CN105566333A - Preparing method for porphyrin nanometer material - Google Patents

Preparing method for porphyrin nanometer material Download PDF

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Publication number
CN105566333A
CN105566333A CN201410550050.7A CN201410550050A CN105566333A CN 105566333 A CN105566333 A CN 105566333A CN 201410550050 A CN201410550050 A CN 201410550050A CN 105566333 A CN105566333 A CN 105566333A
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tpps
porphyrin
tpps1
preparation
nano material
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CN201410550050.7A
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Chinese (zh)
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齐海港
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Xi'an Aifeier Composite Materials Technology Co Ltd
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Xi'an Aifeier Composite Materials Technology Co Ltd
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Abstract

The invention discloses a preparing method for a porphyrin nanometer material. The preparing method specifically comprises the following steps that firstly, benzaldehyde, propionic acid and pyrrole are used for preparing phenyl porphyrin (TPP), and phenyl porphyrin (TPP) and 50% H2SO4 react to prepare monosulfonate phenyl porphyrin (TPPS1); secondly, obtained monosulfonate phenyl porphyrin (TPPS1) is used for preparing the solid TPPS1 nanometer material. By means of the preparing method, the solid TPPS1 nanometer material is prepared through a self-assembly method, the fluorescence intensity of the maximum emission peak of the obtained solid TPPS1 nanometer material is four times that of a TPPS1 monomer, and the fluorescence quantum yield of the obtained solid TPPS1 nanometer material is triple that of the TPPS1 monomer, so that it indicates that the light sensitivity of the obtained solid TPPS1 nanometer material is far higher than that of the TPPS1 monomer, and the application prospects of the obtained solid TPPS1 nanometer material on the aspects of micro sensitive materials, elements and detection are indicated.

Description

A kind of preparation method of porphyrin nano material
Technical field
The invention belongs to technical field of nanometer material preparation, relate to a kind of preparation method of porphyrin nano material.
Background technology
Along with to the raising of environmental requirement and the attention of Environmental pollution, people look forward to finding a kind of simple method, realize the sensitive rapid detection to Environmental Pesticide, VOCs or heavy metal ion etc.Meanwhile, along with the increasing of various countries' national power, military competition and military toxic agent use the seriousness brought, destructive destruction, the fast and convenient detection of toxic agent can desirably be realized.Toxic agent, agricultural chemicals, VOCs etc. are detected to use more be high performance liquid phase (HPLC), gas-chromatography (GC), capillary electrophoresis etc. traditional instrument method, although the sensitivity of these detection methods is higher, can be quantitative exactly, but these large-sized analytic instrument prices are very expensive, and need professional to operate them.So Developing rapidly method for sensing becomes new detection bright spot, these class methods have response, higher sensitivity, operation faster also comparatively simple, become a kind of method of detection toxic agent, agricultural chemicals, VOCs and the heavy metal ion etc. that gain great popularity.
Method for sensing wants realize sensitive and selectively detect, and sensing material is vital.Because porphyrin has various structure (multiple substituted radical, by structure design, can realize the Selective recognition to different testing sample), satisfactory stability and higher sensitivity, it is ideal photochromics/element.And nano material is because small-size effect, specific surface effect, quantum effect and interfacial effect make it have that generally/traditional material does not possess or more excellent than traditional material performance, as: adsorptivity significantly increases, and reactive behavior improves etc. greatly.At present, researcher has used a large amount of method and technologies to carry out the preparation of porphyrin nano/assembled material, the microsome prepared has revealed good luminescent properties and photosensitive property, it is almost zero that porphyrin quencher and porphyrin are revealed, and can be used as new high-level efficiency sensitive material, element or marker material etc.
Summary of the invention
The object of this invention is to provide a kind of preparation method of porphyrin nano material, single sulphenyl porphyrin preparation is become nano material, makes its photosensitive property be further enhanced and optimize.
