CN102940892B - Preparation method of targeting porphyrin fluorescent molecule and gold nanorod dyad - Google Patents
Preparation method of targeting porphyrin fluorescent molecule and gold nanorod dyad Download PDFInfo
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Abstract
The invention relates to a preparation method of dyad, particularly relates to a preparation method of targeting porphyrin fluorescent molecule and gold nanorod dyad and solves technical problems that porphyrin fluorescent molecules are prone to gather on the skin and eyes to generate phototoxicity due to poor targeting when the porphyrin fluorescent molecules are transported in bodies and gold nanorods can not stably exist in polar solvents. The method includes preparing a golden seed solution, preparing a gold nanorod growing solution, preparing a polyethylene glycol stabilized gold nanorod solution, preparing the dyad, mixing biomolecules or anticarcinogen and the dyad with N, N-dimethylformamide for reaction, performing centrifugation, dispersing precipitates in methyl alcohol, and then performing separation again to obtain the targeting porphyrin fluorescent molecule and gold nanorod dyad. According to the prepared targeting porphyrin fluorescent molecule and gold nanorod dyad, effects of early-stage tumor diagnosis and treatment can be improved, side effects on normal organizations can be reduced, and the dyad can be connected with biomacromolecules and the anticarcinogen which have targeting actions so that targeting capacity and tumor treatment effects are further improved.
Description
Technical field
The present invention relates to a kind of preparation method of dyad.
Background technology
Malignant tumor is a kind of disease that current mortality rate is higher, and early diagnosis and therapy is the key scientific problems in tumor research.In diagnosing tumor technology, optical imagery and positron emission tomography, Magnetic Resonance Imaging, ultrasonic and computed tomography etc. compared, and has the advantages such as low-energy radiation, hypersensitivity and enjoys the concern of research worker; The ultimate principle of optical imagery is to add the extrinsic fluorescence probe that can be enriched to tumor tissues, then with the optical excitation probe of certain wavelength, produces fluorescence, by the diagnosis that between monitoring tumor tissues and normal structure, fluorescence signal difference is carried out; The core of optical imagery is light absorption power and the fluorescence quantum yield height of fluorescent probe.Porphyrin fluorescence molecule has the large л key of porphin ring conjugation rigid molecule structure, and absworption peak is positioned at 405,530,570 and 630nm, and wherein 405nm is the strongest absworption peak, has advantages of that light absorption is strong; When can producing, the optical excitation porphyrin fluorescence molecule with 405nm wavelength is positioned at 630nm and 690nm near infrared region fluorescence emission peak, less near infrared region body light absorption, a little less than light scattering, thus the imaging of porphyrin fluorescence molecule to have ambient interferences low, highly sensitive; Advantage that can be to the imaging of deep layer tumor tissues.But porphyrin fluorescence molecule in vivo cyclic process has certain defect to the ability of target tumor tissue, can nonspecificly be gathered in skin or eye, and then generation phototoxicity, therefore how improving porphyrin fluorescence molecule targeting is a research emphasis all the time.
Photo-thermal therapy is a kind of tumour ablation method of novelty, compares with X-ray therapy with traditional chemotherapy, has inorganization Memorability, reproducible remarkable advantage; Its ultimate principle is to organize after photo-thermal agent by the exogenous target tumor adding, and with laser emission, makes the conversion of photo-thermal agent photo-thermal produce high heat, destroys and eliminates tumor cell; The key of this kind of therapy is photo-thermal agent absorbing light intensity and photo-thermal conversion efficiency.Noble metal nanometer material is because having the optical characteristics of surface plasma resonance, and can produce strong absorption therefore to the light of specific wavelength can become a kind of of photo-thermal agent.In noble metal nanometer material, gold nanorods is a kind of golden nanometer particle with transverse axis and longitudinal axis structural asymmetry, with its transverse axis and the longitudinal axis answer structural asymmetry corresponding for horizontal and longitudinal plasma absorption, laterally plasma absorption is positioned at 520nm visible region substantially, and longitudinally plasma absorption can change along with the aspect ratio of gold nanorods, at visible ray and near infrared region, carry out artificial regulation and control.In conjunction with organism for the different character of the light absorption of zones of different (body is less than visual field (be mainly hemoglobin absorb) and ultrared (being mainly moisture absorption) to the absorption of near infrared region (650-1000nm) light), longitudinal absorption of gold nanorods is adjusted to the damage that near infrared region can reduce normal tissue in photo-thermal therapy, and reach the object for the treatment of deep layer tumor tissues, so gold nanorods can become a kind of desirable photo-thermal agent of NIR photo-thermal therapy.The research of Dickerson etc. shows, selects the NIR laser matching with gold nanorods LSPR wavelength as light source, can induce the gold nano-rod particles of subcutaneous deep tissues to produce heat, makes it to heat up and photo-thermal killing tumor cells tissue.
