CN112940272A - Novel rare earth metal-organic framework compound and preparation method and application thereof - Google Patents
Novel rare earth metal-organic framework compound and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 60
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 84
- KMSGJQLNNGJOOD-UHFFFAOYSA-N 5-[3,6-dicarbamoyl-2-(3,5-dicarboxyphenyl)phenyl]benzene-1,3-dicarboxylic acid Chemical group C=1C(C(O)=O)=CC(C(O)=O)=CC=1C=1C(C(=O)N)=CC=C(C(N)=O)C=1C1=CC(C(O)=O)=CC(C(O)=O)=C1 KMSGJQLNNGJOOD-UHFFFAOYSA-N 0.000 claims description 29
- 239000013078 crystal Substances 0.000 claims description 14
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002189 fluorescence spectrum Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000008280 blood Substances 0.000 claims description 3
- 150000000914 Dysprosium Chemical class 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000011895 specific detection Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 8
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 abstract description 7
- IFRDCLSUUCZPMI-UHFFFAOYSA-N 5-(n-(4-carbamoylbenzoyl)-3,5-dicarboxyanilino)benzene-1,3-dicarboxylic acid Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N(C=1C=C(C=C(C=1)C(O)=O)C(O)=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 IFRDCLSUUCZPMI-UHFFFAOYSA-N 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- -1 ferric iron ions Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000004768 organ dysfunction Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
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- 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 relates to a novel rare earth metal-organic framework compound { [ Dy ]2(BDPT)1.5(DMF)4]·H2O}nThe chemical formula is { [ Dy { [2(BDPT)1.5(DMF)4]·H2O } n, belonging to the monoclinic system, space group C2/C, unit cell parameter
α is 90 °, β is 90.535(2), γ is 90 °, unit cell volume is
Z＝8，Dc＝1.233g/cm3. The invention synthesizes a compound { [ Dy ] with a novel structure by using a semi-rigid ligand di (3, 5-dicarboxyphenyl) terephthalamide containing amido bond and dysprosium ion through a solvothermal method2(BDPT)1.5(DMF)4]·H2O } n, which is capable of detecting Fe with high sensitivity3+With Fe2+。
Description
Technical Field
The invention relates to a novel rare earth metal-organic framework compound { [ Dy ]2(BDPT)1.5(DMF)4]·H2O}nAnd in detecting Fe3+With Fe2+The use of (1).
Background
Iron element is not only widely existed in life, but also is an important transition metal in life system. The detection of iron is particularly important because excess or deficiency of iron in a living body can cause a series of diseases such as organ dysfunction, anemia, insomnia, and even cancer. Most of iron elements exist in ferric iron and ferrous iron, the detection of ferric iron ions is reported more, but the detection of ferrous ions is rarely seen, and only a few examples of ferric iron ions are pure organic fluorescent molecules capable of detecting ferrous ions, so that the development of a novel material capable of detecting ferrous ions with high sensitivity is particularly important.
In recent decades, metal organic framework compounds have been favored by researchers because of their diversified structures and their important applications in optical, electrical, magnetic, chiral resolution, catalysis, fluorescence sensing, etc., wherein complexes with good fluorescence properties have great potential application values in fluorescence recognition and sensing of heavy metal ions, volatile organic small molecules, and nitroaromatics, and the selective design of metal organic framework compounds is especially important for exhibiting good fluorescence sensing performance. Therefore, the fluorescent material which can detect and identify ferrous ions with high sensitivity is designed and synthesized, and has great practical application value.
Disclosure of Invention
The invention designs and synthesizes a novel rare earth metal-organic framework compound { [ Dy ] by utilizing a semi-rigid organic ligand containing amido bond2(BDPT)1.5(DMF)4]·H2O}nThe product isThe compound can detect Fe with high sensitivity3+With Fe2+。
The invention provides a novel rare earth metal-organic framework compound, the chemical formula of which is { [ Dy2(BDPT)1.5(DMF)4]·H2O } n, belonging to the monoclinic system, space group C2/C, unit cell parameter
α is 90 °, β is 90.535(2), γ is 90 °, unit cell volume is
Z＝8，Dc＝1.233g/cm3；
In the formula: n is a natural number from 1 to plus infinity, BDPT is bis (3, 5-dicarboxyphenyl) terephthalamide, and DMF is N, N-dimethylformamide.