The technical solution adopted in the present invention is, a kind of preparation method of porphyrin nano material, specifically implements according to the following steps:
Step 1, single sulphenyl porphyrin (TPPS 1) preparation
1.1) synthesis of phenyl porphyrin (TPP)
Phenyl aldehyde adds in propionic acid by 1:9 ~ 11 by volume, backflow; Pyrroles is newly steamed, collect cut, by pyrroles-phenyl aldehyde (V:V=1:3 ~ 5), pyrroles is joined in backflow system, reaction 25 ~ 35min, with refrigerator cooling 14 ~ 16h, filters, then with methyl alcohol and hot water washing leaching cake respectively, the propionic acid being adsorbed on surface is removed in crystal drying, obtains TPP blue colored crystal, keeps in Dark Place in dry environment.
1.2) single sulphenyl porphyrin (TPPS 1) preparation
1.2.1) TPPS 1building-up reactions
TPP is added 50%H by 1:20 ~ 25 in mass ratio 2sO 4in, at 35 DEG C, stir 24h, then 1:2 adds distilled water wherein by volume, generates precipitation.Deng after having cooled by product suction filtration, then with distilled water wash three times, solid product is dissolved in methyl alcohol, uses Na 2cO 3neutralize.Then carry out underpressure distillation, boil off too much solvent, obtain TPPS 1crude product.
1.2.2) separation, purifying
By TPPS 1crude product is dissolved in pyrimidine-chloroform-distilled water (V:V:V=14:9:1) mixing solutions, chromatography is carried out in 100 ~ 200 object silicagel columns, collect first chromatographic band, and carry out twice column chromatography, requirement of experiment is met by its purity of thin-layer chromatography preliminary judgement, carry out underpressure distillation and vacuum-drying again, obtain the TPPS that purity is higher 1, be stored under dry environment stand-by under black out condition.
Step 2, TPPS 1prepared by porphyrin nano material
1:20 ~ 25 are by TPPS in mass ratio 1add dehydrated alcohol, obtain TPPS 1ethanol storing solution; 1:50 is by TPPS by volume 1ethanol storing solution is injected in ultrapure water, and marginal not enters limit and stirs.Heating makes constant in 60 DEG C, stirs 10min, obtains TPPS 1porphyrin nano dispersing material.Again by solvent evaporates, namely obtain TPPS 1solid nano material.
Feature of the present invention is also,
Wherein in step 1, fraction collection temperature is 127 DEG C ~ 128 DEG C.
Wherein in step 1, washing leaching cake hot water temperature is 50 DEG C ~ 60 DEG C.
Distilled water wherein in step 1.2.1 in building-up reactions adds under condition of ice bath.
Wherein in step 2, heated and stirred rotating speed is 1440rpm.
The invention has the beneficial effects as follows, the present invention TPPS that utilized self-assembly method to prepare 1nano material, the TPPS prepared 1fluorescence intensity and the fluorescence quantum yield of the maximum emission peak of nano material are respectively TPPS 14 times of monomer and 3 times, show that its photosensitivity outclass TPPS 1monomer, predictive of its application prospect in micro-quick material, element and context of detection.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
A preparation method for porphyrin nano material, specifically implements according to the following steps:
Step 1, single sulphenyl porphyrin (TPPS 1) preparation
1.1) synthesis of phenyl porphyrin (TPP)
Phenyl aldehyde adds in propionic acid by 1:9 ~ 11 by volume, backflow; Pyrroles is newly steamed, collect the cut of 127 DEG C ~ 128 DEG C, join in backflow system by pyrroles-phenyl aldehyde (V:V=1:3 ~ 5), reaction 25 ~ 35min, with refrigerator cooling 14 ~ 16h, filters, then with methyl alcohol and hot water (50 DEG C ~ 60 DEG C) washing leaching cake respectively, the propionic acid being adsorbed on surface is removed in crystal drying, obtains TPP blue colored crystal, keeps in Dark Place in dry environment.
