CN108392631A - A kind of porphyrin nano material and preparation method thereof and the application in preparing near infrared light heat cure drug - Google Patents
A kind of porphyrin nano material and preparation method thereof and the application in preparing near infrared light heat cure drug Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of porphyrin nano material, belong to materials chemistry and field of biology.The present invention using the cosolvent method of protonic acid doping prepare porphyrin nano scantling is small, near infrared absorption is strong, with very high light thermal property.In the present invention, by regulating and controlling the addition of Bronsted acid to realize the regulation and control of porphyrin presoma protonation, so as to regulate and control controllable preparation of the assembly by nanometer stub, nano wire and nano particle, polar solvent is combined to porphyrin presoma good dissolubility energy, slow down settle out speed of the porphyrin presoma in poor solvent using anion emulsifier, weak interaction force between adjusting porphyrin precursor molecule, realizes the near infrared absorption of porphyrin presoma self-assembly by adjusting the addition of Bronsted acid.
Description
Technical field
The present invention relates to materials chemistry and biology techniques field more particularly to a kind of porphyrin nano material and its preparation sides
Method and the application in preparing near infrared light heat cure drug.
Background technology
With the development of economy and society, environmental pollution, unsound diet problem are outstanding day by day, cancer in global range
Incidence is in the trend of sustainable growth, and Cancer in China incidence accounts for the 21.8% of global cancer morbidity, and becoming influences the mankind
The number one killer of health." cancer " is the full name of all malignant tumours, is not normal by control cell proliferation machinery and causes
A kind of disease.How cancer is effectively prevented and treated, is significant challenge and difficulty urgently to be resolved hurrily that the mankind face at present
Topic.
In recent decades, people have done a large amount of research in terms for the treatment of of cancer, and more traditional three kinds of therapeutic modalities are：
Operative treatment, radiotherapy, chemotherapy, but operative treatment need to cut wound excision sufferer tissue, be brought greatly to patient
It also can not complete removal of lesions while painful；Cancer cell can be all killed in principle of radiotherapy, but can similarly be killed
Normal cell is very big to human injury；The toxic side effect of chemotherapy is big, and taking can make cancer cell develop immunity to drugs for a long time,
Cancer is easy recurrence, and therapeutic effect is limited.And photo-thermal therapy (Photothermal Therapy, PTT) is a kind of novel swells
Tumor therapy, under the action of photothermal conversion reagent, light absorbing energy is converted to local thermal energy, and then it is thin to kill cancer
Born of the same parents.Requirement of this technology to equipment be extremely low, of low cost, easy to operate and be easy to control, the local therapy have it is simple, have
Effect, pain are light, restore the advantages that fast, and to the side effect very little that human normal tissue generates, are referred to as " green remedy ", therefore
Favored in recent years by scientists.
Porphyrin Molecule has the big ring conjugated structure of 18 pi-electrons of rigid plane, the molecular symmetry of height, high mole
Absorptivity, with certain chemically and thermally stability.In addition, Porphyrin Molecule is with good biocompatibility and well
Optical characteristics, be allowed to have good application prospect in terms of biological diagnosis and treatment and treatment.Currently, some researches show that by from group
The method of dress can expand the absorption peak of porphyrin to visible region (ultraviolet wavelength：400nm is hereinafter, visible wavelength：400~
760nm, infrared light:More than 760nm), still, porphyrin nano material is weaker near infrared absorption.
Invention content
In view of this, the purpose of the present invention is to provide a kind of porphyrin nano material and preparation method thereof and biological close red
Application in outer photo-thermal therapy.Porphyrin nano material provided by the invention has stronger absorption in near-infrared, swashs in near-infrared
It can be to reach higher heating in the short time under the irradiation of light.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of preparation method of porphyrin nano material, includes the following steps：
Anion emulsifier is mixed with Bronsted acid and water, obtains anion emulsifier acid solution；
Porphyrin presoma is mixed with polar solvent, obtains porphyrin precursor solution；
Obtained porphyrin precursor solution is mixed with anion emulsifier acid solution, self-assembling reaction occurs, obtains
Porphyrin nano material.
