CN110776649B - Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof - Google Patents
Cadmium-organic supramolecular polymer containing anthracene group and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides cadmium-organic supramolecular polymer containing anthracene group, which has a chemical general formula of [ Cd (Hbtot) ((pyan))1.5]nBelonging to the triclinic system, space group is P-1, cell parameters
Wherein Hbtot2‑Is a semi-rigid triorganic carboxylic acid H3btot from 2 protons, said H3The structure of btot is shown as formula I; the structure of the ligand pyan is shown as formula II,
Hbtot2‑pyan and Cd2+Constructing a two-dimensional metal-mixed body coordination polymerization layer; the coordination polymerization layers are further stacked through pi-pi interaction to form a three-dimensional metal-organic supramolecular polymer. The green fluorescent anthracene-based cadmium-organic supermolecular polymer prepared by the method has a yield of about 75%, and can be used as an environment and chemical industryCO in aqueous solution of equal field3 2‑/EDTA2‑/Pb2+/Cr3+The fluorescent probe has application prospect in the aspects of biological labeling, optical device preparation, color blending and the like.
Description
Technical Field
The invention belongs to the field of advanced luminescent materials and heavy metals, and particularly relates to cadmium-organic supramolecular polymer containing anthracene group, and a preparation method and application thereof.
Background
Luminescent devices (such as ZnS: Mn devices) prepared from inorganic materials have the defects of poor stability, luminous efficiency and the like; the device prepared by the organic small molecular material (such as TBSA fluorene blue light small molecule) is easy to crystallize in the light emitting process, so that the stability of the device is poor; the device prepared by the polymer luminescent material (such as polystyrene quinoline reported in 2001) overcomes the defect, so that the device has good commercial application prospect.
Since the metal-organic complex 8-hydroxyquinoline aluminum (AlQ) was used as a raw material of a light emitting device in 1987, photosensitive metal-organic supramolecular polymers (MOSPs) constructed by noncovalent bond driving such as coordinate bonds and the like have been rapidly developed, and the topological structure of the MOSPs provides the polymers with more new functions (such as molecular motor type, respiratory type and the like) than inorganic or organic components. So far, the chemical reaction process of the supramolecular polymer is limited by various complex factors such as solvent, material, temperature, etc., and the topological structure, performance and structure-activity relationship are difficult to predict, so that obtaining the supramolecular polymer with novel structure and certain application prospect is a very challenging subject.
An anthracene group with a large conjugated system is a typical chromophoric group, and an anthracene group modified functional organic molecule is paid much attention to the field of luminescent materials. In the field of new chemical materials, 9, 10-bis (4-pyridyl) anthracene (abbreviated as pyan) is a typical electron-rich N-ligand, and photosensitive MOSPs constructed by pyan, polycarboxylic acid and transition metal ions are rarely reported.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides an anthracene-based cadmium-organic supramolecular polymer with a chemical formula of [ Cd (Hbtot) (pyan) ]1.5]nThe new substance can be used as a fluorescence detection probe for anions and cations.