Most of tumors have the macromolecular substances of making and strengthen and retention effect at tumor tissues permeability, and this kind of effect promoted the selective distribution of nanoparticle (being less than 100nm) at tumor tissues.Based on this kind of effect of nanoparticle, by after Porphyrin-Based Sensitizer and gold nanorods covalent coupling, can improve the ability of Porphyrin-Based Sensitizer target tumor tissue, reduce the phototoxicity producing in skin and eye non-specific aggregation, realize cancer target optical imagery; Then by NIR laser emission, the gold nanorods that makes to be enriched in tumor tissues carries out photo-thermal conversion, targeting photo-thermal therapy tumor tissues, and organizing of making to close on is injury-free.
Preparing at present the method that gold nanorods widely applies is seeded growth method, the cetyl trimethyl ammonium bromide (CTAB) by using high concentration for surfactant and stabilizing agent can be simply, high yield prepares the gold nanorods of different face diameter ratios.But the gold nanorods obtaining only can be dispersed in the CTAB solution of high concentration, and easily assembles in aqueous solution and organic solvent; And CTAB molecule not only easily departs from and combination again from gold nanorods surface, but also has strong bio-toxicity, has hindered gold nanorods and fluorescence molecule and has carried out chemical coupling and be applied in field of medicaments.Having had a plurality of research groups to attempt application distinct methods is not reducing under gold nanorods stability prerequisite, CTAB molecule to gold nanorods surface replaces, as, by self-assembling method layer by layer, on gold nanorods surface, form silicon layer or build gold nanorods-silicon dixoide nucleocapsid structure by Stober method, although with the toxicity that can reduce gold nanorods surface C TAB molecule after silicon dioxide effect, silicon dioxide is that a kind of difficult degradation material is difficult to study in vivo in vivo; Or by the CTAB molecule positive charge generation electrostatic adsorption on PSS molecule negative charge gold nanorods surface, but this kind of noncovalent interaction has the shortcoming of poor stability in vivo in environment.
Summary of the invention
The object of the invention is poor skin and the eye of being easily gathered in of in order to solve porphyrin fluorescence molecule and to transport in vivo targeting and produce the technical problem that phototoxicity and gold nanorods can not stable existences in polar solvent, the preparation method of a kind of targeting porphyrin fluorescence molecule and gold nanorods dyad is provided.
The preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad is carried out according to following steps:
One, in lucifuge, under the condition of 0 ℃ by 10～100mg porphyrin fluorescence molecule, 2～5g Anhydrous potassium carbonate and 15～30mlN, dinethylformamide mix and blend 5～10 minutes, then in 30～40 minutes, drip 1～5ml chloracetyl chloride, continue reaction 8～12 hours, remove the potassium carbonate in product, in product, add 50ml water and 50ml dichloromethane, separatory takes out dichloromethane solution, in dichloromethane solution, add water extraction 3～5 times, then by the solvent evaporate to dryness in dichloromethane solution, carry out again column chromatography separation, and using mixed solution that dichloromethane and methanol volume ratio be 100: 2～3 as leacheate, collect second color band, obtain 5, 10, 15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin,
Two, by 10ml concentration, be that 0.1mol/L cetyl trimethyl ammonium bromide solution and 0.25ml concentration are that 0.01mol/L chlorauric acid solution mixes, under the condition of 25 ℃, stir 5～15 minutes, adding 0.6ml concentration is the sodium borohydride solution of 0.01mol/L, obtains gold seeds solution;
Three, the ascorbic acid solution that the silver nitrate solution that the chlorauric acid solution that the cetyl trimethyl ammonium bromide solution that is 0.1mol/L by 10ml concentration, 0.25ml concentration are 0.1mol/L, 0.05ml concentration are 0.1mol/L and 2ml concentration are 0.1mol/L mixes, and obtains gold nanorods growth solution;
Four, gold seeds solution is joined in gold nanorods growth solution and reacted 12 hours, obtain the gold nanorods water bath shampoo that CTAB is stable;
Five, by 0.03g methoxy poly (ethylene glycol) mercapto alcohol, 3～4ml oxolane and the stable gold nanorods aqueous solution of 1～5mlCTAB, react 72 hours, then centrifugal with the rotating speed of 10000rpm, precipitation is dispersed in methanol, obtain polyethylene glycol stabilized gold nanorods solution;
Six, by 50mg～100mg 5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 7.5～10.5ml methanol mixed, then in 30～40 minutes, drip polyethylene glycol stabilized gold nanorods solution 2ml～4ml, react 24 hours, rotating speed with 14000rpm is centrifugal, and precipitation is dispersed in methanol, obtains dyad;
Seven, by 50mg biomolecule or anticarcinogen, 50mg～100mg dyad and 10ml N, dinethylformamide hybrid reaction 2 hours, then centrifugal at 4 ℃ of rotating speeds with 14000rpm, separated again after precipitation is dispersed in methanol, obtain targeting porphyrin fluorescence molecule and gold nanorods dyad;
Biomolecule described in step 7 is folic acid or monoclonal antibody Trastuzumab; Anticarcinogen described in step 7 is 10-hydroxycamptothecine, paclitaxel, amycin, 5-fluorouracil or the cry of certain animals of first ammonia butterfly.
Targeting porphyrin fluorescence molecule prepared by the present invention and gold nanorods dyad can improve the effect of early diagnosis of tumor treatment and reduce normal tissue side effect, and in this dyad, can connect biomacromolecule and the cancer therapy drug with targeting, further improve targeting ability and oncotherapy effect.Between the methoxy poly (ethylene glycol) mercapto alcohol that the applying biological compatibility of the present invention is good and gold nanorods, form golden sulfur covalent bond, replace the CTAB molecule that has bio-toxicity, there is good biocompatibility; And form stable dyad by methoxy poly (ethylene glycol) mercapto alcohol and porphyrin fluorescence molecule electrophilic substitution reaction, be difficult for causing in vivo the non-specific release of porphyrin fluorescence molecule.
Accompanying drawing explanation
Fig. 1 is gained 5,10 in experiment one step 1, the uv absorption spectra of 15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin;
Fig. 2 is gained 5,10 in experiment one step 1, the mass spectrum of 15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin;
Fig. 3 is the stable gold nanorods water bath shampoo uv absorption spectra of gained CTAB in experiment one step 4;
Fig. 4 is the stable gold nanorods water bath shampoo images of transmissive electron microscope of gained CTAB in experiment one step 4.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises the combination in any between each specific embodiment.
