Diseases 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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Abstract
The invention discloses a receptor compound for colorimetric detection of fluoride ions, and a preparation method and application thereof, belongs to the technical field of anion detection, and solves the problem that the existing detection method is inconvenient. The acceptor compound of the invention is 2-hydroxy-4-nitrophenylureidopropyltriethoxysilane. The preparation method comprises the following steps: taking acetone as a reaction medium, magnetically stirring the isopropyltriethoxysilane isocyanate and the 2-hydroxy-4-nitroaniline according to the molar ratio of 1: 1.1-1.8 at 30-80 ℃, reacting for 3-5 h, cooling, pouring the medicine into an ice water bath for crystallization, precipitating yellow solid, and carrying out suction filtration to obtain the product. The receptor compounds of the present invention are useful for colorimetric detection of fluoride ions. The 2-hydroxy-4-nitrophenyl group is adopted as a signal reporting group, so that the receptor has the capability of colorimetric identification; the urea group is used as a recognition site, so that the compound can be better combined with fluoride ions, and can be used as a receptor compound for detecting and recognizing the fluoride ions.
Description
Technical Field
The invention belongs to the technical field of anion detection, and particularly relates to a receptor compound for colorimetric detection of fluoride ions, and a preparation method and application thereof.
Background
With the rapid development of supramolecular chemistry, the recognition anion of receptor compound plays an important role in supramolecular chemistry, and the anion has great application value in the scientific fields of life science, chemistry, pharmacy, catalytic chemistry, environmental chemistry and the like, especially the anion with high selectivity recognizes the receptor compoundObjects have received a great deal of attention. However, there are not many receptor compounds that can be used for anion recognition, and noncovalent anion coordination chemistry has been developed more slowly than cationic, neutral molecules. Therefore, the design of synthetic anion sensors is receiving increasing attention from researchers. The fluoride ion is an anion which has important influence on life system, and the proper amount of fluoride ion taken by human body can prevent dental caries and osteoporosis. However, excessive fluorine ion intake can cause fluorosis, which can cause fluorosis, sclerotin hardening and hyperosteogeny of bones, limit the movement of bone joints, even bend over hump, paralysis and completely lose labor capacity. Typically, fluoride ions pass through an ion selective electrode and19f NMR nuclear magnetic resonance, but these methods all require expensive instruments and complex testing procedures. Colorimetric detection of fluoride ions is a method for changing the color of a solution of a receptor compound after the receptor compound selectively binds to fluoride ions, and the method has the advantages of no need of expensive instruments, simplicity in operation and the like, so that the method is widely researched. The designed and synthesized fluorine ion identified receptor compound has the advantages of various structures, strong adjustability, strong selectivity, high sensitivity, wide identification range and the like, develops a novel fluorine ion colorimetric detection material which can be stably stored and is easy to carry, store and use, and has higher application value.
Disclosure of Invention
The invention aims to provide a receptor compound (2-hydroxy-4-nitrophenyl urea propyl triethoxysilane) for colorimetric detection of fluoride ions, so as to solve the problem that the existing detection method is inconvenient.
It is another object of the present invention to provide a method for preparing receptor compounds for colorimetric detection of fluoride ions.
It is a further object of the present invention to provide the use of receptor compounds for colorimetric detection of fluoride ions.
The technical scheme of the invention is as follows:
(I) receptor compound
An acceptor compound, 2-hydroxy-4-nitrophenyl urea propyl triethoxysilane, for colorimetric detection of fluoride ions, having the formula:
(II) preparation method
A method of preparing a receptor compound for colorimetric detection of fluoride ions comprising the steps of:
synthesis of 2-hydroxy-4-nitrophenylureidopropyltriethoxysilane: using acetone as a reaction medium, magnetically stirring the isopropyltriethoxysilane isocyanate and the 2-hydroxy-4-nitroaniline according to a molar ratio of 1: 1.1-1.8 at 30-80 ℃, reacting for 3-5 h, cooling, pouring the medicine into an ice water bath for crystallization, precipitating yellow solid, and performing suction filtration to obtain a target product. The product synthesized by the method is detected by a melting point nuclear magnetic resonance spectrometer, an infrared spectrum, an element analysis and an ultraviolet spectrum, and the success of synthesizing the target product is proved.
