CN111205476A - Preparation method of spherical porphyrin - Google Patents
Preparation method of spherical porphyrin Download PDFInfo
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- CN111205476A CN111205476A CN202010129855.XA CN202010129855A CN111205476A CN 111205476 A CN111205476 A CN 111205476A CN 202010129855 A CN202010129855 A CN 202010129855A CN 111205476 A CN111205476 A CN 111205476A
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
The invention belongs to the field of nano material preparation, and relates to a method for preparing spherical porphyrin by blending solvent proportion, wherein tetrahydroxy tetraphenylporphyrin is dissolved in a benign solvent, and then different amounts of inert solvents are added, so that porphyrin molecules are aggregated to obtain spherical porphyrin aggregates; the benign solvent is one of dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, ethanol and methanol; the inert solvent is water. By adopting the technical scheme, tetrahydroxy tetraphenylporphyrin exists in a molecular form in a solvent with higher solubility, and when a solvent with lower solubility is added, the solubility is reduced, and the aggregation is instantly reached to a saturated state, so that spherical particles are formed.
Description
Technical Field
The invention belongs to the field of nano material preparation, and relates to a novel method for preparing spherical porphyrin.
Background
The porphyrin compound is a rigid coplanar molecule with an 18 pi electron conjugated system, widely exists in the biological world, has high molecular symmetry, strong rigidity, good photo-thermal stability, long excited state life, good photoelectric property, good photosensitivity, strong absorption and high molar extinction coefficient, and has wide application in the fields of novel functional materials and photoelectric materials. Due to pi-pi stacking effect among porphyrin molecules, sequence arrangement and assembly can be formed among the molecules, so that macromolecular polymers with different shapes are formed. In recent years, macromolecular polymers have received increasing attention due to their unique kinetic properties, which have made them useful in a wide range of chemical, biological and physical applications.
Disclosure of Invention
Dissolving tetrahydroxy tetraphenylporphyrin in benign solvent, adding different amounts of inert solvent to aggregate porphyrin molecules, and obtaining spherical porphyrin aggregate. Tetrahydroxytetraphenylporphyrin exists in molecular form in a solvent with high solubility, and when a solvent with low solubility is added, the solubility is reduced, and aggregation occurs when the solvent reaches a saturated state instantly, so that spherical particles are formed.
The benign solvent is one of dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, ethanol and methanol;
the inert solvent is water;
the benign solvent is a solvent with higher solubility, and the inert solvent is a solvent with lower solubility.
A method for preparing spherical porphyrin by adjusting the proportion of solvent comprises the following steps:
dissolving tetrahydroxy tetraphenylporphyrin in benign solvent, and adding different amounts of inert solvent to obtain mixed solutions with different proportions;
the concentration of the porphyrin solution in the step is 1.5 multiplied by 10-6-3.0×10-6mol/L; preferably 2.5X 10-6mol/L。
The volume ratio of the benign solvent to the inert solvent in the mixed solution in the step is 1-10:1-9, and as a technical scheme of the test process, the volume ratio of the benign solvent to the inert solvent designed by the invention comprises 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8 and 1: 9; preferably 4: 6.
Drawings
FIG. 1 is a UV-vis spectrum (normalized) of the spherical porphyrin prepared in example 1.
FIG. 2 is an SEM image of spherical porphyrins prepared in example 1.
FIG. 3 is a TEM image of spherical porphyrin-stabilized gold nanoparticles prepared in example 2.
FIG. 4 is a graph of the UV-vis spectrum (normalized) of the spherical porphyrin prepared in example 3.
FIG. 5 is an SEM image of spherical porphyrins prepared in example 3.