Preferably, the Bronsted acid is inorganic proton acid, and the inorganic proton acid is hydrochloric acid or perchloric acid.
Preferably, the Bronsted acid be organic proton acid, the organic proton acid be formic acid, acetic acid, propionic acid, to methylbenzene
Sulfonic acid or lactic acid.
Preferably, the anion emulsifier is neopelex or lauryl sodium sulfate.
Preferably, in the anion emulsifier acid solution anion emulsifier a concentration of 0.01~0.025mol/
L, pH value are 2.5~3.9.
Preferably, the porphyrin presoma be 5,10,15,20- tetra- (4- aminobenzenes) -21H, 23H- porphyrins or 5,10,15,
20- tetra- (4- aminophenyls) porphyrin；
Preferably, the polar solvent is n,N-Dimethylformamide or dimethyl sulfoxide (DMSO).
Preferably, a concentration of 0.01~0.05mol/L of the porphyrin precursor solution.
The present invention also provides porphyrin nano material made from preparation method described in above-mentioned technical proposal, the porphyrin nano
The absorption peak wave-length coverage of material is 780~950nm, the pattern of the porphyrin nano material include nanometer stub, nano wire and
The length of nano particle, the porphyrin nano material is 50nm~2 μm.
The present invention also provides porphyrin nano materials described in above-mentioned technical proposal to prepare near infrared light heat cure drug
In application.
The present invention provides a kind of preparation methods of porphyrin nano material, and anion emulsifier and Bronsted acid and water are mixed
It closes, obtains anion emulsifier acid solution；Porphyrin presoma is mixed with polar solvent, obtains porphyrin precursor solution；It will
Obtained porphyrin precursor solution is mixed with anion emulsifier acid solution, and self-assembling reaction occurs, obtains porphyrin nano material
Material.The present invention using protonic acid doping cosolvent method prepare porphyrin nano particle size it is small (<100nm), near infrared absorption
(the I at 811nm by forceQ：IB=0.8), with very high light thermal property.Present invention incorporates polar solvent is good to porphyrin presoma
Good solubility property, slows down settle out speed of the porphyrin presoma in poor solvent (water) using anion emulsifier, passes through tune
It saves the addition of Bronsted acid and then adjusts weak interaction force between porphyrin precursor molecule, and then regulate and control assembling, before realizing porphyrin
The near infrared absorption for driving body self-assembly by the accumulation quenching fluorescence of Porphyrin Molecule and generates high light thermal property.The present invention
Since porphyrin presoma largely dissolves in polar solvent, solve production problems, and using anion emulsifier as confinement
Template under the auxiliary of anion emulsifier, passes through molecule by making porphyrin precursor molecule become insoluble state from solvable
Between weak interaction carry out self assembly, and finally obtain the porphyrin self-assembly of morphology controllable, the material after this self assembly
Material has in terms of photo-thermal therapy cancer to play a very important role.Preparation method synthesis technology provided by the invention is simple, to equipment
It is required that low, prepared porphyrin nano material has a stronger absorption in near-infrared, and can be under the irradiation of near-infrared laser
Reach higher heating in short time, there is preferable application prospect in terms of photo-thermal therapy cancer.
