CN116178737A - Cadmium metal coordination polymer and preparation method and application thereof - Google Patents
Cadmium metal coordination polymer and preparation method and application thereof Download PDFInfo
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- CN116178737A CN116178737A CN202211488615.4A CN202211488615A CN116178737A CN 116178737 A CN116178737 A CN 116178737A CN 202211488615 A CN202211488615 A CN 202211488615A CN 116178737 A CN116178737 A CN 116178737A
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 62
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- -1 5- (4 '-cyanobenzyloxy) isophthalic acid Chemical compound 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 229910052793 cadmium Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 9
- GOZATJNCMKPSAV-UHFFFAOYSA-N 5-[(4-carboxyphenyl)methoxy]benzene-1,3-dicarboxylic acid Chemical compound C(=O)(O)C1=CC=C(COC=2C=C(C=C(C(=O)O)C2)C(=O)O)C=C1 GOZATJNCMKPSAV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001917 fluorescence detection Methods 0.000 claims description 8
- 229960002313 ornidazole Drugs 0.000 claims description 8
- IPWKIXLWTCNBKN-UHFFFAOYSA-N Madelen Chemical compound CC1=NC=C([N+]([O-])=O)N1CC(O)CCl IPWKIXLWTCNBKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910020820 NaAc-HAc Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 20
- 150000003384 small molecules Chemical class 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
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- 230000000171 quenching effect Effects 0.000 description 28
- 238000010791 quenching Methods 0.000 description 27
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- 230000005284 excitation Effects 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 239000011651 chromium Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002165 resonance energy transfer Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AUIZLSZEDUYGDE-UHFFFAOYSA-L cadmium(2+);diacetate;dihydrate Chemical compound O.O.[Cd+2].CC([O-])=O.CC([O-])=O AUIZLSZEDUYGDE-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 229960000282 metronidazole Drugs 0.000 description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
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- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- OKBVVJOGVLARMR-QSWIMTSFSA-N cefixime Chemical compound S1C(N)=NC(C(=N\OCC(O)=O)\C(=O)N[C@@H]2C(N3C(=C(C=C)CS[C@@H]32)C(O)=O)=O)=C1 OKBVVJOGVLARMR-QSWIMTSFSA-N 0.000 description 1
- 229960002129 cefixime Drugs 0.000 description 1
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- 230000002860 competitive effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention relates to the field of chemical synthesis, in particular to a cadmium metal coordination polymer and a preparation method and application thereof. The chemical formula of the cadmium metal complex is [ Cd (CIA) 3 (2‑bipy)]·H 2 O, the cadmium metal coordination polymer belongs to a triclinic system, the space group is P-1,
α= 92.194 (2) °, β= 106.335 (01) °, γ= 116.862 (01) °; unit cell volume of cadmium metal coordination polymer
The cadmium metal coordination polymer can conveniently detect ions and small molecules, other factors in the environment have very little influence on detection, the anti-interference capability is strong, and the detection limit is very low, so that the fluorescent probe is very sensitive.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a cadmium metal coordination polymer and a preparation method and application thereof.
Background
The fluorescence detection method has the characteristics of simplicity, convenience, stability, high sensitivity and the like, and can be used for heavy metal pollutants, microbial pollutants and the like.
Fluorescent probes based on metal-organic frameworks (MOFs) are being developed for detecting harmful ions and part of small molecules in the environment, which show increasing advantages including structural design ability, pore size stability, host-guest interactions and stable luminescence.
Metal-organic frameworks (MOFs) are a class of crystalline materials formed by connecting organic molecules and metals or metal clusters, and have potential applications in gas storage, separation, heterogeneous catalysis and the like due to the large specific surface area, various structural topologies and rich active centers. Eu-MOF can be used for quantitative fluorescence detection of quinolone antibiotics and selective detection of tetracycline antibiotics. MOFs crystal materials have attracted much attention as novel multifunctional materials, and research on the use of MOFs crystal materials in environmental detection has great value.
Key to synthesizing MOFs crystalline materials is the design of organic ligands, three carboxylic acid groups of 5- ((4-carboxybenzyl) oxy) isophthalic acid groups coordinate with metal atoms in different patterns, so that the ligands act as multidentate (from one to six coordination sites) nodes to expand the dimensions in the building process, rigid 2,2' -bipyridyl has larger coordination sites, and these macromolecular long frameworks tend to form larger void structures. Because of the specific absorption peaks possessed by its ligands, fluorescence quenching is more favored when mixed with other small molecule substances.