Preferably, any one of Sm (samarium), Er (erbium), Nd (neodymium), Tb (terbium) can replace Dy in the chemical formula.
The invention also provides a preparation method of the novel rare earth metal-organic framework compound, which comprises the following steps:
mixing bis (3, 5-dicarboxyphenyl) terephthalamide and dysprosium salt according to a molar ratio of 1: dissolving 0.5-2 in N, N' -Dimethylformamide (DMF), reacting at 70-120 deg.C for 1-5 days, cooling to room temperature to obtain colorless block crystal, filtering, and drying.
The novel rare earth metal-organic framework compound provided by the invention can be used for detecting Fe3+With Fe2+In particular for detecting Fe in blood2+. The specific detection process is as follows: the compound { [ Dy ]2(BDPT)1.5(DMF)4]·H2O } N in N, N-dimethylformamide to Fe2+And/or Fe3+After being stirred uniformly, the solution of (1) is subjected to fluorescence spectrum detection at 397 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the compound provided by the invention can selectively identify Fe3+With Fe2+And to Fe2+Is more highly recognized, and Fe3+With Fe2+The quenching rates for this compound were 94% and 98%, respectively;
2. the compound provided by the invention is p-Fe2+The detection has higher sensitivity, and the maximum detection limit is 1.03 multiplied by 10-7M。
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a compound;
FIG. 2 is an asymmetric building block of a compound;
FIG. 3 is a diagram of two binuclear dysprosium structures in a compound;
FIG. 4 is the ligand configuration and coordination pattern in the compound;
FIG. 5 is a stacking diagram of compounds (a) viewed along the b-axis, (b) viewed along the c-axis;
FIG. 6 is a TG-DSC profile of the compound;
FIG. 7 shows fluorescence emission peaks of compounds after adding different metal ions in DMF solution;
FIG. 8 is a graph comparing the quenching rates of different metal ions for compounds;
FIG. 9 shows the addition of different amounts of Fe to the compound2+Later SV plot;
FIG. 10 shows the compounds at low concentration of Fe2+And (4) a medium linear relation graph.
Detailed Description
The present invention is further described below by way of examples, but the present invention is not limited by these examples. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and dysprosium nitrate metal salt are mixed according to a molar ratio of 1: dissolving the 1 in N, N' -Dimethylformamide (DMF) solution, placing the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 80 ℃ for 3 days, slowly cooling to room temperature to obtain colorless blocky crystals, filtering, and drying at room temperature. Yield: 70 percent.
Example 2
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and dysprosium nitrate metal salt are mixed according to a molar ratio of 1: 0.5 is dissolved in N, N' -Dimethylformamide (DMF) solution, the whole mixed system is put into a polytetrafluoroethylene stainless steel reaction kettle, reacts for 3 days at 80 ℃, is slowly cooled to room temperature to obtain colorless blocky crystals, and is subjected to suction filtration and drying at room temperature. Yield: 65 percent.
Example 3
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and dysprosium nitrate metal salt are mixed according to a molar ratio of 1: 2 in N, N' -Dimethylformamide (DMF), putting the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 80 ℃ for 3 days, slowly cooling to room temperature to obtain colorless blocky crystals, filtering, and drying at room temperature. Yield: and 69 percent.
Example 4
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and dysprosium nitrate metal salt are mixed according to a molar ratio of 1: 2 in N, N' -Dimethylformamide (DMF), putting the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 70 ℃ for 5 days, slowly cooling to room temperature to obtain colorless blocky crystals, filtering, and drying at room temperature. Yield: 68 percent.
Example 5
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and dysprosium nitrate metal salt are mixed according to a molar ratio of 1: 2 in N, N' -Dimethylformamide (DMF), placing the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 120 ℃ for 1 day, slowly cooling to room temperature to obtain colorless blocky crystals, filtering, and drying at room temperature. Yield: 67%.
Example 6
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and samarium nitrate metal salt are mixed according to a molar ratio of 1: dissolving 1 in N, N' -Dimethylformamide (DMF) solution, placing the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 80 ℃ for 3 days, slowly cooling to room temperature to obtain blocky crystals with the same structure, filtering, and drying at room temperature. Yield: 65 percent.
Example 7
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) was mixed with a bait metal nitrate in a molar ratio of 1: dissolving 1 in N, N' -Dimethylformamide (DMF) solution, placing the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 80 ℃ for 3 days, slowly cooling to room temperature to obtain blocky crystals with the same structure, filtering, and drying at room temperature. Yield: and 64 percent.