In order to achieve the purpose, the invention provides the following technical scheme: cadmium-organic supermolecular polymer containing anthracene group, its chemical formula is [ Cd (Hbtot) (pyan)1.5]nBelonging to the triclinic system, space group is P-1, cell parameters
In the chemical general formula of the cadmium-organic supramolecular polymer, Hbtot2-Is a semi-rigid triorganic carboxylic acid H3btot by stripping 2 protons, H3The structure of btot is shown as formula I; in the chemical general formula, the structural formula of the ligand pyan is shown as formula II:
further, the cadmium-organic supramolecular polymer containing anthracene groups comprises 1 Hbtot in crystallographically independent asymmetric units2-1 Cd2+And 1.5 pyan, thus its periodic formula is expressed as [ Cd (Hbtot) (pyan)1.5]n(ii) a In the crystallographically independent asymmetric unit, Hbtot2-The coordination mode is shown as formula III; the ligand pyan comprises two coordination modes, wherein the two coordination modes are a bridging mode pyan-A shown as a formula IV and a monodentate mode pyan-B shown as a formula V; in the space structure of the cadmium-organic supermolecule polymer containing anthracene group, carboxylate radical, pyridine N atom and Cd2+Form a composition of [ Cd2N4(CO2)4]The dual-core cluster of (1) is shown in formula VI, wherein the distance between O1 & Cd1
Indicating a weaker interaction between them;the dual core cluster is simplified to a secondary building block SBU, where the dotted line indicates pyan-B, as shown in formula VII; the Hbtot2-Constructing a two-dimensional metal-mixed body coordination polymerization layer by pyan and SBU, wherein the two-dimensional metal-mixed body coordination polymerization layer is shown as a formula VIII; hbtot is present in the two-dimensional metal-hybrid coordination polymerization layer2-And a tunnel surrounded by a pyan ligand, and three-dimensional metal-organic supramolecular polymers are further formed by stacking coordination polymerization layers through pi-pi interaction:
the cadmium-organic supramolecular polymer containing the anthracene group is prepared by the following steps: with H3btot、pyan、Cd(NO3)2·4H2O and HNO3The preparation method is characterized in that the raw material is a mixed solution of acetonitrile and water as a solvent, and the solvent thermal synthesis method is adopted for preparation, and the preparation method specifically comprises the following steps:
(1) feeding a raw material H3btot、pyan、Cd(NO3)2·4H2O and HNO3Mixing acetonitrile and water as solvents to form a reaction system, and placing the reaction system in a closed container; said H3btot、pyan、Cd(NO3)2·4H2O and HNO3The mass ratio of (1): 1: 1.5-2.5: 3.5-8.8, wherein the volume ratio of the solvent acetonitrile to water is 1: 9;
(2) and (3) placing the reaction system at room temperature, stirring for 10-30min, then heating the reaction system to 140-160 ℃, reacting for 3-5d, and then naturally cooling, filtering and drying to obtain blocky crystals.
Further, said H in step (1)3btot：pyan：Cd(NO3)2·4H2O：HNO3The mass ratio of (1): 1: 2.5: 5.25.
further, H in the reaction system3The quantitative concentration of the starting material of btot was 4 mmol/L.
Further, the reaction temperature in step (2) was 160 ℃, and the drying means that the crystals were naturally dried in the air at room temperature after being washed with distilled water.
The cadmium-organic supramolecular polymer containing the anthracene group prepared by the preparation method is applied to the detection of anions and cations.
Compared with the prior art, the invention has the following beneficial effects:
(1) [ Cd (Hbtot) (pyan) prepared by the invention1.5]nThe pyan endows the polymer with luminous performance through electron transfer from the ligand to metal ions, and simultaneously, the relative content of heavy metal Cd in the polymer is reduced because the amount of pyan substances is 1.5 times that of the metal ions Cd, so that [ Cd (Hbtot) ((pyan))1.5]nUse of the solution in aqueous solutions of the toxic heavy metal ion lead (Pb)2+) And chromium (Cr)3+) And during fluorescence detection, the method is more environment-friendly.
(2) The cadmium-organic supramolecular polymer containing the anthracene group stably exists in solvents such as water, acetonitrile and the like, and starts to decompose at the temperature of about 370 ℃, so that the cadmium-organic supramolecular polymer has high thermal stability; the crystal material emits green fluorescence under the excitation of light with the wavelength of 415nm at room temperature; the new crystal material can be applied to anion and cation CO in a water solution3 2-/EDTA2-/Pb2+/Cr3+Detection of (2), biomarker, optical device preparation, color blending, and the like.
(3) By adopting the preparation method, the yield of the green fluorescent anthryl-containing cadmium-organic supramolecular polymer is about 75 percent. The cadmium-organic supramolecular polymer containing the anthracene group has positive significance and value in aspects of environmental resource development, new material preparation, application and the like.
