CN107446576A - A kind of nano-luminescent material and its preparation method and application - Google Patents
A kind of nano-luminescent material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of nano-luminescent material and its preparation method and application, belongs to nano-luminescent material field.The nano-luminescent material of the present invention, is the carbonization short tube shape nanometer starch crystal that acyloxy is contained on surface；Outer dia is 10 20 nm, and thickness is 23 nm, and length is 35 nm；Green fluorescence is sent under ultraviolet light；Maximum excitation wavelength and launch wavelength are 486 nm and 538 nm respectively；Available for load medicine, the sustained release of medicine and tracer.Its preparation method：Starch first passes through diluted acid catalyzing hydrolysis, forms the starch nano chip that can be connected and bend by remaining unformed area；Then disappear through ammoniacal liquor or containing the organic alkali process of amino and low temperature latent, make the starch semi-crystalline region of starch nano chip that self assembly occur by the bending of remaining amorphous region, and the mellow and full polygon short tube shape nanometer starch crystal of structure is formed by self-regeneration；The carbonization of short tube shape nanometer starch crystal hydrothermal treatment is formed under the conditions of existing for ammoniacal liquor or organic base containing amino.
Description
Technical field
The present invention relates to a kind of nano-luminescent material and its preparation method and application, belongs to nano-luminescent material field.
Background technology
Carbon quantum dot refers to that size less than 10 nm, the fluorescent carbon nano-particles of tool, typically contains the functional group such as the multiple elements such as carbon, hydrogen, oxygen, nitrogen and carbonyl, amide groups.Carbon quantum dot is found during initially preparing CNT by electrophoresis, in recent years by constantly groping, various synthetic methods, such as high-temperature decomposition, electrochemistry method of stripping, incomplete oxidation combustion method, acid oxidation, laser ablation, hydro-thermal process method, microwave/ultrasonic deactivation method are developed.Synthesis material is also rich and varied, such as graphite oxide, glucose, starch, gelatin, chitosan, various fruit juice, waste paper ash, candle, citric acid, glycerine and various amine.Compared with other semiconductor-quantum-points, carbon quantum dot has that chemical stability is high, toxicity is low, water solubility/water dispersible is good, cost is low, raw material resources are abundant, epigranular, easy functionalization and the fluorescence advantage such as by force under near-infrared and black light.Extensive concern is obtained in multiple fields such as the stabilizations of bio-imaging, biology sensor, tagged fluorescent agent, photocatalysis, ultracapacitor, metal ion detection and the nano-particle of biomolecule/drug delivery/emulsion and emulsion.
As a kind of novel fluorescent material, common carbon quantum dot itself does not simultaneously have the functions such as load medicine, need by means of special material or utilize complex technique, carbon quantum dot or carbon quantum dot compound special shape are assigned, so that medicine or medicine controlled releasing can be carried, if any researcher using bovine serum albumin as raw material, utilize solvent thermal reaction, the hollow carbon quantum dot of the nm of aperture about 2, the nm of diameter about 6.8 is prepared for, so as to carrying medicament, but bovine serum albumin raw material sources are limited；Also there is researcher that carbon quantum dot and hollow porous carbon materials are compounded to form into the diameter with carbon quantum dot shell about 100
Nm fluorescence porous carbon Nano capsule, so as to assign composite fluorescence and carry the multiple functions such as medicine, but this fluorescence porous carbon Nano capsule is with the Fe with core shell structure3O4For/carbon composite as raw material, the building-up process of the raw material needs two luxuriant (network) iron and substantial amounts of organic solvent-acetone, and needs strong acid by Fe3O4Karyolysis, remove, final fluorescence porous carbon Nano capsule could be obtained, complex process, cost is high, is unfavorable for being commercialized.
The content of the invention
It is easy to get it is an object of the invention to provide a kind of raw material, the simple nano-luminescent material of preparation technology, and the preparation method and application of the nano-luminescent material, to realize the sustained release and the tracer that carry medicine and medicine.
