CN110627799A - Preparation method of tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material - Google Patents
Preparation method of tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material Download PDFInfo
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- -1 tetra (hydroxyphenyl) zinc Chemical compound 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000011540 sensing material Substances 0.000 title claims abstract description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 18
- HOEJXJMZXGNCBJ-UHFFFAOYSA-N ethene 4-ethenylbenzoic acid Chemical group C=CC1=CC=C(C=C1)C(=O)O.C=C HOEJXJMZXGNCBJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- KIXZZMBAMXKNER-UHFFFAOYSA-N C1=CC(O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 KIXZZMBAMXKNER-UHFFFAOYSA-N 0.000 claims description 8
- VFHDWGAEEDVVPD-UHFFFAOYSA-N chembl507897 Chemical compound C1=CC(O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(O)=CC=1)=C1C=CC(=N1)C(C=1C=CC(O)=CC=1)=C1C=CC(N1)=C1C=2C=CC(O)=CC=2)=C2N=C1C=C2 VFHDWGAEEDVVPD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- PHALXCJLVYDPKG-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.OC2=C(C=CC=C2)[Zn](C2=C(C=CC=C2)O)(C2=C(C=CC=C2)O)C2=C(C=CC=C2)O Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.OC2=C(C=CC=C2)[Zn](C2=C(C=CC=C2)O)(C2=C(C=CC=C2)O)C2=C(C=CC=C2)O PHALXCJLVYDPKG-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- KEBIPCDXOZMJSW-UHFFFAOYSA-N c1ccc(cc1)[Zr](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound c1ccc(cc1)[Zr](c1ccccc1)(c1ccccc1)c1ccccc1 KEBIPCDXOZMJSW-UHFFFAOYSA-N 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 150000004032 porphyrins Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000004033 porphyrin derivatives Chemical class 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002677 supramolecular polymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
The invention relates to the field of photosensitive sensing materials, and discloses a preparation method of a tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecular composite photosensitive sensing material. And then the tetra (hydroxyphenyl) zinc porphyrin is prepared by the hydrothermal method and zinc nitrate, which is simple and efficient. Finally, tetra (hydroxyphenyl) zinc porphyrin and 1, 2-diphenyl-1, 2-di (4-carboxystyrene) ethylene are compounded to prepare the tetraphenylzirconium porphyrin-AIE fluorescent molecular composite material.
Description
Technical Field
The invention relates to the field of photosensitive sensing materials, in particular to a preparation method of a tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material.
Background
Pure zinc is blue-white and lustrous. Hardness 2.5 (mol)Hardness in durometer). Has ductility. Density 7.14 g/cm3. Melting point 419.58 ℃ and boiling point 907 ℃. Valence + 2. Fifteen isotopes of zinc are known. Is a good heat conductor and electric conductor. The ionization energy 9.394 electron volts. The chemical property is more active, but the hydrogen is more stable in the air, and the hydrogen can be released by the action of the acid and the alkali.
The porphyrin and the derivatives thereof have unique photophysical properties and self-assembly capability. Both porphyrin and metalloporphyrin have high-intensity characteristic absorption peaks (Soret bands) in the ultraviolet visible region of 400-500 nm, and the molar absorption coefficient is usually 105L·mol-1·cm-1Left and right. Thus, porphyrins have also been used as "ultra-high sensitivity detection agents" for the detection of metal ions. In addition, the porphyrin derivative also has good fluorescence performance, the maximum emission wavelength in the fluorescence spectrum exceeds 650nm, the porphyrin derivative is in a red light region, and the intensity is large, so the porphyrin derivative is often used as a doping dye of red light to manufacture an organic electroluminescent device. In addition, stronger host-guest action exists between the porphyrin compound with negative charge and beta-cyclodextrin, and the complexation constant of the porphyrin compound with negative charge is as high as 108(mol/L) -1. Researches show that porphyrin molecules can enter a cavity from the secondary side along the symmetry axis direction of cyclodextrin to form a stable 2: 1 complex, so that the researches on supramolecular aggregates or supramolecular polymers based on porphyrin and cyclodextrin also attract extensive attention.