The synthetic route is as follows:
the characterization data of the prepared receptor compound are as follows, m.p. 115-118 ℃; IR (KBr, cm)-1): 3377(O-H), 2975 (CH2), 1668 (C=O), 1514, 1281(-NO2), 1074(Si-O-C) 822, 778(C-H).1HNMR(DMSO/d 6 , 400 MHz), : 11.55(s, 1H, OH), : 9.02(s, 2H, NH), : 8.20(d,1H, Ar-H), : 7.71 (d, 1H, Ar-H), : 7.03(s, 1H, Ar-H), : 3.76(s, 6H, CH2),: 3.35(d, 2H, CH2), : 3.08(d, 2H, CH2), : 1.16(s, 9H, CH3), : (d,2H,CH2).13C NMR(63 MHz, DMSO-d6, ppm): 140.0(C=O), 129.6(C=N), 111.7, 114.0,112.9。
(III) application
Use of the receptor compound for colorimetric detection of fluoride ion according to claim 1 for colorimetric detection of fluoride ion.
Further, in DMSO solutions of the receptor compounds, F-By adding a DMSO solution of the receptor compoundThe color changed from yellow to red, while the addition of other anions had no significant effect on the color of the DMSO solution of the acceptor compound.
Further, in DMSO solutions of the receptor compounds, F-The addition of (a) causes the ultraviolet-visible spectrum of the DMSO solution of the acceptor compound to have a corresponding absorption peak at 450nm, while the addition of other anions has no obvious influence on the ultraviolet-visible spectrum of the DMSO solution of the acceptor compound.
Further, 1-10 mol/L hydrochloric acid is used for soaking clean filter paper for 1-5 hours, the filter paper is taken out and washed by distilled water to be neutral, and the filter paper is placed in a vacuum oven for drying. Soaking the filter paper in a DMSO solution of the receptor compound until the filter paper is completely uniform, taking out the filter paper, and placing the filter paper in a vacuum oven for drying to obtain the test paper of the receptor compound for colorimetric detection of the fluoride ions.
Further, a DMSO solution containing anions was dropped on a test strip for colorimetric detection of a receptor compound for fluorine ions, and when the test strip for colorimetric detection of a receptor compound for fluorine ions encountered F-containing-The test strip changes color from white to brown, and other ions have no significant color response to the test strip. The change of the color of the test paper shows that the receptor compound shows a single selective colorimetric identification effect on the fluorine ions, which shows that the test paper can efficiently, conveniently, quickly and conveniently detect the fluorine ions.
The invention has the beneficial effects that: the receptor compound 2-hydroxy-4-nitrophenyl urea propyl triethoxysilane provided by the invention adopts a 2-hydroxy-4-nitrophenyl group as a signal reporting group, so that the receptor has a colorimetric identification capability; the urea group is used as a recognition site, so that the compound can be better combined with fluoride ions, and therefore, the compound can be used as a receptor compound for detecting and recognizing the fluoride ions. The preparation method is simple and convenient to operate. The invention can be realized in DMSO and H2F, the fluorine ions are selectively identified by naked eye colorimetry in the O mixed solution-Respectively has a minimum detection limit of 2.8176 × 10 -7And M. The test paper can be used for efficiently, conveniently and quickly detecting fluorine ions.
Drawings
FIG. 1 shows acceptor compounds in DMSO solution (2X 10)-5mol/L) UV-vis spectra when interacting with various anions (50 eqV);
FIG. 2 is a DMSO solution (2X 10-5 mol. L.) of the receptor compound-1) In-line dropwise adding FAUltraviolet-visible spectrum change diagram of (1);
FIG. 3 is a nuclear magnetic resonance carbon spectrum of an acceptor compound;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of an acceptor compound;
fig. 5 is a simulation of the ion identification process.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention in any way.
