CN105418940B - A kind of method for preparing the siliceous polyamide-amide that porphyrin is core - Google Patents
A kind of method for preparing the siliceous polyamide-amide that porphyrin is core Download PDFInfo
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Abstract
The present invention relates to daiamid, refers in particular to a kind of method for preparing the siliceous daiamid that porphyrin is core.The siliceous daiamid of 13 generation end alkynyl radicals is prepared by amidatioon and Michael addition reaction step-reaction, by the 5 of Azide, 10,15,20 tetraphenylporphyrin (PP N3) with the siliceous daiamid (Dm of 13 generation end alkynyl radicals, m=1.0,2.0 or click-reaction 3.0) occurs produce siliceous daiamid (PP SI PAMAM) using porphyrin as core, be freeze-dried after dialyse three days in distilled water after reaction and obtain product PP Dm.
Description
Technical field
The present invention relates to polyamide-amide, refers in particular to a kind of method for preparing the siliceous polyamide-amide that porphyrin is core, is specifically
A kind of prepared using click chemistry method has method of the different topology structure using porphyrin as the siliceous polyamide-amide of core.
Background technology
In recent years, Porphyrin and its derivative is because there is good photosensitive property to be widely used in medicament slow release and tumour
Field of photodynamic;But because Porphyrin and its derivative molecular hydrophobicity is strong, in aqueous solution, between big plane of a loop
Hydrophobic effect result in the stronger aggregation tendency of photosensitizer, this not only brings difficulty to isolating and purifying for photosensitizer, but also generally
Produce aggregation photosensitizer light power effect it is poor so that have impact on its spectrochemical property and in vivo the effect of, pass through height
Molecular function, can synthesize the macromolecule with various topological structures, therefore design and synthesize the functionalization using porphyrin as core
Polymer and functionalization dendrimer are paid close attention to be subject to more and more researchers, meanwhile, it is interior using Porphyrin and its derivative
Core, since the polymer of exterior topological structure can effectively prevent the self-quenching of porphyrin kernel, is expected to efficiently height
The photosensitive drug of concentration is delivered to lesions position.
Due to non-immunogenicity, non-toxic under suitable dosage and to bioactive substance transfer efficiency height etc.
Advantage, dendrimer polyamide-amide (PAMAM) are subject to extensively in medicine controlled release carrier, gene therapy, magnetic resonance contrast agent etc.
General research, moreover, polyamide-amide class dendritic macromole is the gathering with non-traditional luminophore for being reported out at first
Compound, the high molecular polymer of this fluorescence have numerous applications, the especially application on biomedical diagnostic in recent years;
Organosilicon polymer has organic polymer and inorganic silicon compound dual property concurrently, and wherein highly -branched silicon-containing polymer extensively should
Use that medicine is micro- to be transported to artificial red cells, unicellular microorganism device etc., and the polymer containing silicon atom or siloxanes can
Its fluorescence property is influenced to change the stability of polymer and space conformation
Recently, " click chemistry " is in organic synthesis, Polymer Synthesizing, biological hybrid material synthesis, device surface modification etc.
Field is subject to the extensive concern of scientist, and achieves very big success, therefore, different topology knot is prepared using click chemistry method
The porphyrin of structure, different compositions is the siliceous polyamide-amide of core, and the porphyrins for preparing other functionalization for convenience carries
A kind of feasible approach is supplied.
Found through the literature search to the prior art, Hua Chong etc. 2008《Macromolecules》41st
" the Synthesis and Characterization of Linear-Dendron-like delivered on phase 6686-6695
Poiy(ε-caprolactone)-b-poly(ethylene oxide)Copolymers via the Combination of
(Click methods prepare line style-fan PCL- to Ring-Opening Polymerization and Click Chemistry. "
Dm-PBLG block copolymers and its characterization), this article is proposed in this article, and by the method for click, it is not right that synthesis has
Claim the PCL-Dm-PBLG block polymers of structure, wherein PCL is non-linear configuration, and PBLG is fan configuration, both are (poly- by Dm
Amide-amine) link;It is disadvantageous in that:1. the fluorescence property of connection literalness polyamide-amide used is limited, right
There is certain limitation in biologic applications, such as in the application by being detected property deficiency caused by weaker fluorescence property;2.
