CN102924756B - The preparation method of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor - Google Patents
The preparation method of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor, first by soluble in water to the chitosan or chitosan derivatives with certain deacetylation, then under stirring at room temperature condition, in chitosan or the chitosan derivatives aqueous solution, organic fluorescence molecular solution is added, organic fluorescence molecule is combined by electrostatic self-assembled with chitosan or chitosan derivatives, obtains the nano-complex of organic fluorescence molecule and chitosan; After this nano-complex and nitrogen protoxide react the regular hour under room temperature pressurized conditions, react obtained organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor with cupric chloride at buffered soln.Compared with prior art, product of the present invention stably can discharge nitrogen protoxide under physiological environment, and can carry out original position real-time detection to nitric oxide production release, good biocompatibility, without physiological-toxicity, has broad application prospects.
Description
Technical field
The invention belongs to chemistry, the biological crossing domain with material, especially relate to a kind of have discharge nitrogen protoxide and organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor of its release function of original position real-time detection and preparation method thereof.
Background technology
Nitrogen protoxide (NO) is a kind of physiological regulation agent that can be synthesized by human endothelial cells, is distributed in the multiple organ of whole body widely, is important biological messenger molecule.NO can effectively prevent hematoblastic condensation and activation, antithrombotic formation, reduces the adhesion of bacterium, and has the function of killing cancer cells.Nitric oxide production shortage can cause dysfunction of organ, causes hypertension, heart trouble, respiratory system disease etc.The various diseases caused are lacked in order to treat nitrogen protoxide, people have designed and synthesized a variety of nitric oxide donors, and wherein azo diene alcohols nucleophilic nitric oxide donors (diazeniumdiolates) is the nitric oxide donors of a kind of excellent property grown up in recent years.This kind of nucleophilic nitric oxide donors is generally that the nucleophilic compound containing secondary amine group and nitric oxide gas are reacted obtained under certain pressure conditions, can with the spontaneous release nitrogen protoxide of certain speed in physiological environment.In nucleophilic nitric oxide donors material, Chitosan-phospholipid complex receives much concern due to its good biocompatibility and the characteristic such as biodegradability and low cytotoxicity.There are some researches show, chitosan stably can discharge nitrogen protoxide as nitric oxide production solid support material under physiological environment.Singularity on chitosan structure makes it to have the effects such as complexing, absorption and ion-exchange with many organism, ion, biomolecules etc.Therefore, different materials can be utilized to carry out modification to Chitosan-phospholipid complex, make it possess some new functions.
Existing nitric oxide donors can meet the nitric oxide production demand of release, but the overwhelming majority cannot realize the detection to nitric oxide releasing simultaneously.Realize, to discharged nitric oxide production detection, fluorescent probe or other detection means to be used simultaneously, which adds the difficulty of operation, and be unfavorable for the reduction of cost.Chinese invention patent CN102516606 reports a kind of nano-complex of nitric oxide donors-quantum dot, can realize nitric oxide production release and the fluorescence detection to nitric oxide releasing simultaneously.But quantum dot is to nitric oxide production detection based on the fluorescent quenching effect of nitrogen protoxide to quantum dot, and it is not strong to nitric oxide production selectivity, is easily subject to other has the material of fluorescent quenching effect interference to quantum dot.Therefore, how to prepare can Stable Release nitrogen protoxide, can realize again the original position to nitric oxide releasing, in real time, the nitric oxide donors of highly selective detection is a problem highly significant, is also key technical problem urgently to be resolved hurrily.
Have not yet to see the Patents preparing the nano-complex nitric oxide donors with above-mentioned functions that to be combined with chitosan or chitosan derivatives by organic fluorescence molecule to report.
Summary of the invention
Object of the present invention is exactly provide a kind of simple to operate to overcome defect that above-mentioned prior art exists, cost is lower, product stably can discharge nitrogen protoxide under physiological environment, and can the nitric oxide production release of original position real-time detection, high to nitric oxide production selectivity, good biocompatibility, has the preparation method of the organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor of good application prospect in the Diagnosis and Treat of hypertension, heart trouble, respiratory system disease, sexual dysfunction etc.