Technical scheme
A kind of nano-luminescent material, it is the carbonization short tube shape nanometer starch crystal that acyloxy is contained on surface；" short tube " outer dia is 10-20 nm, and thickness is 2-3 nm, and length is 3-5 nm.
Above-mentioned nano-luminescent material, the cross section of " short tube " is in the polygon with rounding off angle.
" polygon with rounding off angle " refers to, the polygon that angle is replaced by corresponding arc.
The polygon includes triangle, quadrangle, pentagon etc..
Above-mentioned nano-luminescent material, green fluorescence is sent under ultraviolet light；Maximum excitation wavelength and launch wavelength are 486 nm and 538 nm respectively；And as the increase of excitation wavelength, its launch wavelength also move to high band direction.
Above-mentioned nano-luminescent material, it is the part amorphous area that diluted acid catalyzing hydrolysis starch is first passed through using cornstarch grain as raw material, forms the starch nano chip that can be connected and bend by remaining unformed area；Then disappear through ammoniacal liquor or containing the organic alkali process of amino and low temperature latent, remove the amorphous region starch and part sheet nanometer starch crystal of dissolution, make the starch semi-crystalline region of starch nano chip that self assembly occur by the bending of remaining amorphous region, and the mellow and full polygon short tube shape nanometer starch crystal of structure is formed by self-regeneration；The carbonization of short tube shape nanometer starch crystal hydrothermal treatment is formed under the conditions of existing for ammoniacal liquor or organic base containing amino.
The preparation method of above-mentioned nano-luminescent material, comprises the following steps：
（1）Prepare starch nano chip：The sulfuric acid solution that native cornstarch and mass concentration are 30% is according to 1:7 mass ratio mixing, is then stirred 5 days under the conditions of 40 DEG C；
（2）Prepare short tube shape nanometer starch crystal：The ammoniacal liquor or organic base containing amino that starch nano chip mass concentration is 1% soak 20 minutes, then stand 5 days at 4 DEG C；
（3）Hydro-thermal process：Ammoniacal liquor or organic base containing amino mix with short tube shape nanometer starch crystal, obtain short tube shape nanometer starch crystal mixed liquor；Short tube shape nanometer starch crystal mixed liquor carries out hydro-thermal process, is then centrifuged for separating except supernatant, you can.
The preparation method of above-mentioned nano-luminescent material, step（2）The operation of " with 5000 revs/min of centrifugation 20 minutes, removing supernatant liquor " is carried out after " and then standing 5 days at 4 DEG C ".
In order to obtain high-strength nano fluorescent material, step（3）The mass concentration of middle ammoniacal liquor or the organic base containing amino is 2-10%.
In order to improve preparation efficiency, while make reaction uniform, the preparation method of above-mentioned nano-luminescent material, the mass concentration of short tube shape nanometer starch crystal mixed liquor is 8-12
%。
In order to prevent " cross and be carbonized ", while shorten the reaction time, the preparation method of above-mentioned nano-luminescent material, hydro-thermal process temperature is 180-220 DEG C.
In order to obtain high-strength nano fluorescent material, the preparation method of above-mentioned nano-luminescent material, hydrothermal conditions are 3-12 hours.
In order to obtain higher intensity nano-luminescent material, the preparation method of above-mentioned nano-luminescent material, it is preferred that
Step（3）In：
The mass concentration of ammoniacal liquor or the organic base containing amino is 6%；
The mass concentration of short tube shape nanometer starch crystal mixed liquor is 10%；
Hydro-thermal process temperature is 200 DEG C
Hydrothermal conditions are 7 hours.
Above-mentioned preparation method, step（1）Concrete operations it is as follows：
Native cornstarch is added in sulfuric acid solution under 100-200 revs/min of stirring, forms homogeneous mixture；40 DEG C are heated the mixture to, and continues to stir 5 days with 100-200 revs/min of rotating speed at such a temperature；Then, with deionized water centrifuge washing, starch nano chip is produced.
