CN102786609A - Macromolecule immobilized cationic porphyrin compound and its preparation method - Google Patents
Macromolecule immobilized cationic porphyrin compound and its preparation method Download PDFInfo
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- CN102786609A CN102786609A CN2012102471486A CN201210247148A CN102786609A CN 102786609 A CN102786609 A CN 102786609A CN 2012102471486 A CN2012102471486 A CN 2012102471486A CN 201210247148 A CN201210247148 A CN 201210247148A CN 102786609 A CN102786609 A CN 102786609A
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Abstract
Belonging to the technical field of porphyrin immobilization, the invention discloses a macromolecule immobilized cationic porphyrin compound and its preparation method. In the invention, benzaldehyde with a benzene ring having a tertiary amine group is taken as one of reaction reagents. One the surface of a chloromethylated crosslinked polystyrene microsphere, synchronous synthesis and immobilization of tertiary amine group-containing phenylporphyrin is performed. Then by means of a quaterisation reaction, the macromolecule immobilized cationic phenylporphyrin can be prepared. A strong host-guest interaction can be generated between immobilized cationic porphyrin and protein molecules, and the feature is of important scientific significance in the fields of biology and medicinal science. The macromolecule immobilized cationic porphyrin compound provided in the invention has the advantages of simple preparation process, high cationic porphyrin immobilization amount, good stability, and reusability.
Description
Technical field
The invention belongs to immobilizedization of the polymer field of porphyrin, be specifically related to a kind of immobilizedization of polymer positively charged ion porphyrin compound and preparation method thereof.
Background technology
Porphyrin is one type of macrocylc compound, extensively is present in nature and the life entity.Big π key molecular orbital(MO) on carbon-nitrogen skeleton gives their unique biological activity and physics-chem characteristics; Such as; They can transmit oxygen molecule, metastatic electron, catalyzed chemical reaction, identification molecule and ion; And having a light sensitive characteristic etc. the structure and the function of simulation porphyrin and metalloporphyrin, synthetic various special construction porphyrinses have become the research field that receives much concern in the present Materials science.In the porphyrins of various structures; The positively charged ion porphyrin is one type of porphyrins that performance is more special, and they have the ability of strong formation host-guest supramolecular aggregation, all has important application [M Haeubl in fields such as biology, medical science, molecular recognition and structure transmitters; S Schuerz; B Svejda e tal. European Journal of Medical Chemistry, 2010,45:760; T-X Ye, S-L Ye, D-M Chen et al. Spectrochimica Acta Part A, 2012,86:467], especially and the strong interaction between the nucleic acid DNA, caused great concern at life science; In addition; The metal complexes of positively charged ion porphyrin also has excellent catalytic activity in the OXIDATION OF HYDROCARBONS process, and relies on the cationic characteristic around its big ring; Can insert in the multiple inorganic carrier through IX, form supported cationic metal porphyrin catalyst.Yet the positively charged ion porphyrin is many at present is employed with micromolecular form, has poor chemical stability, is difficult to separate, and is not easy to reclaim shortcomings such as use again.At present, seldom about the report of the high molecular of positively charged ion porphyrin.
Summary of the invention
Goal of the invention of the present invention: solved existing positively charged ion porphyrin and had poor chemical stability, be difficult to separate, be not easy to reclaim again shortcomings such as use, a kind of positively charged ion porphyrin compound of immobilizedization of polymer is provided; And the preparation method of this immobilizedization of polymer positively charged ion porphyrin compound is provided.
Used aldehyde grouping modified crosslinked polystyrene microsphere (BA-CPS) among the present invention can obtain according to the method described in the document [ten thousand is quick, Gao Baojiao, Cheng Wei, Zhao Xinlong, chemistry circular, 2012,75 (2): 166].
The positively charged ion porphyrin compound of immobilizedization of polymer is characterized in that structural formula is following:
Wherein,
represents crosslinked polystyrene microsphere.