Since the aggregation-induced emission (AIE) phenomenon was discovered by the team of Thanksgiving academists in 2001, research on the light-emitting mechanism and the application prospect of AIE materials was carried out by many scientists at home and abroad. Compared with the traditional organic luminescent dye, the AIE fluorescent dye is a special organic fluorescent material which emits strong light in an aggregation or solid film state and does not emit light or emits weak light in a good solvent. The reported mechanisms of AIE luminescence are broadly classified into intramolecular rotational confinement, intramolecular coplanarity, inhibition of photophysical processes or photochemical reactions, non-close packing, J-aggregate formation, and special excimers, etc. Based on the intensive research on the AIE luminescence mechanism, a large number of luminescent dye systems with AIE properties have been developed, including Tetraphenylethylene (TPE), silole (silole), triphenylamine derivatives, anthracene substitutes, and the like. With the continuous abundance of AIE dye systems, it is necessary to explore the wide application potential. In recent decades, AIE materials have been subject to significant research advances in the fields of biological imaging, chemical/biological sensing, and Organic Light Emitting Diodes (OLEDs).
The construction of AIE fluorescence sensors is yet another important area of research for AIE materials. The fluorescence sensor is a reaction of the material with increased or decreased fluorescence based on the detection of special components, and comprises pH, temperature, hydrogen sulfide gas, explosive substances, biological polysaccharide, biological apoptosis and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material. And then the tetra (hydroxyphenyl) zinc porphyrin is prepared by the hydrothermal method and zinc nitrate, which is simple and efficient. Finally, tetra (hydroxyphenyl) zinc porphyrin and 1, 2-diphenyl-1, 2-di (4-carboxystyrene) ethylene are compounded to prepare the tetraphenylzirconium porphyrin-AIE fluorescent molecular composite material.
The specific technical scheme of the invention is as follows: a preparation method of a tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material comprises the following steps:
step 1: preparation of tetra (p-hydroxyphenylporphyrin): dissolving p-hydroxybenzaldehyde in n-propionic acid, heating to boil, and dropwise adding newly steamed pyrrole; continuously heating and refluxing, stopping heating, adding ethanol, shaking uniformly, standing at room temperature for cooling, cooling to separate out blue crystals, performing suction filtration, washing, and draining; to obtain the tetra (p-hydroxy phenyl) porphyrin.
Pyrrole and p-methoxybenzaldehyde are used as raw materials, two-step reaction is needed, and the synthetic product of the method is not easy to separate and purify. If the general synthesis of other porphyrin derivatives is followed, i.e. p-hydroxybenzaldehyde and pyrrole are reacted directly in propionic acid medium, the product cannot be crystallized out, but only some black hard solids are produced. The invention still adopts the reaction, and after the reaction is finished, the equal volume of ethanol is added to separate out blue crystals.
Step 2, preparing tetra (p-hydroxy phenyl) zinc porphyrin: dissolving tetra (p-hydroxyphenylporphyrin) and zinc nitrate powder in N, N-diethylformamide under vigorous stirring, and further stirring the resulting mixture at room temperature; after stirring, carrying out ultrasonic treatment on the obtained mixed solution; the resulting mixture was then transferred to a teflon lined autoclave, covered with a lid and placed in an oven for reaction, and the solution was cooled to room temperature and stored for future use.
The toxicity of the N, N-diethylformamide is lower than that of the N, N-dimethylformamide and dimethyl sulfoxide, and the N, N-diethylformamide has better solubility and is easy to recycle. The composite material is synthesized by a hydrothermal method, so that the specific surface area of the composite material can be increased, the electron transmission rate and the electron transportation way are increased, and the sensing efficiency is effectively enhanced.