The native cornstarch molecular formula is C6H12O6-(C6H10O5)n, it is a kind of Cereal natural macromolecule amylose, basic structural unit is α-pyrans formula dehydrated glucose, is made up of 28% amylose and 72% amylopectin, and the degree of polymerization of amylose is in 300-1200 or so, and the average degree of polymerization of amylopectin is in 30-200 ten thousand or so.
The present invention stands 5 days at 4 DEG C, disappear latent, the purpose is to joint angle between each side for the polygon short tube shape nanometer starch crystal for by forming hydrogen bond and self-regeneration, making to preliminarily form by self assembly between the starch nano chip by a small amount of unformed starch chain link is smoothened.
The preparation method of above-mentioned nano-luminescent material, centrifuge speed is 4000-8000 revs/min used by the centrifugation or centrifuge washing, centrifugation time 10-25 minutes.
Present invention also offers the purposes of above-mentioned nano-luminescent material.
A kind of purposes of above-mentioned nano-luminescent material as pharmaceutical carrier or pharmaceutical indications.
The medicine can be 5 FU 5 fluorouracil.
Beneficial effect
1st, nano-luminescent material of the invention, green fluorescence is sent under ultraviolet light；Maximum excitation wavelength and launch wavelength are 486 respectively
Nm and 538 nm；And as the increase of excitation wavelength, its launch wavelength also move to high band direction；Available for load medicine, the sustained release of medicine and tracer；
2nd, nano-luminescent material of the invention, is to be prepared by raw material of native cornstarch, raw material is easy to get, and cost is low；
3rd, nano-luminescent material of the invention, is prepared using " diluted acid catalyzing hydrolysis " and " hydro-thermal method ", the preparation method, and technique is simple.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of the nano-luminescent material of the present invention；
Fig. 2 all can compose x- X-ray photoelectron spectroscopy Xs for the fluorescent nano material of the present invention（Illustration）With C1s x- X-ray photoelectron spectroscopy Xs；
Fig. 3 is the fluorescent nano material of the present invention（a）Excitation spectrum and emission spectrum；（b）Emission spectrum under different excitation wavelengths.
Embodiment
With reference to specific embodiment, the invention will be further described, does not form any limitation of the invention.Except as otherwise indicating, the number in embodiment is by weight, " % " is quality " % ".
Embodiment
1
By 30 parts of native cornstarchs under 100 revs/min of stirring, the H of 210 parts of concentration 30% is added2SO4In solution, after being uniformly dispersed, after the mixture is heated into 40 DEG C, continue stirring reaction 5 days under 100 revs/min of mixing speed.The reactant of gained is cooled to room temperature again with 5000 revs/min of centrifugation 20 minutes, removes unformed starch and excessive sulfuric acid in supernatant.Centrifuge washing is repeated with same speed and time with deionized water again afterwards, until supernatant pH is 5, it is that initial starch is nanocrystalline to remove supernatant and obtain infusible precipitate（As starch nano chip, similarly hereinafter）.It is nanocrystalline scattered with 150 parts of initial starch by above-mentioned preparation of weak aqua ammonia that mass concentration is 1% and soak 20 minutes, again with 5000 revs/min of centrifugation 20 minutes, supernatant liquor is removed, and gained sediment is stood 5 days at 4 DEG C, as short tube shape nanometer starch crystal.The short tube shape nanometer starch crystal is diluted to concentration 10% with the weak aqua ammonia of concentration 6%（" concentration 10% " refers to that the concentration of short tube shape nanometer starch crystal is 10%；Similarly hereinafter）Afterwards, it is placed in reactor, hydro-thermal reaction 7 hours at 200 DEG C, with 5000 revs/min of centrifugation 20 minutes, removes supernatant, gained solid content is short tube shape nano-luminescent material.