The preparation method of the positively charged ion porphyrin of above-mentioned immobilizedization of polymer, step is following:
1), the aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g is joined in solvent of 20-30mL, make aldehyde grouping modified crosslinked polystyrene microsphere swelling after, add 1.0-1.2g paradimethy laminobenzaldehyde and 0.008-0.012mol catalyzer successively; Be warming up to 110-130 ℃, slowly drip the solvent that 20mL is dissolved with 0.68-0.72mL pyrroles, isothermal reaction 7-9h, cooling; Suction filtration, washing with alcohol, vacuum-drying; Get immobilized have the phenyl porphyrin that contains tertiary amine groups (TA), i.e. meso-three (right-dimethylamino phenyl) porphyrin microballoon TAPP-CPS
2), 1g meso-three (right-dimethylamino phenyl) porphyrin microballoon TAPP-CPS is inserted in No. two solvents of 30-40 mL N
2Protection down is warming up to 35-45 ℃, adds the 2-3mL quaternizing agent, isothermal reaction 3-4h, and suction filtration repeatedly washs with No. two solvents and zero(ppm) water, and vacuum-drying makes the immobilized positively charged ion phenyl porphyrin that has, and promptly meso-three is (right-trimethylammonio phenyl
)Porphyrin (4-trimethylammoniophenyl porphyrin, polymer microballoon TMAPP-CPS TMAPP),
A described solvent is DMSO 99.8MIN., DMAC N,N or N, and dinethylformamide, described catalyzer are lactic acid, p-Nitrobenzenecarboxylic acid, Whitfield's ointment, Mono Chloro Acetic Acid or propionic acid,
Described No. two solvents are DMSO 99.8MIN., DMAC N,N or N, and dinethylformamide, described quaternizing agent are methyl iodide, Benzyl Chloride or thionyl chloride.
Show aldehyde grouping modified crosslinked polystyrene microsphere (BA-CPS) and the immobilized infrared spectrogram that the functional microsphere TAPP-CPS of tertiary amine groups phenyl porphyrin is arranged like Fig. 1.
In the ir spectra of BA-CPS, at 1683cm
-1The characteristic absorbance of aldehyde carbonyl has appearred in the place; 2736cm
-1The peak at place is that the stretching vibration of aldehyde radical c h bond absorbs 1212 cm
-1The peak at place is that the stretching vibration of fragrant ehter bond key absorbs.In the spectrogram of microballoon TAPP-CPS, 1683cm
-1The aldehyde radical charateristic avsorption band at place greatly weakens, but has clearly shown all characteristic absorbance of phenyl porphyrin: at 1014 cm
-1(obviously strengthening), 824 cm cm
-1And 701 cm
-1The skeletal vibration that has occurred porphyrin at the place absorbs, at 949 cm
-1The stretching vibration that ring N-H key in the porphyrin has then appearred in the place absorbs (this is the key character that porphyrin forms).The variation at above-mentioned these spectrum peaks clearly illustrates that, has realized the synthetic synchronously and immobilized of phenyl porphyrin at microballoon BA-CPS microsphere surface, has formed the microballoon TAPP-CPS of immobilized tertiary amine groups phenyl porphyrin.Because the ir spectra of the microballoon TMAPP-CPS of immobilized positively charged ion porphyrin and microballoon TAPP-CPS are much at one, no longer repeat.
For the host-guest interaction of explanation immobilizedization of polymer positively charged ion porphyrin of the present invention, use fluorescence emission spectrum to study this material and protein interactions.Immobilizedization of the polymer positively charged ion porphyrin of preparation is joined in the proteinic pH=7.4 phosphate buffer soln, survey its supernatant fluorescence emission spectrum.
The relative prior art of the present invention has following beneficial effect: adopt a kind of novelty and simple and direct mode, and the positively charged ion porphyrin is immobilized on cross-linked polystyrene resin, make the immobilized positively charged ion porphyrin of a kind of novel high polymer.The supported quantity of positively charged ion porphyrin is up to 0.14-0.18mmol/g.Immobilizedization of polymer positively charged ion porphyrin that the present invention is prepared and albumen mass-energy produce strong host-guest and interact, and this characteristic all has important scientific meaning in fields such as life science, medicine and pharmacology and heterogeneous catalysiss; And the shortcoming that it has overcome small molecules positively charged ion porphyrin has good stability, reusability, is easy to advantage such as Separation and Recovery.
Description of drawings
Fig. 1 is demonstration aldehyde grouping modified crosslinked polystyrene microsphere (BA-CPS) and the immobilized infrared spectrogram that the functional microsphere TAPP-CPS of tertiary amine groups phenyl porphyrin is arranged,
Fig. 2 is the emmission spectrum figure for the lysozyme soln behind N,O-Diacetylmuramidase and immobilizedization of the adding polymer positively charged ion porphyrin,
Fig. 3 is the emmission spectrum figure of the bovine serum albumin solution behind bovine serum albumin and immobilizedization of the adding polymer positively charged ion porphyrin.