Disclosure of Invention
In order to solve the technical problems in the existing photoluminescence and related ion detection, the invention aims to provide a cadmium metal coordination polymer.
Another object of the present invention is to provide a method for preparing the above-mentioned cadmium metal coordination polymer.
It is another object of the present invention to provide the use of the above-mentioned cadmium metal coordination polymer.
The cadmium metal complex according to the invention has the formula [ Cd (CIA) 3 (2-bipy)]·H 2 O, wherein CIA is 5- ((4-carboxybenzyl) oxy) isophthalic acid, 2-bipy is homo2, 2' -bipyridine, the cadmium metal coordination polymer belongs to a triclinic system, the space group is P-1,
α= 92.194 (2) °, β= 106.335 (01) °, γ= 116.862 (01) °; unit cell volume of cadmium metal coordination polymer>
The cadmium metal complex according to the present invention has a number of molecules in a unit cell of 2.
The method for preparing the cadmium metal complex according to the present invention comprises the steps of:
dissolving 5- (4 '-cyanobenzyloxy) isophthalic acid, 2' -bipyridine and cadmium caproate dihydrate in NaAc-HAc buffer solution with pH of 4.0, and stirring to obtain a reaction solution, wherein the molar ratio of the 5- (4 '-cyanobenzyloxy) isophthalic acid to the 2,2' -bipyridine to the cadmium caproate dihydrate is 1:4:2;
transferring the reaction solution to a hydrothermal reaction kettle, and crystallizing at 135-140 ℃;
and (3) cooling to room temperature by a program, and filtering to obtain the cadmium metal coordination polymer.
The method for preparing the cadmium metal complex comprises the following steps of taking 0.01mol of cadmium caproate dihydrate and NaAc-HAc buffer solution in a molar volume ratio: 0.01mol:3mL.
According to the method for preparing the cadmium metal complex, the reaction solution is heated to 135-140 ℃ after 3 hours.
The method for preparing the cadmium metal complex according to the present invention, wherein the crystallization temperature is 140 ℃ and the time is 5 days.
According to the method for preparing the cadmium metal complex, the reaction liquid after crystallization is cooled to room temperature at a speed of 3 ℃/h.
The invention provides application of the cadmium metal coordination polymer in fluorescence detection.
Preferably, the cadmium metal coordination polymer of the invention can photoluminescence, thus the cadmium metal coordination polymer can be used for luminescence application and detection application, nitrobenzene is detected very sensitively in an environment with certain interference, and Cu of a detection solution is detected 2+ 、Cr 2 O 7 2- Ornidazole, etc.
The invention provides nitrobenzene and Cu in the detection environment of the cadmium metal coordination polymer 2+ 、Cr 2 O 7 2- And the application of small molecules such as ornidazole.
The invention synthesizes a new MOFs crystal material [ Cd (CIA) by using 5- (4 '-cyanobenzyloxy) isophthalic acid, 2' -bipyridine and cadmium acetate dihydrate 3 (2-bipy)]·H 2 O, the structure and stability of which were studied.
The invention discovers that the cadmium metal coordination polymer can be independently used for photoluminescence for the first time, and researches that the cadmium metal coordination polymer has strong fluorescence emission at 420nm under excitation of 364 nm. Coordination polymers have been reported that have the same carboxylic acid ligand synthesized with 4' 4-bipyridine in different coordination environments, and the excitation peak and fluorescence emission are different from the present coordination polymer, possibly because the 2' 2-bipyridine and 4' 4-bipyridine N are in different environments, resulting in a shift in the fluorescence peak position. The chromium metal coordination polymer provided by the invention has the advantages of environment friendliness, convenience and sensitivity when being used for detecting small molecules and ionic materials.