0.1 part of above-mentioned short tube shape nano-luminescent material is taken to be diluted to mass fraction with deionized water to be analyzed after 0.67% concentration with high resolution transmission electron microscope, as shown in Figure 1, outer dia 10-20
Nm, thickness are 2-3 nm, length 3-5
Nm, cross section have irregular polygon-shaped.Using the bonding situation of its surface carbon of x- X-ray photoelectron spectroscopy Xs technical Analysis after film, as shown in Figure 2, it is found that above-mentioned short tube shape nano-luminescent material surface forms acyl-oxygen group（O-C=O）.The above-mentioned short tube shape nano-luminescent material that mass concentration is 0.67% can produce green fluorescence under ultraviolet excitation, analyze its optical property using sepectrophotofluorometer, it is found that the short tube shape nano-luminescent material maximum excitation wavelength and launch wavelength are 486 respectively
Nm and 538 nm, and its launch wavelength also moves to high band direction with the increase of excitation wavelength, as shown in Figure 3.
Take 0.5 part of 5 FU 5 fluorouracil to be dissolved in 75 parts of 0.1mol/L HCl solution, form 5 FU 5 fluorouracil solution, while be passed through nitrogen；0.3 part of above-mentioned short tube shape nano-luminescent material is taken to add under agitation in the 5 FU 5 fluorouracil solution of above-mentioned preparation, after well mixed, said mixture pH is adjusted to 7 using 0.1 mol/L NaOH solution, recycle supercentrifuge to centrifuge said mixture 5 minutes under 10000 revs/min of rotating speed and remove supernatant, and the lower sediment thing obtained under similarity condition with deionized water centrifuge washing is three times, to remove unadsorbed 5 FU 5 fluorouracil, finally the sediment after washing is dried in vacuo at 75 DEG C, obtain the short tube shape nano-luminescent material for being mounted with 5 FU 5 fluorouracil.Above-mentioned short tube shape nano-luminescent material is to the load capacity of 5 FU 5 fluorouracil up to 20.5
mg/g。
Take 200 parts of pH 7.4 phosphate buffer solution and by heating water bath to 37 DEG C；Take 0.2 part of above-mentioned preparation the short tube shape nano-luminescent material for being loaded with 5 FU 5 fluorouracil be added under 100 revs/min of magnetic agitation it is above-mentioned be placed in the phosphate buffer solution in 37 DEG C of water-baths, formed carried medicine sustained-release determination sample；3 mL were taken out every 10 minutes from above-mentioned carried medicine sustained-release determination sample to be centrifuged, add 3 mL phosphate buffers simultaneously, determine the concentration for taking out 5 FU 5 fluorouracil in sample supernatant by absorbance method at 266 nm using ultraviolet-uisible spectrophotometer, finding the short tube shape nano-luminescent material of above-mentioned preparation has good drug controlled-releasing function：A fulminant release in 30 min be present, burst size is about 46%, meets the general feature adsorbed and be sustained inside medicine；After burst is sustained, the rate of release of 5 FU 5 fluorouracil reduces, and burst size reaches 80.4% after 420 min, to 1440 min after close to release completely（Burst size is 98.1%）.
The unsupported 5 FU 5 fluorouracil on short tube shape nano-luminescent material is in pH 7.4, temperature 37oAlmost dissolved immediately in C phosphate buffer solution.
Embodiment
2
By 30 parts of native cornstarchs under 100 revs/min of stirring, the H of 210 parts of concentration 30% is added2SO4In solution, after being uniformly dispersed, after the mixture is heated into 40 DEG C, continue stirring reaction 5 days under 200 revs/min of mixing speed.The reactant of gained is cooled to room temperature again with 4000 revs/min of centrifugation 25 minutes, removes unformed starch and excessive sulfuric acid in supernatant.Centrifuge washing is repeated with same speed and time with deionized water again afterwards, until supernatant pH is 5, it is that initial starch is nanocrystalline to remove supernatant and obtain infusible precipitate.It is nanocrystalline scattered with 150 parts of initial starch by above-mentioned preparation of weak aqua ammonia that mass concentration is 1% and soak 20 minutes, again with 4000 revs/min of centrifugation 25 minutes, supernatant liquor is removed, and gained sediment is stood 5 days at 4 DEG C, as short tube shape nanometer starch crystal.After the short tube shape nanometer starch crystal is diluted into concentration 8% with the weak aqua ammonia of concentration 2%, it is placed in reactor, hydro-thermal reaction 12 hours at 180 DEG C, with 4000 revs/min of centrifugation 25 minutes, supernatant is removed, gained solid content is short tube shape nano-luminescent material.Analyzed through high-resolution transmission microscopy, short tube shape nano-luminescent material prepared by the embodiment has short tubular structure and fluorescence property similar to Example 1（Fluorescence color is identical, and maximum excitation wavelength and launch wavelength are also 486 nm and 538 nm respectively；Similarly hereinafter）, but fluorescence intensity is slightly weak compared with sample prepared by embodiment 1.