Prepared feature block polymer is non-linear configuration and fan configuration, and compared to dendroid configuration, it has the shortcomings that very much,
Therefore application also has certain limitation, and dendritic macromole has complete structure, and inside has wide cavity, surface
With very high functional group densities, possess substantial amounts of reactivity or functional groups, and so far, there is different topology structure
Using porphyrin as the siliceous daiamid material of core, there is not been reported.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, changes macromolecular structure by the introducing of organic element silicon
It is middle to cause the quantity of fluorophor tertiary amine and its steric configuration to strengthen its fluorescence property, after pass through click chemistry reaction and porphyrin core
Connection, the fluorescent both of peripheral dendritic structure can be organically combined with the ability of the generation singlet oxygen of porphyrin core to be expanded significantly
Potential application of such dendrimer in biological field, this method are that the difference using porphyrin as core of complex functionality is opened up
The effective way of the dendrimer of structure is flutterred, design is reasonable, easy to operate, is expected to be suitable for industrialized production.
The purpose of the present invention is what is be achieved through the following technical solutions, the present invention is completed by two-step reaction:
1 prepares siliceous polyamide-amides of the 1-3 for end alkynyl radical by amidatioon and Michael addition reaction step-reaction.
Concretely comprise the following steps:Siliceous daiamid (the D of 1 first generation end alkynyl radical1.0) synthesis:Methyl acrylate (MA) adds
Enter in round-bottomed flask, add absolute methanol, round-bottomed flask is placed in ice-water bath, after sealing stirring 30min, by methanol dilution
Propargylamine (the volume ratio 1 of methanol and propargylamine:1) round-bottomed flask slowly, is added drop-wise to micro syringe, the process of dropwise addition continues 1h
(molar ratio of propargylamine and MA are 1:3-1:5) 24h is stirred after at room temperature, is obtained after rotating and vacuumizing and remove methanol and MA
Intermediate product (D0.5), with D0.5Round-bottomed flask is added for reactant to be placed in ice-water bath, double (the 3- aminopropans of 1,3- of methanol dilution
Base) -1,1,3,3- tetramethyl disiloxane (D0) (methanol and D0Volume ratio 1:1) slowly it is added drop-wise to dropwise in round-bottomed flask,
D0.5With D0Molar ratio be 1:3-1:Excessive D is removed with petroleum ether extraction after stirring reaction 48h at a temperature of 5,50 degree0, then revolve
Methanol is boiled off, vacuum pump obtains product D after vacuumizing 2h1.0。
Siliceous daiamid (the D of 2 second generation end alkynyl radicalizations2.0) synthesis:With D1.0With methyl acrylate (D1.0With rubbing for MA
You are than being 1:6-1:8) it is reactant, methyl acrylate (MA) is added in round-bottomed flask, adds absolute methanol, round-bottomed flask is put
In ice-water bath, after sealing stirring 30min, by the D of methanol dilution1.0(methanol and D1.0Volume ratio 1:1) micro syringe, is used
Slowly be added drop-wise to round-bottomed flask, the process of dropwise addition continues 1h, then 50 degree it is lower stir 72h, through rotate and vacuumize removing methanol and
Intermediate product (D is obtained after MA1.5), with D1.5And D0For reactant (D1.5With D0Molar ratio be 1:6-1-8), by D1.5Add circle
In the flask of bottom, after adding methanol dissolving, the D of methanol dilution0(methanol and D0Volume ratio 1:1) it is added drop-wise to dropwise in round-bottomed flask,
