CN104787745A - New preparation method of fluorescent carbon nanoparticles and application in biological samples - Google Patents
New preparation method of fluorescent carbon nanoparticles and application in biological samples Download PDFInfo
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- CN104787745A CN104787745A CN201410022384.7A CN201410022384A CN104787745A CN 104787745 A CN104787745 A CN 104787745A CN 201410022384 A CN201410022384 A CN 201410022384A CN 104787745 A CN104787745 A CN 104787745A
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Abstract
The invention relates to preparation of novel fluorescent carbon nanoparticles and an application in biological samples and belongs to the technical field of pharmaceutical analysis. By a phosphorus pentoxide dehydration method, a carbohydrate compound is used as a carbon source and reactants are simply mixed to prepare carbon nanoparticles with fluorescent property by a one-step method. The preparation process is a process of a spontaneous reaction. Without external heating or complex operations, a lot of carbon nanoparticles can be rapidly produced. The prepared carbon nanoparticles are characterized in that emission wavelength is fixed and will not change with excitation wavelength. In a phosphate buffered solution, fluorescence intensity of the carbon nanoparticles is obviously reduced with increasing of concentration of quercetin, and influence of other coexisting substances on fluorescence intensity of the carbon nanoparticles is little. Under optimized conditions, a good linear relationship between fluorescence intensity of the carbon nanoparticles and the concentration of quercetin is shown. The preparation method is pollution-free, simple, reliable and low-cost, and the prepared fluorescent carbon nanoparticles have a wide application prospect in aspects of detection of traces of pharmaceuticals in complex biological samples and detection and control of heavy metal in the environment.
Description
Technical field
The invention belongs to pharmaceutical analysis technical field, be specifically related to the preparation of novel fluorescence carbon nano-particles, and it is applied directly to the analysis of trace medicine in complex biological sample.
Background technology
Quercetin is a kind of typical poly-hydroxy flavonoid compound, and this compound is being spent, leaf, and the fruit of bark and many kind of plant exists in a large number.In the past few years, because its many potential Beneficial Effect of seeming to human health, protection is comprised cardiovascular, antitumour activity; antiulcer action, antiallergic activity, antibacterial; antiviral activity and anti-inflammatory action, so, the interest that Quercetin has caused people huge.In clinical treatment, Quercetin etc. have larger side effect while performance result for the treatment of, therefore need to carry out Plasma Concentration detection or urine drug level detection.But due to lower at biological sample drug concentration, matrix contains protein, lipoid and other biological macromole also can cause certain interference to the detection of medicine, so need to carry out pre-treatment to biological sample simultaneously.This process not only consumes a large amount of organic solvent, spends a large amount of time, and needs expensive instrument to detect.Therefore, it is very important for exploring the appropriate means Quercetin detected in different sample.
Quantum dot is a kind of nano material of accurate zero dimension, and they have very good fluorescent stability, wider excitation spectrum and emmission spectrum, makes them have many potential application.But traditional quantum dot is made up of semiconductor material usually, and not only cost is high, and easily pollutes environment.The fluorescent carbon nano-particles of preparation not only can be used for the fluorescent mark of cell imaging, also can be used for photochemical catalysis, energy transformation/storage, bio-imaging, photoelectricity, the more promising field of sensor.Because the characteristic of the fluorescence that carbon nano-particles is stronger (FL), also can be used for analytical applications different in biological sample or environment measuring.The carbon nano-particle of high fluorescent is prepared in a large number by one-step synthesis, and these preparation methods comprise simple chemical oxidization method, thermal decomposition method, electrochemical process, microwave assisting method, ultrasonic method, and template and laser corrode method etc.Nowadays, microwave assisting method and hydrothermal synthesis method have become the method that people commonly use.Aforesaid method is prepared carbon quantum dot and is often needed heat, or needs the condition such as voltage, strong acid, and operate comparatively loaded down with trivial details, productive rate is lower, can not prepare carbon quantum dot in a large number; The fluorescence emission wavelengths of the carbon quantum dot of preparation changes with the change of excitation wavelength, and fluorescence emission wavelengths is unstable.
