CN115636947A - Preparation method of hydrogen bond organic framework material and application of hydrogen bond organic framework material in fluorescence detection - Google Patents
Preparation method of hydrogen bond organic framework material and application of hydrogen bond organic framework material in fluorescence detection Download PDFInfo
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- 239000013384 organic framework Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000001917 fluorescence detection Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 10
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 16
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Abstract
The invention discloses a preparation method and application of a hydrogen bond organic framework with a hexapetalous flower-shaped channel structure. The hydrogen bond organic framework of the invention is prepared by a solvothermal method. The chemical general formula is [ (NBP-DAT) 2 (2‑MOEtOH)] n Wherein n is a natural number of 1 to infinity, NBP-DAT is 4', 4' -nitrile (([ 1,1' -biphenyl)]-4-diaminotriazine)), 2-moethoh being 2-methoxyethanol; the hydrogen bond organic framework belongs to a triclinic system, P-1 space group, and has unit cell parameters of
Axial angle alpha=89.236 °, β =75.028 °, γ =74.389 °, cell volume
Z =2. The hydrogen bond organic framework belongs to a layered stack structure, NBP-DAT molecules are connected in a head-to-shoulder mode through circulation of diamine triazine functional groups, and a hexapetalous flower-shaped pore structure is formed. The hydrogen bond organic framework can be used for preparing an adsorption material, a catalytic material, a biological recognition material and a drug carrier, and is a multifunctional porous material with great potential. The hydrogen bond organic framework can also be applied to fluorescence detection of perfluorooctanoic acid.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of a hydrogen bond organic framework material with a hexapetalous flower-shaped channel structure and application of the hydrogen bond organic framework material in the field of fluorescence recognition.
Background
As a novel highly ordered porous crystalline material, the hydrogen bond organic framework material has the characteristics of high specific surface area, adjustable pore diameter, low density and the like, and becomes one of new research hotspots in the fields of chemistry and material science. Like the traditional molecular sieve and porous carbon material, the hydrogen bond organic framework material has good application prospects in aspects of gas adsorption and separation, chiral separation, small molecule identification, fluorescent probes, proton conduction, drug molecule transfer and the like.
So far, a hydrogen bond organic framework containing a diamino triazine (DAT) functional group has been reported, and the DAT has abundant hydrogen bond giving and receiving sites, so that the hydrogen bond organic framework is endowed with diversified structural characteristics, thereby presenting various characteristics and functions and having great application prospects in the aspects of catalytic chemistry, material science and the like. For example { Yabingg He, shengchang Xiaoing, and Banglin Chen.J.am.chem.Soc.2011,133,14570-14573}, { Hailong Wang, hui Wu, jinglan Kan, wei Zhou, shengchang Xiao, john Cong-Gui Zhu and Banglin Chen.J.Mater.chem.A,2017,5, 2-8296} and { Peng Li, yag He, jie Guang, lingcong Weng, john Cong-Gui Zhu, shengchang Xiao, and Banglin n.J.Amin. Chem.Soc.2014,136, 547-4 ', 4',4 ', 4' -tetrakis (4, 6-diamino-cis-triazine-2-phenyl) tetraphenylmethane, 1,3, 5-tris (2, 4-diamino-1, 3, 5-triazine-6-phenyl) -2,4, 6-trimethylbenzene, and (left) -4,4', 6' -tetrakis (2, 4-diamino-1, 3, 5-triazine-6-phenyl) -2,2 '-diethoxy-1, 1' -binaphthalene are used in the fields of gas adsorption separation, small molecule recognition, and chiral separation, respectively, by self-assembling to hydrogen-bonded organic framework materials with different pore types. The ligands used for constructing the hydrogen bond organic framework are aromatic organic ligands containing diamino triazine functional groups, but the hydrogen bond organic framework material with triphenylamine groups having hexapetalous flower-shaped pore channel structure has not been reported.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a preparation method of a hydrogen bond organic framework material with a hexapetalous flower-shaped channel structure and application of the hydrogen bond organic framework material in the field of fluorescence identification, and enriches the preparation method, channels and structure types of the hydrogen bond organic framework material.