Examples 1,
1. Synthesis of receptor compounds
Adding 2-hydroxy-4-nitroaniline and isocyanatopropyltriethoxysilane into a 50mL round-bottom flask, taking 30mL acetone as a reaction medium, enabling the isocyanatopropyltriethoxysilane and the 2-hydroxy-4-nitroaniline to be in a molar ratio of 1:1.2, magnetically stirring at 40 ℃, reacting for 4 hours, cooling, pouring the medicine into an ice water bath for crystallization, separating out yellow solid, and performing suction filtration to obtain an acceptor compound 2-hydroxy-4-nitrophenyl urea propyltriethoxysilane.
2. Anion recognition assay for receptor compounds
0.5mL of the receptor in DMSO (2X 10) was pipetted separately-4mol/L) in a series of 10mL cuvettes. Separately adding FA、ClA、BrA、IA、CH3COOA、HSO4 A、H2PO4 A、ClO4 A0.5mL of a DMSO solution (0.01mol/L) of tetrabutylammonium salts of anions was diluted to 5mL scales with DMSO so that the concentration of each anion was 50 times the concentration of the receptor, mixed well and left overnight, and the UV-visible absorption spectrum (DMSO as a reference) was measured at 25 ℃ to examine the response of each receptor to anions. As a result, it was found that DMSO solution (2X 10) in the receptor-5mol/L) is added with F—In DMSO (50eqV) of tetrabutylammonium salt, the color of the receptor solution changed significantly: change from yellow to red; while the addition of other anions had no significant effect on the color of the DMSO solution of the receptor. Prove that the receptor can selectively recognize F in colorimetric way—. A large number of experiments prove that the receptor compound for colorimetric detection of fluoride ions has obvious single colorimetric identification capability on fluoride ions in a mixed system of water and DMSO.
FIG. 1 shows the receptor compounds in DMSO solution (2X 10)-5mol/L) UV-vis spectra when interacting with various anions (50 eqV). As can be seen from FIG. 1, F is in the UV-visible spectrum —The addition of (2) causes the corresponding absorption peak of the acceptor solution to appear at 450 nm. While the addition of other anions had no significant effect on the uv spectrum of the DMSO solution of acceptor. These phenomena and results demonstrate that the receptor compounds enable the colorimetric detection of F in DMSO solutions—。
3. Measurement experiment of ultraviolet-visible (UV) spectrum
Preparation of receptor solution: accurately weighing 0.08g of receptor in a 10mL volumetric flask, dissolving with DMSO and diluting to the mark to make the concentration of receptor 2X 10-2mol·L-1. 1mL of the solution was transferred to a 10mL volumetric flask and diluted to the mark with DMSO to a concentration of 2X 10-3mol·L-1. Sequentially diluting to make the concentration of the main solution 2 × 10-4mol·L-1. 0.5mL of the receptor in DMSO (2X 10) was pipetted separately-4mol·L-1) In 5mL cuvettes numbered No. 1, No. 2, No. 3, No. 4, No. 5, No. 6, No. 7, No. 8, No. 9, No. 10. No. 1 tube was made up to 5mL with DMSO without addition of any other reagent (for the purpose: as a reference for the host without any anion), and 9 other cuvettes were made up to 0.5mL F-、Cl-、Br-、I-、HSO4 -、H2PO4 -、NO3 -、AcO-、ClO4 -DMSO solution of tetrabutylammonium salt (0.01 mol. L)-1) Then the volume is determined to be 5mL by DMSO so that the concentration of various anions isThe concentration of the main body is 50 times, the mixture is evenly mixed and then is kept stand overnight, and the ultraviolet-visible absorption spectrum of the mixture is measured at 25 ℃. (DMSO as reference) DMSO (2X 10) receptor -5mol·L-1) In the solution, the UV-Vis spectrum has a maximum absorption peak at 380nm when no anion is added, after 50 times of anion is added, the absorption peak at 380nm disappears, and F at 460nm-A strong absorption peak appears, and F is added-The absorbance is obviously higher than that of other anions added into the receptor, which indicates that the receptor is opposite to F in DMSO solution-Has strong recognition effect.