Embodiment
Embodiment 1: in four-hole boiling flask, add aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g (BA-CPS) and 20mL DMSO 99.8MIN., make microspheres swell up after, add 1.164 g paradimethy laminobenzaldehydes and 0.01mol lactic acid successively; Be warming up to 110 ℃, slowly drip the dimethyl sulphoxide solution that 20mL is dissolved with 0.72mL pyrroles, isothermal reaction 8h; Cooling, suction filtration, washing with alcohol; Vacuum-drying promptly gets the immobilized microballoon TAPP-CPS that phenyl porphyrin meso-three (right-dimethylamino phenyl) porphyrin that contains tertiary amine (TA) base is arranged.
In four-hole boiling flask, add 1g TAPP-CPS microballoon and 30 mL N, dinethylformamide, N then
2Protection is warming up to 40 ℃ down, adds the 2mL methyl iodide; Isothermal reaction 3h, suction filtration, N; Dinethylformamide and zero(ppm) water repeatedly wash, and vacuum-drying makes immobilized positively charged ion porphyrin-meso-three (right-trimethylammonio) phenyl porphyrin (4-trimethylammoniophenyl porphyrin that has; TMAPP) polymer microballoon TMAPP-CPS, the supported quantity of positively charged ion porphyrin are 0.18mmol/g.
A certain amount of immobilizedization of polymer positively charged ion porphyrin of preparation is joined in the pH=7.4 phosphate buffer soln of N,O-Diacetylmuramidase, survey its supernatant fluorescence emission spectrum.Fig. 2 is the emmission spectrum figure of the lysozyme soln behind N,O-Diacetylmuramidase and immobilizedization of the adding polymer positively charged ion porphyrin; Can know by figure; Prepared immobilizedization of polymer positively charged ion porphyrin and N,O-Diacetylmuramidase have produced strong interaction really, and the fluorescent emission intensity of N,O-Diacetylmuramidase is reduced greatly.Wash immobilizedization of polymer positively charged ion porphyrin with the NaOH solution of 0.1 mol/L then; With its repeat function in lysozyme soln; Reuse 15 times, it still can make the fluorescent emission intensity of N,O-Diacetylmuramidase reduce greatly, explains that this immobilizedization of polymer positively charged ion porphyrin has good repeat performance.
Embodiment 2: in four-hole boiling flask, add aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g (BA-CPS) and 20mL DMAC N,N, make microspheres swell up after, add 1.2 g paradimethy laminobenzaldehydes and 0.012mol Whitfield's ointment successively; Be warming up to 120 ℃, slowly drip the DMAC N,N solution that 20mL is dissolved with 0.72mL pyrroles; Isothermal reaction 9h, cooling, suction filtration; Washing with alcohol, vacuum-drying promptly gets the immobilized microballoon TAPP-CPS that phenyl porphyrin meso-three (right-dimethylamino phenyl) porphyrin that contains tertiary amine (TA) base is arranged.
In four-hole boiling flask, add 1g TAPP-CPS microballoon and 30 mL DMSO 99.8MIN.s, N then
2Protection is warming up to 45 ℃ down, adds the 3mL Benzyl Chloride; Isothermal reaction 3h, suction filtration, DMSO 99.8MIN. and zero(ppm) water repeatedly wash; Vacuum-drying; Making immobilizedly has positively charged ion porphyrin-meso-three (right-trimethylammonio) phenyl porphyrin (4-trimethylammoniophenyl porphyrin, polymer microballoon TMAPP-CPS TMAPP), the supported quantity of positively charged ion porphyrin is 0.16mmol/g.
A certain amount of immobilizedization of polymer positively charged ion porphyrin of preparation is joined in the pH=7.4 phosphate buffer soln of bovine serum albumin, survey its supernatant fluorescence emission spectrum.Fig. 3 is the emmission spectrum figure of the bovine serum albumin solution behind bovine serum albumin and immobilizedization of the adding polymer positively charged ion porphyrin; Can know by figure; Prepared immobilizedization of polymer positively charged ion porphyrin and bovine serum albumin have produced strong interaction really, and the fluorescent emission intensity of bovine serum albumin is reduced greatly.Wash immobilizedization of polymer positively charged ion porphyrin with the NaOH solution of 0.1 mol/L then; With its repeat function in lysozyme soln; Reuse 13 times, it still can make the fluorescent emission intensity of N,O-Diacetylmuramidase reduce greatly, explains that this immobilizedization of polymer positively charged ion porphyrin has good repeat performance.
