CN103881070A - Preparation method of tartaric acid and citric acid compound nitrogen-doped fluorescent polymer nano point - Google Patents
Preparation method of tartaric acid and citric acid compound nitrogen-doped fluorescent polymer nano point Download PDFInfo
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- CN103881070A CN103881070A CN201410109451.9A CN201410109451A CN103881070A CN 103881070 A CN103881070 A CN 103881070A CN 201410109451 A CN201410109451 A CN 201410109451A CN 103881070 A CN103881070 A CN 103881070A
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Abstract
The invention discloses a novel synthesis of a fluorescent polymer nano point. By adopting natural products of tartaric acid and citric acid as raw materials, the nitrogen-doped fluorescent polymer nano point is prepared through a reaction with ethanediamine in oleic acid, and a synthesis product is subjected to infrared characterization, ultraviolet characterization, fluorescence characterization, circular dichroism characterization, NMR characterization and a TEM characterization, the quantum yield of the synthesis product is capable of reaching 48.7 percent maximally, and a CD signal is achieved, and thus a method for synthesizing the fluorescent polymer nano point by using a non-fluorescence raw material with biocompatibility is provided.
Description
Technical field
Patent of the present invention relates to the preparation method of a kind of tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point.
Background technology
In recent years, fluorescent polymer has caused people's extensive concern in the application of the aspects such as fluorescence chemical sensor, fluoroscopic visualization, pharmaceutical carrier, fluorescent probe.Fluorescent polymer can be divided into water-soluble, water-insoluble and amphiphilic fluorescent polymer three classes by solubility property, can pass through the approach such as fluorescent functional monomer polymerization, fluorescent chemicals and polymer chemistry bonding, non-fluorescent functional monomer polymerization synthetic.Compared with fluorescence organic molecule, the optical pickocff based on polymkeric substance has and is easily prepared into the advantages such as membrane module, response signal are large, high and identification selection is good to detection substrate bonding efficiency.In the synthetic method of the fluorescent polymer of having reported, generally all adopt the raw material with conjugate ring, this also makes fluorescent polymer have potential bio-toxicity.Prepare inexpensive, durable, biocompatibility or biodegradable fluorescent polymer sensor and be still a challenge.
Prior art scheme
The synthetic method of fluorescent polymer has:
(1) fluorescent chemicals is that initiator is prepared fluorescent polymer.Fluorophore can be introduced to the polymer end of the chain by the initiator initiated polymerization with fluorophore, to prepare fluorescent polymer.
(2) fluorescent chemicals is that chain-transfer agent is prepared fluorescent polymer.The organic molecule that utilization contains fluorophore is introduced the polymer end of the chain as chain-transfer agent by fluorophore, prepares fluorescent polymer.
(3) prepare fluorescent polymer based on fluorescent functional monomer.One of the most frequently used method of synthetic fluorescent polymer by polymerisable fluorescent functional monomer homopolymerization, copolymerization or polycondensation.
(4) chemical bonding of fluorescent chemicals and polymkeric substance is prepared fluorescent polymer.The chemical bonding of fluorescent chemicals and polymkeric substance is one of effective ways of synthetic fluorescent polymer.
(5) fluorescent polymer is prepared in non-fluorescent functional monomer polymerization.As utilize the synthetic fluorescent polymers such as Resorcinol.
The shortcoming of prior art:
(1) front four kinds of methods of synthetic fluorescent polymer all need to use the raw material with fluorophore, and these raw materials are often all with large conjugated structure, have potential bio-toxicity.
(2) utilize non-fluorescent functional monomer polymerization to prepare in the method for fluorescent polymer, effective ways are few, synthetic route trouble, and raw material often also has larger toxicity.
Summary of the invention
The object of patent of the present invention is to provide the preparation method of a kind of tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point, it is characterized in that comprising the following steps:
Step 1, takes raw material
Take 1.5-3.0g L-TARTARIC ACID and 0-1.5g citric acid in three-necked bottle;
Step 2, reacting by heating
10-30ml oleic acid and 0.3-5ml quadrol are added in the three-necked bottle in step 1, be heated to while stirring 180-250 degree, stopped reaction after insulation 10-60min, pours the reaction solution in three-necked bottle in beaker into after reaction stops while hot, and the speed of described heating is 15 ℃/min.
