CN115677530B - Halogenated Schiff base Zn (II) complex Zn- χ -L and preparation method and application thereof - Google Patents
Halogenated Schiff base Zn (II) complex Zn- χ -L and preparation method and application thereof Download PDFInfo
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- 239000002262 Schiff base Substances 0.000 title claims abstract description 28
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 28
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 25
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
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- 239000000126 substance Substances 0.000 claims abstract description 7
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- 229910021645 metal ion Inorganic materials 0.000 description 6
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
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- OHFTVPYOVGHQSI-UHFFFAOYSA-N 3-iminopropan-1-ol Chemical group OCCC=N OHFTVPYOVGHQSI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
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- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
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- 125000006414 CCl Chemical group ClC* 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a halogenated Schiff base Zn (II) complex Zn- χ -L and a preparation method and application thereof, wherein the preparation method of the halogenated Schiff base Zn (II) complex Zn- χ -L is that 3-bromo-5-chlorosalicylaldehyde and 1, 3-propanediamine are added into ethanol solution to be stirred for 1.5-3 h, then zinc chloride (II) and ultrapure water are added, the mixture is stirred for 1-2 hours and then filtered to obtain filtrate, the filtrate is slowly volatilized at room temperature to obtain colorless transparent crystals, the colorless transparent crystals are washed and filtered by polar solvent for multiple times, and finally the target complex is obtained by natural volatilization and drying. The application of the halogenated Schiff base Zn (II) complex Zn- χ -L is the application of the halogenated Schiff base Zn (II) complex Zn- χ -L as a fluorescent probe in detecting specific nitroarene pollutants 2-NP. The halogenated Schiff base Zn (II) complex Zn- χ -L provided by the invention has higher specificity and sensitivity to nitroarene pollutant 2-NP as a probe molecule, and Zn- χ -L not only can be used for 2-NP detection in a solution, but also can be used for visual detection of 2-NP in a gas phase based on a paper sensor, and has high response speed (less than 30 seconds), so that the halogenated Schiff base Zn (II) complex Zn- χ -L has great potential as a chemical sensor of explosive steam.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a halogenated Schiff base Zn (II) complex Zn- χ -L, and a preparation method and application thereof.
Background
Nitroarenes (NACs) are important chemical products, which have been used in industry as early as one hundred years ago, and are important raw materials or intermediates in explosive, dye, pesticide, organic synthesis. With the rapid development of industry and agriculture, the application of nitroaromatics is wider, and the pollution problem is also becoming serious. In industrial production, they are buried in soil as solid waste or discharged into rivers through sewage, which causes serious pollution to soil and water resources and seriously affects the production life and physical health of people. In addition to the environmental hazards, NACs has become the first choice for manufacturing explosives in criminal activity by the international terrorist organization due to its wide sources, ease of manufacture, low cost, etc. However, the nitroarene derivatives are various, and can be classified into mononitrocompounds, dinitro compounds and polynitro compounds according to the number of nitro groups, and can be classified into monocyclic arenes, polycyclic arenes and the like according to the types of parent aromatic rings, so that the different nitrocompounds have great differences in properties, and how to rapidly and accurately identify and distinguish the nitrocompounds is a problem to be solved.
In recent years, a variety of advanced techniques have been developed to detect and differentiate NACs, such as UV-Vis spectrophotometry, gas chromatography, high performance liquid chromatography, fluorescence detection, and the like. However, the above technology generally has the problems of expensive instruments and equipment, complex operation, long sample pre-purification treatment time and the like, and the test environment is easily interfered by external factors, so that a plurality of inconveniences still exist in actual use. Molecular probes can form characteristic macroscopic signals such as light, electricity, magnetism and the like through specific molecular base interaction, and have great interest of scientists due to the advantages of good selectivity, high sensitivity, simple operation, quick response, low detection limit, real-time in-situ detection and the like. At present, the design and synthesis of high-performance NACs fluorescent molecular probes have become a popular topic in various fields such as chemistry, analysis, material science and the like.