Detailed Description
Example 1
The preparation scheme adopted by the invention comprises the following steps
The method comprises the following steps: mixing 2.5X 10-4Dissolving mmol porphyrin in ethanol (10 mL), and stirring to dissolve completely to obtain ethanol solution of porphyrin solution;
step two: taking 0.3 mL of ethanol solution of porphyrin in a reagent bottle, then injecting 2.7 mL of deionized water into the reagent bottle by using an injector, and shaking up;
step three: taking different amounts of the solution obtained in the step two, and slowly adding ethanol and deionized water into the solution respectively by using an injector; keeping the total volume of the solution at 3 mL constant, adjusting the ratio of ethanol to deionized water, such as using a volume of ethanol in the solution of 10mL, or a mixed volume of ethanol and water of 10mL, wherein the volume ratio of ethanol to water is 9:1, or the mixed volume of ethanol and water is 10mL, wherein the volume ratio of ethanol to water is 8:2, or the mixed volume of ethanol to water is 10mL, wherein the volume ratio of ethanol to water is 7:3, or the mixed volume of ethanol to water is 10mL, wherein the volume ratio of ethanol to water is 6:4, or the mixed volume of ethanol to water is 10mL, wherein the volume ratio of ethanol to water is 5:5, or the mixed volume of ethanol to water is 10mL, wherein the volume ratio of ethanol to water is 4:6, or the mixed volume of ethanol to water is 10mL, wherein the volume ratio of ethanol to water is 3:7, or the mixed volume of ethanol to water is 10mL, wherein the volume ratio of the ethanol to the water is 2:8, or the mixed volume of the ethanol and the water is 10ml, wherein the volume ratio of the methanol to the water is 1: 9.
FIG. 1 is a graph of the UV-vis spectrum of spherical porphyrins prepared in example 1 of the present invention, from which it can be seen that the characteristic absorption peak at 420 nm of porphyrin begins to broaden when the volume of ethanol is 40% of the total volume of the solution, indicating that the porphyrin molecules in the solution begin to aggregate. (percentages in the figure represent the percentage of ethanol to the total volume of the solution).
FIG. 2 is a SEM image of spherical porphyrins prepared in example 1 of the present invention, which shows that the spherical porphyrins have smooth surfaces, average particle sizes of 30-40 nm, and relatively uniform surface.
Example 2
Spherical porphyrin-stabilized gold nanoparticles prepared according to example 1 were prepared as follows:
the method comprises the following steps: mixing 2.5X 10-4Dissolving mmol porphyrin in ethanol (10 mL), and stirring to dissolve completely;
step two: 1 mL of porphyrin ethanol solution is put in a round-bottom flask, then 3 mL of ethanol is injected into the porphyrin solution by using a syringe and stirred for 10 min, and 4 mL of deionized water is injected into the mixed solution and stirred for 10 min;
step three: mixing 2.5X 10-4Dissolving mmol tetrachloroauric acid in 1 mL deionized water, dripping into the mixed solution obtained in the second step at a dripping speed of 3 min/mL, and stirring for 10 min;
step four: mixing 7.5X 10-3And (3) mmol sodium borohydride is dissolved in 1 mL deionized water, and the solution is dripped into the mixed solution obtained in the third step at the dripping speed of 3 min/mL, and the reaction is carried out for 2 hours.
FIG. 3 is a TEM image of spherical porphyrin-stabilized gold nanoparticles prepared in example 2 of the present invention, from which it can be seen that the gold nanoparticles are mainly distributed on the surface of the spherical porphyrin nanoparticles, i.e. the spherical porphyrin can still keep its structure from being destroyed while stabilizing the metal nanoparticles.