FIG. 2 shows a DMSO solution of the receptor compound (2X 10)-5mol•L-1) In-line dropwise adding F—Ultraviolet-visible spectrum change diagram. FIG. 2 shows the cumulative loading of increasing amounts of anion F with constant concentration of immobilized acceptor compound in DMSO solution—The ultraviolet-visible spectrum of the concentration of (a) gradually changes. When no anion is added, the maximum absorption peak of the acceptor compound is at 350nm, and anion F is added—The obvious change of the absorption spectrum of the receptor compound is caused later, the maximum absorption peak at 350nm is gradually reduced, two new absorption peaks appear at about 280nm and 450nm and are gradually enhanced, the peaks are the absorption peaks of the receptor compound and anions which are complexed to form a complex, and the phenomenon shows that the binding of the receptor compound and the anions further promotes the intramolecular charge transfer. Absorbance at 280nm, 450nm with F —The concentration is increased until the balance is reached, 2 equal absorption points appear at the positions of about 320nm and 380nm, the color of the solution is changed from light yellow to orange yellow, and the stable complex generation of the main body and the anion is further illustrated.
4. Ultraviolet-visible Spectroscopy (UV-Vis) titration
The concentrations of the two were (2X 10)-5mol·L-1) 3mL of the receptor solution in a quartz cuvette, and adding the anion F separately by an accumulative addition method-、H2PO4 -And AcO-Tetrabutylammonium DMSO (0.01 mol. L)-1) Stirring the solution with a closed capillary tube, standing for 5 min to ensure that the receptor solution and the anion solution in the quartz cuvette are dissolvedThe solution was fully reacted and then the UV-visible absorption spectrum of the system during titration was followed at 25 ℃. Using the absorbance value of the highest peak after red shift to calculate each receptor and F respectively by the least square curve fitting program-、H2PO4 -And AcO-The complexation constant Ks of action and the correlation coefficient R.
The complex constant (Ks) of the receptor compound binding to fluoride ion was determined by uv titration, Ks =0.440 × 10-4It is demonstrated that the synthetic acceptor compounds of the present invention form stable complexes with fluoride ions.
According to the ultraviolet-visible spectrum titration, nuclear magnetic resonance hydrogen spectrum titration and Job curve analysis of the receptor R and the fluorine ions, the receptor and the fluorine ions react in a ratio of 1: 1 and are combined with each other in a hydrogen bond mode. As shown in FIG. 5, a reaction mechanism of the acceptor compound for binding with the fluoride ion is proposed, and it can be seen that N-H in the acceptor compound is simultaneously bound with the fluoride ion with O-H on the aromatic ring to form an acceptor-F-complex, but no significant deprotonation behavior is found.
5. Nuclear magnetic titration experiment
Taking a nuclear magnetic tube, adding a solution of an acceptor compound, measuring the nuclear magnetic resonance hydrogen spectrum of the acceptor compound, then sequentially adding anion tetrabutylammonium salt with different multiples into the nuclear magnetic tube, and respectively measuring the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of the acceptor compound at 25 ℃ (see figure 3 and figure 4), thereby proving that the acceptor compound is successfully synthesized.
6. Determination of the minimum detection limit of an anion by a receptor compound
Similarly, in order to explore the application value of the receptor in real life, a titration fitting curve is made by using a calculation method of CL =3Sb/b (wherein CL is a detection limit, Sb is a standard deviation, and b is the slope of a correction curve in a low concentration region) through ultraviolet spectrum titration data, so that the lowest detection limit is determined, and a main body pair, F, is obtained through calculation-,Respectively has a minimum detection limit of 2.8176 × 10-7And M. 7. Anti-interference experiment in identification system
0.50mL of the recipient in DMSO (2X 10) was pipetted using a 1.00 mL pipette-4mol, L-1) in a series of cuvettes, each cuvetteAdding distilled water in certain proportion, and adding F-, Cl-, Br-, I-, CH3COO-,HSO4 -,H2PO4 -, CN-，CIO4 -，NO3 -0.50mL of DMSO solution (0.01 mol. L-1) of tetrabutylammonium salt, mixing uniformly, standing, measuring its UV-visible absorption spectrum (DMSO as reference) at 25 deg.C to eliminate interference of other anions on selective recognition of receptors, and testing the interference resistance of other anions on receptors in DMSO and H by the above-mentioned interference resistance test 2The selective recognition of the fluorine ions in the O mixed solution has no obvious interference, so that the colorimetric recognition can be realized.