Object of the present invention can be achieved through the following technical solutions: a kind of preparation method of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor, is characterized in that, the method comprises the following steps:
(1) be at room temperature dissolved in deionized water by a certain amount of chitosan or derivatives thereof, obtained concentration is chitosan or the chitosan derivatives aqueous solution of 1-15 mg/mL;
(2) under stirring at room temperature condition, in the obtained chitosan of step (1) or the chitosan derivatives aqueous solution, organic fluorescence molecular solution is added, the mass ratio of organic fluorescence molecule and chitosan or derivatives thereof is 5:1 ~ 1:1, stir 1-2 hour, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying;
(3) in the autoclave of 25-45 DEG C, the organic fluorescence molecule obtained by step (2) and the nano-complex of chitosan are added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan or chitosan derivatives and sodium methylate controls at 1:1-1:3, autoclave is first led to nitrogen to vacuumize again, then nitric oxide gas is passed into, maintain pressure 50-120psi, after stirring reaction 3-8 days, unreacted nitric oxide gas is blown away with nitrogen, product is filtered, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying;
(4) product obtained for step (3) is added fill in the closed glass container of dimethyl formamide, stir at the temperature of-5-5 DEG C and lead to nitrogen protection, then a certain amount of brominated alkanes is added, react after 1.5-5 hour and rise to room temperature continuation stirring 24-60 hour, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven;
(5) at room temperature above-mentioned product and cupric chloride are reacted in neutral buffer, obtain organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.
One or more in the water-soluble chitosan of described chitosan or derivatives thereof to be deacetylation be 40%-60%, cm-chitosan, chitosan quaternary ammonium salt, viscosity-average molecular weight is 2-40 ten thousand.
Described organic fluorescence molecule is the Rhodamine Derivatives containing quinoline group.
The preferred following material of described organic fluorescence molecule, molecular formula is respectively:
The solvent of described organic fluorescence molecular solution is ethyl acetate, hexanaphthene or both mixtures.
Brominated alkanes described in step (4) is monobromethane or ethylene dibromide, and the mass ratio of the product that brominated alkanes and described step (3) obtain is 2:1 ~ 1:1.
Neutral buffer described in step (5) is the mixing solutions of the piperazine Diethanol sulfonic acid aqueous solution and potassium chloride solution, and wherein the mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2.
Cupric chloride described in step (5) and the mol ratio of organic fluorescence molecule are 1.5:1 ~ 1:1.5.
Chitosan or derivatives thereof to be combined with organic fluorescence molecule formation nano-complex by electrostatic self-assembled by the present invention; this nano-complex is reacted with nitric oxide gas under certain pressure condition; utilize the parahelium group in chitosan or derivatives thereof and nitrogen protoxide generation nucleophilic reaction to generate and can discharge nitric oxide production functional group, then use brominated alkanes to protect this functional group.The nano-complex nitric oxide donors of cupric chloride and gained is finally used to react, obtain a kind of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor, it does not have fluorescent effect not discharging in nitric oxide production situation, once release nitrogen protoxide, system will send fluorescence.Preparation method of the present invention is simple to operate, cost is lower, product stably can discharge nitrogen protoxide under physiological environment, and can original position, detect nitric oxide production release in real time, efficiently, good biocompatibility, has good application prospect in the Diagnosis and Treat of hypertension, heart trouble, respiratory system disease, sexual dysfunction etc.