Step 3, preparing the tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material: dissolving 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene and PVP in a mixed solution containing ethanol and DMF under stirring; slowly pouring the tetra (p-hydroxy phenyl) zinc porphyrin solution obtained in the step 2 under continuous stirring; then stirring the obtained mixed solution, and then carrying out ultrasonic treatment; then transferring the obtained mixture solution into a Teflon-lined high-pressure autoclave, and putting the high-pressure autoclave into an oven for reaction; cooling to room temperature, adding water into the obtained mixture, centrifuging, and removing supernatant; drying the precipitate; and finally grinding and collecting powder to obtain the target product.
Preferably, in mol and mL, the preparation of tetra (p-hydroxyphenyl) porphyrin in step 1 is specifically as follows: dissolving 0.5-1.5mol of p-hydroxybenzaldehyde in 400mL of 200-propanoic acid, heating to 295-305 ℃, and dropwise adding 0.5-1.5mol of newly steamed pyrrole; the solution changes from yellow to brownish black in the dropping process; continuously heating and refluxing for 10-30min, stopping heating, adding ethanol with the same volume, shaking, standing at room temperature for cooling, cooling for 2-3 hr to precipitate blue crystal, filtering, washing, and draining; to obtain the tetra (p-hydroxy phenyl) porphyrin.
Preferably, in the step 1, after the blue crystal is obtained, the blue crystal is filtered, washed for a plurality of times by propionic acid/ethanol with the ratio of 1: 1, washed for a plurality of times by chloroform and dried by pumping; the resulting product was dried at 120-180 ℃ for 1-2 hours.
Preferably, in mg and mL, the preparation method of the tetra (p-hydroxyphenyl) zinc porphyrin in the step 2 is as follows: the adding amount of the tetra (p-hydroxy phenyl) zinc porphyrin is 100-120mg, the adding amount of the zinc nitrate powder is 30-50mg, the adding amount of the N, N-diethylformamide is 20-40mL, the obtained mixed solution is stirred for 30-50min at room temperature, and ultrasonic treatment is carried out for 15-25min after stirring; then transferring the obtained mixture into an autoclave with a polytetrafluoroethylene lining, covering the autoclave with a cover, and placing the autoclave in an oven at the temperature of 100 ℃ and 140 ℃ for 20 to 30 hours; and cooling the finally obtained solution to room temperature, and storing for later use.
Preferably, in step 3, the amount of 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene added is 40 to 70mg, the amount of PVP added is 0.8 to 1.2mg, the amount of ethanol added is 15 to 25mL, and the amount of DMF added is 7.5 to 12.5mL, in mg and mL.
Preferably, in step 3, the MW of PVP is 55,000 to 60,000.
Preferably, in mg and mL, the adding amount of the tetra (p-hydroxyphenyl) zinc porphyrin solution in the step 3 is 15-45mL, the stirring is carried out for 20-40min, and the ultrasonic treatment is carried out for 15-25 min; the temperature of the oven is 60-100 ℃, and the reaction is kept for 12-48 hours; the addition amount of the deionized water is 5-15mL, the rotating speed is 3000-7000rpm, the centrifugation time is 5-15min, the drying temperature is 50-70 ℃, and the drying time is 40-50 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the tetra (hydroxyphenyl) zinc porphyrin and the AIE fluorescent molecule are synthesized by a hydrothermal method, which is beneficial to improving the active site, improving the sensitivity of the sensor and improving the transmission efficiency. The tetra (hydroxyphenyl) zinc porphyrin and the AIE fluorescent molecule have strong fluorescence performance, and the fluorescence performance can be enhanced by the combination of the tetra (hydroxyphenyl) zinc porphyrin and the AIE fluorescent molecule and is far greater than the single fluorescence performance.
2. TPE derivatives utilizing the AIE effect may provide a new approach for designing bio-probe molecules because TPE chromophores do not luminesce when dissolved in solution, but have high emissivity in the aggregate and solid states. Taking advantage of this, it is applied to chemical sensors.