For the deficiencies in the prior art, the present invention aims to provide novel method prepared by a kind of fluorescent carbon nano-particles.The carbon nano-particles of preparation all has good consistency in organic solvent, inorganic solvent or biological sample.Selective enumeration method Quercetin can be used for as the effective fluorescent probe of one, thus can be used for the analysis of biological sample as urine sample Chinese traditional medicine, realize the detection of clinical medicine concentration.The advantage of this method is: reaction is simple, easy and simple to handle, quick, mild condition.
Summary of the invention
The invention provides novel method prepared by a kind of fluorescent carbon nano-particles, the fluorescent carbon nano-particles of preparation and polar solvent such as water or biological sample have good affinity.The fluorescent effect of carbon nano-particles, not by the impact of the biomacromolecules such as the lipid in sample, can directly apply to the analyzing and testing of trace medicine Quercetin in complex biological sample, thus substantially increase the processing efficiency of sample.
Fluorescent carbon nano-particles preparation of the present invention realizes by the following technical solutions, specifically comprises the steps:
(1) by the appropriate solubilize of a certain amount of sugar, ultrasonic about 10min, forms the sugar soln of homogeneous transparent; The sugar added and the mass ratio of solution are 1: 10 ~ 2: 1;
(2) joined in the reaction vessel filling 2.5 grams of oxygenants by the sugar soln that step (1) obtains, mixture reacts rapidly, and spontaneous heat release generates a large amount of foams, and liquor capacity expands, and color becomes brownish black, is then cooled to room temperature gradually; The mass ratio of sugar soln and oxygenant is: 3: 1 ~ 1: 2;
(3) the brownish black mixture that step (2) obtains is poured in suitable quantity of water, be uniformly mixed, ultrasonic 10min, then by mixed solution in the centrifugal 30min of 13000rmp, collect supernatant liquor, be positioned in dialysis tubing and dialyse to remove remaining sugar and ion with deionized water; Finally, the fluorescent carbon nano-particles in dialysis tubing is put in vacuum drying oven concentrates in 65 DEG C of vacuum-dryings.
In the present invention, the carbohydrate preparing settled solution described in step (1) is any one in glucose, fructose, sucrose, lactose, maltose, starch, Mierocrystalline cellulose, glycogen and wood sugar.
In the present invention, the solution described in step (1) is deionized water or spirituous solution, preferred deionized water.
In the present invention, the oxygenant described in step (2) is strong oxidizer.
In the present invention, the strong oxidizer described in step (2) is Vanadium Pentoxide in FLAKES or phosphorus trioxide, preferred Vanadium Pentoxide in FLAKES.
In the present invention, the reaction vessel relative response thing described in step (2) is the material of inertia, in glass or Teflon any one.
In the present invention, the purity of step (1) and the sugar described in (2) and oxygenant is all analytical pure.
In the present invention, the diameter of step (3) final product fluorescent carbon nano-particles is 20 ~ 150nm, can be used for the rapid detection of Quercetin medicine in the biological sample such as blood and urine, also can be used for the detection of heavy metal ion in environment.
Beneficial effect of the present invention:
The present invention adopts chemical oxidization method, is simply mixed by reactant, and single stage method preparation has the carbon nano-particles of hyperfluorescenceZeng Yongminggaoyingguang character.This preparation process is the process of a spontaneous reaction, does not also need complicated operation, namely can produce a large amount of carbon nanoparticles fast without the need to indirect heating; The feature of prepared carbon nano-particles is that its maximum emission wavelength is fixed, and does not change with the change of excitation wavelength.This preparation method green non-pollution, simple and reliable, cost is low, in the detection of fluorescent carbon nano-particles trace medicine in complex biological sample of preparation and environment heavy metal detection and control in have broad application prospects.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of gained fluorescent carbon nano-particles in the embodiment of the present invention 1;
Fig. 2 is the infrared spectrogram (FTIR) of gained fluorescent carbon nano-particles (b) and glucose (a) in the embodiment of the present invention 1.
Fig. 3 is UV spectrum and the fluorescence emission spectrogram (excitation wavelength is 370nm, 375nm, 380nm, 385nm, 390nm, 395nm, 400nm) of gained fluorescent carbon nano-particles in the embodiment of the present invention 1.