Take 0.5 part of 5 FU 5 fluorouracil to be dissolved in 75 parts of 0.1mol/L HCl solution, form 5 FU 5 fluorouracil solution, while be passed through nitrogen；0.3 part of above-mentioned short tube shape nano-luminescent material is taken to add under agitation in the 5 FU 5 fluorouracil solution of above-mentioned preparation, after well mixed, said mixture pH is adjusted to 7 using 0.1 mol/L NaOH solution, recycle supercentrifuge to centrifuge said mixture 5 minutes under 10000 revs/min of rotating speed and remove supernatant, and the lower sediment thing obtained under similarity condition with deionized water centrifuge washing is three times, to remove unadsorbed 5 FU 5 fluorouracil, finally the sediment after washing is dried in vacuo at 75 DEG C, obtain the short tube shape nano-luminescent material for being mounted with 5 FU 5 fluorouracil；Short tube shape nano-luminescent material is to the load capacity of 5 FU 5 fluorouracil up to 18.3
mg/g。
Take 200 parts of pH 7.4 phosphate buffer solution and by heating water bath to 37 DEG C；Take 0.2 part of above-mentioned preparation the short tube shape nano-luminescent material for being loaded with 5 FU 5 fluorouracil be added under 100 revs/min of magnetic agitation it is above-mentioned be placed in the phosphate buffer solution in 37 DEG C of water-baths, formed carried medicine sustained-release determination sample；3 mL were taken out every 10 minutes from above-mentioned carried medicine sustained-release determination sample to be centrifuged, add 3 mL phosphate buffers simultaneously, the concentration for taking out 5 FU 5 fluorouracil in sample supernatant is determined using ultraviolet-uisible spectrophotometer, it was found that the 5 FU 5 fluorouracil being carried on the short tube shape nano-luminescent material of above-mentioned preparation meets the general feature of medicament slow release, and to after 1320 min just close to release completely（Burst size is 98.3%）.
Embodiment
3
By 30 parts of native cornstarchs under 150 revs/min of stirring, the H of 210 parts of concentration 30% is added2SO4In solution, after being uniformly dispersed, after the mixture is heated into 40 DEG C, continue stirring reaction 5 days under 150 revs/min of mixing speed.The reactant of gained is cooled to room temperature again with 8000 revs/min of centrifugation 10 minutes, removes unformed starch and excessive sulfuric acid in supernatant.Centrifuge washing is repeated with same speed and time with deionized water again afterwards, until supernatant pH is 5, it is that initial starch is nanocrystalline to remove supernatant and obtain infusible precipitate.It is nanocrystalline scattered with 150 parts of initial starch by above-mentioned preparation of weak aqua ammonia that mass concentration is 1% and soak 20 minutes, again with 8000 revs/min of centrifugation 10 minutes, supernatant liquor is removed, and gained sediment is stood 5 days at 4 DEG C, as short tube shape nanometer starch crystal.After the short tube shape nanometer starch crystal is diluted into concentration 12% with the weak aqua ammonia of concentration 10%, it is placed in reactor, hydro-thermal reaction 3 hours at 220 DEG C, with 8000 revs/min of centrifugation 10 minutes, supernatant is removed, gained solid content is short tube shape nano-luminescent material.Through the analysis of high-resolution transmission microscopy and ultraviolet light, short tube shape nano-luminescent material prepared by the embodiment has short a tubular structure and fluorescence property similar to Example 1, and fluorescence intensity is slightly strong compared with sample prepared by embodiment 1.