Example 8
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) was mixed with a neodymium nitrate metal salt in a molar ratio of 1: dissolving 1 in N, N' -Dimethylformamide (DMF) solution, placing the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 80 ℃ for 3 days, slowly cooling to room temperature to obtain blocky crystals with the same structure, filtering, and drying at room temperature. Yield: and 63 percent.
Example 9
Bis (3, 5-dicarboxyphenyl) terephthalamide (BDPT) and terbium nitrate metal salt were mixed in a molar ratio of 1: dissolving 1 in N, N' -Dimethylformamide (DMF) solution, placing the whole mixed system in a polytetrafluoroethylene stainless steel reaction kettle, reacting at 80 ℃ for 3 days, slowly cooling to room temperature to obtain blocky crystals with the same structure, filtering, and drying at room temperature. Yield: 66 percent.
The properties of the novel rare earth metal-organic framework compounds prepared in the above embodiments are basically the same, and all the compounds can be used for detecting Fe3+With Fe2+In particular for detecting Fe in blood2+Therefore, the effects of the compound prepared in example 1 will be described below.
The powder diffractometer data of the compound was measured with an X-ray powder diffractometer, and the measured peak was consistent with the peak position fitted by the crystal structure data, demonstrating the purity of the compound crystal form powder, as shown in fig. 1.
X-ray single crystal diffraction measurements showed that the compound belongs to the monoclinic C2/C space group. The minimum asymmetric unit structure is shown in FIG. 2, and comprises two crystallographically independent dysprosium ions and one half-matchBody, 4 coordinated DMF molecules and one free water molecule. Wherein, one dysprosium ion is in polyhedral configuration and is connected with 8 oxygen atoms from 4 carboxyl groups and 2 DMF molecules; the other dysprosium ion is also polyhedral in configuration, linking 8 oxygen atoms from 5 carboxyl groups and 2 DMF molecules. Dysprosium ion is connected by two carboxyl groups to form dual-core dysprosium [ Dy ]2(COO)6(DMF)4]The structure of two double-core dysprosium structures is shown in FIG. 3.
Four carboxyl groups in the ligand are deprotonated, and a total of 6 dysprosium ions are connected by two monodentate chelation and two monodentate bonding. One BDPT ligand (with the occupancy of 0.5) adopts a mirror symmetry configuration and is connected with two Dy13+Ion and four Dy23+Ions, wherein the benzene ring in the middle of the ions is twisted in a point way, and the benzene rings at two ends of the ions are coplanar, as shown in the following (1); the other BDPT ligand (occupancy of 1) configuration is also somewhat distorted, connecting 3 Dy13+Ion and 3 Dy23+The benzene ring at one end is nearly coplanar with the benzene ring at the middle (dihedral angle of 11.9 °), and the other benzene ring is nearly perpendicular to the benzene ring at the middle (dihedral angle of 88.9 °), as shown in (2) below.
Double-core cluster composed of Dy1 and Dy2 ([ Dy)2(COO)6(DMF)4]) A total of 4 ligands are connected and extend infinitely on the (010) plane to form a three-position network structure, and a free water molecule is connected with an oxygen atom of the ligand through intermolecular hydrogen bonds, and the configuration and coordination mode of the ligand in the compound are shown in fig. 4. The three-dimensional network structure of the compound has one-dimensional spiral channels, the stacking diagram of the compound is shown in figure 5, and the porosity is 30 percent (the total volume in each unit cell is 30 percent) by using Mercury software analysis
Pore volume of
)。
The thermal stability of the compounds was measured with a simultaneous thermal analyzer, as shown in fig. 6.