Embodiment
Provide specific embodiments of the invention below:
Example 1:
Being prepared as follows of fluorescent carbon nano-particles of the present invention:
(1) sugar soln preparation: take 0.5g glucose and join in 2mL deionized water, ultrasonic mixing 10min, forms the sugar soln of homogeneous transparent;
(2) fluorescent carbon nano-particles preparation: the sugar soln that step (1) obtains is joined and fills 2.5 grams of P
2o
5small beaker in, mixture reacts rapidly, and spontaneous heat release generates a large amount of foams, liquor capacity expand, color becomes brownish black, and after 10min, mixture is cooled to room temperature gradually;
(3) fluorescent carbon nano-particles purifying: the brownish black mixture that step (2) obtains is poured in suitable quantity of water, be uniformly mixed, ultrasonic 10min, then by mixed solution in the centrifugal 30min of 13000rmp, collect supernatant liquor, be positioned in dialysis tubing and dialyse to remove remaining sugar and ion with deionized water, finally, the fluorescent carbon nano-particles in dialysis tubing is put in vacuum drying oven and concentrates in 65 DEG C of vacuum-dryings.
Example 2:
(1) sugar soln preparation: take 0.5g sucrose and join in 2mL deionized water, ultrasonic mixing 10min, forms the sugar soln of homogeneous transparent;
(2) fluorescent carbon nano-particles preparation: the sugar soln that step (1) obtains is heated to 80 DEG C, joins and fill 2.5 grams of P
2o
3small beaker in, mixture reacts rapidly, and spontaneous heat release generates a large amount of foams, liquor capacity expand, color becomes brownish black, and after 10min, mixture is cooled to room temperature gradually;
(3) fluorescent carbon nano-particles purifying: the brownish black mixture that step (2) obtains is poured in suitable quantity of water, be uniformly mixed, ultrasonic 10min, then by mixed solution in the centrifugal 30min of 13000rmp, collect supernatant, be positioned in dialysis tubing and dialyse to remove remaining sugar and ion with deionized water, finally, the fluorescent carbon nano-particles in dialysis tubing is put in vacuum drying oven and concentrates in 65 DEG C of vacuum-dryings.
The fluorescent carbon nano-particles of synthesis is characterized:
As shown in Figure 1, nanoparticle is spherical in rule, and particle size range is 20 ~ 150nm for fluorescent carbon nano-particles configuration of surface prepared by above-mentioned example 1.The absorption peak of the infared spectrum of fluorescent carbon nano-particles and glucose is as shown in Figure 2: 3369cm
-1for the stretching vibration peak of O-H key in hydroxyl, 1636cm
-1place is C=O stretching vibration absorption peak.1047cm
-1belong to the C-O stretching vibration of glucose, and the C-O stretching vibration of fluorescent carbon nano-particles is at 1006cm
-1.These data show there is a large amount of carboxylic groups on the surface of fluorescent carbon nano-particles.As shown in Figure 3, fluorescent carbon nano-particles excites in UV, visible light optical range, and excitation wavelength is 370nm, 375nm, 380nm, 385nm, 390mm, 395nm, 400nm, with the increase of excitation wavelength, its fluorescence intensity weakens gradually, but fluorescence maximum emission wavelength is constant, is 438nm.
Example 3:
Fluorescent carbon nano-particles is used for the detection of Quercetin in urine
By the urine of 1.5mL healthy volunteer, adopt Quercetin standardized solution to carry out mark-on to it, be then diluted to 100 μ g/ml.In the volumetric flask of 5mL, add the fluorescent carbon nano-particles of 330 μ L, add target urine 100 μ L, be diluted to scale with the phosphate buffer soln that 0.01M, pH are 6.0, mixing is also ultrasonic.Adopt spectrophotofluorometer to carry out spectroscopic analysis after ultrasonic 22min, excitation wavelength is 370nm, excites and launch slit width to be all 5nm, at 300-700nm scope interscan fluorescence emission spectrum.Determine the concentration of Quercetin in sample solution, calculate the amount of Quercetin in solution.Correspondingly, do not add the experiment of target control group in urine to measure together yet.Experiment shows, carbon nano-particles is good dispersion property in biological sample urine, and can remove matrix composition complicated in urine to the interference of carbon nano-particles fluorescent emission, average recovery is 94.0 ~ 105.6%, relative standard deviation is 2.3%, obtains good effect.