NACs are electron-deficient entities and the detection mechanism associated with probe molecules is mainly due to Photoinduced Electron Transfer (PET), although fluorescence detection of NACs has achieved many good results, traditional molecular probes are mostly pi conjugated systems, and the interaction between NACs and probe molecules is pi interaction and binding force is limited, so that it is still a challenge how to enhance the intensity of the interaction between probe molecules and NACs and improve the sensitivity. It is noted that structurally 2-NPs, unlike many NACs, exist as a special chelate structure formed by a special-OH and nitro group that can theoretically interact with a strongly electronegative molecule to form a strong hydrogen bond. Among the numerous molecular probes, the easily available Schiff base complex is widely used in the field of luminescence sensors due to its unique characteristics of narrow emission band, large Stokes shift, long luminescence lifetime, etc. In addition, salen as an organic ligand can provide a stable N2O2 coordination environment for binding to different transition metal atoms at the horizontal plane, and the remaining two axial coordination sites can bind to different functional fragments and various molecular types of materials. The water molecules can be used as a hydrogen bond formed by coordination of the ligand and the metal atom, plays an important role in self-assembled supermolecular frames, and provides an effective path for molecular recognition and electron transmission or proton conduction. Therefore, effective utilization of the coordinated water molecules is expected to become a key for constructing a high-performance probe. Unfortunately, since water molecules often act as 'quenchers' in fluorescent materials, the role of water molecules in probe molecules is rarely mentioned and studied.
On the other hand, the modification and regulation effects of halogen atoms on functional molecules gradually become research hot spots of various subjects such as life sciences and material sciences in recent years. The o-nitrophenol (2-NP) is a pollutant seriously harming social safety and ecological environment, and has important significance for detection. However, because the composition and the structure of different nitroaromatic compounds are similar, the general molecular probe is difficult to accurately distinguish the ortho-nitrophenol from other nitroaromatic compounds, so that the development of a simple, quick and effective 2-NP trace detection and identification probe has important significance.
Disclosure of Invention
The first object of the invention is to provide a halogenated Schiff base Zn (II) complex Zn- χ -L, the second object of the invention is to provide a preparation method of the halogenated Schiff base Zn (II) complex Zn- χ -L, and the third object of the invention is to provide application of the halogenated Schiff base Zn (II) complex Zn- χ -L.
The first object of the invention is achieved in that the structural formula of the complex Zn- χ -L is shown as the formula (I):
。
the second object of the invention is achieved in that the preparation method of the halogenated Schiff base Zn (II) complex Zn- χ -L is characterized by comprising the following steps:
1) Adding 3-bromo-5-chlorosalicylaldehyde and 1, 3-propanediamine into an ethanol solution, and stirring for 1.5-3 hours;
2) Adding zinc (II) chloride and ultrapure water, stirring for 1-2 hours, and filtering to obtain a filtrate;
3) And slowly volatilizing the filtrate at room temperature to obtain colorless transparent crystals, washing with a polar solvent for multiple times, filtering, and finally naturally volatilizing and drying to obtain the target complex.
The third object of the invention is realized in such a way that the application of the halogenated Schiff base Zn (II) complex Zn- χ -L is the application of the halogenated Schiff base Zn (II) complex Zn- χ -L as a fluorescent probe in the detection of specific nitroarene pollutants 2-NP.
The beneficial effects of the invention are as follows:
1. the invention provides a halogenated Schiff base Zn (II) complex Zn- χ -L composed of heterohalogen salen ligand, which has simple preparation method, can be prepared at normal temperature, and has the yield as high as 52 percent.
2. The halogenated Schiff base Zn (II) complex Zn- χ -L provided by the invention has higher specificity and sensitivity to nitroarene pollutant 2-NP as a probe molecule. The test result shows that the introduction of halogen atoms can obviously reduce the delta E of the probe molecules, thereby improving the light excitation efficiency. The Zn central axis coordinated water molecule can obviously improve the detection rate of 2-NP. In addition, the probe molecule can overcome the interference of various external bad factors (for example, the influence of the solvent is very small, the intensity in different solvents is basically unchanged, and the same fluorescence quenching result can be generated under the interference of metal ions or other nitroaromatic compounds), thereby improving the accurate identification of 2-NP. In addition, zn- χ -L can be used for detecting 2-NP in solution, a paper sensor based on the Zn- χ -L can be used for detecting 2-NP in gas phase in a visual way, and the response speed is high (less than 30 seconds), so that the Zn- χ -L has great potential as a chemical sensor of explosive steam.
