CN102516606B - Preparation method of nitrogen oxide donor - quantum dots compound - Google Patents
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- CN102516606B CN102516606B CN201110383271.6A CN201110383271A CN102516606B CN 102516606 B CN102516606 B CN 102516606B CN 201110383271 A CN201110383271 A CN 201110383271A CN 102516606 B CN102516606 B CN 102516606B
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Abstract
The invention relates to a nitrogen oxide donor-quantum dots compound and a preparation method thereof. The preparation method comprises the following steps that: chitosan or chitosan derivative with certain deacelation degree is dissolved in the water, metal salt solution and chalcogenide solution with appropriate quantity are sequentially added into the chitosan or the chitosan derivative solution under a room-temperature stirring condition, a compound of chitosan or the chitosan derivative and quantum dots is obtained by heating and backflowing, dialyzing, evaporating and drying the mixture solution, and then the compound is reacted with nitrogen oxide under a pressurizing condition to prepare a nitrogen oxide donor. Compared with the prior art, chitosan is adopted as a carrier for releasing the nitrogen oxide, quantum dots are adopted as a fluorescent probe for detecting the release of the nitrogen oxide, the nitrogen oxide can be stably released under the phycological environment, a function on detecting the release of the nitrogen oxide can be realized, the biocompatibility is good, no physiological toxicity exists, and a promising prospect can be realized on the diagnosis and treatment aspects of hypertension, heat diseases, respiratory diseases, sexual disorder and the like.
Description
Technical field
The invention belongs to the crossing domain of chemistry, biological and material, especially relate to and a kind ofly there is release nitrogen protoxide and survey nitric oxide donors of its release conditions function and preparation method thereof.
Background technology
Nitrogen protoxide (NO) is very important biological messenger molecule, and nitric oxide production shortage can cause dysfunction of organ, causes hypertension, heart trouble, respiratory system disease etc.In order to treat nitrogen protoxide, lack the various diseases causing, people have designed and synthesized a variety of nitric oxide donors, and wherein nucleophilic nitric oxide donors diazeniumdiolate is the nitrogen oxide donor-quantum dots compound that a kind of in-situ investigation nitrogen protoxide of a kind of excellent property of growing up in recent years discharges.This class nucleophilic nitric oxide donors is generally that the nucleophilic compound that contains secondary amine group is reacted and made at the molten thorn mesohigh of polarity with nitric oxide gas, can be with the spontaneous release nitric oxide donors of different speed under physiological condition.In nucleophilic nitric oxide donors material, chitosan and derivative thereof are because the characteristics such as its good biocompatibility and biodegradability and low cytotoxicity receive much concern.There are some researches show, chitosan can stably discharge nitrogen protoxide as a kind of nucleophilic nitric oxide donors material under physiological environment.Semiconductor fluorescence quantum dot (QD) has exciting light spectrum width, emmission spectrum is narrow, the advantage such as emission wavelength can accuracy controlling, photochemical stability is good.Compare with traditional fluorescence dye, quantum dot has unique advantage at aspects such as fluorescent probe, biomarker, medicals diagnosis on disease.Singularity on chitosan structure makes it to have the effects such as complexing, absorption and ion-exchange with many ions, organism, biomolecules etc.Utilize chitosan and derivative thereof to be combined with quantum dot, it is carried out to modification and using and improve quantum dot as stability and the existing patent report (Chinese patent CN 101962450A, CN 1831080A) of biocompatibility of fluorescent probe.
Although existing nitric oxide donors can stably discharge nitrogen protoxide, also has good biocompatibility, cannot survey nitric oxide production release conditions.Realize discharged nitric oxide production fluorescence detection, must use fluorescent probe simultaneously, so just increased the difficulty of operation, and be unfavorable for the reduction of cost.Therefore, how to prepare can Stable Release nitrogen protoxide, can realize again the fluorescence detection that nitrogen protoxide is discharged, and the nitric oxide donors with good biocompatibility is a problem highly significant, is also key technical problem urgently to be resolved hurrily.
Have not yet to see and chitosan or chitosan derivatives are combined to the mixture that forms react the Patents of preparing nitric oxide donors with nitric oxide gas and report with quantum dot.
Summary of the invention
Object of the present invention is exactly to provide a kind of simple to operate in order to overcome the defect of above-mentioned prior art existence, cost is lower, product can stably discharge nitrogen protoxide under physiological environment, and can effectively survey nitric oxide production release conditions, good biocompatibility, is having the preparation method of the nitrogen oxide donor-quantum dots compound of good application prospect aspect the diagnosis of hypertension, heart trouble, respiratory system disease, sexual dysfunction etc. and treatment.