The technical scheme for solving the technical problems is as follows: a preparation method and fluorescence identification application of a hydrogen bond organic framework with a hexapetalous flower-shaped channel structure are provided. The chemical general formula is [ (NBP-DAT) 2 (2-MOEtOH) ] n, wherein n is a natural number from 1 to infinity, NBP-DAT is 4', 4' -nitrile (([ 1,1' -biphenyl ] -4-diaminotriazine)), and 2-MOEtOH is 2-methoxyethanol;
wherein the hydrogen bond organic framework with the hexapetalous flower-shaped pore structure belongs to a triclinic system, P-1 space group, and the unit cell parameter is
Shaft angle α =89.236 °, β =75.028 °, γ =74.389 °, unit cell volume of
Z＝2。
The beneficial effects of the invention are: the hydrogen bond organic framework belongs to a layered stacking structure and can be used for preparing an adsorption material, an antibacterial material, a catalytic material, a fluorescence detection material, a photo-electromagnetic material and a drug carrier. The crystal structure of the hydrogen bond organic framework is tested by a SuperNova micro-focal spot X-ray single crystal diffractometer of Agilent under the condition of 298K, and data reception is carried out on an Eos CCD. Data analysis absorption correction was performed with a graphite monochromator with λ (Cu K α) as a variable arbitrary angle scan at ω -2 θ using a crystalispro tool. All structures are directly solved by a ShelXs program packaged by ShelXtl, and are refined by a ShelXl full matrix least square method. All non-hydrogen atoms are treated anisotropically, the hydrogen atoms of the organic ligands being generated by geometric symmetry
The organic frame structure of the key of the invention belongs to a triclinic system P-1 space group, and the basic structural unit of the crystal is formed by asymmetric units through symmetric operation (the symmetric operation code is #1 -x, -y, -z) in a layered packing structure.
The asymmetric unit consists of two 4', 4' -nitriles (([ 1,1' -biphenyl ] -4-diaminotriazine)) and one 2-methoxyethanol molecule.
The hydrogen bond organic framework material is formed by intermolecular hydrogen bond connection and has a three-dimensional structure, wherein a single monomer molecule is connected with 4 adjacent molecules through 12N-H8230, N is connected, a 2D supermolecule layer is formed by self-assembly, and the adjacent 2D supermolecule layers are stacked through pi-pi action to form a 3D hydrogen bond organic framework. After the Van der Waals radius of atoms is removed, a six-petal flower-shaped pore channel exists in the hydrogen bond organic framework in the vertical direction of the (-1-22) crystal face, and disordered object molecules exist in the pore channel. The monomer molecule is 4', 4' -nitrile (([ 1,1' -biphenyl ] -4-diaminotriazine)), and the structural formula is as follows:
the invention also provides a preparation method of the hydrogen bond organic framework material with the hexapetalous pore canal structure, which comprises the following steps:
1) Preparing the hydrogen bond organic framework reaction solution: in a three-necked flask, 4 '-nitrile (([ 1,1' -biphenyl ] -4-nitrile)), dicyandiamide and potassium hydroxide were dissolved in a solvent, 2-methoxyethanol, under a nitrogen atmosphere at a certain temperature to obtain a light yellow reaction solution.
2) Preparing the hydrogen bond organic framework: and standing the reaction solution at a certain temperature, preserving the temperature for a period of time, and filtering to obtain the hydrogen bond organic framework.
In the step 1), the purity of the solvent 2-methoxyethanol is 98%, and the volume is 20mL;4', 4' ",4" "'-nitrile (([ 1,1' -biphenyl ] -4-carbonitrile)) had a purity of 97%, a concentration of 0.046mmol/mL and a volume of 20mL; the purity of dicyandiamide is 99%, the concentration is 0.54mmol/mL, and the volume is 20mL; the purity of potassium hydroxide was 95%, the concentration was 0.133mmol/mL, and the volume was 20mL. The dissolving temperature is 125 ℃, and the dissolving time is 0.5h. The synthetic monomer raw materials 4', 4' -nitrile (([ 1,1' -biphenyl ] -4-nitrile) and dicyandiamide have the structural formula:
in step 2), the reaction temperature is 125 ℃; the reaction time was 48h.
