CN107151555B - A kind of controllable luminous carbon nano-particles and preparation method and application - Google Patents

A kind of controllable luminous carbon nano-particles and preparation method and application Download PDF

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CN107151555B
CN107151555B CN201710482086.XA CN201710482086A CN107151555B CN 107151555 B CN107151555 B CN 107151555B CN 201710482086 A CN201710482086 A CN 201710482086A CN 107151555 B CN107151555 B CN 107151555B
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刘�文
刁海鹏
李婷婷
王浩江
张�荣
孙体健
张晓瑛
弓辉
李波
魏文珑
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Abstract

The invention belongs to the carbon nano-particles technical fields that shines, and in particular to a kind of controllable luminous carbon nano-particles and preparation method and application.A kind of controllable luminous carbon nano-particles of the present invention, it is made up of following steps: (1) drying fresh cloves petal, it is ground into powder, 1-2g is weighed in small beaker and deionized water 10mL, which is added, and then passes through that 0-3gNaOH solid is added and stirs dissolves it sufficiently, it is added in autoclave, is put into 150-250 DEG C of baking oven pyroreaction 3-5 hours;(2) cooling obtains brown or dark brown solution after reaction, and by centrifugation, then 0.22 μm of filter filtering dialyses 3 days in 500-1000D bag filter, obtains brown color or brown liquid is pure carbon nano-particles solution;(3) the carbon nano-particles solution vacuum freezedrying in step (2) is obtained into brown color or brown ceramic powder, that is, is purpose carbon nano-particles, it is soluble in water to issue strong blue or green fluorescence.