Further, in the present invention, by regulating and controlling the addition of Bronsted acid to realize the protonated journey of porphyrin forerunner
The regulation and control of degree, so as to regulate and control controllable preparation of the porphyrin nano material assembly by nanometer stub, nano wire and nano particle.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the uv absorption spectra of porphyrin nano material made from embodiment 1；
The SEM of Fig. 2 is 1 anion emulsifier acid solution pH value of embodiment when being 6.66 porphyrin nano material obtained
Figure；
The SEM of Fig. 3 is 1 anion emulsifier acid solution pH value of embodiment when being 3.21 porphyrin nano material obtained
Figure；
The SEM of Fig. 4 is 1 anion emulsifier acid solution pH value of embodiment when being 2.71 porphyrin nano material obtained
Figure；
The TEM of Fig. 5 is 1 anion emulsifier acid solution pH value of embodiment when being 2.71 porphyrin nano material obtained
Figure；
Fig. 6 is the uv absorption spectra of porphyrin nano material under the different protonic acid dopings of embodiment 2；
Fig. 7 is the photo-thermal test chart of porphyrin nano material under 3 various concentration of embodiment；
Fig. 8 is the solar thermochemical cycle test chart of 3 porphyrin nano material of embodiment；
Fig. 9 is the burnt cell imaging figure of external copolymerization of 4 porphyrin nano material of embodiment；
Figure 10 is the cell phototoxicity test chart of 5 porphyrin nano material of embodiment.
Specific implementation mode
The present invention provides a kind of preparation methods of porphyrin nano material, include the following steps：
Anion emulsifier is mixed with Bronsted acid and water, obtains anion emulsifier acid solution；
Porphyrin presoma is mixed with polar solvent, obtains porphyrin precursor solution；
Obtained porphyrin precursor solution is mixed with anion emulsifier acid solution, self-assembling reaction occurs, obtains
Porphyrin nano material.
The present invention mixes anion emulsifier with Bronsted acid and water, obtains anion emulsifier acid solution.In this hair
In bright, the Bronsted acid is preferably inorganic proton acid or organic proton acid.In the present invention, the inorganic proton acid is preferably salt
Acid or perchloric acid.In the present invention, the concentration of the inorganic proton acid is preferably 0.3M.In the present invention, the organic proton
Acid is preferably formic acid, acetic acid, propionic acid, p-methyl benzenesulfonic acid or lactic acid, and the concentration of the organic proton acid is preferably pure organic
Proton concentrated acid is with volume ratio for 1：400~3000 dilutions.The present invention is received using porphyrin prepared by the cosolvent method of protonic acid doping
Rice scantling is small, near infrared absorption is strong, with very high light thermal property.In the present invention, pass through the addition of regulation and control Bronsted acid
Amount adjusts weak interaction force between porphyrin precursor molecule to realize the regulation and control of phenylamino porphyrin protonation, so as to
To regulate and control controllable preparation of the assembly by nanometer stub, nano wire and nano particle, pass through the accumulation quenching fluorescence of Porphyrin Molecule
And generate high light thermal property.In the present invention, gradually increasing with protonic acid doping amount, the nanometer stub cluster of 200nm by
Cumulative length, the gradual red shift of absorption spectrum；When it is 3.21 to increase to pH value of solution, the nano wire that assembly is 1~2 μm, Q bands
Absorption peak red shift is to 811nm；It continuing growing, pH value of solution continuously decreases, and assembly is that nano wire and nano particle are co-doped with state,
When it is 2.71 to increase to pH, assembly is the nano particle of 100nm, and the absorption peak of nano particle is due to assembly size at this time
It reduces and occurs being blue shifted to 800nm.
In the present invention, the anion emulsifier is preferably neopelex (SDBS) or dodecyl sulphate
Sodium (SDS).In the present invention, the anion emulsifier can slow down settle out speed of the porphyrin presoma in poor solvent,
While weak interaction force between porphyrin precursor molecule is adjusted by adjusting the addition of Bronsted acid, and then regulate and control assembling,
The near infrared absorption for realizing porphyrin presoma self-assembly by the accumulation quenching fluorescence of Porphyrin Molecule and generates high photo-thermal
Energy.
In the present invention, in the anion emulsifier acid solution concentration of anion emulsifier be preferably 0.01~
0.025mol/L, more preferably 0.01~0.02mol/L；The pH value of the anion emulsifier acid solution is preferably 2.5~
3.9, more preferably 2.71~2.87.
The present invention does not have the addition sequence of the anion emulsifier, Bronsted acid and water special restriction, using ability
Addition sequence known to field technique personnel, specifically, being such as first mixed to get anion emulsifier with water anionic emulsifying
After agent solution, then mix with Bronsted acid.