The specific embodiment one: the preparation method of present embodiment targeting porphyrin fluorescence molecule and gold nanorods dyad is carried out according to following steps:
One, in lucifuge, under the condition of 0 ℃ by 10～100mg porphyrin fluorescence molecule, 2～5g Anhydrous potassium carbonate and 15～30mlN, dinethylformamide mix and blend 5～10 minutes, then in 30～40 minutes, drip 1～5ml chloracetyl chloride, continue reaction 8～12 hours, remove the potassium carbonate in product, in product, add 50ml water and 50ml dichloromethane, separatory takes out dichloromethane solution, in dichloromethane solution, add water extraction 3～5 times, then by the solvent evaporate to dryness in dichloromethane solution, carry out again column chromatography separation, and using mixed solution that dichloromethane and methanol volume ratio be 100: 2～3 as leacheate, collect second color band, obtain 5, 10, 15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin,
Two, by 10ml concentration, be that 0.1mol/L cetyl trimethyl ammonium bromide solution and 0.25ml concentration are that 0.01mol/L chlorauric acid solution mixes, under the condition of 25 ℃, stir 5～15 minutes, adding 0.6ml concentration is the sodium borohydride solution of 0.01mol/L, obtains gold seeds solution;
Three, the ascorbic acid solution that the silver nitrate solution that the chlorauric acid solution that the cetyl trimethyl ammonium bromide solution that is 0.1mol/L by 10ml concentration, 0.25ml concentration are 0.1mol/L, 0.05ml concentration are 0.1mol/L and 2ml concentration are 0.1mol/L mixes, and obtains gold nanorods growth solution;
Four, gold seeds solution is joined in gold nanorods growth solution and reacted 12 hours, obtain the gold nanorods water bath shampoo that CTAB is stable;
Five, by 0.03g methoxy poly (ethylene glycol) mercapto alcohol, 3～4ml oxolane and the stable gold nanorods aqueous solution of 1～5mlCTAB, react 72 hours, then centrifugal with the rotating speed of 10000rpm, precipitation is dispersed in methanol, obtain polyethylene glycol stabilized gold nanorods solution;
Six, by 50mg～100mg 5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 7.5～10.5ml methanol mixed, then in 30～40 minutes, drip polyethylene glycol stabilized gold nanorods solution 2ml～4ml, react 24 hours, rotating speed with 14000rpm is centrifugal, and precipitation is dispersed in methanol, obtains dyad;
Seven, by 50mg biomolecule or anticarcinogen, 50mg～100mg dyad and 10ml N, dinethylformamide hybrid reaction 2 hours, then centrifugal at 4 ℃ of rotating speeds with 14000rpm, separated again after precipitation is dispersed in methanol, obtain targeting porphyrin fluorescence molecule and gold nanorods dyad;
Biomolecule described in step 7 is folic acid or monoclonal antibody Trastuzumab; Anticarcinogen described in step 7 is 10-hydroxycamptothecine, paclitaxel, amycin, 5-fluorouracil or the cry of certain animals of first ammonia butterfly.
The structural formula of present embodiment Folic Acid is as follows:
In present embodiment, the structural formula of 10-hydroxycamptothecine is as follows:
In present embodiment, the structural formula of paclitaxel is as follows:
In present embodiment, the structural formula of amycin is as follows:
In present embodiment, the structural formula of 5-fluorouracil is as follows:
In present embodiment, the structural formula of first ammonia butterfly cry of certain animals is as follows:
The specific embodiment two: what present embodiment was different from the specific embodiment one is that the porphyrin fluorescence molecule described in step 1 is tetrahydroxy phenyl porphyrin, trihydroxy phenyl porphyrin, tetracarboxylic phenyl porphyrin.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one be in step 1 under lucifuge, the condition of 0 ℃ by 50mg porphyrin fluorescence molecule, 5g Anhydrous potassium carbonate and 20ml DMF mix and blend 8 minutes.Other is identical with the specific embodiment one.
The specific embodiment four: present embodiment is different from the specific embodiment one be in step 1 under lucifuge, the condition of 0 ℃ by 20～90mg porphyrin fluorescence molecule, 3～4g Anhydrous potassium carbonate and 16～29ml DMF mix and blend 6～9 minutes.Other is identical with the specific embodiment one.
The specific embodiment five: present embodiment is different from the specific embodiment one be in step 1 under lucifuge, the condition of 0 ℃ by 30～80mg porphyrin fluorescence molecule, 3.5g Anhydrous potassium carbonate and 20～25ml DMF mix and blend 7～8 minutes.Other is identical with the specific embodiment one.
The specific embodiment six: present embodiment is different from the specific embodiment one is to using mixed solution that dichloromethane and methanol volume ratio be 100: 3 in step 1 as leacheate.Other is identical with the specific embodiment one.
The specific embodiment seven: what present embodiment was different from the specific embodiment one is by 0.03g methoxy poly (ethylene glycol) mercapto alcohol, 4ml oxolane and the stable gold nanorods aqueous solution of 4mlCTAB in step 5.Other is identical with the specific embodiment one.
The specific embodiment eight: present embodiment is different from the specific embodiment one be in step 6 by 60mg～90mg 5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 8～10ml methanol mixed.Other is identical with the specific embodiment one.
The specific embodiment nine: present embodiment is different from the specific embodiment one be in step 6 by 70mg 5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 9ml methanol mixed.Other is identical with the specific embodiment one.
