CN101402858A - Process for producing low-toxicity fluorescent carbon point - Google Patents
Process for producing low-toxicity fluorescent carbon point Download PDFInfo
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- CN101402858A CN101402858A CNA2008101976951A CN200810197695A CN101402858A CN 101402858 A CN101402858 A CN 101402858A CN A2008101976951 A CNA2008101976951 A CN A2008101976951A CN 200810197695 A CN200810197695 A CN 200810197695A CN 101402858 A CN101402858 A CN 101402858A
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Abstract
The invention provides a preparation method for a low-toxic fluorescence carbon point. The method comprises the steps as follows: a washed carbon electrode is added into an electrolyte liquid and oxidation is carried out on the carbon electrode by a constant potential electrolytic oxidation method at a more positive potential position; then the carbon electrode after being oxidized is washed by ultra-pure water; the water liquid after washing is collected; the electrolyte liquid and the water liquid after washing are combined and centrifugated for collecting supernatant and removing the deposits; finally the collected supernatant is filtered in sequence by ultrafilter pipes the retained molecular weights of which are respectively 30, 10 and 5kDa; the components with the retained molecular weights of 5-10kDa and less than 5kDa are collected, wherein, the component of the retained molecular weight of 5-10kDa is the carbon point which gives out yellow fluorescence; and the component less than 5kDa is the carbon point which gives out blue fluorescence. The method is simple and easy to carry; the material resources are broad and cheap; and the obtained carbon points do not have cytotoxicity and resist light bleaching.
Description
Technical field
The present invention relates to a kind of preparation method of low-toxicity fluorescent carbon point, belong to chemistry and material science.
Background technology
In recent years, (strong as fluorescence intensity, excitation wavelength range is wide, can realize the polynary emission of an elementary excitation because of its unique fluorescence property for fluorescence semiconductor quantum dots, emission peak peak width at half height very narrow (about 20nm), emission wavelength is controlled, fast light float etc.) and receive much concern, at cell imaging, the living organisms mark, foranalysis of nucleic acids and detection, protein analysis and detection, aspects such as ion probe have obtained widespread use.But, at present the fluorescence semiconductor quantum dots that uses mainly be II B and VI A family elementary composition as: CdSe@ZnS, CdTe etc., Cd
2+Existence the environment structure potential is threatened.Although by behind quantum dot coated outside ZnS or hydrophilic shell, quantum dot on cell proliferation and developmental potency do not show toxicity, but when the shell of quantum dot is unstable, because atmospheric oxidation or ultraviolet damage can make the lattice surface of quantum dot be damaged, thereby cause Cd
2+Discharge, bring cytotoxicity and environmental pollution.Except cytotoxicity and environmental pollution, the preparation process of quantum dot is also more loaded down with trivial details.At present, the preparation of the quantum dot of high-fluorescence quantum yield generally all will be carried out in anhydrous and oxygen-free, high temperature, organic solvent, and severe reaction conditions makes technology of preparing only grasp in minority seminar, also fails to obtain to promote, and this has also limited its application undoubtedly.Therefore, seek nontoxic, environmental friendliness, the simple fluorescence of preparation method receives meter particle to become the task of top priority in biomarker field.
In the recent period, the carbon nano-particle (carbon point) with fluorescent characteristic has been successfully applied to cell marking, and does not show cytotoxicity, therefore might replace the quantum dot of being made up of heavy metal element, is applied to fields such as biomarker, cancer diagnosis.At present, the preparation method of fluorescent carbon point mainly contains nitric acid oxidation method and electrochemistry cyclic voltammetric oxidation style.Nitric acid oxidation method is consuming time many and carbon point that prepare is not easily separated, and fluorescence quantum yield is very low, and the fluorescence spectrum half-peak is wide.And the material that electrochemistry cyclic voltammetric oxidation style is fit to only is a carbon nanotube, the material price costliness, and can only in organic phase, prepare, can only obtain a kind of fluorescent carbon point of color.Therefore the application that will promote carbon point prepares fluorescent carbon point with regard to seeking simpler, more economical method.
Summary of the invention
For the preparation method that simplifies fluorescent carbon point, reduce cost, the invention provides a kind of preparation method of low-toxicity fluorescent carbon point, this method is the novel method for preparing fluorescent carbon point with the electrochemical oxidation carbon dioxide process carbon electrode, this method is simple, material source is extensively cheap, the carbon point no cytotoxicity of gained, fast light floating.