1.2) single sulphenyl porphyrin (TPPS 1) preparation
1.2.1) TPPS 1building-up reactions
TPP is added 50%H by 1:20 ~ 25 in mass ratio 2sO 4in, at 35 DEG C, stir 24h, then under condition of ice bath, add distilled water wherein by with reaction solution volume ratio 2:1, generate precipitation.Deng after having cooled by product suction filtration, then with distilled water wash three times, solid product is dissolved in methyl alcohol, uses Na 2cO 3neutralize.Then carry out underpressure distillation, boil off too much solvent, obtain TPPS 1crude product.Reaction process is as follows:
1.2.2) separation, purifying
By TPPS 1crude product is dissolved in pyrimidine-chloroform-distilled water (V:V:V=14:9:1) mixing solutions, and in 100 ~ 200 object silicagel columns, carry out chromatography, the first carries product is: TPPS 1; Second band is: disulfonic acid base para-orientation phenyl porphyrin (TPPS 2A) and disulfonic acid base ortho position substituted-phenyl porphyrin (TPPS 2O) (isomers); 3rd band is: trisulfonic acid substituting group phenyl porphyrin (TPPS 3); 4th band is: tetrasulfonic acid substituting group phenyl porphyrin (TPPS 4).Collect first chromatographic band, and carry out twice column chromatography, meet requirement of experiment by its purity of thin-layer chromatography preliminary judgement, then carry out underpressure distillation and vacuum-drying, obtain the TPPS that purity is higher 1, be stored under dry environment stand-by under black out condition.
Step 2, TPPS 1prepared by porphyrin nano material
1:20 ~ 25 are by TPPS in mass ratio 1add dehydrated alcohol, obtain TPPS 1ethanol storing solution; 1:50 is by TPPS by volume 1ethanol storing solution is injected in ultrapure water, and marginal not enters limit and stirs.Heating makes constant in 60 DEG C, stirs 10min with the speed of 1440rpm.Obtain TPPS 1porphyrin nano dispersing material, solution is in neutral.Again by solvent evaporates, namely obtain TPPS 1solid nano material.
The present invention TPPS that utilized self-assembly method to prepare 1nano material, the TPPS prepared 1fluorescence intensity and the fluorescence quantum yield of the maximum emission peak of nano material are respectively TPPS 14 times of monomer and 3 times, show that its photosensitivity outclass TPPS 1monomer, predictive of its application prospect in micro-quick material, element and context of detection.
Embodiment 1
A preparation method for porphyrin nano material, concrete enforcement is implemented according to the following steps:
Step 1, single sulphenyl porphyrin (TPPS 1) preparation
1.1) synthesis of phenyl porphyrin (TPP)
20mL phenyl aldehyde is added in 180mL propionic acid, backflow; Pyrroles is newly steamed, collect the cut 7mL of 127 DEG C ~ 128 DEG C, join in backflow system, reaction 25 ~ 35min, cools 14h with refrigerator, filters, then washing leaching cake is distinguished with the hot water of methyl alcohol and 50 DEG C ~ 60 DEG C, the propionic acid being adsorbed on surface is removed in crystal drying, obtains TPP blue colored crystal, keeps in Dark Place in dry environment.
1.2) single sulphenyl porphyrin (TPPS 1) preparation
1.2.1) TPPS 1building-up reactions
1gTPP is added 20g50%H 2sO 4in, at 35 DEG C, stir 24h, then under condition of ice bath, add 28mL distilled water wherein, generate precipitation.Deng after having cooled by product suction filtration, then with distilled water wash three times, solid product is dissolved in methyl alcohol, uses Na 2cO 3neutralize.Then carry out underpressure distillation, boil off too much solvent, obtain TPPS 1crude product.
1.2.2) separation, purifying
By TPPS 1crude product is dissolved in 14mL pyrimidine, 9mL chloroform, in the mixing solutions of 1mL distilled water, chromatography is carried out in 100 ~ 200 object silicagel columns, collect first chromatographic band, and carry out twice column chromatography, meet requirement of experiment by its purity of thin-layer chromatography preliminary judgement, carry out underpressure distillation and vacuum-drying again, obtain the TPPS that purity is higher 1, be stored under dry environment stand-by under black out condition.
Step 2, TPPS 1prepared by porphyrin nano material
By TPPS 1add 20g dehydrated alcohol, obtain TPPS 1ethanol storing solution; By 100 μ LTPPS 1ethanol storing solution is injected in 5mL ultrapure water, and marginal not enters limit and stirs.Heating makes constant in 60 DEG C, stirs 10min with the speed of 1440rpm.Obtain TPPS 1porphyrin nano dispersing material, solution is in neutral.Again by solvent evaporates, namely obtain TPPS 1solid nano material.
