CN1831080A - Stable, water soluble chitin derivatives fluorescent quantal-points and prepn. method therefor - Google Patents
Stable, water soluble chitin derivatives fluorescent quantal-points and prepn. method therefor Download PDFInfo
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- CN1831080A CN1831080A CN 200610018657 CN200610018657A CN1831080A CN 1831080 A CN1831080 A CN 1831080A CN 200610018657 CN200610018657 CN 200610018657 CN 200610018657 A CN200610018657 A CN 200610018657A CN 1831080 A CN1831080 A CN 1831080A
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Abstract
This invention discloses a stable water soluble shell polysaccharide derivant fluorescence quanta point and its preparation method. The template is the shell polysaccharide derivant, its production method is home position grown in molecular grid form nm micro-crystal, particle diameter is between 2-6nm. The preparation method is that the derivant is dissolved in pure water, metal salt solution is added under agitation condition at house temperature to form complex, chalcogen predecessor solution is high speed agitated added the formed nm semiconductor micro-crystal, it is quanta point, finally high fluorescence efficiency quanta point solution is got after heat reflow and dialysis. The fluorescence point made in neutral water solution can effectively avoid poisonous side effect of organic solvent, the energy needed is large less than ordinary method, and it is specially to combination of bio-molecular. It has great application prospect in cell recognition, organism mark and disease diagnosis fields.
Description
Technical field
The present invention relates to a kind of stable water soluble chitin derivatives fluorescent quantal-points that is used as fluorescent probe and preparation method thereof, belong to biochemical field.
Background technology
Fluorescence quantum has caused people's very big concern in recent years because of the photoluminescent property that it has narrow emission, nothing bleaching and high stable.Compare with traditional fluorescence dye, fluorescence quantum has advantageous advantage at aspects such as fluorescent probe, biomarker, medicals diagnosis on disease.Present high-quality fluorescence quantum is mainly made under High Temperature High Pressure by organometallics, the quantum dot for preparing in this oil phase must be modified through complicated wetting ability if be applied to biomedical sector, the process of modifying tends to cause the remarkable reduction of fluorescence efficiency, the more important thing is the bio-toxicity that can't solve quantum dot and the problem of biocompatibility difference, hindered the application of quantum dot greatly.
Summary of the invention
In order to overcome the deficiency of existing fluorescence quantum, the invention provides a kind of stable chitosan derivatives water soluble fluorescence quantum dot and preparation method thereof, chitosan derivatives is water-soluble all fine under acid-base condition, can under neutrallty condition, prepare nanoparticle, can avoid the toxic action of organic solvent, be fit to the application of fluorescence quantum at biomedicine field.And preparation method's process safety of the present invention, simple effectively, compliance with environmental protection requirements, prepared fluorescence quantum fluorescence efficiency height, good stability.
Technical scheme provided by the invention is: a kind of chitosan derivatives water soluble fluorescence quantum dot as fluorescent probe, quantum dot is a template in order to the chitosan quaternary ammonium salt in the chitosan derivatives, cm-chitosan, sulfated chitosan or water-soluble chitosan, the method that forms CdS, ZnS, PbS, CdSe, ZnSe or PbSe nano microcrystalline (quantum dot) in its position, molecule grid Central Plains growth makes, and the nano microcrystalline particle diameter is that diameter is between 2-6nm.
The present invention also provides the preparation method of this water soluble fluorescence quantum dot, and its concrete steps are as follows:
(1) in room temperature chitosan derivatives is dissolved in the distilled water, making concentration is the chitosan derivatives aqueous solution of 2.5-10mg/ml,
(2) adding concentration in the chitosan derivatives aqueous solution that makes under agitation condition is 5 * 10
-4-10
-2The mol/l metal-salt precursor aqueous solution stirred 8-12 hour, and products therefrom is the metal complex of chitosan derivatives.
(3) products therefrom is placed there-necked flask; the logical nitrogen protection of sealing; high-speed stirring adds and the equimolar sulfur family precursor solution of metal-salt precursor in solution rapidly simultaneously; the molar ratio range of metal and sulphur is between 1: 3～3: 1, and solution becomes the transparent even colloidal sol that has the semiconductor microcrystallite characteristic color immediately.
(4) continue under nitrogen protection, to stir, be heated to 80-100 ℃ of backflow 2-3 hour, cooling rapidly, gained solution was dialysed in deionized water 2-3 days with the dialysis tubing of 1-2 ten thousand, promptly got stable chitin derivatives fluorescent quantal-points solution.