The present invention does not have the mode of the mixing special restriction, using hybrid mode well known to those skilled in the art
, specifically, as stirred.
The present invention mixes porphyrin presoma with polar solvent, obtains porphyrin precursor solution.In the present invention, the porphin
Quinoline presoma is preferably 5,10,15,20- tetra- (4- aminobenzenes) -21H, 23H- porphyrins (TAPP, phenylamino porphyrin) or 5, and 10,15,
20- tetra- (4- aminophenyls) porphyrin, the polar solvent are preferably n,N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO)
(DMSO).In the present invention, for the polar solvent to porphyrin presoma good dissolubility energy, water is the bad molten of porphyrin presoma
Agent, while slowing down settle out speed of the porphyrin presoma in poor solvent using anion emulsifier, by adjusting Bronsted acid
Weak interaction force between addition and then adjusting porphyrin precursor molecule, and then regulate and control assembling, realize porphyrin presoma self assembly
The near infrared absorption of body by the accumulation quenching fluorescence of Porphyrin Molecule and generates high light thermal property, and due to porphyrin presoma
It is largely dissolved in polar solvent, solves production problems, and using anion emulsifier as confinement template, by making porphyrin
Precursor molecule becomes insoluble state from solvable, under the auxiliary of anion emulsifier, passes through weak interaction between molecule
Self assembly is carried out, the porphyrin self-assembly of morphology controllable is finally obtained.
In the present invention, the concentration of the porphyrin precursor solution is preferably 0.01~0.05mol/L, more preferably
0.01mol/L。
The present invention does not have special restriction to the addition sequence of the porphyrin presoma and polar solvent, using this field skill
Addition sequence known to art personnel, specifically, such as porphyrin presoma is added in polar solvent.
The present invention does not have the mode of the mixing special restriction, using hybrid mode well known to those skilled in the art
, specifically, as stirred.
Porphyrin precursor solution is obtained with after anion emulsifier acid solution, the present invention is molten by obtained porphyrin presoma
Liquid is mixed with anion emulsifier acid solution, and self-assembling reaction occurs, obtains porphyrin nano material.In the present invention, described
Porphyrin precursor solution and the volume ratio of anion emulsifier acid solution are preferably 1:8~19, more preferably 1:10~19, most
Preferably 1:19.
The porphyrin precursor solution is preferably added in anion emulsifier acid solution and is stirred hair by the present invention
Raw self-assembling reaction.In the present invention, the stirring preferably carries out at room temperature, more preferable 20~30 DEG C, most preferably 25 DEG C；
The time of the stirring is preferably 40~50h, more preferably 45~48h；The rotating speed of the stirring is preferably 9000~
20000rpm, more preferably 11000~13000rpm.
After the completion of self-assembling reaction, preferably self-assembling reaction product is centrifuged by the present invention, obtains porphyrin nano
Material.The present invention does not have the time of the centrifugation, rotating speed special restriction, can realize separation of solid and liquid, specifically
Such as centrifuge 30min at 13000rpm.
The present invention also provides porphyrin nano material made from preparation method described in above-mentioned technical proposal, the porphyrin nano
The near ir absorption peaks wave-length coverage of material is 780~950nm, preferably 800~850nm；The porphyrin nano material
Pattern includes nanometer stub, nano wire and nano particle, and the length of the porphyrin nano material is 50nm~2 μm.
In the present invention, the nanometer stub length is more preferably 200nm, and Q band absorption peaks are at 690nm；The nanometer
Line length is preferably 1~2 μm, and Q band absorption peaks are located at 811nm；The nano particle length is preferably 50~100nm, and Q bands absorb
Peak is located at 800nm.
In the present invention, the phase of the absorption intensity and B bands at the porphyrin nano material near-infrared maximum absorption band 811nm
Reduced value is 0.1~0.8.