The beneficial effects of the invention are: the preparation method has the advantages of simple reaction conditions, rapid reaction, energy conservation and time conservation. The preparation method has high yield, saves cost and can be used for batch production.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the reaction conditions in the step 2) can be adjusted to be magnetic stirring and heat preservation for 48 hours at 125 ℃, and further the hydrogen bond organic framework material with smaller size can be obtained.
The hydrogen bond organic framework material with smaller size has higher external specific surface area and exposes more active recognition sites on the basis of the material obtained in the step 2).
The invention also provides application of the hydrogen bond organic framework material in the field of fluorescence detection, the hydrogen bond organic framework material is used as a fluorescent material and is dispersed in a solvent to be detected, and then fluorescence intensity is detected through a fluorescence spectrometer, so that fluorescence detection is realized.
The invention has the beneficial effects that: the hydrogen bond organic framework material has strong yellow fluorescence emission at 552nm, can be used for fluorescence detection, and is a very efficient and accurate detection material.
The invention also provides application of the hydrogen bond organic framework material in the field of detection of perfluorooctanoic acid, wherein the aqueous solution of the perfluorooctanoic acid is added into the aqueous suspension of the hydrogen bond organic framework to generate red shift of a fluorescence emission peak so as to detect the perfluorooctanoic acid.
The beneficial effects of the invention are: the hydrogen bond organic framework can be used for identification and detection of perfluorooctanoic acid
Drawings
FIG. 1 is a diagram of an asymmetric unit structure of a hydrogen bonding organic framework of the present invention;
FIG. 2 is a diagram of a hydrogen bonding organic framework of the present invention;
FIG. 3 is a graph of the thermal weight loss of the hydrogen bond organic framework of the present invention, with the abscissa being temperature and the ordinate being weight loss percentage;
FIG. 4 is an infrared spectrogram of the hydrogen bonding organic framework of the present invention, the abscissa is the wave number and the ordinate is the transmittance;
FIG. 5 is a solid state fluorescence spectrum of a hydrogen bonding organic framework of the present invention, with wavelength on the abscissa and brightness on the ordinate;
FIG. 6 is a graph showing the effect of perfluorooctanoic acid on the fluorescence shift of hydrogen bond organic frameworks, where the abscissa is the wavelength and the emission peak position, and the ordinate is the relative brightness.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for preparing a hydrogen bonding organic framework comprises the following steps:
1) Preparing the hydrogen bond organic framework reaction solution: accurately weighing 0.400g of preparation raw materials 4', 4' -nitrile (([ 1,1' -biphenyl ] -4-nitrile)), 0.900g of dicyandiamide and 0.1500g of potassium hydroxide in a three-opening reaction bottle by using an analytical balance, adding 20mL of 2-methoxy ethanol solvent at room temperature, and heating for a period of time at a certain temperature to dissolve the mixture to obtain a light yellow reaction solution.
2) Preparing the hydrogen bond organic framework: and standing the reaction solution at a certain temperature, keeping the temperature for a period of time, and filtering to obtain the hydrogen bond organic framework.
The purity of the solvent 2-methoxy ethanol in the step 1) is 98%. The 4',4"',4" "'-nitrile (([ 1,1' -biphenyl ] -4-carbonitrile)) had a purity of 97%, a concentration of 0.046mmol/mL, and a volume of 20mL; the purity of dicyandiamide is 99%, the concentration is 0.54mmol/mL, and the volume is 20mL; the purity of potassium hydroxide was 95%, the concentration was 0.133mmol/mL, and the volume was 20mL. The dissolving temperature is 125 ℃, and the dissolving time is 0.5h.
In step 2), the reaction temperature is 125 ℃; the time is 48h.