The chitin derivatives fluorescent quantal-points solution that gained is stable was in the room temperature centrifugation below 20 ℃ 20-30 minute, and centrifugal speed more than the 000rpm, is abandoned supernatant generally 15, and lyophilize promptly gets respective shell polysaccharid derivative stable fluorescence quantum dot powder.
As stated above, prepared fluorescence quantum comprises CdS, ZnS, PbS, CdSe, ZnSe, PbSe; Used chitosan derivatives has chitosan quaternary ammonium salt, cm-chitosan, sulfated chitosan or water-soluble chitosan; Used metal-salt precursor is analytically pure cadmium acetate, zinc acetate or mercuric acetate powder, and used sulfur family precursor is sodium disulfide or sodium hydrogen selenide.
Chitosan has more active function group, is easy to complexing of metal ion, can be used as the template of preparation quantum dot.But chitosan is that PH is just water insoluble more than 6 in potential of hydrogen, makes it be not suitable for using under neutrallty condition.And use the soluble derivative of chitosan to make template, and in the aqueous solution, prepare quantum dot, not only given quantum dot splendid water-soluble, more because the coating of biologically active substance has fundamentally solved the problem of biocompatibility.Fluorescence quantum provided by the invention is exactly to be the chitosan derivatives of the surperficial coated biologically active of quantum dot between the 2-6nm at diameter.Used chitosan quaternary ammonium salt, cm-chitosan, sulfated chitosan and water-soluble chitosan all is to have bioactive water-solubility chitosan derivative in the preparation, they have been used as pharmaceutical carrier, anticoagulation, biomaterial antibiotic, antiblocking widely and have been applied to biomedical sector, facts have proved that these materials have excellent biological compatibility, nontoxicity and immunogenicity.Can not need directly apply to living things system with these chitosan derivatives as the water soluble fluorescence quantum dot of stablizer preparation through wetting ability and consistency modification.And the various active groups on chitosan derivatives surface can also make this quantum dot combine with various biomolecules such as antibody, DNA easily, widen its range of application.Therefore water soluble fluorescence quantum dot provided by the invention can be widely used in fields such as cell recognition, biomarker, medical diagnosis on disease.
And this fluorescence quantum prepares in neutral aqueous solution, can avoid the toxic side effect of organic solvent, institute's energy requirement greatly reduces than common preparation method (solvent thermal and sol-gel method), can make under the mild conditions of normal temperature and pressure, is particularly suitable for the combination of biomolecules.From operating process preparation method's process safety provided by the invention as can be known, simple effective, compliance with environmental protection requirements,
Embodiment
Embodiment 1: with molecular weight ranges is that the chitosan quaternary ammonium salt of 1-2 ten thousand is dissolved in distilled water and makes the 5mg/ml aqueous solution, adds 5 * 10 under agitation condition
-3The cadmium acetate aqueous solution of mol/l; reacted 12 hours; products therefrom is placed there-necked flask; the logical nitrogen protection of sealing, high-speed stirring in solution, add prepared fresh simultaneously rapidly with the equimolar sodium sulfide solution of cadmium acetate, continue to stir; 80 ℃ of reflux 2 hours; cooling rapidly, gained solution was dialysed in distilled water 2 days with 20,000 dialysis tubing, promptly got glassy yellow fluorescence CdS quantum dot solution.In the room temperature centrifugation below 20 ℃ 20-30 minute, centrifugal speed more than the 000rpm, was abandoned supernatant generally 15 with solution, and lyophilize promptly gets corresponding fluorescence quantum powder.
Embodiment 2: with molecular weight ranges is that the cm-chitosan of 1-2 ten thousand is dissolved in distilled water and makes the 5mg/ml aqueous solution, adds 5 * 10 under agitation condition
-3The lead acetate water solution of mol/l; reacted 12 hours; products therefrom is placed there-necked flask; the logical nitrogen protection of sealing, high-speed stirring in solution, add prepared fresh simultaneously rapidly with the equimolar sodium sulfide solution of plumbic acetate, continue to stir; 100 ℃ of reflux 2 hours; cooling rapidly, gained solution was dialysed in distilled water 2 days with 20,000 dialysis tubing, promptly got scarlet fluorescence PbS quantum dot solution.
Embodiment 3: with molecular weight ranges is that the sulfated chitosan of 1-2 ten thousand is made the 5mg/ml aqueous solution, adds 5 * 10 under agitation condition
-3The cadmium acetate aqueous solution of mol/l; reacted 12 hours; products therefrom is placed there-necked flask; the logical nitrogen protection of sealing, high-speed stirring in solution, add prepared fresh simultaneously rapidly with the equimolar sodium hydrogen selenide aqueous solution of cadmium acetate, continue to stir; 80 ℃ of reflux 2 hours; cooling rapidly, gained solution was dialysed in distilled water 2 days with 20,000 dialysis tubing, promptly got shiny red fluorescence CdSe quantum dots solution.