Object of the present invention can be achieved through the following technical solutions: the preparation method of nitrogen oxide donor-quantum dots compound, it is characterized in that, and the method comprises the following steps:
(1) at room temperature a certain amount of chitosan or derivatives thereof is dissolved in deionized water, makes chitosan or the chitosan derivatives aqueous solution that concentration is 2-12mg/ml;
(2) the metal-salt precursor aqueous solution that adds 0.0002-0.01mol/L under stirring at room or ultra-sonic oscillation condition in the chitosan making to step (1) or the chitosan derivatives aqueous solution, stir 6-15 hour, obtain the metal ion complex solution of chitosan or chitosan derivatives;
(3) gained metal ion complex solution is placed in to reactor, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add chalcogenide solution, the mol ratio of the sulfur family element in the metallic element in metal ion complex and chalcogenide solution is controlled at 1: 3-3: between 1, obtain the colloidal solution of homogeneous transparent;
(4) by above-mentioned colloidal solution under nitrogen protection and agitation condition, 2-4 hour refluxes at the temperature of 80-100 ℃, the quick cooling rear 2-5 days that dialyses in deionized water with dialysis tubing, then in Rotary Evaporators, concentrate, then through lyophilize, obtain the mixture of stable chitosan or chitosan derivatives and quantum dot;
(5) in the autoclave of 25-45 ℃, the mixture of above-mentioned chitosan or chitosan derivatives and quantum dot is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan or chitosan derivatives and sodium methylate is controlled at 1: 1-1: 3, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 50-120psi, after stirring reaction 5-9 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, in succession with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges.
Described chitosan or derivatives thereof is one or more in the water-soluble chitosan with different deacetylations, cm-chitosan, chitosan quaternary ammonium salt, and viscosity-average molecular weight is 2-80 ten thousand.
The deacetylation of described chitosan or derivatives thereof is 45%-60%.
Described metal-salt precursor is Cadmium chloride fine powder, cadmium acetate, zinc chloride or zinc acetate.
Described chalcogenide is sodium hydrogen selenide, sodium hydrogen telluride or sodium sulphite.
Described dialysis tubing is the dialysis tubing with molecular weight cut-off.
The speed of the stirring at room that step (2) is described is 200-800r/min, and the speed of the high-speed stirring that step (3) is described is 800-2000r/min, and the speed of the stirring that step (4) is described is 100-500r/min.
Described quick cooling the referring to of step (4) is being cooled to room temperature in 1-10min.
The chitosan or derivatives thereof molecular chain that the present invention be take in water is template, by the synthetic method of original position, obtain the mixture of chitosan or derivatives thereof and fluorescence quantum, then this mixture is reacted under pressurized conditions to the nitrogen oxide donor-quantum dots compound that preparation can in-situ investigation nitrogen protoxide discharges with nitric oxide gas.Quantum dot combines by complexing action with chitosan or derivatives thereof, thereby chitosan or derivatives thereof combines with nitrogen protoxide with nitrogen protoxide generation nucleophilic reaction by contained parahelium group.Preparation method of the present invention is simple to operate, cost is lower, product can stably discharge nitrogen protoxide under physiological environment, and can effectively survey nitric oxide production release conditions, good biocompatibility, is having good application prospect aspect the diagnosis of hypertension, heart trouble, respiratory system disease, sexual dysfunction etc. and treatment.
Compared with prior art, the present invention has the following advantages and effect:
1. preparation method is simple, and consumption of organic solvent is few;
2. the good biocompatibility of the nitrogen oxide donor-quantum dots compound that the in-situ investigation nitrogen protoxide of preparation discharges, stability is high, and nitrogen protoxide releasing effect is good;
3. have the function that fluorescence detection nitrogen protoxide discharges, fluorescence efficiency is high, and Effect on Detecting is good.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of the nitrogen oxide donor-quantum dots compound of in-situ investigation nitrogen protoxide release of the present invention;
Fig. 2 is the transmission electron microscope photo of the nitrogen oxide donor-quantum dots compound of in-situ investigation nitrogen protoxide release of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
As shown in Figure 1, the preparation process schematic diagram of the nitrogen oxide donor-quantum dots compound discharging for in-situ investigation nitrogen protoxide of the present invention, the chitosan that by molecular weight be at room temperature 80,000, deacetylation is 58% is dissolved in deionized water, makes the chitosan aqueous solution that concentration is 3mg/ml, under stirring at room condition, to adding concentration in this chitosan aqueous solution, be the Cadmium chloride fine powder aqueous solution of 0.005mol/L, stir 8 hours, obtain the cadmium ion complex solution of chitosan, gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium hydrogen selenide of Cadmium chloride fine powder, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 90 ℃, reflux 2.5 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.8 ten thousand is fast dialysed 3 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable chitosan and the mixture of CdSe quantum dots through lyophilize, in temperature is the autoclave of 40 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.5, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 80psi, after stirring reaction 6 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, in succession with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges, the transmission electron microscope photo of this mixture as shown in Figure 2.