Stirring reaction 7 days at a temperature of 50 degree, petroleum ether extraction removes excessive D0, then rotate and remove methanol, after vacuum pump vacuumizes 2h
D is made2.0。
3:Siliceous daiamid (the D of third generation end alkynyl radical3.0) synthesis:With D2.0It is reactant (D with MA2.0With MA's
Molar ratio is 1:12-1:20), methyl acrylate (MA) is added in round-bottomed flask, adds absolute methanol, round-bottomed flask is placed in ice
In water-bath, after sealing stirring 30min, by the D of methanol dilution2.0(methanol and D2.0Volume ratio 1:1), with micro syringe slowly
Round-bottomed flask is added drop-wise to, the process of dropwise addition continues 1h, then 50 degree of lower stirring 72h, after rotating and vacuumizing and remove methanol and MA
Obtain intermediate product (D2.5), D is made in 50 degree of lower stirring reaction 72h2.5, with D2.5And D0For reactant (D2.5With D0Molar ratio be
1:12-1:20), by D2.5Add in round-bottomed flask, after adding methanol dissolving, the D of methanol dilution0(methanol and D0Volume ratio 1:
1) it is added drop-wise to dropwise in round-bottomed flask, stirring reaction 7 days at a temperature of 50 degree, petroleum ether extraction removes excessive D0, then rotate
Fall methanol, D is made after vacuumizing 2h in vacuum pump3.0。
2 by Azide 5,10,15,20- tetraphenylporphyrin (PP-N3) with 1-3 for end alkynyl radical siliceous polyamide-amide
(3.0) Dm, m=1.0,2.0 occur click-reaction and produce siliceous polyamide-amide (PP-SI-PAMAM) using porphyrin as core.
Concretely comprise the following steps:
1 weighs quantitative Dm, and (3.0) m=1.0,2.0 or is added in round-bottomed flask, by sodium ascorbate and CuSO4·
5H2It is added in round-bottomed flask, is stirred to Dm dissolvings and solution changes color after O is soluble in water.
After 2 accurately pipette suitable DMSO in round-bottomed flask, the PP-N of DMSO dissolvings is added after stirring3, sealing is taken out true
Inflated with nitrogen 3 minutes, so operation are reacted three days after 40 degree of oil bath stirrings in triplicate again within empty 3 minutes.
Wherein Dm and PP-N3Molar ratio be 6-8:1, sodium ascorbate, CuSO4·5H2O and PP-N3Molar ratio be
18:6:1.
3 dialyse three days in distilled water after reaction after freeze-drying obtain product PP-Dm (m=1.0,2.0 or
3.0)。
The invention has the advantages that:
1. the dendritic macromole has complete structure, inside has wide cavity, and surface has very high function
Group's density, has preferable reactivity, it is possessed substantial amounts of reactivity or functional groups.
2. introducing the preferable element silicon of fluorescence property on side chain, the light sensitivity for effectively strengthening porphyrins improves it
Performance.Also, at low algebraically (below 3 generations), PAMAM has unlimited and of a relatively loose structure, in high algebraically (4 is more than generation)
It is in then the closelypacked structure in surface.
3. the topological structure of porphyrin compound, is accurately controlled by the siliceous polyamide-amide of the end alkynyl radical of different algebraically
System.
4. provide a kind of simple efficient method to prepare functional porphyrin boiomacromolecule.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of Dm.
Fig. 2 reacts schematic diagram for Click.
Fig. 3 is the structure diagram of Dm (m=1,2,3).
Fig. 4 is PP-D1Structure diagram.
Fig. 5 is PP-D2Structure diagram.
Fig. 6 is PP-D3Structure diagram.
Embodiment
Elaborate below to the embodiment of the present invention:The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
The synthetic route of the embodiment of the present invention is as shown in Figure 1.