Embodiment 4: with molecular weight ranges is that the cm-chitosan of 1-2 ten thousand is made the 5mg/ml aqueous solution, adds 5 * 10 under agitation condition
-3The zinc acetate aqueous solution of mol/l; reacted 12 hours; products therefrom is placed there-necked flask; the logical nitrogen protection of sealing, high-speed stirring in solution, add prepared fresh simultaneously rapidly with the equimolar sodium sulfide solution of zinc acetate, continue to stir; 80 ℃ of reflux 2 hours; cooling rapidly, gained solution was dialysed in distilled water 2 days with 20,000 dialysis tubing, promptly got brilliant white fluorescence ZnS quantum dot solution.
Claims (7)
1, a kind of stable water soluble chitin derivatives fluorescent quantal-points, it is characterized in that: quantum dot is a template in order to the chitosan quaternary ammonium salt in the chitosan derivatives, cm-chitosan, sulfated chitosan or water-soluble chitosan, the method that forms CdS, ZnS, PbS, CdSe, ZnSe or PbSe nano microcrystalline (quantum dot) in its position, molecule grid Central Plains growth makes, and the nano microcrystalline particle diameter is that diameter is between 2-6nm.
2, the preparation method of the described chitin derivatives fluorescent quantal-points of claim 1 is characterized in that adopting step as follows:
(1) in room temperature chitosan derivatives is dissolved in the distilled water, making concentration is the chitosan derivatives aqueous solution of 2.5-10mg/ml,
(2) adding concentration in the chitosan derivatives aqueous solution that makes under agitation condition is 5 * 10
-4-10
-2The mol/l metal-salt precursor aqueous solution stirred 8-12 hour, and products therefrom is the metal complex of chitosan derivatives.
(3) products therefrom is placed there-necked flask; the logical nitrogen protection of sealing; high-speed stirring adds the sulfur family precursor solution simultaneously rapidly in solution, the molar ratio range of metal and sulphur is between 1: 3～3: 1, and solution becomes the transparent even colloidal sol that has the semiconductor microcrystallite characteristic color immediately.
(4) continue under nitrogen protection, to stir, be heated to 80-100 ℃ of backflow 2-3 hour, cooling rapidly, gained solution was dialysed in deionized water 2-3 days with the dialysis tubing of 1-2 ten thousand, promptly got stable chitin derivatives fluorescent quantal-points solution.
3, the preparation method of stable chitin derivatives fluorescent quantal-points according to claim 2, it is characterized in that: the chitin derivatives fluorescent quantal-points solution that gained is stable was in the room temperature centrifugation below 20 ℃ 20-30 minute, abandon supernatant, lyophilize promptly gets respective shell polysaccharid derivative stable fluorescence quantum dot powder.
4, the preparation method of stable chitin derivatives fluorescent quantal-points according to claim 2, it is characterized in that: employed chitosan derivatives is chitosan quaternary ammonium salt, cm-chitosan, sulfated chitosan or water-soluble chitosan, and its molecular weight ranges is 1-2 ten thousand.
5, the preparation method of stable chitin derivatives fluorescent quantal-points according to claim 2, it is characterized in that: used metal-salt precursor is analytically pure cadmium acetate, zinc acetate or plumbic acetate powder.
6, the preparation method of chitosan derivatives stable fluorescence quantum dot according to claim 2 is characterized in that: the sulfur family precursor that uses in the step (3) is sodium disulfide or sodium hydrogen selenide.
7, the preparation method of stable chitin derivatives fluorescent quantal-points according to claim 2, it is characterized in that: the semiconductor nano crystallite (quantum dot) that step (3) obtains comprises CdS, ZnS, PbS, CdSe, ZnSe, PbSe.