Embodiment 3: in four-hole boiling flask, add aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g (BA-CPS) and 30mL N, dinethylformamide, make microspheres swell up after, add 1.0 g paradimethy laminobenzaldehydes and 0.008mol Mono Chloro Acetic Acid successively; Be warming up to 130 ℃, slowly drip the N that 20mL is dissolved with 0.68mL pyrroles, dinethylformamide solution; Isothermal reaction 7h, cooling, suction filtration; Washing with alcohol, vacuum-drying promptly gets the immobilized microballoon TAPP-CPS that phenyl porphyrin meso-three (right-dimethylamino phenyl) porphyrin that contains tertiary amine (TA) base is arranged.
In four-hole boiling flask, add 1g TAPP-CPS microballoon and 30 mL DMAC N,Ns, N then
2Protection is warming up to 35 ℃ down, adds the 2mL thionyl chloride; Isothermal reaction 4h, suction filtration, N; N-N,N-DIMETHYLACETAMIDE and zero(ppm) water repeatedly wash, and vacuum-drying makes immobilized positively charged ion porphyrin-meso-three (right-trimethylammonio) phenyl porphyrin (4-trimethylammoniophenyl porphyrin that has; TMAPP) polymer microballoon TMAPP-CPS, the supported quantity of positively charged ion porphyrin are 0.14mmol/g.
Embodiment 4: in four-hole boiling flask, add aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g (BA-CPS) and 20mL DMSO 99.8MIN., make microspheres swell up after, add 1.2 g paradimethy laminobenzaldehydes and 0.01mol propionic acid successively; Be warming up to 130 ℃, slowly drip the dimethyl sulphoxide solution that 20mL is dissolved with 0.72mL pyrroles, isothermal reaction 8h; Cooling, suction filtration, washing with alcohol; Vacuum-drying promptly gets the immobilized microballoon TAPP-CPS that phenyl porphyrin meso-three (right-dimethylamino phenyl) porphyrin that contains tertiary amine (TA) base is arranged.
In four-hole boiling flask, add 1g TAPP-CPS microballoon and 40 mL DMAC N,Ns, N then
2Protection is warming up to 40 ℃ down, adds the 2mL methyl iodide; Isothermal reaction 4h, suction filtration, N; N-N,N-DIMETHYLACETAMIDE and zero(ppm) water repeatedly wash, and vacuum-drying makes immobilized positively charged ion porphyrin-meso-three (right-trimethylammonio) phenyl porphyrin (4-trimethylammoniophenyl porphyrin that has; TMAPP) polymer microballoon TMAPP-CPS, the supported quantity of positively charged ion porphyrin are 0.15mmol/g.
Embodiment 5: in four-hole boiling flask, add aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g (BA-CPS) and 20mL DMSO 99.8MIN., make microspheres swell up after, add 1.2 g paradimethy laminobenzaldehydes and 0.01mol p-Nitrobenzenecarboxylic acid successively; Be warming up to 130 ℃, slowly drip the dimethyl sulphoxide solution that 20mL is dissolved with 0.72mL pyrroles, isothermal reaction 8h; Cooling, suction filtration, washing with alcohol; Vacuum-drying promptly gets the immobilized microballoon TAPP-CPS that phenyl porphyrin meso-three (right-dimethylamino phenyl) porphyrin that contains tertiary amine (TA) base is arranged.
In four-hole boiling flask, add 1g TAPP-CPS microballoon and 30 mL DMAC N,Ns, N then
2Protection is warming up to 45 ℃ down, adds the 2mL methyl iodide; Isothermal reaction 4h, suction filtration, N; N-N,N-DIMETHYLACETAMIDE and zero(ppm) water repeatedly wash, and vacuum-drying makes immobilized positively charged ion porphyrin-meso-three (right-trimethylammonio) phenyl porphyrin (4-trimethylammoniophenyl porphyrin that has; TMAPP) polymer microballoon TMAPP-CPS, the supported quantity of positively charged ion porphyrin are 0.16mmol/g.