A sample of 1mg of compound was ultrasonically dispersed in DMF solvent and its fluorescence spectrum was measured under the same test conditions. The measurement results show that the fluorescence emission spectrum of the compound in DMF is stronger than that of solid state, the maximum emission is 397nm, and the maximum emission peak has blue shift. DMF was chosen as the measurement solvent. In order to measure the fluorescence response of different metal ions to the compound, different metal ions M are added into DMF of the compoundn+(Mn+＝Na+、K+、Ca2+、Mg2+、Li+、Al3+、Ag+、Hg2+、Cd2+、Zn2+、Pb2+、Cr3+、Cu2+、Fe3+And Fe2+Nitrate or chloride at a concentration of 1mM) was thoroughly mixed, and then the fluorescence spectrum of the compound was measured again under the same measurement parameters, and the results are shown in fig. 7 to 8. The maximum fluorescence emission peak of the compound is unchanged, but the fluorescence intensity and the type of metal ions have obvious relationship. The experimental result shows that most metal ions have little influence on the fluorescence intensity of the compound, but Fe3+With Fe2+Has obvious quenching effect on the compound, and the quenching rate is 94 percent and 98 percent. This result indicates that the compound can selectively recognize Fe3+With Fe2+And to Fe2+The degree of recognition of (2) is higher.
To further explore the heavy metal ion Fe2+For quantitative fluorescence response of the compound, Fe with different concentrations is added into DMF solution of the compound2+Thereafter, the fluorescence intensity was measured again as shown in FIG. 9. The experimental result shows that the fluorescence intensity of the compound is dependent on Fe2+The concentration increases and decreases regularly.
To further study Fe2+Quantitative relationship between concentration and fluorescence intensity of compound by Stern-Volmer equation (I0/I) -1 ═ Ksv[M]To investigate Fe2+The quenching degree of the fluorescence of the compound by the ion pair, wherein I0 is the fluorescence intensity of the compound in DMF, and I is the fluorescence intensity after the addition of metal ionsFluorescence intensity, [ M ]]For adding the concentration (mol. L) of metal ions-1)，KsvIs the slope in the linear relationship obtained according to the formula.
The results show that at low concentrations, Fe2+The ion concentration of (A) shows a good linear response relation to the fluorescence intensity of the compound. Calculated from the linear fit (as shown in FIG. 10), compound vs. Fe2+K ofsv7.30X 104M each-11，R2The value is 0.99233. Using the formula DT-3 σ/Ksv(DT is detection limit, K)svSlope of linear relation summary, sigma is standard deviation measured 10 times) to calculate its maximum detection limit to 1.03 × 10-7M。KsvThe larger the ion concentration, the larger the influence of the ion concentration on the fluorescence intensity, and the higher the detection sensitivity. Compound pair Fe2+The detection of (2) achieves a relatively high sensitivity. Compound P-Fe in DMF solution2+The highly sensitive fluorescent response behavior of the ions is attributed to the uncomplexed amide active groups capable of interacting with the metal ions in the compound and Fe2+The presence of electron transfer processes between ions. Compound pair Fe2+The fluorescence detection system with high ion selectivity and high sensitivity has certain practical application value.
The above disclosure is only for the specific embodiment of the present invention, but the embodiment of the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (6)
1. A novel rare earth metal-organic framework compound is characterized in that the chemical formula is { [ Dy ]2(BDPT)1.5(DMF)4]·H2O } n, belonging to the monoclinic system, space group C2/C, unit cell parameter
α is 90 °, β is 90.535(2), γ is 90 °, unit cell volume is
Z＝8，Dc＝1.233g/cm3；
In the formula: n is a natural number from 1 to plus infinity, BDPT is bis (3, 5-dicarboxyphenyl) terephthalamide, and DMF is N, N-dimethylformamide.
2. The novel rare earth metal-organic framework compound according to claim 1, wherein any of Sm, Er, Nd, Tb can replace Dy in the chemical formula.
3. The process for the preparation of a novel rare earth metal-organic framework compound according to claim 1, characterized in that it comprises the following steps:
mixing bis (3, 5-dicarboxyphenyl) terephthalamide and dysprosium salt according to a molar ratio of 1: dissolving 0.5-2 in N, N' -dimethylformamide solution, reacting at 70-120 deg.C for 1-5 days, cooling to room temperature to obtain colorless bulk crystal, filtering, and drying.
4. The use of the novel rare earth metal-organic framework compound according to claim 1 for detecting Fe3+With Fe2+The use of (1).
5. The use of the novel rare earth metal-organic framework compound according to claim 4 in the detection of Fe in blood2+The use of (1).
6. The use according to claim 4 or 5, wherein the specific detection process is as follows: the compound { [ Dy ]2(BDPT)1.5(DMF)4]·H2O } N in N, N-dimethylformamide to Fe2+And/or Fe3+After being stirred uniformly, the solution of (1) is subjected to fluorescence spectrum detection at 397 nm.
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