The present invention also provides porphyrin nano materials described in above-mentioned technical proposal to prepare near infrared light heat cure drug
In application, specifically, such as by the HeLa cells (8 × 10 of 100 μ L3It is a) complete medium solution be placed in Glass bottom culture dish
(10mm types), in 37 DEG C and 5%CO2Incubator in cultivate for 24 hours after it is adherent, remove supernatant, replace fresh complete medium
And different amounts of nano particle is added, then 808nm, 0.5W/cm2Laser irradiation under detect cell survival rate.
In the present invention, the porphyrin nano material is preferably used for biological near infrared light heat cure in form of an aqueous solutions,
The concentration of porphyrin nano material aqueous solution is preferably 0.02~0.2mg/mL, more preferably 0.05~0.1mg/mL.
With reference to embodiment to porphyrin nano material provided by the invention and preparation method thereof and in biological near infrared light
Application in heat cure is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) SDBS (purity 99.99%) is soluble in water, prepare the SDBS solution of 0.01M；
(2) standard 1M hydrochloric acid solutions are added drop-wise in SDBS solution, are made into the aqueous solution of the SDBS of different pH value, pH value is
6.66、3.90、3.56、3.21、2.87、2.71。
(3) TAPP is dissolved in DMF, the DMF solution of 0.01M TAPP is made；
(4) solution that 0.5mL steps (3) are prepared is injected into the solution of different pH value of 9.5mL steps (2) preparation,
Supernatant is outwelled after 25 DEG C of stirring 48h, 13000rpm centrifugation 30min, collects precipitation to get to porphyrin nano material.
The UV-vis spectrum of the porphyrin nano material obtained under different pH value as shown in Figure 1, as seen from Figure 1, when
When the pH value of SDBS solution is less than 3.50, Q bands, which occurs, in porphyrin nano material the absorption peak absorbed more by force near infrared region.By scheming
1 finds out, as pH=2.71, obtained nano particle IQ/IB=0.4765:When 078049=0.61, pH=2.87, obtain
Nano particle IQ/IB=0.59359；0.8175=0.73, as pH=3.21, obtained nano wire IQ/IB=0.589:
0.821=0.72, as pH=3.59, obtained nano wire IQ/IB=0.094:0.8358=0.11, as pH=3.90,
Obtained nano wire IQ/IB=0.03556:0.77387=0.046, as pH=6.66, obtained nanometer rods IQ/IB=
0.0252:0.8014=0.031 (is not added with Bronsted acid), and intensity IQ, B band position maximum is inhaled at Q bands position maximum absorption band 811nm
Receive intensity IB at peak.
When the pH value of (2) solution is 6.66, i.e., when hydrochloric acid not being added, obtained porphyrin nano material morphology such as Fig. 2 institutes
It is shown as graininess, size is 200nm or so (having extremely weak near infrared absorption)；When the pH value of (2) solution is 3.21, assembling
Bodily form looks (Fig. 3) are linear, at the maximum absorption band red shift to 811nm of Q bands；(2) pH value of solution is further reduced to
When 2.71, obtained porphyrin nano material morphology becomes particle (Fig. 4, Fig. 5) from long line.As seen from the figure, with pH value by
6.66 originally gradually decrease when being 3.21, nano-rod assembly length gradually increase plus, there is the assembly of nanometer threadiness, Q
At band absorption peak red shift to 811nm.PH value is reduced from 3.21 to gradually appearing granular assembly during 2.71,
It is nano particle when 2.71, Q band absorption peaks are located at 800nm.
Embodiment 2
The type for changing Bronsted acid in embodiment 1, includes the following steps：
(1) SDBS (purity 99.99%) is soluble in water, prepare the SDBS solution of 0.01M；
(2) different Bronsted acids (formic acid, acetic acid, propionic acid, p-methyl benzenesulfonic acid, lactic acid) are added drop-wise in (1), are made into pH value
For the aqueous solution of 2.71 SDBS
(3) phenylamino porphyrin is dissolved in DMF, the DMF solution of 0.01M phenylamino porphyrins is made；
(4) solution that 0.5mL steps (3) are prepared is rapidly injected in the solution of 9.5mL steps (2), 25 DEG C of stirrings
Supernatant is outwelled after 48h, 13000r centrifugation 30min, collects precipitation to get to porphyrin nano material.