3. The invention provides a simple and effective method for detecting trace o-nitrophenol 2-NP in time, which is easy to operate, good in stability and high in precision and reliability. The Zn- χ -L is used as a chemical sensor of 2-NP, which is not only suitable for long-term outdoor detection, but also can meet the requirements of national security and environmental detection in certain fields.
Drawings
FIG. 1 is a synthetic scheme of Zn- χ -L, zn- χ -L-Non aqueous and Zn-L in example 1, comparative example 1 and comparative example 2;
FIG. 2 is a diagram of a bat of Zn-X-L molecular structure of example 1;
FIG. 3 is a graph showing the intermolecular interactions of Zn- χ -L in example 1; a is a supermolecular dimer formed by multiple O.H bonds between adjacent molecules, b is a dislocation face-to-face pi-pi stacking action schematic diagram between adjacent molecules, c is a unit cell three-dimensional stacking diagram of Zn- χ -L along a c axis;
FIG. 4 is a three-dimensional packing diagram of Zn-X-L unit cells, wherein the left diagram is a three-dimensional packing diagram of Zn-X-L unit cells along the a-axis, and the right diagram is a three-dimensional packing diagram of Zn-X-L unit cells along the b-axis;
FIG. 5 is a FT-IR chart of Zn-X-L-Non aque prepared in comparative example 1;
FIG. 6 is a FT-IR chart of Zn-L prepared in comparative example 2;
FIG. 7 is a graph of fluorescence quenching efficiency for the same concentrations (120. Mu.M) of 2-NP,4-NP,2-NT,4-NT, DNT, and TNT added to different Schiff bases;
FIG. 8 is a graph of the variation of the emission spectrum of Zn- χ -L prepared in example 1 (λex=393 nm) versus different concentrations (0-120. Mu.M) of 2-NP;
FIGS. 9A, b and c are Stern-Volmer plots of different concentrations of 2-NP in Zn- χ -L-Non-aqueous, zn-L and Zn- χ -L, respectively;
FIG. 10 is a fitted plot of Zn- χ -L quenched by 2-NP;
in FIG. 11, a is a competition test of different solvents for Zn- χ -L, blue bar: quenching efficiency of the Zn- χ -L solution with different solvents (100. Mu.L), red bars: different solvents (100. Mu.L) were added to the Zn- χ -L solution, followed by quenching efficiency after adding 2-NP at the same concentration (120. Mu.M); b is a competition test of different nitroaromatics on Zn- χ -L, wherein the Zn- χ -L solution is added with different aromatics with the same concentration (120 mu M) and then added with 2-NP with the same concentration (120 mu M) to quench the Zn- χ -L solution; c is a competitive test of different metal ions on Zn- χ -L, wherein the quenching efficiency after adding different metal ions with the same concentration (120 mu M) and 2-NP with the same concentration (120 mu M) into the Zn- χ -L solution;
FIG. 12 is a schematic diagram of the fluorescent sensor strip prepared in example 2 for detecting 2-NP vapor.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples, but is not limited in any way to any changes or modifications made based on the teachings of the invention, which fall within the scope of the invention.
The invention provides a halogenated Schiff base Zn (II) complex Zn- χ -L, the structural formula of which is shown as the formula (I):
the crystallographic data and structural refinement parameters of the complex Zn- χ -L are shown in Table 1:
table 1 crystallographic data and structural refinement parameters of Zn- χ -L
The invention also provides a preparation method of the halogenated Schiff base Zn (II) complex Zn- χ -L, which is realized according to the following steps:
1) Adding 3-bromo-5-chlorosalicylaldehyde and 1, 3-propanediamine into an ethanol solution, and stirring for 1.5-3 hours;
2) Adding zinc (II) chloride and ultrapure water, stirring for 1-2h, and filtering to obtain filtrate;
3) And slowly volatilizing the filtrate at room temperature to obtain colorless transparent crystals, washing with a polar solvent for multiple times, filtering, and finally naturally volatilizing and drying to obtain the target complex.
The molar ratio of the 3-bromo-5-chlorosalicylaldehyde, the 1, 3-propanediamine and the zinc (II) chloride is 2:1:1.