Step 3, washing
Prepared step 2 reaction solution is fully washed with normal hexane, ethanol and three kinds of washingss of chloroform successively, three kinds of each washings 5 times of washings, 10 milliliters of each consumptions, filter and obtain sample after immersion 10min.
Step 4, dry
To in step 3, make final product through the sample of fully washing in 50 ℃ of vacuum-dryings.
Tartrate described in step 1 is selected from L-TARTARIC ACID or D-tartrate.
The fluorescence quantum yield of the final product obtaining is 48.7%.
The final product obtaining is blue light-emitting or blue green light under 365nm UV-irradiation.
Beneficial effect:
1, raw material tartrate and citric acid are natural product, have biocompatibility.
2, use oleic acid as solvent, temperature of reaction is suitable.
3, method is easy to operate, easily amplifies, and product fluorescence quantum yield can reach 48.7%.
4, process NIH3T3 cell with synthetic fluorescent polymer nano dot, from processing, CCK8 detects the data of cell viability, final concentration during lower than 50 μ g/ml cytotoxicity not obvious.Laser confocal microscope analysis shows, fluorescent polymer nano dot can enter cell, can be used for cell imaging.
Accompanying drawing explanation
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Fig. 1 is uv-absorbing spectrogram of the present invention, excitation wavelength dependency fluorescent emission spectrogram;
Fig. 2 is TEM figure of the present invention.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
A preparation method for tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point, is characterized in that comprising the following steps:
Step 1, takes raw material
Take 1.5-3.0g L-TARTARIC ACID and 0-1.5g citric acid in three-necked bottle;
Step 2, reacting by heating
10-30ml oleic acid and 0.3-5ml quadrol are added in the three-necked bottle in step 1, be heated to while stirring 180-250 degree, stopped reaction after insulation 10-60min, pours the reaction solution in three-necked bottle in beaker into after reaction stops while hot, and the speed of described heating is 15 ℃/min.
Step 3, washing
Prepared step 2 reaction solution is fully washed with normal hexane, ethanol and three kinds of washingss of chloroform successively, three kinds of each washings 5 times of washings, 10 milliliters of each consumptions, filter and obtain sample after immersion 10min.
Step 4, dry
To in step 3, make final product through the sample of fully washing in 50 ℃ of vacuum-dryings.
Tartrate described in step 1 is selected from L-TARTARIC ACID or D-tartrate.
The fluorescence quantum yield of the final product obtaining is 48.7%.
The final product obtaining is blue light-emitting or blue green light under 365nm UV-irradiation.
The fluorescence quantum yield of tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point is at room temperature measured, and take Quinine Sulphate Di HC, (solvent is as the H of 0.1M
2sO
4, quantum yield is 0.54) and as reference substance, the ultraviolet absorption value under Fluorescence integral intensity and this excitation wavelength obtaining under identical shooting conditions by the dilute solution of measurement polymkeric substance and reference material, calculates fluorescence quantum yield.Product is all dissolved in ultrapure water.Calculation formula is:
The quantum yield that wherein Φ is determinand, subscript R represents reference substance.I is Fluorescence integral intensity, and A is ultraviolet absorption value.η is solvent specific refractory power.General requirement absorbance A, A
rall be less than 0.1.The fluorescence quantum yield that records tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point with this method reaches as high as 48.7%.Fig. 1 is uv-absorbing spectrogram, excitation wavelength dependency fluorescent emission spectrogram and the 365nm uv irradiating figure of synthetic product, and synthetic product is blue light-emitting under 365nm UV-irradiation.Fig. 2 is the typical TEM figure of synthetic product.Circular dichroism spectrum shows, synthetic product still has CD signal, illustrates that chiral structure obtains certain reservation.
Process NIH3T3 cell with synthetic fluorescent polymer nano dot, from processing, CCK8 detects the data of cell viability, final concentration during lower than 50 μ g/ml cytotoxicity not obvious.
Laser confocal microscope analysis shows, fluorescent polymer nano dot can enter cell, can be used for cell imaging.