Drawings
FIG. 1 is a crystal structure diagram of anthracene-based cadmium-organic supramolecular polymer of the invention, (a) coordination mode of organic ligand and metal ion, and (b) composition [ Cd2N4(CO2)4]The binuclear cluster of (a) is simplified to a 6-linked secondary building unit (6-c SBU) after omitting pyan-B for clarity;
FIG. 2 is a steric structure diagram of the anthracene-based cadmium-organic supramolecular polymer of the present invention, (a) Hbtot2-pyan-A and Cd2+Constructed coordination polymerization layer andits 6-linked lamellar simplified structure, (b) Hbtot2-pyan-A, pyan-B and Cd2+Construction of [ Cd (Hbtot) (pyan)1.5]nStacking the polymerization layers, (c) stacking the coordination polymerization layers into a three-dimensional metal-organic supramolecular polymerization network through pi-pi interaction;
FIG. 3 is a graph of X-ray powder diffraction patterns of cadmium-organic supramolecular polymers including anthracene groups according to the present invention;
FIG. 4 is a thermogravimetric plot of the cadmium-organic supramolecular polymer with anthracene group of the present invention;
FIG. 5 is an infrared spectrum of cadmium-organic supramolecular polymers including anthracene groups according to the present invention;
FIG. 6 is a solid state fluorescence spectrum of cadmium-organic supramolecular polymers including anthracene group at room temperature;
FIG. 7 is a fluorescence spectrum of anion detection in an anthracene-based cadmium-organic supramolecular polymer aqueous solution according to the present invention;
FIG. 8 is a fluorescence spectrum of cations detected by the anthracene-based cadmium-organic supramolecular polymer aqueous solution of the invention;
Detailed Description
The process of the present invention will be described in detail with reference to specific examples. The cadmium-organic supramolecular polymer containing the anthracene group can be abbreviated as CdOSP, and the final product is subjected to X-ray single crystal diffraction test and analyzed to obtain an accurate electronic structure; and performing a series of characterizations such as infrared, fluorescence, X-ray powder diffraction, thermogravimetry and the like on the final product to determine that the chemical composition general formula is [ Cd (Hbtot) (pyan) ])1.5]nWherein the amount of pyan agent is 1.5 times that of Cd. And calculating the yield by taking the dosage of the N-ligand pyan as a basis, namely calculating the mass of the theoretically obtained supramolecular polymer according to the ratio of the dosage of pyan substances in the product composition, wherein the ratio of the actually obtained product mass to the former is the yield. The Chinese name of pyan in the present invention is 9, 10-bis (4-pyridyl) anthracene.
Preparation of cadmium-organic supermolecule polymer containing anthracene group
Example 1
Taking the following materials according to the specific mass or volume: h3btot(19.4mg，0.04mmol)，pyan(13.3mg，0.04mmol)，Cd(NO3)2·4H2O(30.8mg，0.1mmol)，CH3CN(1mL)，H2O(9mL)，HNO3(30uL, 7mol/L, 0.21 mmol). And (2) placing the materials in a 25mL reaction kettle, stirring for about 10min, heating to 160 ℃, reacting for 3 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing the blocky crystal sample with distilled water, and naturally drying the blocky crystal sample in the air at room temperature.
The prepared cadmium-organic supramolecular polymer crystal sample containing the anthracene group is subjected to powder diffraction test by using an Shimadzu XRD-6100X-ray diffractometer (see figure 3, abscissa-angle; ordinate-diffraction intensity), and the peak of the test spectrum can be well matched with the peak of a crystal structure fitting spectrum (software Mercury), so that the structure of the obtained crystal sample is the same as that of the obtained single crystal data, and the purity of the sample is high.