The cadmium metal coordination polymer is synthesized by a simple hydrothermal synthesis method, and compared with other crystals synthesized by a solvent volatilization method, a diffusion method and the like, the method is simpler and more convenient. The buffer solution with pH of 4.0 is adopted to regulate the synthesis environment, so that the method is environment-friendly and convenient. If the reaction environment is adjusted with hydrochloric acid having pH4.0, crystals cannot be formed, and the effect of hydrochloric acid on the environment is greater than that of acetic acid buffer solvent. The cadmium metal coordination polymer can conveniently detect ions and small molecules, other factors in the environment have very little influence on detection, the anti-interference capability is strong, and the detection limit is very low, so that the fluorescent probe is very sensitive.
Drawings
FIG. 1a is a schematic representation of the coordination environment of a cadmium metal coordination polymer of the present invention;
FIG. 1b is a one-dimensional chain-like diagram of a coordination polymer of the present invention;
FIG. 1c is a two-dimensional network of coordination polymers of the present invention formed by pi-pi stacking;
FIG. 1d is a three-dimensional supramolecular structure of the coordination polymer of the present invention;
FIG. 2a is a thermogravimetric analysis of a cadmium metal coordination polymer of the present invention;
FIG. 2b is an infrared spectrum of a cadmium metal coordination polymer of the present invention;
FIGS. 3a1 and 3a2 show fluorescence quenching of nitrobenzene using the cadmium metal coordination polymer of the present application;
FIGS. 3b1 and 3b2 show fluorescence quenching for detecting nitrate cations using the cadmium metal coordination polymer of the present application;
FIGS. 3c1 and 3c2 show fluorescence quenching for detecting nitrate anions using the cadmium metal coordination polymer of the present application;
FIGS. 3d1 and 3d2 show fluorescence quenching for detection of antibiotics using the cadmium metal coordination polymers of the present application.
Detailed Description
In the following examples, first preparedA cadmium metal coordination polymer comprising the steps of: at normal temperature, CIP, 2' -bipyridine and cadmium caproate dihydrate were dissolved in NaA at ph=4 C -HA C And (3) stirring the solution in a buffer solution for about 20Min, transferring the solution to a hydrothermal reaction kettle, heating the solution in an oven at 140 ℃ for 5 days, then reducing the temperature to room temperature through a program, and filtering the solution to obtain the cadmium metal coordination polymer, wherein the molar ratio of CIP (5- (4 '-cyanobenzyloxy) isophthalic acid), 2' -bipyridine and cadmium caproate dihydrate is about 1:4:2. Cyano groups in CIP are converted to carboxyl groups under acidic, high temperature and pressure conditions, i.e., 5- (4' -cyanobenzyloxy) isophthalic acid is converted to 5- ((4-carboxybenzyl) oxy) isophthalic acid.
The chemical formula of the prepared metal coordination polymer is [ Cd (CIA) 3 (2-bipy)]·H 2 O, the cadmium metal coordination polymer belongs to a triclinic system, the space group is P-1,
α＝92.194(2)°,β＝106.335(01)°，γ＝116.862(01)°。/>
z=2. The invention provides a unit cell volume of the cadmium metal coordination polymer>
The number of molecules in the unit cell of the cadmium metal coordination polymer is z=2.
Then, the crystal structure of the cadmium metal coordination polymer of the invention is analyzed, and the result shows that the basic building element of the crystal structure comprises 1 Cd atom, 3 5- ((4-carboxybenzyl) oxy) isophthalic acid and 1 2,2' -bipyridine molecule, and 1 molecule of crystal water. The coordination number of Cd1 is 7, forming a distorted tetrahedral geometry (see fig. 1 a). Wherein the bond length between Cd-O ranges from
The bond length between Cd-N is in the range +.>
These data parameters are comparable to those reported in the literature. The chemical formula is [ Cd (CIA) 3 (2-bipy)]·H 2 O
According to the cadmium metal coordination polymer, each 5- ((4-carboxybenzyl) oxy) isophthalic acid ligand is connected with three Cd (II) ions to form a one-dimensional chain structure (see figure 1 b), and meanwhile, 2' -bipyridine among different chains forms a two-dimensional network structure through pi-pi stacking effect (see figure 1 c). The 5- ((4-carboxybenzyl) oxy) isophthalic acid ligands of the adjacent layers form a complex three-dimensional supermolecular structure (see figure 1 d) through pi-pi accumulation of the layers, and meanwhile, the crystallization water and the 5- ((4-carboxybenzyl) oxy) isophthalic acid ligands have stronger hydrogen bonds,
further enhancing the stability of the three-dimensional body.