Embodiment 1
Take 1.5g citric acid and 1.5g L-TARTARIC ACID in three-necked bottle, then add 30ml oleic acid and 5ml quadrol, stirring heating, temperature is made as 220 degree.Temperature rises to 150 dissolution of solids while spending, and solution comes to life, and color gradually becomes brown by colourless, along with the chocolate that becomes of reaction.Stopped reaction after 30min, pours out reaction solution while hot, and product fully washs with normal hexane, ethanol and chloroform successively, in 50 degree vacuum-dryings, obtains tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point.
Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (4)
1. a preparation method for tartrate and citric acid composite nitrogen doping fluorescent polymer nanocomposite point, is characterized in that comprising the following steps:
Step 1, takes raw material
Take 1.5-3.0g L-TARTARIC ACID and 0-1.5g citric acid in three-necked bottle;
Step 2, reacting by heating
10-30ml oleic acid and 0.3-5ml quadrol are added in the three-necked bottle in step 1, be heated to while stirring 180-250 degree, stopped reaction after insulation 10-60min, pours the reaction solution in three-necked bottle in beaker into after reaction stops while hot, and the speed of described heating is 15 ℃/min;
Step 3, washing
Prepared step 2 reaction solution is fully washed with normal hexane, ethanol and three kinds of washingss of chloroform successively, three kinds of each washings 5 times of washings, 10 milliliters of each consumptions, filter and obtain sample after immersion 10min;
Step 4, dry
To in step 3, make final product through the sample of fully washing in 50 ℃ of vacuum-dryings.
2. the preparation method of a kind of tartrate as claimed in claim 1 and citric acid composite nitrogen doping fluorescent polymer nanocomposite point, is characterized in that tartrate described in step 1 is selected from L-TARTARIC ACID or D-tartrate.
3. the preparation method of a kind of tartrate as claimed in claim 1 and citric acid composite nitrogen doping fluorescent polymer nanocomposite point, the fluorescence quantum yield that it is characterized in that obtained final product is 48.7%.
4. the preparation method of a kind of tartrate as claimed in claim 1 and citric acid composite nitrogen doping fluorescent polymer nanocomposite point, is characterized in that obtained final product blue light-emitting or blue green light under 365nm UV-irradiation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945621A (en) * | 2015-06-23 | 2015-09-30 | 闽南师范大学 | Preparation method of phenylalanine and citric acid composited silicon-doped fluorescent nanometer point |
| CN105038768A (en) * | 2015-07-14 | 2015-11-11 | 闽南师范大学 | Cysteine and citric acid derivative fluorescent powder and preparation method therefor |
| CN109580570A (en) * | 2019-01-02 | 2019-04-05 | 齐鲁工业大学 | A kind of biological tissue's fluorescence microscopic analysis method |
Citations (1)
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| CN103435730A (en) * | 2013-07-30 | 2013-12-11 | 湖南科技大学 | Water-dispersible fluorescent polymer nano particle with copper ion and negative sulfur ion identification function, and preparation method and application of water-dispersible fluorescent polymer nano particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435730A (en) * | 2013-07-30 | 2013-12-11 | 湖南科技大学 | Water-dispersible fluorescent polymer nano particle with copper ion and negative sulfur ion identification function, and preparation method and application of water-dispersible fluorescent polymer nano particle |
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| 陈建等: ""一步法制备新型荧光聚合物纳米粒子"", 《合成材料老化与应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945621A (en) * | 2015-06-23 | 2015-09-30 | 闽南师范大学 | Preparation method of phenylalanine and citric acid composited silicon-doped fluorescent nanometer point |
| CN105038768A (en) * | 2015-07-14 | 2015-11-11 | 闽南师范大学 | Cysteine and citric acid derivative fluorescent powder and preparation method therefor |
| CN109580570A (en) * | 2019-01-02 | 2019-04-05 | 齐鲁工业大学 | A kind of biological tissue's fluorescence microscopic analysis method |
| CN109580570B (en) * | 2019-01-02 | 2021-03-12 | 齐鲁工业大学 | Biological tissue fluorescence microscopic analysis method |
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