And testing the obtained hydrogen bond organic frame by using a Supernova micro-focal spot X-ray single crystal derivator of Agilent company under the condition of 298K, and performing data receiving on an Eos CCD. Data analysis absorption correction was performed with a graphite monochromator, with lambda (Cu K alpha) as a variable arbitrary angle scan at omega-2 theta using a crystalispro tool. All structures are directly solved by a ShelXs program packaged by ShelXtl, and are refined by a ShelXl full matrix least square method. All non-hydrogen atoms are subjected to anisotropic treatment, and the hydrogen atoms of the organic ligand are generated by geometric symmetry to obtain crystal data shown in table 1, typical hydrogen bond length data of crystals shown in table 2, and typical hydrogen bond angle data of crystals shown in table 3. Table 1, table 2 and table 3 are as follows:
table 1: crystal data
Table 2: typical hydrogen bond length data for crystals (unit:
)
table 3: typical hydrogen bond angle data of crystal (unit:. Degree.)
| Nitrogen atom (N1) | Hydrogen atom (H) | Nitrogen atom (N2) | Key angle/° C |
| N24 | H43B | N43 | 153.475 |
| N26 | H11A | N11 | 165.25 |
| N3 | H32B | N32 | 163.597 |
| N5 | H2A | N2 | 155.376 |
| N15 | H41A | N41 | 176.618 |
| N25 | H21B | N21 | 168.586 |
| N12 | H22A | N22 | 170.417 |
| N18 | H8B | N8 | 170.831 |
| N19 | H52B | N52 | 176.479 |
| N39 | H38B | N38 | 167.852 |
| N13 | H0AC | N0 | 167.852 |
| N29 | H48A | N48 | 175.432 |
The hydrogen bonded organic framework belongs to the triclinic system, P-1 space group. Having a cell parameter of
Axial angle α =89.236 °, β =75.028 °, γ =74.389 °, cell volume
Z＝2。
As shown in FIG. 1, the asymmetric unit consists of two NBP-DATs and one 2-MOEtOH.
As shown in FIG. 2, each NBP-DAT molecule is cyclically linked in a head-to-side manner with three adjacent NBP-DAT molecules through 12 hydrogen bonds, forming a two-dimensional layered structure. The two-dimensional layered structure forms the three-dimensional hydrogen bond organic framework material through the inter-layer pi-pi stacking interaction.
As shown in FIG. 3, the hydrogen bond organic framework is subjected to thermogravimetric curve analysis, thermogravimetric test is carried out on a Mettler synchronous thermogravimetric analyzer, the model of the machine is RGA/DSC-1, reaction gas and protective gas are nitrogen, the flow rates are respectively 50ml/min, the running time is 50 minutes, and the heating rate is 10 ℃/min. The testing temperature range is 40-900 ℃. From the thermogravimetric curve, the organic framework of the hydrogen bond loses crystal water in the system at 40-100 ℃, and then the complex can be stabilized to 450 ℃ and decomposed at 450 ℃. The hydrogen bond organic framework has good stability and can be decomposed at high temperature.
As shown in figure 4, the hydrogen bond organic framework is detected by infrared spectroscopy, KBr tabletting method is adopted in the infrared testing, and 4000-500 cm are collected on a Nicolet 330FTIR spectrometer -1 Infrared (IR) spectrum in the region. As can be seen in FIG. 4, the complex is located at 3420cm -1 The nearby absorption peak can be assigned as the stretching vibration peak of the amine group.
As shown in FIG. 5, the hydrogen bond organic frame was tested on an F-7000 type fluorescence spectrophotometer with an excitation wavelength of 360nm and entrance and exit slits of 5nm to obtain a solid state fluorescence spectrum. The fluorescence emission wavelength of the hydrogen bond organic framework is near 552nm, which shows that the hydrogen bond organic framework has stronger fluorescence at 552nm and can be applied to the field of fluorescence detection.