Example 3
The preparation scheme adopted by the invention comprises the following steps
The method comprises the following steps: mixing 2.5X 10-4Dissolving mmol porphyrin in methanol (10 mL), and stirring to dissolve completely to obtain methanol solution of porphyrin solution;
step two: taking 0.3 mL of methanol solution of porphyrin in a reagent bottle, then injecting 2.7 mL of deionized water into the reagent bottle by using an injector and shaking up;
step three: taking different amounts of the solution in the second step, and slowly adding methanol and deionized water respectively by using an injector; keeping the total volume of the solution to be 3 mL unchanged, adjusting the proportion of the methanol to the deionized water to ensure that the volume of the methanol in the solution is 10mL or the mixed volume of the methanol and the water is 10mL, wherein the volume ratio of the methanol to the water is 9:1 or the mixed volume of the methanol and the water is 10mL, wherein the volume ratio of the methanol to the water is 8:2 or the mixed volume of the methanol to the water is 10mL, wherein the volume ratio of the methanol to the water is 7:3 or the mixed volume of the methanol and the water is 10mL, wherein the volume ratio of the methanol to the water is 6:4 or the mixed volume of the methanol to the water is 10mL, wherein the volume ratio of the methanol to the water is 5:5 or the mixed volume of the methanol to the water is 10mL, wherein the volume ratio of the methanol to the water is 4:6 or the mixed volume of the methanol to the water is 10mL, wherein the volume ratio of the methanol to the water is 3:7 or the mixed volume of the methanol to the water is 10mL, wherein the volume ratio of the methanol to the water is 2:8, or the mixed volume of the methanol and the water is 10ml, wherein the volume ratio of the methanol to the water is 1: 9.
FIG. 4 is a graph (normalized) of the UV-vis spectrum of a spherical porphyrin prepared according to the present invention, from which it can be seen that the characteristic absorption peak at porphyrin 420 nm begins to broaden when the volume of ethanol is 40% relative to the total volume of the solution, indicating that the porphyrin molecules in the solution begin to aggregate. (the figure example percentages indicate the percentage of methanol to the total volume of the solution). FIG. 5 is an SEM image of spherical porphyrin prepared by the present invention, which shows that the spherical porphyrin has smooth surface, relatively uniform particle size (average particle size of 80-100 nm) and good dispersibility.
Claims (5)
1. A preparation method of spherical porphyrin is characterized in that tetrahydroxy tetraphenylporphyrin is dissolved in a benign solvent at room temperature, then an inert solvent is dropwise added, and the mixed solution is fully oscillated and uniformly mixed to obtain spherical porphyrin aggregate, namely the spherical porphyrin.
2. The method for preparing spherical porphyrin according to claim 1, wherein the benign solvent is any one of dimethyl sulfoxide, N-dimethylformamide, acetonitrile, ethanol and methanol.
3. The method for preparing spherical porphyrin according to claim 1, wherein the inert solvent is water.
4. The method for preparing spherical porphyrin according to claim 1, wherein the concentration of tetrahydroxytetraphenylporphyrin is 1.5 x 10-6-3.0×10-6mol/L。
5. The method for preparing spherical porphyrin according to claim 1, wherein the volume ratio of the benign solvent to the inert solvent is 1-10: 1-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086681A (en) * | 1998-09-14 | 2000-03-28 | Japan Science & Technology Corp | PORPHYRIN pi-RADICAL SINGLE CRYSTAL AND ITS PRODUCTION |
| CN104557948A (en) * | 2013-10-09 | 2015-04-29 | 中国科学院化学研究所 | Method for preparing monodispersed porphyrin molecule particles by water droplet templating method |
| CN109575068A (en) * | 2018-10-31 | 2019-04-05 | 泰山学院 | A kind of solvent regulation prepares the method and application of the porphyrin-POSS aggregation of different-shape |
| CN109847797A (en) * | 2019-01-28 | 2019-06-07 | 三峡大学 | A kind of preparation method and applications for the gold nano catalyst that porphyrin is stable |
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2020
- 2020-02-28 CN CN202010129855.XA patent/CN111205476A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086681A (en) * | 1998-09-14 | 2000-03-28 | Japan Science & Technology Corp | PORPHYRIN pi-RADICAL SINGLE CRYSTAL AND ITS PRODUCTION |
| CN104557948A (en) * | 2013-10-09 | 2015-04-29 | 中国科学院化学研究所 | Method for preparing monodispersed porphyrin molecule particles by water droplet templating method |
| CN109575068A (en) * | 2018-10-31 | 2019-04-05 | 泰山学院 | A kind of solvent regulation prepares the method and application of the porphyrin-POSS aggregation of different-shape |
| CN109847797A (en) * | 2019-01-28 | 2019-06-07 | 三峡大学 | A kind of preparation method and applications for the gold nano catalyst that porphyrin is stable |
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