Example 1:Siliceous daiamid (the Si-PAMAM-D of the first generation1.0) synthesis
Pipette accurately pipettes the methyl acrylate (1.6ml, 18mmol) newly steamed and 2ml absolute methanols are added to 25ml circles
In the flask of bottom, flask is placed in ice-water bath, is measured propargylamine (311 μ l, 4.6mmol) in solvent bottle with microsyringe, is moved
Liquid pipe measures 1ml absolute methanols in solvent bottle, is added dropwise to after mixing with injector in round-bottomed flask, about 1h adds
Complete, 24h is reacted in stirring at room temperature.After reaction methanol and unreacted acrylic acid first are removed with 45 degree of revolvings of Rotary Evaporators
Ester, uses vacuum pumping 2h afterwards, to ensure that methyl acrylate removes completely, obtains D0.5(0.93g, yield 89%).Weigh D0.5
(0.93g, 4.1mmol), measures 5ml absolute methanols and adds in round-bottomed flask, round-bottomed flask is placed in ice-water bath;1,3- is double
(3- aminopropyls) -1,1,3,3- tetramethyl disiloxane (4.5ml, 16.4mmol) are mixed with 5ml absolute methanols, are added dropwise
To round-bottomed flask, about 1h, in 50 degree of stirring reaction 48h.It is double to remove unreacted 1,3- three times for petroleum ether extraction after reaction
(3- aminopropyls) -1,1,3,3- tetramethyl disiloxanes, then rotate and remove methanol acquisition D1.0(2.52g, yield 85%).
The reaction has obtained the alkynyl-modified siliceous daiamid containing two end amidos with two side chains using propargylamine as core
D1.0。
Example 2:Siliceous daiamid (the Si-PAMAM-D of the second generation2.0) synthesis
Precise D1.0(2.52g, 3.5mmol) and 10ml absolute methanols are added in 25ml round-bottomed flasks, and flask is placed in
In ice-water bath, pipette accurately pipettes the methyl acrylate (2.5ml, 28mmol) newly steamed, after mixing with injector dropwise
It is added in round-bottomed flask, 50 degree of lower stirring reaction 72h.After reaction with 45 degree of revolving removing methanol of Rotary Evaporators and not
The methyl acrylate of reaction, uses vacuum pumping 2h afterwards, to ensure that methyl acrylate removes completely, obtains D1.5(3.05g, yield
87%).Weigh D1.5(3.05g, 3.04mmol), measures 5ml absolute methanols and adds in round-bottomed flask, round-bottomed flask is placed in ice
In water-bath;1,3- double (3- aminopropyls) -1,1,3,3- tetramethyl disiloxanes (6.7ml, 24.32mmol) are with 6ml without water beetle
Alcohol mixes, and is added dropwise to round-bottomed flask, about 1h, is reacted 7 days in 50 degree of stirrings.Petroleum ether extraction removes three times after reaction
Double (the 3- aminopropyls) -1,1 of unreacted 1,3-, 3,3- tetramethyl disiloxanes, then rotate and remove methanol acquisition D2.0
(4.39g, yield 81.5%).The reaction is in D1.0On the basis of further synthesis obtained have four side chains contain four ends
The siliceous polyamide D of amido2.0。
Example 3:Siliceous daiamid (the Si-PAMAM-D of the third generation3.0) synthesis
Precise D2.0(2.66g, 1.5mmol) and 10ml absolute methanols are added in 25ml round-bottomed flasks, and flask is placed in
In ice-water bath, pipette accurately pipettes the methyl acrylate (2.2ml, 24mmol) newly steamed, after mixing with injector dropwise
It is added in round-bottomed flask, 50 degree of lower stirring reaction 72h.After reaction with 45 degree of revolving removing methanol of Rotary Evaporators and not
The methyl acrylate of reaction, uses vacuum pumping 2h afterwards, to ensure that methyl acrylate removes completely, obtains D2.5(3.02g, yield
86.5%).Weigh D2.5(3.02g, 1.3mmol), measures 10ml absolute methanols and adds in round-bottomed flask, round-bottomed flask is placed in
In ice-water bath;1,3- double (3- aminopropyls) -1,1,3,3- tetramethyl disiloxanes (5.7ml, 20.8mmol) and 6ml are anhydrous
Methanol mixes, and is added dropwise to round-bottomed flask, about 1h, is reacted 7 days in 50 degree of stirrings.Petroleum ether extraction removes three times after reaction
Double (the 3- aminopropyls) -1,1 of unreacted 1,3- are removed, 3,3- tetramethyl disiloxanes, then rotate and remove methanol acquisition D3.0
(4.35g, yield 86.6%).With D2.0For reactant, can synthesize to obtain containing eight side chains by the method progressively dissipated