The volume ratio of the 1, 3-propylene diamine, the ethanol and the ultrapure water is 1:5000-500000:250-25000.
The polar solvent is ethanol.
The invention further provides application of the halogenated Schiff base Zn (II) complex Zn- χ -L as a fluorescent probe for detecting specific nitroarene pollutants 2-NP.
Example 1
0.024g of 3-bromo-5-chlorosalicylaldehyde (0.1 mmol) and 4.28. Mu.l of 1, 3-propanediamine (0.05 mmol) were added sequentially to an ethanol solution (20 mL) and stirred at room temperature for 2h. Then, 0.007g of zinc (II) chloride (0.05 mmol) was added to the above mixture, and 1mL of ultrapure water was further added, and the resulting yellow solution was stirred for 1 hour and filtered. After slow evaporation for 3 days, colorless transparent crystals were obtained, which were washed with ethanol several times and dried in air to give [ Zn (3 Br5 Cl-salpn) ] (Zn- χ -L) in a yield of 52%. The reaction formula is as shown in the following formula (II) (figure 1):
。
structural characterization:
and determining the structure of Zn-X-L in a Zn-X-L crystal sample conforming to the single crystal test at 148K. X-ray structural analysis shows that Zn- χ -L crystals belong to orthorhombic system, pnma space group, and are typical mononuclear salen complexes with 0D structure. As shown in FIG. 2, the asymmetric unit is composed of a neutral Zn- χ -L unit with independent crystallization, the asymmetric unit is composed of zinc atoms at the special position of the symmetry axis, and the other half of the molecules are symmetrically generated by symmetry codes (x, 1/2-y, z). The coordination environment of the Zn atom is in a double pyramid configuration (a in fig. 3), the zinc atom level is occupied by two oxygen atoms and two nitrogen atoms from the chelate heterohalogen salen ligand, and the two water molecules are coordinated in the axial direction. Search results from the sisal-bridge crystallography database (CSD) showed that Znsalen compounds with axial occupation by water molecules were less common in salen family, zn- χ -L represented the first Znsalen compound composed of heterohalogensalen ligands, as shown in fig. 3b and c, each heterohalogen salen-as a tetradentate ligand provided a { N2O2} level coordinated with Zn center, i.e., two imino nitrogen atoms (Nim) and two phenolic oxygen atoms O, where Ni-Nam bond length was 2.122, ni-O bond 2.087, and water molecules in axial direction were 2.17 and 2.12, respectively, bond angles ranging from 87.00 (7) ° to 95.86 (8) °, bond length and bond angle such that the center Zn ion exhibited slightly distorted octahedral geometry. These characteristic bond lengths of the Zn- χ -L studied were substantially consistent with those reported previously for salen-type complexes. 3-iminopropan-1-ol group A (N1/C7/C1/N2/O1) and 3-bromoo-5-chlorobenzene group (C1-C6/Br 1/Cl 2) are planar.
Ring folding studies showed the folding amplitude of chelate ring (Zn 1/O1/C2/C1/C7/N1)Q=0.312(3)Å，θ=63.6(6)°，ϕThe folding amplitude of chelate ring (Zn 1/N1/C8/C9/C8i/C9 i) =3.7 (7) °, andQ=0.534(5)Å，θ=138.7(4)°，ϕfolding amplitude of chelate ring (Zn 1/O1i/C2i/C1i/C7i/N1 i) =360.0 (6) °Q=0.312(3)Å，θ=116.4(6)°，ϕ=183.7 (7) °, these molecules are linked to each other by an O-H … O bond, forming a one-dimensional supramolecular chain along the a-axis, where OH is from water and the acceptor O-atom is from a 3-iminopropan-1-ol group, as shown in fig. 4 and table 2. In addition to hydrogen bonding, pi-pi stacking interactions are formed between the interdigitated molecules, which contributes to further stabilization of the crystal stack. Benzene rings (C1-C6) at asymmetric positions participate in pi-pi stacking interactions of benzene ring misplanes at (1/2+x, 1/2-y, 3/2-z) and (-1/2+x, 1/2-y, 3/2-z) positions, and the centroid distance is 3.917A.