Crystals of a cadmium metal coordination polymer were studied using thermogravimetric analysis, the thermogravimetric analysis profile of which included a weight loss at a first stage of 45-140 ℃ and a weight loss at a second stage of 210-500 ℃.
The invention analyzes the infrared spectrum of the chromium metal coordination polymer.
Finally, the photoluminescence and ion detection of the nickel metal coordination polymer and the property of small molecule detection are studied.
The principle that the cadmium metal coordination polymer can be subjected to fluorescence quenching is as follows:
resonance Energy Transfer (RET) is another frequently invoked photoluminescence sensing mechanism in which excited donors return to the ground state while acceptors are promoted to the excited state by non-radiative energy transfer between the two processes, resulting in quenching of the emission of the donor and enhancement of the emission of the acceptors. Energy transfer is a distance-dependent physical process, and the efficiency of energy transfer is generally dependent on the degree of spectral overlap, i.e., the emission spectrum and absorption spectrum of the host and object; and dipole-dipole interactions, distance and relative orientation of the host and the object. If the ultraviolet-visible absorption spectrum of the guest overlaps with the emission spectrum of the MOF, the spectral overlap can be determined experimentally that RET may occur and result in luminescence quenching of the MOF. This process is commonly referred to as pre-resonance energy transfer (FRET). In addition to the extent of spectral overlap, the efficiency of energy transfer can also be tuned by host-guest dipole-dipole interactions.
The absorption spectrum of the substance detected by the application has great spectrum overlap with the excitation peaks of the ligand and the cadmium metal complex, which indicates that competitive energy absorption can be the cause of fluorescence quenching, and in addition, photoinduced electron transfer is also a possible mechanism for fluorescence quenching of the antibiotic-induced MOF.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally performed under conventional conditions or under conditions recommended by the manufacturer. Percentages are by weight unless otherwise indicated.
Example 1
1. Synthesis of cadmium metal coordination polymer
16.0mg (0.05 mmol) of CIP, 26.0mg (0.01 mmol) of cadmium benzene dihydrate and 32.0 (0.2 mmol) of 2,2' -bipyridine are dissolved in 3mL of NaAC-HAC buffer solution with pH=4, stirred for 20min, then put into a 20mL hydrothermal reaction kettle, heated to 140 ℃ from 20 ℃ for 3h, crystallized for 5 days at 140 ℃ and cooled to room temperature at a rate of 3 ℃/h. The reaction solution was filtered to obtain a white transparent bulk crystal.
2. Selecting the above prepared single crystal with proper size, placing in a Germany BRUKER SMARTAPEX-II type CCD four-round single crystal diffractometer with graphite monochromator, and using MoK α (λ= 0.071073 nm) rays, data were collected in an ω/2θ scan at 293 (2) K. All diffraction intensity data are corrected by LP factors and empirical absorption, a crystal structure is solved by a direct method, data reduction and structure analysis work are completed by SAINT-5.0 and SHELXTL-97 programs respectively, and all non-hydrogen atom coordinates and anisotropic parameters are subjected to a full matrix least square method F 2 And (5) finishing. Complex compoundThe crystallographic data, bond length and bond angle, hydrogen bonding are shown in tables 1, 2 and 3.
TABLE 1 crystallographic data and structural parameters of coordination polymers
TABLE 2 partial bond lengths of coordination polymers
Bond angle (°)
An atomic symmetry code is #1x-1, y, z; #2-x, -y-1, -z; #3x+1, y, z.
TABLE 3 Hydrogen bonding parameters of coordination polymers
| D-H...A | d(D-H) | d(H...A) | d(D...A) | <(DHA) |
| O8--H8D..O2 | 0.85 | 2.19 | 2.9628(2) | 151 |
。
The prepared metal coordination polymer was analyzed by Shimadzu corporation IRAFFINITY-1S infrared spectrometer (KBr pellet) as shown in FIG. 2b, and the obtained infrared spectrum had the following characteristics: its IR spectrum (KBr) is about 3855cm -1 ,3665cm -1 ,2350cm -1 ,1770cm -1 ,1545cm -1 ,1375cm -1 ,875cm -1 ,760cm -1 ，400cm -1 There is a characteristic absorption peak.