As shown in FIG. 6, 2.0mg of the hydrogen bond organic framework is weighed and dispersed in 2mL of water, and the detection solution is prepared by ultrasonic treatment for 15 min. The detection equipment is a Hitachi F7000 fluorescence spectrometer, the excitation wavelength is 360nm, and the entrance slit and the exit slit are both 5nm.
Gradually adding 1mmol/L aqueous solution of perfluorooctanoic acid into the aqueous suspension containing the hydrogen bond organic framework, wherein the fluorescence emission peak of the hydrogen bond organic framework can generate red shift, and the detection capability of the perfluorooctanoic acid is realized. The hydrogen bond organic framework can be used for identification and detection of perfluorooctanoic acid.
The specific examples of the present invention have been described above. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The hydrogen bond organic framework material is characterized in that the chemical general formula of the hydrogen bond organic framework material is [ (NBP-DAT) 2 (2-MOEtOH)]n, wherein n is a natural number from 1 to infinity, NBP-DAT is 4', 4' -nitrile (([ 1,1' -biphenyl)]-4-diaminotriazine)), 2-moethoh is 2-methoxyethanol; wherein the hydrogen bonding organic framework belongs to a triclinic system, P-1 space group, and has a unit cell parameter of
Axial angle α =89.236 °, β =75.028 °, γ =74.389 °, cell volume
Z＝2。
2. The hydrogen bonding organic framework material of claim 1 wherein the hydrogen bonding organic framework material has a hexapetalous flower-shaped channel structure.
3. The method for preparing hydrogen bonding organic framework material according to claim 1, wherein the step of synthesizing the hydrogen bonding organic framework comprises the following processes:
1) Preparing the hydrogen bond organic framework reaction solution: dissolving 4', 4' -nitrile (([ 1,1' -biphenyl ] -4-nitrile)), dicyandiamide and potassium hydroxide in a solvent 2-methoxyethanol in a three-necked flask at a certain temperature under a nitrogen atmosphere to obtain a light yellow reaction solution;
2) Preparing the hydrogen bond organic framework: and standing the reaction solution at a certain temperature, preserving the temperature for a period of time, and filtering to obtain the hydrogen bond organic framework.
4. The method for preparing the hydrogen bonding organic framework material according to claim 3, wherein in the step 1), the purity of the solvent 2-methoxyethanol is 98%, and the volume is 20mL;4', 4' ",4" "'-nitrile (([ 1,1' -biphenyl ] -4-carbonitrile)) had a purity of 97%, a concentration of 0.046mmol/mL and a volume of 20mL; the purity of dicyandiamide is 99%, the concentration is 0.54mmol/mL, and the volume is 20mL; the purity of potassium hydroxide was 95%, the concentration was 0.133mmol/mL, and the volume was 20mL. The dissolving temperature is 125 ℃, and the dissolving time is 0.5h.
5. The method for preparing the hydrogen bonding organic framework material according to claim 3, wherein in the step 2), the reaction temperature is 125 ℃; the reaction time was 48h.
6. The method for preparing hydrogen bonding organic framework material according to claim 5, wherein the heat preservation in the step 2) is carried out under magnetic stirring.
7. Use of a hydrogen-bonding organic framework as defined in claim 1 or 2 in the field of fluorescence detection.
8. The application of the hydrogen bond organic framework as claimed in claim 6 in the field of fluorescence detection, which is applied to perfluorooctanoic acid fluorescence recognition.
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| CN110938282A (en) * | 2019-10-30 | 2020-03-31 | 中国石油化工股份有限公司 | Composite material with covalent organic framework and core-shell structure and preparation method and application thereof |
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| HUA-QING YIN等: "A switchable sensor and scavenger: detection and removal of fluorinated chemical species by a luminescent metal–organic framework", 《CHEM. SCI》, vol. 12, pages 14195 * |
| SHOU FENG等: "Fabrication of a Hydrogen-Bonded Organic Framework Membrane through Solution Processing for Pressure-Regulated Gas Separation", 《ANGEW. CHEM. INT. ED.》, vol. 59, pages 3 * |
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