Take 0.5 part of 5 FU 5 fluorouracil to be dissolved in 75 parts of 0.1mol/L HCl solution, form 5 FU 5 fluorouracil solution, while be passed through nitrogen；0.3 part of above-mentioned short tube shape nano-luminescent material is taken to add under agitation in the 5 FU 5 fluorouracil solution of above-mentioned preparation, after well mixed, said mixture pH is adjusted to 7 using 0.1 mol/L NaOH solution, recycle supercentrifuge to centrifuge said mixture 5 minutes under 10000 revs/min of rotating speed and remove supernatant, and the lower sediment thing obtained under similarity condition with deionized water centrifuge washing is three times, to remove unadsorbed 5 FU 5 fluorouracil, finally the sediment after washing is dried in vacuo at 75 DEG C, obtain the short tube shape nano-luminescent material for being mounted with 5 FU 5 fluorouracil；Short tube shape nano-luminescent material is to the load capacity of 5 FU 5 fluorouracil up to 20.2mg/g.
Take 200 parts of pH 7.4 phosphate buffer solution and by heating water bath to 37 DEG C；Take 0.2 part of above-mentioned preparation the short tube shape nano-luminescent material for being loaded with 5 FU 5 fluorouracil be added under 100 revs/min of magnetic agitation it is above-mentioned be placed in the phosphate buffer solution in 37 DEG C of water-baths, formed carried medicine sustained-release determination sample；3 mL were taken out every 10 minutes from above-mentioned carried medicine sustained-release determination sample to be centrifuged, add 3 mL phosphate buffers simultaneously, the concentration for taking out 5 FU 5 fluorouracil in sample supernatant is determined using ultraviolet-uisible spectrophotometer, it was found that the 5 FU 5 fluorouracil being carried on the short tube shape nano-luminescent material of above-mentioned preparation meets the general feature of medicament slow release, and to after 1620 min just close to release completely（Burst size is 97.9%）.
Embodiment
4
By 30 parts of native cornstarchs under 100 revs/min of stirring, the H of 210 parts of concentration 30% is added2SO4In solution, after being uniformly dispersed, after the mixture is heated into 40 DEG C, continue stirring reaction 5 days under 100 revs/min of mixing speed.The reactant of gained is cooled to room temperature again with 6000 revs/min of centrifugation 15 minutes, removes unformed starch and excessive sulfuric acid in supernatant.Centrifuge washing is repeated with same speed and time with deionized water again afterwards, until supernatant pH is 5, it is that initial starch is nanocrystalline to remove supernatant and obtain infusible precipitate.It is nanocrystalline scattered with 150 parts of initial starch by above-mentioned preparation of weak aqua ammonia that mass concentration is 1% and soak 20 minutes, then with 6000 revs/min of centrifugation 15 minutes, supernatant liquor is removed, sediment is short tube shape nanometer starch crystal.After the short tube shape nanometer starch crystal is diluted into concentration 9% with the weak aqua ammonia of concentration 8%, it is placed in reactor, hydro-thermal reaction 5 hours at 200 DEG C, with 4000 revs/min of centrifugation 25 minutes, supernatant is removed, and gained solid content is stood 5 days at 4 DEG C, as short tube shape nano-luminescent material.Analyzed through high-resolution transmission microscopy, short tube shape nano-luminescent material prepared by the embodiment has short tubular structure and fluorescence property similar to Example 1, but fluorescence intensity is slightly weak compared with sample prepared by embodiment 1, slightly strong compared with sample prepared by embodiment 2.