The absorption of the porphyrin nano obtained after different protonic acid dopings is summarized, as shown in Figure 6, it can be seen that different matter
The porphyrin nano that sub- acid obtains absorbs near infrared region, and the acid sequence of Bronsted acid is p-methyl benzenesulfonic acid>Hydrochloric acid>Formic acid
>Acetic acid needs more Bronsted acids are added just the maximum of the Q bands that can make porphyrin assembly and inhales with the decrease of Bronsted acid acidity
Peak is received to reach at 811nm.Addition gradually increases, and can make the N matter of porphyrin peripheral substituent phenylamino and center pyrrole ring
Sonization.
Embodiment 3
The photo-thermal of porphyrin nano material is tested, and is included the following steps：
(1) by the pH value in embodiment 1 be 2.71 the obtained nano particle Centrifugal dispersion of SDBS solution in water three times
In；
(2) (1) solution is demarcated to the solution at various concentration by UV absorption：0mg/mL、0.02mg/mL、0.05mg/
mL、0.1mg/mL、0.2mg/mL；
(3) it takes 1mL to be placed in quartz colorimetric utensil solution different in (2), is 1W/cm with optical power density2808nm
Laser illumination 5min, per 30s thermocouple probe recording solution temperature.
(4) take 1mL to be placed in quartz colorimetric utensil the solution of a concentration of 0.1mg/mL in (2), use optical power density for
Stop illumination 10min after the 808nm laser illuminations 10min of 1W/cm2, per 30s thermocouple probe recording solution temperature.It follows
The heating temperature lowering curve of 3 test solution of ring.
Porphyrin nano material warms change curve is as shown in Figure 7 under various concentration, it can be seen that the liter of porphyrin nano material
Warm curve has certain concentration dependent, and under the concentration of 0.2mg/mL, the temperature of solution after 808nm laser illuminations 5min
80 DEG C are increased to, and the temperature of water as a control group only rises 3 DEG C or so.According to the heating temperature lowering curve (Fig. 8) of solution
As can be seen that porphyrin nano material has good photostability and thermal stability.
Embodiment 4
The co-focusing imaging of porphyrin nano material, includes the following steps：
(1) by the HeLa cells (8 × 10 of 100 μ L3It is a) complete medium solution be placed in Glass bottom culture dish (10mm
Type), in 37 DEG C and 5%CO2Incubator in cultivate for 24 hours after it is adherent.
(2) supernatant is removed, fresh complete medium is replaced and the 100 μ L of porphyrin nano particle of 0.02mg/mL is added, after
Continue and cultivates 2h at 37 DEG C.
(3) it discards supernatant and is rinsed 3 times with PBS, wash away extra nano particle, add fresh culture medium and in 60 times of oil
Its laser confocal imaging effect under the microscope.
It can be seen from co-focusing imaging figure (Fig. 9) within a short period of time, porphyrin nano particle quickly enters intracellular
Portion.
Embodiment 5
Cell photo-thermal (phototoxicity) is tested, and following steps are specifically included：
(1) HeLa cells (8 × 10 are cultivated in 98 orifice plates3/ hole) for 24 hours, it replaces fresh complete medium and is added not
The porphyrin nano material of same amount (0.08mg/ml, 0.06mg/ml, 0.04mg/ml, 0.02mg/ml) is protected from light culture 2h.
(2) with discarding supernatant under the conditions of being protected from light, 100 μ L PBS are added after cleaning 2 times in PBS.
(3) it is placed in 808nm laser (500mW/cm2) under after irradiation different time (3min, 6min, 9min), PBS is replaced
At fresh culture medium, continue to cultivate 12h.
(4) 10 μ L CCK-8 (2- (2- methoxyl group -4- nitrobenzophenones) -3- (4- nitrobenzophenones) -5- (2,4- are added per hole
Disulfonic acid benzene) -2H- tetrazolium monosodium salts) solution, continues to cultivate 2h, is placed on shaking table and shakes up, be finally placed in microplate reader and survey solution
Absorption value at 450nm calculates the survival rate of cell.