Realize that the technical scheme that the object of the invention adopted is, as follows carbon dioxide process carbon electrode carried out electrochemical oxidation and handle, obtain hypotoxic fluorescent carbon point:
(1) carbon dioxide process carbon electrode is cleaned;
(2) cleaned carbon dioxide process carbon electrode is placed electrolyte solution, with the platinum electrode is supporting electrode, with the saturated calomel electrode is reference electrode, in the potentiostatic deposition oxidation style carbon dioxide process carbon electrode being carried out oxidation than the positive potential place, used constant potential with respect to saturated calomel electrode between 1.5-10V;
(3) carbon dioxide process carbon electrode after the oxidation is clean with ultrapure water drip washing, the aqueous solution after the collection drip washing;
(4) aqueous solution in the electrolyte solution in the merging (2) and (3) is centrifugal, collects supernatant, removes precipitation;
(5) supernatant of collecting is respectively 30,10 with molecular weight cut-off, the ultrafiltration pipe ultrafiltration successively of 5kDa, collect molecular weight cut-off and be 5-10kDa and＜component of 5kDa, wherein, molecular weight cut-off is the carbon point of the component of 5-10kDa for jaundice look fluorescence, and the component of＜5kDa is the carbon point of look fluorescence of turning blue.
Wherein, the material of used carbon dioxide process carbon electrode is glass carbon, graphite and/or carbon fiber.Used electrolyte solution is the oxysalt solution of pH value between 2-11.
As shown from the above technical solution, the present invention utilizes potentiostatic deposition oxidation style (promptly working electrode is applied a constant voltage and carry out electrolytic oxidation), by carbon dioxide process carbon electrode being placed electrolyte solution, prepare the carbon point of hypotoxic jaundice look fluorescence and blue-fluorescence in carbon dioxide process carbon electrode being carried out oxidation than positive potential place potentiostatic deposition.This method is easy and simple to handle, weak point consuming time, and the instrument of use is simple, starting material wide material sources cheapness, so preparation cost is low, all can finish at general chemical laboratory.
Embodiment
Below with carbon electrode material be respectively carbon fiber, graphite is that example is done detailed explanation to preparing hypotoxic fluorescent carbon point, the material of carbon dioxide process carbon electrode also can be glass carbon among the embodiment.
Embodiment 1
(1) multi-strand carbon fiber is cut into 4-5cm length, an end is fixed on the graphite for spectroanalysis with sealing compound, uses ultrapure water drip washing.
(2) cleaned carbon fiber electrode is put into filled about 1mol, the pH value is in the platinum beaker of 4.5 sodium dihydrogen phosphate, with platinum beaker electrode is supporting electrode, with saturated calomel electrode (SCE) is reference electrode, with respect to the positive 2V current potential of saturated calomel electrode place's potentiostatic deposition oxidation 120 minutes.
(3) carbon fiber electrode after the oxidation is clean with ultrapure water drip washing, the aqueous solution colourless get final product of drip washing to the drip washing usually, the aqueous solution after the collection drip washing.
(4) merge in (2) aqueous solution in sodium dihydrogen phosphate and (3), under RCF 28000g centrifugal force centrifugal 0.5-1 hour.Collect supernatant, remove precipitation.
(5) supernatant of collecting is respectively 30,10 with molecular weight cut-off, ultrafiltration pipe (Millipore) ultrafiltration successively of 5kDa, collect molecular weight cut-off and be 5-10kDa and＜component of 5kDa.Wherein, molecular weight cut-off is the carbon point of the component of 5-10kDa for jaundice look fluorescence, and the component of＜5kDa is the carbon point of look fluorescence of turning blue.
Embodiment 2
(1) with graphite for spectroanalysis ultrasonic cleaning in dehydrated alcohol and ultrapure water successively, dries up through nitrogen;
(2) cleaned graphite for spectroanalysis is put into filled 0.1mol/L, the pH value is in the platinum beaker of 10.2 disodium phosphate soln, with platinum beaker electrode is supporting electrode, with saturated calomel electrode (SCE) is reference electrode, with respect to the positive 9V current potential of saturated calomel electrode place's potentiostatic deposition oxidation 60 minutes.
(3) graphite for spectroanalysis after the oxidation is clean with ultrapure water drip washing, the aqueous solution colourless get final product of drip washing to the drip washing usually, the aqueous solution after the collection drip washing.
(4) merge in (2) aqueous solution in disodium phosphate soln and (3), under RCF 28000g centrifugal force centrifugal 0.5-1 hour.Collect supernatant, remove precipitation.