In the crystal sample, a suitable single crystal was selected and subjected to X-ray single crystal diffraction analysis to analyze the crystal structure (see fig. 1 and 2). Wherein FIG. 1(a) shows a coordination pattern of an organic ligand and a metal ion, and FIG. 1(b) shows a composition of [ Cd2N4(CO2)4]The distance between O1. Cd1 is the double-core cluster
Indicating a weaker interaction between them; for clarity, pyan-B is omitted and simplified to the 6-linked secondary building block (6-c SBU). FIG. 2(a) shows Hbtot2-pyan-A and Cd2 +The constructed coordination polymerization layer and the 6-linked layered simplified structure thereof are shown in FIG. 2(b) as Hbtot2-pyan-A, pyan-B and Cd2+Construction of [ Cd (Hbtot) (pyan)1.5]nStacking pattern of polymerized layer in [ Cd (Hbtot) (pyan)1.5]nStacking diagram of polymerized layer, Hbtot existing in two-dimensional metal-compound coordination polymerized layer2-And a channel surrounded by a pyan ligand, the channel having a diameter of about
(schematic column), FIG. 2(c) is a schematic diagram ofThe polymerization layers are stacked into a three-dimensional metal-organic supermolecule polymerization network through pi-pi interaction.
Determination of the Single Crystal Structure: selecting proper single crystal, and making the selected single crystal pass through a SMARTAPEXII CCD single crystal diffractometer (Mo-Ka,
graphite monochromator) were collected at room temperature and X-ray diffraction data were corrected for Lp factor. The crystal structure is solved by direct method, the analysis and refinement of the structure are completed by SHELXTL-97 program package, and then the full matrix least square method F is used2All non-hydrogen atoms are anisotropically refined. The hydrogen atom coordinates of the organic ligand are obtained by theoretical hydrogenation. The main crystallographic data are shown in table 1; the length of the coordination bond is shown in Table 2.
Table 1 main crystallographic data
*R1＝Σ||Fo|-|Fc||/Σ|Fo|,wR2＝[Σw(Fo 2-Fc 2)2/Σw(Fo 2)2]1/2
TABLE 2 length of coordination bond
Symmetric conversion, #1-x +1, -y, -z + 1; #2x, y, z +1
Thermogravimetric data analysis of the crystalline sample obtained showed (see figure 4, air atmosphere, abscissa-temperature; ordinate-residue) that the framework started to decompose after 370 ℃. Thermogravimetric data show that the cadmium-organic supermolecule containing the anthracene group has higher thermal stability.
The chemical formula of the cadmium-organic supermolecular polymer containing anthracene group is C63H40N3O9Cd, formula weight 1095.39, with C, H, N elemental analysis, calculated (%): c69.08, H3.68, N3.84; actually measured (%): c69.06, H3.64, N3.88. FIG. 5 is the infrared spectrum (abscissa-wavenumber; ordinate-transmittance) FT-IR (KBr, cm) of cadmium-organic supramolecular polymers containing anthracene group-1): 3068(w),1713(m),1601(vs),1545(s),1395(vs),1217(vs),1157(s),1000(s),784(m),641 (w). Description of the drawings: the infrared spectrum is obtained by a Nicolet Impact 410FTIR spectrometer with KBr as the bottom at 400-4000cm-1Measured within the range.
The solid state fluorescence spectrum of the crystal product is tested by the crystal sample at room temperature (see figure 6, abscissa-wavelength; ordinate-fluorescence intensity), and the data shows that under the excitation of the light with the wavelength of 415nm, the crystal has an obvious fluorescence emission peak at 530nm and a slightly weak shoulder at 490nm, and the whole crystal emits green fluorescence. In contrast to the fluorescence emission spectrum (439nm) of the chromophoric material pyan, the CdOSP luminescence mechanism may be due to charge transport of the ligand to the metal ion center.
The method is repeated for many times, the mass of the practically obtained supramolecular polymer is kept between 18.5 and 22.0mg, and the yield is 63.3 to 75.3 percent based on the dose of pyan.
Example 2
Taking the following materials according to the specific mass or volume: h3btot(19.4mg，0.04mmol)，pyan(13.3mg，0.04mmol)，Cd(NO3)2·4H2O(18.6mg，0.06mmol)，CH3CN(1mL)，H2O(9mL)，HNO3(20uL, 7mol/L, 0.14 mmol). Placing the materials in a 25mL reaction kettle, stirring for 30min, heating to 140 ℃, reacting for 4 days, naturally cooling to room temperature to obtain blocky crystals, filtering out the blocky crystals from mother liquor, washing with distilled water, and naturally drying in the air at room temperature.