The result of embodiment 5 is as shown in table 1 and Figure 10, and under lower concentration (0.08mg/mL), cell kill rate reaches
80%.Show high photo-thermal therapy performance.
Table 1 cell photo-thermal (phototoxicity) experimental result
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of porphyrin nano material, includes the following steps：
Anion emulsifier is mixed with Bronsted acid and water, obtains anion emulsifier acid solution；
Porphyrin presoma is mixed with polar solvent, obtains porphyrin precursor solution；
The porphyrin precursor solution is mixed with anion emulsifier acid solution, self-assembling reaction occurs, obtains porphyrin and receives
Rice material.
2. preparation method according to claim 1, which is characterized in that the Bronsted acid is inorganic proton acid, described inorganic
Bronsted acid is hydrochloric acid or perchloric acid.
3. preparation method according to claim 1, which is characterized in that the Bronsted acid is organic proton acid, described organic
Bronsted acid is formic acid, acetic acid, propionic acid, p-methyl benzenesulfonic acid or lactic acid.
4. preparation method according to claim 1, which is characterized in that the anion emulsifier is dodecyl benzene sulfonic acid
Sodium or lauryl sodium sulfate.
5. preparation method according to claim 1 or 4, which is characterized in that cloudy in the anion emulsifier acid solution
A concentration of 0.01~0.025mol/L of ionic emulsifying agent, pH value are 2.5~3.9.
6. preparation method according to claim 1, which is characterized in that the porphyrin presoma is 5,10,15,20- tetra- (4-
Aminobenzene) -21H, 23H- porphyrins or 5,10,15,20- tetra- (4- aminophenyls) porphyrin.
7. preparation method according to claim 1, which is characterized in that the polar solvent be n,N-Dimethylformamide or
Dimethyl sulfoxide (DMSO).
8. preparation method according to claim 1, which is characterized in that a concentration of the 0.01 of the porphyrin precursor solution~
0.05mol/L。
9. porphyrin nano material made from preparation method described in claim 1~8 any one, the suction of the porphyrin nano material
It receives spike and grows ranging from 780~950nm, the pattern of the porphyrin nano material includes nanometer stub, nano wire and nano particle,
The length of the porphyrin nano material is 50nm~2 μm.
10. application of the porphyrin nano material in preparing near infrared light heat cure drug described in claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810175594.8A CN108392631A (en) | 2018-03-02 | 2018-03-02 | A kind of porphyrin nano material and preparation method thereof and the application in preparing near infrared light heat cure drug |
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| CN109010829A (en) * | 2018-10-15 | 2018-12-18 | 河南大学 | A kind of self assembly porphyrin nano material difunctional with photo-thermal chemotherapy and its preparation method and application |
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|---|---|---|---|---|
| US8871926B1 (en) * | 2010-09-28 | 2014-10-28 | Sandia Corporation | Synthesis of porphyrin nanostructures |
| CN106220636A (en) * | 2016-07-26 | 2016-12-14 | 河南大学 | A kind of method using cosolvent method to prepare phenylamino porphyrin self-assembled nanometer material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8871926B1 (en) * | 2010-09-28 | 2014-10-28 | Sandia Corporation | Synthesis of porphyrin nanostructures |
| CN106220636A (en) * | 2016-07-26 | 2016-12-14 | 河南大学 | A kind of method using cosolvent method to prepare phenylamino porphyrin self-assembled nanometer material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109010829A (en) * | 2018-10-15 | 2018-12-18 | 河南大学 | A kind of self assembly porphyrin nano material difunctional with photo-thermal chemotherapy and its preparation method and application |
| CN109010829B (en) * | 2018-10-15 | 2021-01-15 | 河南大学 | Self-assembled porphyrin nano material with photothermal and chemotherapy dual functions as well as preparation method and application thereof |
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