TABLE 2 geometric information of Hydrogen bonds
Symmetry codes: (i) x+1/2, -y+1/2, -z+3/2; (ii) x-1/2, -y+1/2, -z+3/2
Example 2
The test method of this example was essentially the same as that of example 1, with 200mL of ethanol solution and 10mL of ultrapure water being added.
Example 3
The test method of this example was basically the same as that of example 1, and the stirring time after adding the ethanol solution was 3 hours, and the stirring time after adding zinc chloride was 2 hours.
Example 4
The test method of this example was basically the same as that of example 1, and the stirring time after adding the ethanol solution was 2.5 hours, and the stirring time after adding zinc chloride was 1.5 hours.
Example 5
The test method of this example was basically the same as that of example 1, and the stirring time after adding the ethanol solution was 2 hours, and the stirring time after adding zinc chloride was 2 hours.
Example 6 preparation of fluorescence sensing test paper for detection of 2-NP
A round test paper with a radius of 7cm was placed in the concentration of 1X 10 prepared in example 1 -2 Soaking in ethanol solution of Zn- χ -L for 24h to ensure that solute can be absorbed to the surface and enter the pores of all test papers, then taking out with tweezers, putting into a beaker, and drying for 30min at 80 ℃ in an oven to obtain the fluorescent sensing test papers.
Comparative example 1 Synthesis of Zn- χ -L-Non aque
0.024g of 3Br5 Cl-salicylaldehyde (0.1 mmol) and 4.28. Mu.l of 1, 3-propanediamine (0.05 mmol) were added sequentially to an ethanol solution (20 mL) and stirred at room temperature for 2h. Then, 0.007g of zinc (II) chloride (0.05 mmol) was added to the above mixture, and the resulting yellow solution was stirred for another 1h and filtered. The prepared solution was dried in vacuo at 110 ℃ for 4h in a rotary evaporator to give a yellow powder (yield 48%). FT-IR (KBr, cm) -1 ):1590(C=N),1349(C=C),1194(C-O),1105(C-N),656(C-Br), 606(C-Cl), 417 (Zn-O, zn-N) (FIG. 5), formula (III) (FIG. 1):
synthesis of comparative example 2 Zn-L
10.2. Mu.L of salicylaldehyde (0.1 mmol) and 4.28. Mu.L of 1, 3-propanediamine (0.05 mmol) were added sequentially to an ethanol solution (20 mL) and stirred at room temperature for 2h. Then, 0.007g of zinc (II) chloride (0.05 mmol) was added to the above mixture, and the resulting brown-yellow solution was stirred for 1 hour and filtered. The prepared solution was dried in vacuo at 110 ℃ for 4h in a rotary evaporator to give a tan powder (43% yield). FT-IR (KBr, cm) -1 ) 1594 (c=n), 1351 (c=c), 1191 (C-O), 1106 (C-N), 424 (Zn-O, zn-N) (fig. 6), formula (IV) (fig. 1):
detection example 1 Zn- χ -L for detection of nitroaromatic 2-NP
The prepared concentration is 1×10 -2 The Zn-X-L ethanol solution, the Zn-X-L-Non-aque ethanol solution and the Zn-L ethanol solution are respectively diluted to 1X 10 -4 mmol/mL, then shaken at room temperature for 10s to ensure adequate mixing. 0-120. Mu.M of 2-NP was mixed with each of the above solutions, respectively, and then fluorescence spectra were immediately measured, while 120. Mu.M of a mixed solution of 4-NP,2-NT,4-NT, DNT, TNT and Zn- χ -L was also prepared, and fluorescence spectra thereof were measured (λex=393 nm).
1. Comparison of quenching efficiency of different Schiff bases on different nitroaromatics
The six most typical nitroaromatic contaminants 2-NP,4-NP,2-NT,4-NT, DNT and TNT in commercial production were selected and compared for their fluorescent response in different Schiff bases (Zn- χ -L, zn- χ -L-Non aqueouse, zn-L) under the same conditions.
Results: as can be seen from FIG. 7, the 2-NP has the strongest fluorescence quenching effect among the six substances, and the quenching efficiency of Zn- χ -L is extremely high, which indicates that Zn- χ -L can be used as a high-sensitivity fluorescence sensing platform for detecting 2-NP.