8. Applications of
In DMSO solutions of the receptor compounds, F-The addition of (b) changed the color of the DMSO solution of the acceptor compound from yellow to red, while the addition of the other anion had no significant effect on the color of the DMSO solution of L.
In DMSO solutions of the receptor compounds, F-The addition of (a) causes the ultraviolet-visible spectrum of the DMSO solution of the acceptor compound to have a corresponding absorption peak at 450nm, while the addition of other anions has no obvious influence on the ultraviolet-visible spectrum of the DMSO solution of the acceptor compound.
Manufacturing the anion identification test paper: the clean filter paper is soaked in 1 mol of hydrochloric acid per liter for 1 hour, the filter paper is taken out and washed by distilled water to be neutral, and the filter paper is placed in a vacuum oven for drying. Soaking filter paper in DMSO (dimethylsulfoxide) solution of an acceptor compound until the filter paper is completely uniform, taking out the filter paper, placing the filter paper in a vacuum oven for drying to obtain test paper of the acceptor compound for colorimetric detection of fluorine ions, and cutting the test paper into the test paper for later use. Adding DMSO solution containing anions dropwise onto a test strip for colorimetric detection of a receptor compound for fluorine ions, when the test strip for colorimetric detection of a receptor compound for fluorine ions encounters a test strip containing F -The test strip changes color from white to brown, and other ions have no significant color response to the test strip.
Examples 2,
Adding 2-hydroxy-4-nitroaniline and isocyanatopropyltriethoxysilane into a 50mL round-bottom flask, taking 30mL acetone as a reaction medium, enabling the isocyanatopropyltriethoxysilane and the 2-hydroxy-4-nitroaniline to be in a molar ratio of 1:1.8, magnetically stirring at 30 ℃, reacting for 4 hours, cooling, pouring the medicine into an ice water bath for crystallization, separating out yellow solid, and performing suction filtration to obtain an acceptor compound 2-hydroxy-4-nitrophenyl urea propyltriethoxysilane.
Examples 3,
Adding 2-hydroxy-4-nitroaniline and isocyanatopropyltriethoxysilane into a 50mL round-bottom flask, taking 30mL acetone as a reaction medium, enabling the isocyanatopropyltriethoxysilane and the 2-hydroxy-4-nitroaniline to be in a molar ratio of 1:1.5, magnetically stirring at 50 ℃, reacting for 4 hours, cooling, pouring the medicine into an ice water bath for crystallization, separating out yellow solid, and performing suction filtration to obtain an acceptor compound 2-hydroxy-4-nitrophenyl urea propyltriethoxysilane.
Examples 4,
Adding 2-hydroxy-4-nitroaniline and isocyanatopropyltriethoxysilane into a 50mL round-bottom flask, taking 30mL acetone as a reaction medium, enabling the isocyanatopropyltriethoxysilane and the 2-hydroxy-4-nitroaniline to be in a molar ratio of 1:1.5, magnetically stirring at 60 ℃, reacting for 4 hours, cooling, pouring the medicine into an ice water bath for crystallization, separating out yellow solid, and performing suction filtration to obtain an acceptor compound 2-hydroxy-4-nitrophenyl urea propyltriethoxysilane.
Examples 5,
Adding 2-hydroxy-4-nitroaniline and isocyanatopropyltriethoxysilane into a 50mL round-bottom flask, taking 30mL acetone as a reaction medium, enabling the isocyanatopropyltriethoxysilane and the 2-hydroxy-4-nitroaniline to be in a molar ratio of 1:1.1, magnetically stirring at 70 ℃, reacting for 3h, cooling, pouring the medicine into an ice water bath for crystallization, separating out yellow solid, and performing suction filtration to obtain an acceptor compound 2-hydroxy-4-nitrophenyl urea propyltriethoxysilane.