(5) supernatant of collecting is respectively 30,10 with molecular weight cut-off, ultrafiltration pipe (Millipore) ultrafiltration successively of 5kDa, collect molecular weight cut-off and be 5-10kDa and＜component of 5kDa.Wherein, molecular weight cut-off is the carbon point of the component of 5-10kDa for jaundice look fluorescence, and the component of＜5kDa is the carbon point of look fluorescence of turning blue.
Claims (4)
1. the preparation method of a low-toxicity fluorescent carbon point is characterized in that adopting following steps that carbon dioxide process carbon electrode is carried out electrochemical oxidation and handles, and obtains hypotoxic fluorescent carbon point:
(1) carbon dioxide process carbon electrode is cleaned;
(2) cleaned carbon dioxide process carbon electrode is placed electrolyte solution, with the platinum electrode is supporting electrode, with the saturated calomel electrode is reference electrode, in the potentiostatic deposition oxidation style carbon dioxide process carbon electrode being carried out oxidation than the positive potential place, used constant potential with respect to saturated calomel electrode between 1.5-10V;
(3) carbon dioxide process carbon electrode after the oxidation is clean with ultrapure water drip washing, the aqueous solution after the collection drip washing;
(4) aqueous solution in the electrolyte solution in the merging (2) and (3) is centrifugal, collects supernatant, removes precipitation;
(5) supernatant of collecting is respectively 30,10 with molecular weight cut-off, the ultrafiltration pipe ultrafiltration successively of 5kDa, collect molecular weight cut-off and be 5-10kDa and＜component of 5kDa, wherein, molecular weight cut-off is the carbon point of the component of 5-10kDa for jaundice look fluorescence, and the component of＜5kDa is the carbon point of look fluorescence of turning blue.
2. according to the preparation method of the described low-toxicity fluorescent carbon point of claim 1, it is characterized in that: the material of used carbon dioxide process carbon electrode is glass carbon, graphite and/or carbon fiber.
3. according to the preparation method of the described low-toxicity fluorescent carbon point of claim 1, it is characterized in that: electrolyte solution is the oxysalt solution of pH value between 2-11 in the step (2).
4. according to the preparation method of the described low-toxicity fluorescent carbon point of claim 3, it is characterized in that: electrolyte solution is phosphate solution, nitrate solution, sulfate liquor, acetate solution.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973541A (en) * | 2010-10-11 | 2011-02-16 | 福州大学 | Method for extracting carbon quantum dots from activated carbon |
| CN101982519A (en) * | 2010-10-22 | 2011-03-02 | 张淑英 | Preparation method of non-toxic fluorescent material |
| CN102492421A (en) * | 2011-11-11 | 2012-06-13 | 武汉大学 | Method for preparing fluorescence carbon points in controlled manner |
| CN102583307A (en) * | 2012-01-17 | 2012-07-18 | 南京工业大学 | Fluorescent carbon quantum dots extracted from eggs and preparation method and application thereof |
| CN102604629A (en) * | 2012-02-08 | 2012-07-25 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation method and applications of amino carbon quantum dots |
| CN102899677A (en) * | 2012-10-24 | 2013-01-30 | 湖北大学 | Method for electrochemically synthesizing ionic liquid/carbon dot gel in one step |
| CN103449404A (en) * | 2013-08-27 | 2013-12-18 | 湖南师范大学 | Method for preparing fluorescent carbon dots (C-dots) from alcohol through electrochemical carbonization |
| CN104386665A (en) * | 2014-10-09 | 2015-03-04 | 华东理工大学 | Preparation method and bioapplication of single photon/double photon amorphous carbon dot |
| CN104611715A (en) * | 2015-02-05 | 2015-05-13 | 青岛大学 | Method for preparing carbon dots based on carbon-printed electrodes on chip |
| CN105044071A (en) * | 2015-08-18 | 2015-11-11 | 太原理工大学 | Method for detecting Hg<2+> of clean water by using nitrogen-doped carbon dots |