2. Detection limit calculation of Zn- χ -L on 2-NP
As shown in fig. 8, the fluorescence intensity gradually decreased with increasing 2-NP concentration and reached the maximum quenching degree at 120 μm (qe=97%). The increase in the number of nitro groups increases the electron deficiency of the nitroaromatic molecules, thereby increasing the degree of fluorescence quenching, indicating that the fluorescence intensity of Zn- χ -L is largely dependent on the concentration of 2-NP, confirming the sensitivity of Zn- χ -L to 2-NP.
We calculated the quench coefficients using the stem-Volmer (SV) equation (fig. 9): i 0 /I=1+Ksv[A]Wherein I is 0 And I are the luminescence intensity before and after addition of 2-NP, ksv is the quenching coefficient, [ A ]]The molar concentration of the 2-NP, zn- χ -L, zn- χ -L-Non-aquos, and the quenching coefficient Ksv of the Zn-L to the 2-NP were 3.3X10, respectively 4 M -1 ，5.2×10 3 M -1 ，4.1×10 2 M -1 . The detection limits (which may be standard deviation according to equation 3σ/S, σ, and S is the slope of the linear fit) are 2.2 μM,7.5 μM, and 11.6 μM, respectively. At the same time (I) 0 There is a good linear relationship between-I)/I and 2-NP concentration, as shown in FIG. 10, and the calibration equation is Y=0.012X+0.008 (R) in the range of 0-60. Mu.M 2 =0.998), in another linear relationship y=0.004x+0.503 (R) at high concentrations (60-120 μm 2 =0.992), the detection limit of 2-NP (standard deviation can be found according to equation 3σ/S, σ, and the slope of the linear fit is found for S) is 2.2 μm, and compared with the organic substances known in the art (table 3), zn- χ -L provided by the present invention is most sensitive to 2-NP.
TABLE 3 detection limit comparison of Complex probes for 2-NP assay
3. Determination of quenching time of Zn- χ -L to 2-NP
The detection method comprises the following steps: the concentration was 1X 10 -2 The Zn- χ -L ethanol solution was placed under an ultraviolet lamp (365 nm) and then dropped into 120. Mu.M 2-NP solutionImmediately, the fluorescent light was quenched and then the time was ended.
The determination shows that the Zn- χ -L ethanol solution has very strong fluorescence, but after 120 mu M of 2-NP is added, the fluorescence is quenched rapidly at about 15s, and compared with Zn- χ -L-Non-aque, under the same condition, the sensitivity of Zn- χ -L-Non-aque to 2-NP is reduced greatly, and the fluorescence is quenched completely at about 2 min. This may be related to strong hydrogen bonding on Zn- χ -L, i.e., the water molecules bound on Zn- χ -L form hydrogen bonding paths, providing an efficient transport path for electrons. The current study of 2-NP quenching time is less, but the known quenching time is longer for its analog 4-NP, which also indicates that Zn- χ -L has extremely high sensitivity to 2-NP.
Detection example 2 Zn- χ -L anti-interference Capacity detection
1. Anti-solvent tamper capability detection
The prepared concentration is 1×10 -2 Is diluted to 1X 10 in ethanol solution of Zn- χ -L -4 mmol/mL, and shaken at room temperature for 10s to ensure thorough mixing. Then the same volume (100. Mu.L) of a different type of solvent (EtOH, meOH, ACN, THF, DMAC, DMF, BDO, GL, NMP, EG, DMSO) was added and mixed with Zn-X-L, and then the fluorescence spectrum was measured immediately. Meanwhile, based on the above solution, a mixed solution of 2-NP was prepared with 120 μm added thereto, and its fluorescence spectrum (λex=393 nm) was measured.
Results: as shown in FIG. 11 a, zn- χ -L is insensitive to the effects of solvents of different polarities, and even the most polar water does not quench much of its fluorescence and does not affect the sensitivity of fluorescence sensing of 2-NP. This may be related to the fact that Zn- χ -L has both a non-polar halogenated ligand and a polar metal ion and a coordinated water molecule in the structure, so that the combination of different polar fragments results in the dissolution of Zn- χ -L in solvents of different polarities to show a trend toward the same.