Examples 6,
Adding 2-hydroxy-4-nitroaniline and isocyanatopropyltriethoxysilane into a 50mL round-bottom flask, taking 30mL acetone as a reaction medium, enabling the isocyanatopropyltriethoxysilane and the 2-hydroxy-4-nitroaniline to be in a molar ratio of 1:1.1, magnetically stirring at 80 ℃, reacting for 5 hours, cooling, pouring the medicine into an ice water bath for crystallization, separating out yellow solid, and performing suction filtration to obtain an acceptor compound 2-hydroxy-4-nitrophenyl urea propyltriethoxysilane.
Example 7,
Manufacturing the anion identification test paper: the clean filter paper is soaked in 10 mol/L hydrochloric acid for 5 hours, the filter paper is taken out and washed by distilled water to be neutral, and the filter paper is placed in a vacuum oven for drying. Soaking filter paper in DMSO (dimethylsulfoxide) solution of an acceptor compound until the filter paper is completely uniform, taking out the filter paper, placing the filter paper in a vacuum oven for drying to obtain test paper of the acceptor compound for colorimetric detection of fluorine ions, and cutting the test paper into the test paper for later use. Adding DMSO solution containing anions dropwise onto a test strip for colorimetric detection of a receptor compound for fluorine ions, when the test strip for colorimetric detection of a receptor compound for fluorine ions encounters a test strip containing F -The test strip changes color from white to brown, and other ions have no significant color response to the test strip.
Claims (7)
1. A receptor compound for colorimetric detection of fluoride ions characterized by the structural formula:
a method of preparing the receptor compound for colorimetric detection of fluoride ion according to claim 1, comprising the steps of:
synthesis of 2-hydroxy-4-nitrophenylureidopropyltriethoxysilane: using acetone as a reaction medium, magnetically stirring the isopropyltriethoxysilane isocyanate and the 2-hydroxy-4-nitroaniline according to a molar ratio of 1: 1.1-1.8 at 30-80 ℃, reacting for 3-5 h, cooling, pouring the medicine into an ice water bath for crystallization, precipitating yellow solid, and performing suction filtration to obtain a target product.
2. Use of the receptor compound for colorimetric detection of fluoride ion according to claim 1 for colorimetric detection of fluoride ion.
3. Use of the receptor compound for the colorimetric detection of fluoride ions according to claim 3, characterized in that: in DMSO solutions of the receptor compounds, F-The addition of (a) causes the color of the DMSO solution of the acceptor compound to change from yellow to red, while the addition of other anions has no significant effect on the color of the DMSO solution of the acceptor compound.
4. Use of the receptor compound for the colorimetric detection of fluoride ions according to claim 3, characterized in that: in DMSO solutions of the receptor compounds, F-The addition of (a) causes the ultraviolet-visible spectrum of the DMSO solution of the acceptor compound to have a corresponding absorption peak at 450nm, while the addition of other anions has no obvious influence on the ultraviolet-visible spectrum of the DMSO solution of the acceptor compound.
5. Use of the receptor compound for the colorimetric detection of fluoride ions according to claim 3, characterized in that: soaking clean filter paper for 1-5 hours by using 1-10 mol of hydrochloric acid per liter, taking out the filter paper, washing the filter paper to be neutral by using distilled water, and placing the filter paper in a vacuum oven for drying.
6. Soaking the filter paper by using the receptor compound until the filter paper is completely and uniformly soaked, taking out the filter paper, and placing the filter paper in a vacuum oven for drying to obtain the receptor compound test paper for colorimetric detection of the fluoride ions.
7. Use of the receptor compound for the colorimetric detection of fluoride ions according to claim 6, characterized in that: adding DMSO solution containing anions dropwise onto a test strip for colorimetric detection of a receptor compound for fluorine ions, when the test strip for colorimetric detection of a receptor compound for fluorine ions encounters a test strip containing F -The test strip changes color from white to brown, and other ions have no significant color response to the test strip.
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