The product was characterized by X-ray diffraction (see FIG. 2), and data similar to example 1 were obtained. It is shown that the crystal structure obtained in example 2 is unchanged and the product purity is high.
The method is repeated for a plurality of times, the mass of the practically obtained supramolecular polymer is kept between 15.1 and 18.2mg, and the yield is 51.7 to 62.3 percent based on the pyan dosage calculation.
Example 3
Taking the following materials according to the specific mass or volume: h3btot(19.5mg，0.04mmol)，pyan(13.3mg，0.04mmol)，Cd(NO3)2·4H2O(30.8mg，0.1mmol)，CH3CN(1mL)，H2O(9mL)，HNO3(50uL, 7mol/L, 0.35 mmol). Placing the materials in a 25mL reaction kettle, stirring for about 20min, heating to 150 ℃, reacting for 5 days, naturally cooling to room temperature to obtain blocky crystals, filtering out the blocky crystals from mother liquor, washing with distilled water, and naturally drying in the air at room temperature.
The product was characterized by X-ray diffraction (see FIG. 2), and data similar to example 1 were obtained. For description purpose
The crystal structure of the product obtained in example 3 was unchanged and the product was purer.
The method is repeated for a plurality of times, the mass of the practically obtained supermolecule polymer is kept between 17.6 and 19.4mg, and the yield is 60.2 to 66.4 percent based on the pyan dosage calculation.
Example 4 fluorescence detection of anion and cation by cadmium-organic supramolecular polymer solution containing anthracene group
Preparing a detection solution of cadmium-organic supramolecular polymer (CdOSP) containing anthracene group in a 250mL conical flask, dissolving 0.0586g of ground crystal powder in 200mL of water, oscillating, shaking up, performing ultrasonic dispersion for 30min to obtain a suspension, aging the suspension for 3 days, and taking an upper clear solution for later use when the solution is stable.
4.5mL of anionic Cl were each metered in with a pipette-、Br-、I-、NO2 -、CH3CO2 -、C10H14N2O8 2-(EDTA2-Divalent negative ethylenediaminetetraacetate), WO4 2-And CO3 2-Aqueous sodium salt solution of(the concentration is 0.01mol/L) is put into a clean glass bottle with a serial number, 0.5mL of prepared CdOSP upper clear liquid is transferred into the glass bottle with the serial number by a transfer pipette, and the CdOSP upper clear liquid is shaken and ultrasonically mixed for 30min to obtain a solution to be detected for standby.
Similarly, 4.5mL of cationic Ag was pipetted+、Cr3+、Cu2+、Cd2+、Co2+、Mg2+、Ni2+、Pb2+And Zn2+Nitrate aqueous solution (concentration: 0.01 mol. L)-1) And (3) transferring 0.5mL of the prepared CdOSP supernatant clear solution into a clean glass bottle with a number by using a pipette, and performing ultrasonic treatment for 30min to uniformly mix the solution to be detected for later use.
Fluorescence analysis the fluorescence spectra of the above mentioned CdOSP solutions containing anions or cations, respectively, were measured by a Perkin-Elmer model LS55 fluorescence spectrometer under excitation by UV light at a wavelength of 374 nm.
From the fluorescence spectrum of FIG. 7 (abscissa-wavelength; ordinate-fluorescence intensity), the fluorescence emission of the CdOSP aqueous solution has a peak at 433 nm. Added anionic sodium salt solution, except Cl-In addition to the sodium salt of (A), the remaining sodium salts all enhance the fluorescence intensity of the original CdOSP solution, and CO3 2-The sodium salt of (A) makes the fluorescence enhancement of the CdOSP solution most pronounced, while EDTA2-The sodium salt causes the CdOSP solution to have fluorescence peaks at 485nm and 514 nm. As can be seen, the CdOSP aqueous solution can be used for anionic CO in a high-resolution fluorescence detection system3 2-And EDTA2-And (5) identifying the sodium salt.