3. Based on the excellent properties of porphyrin and AIE molecules, the sensitivity of the material to light can be improved, and the method has profound significance for the research and development of novel photosensitive sensors.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparation of tetra (p-hydroxyphenylporphyrin)
0.5mol of p-hydroxybenzaldehyde is dissolved in 200ml of n-propionic acid, heated to boiling and freshly distilled 0.5mol of pyrrole is added dropwise. Heating and refluxing were continued for 10 minutes. Stopping heating, adding ethanol with approximately equal volume, shaking, standing at room temperature for cooling, then placing in a refrigerator for cooling for 2-3h to precipitate blue crystals, washing with propionic acid/ethanol at a ratio of 1: 1 for three times, washing with chloroform for several times, and draining. The product was dried in an oven at 120 ℃ for 1 hour.
2) Preparation of tetra (p-hydroxybenzene) zinc porphyrin
100mg of the synthesized tetra (p-hydroxyphenyl) porphyrin and 30mg of zinc nitrate powder were dissolved in 20ml of N, N-diethylformamide under vigorous stirring, and the mixture was further stirred at room temperature for 30 min. After stirring, the mixed solution was subjected to ultrasonic treatment for 15 min. The mixture was then transferred to a teflon-lined autoclave (capacity 100mL), capped and placed in an oven at 100 ℃ for 24 hours. The solution is cooled to room temperature and stored for later use.
3) Preparation of tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material
40mg of 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene and 0.8mg of PVP (MW 58,000) were dissolved in a mixed solution containing 15ml of ethanol and 7.5ml of DMF with gentle stirring. 15ml of the zinc porphyrin solution thus prepared was slowly poured in under continuous stirring. The mixture was then stirred and then sonicated. After that, the mixture solution was transferred to a Teflon-lined autoclave. The autoclave was placed in an oven at 60 ℃ for 12 hours. After cooling to room temperature, the resulting mixture was poured into centrifuge tubes uniformly and 5ml of deionized water was added to each centrifuge tube. The mixture was then centrifuged in a centrifuge at 3000 rpm for 5 minutes and the supernatant discarded. The centrifuge tube containing the precipitate was placed in an oven at 60 ℃ for 48 hours. And finally, grinding and drying to obtain the tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material.
The purity of the porphyrin prepared by the method reaches more than 90 percent, the yield can be improved, and the sensitivity can be improved to a great extent by compounding the porphyrin and the porphyrin. The composite photosensitive sensing material prepared by the preparation method can be used for detecting hydrogen and explosive substances.
Example 2
1) Preparation of tetra (p-hydroxyphenylporphyrin)
1.0mol of p-hydroxybenzaldehyde is dissolved in 300ml of n-propionic acid, heated to boiling and freshly distilled 1.0mol of pyrrole are added dropwise. Heating and refluxing were continued for 20 minutes. Stopping heating, adding ethanol with approximately equal volume, shaking, standing at room temperature for cooling, then placing in a refrigerator for cooling for 2-3h to precipitate blue crystals, washing with propionic acid/ethanol at a ratio of 1: 1 for three times, washing with chloroform for several times, and draining. The product was oven dried at 150 ℃ for 1.5 hours.
2) Preparation of tetra (p-hydroxybenzene) zinc porphyrin
The synthesized 110mg of tetra (p-hydroxyphenylporphyrin) and 40mg of zinc nitrate powder were dissolved in 30ml of N, N-diethylformamide with vigorous stirring, and the mixture was further stirred at room temperature for 40 min. After stirring, the mixed solution was subjected to ultrasonic treatment for 20 min. The mixture was then transferred to a teflon-lined autoclave (capacity 100mL), capped and placed in an oven at 120 ℃ for 24 hours. The solution is cooled to room temperature and stored for later use.