Embodiment 2
A preparation method for porphyrin nano material, concrete enforcement is implemented according to the following steps:
Step 1, single sulphenyl porphyrin (TPPS 1) preparation
1.1) synthesis of phenyl porphyrin (TPP)
20mL phenyl aldehyde is added in 200mL propionic acid, backflow; Pyrroles is newly steamed, collect the cut 5mL of 127 DEG C ~ 128 DEG C, join in backflow system, reaction 30min, cools 15h with refrigerator, filters, then washing leaching cake is distinguished with the hot water of methyl alcohol and 50 DEG C ~ 60 DEG C, the propionic acid being adsorbed on surface is removed in crystal drying, obtains TPP blue colored crystal, keeps in Dark Place in dry environment.
1.2) single sulphenyl porphyrin (TPPS 1) preparation
1.2.1) TPPS 1building-up reactions
1gTPP is added 23g50%H 2sO 4in, at 35 DEG C, stir 24h, then under condition of ice bath, add 32mL distilled water wherein, generate precipitation.Deng after having cooled by product suction filtration, then with distilled water wash three times, solid product is dissolved in methyl alcohol, uses Na 2cO 3neutralize.Then carry out underpressure distillation, boil off too much solvent, obtain TPPS 1crude product.
1.2.2) separation, purifying
By TPPS 1crude product is dissolved in 28mL pyrimidine, 18mL chloroform, in the mixing solutions of 2mL distilled water, chromatography is carried out in 100 ~ 200 object silicagel columns, collect first chromatographic band, and carry out twice column chromatography, meet requirement of experiment by its purity of thin-layer chromatography preliminary judgement, carry out underpressure distillation and vacuum-drying again, obtain the TPPS that purity is higher 1, be stored under dry environment stand-by under black out condition.
Step 2, TPPS 1prepared by porphyrin nano material
By TPPS 1add 23g dehydrated alcohol, obtain TPPS 1ethanol storing solution; By 200 μ LTPPS 1ethanol storing solution is injected in 10mL ultrapure water, and marginal not enters limit and stirs.Heating makes constant in 60 DEG C, stirs 10min with the speed of 1440rpm.Obtain TPPS 1porphyrin nano dispersing material, solution is in neutral.Again by solvent evaporates, namely obtain TPPS 1solid nano material.
Embodiment 3
A preparation method for porphyrin nano material, concrete enforcement is implemented according to the following steps:
Step 1, single sulphenyl porphyrin (TPPS 1) preparation
1.1) synthesis of phenyl porphyrin (TPP)
20mL phenyl aldehyde is added in 220mL propionic acid, backflow; Pyrroles is newly steamed, collect the cut 4mL of 127 DEG C ~ 128 DEG C, join in backflow system, reaction 35min, cools 16h with refrigerator, filters, then washing leaching cake is distinguished with the hot water of methyl alcohol and 50 DEG C ~ 60 DEG C, the propionic acid being adsorbed on surface is removed in crystal drying, obtains TPP blue colored crystal, keeps in Dark Place in dry environment.
1.2) single sulphenyl porphyrin (TPPS 1) preparation
1.2.1) TPPS 1building-up reactions
1gTPP is added 25g50%H 2sO 4in, at 35 DEG C, stir 24h, then under condition of ice bath, add 35mL distilled water wherein, generate precipitation.Deng after having cooled by product suction filtration, then with distilled water wash three times, solid product is dissolved in methyl alcohol, uses Na 2cO 3neutralize.Then carry out underpressure distillation, boil off too much solvent, obtain TPPS 1crude product.
1.2.2) separation, purifying
By TPPS 1crude product is dissolved in 42mL pyrimidine, 27mL chloroform, in the mixing solutions of 3mL distilled water, chromatography is carried out in 100 ~ 200 object silicagel columns, collect first chromatographic band, and carry out twice column chromatography, meet requirement of experiment by its purity of thin-layer chromatography preliminary judgement, carry out underpressure distillation and vacuum-drying again, obtain the TPPS that purity is higher 1, be stored under dry environment stand-by under black out condition.
Step 2, TPPS 1prepared by porphyrin nano material
By TPPS 1add 25g dehydrated alcohol, obtain TPPS 1ethanol storing solution; By 300 μ LTPPS 1ethanol storing solution is injected in 15mL ultrapure water, and marginal not enters limit and stirs.Heating makes constant in 60 DEG C, stirs 10min with the speed of 1440rpm.Obtain TPPS 1porphyrin nano dispersing material, solution is in neutral.Again by solvent evaporates, namely obtain TPPS 1solid nano material.