Take 0.5 part of 5 FU 5 fluorouracil to be dissolved in 75 parts of 0.1mol/L HCl solution, form 5 FU 5 fluorouracil solution, while be passed through nitrogen；0.3 part of above-mentioned short tube shape nano-luminescent material is taken to add under agitation in the 5 FU 5 fluorouracil solution of above-mentioned preparation, after well mixed, said mixture pH is adjusted to 7 using 0.1 mol/L NaOH solution, recycle supercentrifuge to centrifuge said mixture 5 minutes under 10000 revs/min of rotating speed and remove supernatant, and the lower sediment thing obtained under similarity condition with deionized water centrifuge washing is three times, to remove unadsorbed 5 FU 5 fluorouracil, finally the sediment after washing is dried in vacuo at 75 DEG C, obtain the short tube shape nano-luminescent material for being mounted with 5 FU 5 fluorouracil, short tube shape nano-luminescent material is to the load capacity of 5 FU 5 fluorouracil up to 20.3
mg/g。
Take 200 parts of pH 7.4 phosphate buffer solution and by heating water bath to 37 DEG C；Take 0.2 part of above-mentioned preparation the short tube shape nano-luminescent material for being loaded with 5 FU 5 fluorouracil be added under 100 revs/min of magnetic agitation it is above-mentioned be placed in the phosphate buffer solution in 37 DEG C of water-baths, formed carried medicine sustained-release determination sample；3 mL were taken out every 10 minutes from above-mentioned carried medicine sustained-release determination sample to be centrifuged, add 3 mL phosphate buffers simultaneously, the concentration for taking out 5 FU 5 fluorouracil in sample supernatant is determined using ultraviolet-uisible spectrophotometer, it was found that the 5 FU 5 fluorouracil being carried on the short tube shape nano-luminescent material of above-mentioned preparation meets the general feature of medicament slow release, and to after 1440 min just close to release completely（Burst size is 98.7%）.
Embodiment
5
By 30 parts of native cornstarchs under 100 revs/min of stirring, the H of 210 parts of concentration 30% is added2SO4In solution, after being uniformly dispersed, after the mixture is heated into 40 DEG C, continue stirring reaction 5 days under 100 revs/min of mixing speed.The reactant of gained is cooled to room temperature again with 7000 revs/min of centrifugation 15 minutes, removes unformed starch and excessive sulfuric acid in supernatant.Centrifuge washing is repeated with same speed and time with deionized water again afterwards, until supernatant pH is 5, it is that initial starch is nanocrystalline to remove supernatant and obtain infusible precipitate.It is nanocrystalline scattered with 150 parts of initial starch by above-mentioned preparation of weak aqua ammonia that mass concentration is 1% and soak 20 minutes, then with 7000 revs/min of centrifugation 15 minutes, supernatant liquor is removed, sediment is short tube shape nanometer starch crystal.After the short tube shape nanometer starch crystal is diluted into concentration 10% with the weak aqua ammonia of concentration 4%, it is placed in reactor, hydro-thermal reaction 10 hours at 200 DEG C, with 7000 revs/min of centrifugation 15 minutes, remove supernatant, and gained solid content is stood 5 days at 4 DEG C, as short tube shape nano-luminescent material.Analyzed through high-resolution transmission microscopy, short tube shape nano-luminescent material prepared by the embodiment has short tubular structure and fluorescence property similar to Example 1.But fluorescence intensity is slightly weak compared with sample prepared by embodiment 3, slightly strong compared with sample prepared by embodiment 4.
Take 0.5 part of 5 FU 5 fluorouracil to be dissolved in 75 parts of 0.1mol/L HCl solution, form 5 FU 5 fluorouracil solution, while be passed through nitrogen；0.3 part of above-mentioned short tube shape nano-luminescent material is taken to add under agitation in the 5 FU 5 fluorouracil solution of above-mentioned preparation, after well mixed, said mixture pH is adjusted to 7 using 0.1 mol/L NaOH solution, recycle supercentrifuge to centrifuge said mixture 5 minutes under 10000 revs/min of rotating speed and remove supernatant, and the lower sediment thing obtained under similarity condition with deionized water centrifuge washing is three times, to remove unadsorbed 5 FU 5 fluorouracil, finally the sediment after washing is dried in vacuo at 75 DEG C, obtain the short tube shape nano-luminescent material for being mounted with 5 FU 5 fluorouracil.Above-mentioned short tube shape nano-luminescent material is to the load capacity of 5 FU 5 fluorouracil up to 21.8
mg/g。
Take 200 parts of pH 7.4 phosphate buffer solution and by heating water bath to 37 DEG C；Take 0.2 part of above-mentioned preparation the short tube shape nano-luminescent material for being loaded with 5 FU 5 fluorouracil be added under 100 revs/min of magnetic agitation it is above-mentioned be placed in the phosphate buffer solution in 37 DEG C of water-baths, formed carried medicine sustained-release determination sample；3 mL were taken out every 10 minutes from above-mentioned carried medicine sustained-release determination sample to be centrifuged, add 3 mL phosphate buffers simultaneously, the concentration for taking out 5 FU 5 fluorouracil in sample supernatant is determined using ultraviolet-uisible spectrophotometer, it was found that the 5 FU 5 fluorouracil being carried on the short tube shape nano-luminescent material of above-mentioned preparation meets the general feature of medicament slow release, and to after 1510 min just close to release completely（Burst size is 98.5%）.