From the fluorescence spectrum chart 8 (abscissa-wavelength; ordinate-fluorescence intensity), it can be seen that Pb was added2+The nitrate slightly enhances the fluorescence intensity of the CdOSP solution; the addition of the rest metal nitrate weakens the fluorescence intensity of the CdOSP solution, wherein the Cr3+The nitrate reduced the fluorescence intensity of the CdOSP solution most significantly and the position of the main peak red shifted to 464 nm. This shows that the CdOSP solution can be used for toxic heavy metal ion lead (Pb) in aqueous solution in the fields of environment, chemical industry and the like2+) And chromium (Cr)3+) And (4) detecting fluorescence.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (6)
1. The cadmium-organic supermolecular polymer containing anthracene group is characterized in that the chemical general formula is [ Cd (Hbtot) ((pyan))1.5]nBelonging to the triclinic system, space group is P-1, cell parameters
In the chemical general formula of the cadmium-organic supramolecular polymer, Hbtot2-Is a semi-rigid triorganic carboxylic acid H3btot by stripping 2 protons, H3The structure of btot is shown as formula I; in the chemical general formula, the structural formula of the ligand pyan is shown as formula II:
the cadmium-organic supramolecular polymer containing anthracene groups comprises 1 Hbtot in crystallographically independent asymmetric units2-1 Cd2+And 1.5 pyan; in the crystallographically independent asymmetric unit, Hbtot2-The coordination mode is shown as formula III; the ligand pyan comprises two coordination modes, wherein the two coordination modes are a bridging mode pyan-A shown as a formula IV and a monodentate mode pyan-B shown as a formula V; in the space structure of the cadmium-organic supermolecule polymer containing anthracene group, carboxylate radical, pyridine N atom and Cd2+Form a composition of [ Cd2N4(CO2)4]A dual core cluster of, e.g.The binuclear cluster is simplified to a secondary building unit SBU, as shown in formula VI, wherein the dotted line indicates pyan-B, as shown in formula VII; the Hbtot2-Constructing a two-dimensional metal-mixed body coordination polymerization layer by pyan and SBU, wherein the two-dimensional metal-mixed body coordination polymerization layer is shown as a formula VIII; the coordination polymerization layers are further stacked through pi-pi interaction to form a three-dimensional metal-organic supramolecular polymer:
2. a method for preparing cadmium-organic supramolecular polymer containing anthracene group according to claim 1, wherein the cadmium-organic supramolecular polymer containing anthracene group is H3btot、pyan、Cd(NO3)2·4H2O and HNO3The preparation method is characterized in that the raw material is a mixed solution of acetonitrile and water as a solvent, and the solvent thermal synthesis method is adopted for preparation, and the preparation method specifically comprises the following steps:
(1) feeding a raw material H3btot、pyan、Cd(NO3)2·4H2O and HNO3Mixing acetonitrile and water as solvents to form a reaction system, and placing the reaction system in a closed container; said H3btot、pyan、Cd(NO3)2·4H2O and HNO3The mass ratio of (1): 1: 1.5-2.5: 3.5-8.8, wherein the volume ratio of the solvent acetonitrile to water is 1: 9;
(2) and (3) placing the reaction system at room temperature, stirring for 10-30min, then heating the reaction system to 140-160 ℃, reacting for 3-5d, and then naturally cooling, filtering and drying to obtain blocky crystals.
3. The method for preparing cadmium-organic supramolecular polymers with anthracene group according to claim 2, wherein H is in step (1)3btot：pyan：Cd(NO3)2·4H2O：HNO3The mass ratio of (1): 1: 2.5: 5.25.
4. the method for preparing cadmium-organic supramolecular polymers containing anthracene group as claimed in claim 2,characterized in that H is contained in the reaction system3The quantitative concentration of the starting material of btot was 4 mmol/L.
5. The method for preparing cadmium-organic supramolecular polymers with anthracene group according to claim 2, wherein the reaction temperature in step (2) is 160 ℃, and the drying is natural drying in air at room temperature after the crystals are washed with distilled water.