Compared with prior art, the present invention has the following advantages and effect:
1. used raw material is easy to obtain;
2. the nitric oxide releasing of the organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor of preparation is effective, and stability is high, has the function of original position, real-time fluorescence detection nitric oxide releasing;
3. fluorescence efficiency is high, and strong to nitric oxide production selectivity, Effect on Detecting is good;
4. preparation method is simple, and cost is lower.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Be at room temperature 120,000 by molecular weight, deacetylation is that the chitosan of 50 % is dissolved in deionized water, obtained concentration is the chitosan aqueous solution of 4mg/ml; Under stirring at room temperature condition, add organic fluorescence molecular solution in this chitosan aqueous solution, stir 1.5 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying; Wherein the structural formula of organic fluorescence molecule is as follows:
the mass ratio of organic fluorescence molecule and chitosan is 5:1;
In the autoclave of 30 DEG C, above-mentioned nano-complex is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is 1:1.5, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 70 psi, stirring reaction, after 4 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying; Being added by above-mentioned product fills in the closed glass container of dimethyl formamide, stir at the temperature of-1 DEG C and lead to nitrogen protection, then a certain amount of ethylene dibromide is added, the mass ratio of this ethylene dibromide and described product is 1.5:1, react after 3 hours and rise to room temperature continuation stirring 40 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven; At room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1:1, obtains organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.The transmission electron microscope photo of this mixture as shown in Figure 1.The organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor release obtained and to detect nitric oxide production reaction formula as follows:
Embodiment 2
Be at room temperature 200,000 by molecular weight, deacetylation is that the chitosan of 53 % is dissolved in deionized water, obtained concentration is the chitosan aqueous solution of 3mg/ml; Under stirring at room temperature condition, add organic fluorescence molecular solution in this chitosan aqueous solution, stir 2 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying; Wherein the structural formula of organic fluorescence molecule is as follows:
the mass ratio of organic fluorescence molecule and chitosan is 1:1;
In the autoclave of 35 DEG C, above-mentioned nano-complex is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is 1:1.5, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 80 psi, stirring reaction, after 4 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying; Being added by above-mentioned product fills in the closed glass container of dimethyl formamide, stir at the temperature of 0 DEG C and lead to nitrogen protection, then a certain amount of ethylene dibromide is added, the mass ratio of this ethylene dibromide and described product is 1.5:1, react after 4 hours and rise to room temperature continuation stirring 48 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven; At room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1.1:1, obtains organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.
Embodiment 3
Be at room temperature 80,000 by molecular weight, deacetylation is that the chitosan of 46 % is dissolved in deionized water, obtained concentration is the chitosan aqueous solution of 4mg/ml; Under stirring at room temperature condition, add organic fluorescence molecular solution in this chitosan aqueous solution, stir 1.5 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying; Wherein the structural formula of organic fluorescence molecule is as follows:
the mass ratio of organic fluorescence molecule and chitosan is 3:1;
In the autoclave of 25 DEG C, above-mentioned nano-complex is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is 1:2, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 70 psi, stirring reaction, after 5 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying; Being added by above-mentioned product fills in the closed glass container of dimethyl formamide, stir at the temperature of 0 DEG C and lead to nitrogen protection, then a certain amount of monobromethane is added, the mass ratio of this ethylene dibromide and described product is 2:1, react after 4 hours and rise to room temperature continuation stirring 30 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven; At room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1:1.2, obtains organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.
Embodiment 4
Be at room temperature 250,000 by molecular weight, deacetylation is that the cm-chitosan of 40 % is dissolved in deionized water, obtained concentration is the carboxymethyl chitosan sugar aqueous solution of 6 mg/ml; Under stirring at room temperature condition, add organic fluorescence molecular solution in this carboxymethyl chitosan sugar aqueous solution, stir 2 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and cm-chitosan after vacuum-drying; Wherein the structural formula of organic fluorescence molecule is as follows:
the mass ratio of organic fluorescence molecule and chitosan is 2:1;
In the autoclave of 35 DEG C, above-mentioned nano-complex is added in the absolute methanol solution of sodium methylate, the mass ratio of cm-chitosan and sodium methylate is 1:2, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 90 psi, stirring reaction, after 3 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying; Being added by above-mentioned product fills in the closed glass container of dimethyl formamide, stir at the temperature of 1 DEG C and lead to nitrogen protection, then a certain amount of ethylene dibromide is added, the mass ratio of this ethylene dibromide and described product is 1:1, react after 3 hours and rise to room temperature continuation stirring 48 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven; At room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, obtain organic fluorescence molecule-cm-chitosan nano-complex nitric oxide donors.