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Cited By (12)
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| WO2008043255A1 (en) * | 2006-09-18 | 2008-04-17 | Institute Of Process Engineering, Chinese Academy Of Sciences | Fluorescent microspheres, their preparing-method and uses |
| CN101962450A (en) * | 2010-10-20 | 2011-02-02 | 武汉大学 | Aqueous phase preparation method for chitosan-quantum dot fluorescent probe |
| CN101980005A (en) * | 2010-10-20 | 2011-02-23 | 武汉市疾病预防控制中心 | Method for marking canine kidney cells through chitosan-quantum dot fluorescent probe |
| CN101008642B (en) * | 2007-01-25 | 2011-04-13 | 上海交通大学 | Preparation method of nanometer semiconductor biocompatible materials |
| CN102053151A (en) * | 2010-10-26 | 2011-05-11 | 华南理工大学 | Fluorescent probe and method for rapidly detecting staphylococcus aureus by using same |
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| CN103224654A (en) * | 2013-05-02 | 2013-07-31 | 上海交通大学 | Silver sulfide quantum dot-chitosan nanometer complex preparation method |
| CN110220873A (en) * | 2019-03-25 | 2019-09-10 | 浙江大学 | A kind of preparation method of FITC label chitosan fluorescent slurry |
| CN111661826A (en) * | 2020-06-04 | 2020-09-15 | 南京耶拿光电技术有限公司 | High heat-resistant zinc selenide material and preparation method thereof |
| CN112494517A (en) * | 2020-12-15 | 2021-03-16 | 中南民族大学 | Fluorescent antibacterial carbon dot, and preparation method and application thereof |
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- 2006-03-29 CN CNB2006100186576A patent/CN100497516C/en not_active Expired - Fee Related
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| US8460638B2 (en) | 2006-09-18 | 2013-06-11 | Institute of Process Engineering, Chinese Academy od Science | Method of imaging with fluorescent microspheres |
| WO2008043255A1 (en) * | 2006-09-18 | 2008-04-17 | Institute Of Process Engineering, Chinese Academy Of Sciences | Fluorescent microspheres, their preparing-method and uses |
| CN101008642B (en) * | 2007-01-25 | 2011-04-13 | 上海交通大学 | Preparation method of nanometer semiconductor biocompatible materials |
| CN101962450A (en) * | 2010-10-20 | 2011-02-02 | 武汉大学 | Aqueous phase preparation method for chitosan-quantum dot fluorescent probe |
| CN101980005A (en) * | 2010-10-20 | 2011-02-23 | 武汉市疾病预防控制中心 | Method for marking canine kidney cells through chitosan-quantum dot fluorescent probe |
| CN101980005B (en) * | 2010-10-20 | 2011-11-30 | 武汉市疾病预防控制中心 | Method for marking canine kidney cells through chitosan-quantum dot fluorescent probe |
| CN101962450B (en) * | 2010-10-20 | 2012-08-29 | 武汉大学 | Aqueous phase preparation method for chitosan-quantum dot fluorescent probe |
| CN102053151A (en) * | 2010-10-26 | 2011-05-11 | 华南理工大学 | Fluorescent probe and method for rapidly detecting staphylococcus aureus by using same |
| CN102274002B (en) * | 2011-04-26 | 2014-02-26 | 中国药科大学 | In-situ tumor nondestructive detection kit and preparation method thereof |
| CN102274002A (en) * | 2011-04-26 | 2011-12-14 | 中国药科大学 | In-situ tumor nondestructive detection kit and preparation method thereof |
| CN102516606A (en) * | 2011-11-25 | 2012-06-27 | 上海交通大学 | Preparation method of nitrogen oxide donor - quantum dots compound |
| CN102516606B (en) * | 2011-11-25 | 2014-08-20 | 上海交通大学 | Preparation method of nitrogen oxide donor - quantum dots compound |
| CN103204634A (en) * | 2013-03-15 | 2013-07-17 | 北京科技大学 | Method for manufacturing semiconductor sulfide biopolymer nano-composite film |
| CN103204634B (en) * | 2013-03-15 | 2014-12-17 | 北京科技大学 | Method for manufacturing semiconductor sulfide biopolymer nano-composite film |
| CN103224654A (en) * | 2013-05-02 | 2013-07-31 | 上海交通大学 | Silver sulfide quantum dot-chitosan nanometer complex preparation method |
| CN103224654B (en) * | 2013-05-02 | 2015-07-08 | 上海交通大学 | Silver sulfide quantum dot-chitosan nanometer complex preparation method |
| CN110220873A (en) * | 2019-03-25 | 2019-09-10 | 浙江大学 | A kind of preparation method of FITC label chitosan fluorescent slurry |
| CN111661826A (en) * | 2020-06-04 | 2020-09-15 | 南京耶拿光电技术有限公司 | High heat-resistant zinc selenide material and preparation method thereof |
| CN111661826B (en) * | 2020-06-04 | 2022-05-24 | 南京耶拿光电技术有限公司 | High heat-resistant zinc selenide material and preparation method thereof |
| CN112494517A (en) * | 2020-12-15 | 2021-03-16 | 中南民族大学 | Fluorescent antibacterial carbon dot, and preparation method and application thereof |
| CN112494517B (en) * | 2020-12-15 | 2022-07-15 | 中南民族大学 | Fluorescent antibacterial carbon dot, and preparation method and application thereof |
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