Claims (10)
1. a kind of nano-luminescent material, it is characterised in that be the carbonization short tube shape nanometer starch crystal that acyloxy is contained on surface；" short tube " outer dia is 10-20 nm, and thickness is 2-3 nm, and length is 3-5 nm.
2. nano-luminescent material according to claim 1, it is characterised in that the cross section of " short tube " is in the polygon with rounding off angle.
3. short tube shape nanometer starch crystal according to claim 2, it is characterised in that " polygon with rounding off angle " refers to, the polygon that angle is replaced by corresponding arc.
4. according to the nano-luminescent material of claim 1,2 or 3, it is characterised in that above-mentioned nano-luminescent material, green fluorescence is sent under ultraviolet light；Maximum excitation wavelength and launch wavelength are 486 nm and 538 nm respectively.
5. nano-luminescent material according to claim 4, it is characterised in that with the increase of excitation wavelength, its launch wavelength also moves to high band direction.
6. the preparation method of nano-luminescent material described in any one in a kind of claim 1-5, it is characterised in that comprise the following steps：
（1）Prepare starch nano chip：The sulfuric acid solution that native cornstarch and mass concentration are 30% is according to 1:7 mass ratio mixing, is then stirred 5 days under the conditions of 40 DEG C；
（2）Prepare short tube shape nanometer starch crystal：The ammoniacal liquor or organic base containing amino that starch nano chip mass concentration is 1% soak 20 minutes, then stand 5 days at 4 DEG C；
（3）Hydro-thermal process：Ammoniacal liquor or organic base containing amino mix with short tube shape nanometer starch crystal, obtain short tube shape nanometer starch crystal mixed liquor；Short tube shape nanometer starch crystal mixed liquor carries out hydro-thermal process, is then centrifuged for separating except supernatant, you can.
7. preparation method according to claim 6, it is characterised in that step（3）In：
The mass concentration of ammoniacal liquor or the organic base containing amino is 2-10%；
The mass concentration of short tube shape nanometer starch crystal mixed liquor is 8-12 %；
Hydro-thermal process temperature is 180-220
℃;
Hydrothermal conditions are 3-2 hours.
8. preparation method according to claim 7, it is characterised in that step（3）In：
The mass concentration of ammoniacal liquor or the organic base containing amino is 6%；
The mass concentration of short tube shape nanometer starch crystal mixed liquor is 10%；
Hydro-thermal process temperature is 200 DEG C
Hydrothermal conditions are 7 hours.
A kind of 9. purposes of the nano-luminescent material as pharmaceutical carrier or pharmaceutical indications described in claim 1-5 any one.
10. purposes according to claim 9, it is characterised in that the medicine is 5 FU 5 fluorouracil.
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| CN103193890A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院化学研究所 | Functionalized starch nano-crystals and preparation method thereof |
| CN105061608A (en) * | 2015-08-04 | 2015-11-18 | 江南大学 | Fluorescent starch nanocrystal and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103193890A (en) * | 2012-01-05 | 2013-07-10 | 中国科学院化学研究所 | Functionalized starch nano-crystals and preparation method thereof |
| CN105061608A (en) * | 2015-08-04 | 2015-11-18 | 江南大学 | Fluorescent starch nanocrystal and preparation method and application thereof |
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