Claims (4)
1. the positively charged ion porphyrin compound of immobilizedization of polymer is characterized in that structural formula is following:
Wherein,
represents crosslinked polystyrene microsphere.
2. the preparation method of the positively charged ion porphyrin of immobilizedization of polymer according to claim 1 is characterized in that step is following:
1), the aldehyde grouping modified crosslinked polystyrene microsphere of 0.5g is joined in solvent of 20-30mL, make aldehyde grouping modified crosslinked polystyrene microsphere swelling after, add 1.0-1.2g paradimethy laminobenzaldehyde and 0.008-0.012mol catalyzer successively; Be warming up to 110-130 ℃, slowly drip the solvent that 20mL is dissolved with 0.68-0.72mL pyrroles, isothermal reaction 7-9h, cooling; Suction filtration, washing with alcohol, vacuum-drying; Make the immobilized phenyl porphyrin microballoon that contains tertiary amine groups that has, i.e. meso-three (right-dimethylamino phenyl) porphyrin microballoon
2), 1g meso-three (right-dimethylamino phenyl) porphyrin microballoon is inserted in No. two solvents of 30-40 mL N
2Protection down is warming up to 35-45 ℃, adds the 2-3mL quaternizing agent, isothermal reaction 3-4h, and suction filtration repeatedly washs with No. two solvents and zero(ppm) water, and vacuum-drying makes the immobilized cationic phenyl porphyrin that has, and promptly meso-three is (right-trimethylammonio phenyl
)The polymer microballoon of porphyrin.
3. the preparation method of the positively charged ion porphyrin of immobilizedization of polymer according to claim 2; It is characterized in that a solvent described in the step 1) is DMSO 99.8MIN., N; N-N,N-DIMETHYLACETAMIDE or N; Dinethylformamide, described catalyzer are lactic acid, p-Nitrobenzenecarboxylic acid, Whitfield's ointment, Mono Chloro Acetic Acid or propionic acid.
4. the preparation method of the positively charged ion porphyrin of immobilizedization of polymer according to claim 2; It is characterized in that step 2) described in No. two solvents be DMSO 99.8MIN., N; N-N,N-DIMETHYLACETAMIDE or N; Dinethylformamide, described quaternizing agent are methyl iodide, Benzyl Chloride or thionyl chloride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080604A (en) * | 2014-05-16 | 2015-11-25 | 中北大学 | Preparation method of crosslinked polystyrene microsphere surface synthesized and immobilized N-hydroxyphthalimide catalyst |
| CN105968245A (en) * | 2016-05-17 | 2016-09-28 | 仲恺农业工程学院 | Particle size-adjustable formyl group-containing nanoparticles with core-shell structure and preparation method thereof |
| CN110387020A (en) * | 2018-04-19 | 2019-10-29 | 四川大学 | A kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes |
| CN110387001A (en) * | 2018-04-19 | 2019-10-29 | 四川大学 | A kind of porphyrin polystyrene type elastomer and preparation method thereof and purposes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940948A (en) * | 2010-07-13 | 2011-01-12 | 中北大学 | Method for immobilizing metalloporphyrin by crosslinked polystyrene microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101940948A (en) * | 2010-07-13 | 2011-01-12 | 中北大学 | Method for immobilizing metalloporphyrin by crosslinked polystyrene microspheres |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080604A (en) * | 2014-05-16 | 2015-11-25 | 中北大学 | Preparation method of crosslinked polystyrene microsphere surface synthesized and immobilized N-hydroxyphthalimide catalyst |
| CN105080604B (en) * | 2014-05-16 | 2017-09-05 | 中北大学 | A kind of crosslinked polystyrene microsphere surface synthesis and the preparation method of immobilized N hydroxyphthalimides catalyst |
| CN105968245A (en) * | 2016-05-17 | 2016-09-28 | 仲恺农业工程学院 | Particle size-adjustable formyl group-containing nanoparticles with core-shell structure and preparation method thereof |
| CN105968245B (en) * | 2016-05-17 | 2018-04-20 | 仲恺农业工程学院 | Adjustable nanoparticle containing aldehyde radical with core shell structure of a kind of particle diameter and preparation method thereof |
| CN110387020A (en) * | 2018-04-19 | 2019-10-29 | 四川大学 | A kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes |
| CN110387001A (en) * | 2018-04-19 | 2019-10-29 | 四川大学 | A kind of porphyrin polystyrene type elastomer and preparation method thereof and purposes |
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