The specific embodiment ten: present embodiment is different from the specific embodiment one is by 50mg biomolecule or anticarcinogen, 60mg dyad and 10ml DMF hybrid reaction 2 hours in step 7.Other is identical with the specific embodiment one.
Adopt following experimental verification effect of the present invention:
Experiment one:
The preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad is carried out according to following steps:
One, in lucifuge, under the condition of 0 ℃ by 100mg porphyrin fluorescence molecule, 5g Anhydrous potassium carbonate and 30ml N, dinethylformamide mix and blend 10 minutes, then in 40 minutes, drip 5ml chloracetyl chloride, continue reaction 12 hours, remove the potassium carbonate in product, in product, add 50ml water and 50ml dichloromethane, separatory takes out dichloromethane solution, in dichloromethane solution, add water extraction 5 times, then by the solvent evaporate to dryness in dichloromethane solution, carry out again column chromatography separation, and using mixed solution that dichloromethane and methanol volume ratio be 100: 2 as leacheate, collect second color band, obtain 5, 10, 15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin (UV-vis (methanol)/nm421, 517, 557, 597, 651, mass spectrum: 908.3 (theoretical values 908.6)),
Two, by 10ml concentration, be that 0.1mol/L cetyl trimethyl ammonium bromide solution and 0.25ml concentration are that 0.01mol/L chlorauric acid solution mixes, under the condition of 25 ℃, stir 15 minutes, adding 0.6ml concentration is the sodium borohydride solution of 0.01mol/L, obtains gold seeds solution;
Three, the ascorbic acid solution that the silver nitrate solution that the chlorauric acid solution that the cetyl trimethyl ammonium bromide solution that is 0.1mol/L by 10ml concentration, 0.25ml concentration are 0.1mol/L, 0.05ml concentration are 0.1mol/L and 2ml concentration are 0.1mol/L mixes, and obtains gold nanorods growth solution;
Four, gold seeds solution is joined in gold nanorods growth solution and reacted 12 hours, obtain the gold nanorods water bath shampoo that CTAB is stable;
Five, by 0.03g methoxy poly (ethylene glycol) mercapto alcohol, 4ml oxolane and the stable gold nanorods aqueous solution of 5mlCTAB, react 72 hours, then centrifugal with the rotating speed of 10000rpm, precipitation is dispersed in methanol, obtain polyethylene glycol stabilized gold nanorods solution (UV-vis/nm512,774; The about 33nm of TEM length, diameter is about 10nm, draw ratio is about 3.3);
Six, by 100mg 5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 10.5ml methanol mixed, then in 40 minutes, drip polyethylene glycol stabilized gold nanorods solution 4ml, react 24 hours, rotating speed with 14000rpm is centrifugal, and precipitation is dispersed in methanol, obtains dyad;
Seven, by 50mg biomolecule, 100mg dyad and 10ml N, dinethylformamide hybrid reaction 2 hours, then centrifugal at 4 ℃ of rotating speeds with 14000rpm, separated again after precipitation is dispersed in methanol, obtain targeting porphyrin fluorescence molecule and gold nanorods dyad;
Biomolecule described in step 7 is monoclonal antibody Trastuzumab.