6. The application of cadmium-organic supramolecular polymer containing anthracene group is characterized in that the cadmium-organic supramolecular polymer containing anthracene group prepared by the method of any one of claims 2-5 is applied to CO3 2-、EDTA2-、Pb2+And Cr3+And for the use of biomarkers, optical device preparation, color formulation for non-disease diagnosis and treatment.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259939A (en) * | 1997-06-11 | 2000-07-12 | 伯拉考公司 | Process for preparing macrocyclic chelants and chelates thereof with paramagnetic metal ions |
| CN1294519A (en) * | 1999-02-18 | 2001-05-09 | 英法马有限公司 | Pharmaceutical Compsns. contg. compounds with activity for enhancement of absorption of active ingredients |
| CN106317090A (en) * | 2016-08-15 | 2017-01-11 | 衡阳师范学院 | Cadmium complex containing naphthyl methyl carboxyl and phenanthroline and preparation method and application of cadmium complex |
| CN107428837A (en) * | 2015-04-22 | 2017-12-01 | 免疫医疗公司 | Circulate separation, detection, diagnosis and/or the identification of the positive cancer cells of TROP 2 |
| CN107602596A (en) * | 2017-09-14 | 2018-01-19 | 河南城建学院 | A kind of Zn MOF fluorescent sensing materials and preparation method thereof |
| CN108640934A (en) * | 2018-05-30 | 2018-10-12 | 山西大学 | A kind of cadmium metal organic framework material and its preparation method and application |
| CN109749091A (en) * | 2019-02-21 | 2019-05-14 | 重庆师范大学 | Organic cyclic annular supermolecule of a kind of sky blue fluorescence cadmium and the preparation method and application thereof |
-
2019
- 2019-11-11 CN CN201911092984.XA patent/CN110776649B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259939A (en) * | 1997-06-11 | 2000-07-12 | 伯拉考公司 | Process for preparing macrocyclic chelants and chelates thereof with paramagnetic metal ions |
| CN1294519A (en) * | 1999-02-18 | 2001-05-09 | 英法马有限公司 | Pharmaceutical Compsns. contg. compounds with activity for enhancement of absorption of active ingredients |
| CN107428837A (en) * | 2015-04-22 | 2017-12-01 | 免疫医疗公司 | Circulate separation, detection, diagnosis and/or the identification of the positive cancer cells of TROP 2 |
| CN106317090A (en) * | 2016-08-15 | 2017-01-11 | 衡阳师范学院 | Cadmium complex containing naphthyl methyl carboxyl and phenanthroline and preparation method and application of cadmium complex |
| CN107602596A (en) * | 2017-09-14 | 2018-01-19 | 河南城建学院 | A kind of Zn MOF fluorescent sensing materials and preparation method thereof |
| CN108640934A (en) * | 2018-05-30 | 2018-10-12 | 山西大学 | A kind of cadmium metal organic framework material and its preparation method and application |
| CN109749091A (en) * | 2019-02-21 | 2019-05-14 | 重庆师范大学 | Organic cyclic annular supermolecule of a kind of sky blue fluorescence cadmium and the preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| A fluorescent anthracene-based metal–organic framework for highly selective detection of nitroanilines;Jian-Hong Wang，等;《Inorganica Chimica Acta》;20171227;第473卷;第70-74页 * |
| Luminescent and magnetic properties of three novel metal-organic polymers based on a semi-rigid tripodal carboxylic ligand;Jie Zhang，等;《Polyhedron》;20171231;第137卷;第238–245页 * |
| Structural Diversity, Magnetic Properties, and Luminescent Sensing of the Flexible Tripodal Ligand of 1,3,5-Tris(4-carbonylphenyloxy)benzene Based Mn(II)/Cd(II) Coordination Polymers;Jie Zhang,等;《Cryst. Growth Des.》;20170927;第17卷;第5887-5897页 * |
| Three coordination polymers based on 9,10-di(pyridine-4-yl)anthracene ligand: Syntheses, structures and fluorescent properties;Jun-Liang Dong，等;《Journal of Molecular Structure》;20171231;第1142卷;第304-310页 * |
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