Claims (5)

1. a preparation method for porphyrin nano material, specifically implements according to the following steps:
Step 1, single sulphenyl porphyrin (TPPS 1) preparation
1.1) synthesis of phenyl porphyrin (TPP)
Phenyl aldehyde adds in propionic acid by 1:9 ~ 11 by volume, backflow; Pyrroles is newly steamed, the cut collected, by pyrroles-phenyl aldehyde (V:V=1:3 ~ 5), pyrroles is joined in backflow system, reaction 25 ~ 35min, with refrigerator cooling 14 ~ 16h, filters, then with methyl alcohol and hot water washing leaching cake respectively, the propionic acid being adsorbed on surface is removed in crystal drying, obtains TPP blue colored crystal, keeps in Dark Place in dry environment;
1.2) single sulphenyl porphyrin (TPPS 1) preparation
1.2.1) TPPS 1building-up reactions
TPP is added 50%H by 1:20 ~ 25 in mass ratio 2sO 4in, at 35 DEG C, stir 24h, then 1:2 adds distilled water wherein by volume, generates precipitation.Deng after having cooled by product suction filtration, then with distilled water wash three times, solid product is dissolved in methyl alcohol, uses Na 2cO 3neutralize.Then carry out underpressure distillation, boil off too much solvent, obtain TPPS 1crude product;
1.2.2) separation, purifying
Crude product is above dissolved in pyrimidine-chloroform-distilled water (V:V:V=14:9:1) mixing solutions, chromatography is carried out in 100 ~ 200 object silicagel columns, collect first chromatographic band, and carry out twice column chromatography, requirement of experiment is met by its purity of thin-layer chromatography preliminary judgement, carry out underpressure distillation and vacuum-drying again, obtain the TPPS that purity is higher 1, be stored under dry environment stand-by under black out condition;
Step 2, TPPS 1prepared by porphyrin nano material
1:20 ~ 25 are by TPPS in mass ratio 1add dehydrated alcohol, obtain TPPS 1ethanol storing solution; 1:50 is by TPPS by volume 1ethanol storing solution is injected in ultrapure water, and marginal not enters limit and stirs.Heating makes constant in 60 DEG C, stirs 10min, obtains TPPS 1porphyrin nano dispersing material.Again by solvent evaporates, namely obtain TPPS 1solid nano material.
2. the preparation method of a kind of porphyrin nano material according to claim 1, is characterized in that, the temperature of fraction collection described in step 1 is 127 DEG C ~ 128 DEG C.
3. the preparation method of a kind of porphyrin nano material according to claim 1, is characterized in that, the hot water temperature of washing leaching cake described in step 1 is 50 DEG C ~ 60 DEG C.
4. the preparation method of a kind of porphyrin nano material according to claim 1, it is characterized in that, the distilled water in building-up reactions described in step 1.2.1 adds under condition of ice bath.
5. the preparation method of a kind of porphyrin nano material according to claim 1, is characterized in that, the rotating speed of heated and stirred described in step 2 is 1440rpm.
CN201410550050.7A 2014-10-15 2014-10-15 Preparing method for porphyrin nanometer material Pending CN105566333A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705161A (en) * 2017-10-26 2019-05-03 湖南科技大学 A kind of phosphorylation water-soluble porphyrin and preparation method thereof
CN110423605A (en) * 2019-07-31 2019-11-08 重庆科技学院 A kind of preparation method of porphyrin nanogold
CN110849502A (en) * 2019-10-14 2020-02-28 浙江理工大学 Preparation method of tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705161A (en) * 2017-10-26 2019-05-03 湖南科技大学 A kind of phosphorylation water-soluble porphyrin and preparation method thereof
CN110423605A (en) * 2019-07-31 2019-11-08 重庆科技学院 A kind of preparation method of porphyrin nanogold
CN110849502A (en) * 2019-10-14 2020-02-28 浙江理工大学 Preparation method of tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material
CN110849502B (en) * 2019-10-14 2021-03-23 浙江理工大学 Preparation method of tetramethoxyphenyl zirconium porphyrin nanotube-selenium trioxide nanosheet composite thermosensitive sensing material

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