The equation of preparing targeting porphyrin fluorescence molecule and gold nanorods dyad in this experiment is as follows:
Claims (9)
1. the preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad, is characterized in that the preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad is carried out according to following steps:
One, in lucifuge, under the condition of 0 ℃ by 10～100mg porphyrin fluorescence molecule, 2～5g Anhydrous potassium carbonate and 15～30mlN, dinethylformamide mix and blend 5～10 minutes, then in 30～40 minutes, drip 1～5ml chloracetyl chloride, continue reaction 8～12 hours, remove the potassium carbonate in product, in product, add 50ml water and 50ml dichloromethane, separatory takes out dichloromethane solution, in dichloromethane solution, add water extraction 3～5 times, then by the solvent evaporate to dryness in dichloromethane solution, carry out again column chromatography separation, and using mixed solution that dichloromethane and methanol volume ratio be 100 ﹕ 2～3 as leacheate, collect second color band, obtain 5, 10, 15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin,
Two, by 10ml concentration, be that 0.1mol/L cetyl trimethyl ammonium bromide solution and 0.25ml concentration are that 0.01mol/L chlorauric acid solution mixes, under the condition of 25 ℃, stir 5～15 minutes, adding 0.6ml concentration is the sodium borohydride solution of 0.01mol/L, obtains gold seeds solution;
Three, the ascorbic acid solution that the silver nitrate solution that the chlorauric acid solution that the cetyl trimethyl ammonium bromide solution that is 0.1mol/L by 10ml concentration, 0.25ml concentration are 0.1mol/L, 0.05ml concentration are 0.1mol/L and 2ml concentration are 0.1mol/L mixes, and obtains gold nanorods growth solution;
Four, gold seeds solution is joined in gold nanorods growth solution and reacted 12 hours, obtain the gold nanorods water bath shampoo that CTAB is stable;
Five, by 0.03g methoxy poly (ethylene glycol) mercapto alcohol, 3～4ml oxolane and the stable gold nanorods aqueous solution of 1～5mlCTAB, react 72 hours, then centrifugal with the rotating speed of 10000rpm, precipitation is dispersed in methanol, obtain polyethylene glycol stabilized gold nanorods solution;
Six, by 50mg～100mg5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 7.5～10.5ml methanol mixed, then in 30～40 minutes, drip polyethylene glycol stabilized gold nanorods solution 2ml～4ml, react 24 hours, rotating speed with 14000rpm is centrifugal, and precipitation is dispersed in methanol, obtains dyad;
Seven, by 50mg biomolecule, 50mg～100mg dyad and 10mlN, dinethylformamide hybrid reaction 2 hours, then centrifugal at 4 ℃ of rotating speeds with 14000rpm, separated again after precipitation is dispersed in methanol, obtain targeting porphyrin fluorescence molecule and gold nanorods dyad;
Porphyrin fluorescence molecule described in step 1 is tetrahydroxy phenyl porphyrin; Biomolecule described in step 7 is monoclonal antibody Trastuzumab.
2. the preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad according to claim 1, it is characterized in that in step 1 under lucifuge, the condition of 0 ℃ by 50mg porphyrin fluorescence molecule, 5g Anhydrous potassium carbonate and 20mlN dinethylformamide mix and blend 8 minutes.
3. the preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad according to claim 1, it is characterized in that in step 1 under lucifuge, the condition of 0 ℃ by 20～90mg porphyrin fluorescence molecule, 3～4g Anhydrous potassium carbonate and 16～29mlN dinethylformamide mix and blend 6～9 minutes.
4. the preparation method of targeting porphyrin fluorescence molecule and gold nanorods dyad according to claim 1, it is characterized in that in step 1 under lucifuge, the condition of 0 ℃ by 30～80mg porphyrin fluorescence molecule, 3.5g Anhydrous potassium carbonate and 20～25mlN dinethylformamide mix and blend 7～8 minutes.
5. according to the preparation method of targeting porphyrin fluorescence molecule described in claim 1 or 2 and gold nanorods dyad, it is characterized in that usining in step 1 that mixed solution that dichloromethane and methanol volume ratio are 100 ﹕ 3 is as leacheate.
6. according to the preparation method of targeting porphyrin fluorescence molecule described in claim 1 or 2 and gold nanorods dyad, it is characterized in that in step 5 0.03g methoxy poly (ethylene glycol) mercapto alcohol, 4ml oxolane and the stable gold nanorods aqueous solution of 4mlCTAB.
7. according to the preparation method of targeting porphyrin fluorescence molecule described in claim 1 or 2 and gold nanorods dyad, it is characterized in that in step 6 60mg～90mg5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 8～10ml methanol mixed.
8. according to the preparation method of targeting porphyrin fluorescence molecule described in claim 1 or 2 and gold nanorods dyad, it is characterized in that in step 6 70mg5,10,15-tri-(4-chloroethene acyloxy phenyl)-20-(4-hydroxy phenyl) porphyrin and 9ml methanol mixed.
9. according to the preparation method of targeting porphyrin fluorescence molecule described in claim 1 or 2 and gold nanorods dyad, it is characterized in that in step 7 by 50mg biomolecule, 60mg dyad and 10mlN dinethylformamide hybrid reaction 2 hours.
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