Siliceous daiamid D containing eight Amino End Groups3.0。
Example 4:Click chemistry method prepares the polyamide-amide (PP-Si-PAMAM-D using porphyrin as core1.0)
D1(138.6mg 0.192mmol) is added in 25ml round-bottomed flasks, CuSO4·5H2O (36mg, 0.048mmol), resist
Bad hematic acid sodium (85.5mg, 0.192mmol) is added separately to solvent bottle, and then adding 1ml deionized waters makes to form catalysis
Cu1+, slowly it is added dropwise to after abundant dissolving with dropper in flask and (adds the processing step of catalyst to whole reaction and its again
Will, and where the difficult point of this reaction, because reactant is dendritic, if deal with improperly easily generate it is sticky insoluble
Thing, and if directly CuSO4·5H2O, sodium ascorbate, which is added directly into reaction system, occurs that insoluble phenomenon makes catalyst
Catalyst, by groping just to obtain suitable processing mode repeatedly, is first formed univalent copper ion and added by inactivation in water, this
Process is rapid, prevent sodium ascorbate from being aoxidized and lost activity), pipette pipettes 3mlDMSO in flask, stir about 15
THPP-N is added after minute3(20mg, 0.024mmol), is sealed with latex turned welt plug, is vacuumized, each 3 minutes of inflated with nitrogen, so
Operation in triplicate, stirs reaction 48h in 40 degree of oil baths.Gone after reaction with the bag filter that molecular cut off is 2000
Dialyse 3 days in ionized water, a water is changed when each two is small, solution, which is poured into 100ml beakers, after dialysis is put into refrigerator progress
Pre-freeze 24h, carries out freeze-drying in freeze drier after pre-freeze and obtains product PP-D1(61mg, yield 68.3%).This is anti-
Should react that successfully to have synthesized porphyrin be that core contains 8 Amino End Groups by click chemistry using nitrine porphyrin and D1 as reactant
Siliceous daiamid PP-Si-PAMAM-D1.0。
Example 5:Click chemistry method prepares the polyamide-amide (PP-Si-PAMAM-D using porphyrin as core2.0)
D2(339.8mg/0.192mmol) is added in 25ml round-bottomed flasks, CuSO4·5H2O (36mg, 0.048mmol), resist
Bad hematic acid sodium (85.5mg, 0.192mmol) is added separately to solvent bottle, and then adding 1ml deionized waters makes to form catalysis
Cu1+, slowly it is added dropwise to after abundant dissolving with dropper in flask, pipette pipettes 6.4mlDMSO in flask, and stir about 15 divides
THPP-N is added after clock3(20mg, 0.024mmol), is sealed with latex turned welt plug, is vacuumized, each 3 minutes of inflated with nitrogen, so behaviour
Make in triplicate, the stirring reaction 48h in 40 degree of oil baths.After reaction with molecular cut off be 3500 bag filter go from
Dialyse 3 days in sub- water, a water is changed when each two is small, solution, which is poured into 100ml beakers, after dialysis is put into refrigerator progress in advance
Freeze 24h, carrying out freeze-drying in freeze drier after pre-freeze obtains product PP-D2(120.6mg, yield 63.5%).Should
Reaction react by click chemistry using nitrine porphyrin and D1 as reactant and has successfully synthesized porphyrin and hold ammonia containing 16 for core
The siliceous daiamid PP-Si-PAMAM-D of base2.0。
Example 6:Click chemistry method prepares the polyamide-amide (PP-Si-PAMAM-D using porphyrin as core3.0)
D3(742.3mg, 0.192mmol) is added in 25ml round-bottomed flasks, CuSO4·5H2O (36mg, 0.048mmol), resist
Bad hematic acid sodium (85.5mg, 0.192mmol) is added separately to solvent bottle, and then adding 1ml deionized waters makes to form catalysis
Cu1+, slowly it is added dropwise to after abundant dissolving with dropper in flask, pipette pipettes 13.5mlDMSO in flask, stir about 15
THPP-N is added after minute3(20mg, 0.024mmol), is sealed with latex turned welt plug, is vacuumized, each 3 minutes of inflated with nitrogen, so
Operation in triplicate, stirs reaction 48h in 40 degree of oil baths.Gone after reaction with the bag filter that molecular cut off is 3500
Dialyse 3 days in ionized water, a water is changed when each two is small, solution, which is poured into 100ml beakers, after dialysis is put into refrigerator progress
Pre-freeze 24h, carries out freeze-drying in freeze drier after pre-freeze and obtains product PP-D3-(239.37mg, yield 61.2%).