Embodiment 2
The chitosan that by molecular weight be at room temperature 100,000, deacetylation is 60% is dissolved in deionized water, makes the chitosan aqueous solution that concentration is 3.5mg/ml; Under stirring at room condition, to adding concentration in this chitosan aqueous solution, be the cadmium acetate aqueous solution of 0.005mol/L, stir 10 hours, obtain the cadmium ion complex solution of chitosan; Gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium hydrogen telluride of cadmium acetate, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 85 ℃, reflux 3 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.5 ten thousand is fast dialysed 4 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable chitosan and the mixture of cadmium telluride quantum dot through lyophilize; In temperature is the autoclave of 30 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.5, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 80psi, after stirring reaction 8 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 3
The chitosan that by molecular weight be at room temperature 50,000, deacetylation is 60% is dissolved in deionized water, makes the chitosan aqueous solution that concentration is 5mg/ml; Under stirring at room condition, to adding concentration in this chitosan aqueous solution, be the cadmium acetate aqueous solution of 0.0008mol/L, stir 10 hours, obtain the cadmium ion complex solution of chitosan; Gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium hydrogen telluride of cadmium acetate, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 85 ℃, reflux 3 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.5 ten thousand is fast dialysed 4 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable chitosan and the mixture of cadmium telluride quantum dot through lyophilize; In temperature is the autoclave of 30 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.5, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 80psi, after stirring reaction 7 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 4
The cm-chitosan that by molecular weight be at room temperature 300,000, deacetylation is 45% is dissolved in deionized water, and making concentration is the carboxymethyl chitosan sugar aqueous solution of 5mg/ml; Under stirring at room condition, to adding concentration in this carboxymethyl chitosan sugar aqueous solution, be the cadmium acetate aqueous solution of 0.00lmol/L, stir 8 hours, obtain the cadmium ion complex solution of cm-chitosan; Gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium hydrogen telluride of cadmium acetate, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 95 ℃, reflux 2 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.5 ten thousand is fast dialysed 5 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable cm-chitosan and the mixture of cadmium telluride quantum dot through lyophilize; In temperature is the autoclave of 25 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.2, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 90psi, after stirring reaction 6 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 5
The chitosan quaternary ammonium salt that by molecular weight be at room temperature 250,000, deacetylation is 50% is dissolved in deionized water, and making concentration is the chitosan quaternary ammonium salt brine solution of 5mg/ml; Under stirring at room condition, to adding concentration in this chitosan quaternary ammonium salt brine solution, be the Cadmium chloride fine powder aqueous solution of 0.005mol/L, stir 11 hours, obtain the cadmium ion complex solution of chitosan quaternary ammonium salt; Gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium hydrogen selenide of Cadmium chloride fine powder, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 85 ℃, reflux 3.5 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.2 ten thousand is fast dialysed 5 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable chitosan quaternary ammonium salt and the mixture of CdSe quantum dots through lyophilize; In temperature is the autoclave of 30 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.3, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 100psi, after stirring reaction 5 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 6
The chitosan quaternary ammonium salt that by molecular weight be at room temperature 420,000, deacetylation is 50% is dissolved in deionized water, and making concentration is the chitosan quaternary ammonium salt brine solution of 4mg/ml, under stirring at room (speed of stirring at room is 200r/min) condition, to adding concentration in this chitosan quaternary ammonium salt brine solution, be the zinc acetate aqueous solution of 0.003mol/L, stir 10 hours, obtain the zine ion complex solution of chitosan quaternary ammonium salt, gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring (speed of high-speed stirring is 800r/min) condition, add the aqueous solution containing with the equimolar sodium sulphite of zinc acetate, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition (speed of stirring is 100r/min), at the temperature of 90 ℃, reflux 3 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.8 ten thousand is fast dialysed 4 days in deionized water, then concentrated in Rotary Evaporators, through lyophilize, obtain stable chitosan quaternary ammonium salt and the mixture of ZnS quantum dots again, in temperature is the autoclave of 25 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.6, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 100psi, after stirring reaction 5 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 7