2. Detection of anti-metal ion and other nitroaromatic interference capability
The prepared concentration is 1×10 -2 120. Mu.M of the analyte (4-NP, 2-NT,4-NT, etc.) was added to the ethanol solution of Zn- χ -L,DNT、TNT、Ag + 、Al 3+ 、Bi 3+ 、Ca 2+ 、Co 2+ 、Cr 2+ 、Cu 2+ 、Fe 3+ 、K + 、Mg 2+ 、Mn 2+ ，Na + 、Li + 、Sr 2+ 、Zn 2 + ) Then shake-up, add 120 μm of 2-NP solution again, shake-up again, and immediately measure fluorescence spectrum (λex=393 nm).
Results: as can be seen from FIGS. 11 b and c, the decrease in Zn- χ -L emission intensity was not affected in the context of other nitroaromatics, and fluorescence quenching time was hardly affected by adding 2-NP (120. Mu.M) after adding other metal ions (120. Mu.M). The Zn- χ -L has higher anti-interference capability and excellent sensitivity.
Detection example 3 detection of detection Performance of sensor paper
The test strip prepared in example 6 was exposed to 2-NP vapor and the fluorescence intensity was measured. Specifically, the prepared fluorescence sensing test paper is covered on a cuvette filled with 2-NP ethanol solution, and the change condition of fluorescence is observed.
Results: at 30s, fluorescence quenched rapidly and was clearly visible under ultraviolet light (FIG. 12). This result clearly shows that the quenching of the system by 2-NP vapor is rapid and stable, indicating that the sensor strip prepared in example 2 has significant potential in rapid and convenient detection of nitroaromatic 2-NP gas.
Claims (7)
1. The halogenated Schiff base Zn (II) complex Zn- χ -L is characterized in that the structural formula of the complex Zn- χ -L is shown as the formula (I):
。
2. the halogenated Schiff base Zn (II) complex Zn- χ -L according to claim 1, wherein the crystallographic data and structural refinement parameters of the complex Zn- χ -L are shown in the following table:
。
3. The preparation method of the halogenated Schiff base Zn (II) complex Zn- χ -L as claimed in claim 1, which is characterized by comprising the following steps:
1) Adding 3-bromo-5-chlorosalicylaldehyde and 1, 3-propanediamine into an ethanol solution, and stirring for 1.5-3 hours;
2) Adding zinc (II) chloride and ultrapure water, stirring for 1-2 hours, and filtering to obtain a filtrate;
3) And slowly volatilizing the filtrate at room temperature to obtain colorless transparent crystals, washing with a polar solvent for multiple times, filtering, and finally naturally volatilizing and drying to obtain the target complex.
4. A process according to claim 3, characterized in that the molar ratio of 3-bromo-5-chlorosalicylaldehyde, 1, 3-propanediamine and zinc (II) chloride is 2:1:1.
5. The method according to claim 3, wherein the volume ratio of 1, 3-propanediamine, ethanol and ultrapure water is 1:5000-500000:250-25000.
6. A method of preparation according to claim 3, wherein the polar solvent is ethanol.
7. Use of the halogenated Schiff base Zn (II) complex Zn- χ -L as a fluorescent probe for detecting specific nitroarene contaminants o-nitrophenol.
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| KR20190070848A (en) * | 2017-12-13 | 2019-06-21 | 울산대학교 산학협력단 | Fluorescent sensor for detecting aromatic nitro compounds |
| CN114805116A (en) * | 2022-03-03 | 2022-07-29 | 北京理工大学 | Zn-based Schiff base complex, and preparation method and application thereof |
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| KR20190070848A (en) * | 2017-12-13 | 2019-06-21 | 울산대학교 산학협력단 | Fluorescent sensor for detecting aromatic nitro compounds |
| CN114805116A (en) * | 2022-03-03 | 2022-07-29 | 北京理工大学 | Zn-based Schiff base complex, and preparation method and application thereof |
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| Synthesis and structural characterisation of new manganese (II) and (III) complexes. Study of their photolytic and catalase activity and X-ray crystal structure of [Mn(3-OMe, 5-Br- salpn)(EtOH)(H2O)]ClO4;M. Maneiro等;Polyhedron;第19卷;第47-54页 * |
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