Claims (8)
1. the novel method prepared of fluorescent carbon nano-particles, comprises the steps:
(1) by the appropriate solubilize of a certain amount of sugar, ultrasonic about 10min, forms the sugar soln of homogeneous transparent; The sugar added and the mass ratio of solution are 1: 10 ~ 2: 1;
(2) joined in the reaction vessel filling 2.5g oxygenant by the sugar soln that step (1) obtains, mixture reacts rapidly, and spontaneous heat release generates a large amount of foams, and liquor capacity expands, and color becomes brownish black, is then cooled to room temperature gradually; The mass ratio of sugar soln and oxygenant is: 3: 1 ~ 1: 2;
(3) the brownish black mixture that step (2) obtains is poured in suitable quantity of water, be uniformly mixed, ultrasonic 10min, then by mixed solution in the centrifugal 30min of 13000rmp, collect supernatant liquor, be positioned in dialysis tubing and dialyse to remove remaining sugar and ion with deionized water; Finally, the fluorescent carbon nano-particles in dialysis tubing is put in vacuum drying oven concentrates in 65 DEG C of vacuum-dryings.
2. the preparation method of fluorescent carbon nano-particles according to claim 1, the carbohydrate that it is characterized in that preparing described in step (1) settled solution is any one in glucose, fructose, sucrose, lactose, maltose, starch, Mierocrystalline cellulose, glycogen and wood sugar.
3. the preparation method of fluorescent carbon nano-particles according to claim 1, is characterized in that the solution described in step (1) is deionized water or spirituous solution, preferred deionized water.
4. the preparation method of fluorescent carbon nano-particles according to claim 1, is characterized in that the oxygenant described in step (2) is strong oxidizer.
5. the preparation method of fluorescent carbon nano-particles according to claim 1, is characterized in that the strong oxidizer described in step (2) is Vanadium Pentoxide in FLAKES or phosphorus trioxide, preferred Vanadium Pentoxide in FLAKES.
6. the preparation method of fluorescent carbon nano-particles according to claim 1, is characterized in that the reaction vessel relative response thing described in step (2) is the material of inertia, in glass or Teflon any one.
7. the preparation method of fluorescent carbon nano-particles according to claim 1, is characterized in that the purity of step (1) and the sugar described in (2) and oxygenant is all analytical pure.
8. the preparation method of fluorescent carbon nano-particles according to claim 1, it is characterized in that the diameter of step (3) final product fluorescent carbon nano-particles is 20 ~ 150nm, can be used for the rapid detection of Quercetin medicine in the biological sample such as blood and urine, also can be used for the detection of heavy metal ion in environment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105950145A (en) * | 2016-05-30 | 2016-09-21 | 山西大学 | Preparation method and application of phosphorus-doped fluorescent carbon quantum dots |
| CN108128767A (en) * | 2018-01-03 | 2018-06-08 | 辽宁大学 | A kind of method and its application that carbon quantum dot is quickly prepared in room temperature environment |
-
2014
- 2014-01-16 CN CN201410022384.7A patent/CN104787745A/en active Pending
Non-Patent Citations (4)
| Title |
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| SOMEN MONDAL ET AL.,: "Exploring the Interior of Hollow Fluorescent Carbon Nanoparticles", 《J.PHYS.CHEM.》 * |
| XIAOMING YANG ET AL.,: "One-pot synthesis of high fluorescent carbon nanoparticles and their applications as probes for detection of tetracyclines", 《BIOSENSORS AND BIOELECTRONICS》 * |
| YOUXING FANG ET AL.,: "Easy synthesis and imaging applications of cross-linked green fluorescent hollow carbon nanoparticles", 《ACS NANO》 * |
| 窦相南: "新型碳纳米材料的化学发光性能及其应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105950145A (en) * | 2016-05-30 | 2016-09-21 | 山西大学 | Preparation method and application of phosphorus-doped fluorescent carbon quantum dots |
| CN108128767A (en) * | 2018-01-03 | 2018-06-08 | 辽宁大学 | A kind of method and its application that carbon quantum dot is quickly prepared in room temperature environment |
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Application publication date: 20150722 |