The thermal stability analysis (TGA) was performed on the prepared cadmium metal coordination polymer by using an STA-449C type thermal analyzer, and the thermal weight analysis curve of the cadmium metal coordination polymer includes a weight loss at the first stage of 45-140 ℃ and a weight loss at the second stage of 210-500 ℃ under the air atmosphere condition, and the thermal weight loss curve of the complex was measured at a heating rate of 10 ℃/min (static air), as shown in fig. 2 a.
Example 2 application of the procedure
1. Detection of nitrobenzene
30mg of the prepared crystals were weighed, prepared as 100mL, sonicated for 2h and left for 3 days. A series of 10mmol/L nitroexplosive solutions of p-nitrophenol, o-nitroaniline, nitrobenzene and the like are prepared and used for fluorescence detection.
1mL of cadmium complex supernatant which is kept stand for three days is taken, and fluorescence excitation and emission peaks of the supernatant are tested by using an Agilent MY15090002 fluorescence spectrophotometer. Then excitation (Ex) was fixed, 10 groups of emissions (Em) were tested as blanks, 20. Mu.L of different kinds of 10mmol/L nitroexplosives were added respectively, fluorescence quenching was observed, and the emission peak position and peak intensity of fluorescence were measured. As can be seen, fluorescence quenching is very pronounced after nitrobenzene addition (FIG. 3a 1) "). The cadmium complex has good correspondence to nitrobenzene. Then, more refined quantitative analysis was performed on nitrobenzene (as in FIG. 3a 2): another 1mL supernatant, fixed excitation (Ex), was assayed for 3 sets of emissions (Em) As a blank, 1. Mu.L of nitrobenzene was gradually added until the quenching rate reached 99%, and the detection limit of nitrobenzene was calculated to be 2.14X10 -7 mol/L. A reported Cd metal coordination polymer synthesized by adopting the same carboxylic acid ligand and Lin Feiluo tourmaline has strong quenching on nitrobenzene, but has no good detection limit when the quenching rate reaches 93.97 percent.
2.Cu 2+ Is detected by (a)
Configuring a series of 5mmol/L Fe 3+ 、Cu 2+ 、Ni 3+ 、Mg 2+ Nitrate cationic solution for fluorescence detection. 1mL of cadmium complex supernatant which is kept stand for three days is taken, the fixed excitation (Ex) of Agilent MY15090002 fluorescence spectrophotometer is adopted, 10 groups of emissions (Em) are tested as blank, 20 mu L of different types of cation solutions are respectively added, and fluorescence quenching conditions are observed. It was observed that Cu was added 2+ After which a significant quenching occurred, the peak position and corresponding peak height were recorded (see fig. 3b 1). Another 1mL supernatant was taken for Cu 2+ Quantitative analysis (FIG. 3b 2), fixed excitation (Ex), test 3 groups of emission (Em) as blank, adding into supernatant at a frequency of 1 μl/time, measuring once every 1 μl, observing quenching condition until quenching rate reaches above 95%, and calculating to obtain Cu 2+ The detection limit of (2) was 9.07X 10 -5 mol/L. The quenching effect of other cations is better than that of other Cd metal coordination polymers, but the quenching effect of the Cd metal coordination polymer on Cu 2+ The quenched phase was very small.
3.Cr 2 O 7 2- Is detected by (a)
Configuring a series of 5mmol/L para-Br - 、Cr 2 O 7 2- 、NO 2 - 、I - And (3) an isocratic anion solution for fluorescence detection. 1mL of cadmium complex supernatant which is kept standing for three days is taken, the fixed excitation (Ex) is carried out by using an Agilent MY15090002 fluorescence spectrophotometer, 10 groups of emissions (Em) are tested as blanks, 20 mu L of different types of anion solutions are respectively added, and fluorescence quenching conditions are observed (as shown in figure 3c 1). It was found that Cr was added 2 O 7 2- After which a significant quench occurred, the peak position and corresponding peak height were recorded. In addition, another1mL of supernatant was taken, excitation fixed (Ex), 3 emission groups (Em) were tested as blank, and Cr was added 2 O 7 2- Adding into the supernatant at a rate of 1 μl/time, measuring once every 1 μl, observing quenching condition (as shown in FIG. 3c 2) until quenching rate reaches above 95%, and calculating to obtain Cr 2 O 7 2- The detection limit of (2) is 5.47×10 -5 mol/L. Cd coordination polymer with the same carboxylic acid ligand, without the ligand for Cr 2 O 7 2- And (5) detecting.