Embodiment 5
Be at room temperature 150,000 by molecular weight, deacetylation is that the chitosan of 50 % is dissolved in deionized water, obtained concentration is the chitosan aqueous solution of 9 mg/ml; Under stirring at room temperature condition, add organic fluorescence molecular solution in this chitosan aqueous solution, stir 1.5 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying; Wherein the structural formula of organic fluorescence molecule is as follows:
the mass ratio of organic fluorescence molecule and chitosan is 4:1;
In the autoclave of 35 DEG C, above-mentioned nano-complex is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is 1:1.2, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 80 psi, stirring reaction, after 6 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying; Being added by above-mentioned product fills in the closed glass container of dimethyl formamide, stir at the temperature of 0 DEG C and lead to nitrogen protection, then a certain amount of monobromethane is added, the mass ratio of this monobromethane and described product is 1.5:1, react after 3.5 hours and rise to room temperature continuation stirring 36 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven; At room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1.2:1, obtains organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.
Embodiment 6
Be at room temperature 30,000 by molecular weight, deacetylation be 45% chitosan be dissolved in deionized water, obtained concentration is the chitosan aqueous solution of 13mg/ml; Under stirring at room temperature condition, add organic fluorescence molecular solution in this chitosan aqueous solution, stir 1 hour, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying; Wherein the structural formula of organic fluorescence molecule is as follows:
the mass ratio of organic fluorescence molecule and chitosan is 4:1;
In the autoclave of 25 DEG C, above-mentioned nano-complex is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is 1:1, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 70 psi, stirring reaction, after 3 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying; Being added by above-mentioned product fills in the closed glass container of dimethyl formamide, stir at the temperature of 0 DEG C and lead to nitrogen protection, then a certain amount of ethylene dibromide is added, the mass ratio of this ethylene dibromide and described product is 1.5:1, react after 3 hours and rise to room temperature continuation stirring 48 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven; At room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1:1, obtains organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.
Embodiment 7
Organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor and preparation method thereof, comprises the following steps:
(1) be at room temperature 70,000 by molecular weight, deacetylation is that the chitosan of 45 % is dissolved in deionized water, and obtained concentration is the chitosan aqueous solution of 5mg/mL;
(2) under stirring at room temperature condition, add organic fluorescence molecular solution in the obtained chitosan aqueous solution of step (1), stir 2 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying; Wherein the molecular formula of organic fluorescence molecule is:
(3) in the autoclave of 25 DEG C, the organic fluorescence molecule obtained by step (2) and the nano-complex of chitosan are added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is 1:2.5, autoclave is first led to nitrogen and vacuumizes, then pass into nitric oxide gas, maintain pressure 100psi, stirring reaction, after 6 days, blows away unreacted nitric oxide gas with nitrogen, is filtered by product, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying;
(4) product obtained for step (3) is added fill in the closed glass container of dimethyl formamide, stir at the temperature of 2 DEG C and lead to nitrogen protection, then a certain amount of monobromethane is added, the mass ratio of the product that this monobromethane and step (3) obtain is 1:1, react after 4 hours and rise to room temperature continuation stirring 48 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven;
(5) at room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (wherein the mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1:1.5, obtains organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor.