3) Preparation of tetrakis (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material 55mg of 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene and 1.0mg of PVP (MW 58,000) were dissolved in a mixed solution containing 20ml of ethanol and 10ml of DMF under mild stirring. 30ml of the zinc porphyrin solution thus prepared was slowly poured in under continuous stirring. The mixture was then stirred and then sonicated. After that, the mixture solution was transferred to a Teflon-lined autoclave. The autoclave was placed in an oven at 80 ℃ for 24 hours. After cooling to room temperature, the resulting mixture was poured into centrifuge tubes uniformly and 10ml of deionized water was added to each centrifuge tube. The mixture was then centrifuged in a centrifuge at 5000 rpm for 10 minutes and the supernatant discarded. The centrifuge tube containing the precipitate was placed in an oven at 60 ℃ for 48 hours. And finally, grinding and drying to obtain the tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material.
Example 3
1) Preparation of tetra (p-hydroxyphenylporphyrin)
1.5mol of p-hydroxybenzaldehyde is dissolved in 400ml of n-propionic acid, heated to boiling and freshly distilled 1.5mol of pyrrole are added dropwise. Heating and refluxing were continued for 30 minutes. Stopping heating, adding ethanol with approximately equal volume, shaking, standing at room temperature for cooling, then placing in a refrigerator for cooling for 2-3h to precipitate blue crystals, washing with propionic acid/ethanol at a ratio of 1: 1 for three times, washing with chloroform for several times, and draining. The product was oven dried at 180 ℃ for 1.5 hours.
2) Preparation of tetra (p-hydroxybenzene) zinc porphyrin
120mg of the synthesized tetra (p-hydroxyphenyl) porphyrin and 50mg of zinc nitrate powder were dissolved in 40ml of N, N-diethylformamide under vigorous stirring, and the mixture was further stirred at room temperature for 50 min. After stirring, the mixed solution was subjected to ultrasonic treatment for 25 min. The mixture was then transferred to a teflon-lined autoclave (capacity 100mL), capped and placed in an oven at 140 ℃ for 24 hours. The solution is cooled to room temperature and stored for later use.
3) Preparation of tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material
70mg of 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene and 1.2mg of PVP (MW 58,000) were dissolved in a mixed solution containing 25ml of ethanol and 12.5ml of DMF with gentle stirring. The 45ml of zinc porphyrin solution thus prepared was slowly poured in under continuous stirring. The mixture was then stirred and then sonicated. After that, the mixture solution was transferred to a Teflon-lined autoclave. The autoclave was placed in an oven at 100 ℃ for 48 hours. After cooling to room temperature, the resulting mixture was poured into centrifuge tubes uniformly and 15ml of deionized water was added to each centrifuge tube. The mixture was then centrifuged in a centrifuge at 3000 rpm for 5 minutes and the supernatant discarded. The centrifuge tube containing the precipitate was placed in an oven at 60 ℃ for 48 hours. And finally, grinding and drying to obtain the tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material is characterized by comprising the following steps:
step 1: preparation of tetra (p-hydroxyphenylporphyrin): dissolving p-hydroxybenzaldehyde in n-propionic acid, heating to boil, and dropwise adding newly steamed pyrrole; continuously heating and refluxing, stopping heating, adding ethanol, shaking uniformly, standing at room temperature for cooling, cooling to separate out blue crystals, performing suction filtration, washing, and draining; to obtain tetra (p-hydroxy phenyl) porphyrin;
step 2, preparing tetra (p-hydroxy phenyl) zinc porphyrin: dissolving tetra (p-hydroxyphenylporphyrin) and zinc nitrate powder in N, N-diethylformamide under vigorous stirring, and further stirring the resulting mixture at room temperature; after stirring, carrying out ultrasonic treatment on the obtained mixed solution; then transferring the obtained mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, covering the high-pressure reaction kettle with a cover, placing the high-pressure reaction kettle into an oven for reaction, cooling the solution to room temperature, and storing the solution for later use;
step 3, preparing the tetra (hydroxyphenyl) zinc porphyrin-AIE fluorescent molecule composite photosensitive sensing material: dissolving 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene and PVP in a mixed solution containing ethanol and DMF under stirring; slowly pouring the tetra (p-hydroxy phenyl) zinc porphyrin solution obtained in the step 2 under continuous stirring; then stirring the obtained mixed solution, and then carrying out ultrasonic treatment; then transferring the obtained mixture solution into a Teflon-lined high-pressure autoclave, and putting the high-pressure autoclave into an oven for reaction; cooling to room temperature, adding water into the obtained mixture, centrifuging, and removing supernatant; drying the precipitate; and finally grinding and collecting powder to obtain the target product.