The reaction react by click chemistry using nitrine porphyrin and D1 as reactant and has successfully synthesized porphyrin and held for core containing 32
The siliceous daiamid PP-Si-PAMAM-D of amino3.0。
The measuring method of compound fluorescence intensity is:Compound is made into the aqueous solution that 5ml concentration is 0.05mmol/L, profit
With fluorescence spectrophotometer degree instrument, using the excitation wavelength of 425nm, relative intensity of fluorescence of the compound under the excitation wavelength is measured, is had
Volume data see the table below:
Polymer | Fluorescence intensity | Polymer | Fluorescence intensity |
Si-PAMAM-D1.0 | 216.536 | PAMAM-D1.0 | 157.359 |
Si-PAMAM-D2.0 | 387.761 | PAMAM-D2.0 | 203.257 |
Si-PAMAM-D3.0 | 557.473 | PAMAM-D3.0 | 330.861 |
It can be seen that by the contrast of the relative intensity in upper table:1 is with the growth of compound algebraically, its fluorescence intensity
Constantly strengthen;2 by contrast, and the siliceous daiamid (Si-PAMAM-Dm) that this synthetic method obtains is synthesized than the prior art
Daiamid (PAMAM-Dm) fluorescence intensity have enhancing largely;Therefore, the fluorescent both prepared by this method
The siliceous daiamid of energy can be applied to the preparation with the photosensitive agent material and medicine carrying material for being detected performance.
Claims (9)
- A kind of 1. method for preparing the siliceous polyamide-amide that porphyrin is core, it is characterised in that step is as follows:(1) the siliceous daiamid D of first generation end alkynyl radical1.0Synthesis:Methyl acrylate is added in round-bottomed flask, adds nothing Water methanol, round-bottomed flask is placed in ice-water bath, and after sealing stirring, the propargylamine of methanol dilution is added drop-wise to micro syringe Stir 24h after round-bottomed flask at room temperature, the molar ratio of propargylamine and methyl acrylate is 1:3-1:5, removed through rotating and vacuumizing Intermediate product D is obtained after removing methanol and methyl acrylate0.5, with D0.5Round-bottomed flask is added for reactant to be placed in ice-water bath, first Double (3- aminopropyls) -1,1,3, the 3- tetramethyl disiloxane D of diluted 1, the 3- of alcohol0It is added drop-wise to dropwise in round-bottomed flask, D0.5With D0Molar ratio be 1:3-1:Excessive D is removed with petroleum ether extraction after stirring reaction 48h at a temperature of 5,50 degree0, then rotate and remove Methanol, obtains product D after vacuumizing1.0;(2) the siliceous daiamid D of second generation end alkynyl radicalization2.0Synthesis:With D1.0It is reactant with methyl acrylate, D1.0With third The molar ratio of e pioic acid methyl ester is 1:6-1:8, methyl acrylate is added in round-bottomed flask, adds absolute methanol, round-bottomed flask is put In ice-water bath, after sealing stirring, by the D of methanol dilution1.050 degree of lower stirrings after being added drop-wise to round-bottomed flask with micro syringe 72h, intermediate product D is obtained after rotating and vacuumizing and remove methanol and methyl acrylate1.5, with D1.5And D0For reactant, D1.5 With D0Molar ratio be 1:6-1:8, by D1.5Add in round-bottomed flask, after adding methanol dissolving, the D of methanol dilution0It is added dropwise dropwise Into round-bottomed flask, stirring reaction 7 days at a temperature of 50 degree, petroleum ether extraction removes excessive D0, then rotate and remove methanol, take out true D is made after sky2.0;(3) the siliceous daiamid D of third generation end