4. Detection of ornidazole
A series of 5mmol/L antibiotic solutions such as tetracycline, metronidazole, ornidazole, cefixime and the like are prepared for fluorescence detection. 1mL of cadmium complex supernatant which is kept standing for three days is taken, the fixed excitation (Ex) is carried out by using an Agilent MY15090002 fluorescence spectrophotometer, 10 groups of emissions (Em) are tested as blank, 20 mu L of different types of antibiotic solutions are respectively added, and fluorescence quenching conditions are observed (as shown in figure 3d 1). It was observed that significant quenching occurred after the addition of ornidazole, and peak positions and corresponding peak heights were recorded. Taking 1mL of supernatant, fixing excitation (Ex), testing 3 groups of emission (Em) as blank, adding metronidazole into the supernatant at a frequency of 1 μL/time, measuring once every 1 μL, observing quenching condition (as shown in figure 3d 2) until quenching rate reaches above 95%, and calculating to obtain detection limit of ornidazole of 1.16X10 -6 mol/L. Cd coordination polymer with the same carboxylic acid ligand, without the ligand for Cr 2 O 7 2- And (5) detecting.
The present application synthesizes new MOFs crystal material [ Cd (CIA) using 5- (4 '-cyanobenzyloxy) isophthalic acid, 2' -bipyridine and cadmium acetate dihydrate 3 (2-bipy)]·H 2 O, nitrobenzene, ornidazole, cu in very sensitive detection environment of MOFs 2+ 、Cr 2 O 7 2- Etc., which are characteristics not possessed by other cadmium polymers.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and various modifications can be made to the above-described embodiment of the present invention. All simple, equivalent changes and modifications made in accordance with the claims and the specification of this application fall within the scope of the patent claims. The present invention is not described in detail in the conventional art.
Claims (9)
1. A cadmium metal complex is characterized in that the chemical formula of the cadmium metal complex is
[Cd(CIA) 3 (2-bipy)]·H 2 O, wherein CIA is 5- ((4-carboxybenzyl) oxy) isophthalic acid, 2-bipy is homo2, 2' -bipyridine, the cadmium metal coordination polymer belongs to a triclinic system, the space group is P-1,
α= 92.194 (2) °, β= 106.335 (01) °, γ= 116.862 (01) °; unit cell volume of cadmium metal coordination polymer>
2. The cadmium metal complex according to claim 1, wherein the number of molecules in the unit cell of the cadmium metal coordination polymer is 2.
3. A method of preparing the cadmium metal complex of claim 1, said method comprising the steps of:
dissolving 5- (4 '-cyanobenzyloxy) isophthalic acid, 2' -bipyridine and cadmium caproate dihydrate in NaAc-HAc buffer solution with pH of 4.0, and stirring to obtain a reaction solution, wherein the molar ratio of the 5- (4 '-cyanobenzyloxy) isophthalic acid to the 2,2' -bipyridine to the cadmium caproate dihydrate is 1:4:2;
transferring the reaction solution to a hydrothermal reaction kettle, and crystallizing at 135-140 ℃;
and (3) cooling to room temperature by a program, and filtering to obtain the cadmium metal coordination polymer.
4. A method according to claim 3, characterized in that 0.01mol of cadmium caproate dihydrate is taken in a molar volume ratio to NaAc-HAc buffer solution: 0.01mol:3mL.
5. A method according to claim 3, wherein the reaction solution is heated to 135-140 ℃ over 3 hours.
6. A method according to claim 3, wherein the crystallization temperature is 140 ℃ and the time is 5 days.
7. A method according to claim 3, wherein the crystallized reaction solution is cooled to room temperature at a rate of 3 ℃/h.
8. Use of the cadmium metal complex according to claim 1 in fluorescence detection.
9. The use according to claim 8, wherein the cadmium metal complex is used to detect:
nitrobenzene, cu 2+ 、Cr 2 O 7 2- Or ornidazole.
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