2. The method according to claim 1, wherein in step 1, the tetra (p-hydroxyphenyl) porphyrin is prepared by: dissolving 0.5-1.5mol of p-hydroxybenzaldehyde in 400mL of 200-propanoic acid, heating to 295-305 ℃, and dropwise adding 0.5-1.5mol of newly steamed pyrrole; the solution changes from yellow to brownish black in the dropping process; continuously heating and refluxing for 10-30min, stopping heating, adding ethanol with the same volume, shaking, standing at room temperature for cooling, cooling for 2-3 hr to precipitate blue crystal, filtering, washing, and draining; to obtain the tetra (p-hydroxy phenyl) porphyrin.
3. The process according to claim 1 or 2, wherein in step 1, the blue crystals are obtained and then filtered, washed several times with 1: 1 propionic acid/ethanol, washed several times with chloroform and dried; the resulting product was dried at 120-180 ℃ for 1-2 hours.
4. The method of claim 1, wherein the tetra (p-hydroxyphenyl) zinc porphyrin is prepared in step 2 in mg and mL as follows: the adding amount of the tetra (p-hydroxy phenyl) zinc porphyrin is 100-120mg, the adding amount of the zinc nitrate powder is 30-50mg, the adding amount of the N, N-diethylformamide is 20-40mL, the obtained mixed solution is stirred for 30-50min at room temperature, and ultrasonic treatment is carried out for 15-25min after stirring; then transferring the obtained mixture into an autoclave with a polytetrafluoroethylene lining, covering the autoclave with a cover, and placing the autoclave in an oven at the temperature of 100 ℃ and 140 ℃ for 20 to 30 hours; and cooling the finally obtained solution to room temperature, and storing for later use.
5. The method according to claim 1, wherein in step 3, the amount of 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene added is 40 to 70mg, the amount of PVP added is 0.8 to 1.2mg, the amount of ethanol added is 15 to 25mL, and the amount of DMF added is 7.5 to 12.5mL, in mg and mL.
6. The method of claim 1, wherein in step 3, the MW of PVP is 55,000-60,000.
7. The preparation method of claim 5, wherein in step 3, the addition amount of the tetra (p-hydroxyphenyl) zinc porphyrin solution is 15-45mL in mg and mL, stirring is performed for 20-40min, and ultrasonic treatment is performed for 15-25 min; the temperature of the oven is 60-100 ℃, and the reaction is kept for 12-48 hours; the addition amount of the deionized water is 5-15mL, the rotating speed is 3000-7000rpm, the centrifugation time is 5-15min, the drying temperature is 50-70 ℃, and the drying time is 40-50 h.
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| CN113234235A (en) * | 2021-06-22 | 2021-08-10 | 浙江理工大学 | Preparation method of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead |
| CN114892305A (en) * | 2022-05-05 | 2022-08-12 | 浙江理工大学 | Preparation method of tetra-p-aminophenyl zinc porphyrin-AIE-based MOF fluorescent fiber for anti-counterfeiting |
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| CN113234235A (en) * | 2021-06-22 | 2021-08-10 | 浙江理工大学 | Preparation method of meso-tetra (4-carboxyphenyl) zinc porphyrin-MOF material for detecting lead |
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| CN114892305A (en) * | 2022-05-05 | 2022-08-12 | 浙江理工大学 | Preparation method of tetra-p-aminophenyl zinc porphyrin-AIE-based MOF fluorescent fiber for anti-counterfeiting |
| CN114892305B (en) * | 2022-05-05 | 2024-04-19 | 浙江理工大学 | Preparation method of anti-counterfeiting tetra-p-aminophenyl zinc porphyrin-AIE-based MOF fluorescent fiber |
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