Embodiment 8
Organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor and preparation method thereof, comprises the following steps:
(1) be at room temperature 180,000 by molecular weight, deacetylation be 50% chitosan be dissolved in deionized water, obtained concentration is the chitosan aqueous solution of 7mg/mL;
(2) under stirring at room temperature condition, in the obtained chitosan quaternary ammonium salt brine solution of step (1), organic fluorescence molecular solution is added, stir 2 hours, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan quaternary ammonium salt after vacuum-drying; Wherein the molecular formula of organic fluorescence molecule is:
(3) in the autoclave of 25 DEG C, the organic fluorescence molecule obtained by step (2) and the nano-complex of chitosan quaternary ammonium salt are added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan quaternary ammonium salt and sodium methylate is 1:2, autoclave is first led to nitrogen to vacuumize again, then nitric oxide gas is passed into, maintain pressure 90 psi, stirring reaction is after 5 days, unreacted nitric oxide gas is blown away with nitrogen, product is filtered, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying;
(4) product obtained for step (3) is added fill in the closed glass container of dimethyl formamide, stir at the temperature of-1 DEG C and lead to nitrogen protection, then a certain amount of monobromethane is added, the mass ratio of the product that this monobromethane and step (3) obtain is 2:1, react after 4 hours and rise to room temperature continuation stirring 48 hours, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven;
(5) at room temperature above-mentioned product and cupric chloride are reacted in the mixed aqueous solution (wherein the mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1: 2) of piperazine Diethanol sulfonic acid and Repone K, the mol ratio of cupric chloride and organic fluorescence molecule is 1.5:1, obtains organic fluorescence molecule-chitosan quaternary ammonium salt nano-complex nitric oxide donors.
Claims (5)
1. a preparation method for organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor, is characterized in that, the method comprises the following steps:
(1) be at room temperature dissolved in deionized water by a certain amount of chitosan or derivatives thereof, obtained concentration is chitosan or the chitosan derivatives aqueous solution of 1-15mg/mL;
(2) under stirring at room temperature condition, in the obtained chitosan of step (1) or the chitosan derivatives aqueous solution, organic fluorescence molecular solution is added, the mass ratio of organic fluorescence molecule and chitosan or derivatives thereof is 5:1 ~ 1:1, stir 1-2 hour, then evaporation concentration in Rotary Evaporators, obtains the nano-complex of organic fluorescence molecule and chitosan after vacuum-drying;
(3) in the autoclave of 25-45 DEG C, the organic fluorescence molecule obtained by step (2) and the nano-complex of chitosan are added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan or chitosan derivatives and sodium methylate controls at 1:1-1:3, autoclave is first led to nitrogen to vacuumize again, then nitric oxide gas is passed into, maintain pressure 50-120psi, after stirring reaction 3-8 days, unreacted nitric oxide gas is blown away with nitrogen, product is filtered, in succession use anhydrous methanol and washed with diethylether, at room temperature vacuum-drying;
(4) product obtained for step (3) is added fill in the closed glass container of dimethyl formamide, stir at the temperature of-5-5 DEG C and lead to nitrogen protection, then a certain amount of brominated alkanes is added, react after 1.5-5 hour and rise to room temperature continuation stirring 24-60 hour, filter the solid washed with ether obtained, drying at room temperature 24 hours in vacuum drying oven;
(5) at room temperature above-mentioned product and cupric chloride are reacted in neutral buffer, obtain organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor;
One or more in the water-soluble chitosan of described chitosan or derivatives thereof to be deacetylation be 40%-60%, cm-chitosan, chitosan quaternary ammonium salt, viscosity-average molecular weight is 2-40 ten thousand;
Described organic fluorescence molecule is selected from following material, and molecular formula is respectively:
2. the preparation method of a kind of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor according to claim 1, is characterized in that, the solvent of described organic fluorescence molecular solution is ethyl acetate, hexanaphthene or both mixtures.
3. the preparation method of a kind of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor according to claim 1, it is characterized in that, brominated alkanes described in step (4) is monobromethane or ethylene dibromide, and the mass ratio of the product that brominated alkanes and described step (3) obtain is 2:1 ~ 1:1.
4. the preparation method of a kind of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor according to claim 1, it is characterized in that, neutral buffer described in step (5) is the mixing solutions of the piperazine Diethanol sulfonic acid aqueous solution and potassium chloride solution, and wherein the mass ratio of piperazine Diethanol sulfonic acid and Repone K is 1:2.
5. the preparation method of a kind of organic fluorescent molecule-chitosan nano-composite-nitrioxide oxide donor according to claim 1, is characterized in that, the cupric chloride described in step (5) and the mol ratio of organic fluorescence molecule are 1.5:1 ~ 1:1.5.
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