alkynyl radical3.0Synthesis:With D2.0It is reactant with methyl acrylate, D2.0With The molar ratio of methyl acrylate is 1:12-1:20, methyl acrylate is added in round-bottomed flask, adds absolute methanol, round bottom is burnt Bottle is placed in ice-water bath, after sealing stirring, by the D of methanol dilution2.0Stirred after being added drop-wise to round-bottomed flask with micro syringe under 50 degree 72h is mixed, intermediate product D is obtained after rotating and vacuumizing and remove methanol and methyl acrylate2.5, with D2.5And D0For reactant, D2.5With D0Molar ratio be 1:12-1:20, by D2.5Add in round-bottomed flask, after adding methanol dissolving, the D of methanol dilution0Dropwise It is added drop-wise in round-bottomed flask, stirring reaction 7 days at a temperature of 50 degree, petroleum ether extraction removes excessive D0, then rotate and remove methanol, D is made after vacuumizing3.0;(4) by the 5 of Azide, 10,15,20- tetraphenylporphyrin PP-N3With Dm, m=1.0,2.0 or 3.0, click-reaction system occurs Take the siliceous polyamide-amide PP-SI-PAMAM using porphyrin as core;(5) dialyse after reaction in distilled water, freeze-drying obtains product PP-Dm, m=1.0,2.0 or 3.0.
- A kind of 2. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that step (4) concretely comprise the following steps:Quantitative Dm, m=1.0,2.0 or 3.0 are weighed, are added in round-bottomed flask, by sodium ascorbate and CuSO4·5H2O is molten It is added in round-bottomed flask, is stirred to Dm dissolvings and solution changes color after Yu Shuizhong;After suitable DMSO is accurately pipetted in round-bottomed flask, the PP-N of DMSO dissolvings is added after stirring3, seal and vacuumize 3 minutes Inflated with nitrogen 3 minutes again, so operation are reacted three days after 40 degree of oil bath stirrings in triplicate.
- A kind of 3. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 2, it is characterised in that:Dm, M=1.0,2.0 or 3.0, with PP-N3Molar ratio be 6-8:1, sodium ascorbate, CuSO4·5H2O and PP-N3Molar ratio be 18:6:1.
- A kind of 4. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that:Step Suddenly (1), (2), the sealing mixing time of (3) are 30min.
- A kind of 5. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that:Step Suddenly in (1), in the propargylamine of methanol dilution, the volume ratio 1 of methanol and propargylamine:1;The D of methanol dilution0In, methanol and D0Body Product ratio 1:1.
- A kind of 6. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that:Step Suddenly in (2), the D of methanol dilution1.0In, methanol and D1.0Volume ratio 1:1;The D of methanol dilution0In, methanol and D0Volume ratio 1: 1。
- A kind of 7. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that:Step Suddenly in (3), the D of methanol dilution2.0In, methanol and D2.0Volume ratio 1:1;The D of methanol dilution0In, methanol and D0Volume ratio 1: 1。
- A kind of 8. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that:Step Suddenly in (4), by the 5 of Azide, 10,15,20- tetraphenylporphyrin PP-N3With the siliceous daiamid of third generation end alkynyl radical D3.0, generation click-reaction produces the siliceous polyamide-amide PP-SI-PAMAM using porphyrin as core, after reaction in distilled water Dialysis is freeze-dried after three days and obtains product PP-D3.0。
- A kind of 9. method for preparing the siliceous polyamide-amide that porphyrin is core as claimed in claim 1, it is characterised in that:Step Suddenly the time dialysed in (5) in distilled water is three days.
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