The chitosan that by molecular weight be at room temperature 50,000, deacetylation is 58% is dissolved in deionized water, makes the chitosan aqueous solution that concentration is 2.5mg/ml; Under room temperature ultrasonic oscillating condition, to adding concentration in this chitosan aqueous solution, be 0.001mol/L solder(ing)acid, stir 12 hours, obtain the zine ion complex solution of chitosan; Gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium sulphite of zinc chloride, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 95 ℃, reflux 2 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 20,000 is fast dialysed 3 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable chitosan and the mixture of ZnS quantum dots through lyophilize; In temperature is the autoclave of 30 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.4, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 100psi, after stirring reaction 5 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 8
The chitosan that by molecular weight be at room temperature 120,000, deacetylation is 60% is dissolved in deionized water, makes the chitosan aqueous solution that concentration is 2.5mg/ml; Under room temperature ultrasonic oscillating condition, to adding concentration in this chitosan aqueous solution, be the zinc acetate aqueous solution of 0.005mol/L, stir 9 hours, obtain the zine ion complex solution of chitosan; Gained solution is placed in to there-necked flask, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add the aqueous solution containing with the equimolar sodium sulphite of zinc acetate, obtain the colloidal solution of homogeneous transparent, continuation is under nitrogen protection and agitation condition, at the temperature of 85 ℃, reflux 4 hours, the dialysis tubing that cooling rear use molecular weight cut-off is 1.5 ten thousand is fast dialysed 4 days in deionized water, then concentrated in Rotary Evaporators, then obtain stable chitosan and the mixture of ZnS quantum dots through lyophilize; In temperature is the autoclave of 25 ℃, above-mentioned mixture is added in the absolute methanol solution of sodium methylate, the mass ratio of mixture and sodium methylate is controlled at 1: 1.8, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 80psi, after stirring reaction 10 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 9
The preparation method of nitrogen oxide donor-quantum dots compound, the method comprises the following steps:
(1) water-soluble chitosan that by viscosity-average molecular weight be at room temperature 20,000, deacetylation is 60% is dissolved in deionized water, makes the chitosan aqueous solution that concentration is 2mg/ml;
(2) the Cadmium chloride fine powder aqueous solution that adds 0.0002mol/L under stirring at room condition in the chitosan aqueous solution making to step (1), stirs 6 hours, and the speed of stirring at room is 800r/min, obtains the metal ion complex solution of chitosan;
(3) gained metal ion complex solution is placed in to reactor, sealing logical nitrogen protection, under room temperature high-speed stirring (speed of high-speed stirring is 2000r/min) condition, add sodium hydrogen selenide solution, the mol ratio of the sulfur family element in the cadmium element in metal ion complex and sodium hydrogen selenide solution is controlled between 1: 3, obtains the colloidal solution of homogeneous transparent;
(4) by above-mentioned colloidal solution under nitrogen protection and agitation condition (speed of stirring is 500r/min), at the temperature of 80 ℃, reflux 2 hours, after being cooled to room temperature in 1min, with the dialysis tubing with molecular weight cut-off, in deionized water, dialyse 2 days, then concentrated in Rotary Evaporators, then obtain stable chitosan and the mixture of quantum dot through lyophilize;
(5) in the autoclave of 25 ℃, the mixture of above-mentioned chitosan and quantum dot is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan and sodium methylate is controlled at 1: 1, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 50psi, after stirring reaction 5 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Embodiment 10
The preparation method of nitrogen oxide donor-quantum dots compound, the method comprises the following steps:
(1) chitosan quaternary ammonium salt that by viscosity-average molecular weight be at room temperature 800,000, deacetylation is 60% is dissolved in deionized water, and making concentration is the chitosan quaternary ammonium salt brine solution of 12mg/ml;
(2) zinc acetate aqueous solution that adds 0.01mol/L under ultra-sonic oscillation condition in the chitosan quaternary ammonium salt brine solution making to step (1), stirs 15 hours, obtains the metal ion complex solution of chitosan quaternary ammonium salt;
(3) gained metal ion complex solution is placed in to reactor, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add sodium sulfide solution, zinc element in metal ion complex and the mol ratio of the sulfur family element in sodium sulfide solution are controlled between 3: 1, obtain the colloidal solution of homogeneous transparent;
(4) by above-mentioned colloidal solution under nitrogen protection and agitation condition, at the temperature of 100 ℃, reflux 4 hours, after being cooled to room temperature in 10min, with the dialysis tubing with molecular weight cut-off, in deionized water, dialyse 5 days, then concentrated in Rotary Evaporators, then obtain stable chitosan quaternary ammonium salt and the mixture of quantum dot through lyophilize;
(5) in the autoclave of 45 ℃, the mixture of above-mentioned chitosan quaternary ammonium salt and quantum dot is added in the absolute methanol solution of sodium methylate, the mass ratio of chitosan quaternary ammonium salt and sodium methylate is controlled at 1: 3, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 120psi, after stirring reaction 9 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges in succession.