| CN105295910A (en) * | 2015-11-27 | 2016-02-03 | 中国科学院山西煤炭化学研究所 | Method for preparing red light carbon dots by taking biomass as precursor |
| CN105524613A (en) * | 2015-11-27 | 2016-04-27 | 中国科学院山西煤炭化学研究所 | Fluorescent carbon dots, and fused salt preparation method and application thereof |
| CN105602558A (en) * | 2016-03-03 | 2016-05-25 | 东南大学 | Fluorescent carbon dot narrow in full width at half maximum and preparation method and application thereof |
| CN105733573A (en) * | 2015-09-24 | 2016-07-06 | 中国石油大学(华东) | Electrolytic and nitrogen-doping one-step method for preparing petroleum coke-based carbon quantum dots |
| CN106947475A (en) * | 2017-03-30 | 2017-07-14 | 皖西学院 | Al in fluorescent carbon quantum dot preparation method and its detection water3+Ion application |
| CN108033437A (en) * | 2017-12-08 | 2018-05-15 | 中国矿业大学 | A kind of quick method for preparing carbon dots of salt auxiliary |
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2008
- 2008-11-19 CN CNA2008101976951A patent/CN101402858A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973541A (en) * | 2010-10-11 | 2011-02-16 | 福州大学 | Method for extracting carbon quantum dots from activated carbon |
| CN101982519A (en) * | 2010-10-22 | 2011-03-02 | 张淑英 | Preparation method of non-toxic fluorescent material |
| CN101982519B (en) * | 2010-10-22 | 2013-09-25 | 张淑英 | Preparation method of non-toxic fluorescent material |
| CN102492421A (en) * | 2011-11-11 | 2012-06-13 | 武汉大学 | Method for preparing fluorescence carbon points in controlled manner |
| CN102583307A (en) * | 2012-01-17 | 2012-07-18 | 南京工业大学 | Fluorescent carbon quantum dots extracted from eggs and preparation method and application thereof |
| CN102583307B (en) * | 2012-01-17 | 2013-08-21 | 南京工业大学 | Fluorescent carbon quantum dots extracted from eggs and preparation method and application thereof |
| CN102604629A (en) * | 2012-02-08 | 2012-07-25 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation method and applications of amino carbon quantum dots |
| CN102899677A (en) * | 2012-10-24 | 2013-01-30 | 湖北大学 | Method for electrochemically synthesizing ionic liquid/carbon dot gel in one step |
| CN103449404B (en) * | 2013-08-27 | 2016-04-27 | 湖南师范大学 | The method of fluorescent carbon point is prepared in the carbonization of a kind of alcohol electrochemistry |
| CN103449404A (en) * | 2013-08-27 | 2013-12-18 | 湖南师范大学 | Method for preparing fluorescent carbon dots (C-dots) from alcohol through electrochemical carbonization |
| CN104386665A (en) * | 2014-10-09 | 2015-03-04 | 华东理工大学 | Preparation method and bioapplication of single photon/double photon amorphous carbon dot |
| CN104611715A (en) * | 2015-02-05 | 2015-05-13 | 青岛大学 | Method for preparing carbon dots based on carbon-printed electrodes on chip |
| CN104611715B (en) * | 2015-02-05 | 2017-06-13 | 青岛大学 | A kind of method for preparing carbon quantum dot that printed electrode based on carbon on chip |
| CN105044071A (en) * | 2015-08-18 | 2015-11-11 | 太原理工大学 | Method for detecting Hg<2+> of clean water by using nitrogen-doped carbon dots |
| CN105733573A (en) * | 2015-09-24 | 2016-07-06 | 中国石油大学(华东) | Electrolytic and nitrogen-doping one-step method for preparing petroleum coke-based carbon quantum dots |
| CN105733573B (en) * | 2015-09-24 | 2018-11-06 | 中国石油大学(华东) | Electrolysis nitrating one-step method prepares petroleum coke base carbon quantum dot |
| CN105295910A (en) * | 2015-11-27 | 2016-02-03 | 中国科学院山西煤炭化学研究所 | Method for preparing red light carbon dots by taking biomass as precursor |
| CN105524613A (en) * | 2015-11-27 | 2016-04-27 | 中国科学院山西煤炭化学研究所 | Fluorescent carbon dots, and fused salt preparation method and application thereof |
| CN105602558A (en) * | 2016-03-03 | 2016-05-25 | 东南大学 | Fluorescent carbon dot narrow in full width at half maximum and preparation method and application thereof |
| CN106947475A (en) * | 2017-03-30 | 2017-07-14 | 皖西学院 | Al in fluorescent carbon quantum dot preparation method and its detection water3+Ion application |
| CN108033437A (en) * | 2017-12-08 | 2018-05-15 | 中国矿业大学 | A kind of quick method for preparing carbon dots of salt auxiliary |
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