Claims (5)
1. the preparation method of nitrogen oxide donor-quantum dots compound, is characterized in that, the method comprises the following steps:
(1) at room temperature a certain amount of chitosan or derivatives thereof is dissolved in deionized water, makes chitosan or the chitosan derivatives aqueous solution that concentration is 2-12mg/ml;
(2) the metal-salt precursor aqueous solution that adds 0.0002-0.01mol/L under stirring at room or ultra-sonic oscillation condition in the chitosan making to step (1) or the chitosan derivatives aqueous solution, stir 6-15 hour, obtain the metal ion complex solution of chitosan or chitosan derivatives;
(3) gained metal ion complex solution is placed in to reactor, sealing logical nitrogen protection, under room temperature high-speed stirring condition, add chalcogenide solution, the mol ratio of the sulfur family element in the metallic element in metal ion complex and chalcogenide solution is controlled between 1:3 – 3:1, obtains the colloidal solution of homogeneous transparent;
(4) by above-mentioned colloidal solution under nitrogen protection and agitation condition, 2-4 hour refluxes at the temperature of 80-100 ℃, the quick cooling rear 2-5 days that dialyses in deionized water with dialysis tubing, then in Rotary Evaporators, concentrate, then through lyophilize, obtain the mixture of stable chitosan or chitosan derivatives and quantum dot;
(5) in the autoclave of 25-45 ℃, the mixture of above-mentioned chitosan or chitosan derivatives and quantum dot is added in the absolute methanol solution of sodium methylate, the mixture of chitosan or chitosan derivatives and quantum dot and the mass ratio of sodium methylate are controlled at 1:1.2, 1:1.4, 1:1.5 or 1:1.6, autoclave is first led to nitrogen to be vacuumized again, then pass into nitric oxide gas, maintain pressure 50-120psi, after stirring reaction 5-9 days, with nitrogen, blow away unreacted nitric oxide gas, product is filtered, in succession with anhydrous methanol and ether washing, at room temperature vacuum-drying obtains the nitrogen oxide donor-quantum dots compound that in-situ investigation nitrogen protoxide discharges,
Described metal-salt precursor is Cadmium chloride fine powder, cadmium acetate, zinc chloride or zinc acetate;
Described chalcogenide is sodium hydrogen selenide, sodium hydrogen telluride or sodium sulphite;
Described dialysis tubing is the dialysis tubing with molecular weight cut-off.
2. the preparation method of nitrogen oxide donor-quantum dots compound according to claim 1, it is characterized in that, described chitosan or derivatives thereof is to have the cm-chitosan of different deacetylations, one or more in chitosan quaternary ammonium salt, and viscosity-average molecular weight is 2-80 ten thousand.
3. the preparation method of nitrogen oxide donor-quantum dots compound according to claim 2, is characterized in that, the deacetylation of described chitosan or derivatives thereof is 45%-60%.
4. the preparation method of nitrogen oxide donor-quantum dots compound according to claim 1, it is characterized in that, the speed of the stirring at room that step (2) is described is 200-800r/min, the speed of the high-speed stirring that step (3) is described is 800-2000r/min, and the speed of the stirring that step (4) is described is 100-500r/min.
5. the preparation method of nitrogen oxide donor-quantum dots compound according to claim 1, is characterized in that, described quick cooling the referring to of step (4) is cooled to room temperature in 1-10min.
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| CN103041409B (en) * | 2013-01-10 | 2014-08-20 | 上海交通大学 | Preparation method of pH and thermal dual-sensitive lipidosome loaded with magnetic carbon quantum dots on internal water phase |
| CN103656668B (en) * | 2013-12-06 | 2016-08-17 | 山东省医学科学院药物研究所 | Bortezomib slow releasing preparation and preparation method thereof |
| CN104449673B (en) * | 2014-11-25 | 2016-08-24 | 上海交通大学 | The preparation method of the nitric oxide fluorescence polymer probe of item chain |
| CN107126439B (en) * | 2017-04-24 | 2021-03-09 | 上海陶盛生物技术有限公司 | Application of carboxymethyl chitosan in preparation or screening of products for reducing blood pressure |
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