Description

A kind of controllable luminous carbon nano-particles and preparation method and application
Technical field
The invention belongs to the carbon nano-particles technical fields that shines, and in particular to a kind of controllable luminous carbon nano-particles and preparation Methods and applications.
Technical background
With the generation and development of nanotechnology, carbon material big family goes from strength to strength.Carbon nano-particles are big as carbon material Newcomer in family is a kind of unique Illuminant nanometer material, because its with partial size small (size is less than 10nm), toxicity It is low, the advantages that good water solubility, fluorescence property is excellent and photostability is strong and by the concern of researcher.Carbon nano-particles (Carbon Nanoparticles, CNPs) has been constantly subjected to the favor of researcher, relatively since 2004 find for the first time Some distinctive advantages have been embodied in traditional quantum dot (QDs) and fluorescent small molecule, comprising: compared with QDs, CDs has Preferable biocompatibility and environment friendly;Compared to organic fluorescent dye, CDs have fluorescent stabilization, excitation wave spectrum width and The advantages that at low cost.
Currently, many synthetic methods and material can be used for the preparation of carbon nano-particles, but still with the presence of some problems, such as Some method and steps are excessively cumbersome, and the quantum yield of some carbon nano-particles is not high, and some preparation methods, which need to be added with, to be poisoned Reagent is learned, shines and concentrates on short wavelength, the limitation of controlledly synthesis, which has limited carbon nano-particles answering in actually detected With.Therefore, the carbon nano-particles synthetic method for developing simple, quick, green and low-loss and its controllable property is very must It wants.
Still in its infancy, there are many more the problem of experiment and theoretical side to be worth visiting for the research of carbon nano-particles at present Rope and solution.Such as more environmentally protective carbon source is found, it is more preferable come synthesis performance by more simple and safe, easy-operating method, The luminous fluorescent carbon nano-particles of controllable preparation difference, carbon nano-particles as novel fluorescence probe biomarker and from Son, have in pH detection deeper into application.
Summary of the invention
In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a kind of simple, quick methods to use In the preparation that controllable fluorescent carbon nano-particles shine, carbon nano-particles preparation method is easy, equipment is simple, carbon source is cheap and green Environmental protection, reaction time are short, and controlledly synthesis difference shines carbon nano-particles;Prepared carbon nano-particles can be applied to metal ion Detection, the detection of pH and cell imaging etc., detection sensitivity, detection limit and cell imaging effect are superior to ought be above Report is offered, has important directive significance in actual sample, biology and medical application to carbon nano-particles.
The technical solution that the present invention takes to achieve the above object are as follows:
A kind of controllable luminous carbon nano-particles, are made up of following steps:
(1) fresh cloves petal is dried, is ground into powder, weigh 1-2g in small beaker and deionized water 10mL is added and is right It is dissolved sufficiently by the way that the stirring of 0-3gNaOH solid is added afterwards, is added in autoclave, is put into 150-250 DEG C of height of baking oven Temperature reaction 3-5 hours;
(2) cooling obtains brown or dark brown solution after reaction, and by centrifugation, 0.22 μm of filter is filtered, then It dialyses 3 days in 500-1000D bag filter, obtains brown color or brown liquid is pure carbon nano-particles solution;
(3) the carbon nano-particles solution vacuum freezedrying in step (2) is obtained into brown color or brown ceramic powder, as mesh Carbon nano-particles, it is soluble in water to issue strong blue or green fluorescence.
The preparation method of the controllable luminous carbon nano-particles of the present invention, comprising the following steps:
(1) fresh cloves petal is dried, is ground into powder, weigh 1-2g in small beaker and deionized water 10mL is added and is right It is dissolved sufficiently by the way that the stirring of 0-3gNaOH solid is added afterwards, is added in autoclave, is put into 150-250 DEG C of height of baking oven Temperature reaction 3-5 hours;
(2) cooling obtains brown or dark brown solution after reaction, and by centrifugation, 0.22 μm of filter is filtered, then It dialyses 3 days in 500-1000D bag filter, obtains brown color or brown liquid is pure carbon nano-particles solution;
(3) the carbon nano-particles solution vacuum freezedrying in step (2) is obtained into brown color or brown ceramic powder, as mesh Carbon nano-particles, it is soluble in water to issue strong blue or green fluorescence.
The application of the controllable luminous carbon nano-particles of the present invention is used to detect the Fe in aqueous solution as fluorescence probe3+Concentration With the pH value of aqueous solution or pass through the Fe in live cell fluorescent image checking living cells3+The pH value of concentration and living cells.
Further, the present invention is used to detect the Fe in aqueous solution3+Fe in concentration and living cells3+When concentration, preparing The additional amount of NaOH solid is 0g in the step of luminous carbon nano-particles (1);For detecting the pH value and living cells of aqueous solution When pH value, the additional amount of NaOH solid is 1-3g in preparing the step of shining carbon nano-particles (1).
The present invention by adopting the above technical scheme, has the advantages that
(1) operation of the present invention step is simple, conventional typical medicine need to only be added, shining for carbon nano-particles is just adjusted, i.e., Shining can be mobile to long wavelength, and for there is critically important value in bio-sensing application, reactant carries out in same system, Target carbon nano-particles can be obtained.
(2) raw material are lilac, are very cheap green materials, from a wealth of sources, economic and environment-friendly.
(3) production equipment is simple, at low cost, and reaction time is short, and yield is high.
(4) carbon nano-particles synthesized have good water solubility, and fluorescent yield is high, biocompatibility, and good light is steady It is qualitative, it is suitble to volume production.
(5) application value is high, and preparing carbon nano-particles can be applied to metal Fe3+Ion detection, detection sensitivity is high, inspection Rising limit is the smallest in pertinent literature report;Carbon nano-particles by simply regulating and controlling preparation apply also for the inspection of pH value of solution It surveys;The carbon nano-particles of all preparations can all be successfully applied to biomarker, Fe in living cells3+Ion and pH detection, effect Obviously,
In short, synthesis technology of the present invention is easy to operate, raw material sources are extensive and cheap environmental protection, and preparation condition requires low and warm With gained carbon nano-particles yield is high, solves existing carbon nano-particles preparation method due to technique and raw material limit without regulation Modelling produce problem, the carbon nano-particles can be applied to metal ion detection, biomarker, Biological imaging, electrooptical device and The fields such as anti-fake mark.
Detailed description of the invention
Fig. 1 is the present invention by the obtained pure carbon nano-particles progress fluorescence spectrum test of embodiment 1-8, and Figure 1A, B are The fluorogram of embodiment 1-5, Fig. 1 C are the fluorescence spectra of embodiment 6-8.
Fig. 2 is the ultra-violet absorption spectrum of the pure carbon nano-particles prepared in embodiment 2, the excitation of best fluorescence and transmitting light Spectrum.
Fig. 3 is the ultra-violet absorption spectrum of the pure carbon nano-particles prepared in embodiment 7, the excitation of best fluorescence and transmitting light Spectrum.
Fig. 4 be embodiment 2, embodiment 7 prepare pure carbon nano-particles fluorescence emission spectrum with excitation wavelength change Spectrogram.
Fig. 5 be embodiment 2, embodiment 7 prepare pure carbon nano-particles infrared spectrogram.
Fig. 6 be embodiment 2, embodiment 7 prepare pure carbon nano-particles TEM, HRTEM and grain size distribution.
Fig. 7 be embodiment 2, embodiment 7 prepare pure carbon nano-particles XPS spectrum figure.
Fig. 8 be embodiment 2, embodiment 7 prepare pure carbon nano-particles XRD spectra.
Fig. 9 is that pure carbon nano-particles prepared by embodiment 2, embodiment 7 prepare Metal Ion Selective Electrode and embodiment 2 Pure carbon nano-particles to iron ion quench scheme.
Figure 10 is fluorogram and different circulation time of the pure carbon nano-particles of the preparation of embodiment 7 under different pH environment Several lower change in fluorescence figures.
Figure 11 is the pure carbon nano-particles that prepare of embodiment 2, embodiment 7 to the cytotoxicity of breast cancer cell MCF-7 MTT experiment figure.
Figure 12 is the pure carbon nano-particles label breast cancer cell MCF-7 and detection iron ion prepared in embodiment 2 Laser co-focusing figure.
Figure 13 is that the pure carbon nano-particles prepared in embodiment 7 mark breast cancer cell MCF-7 under different pH environment to swash Light is total to focused view.
Specific embodiment
The present invention is described in detail with reference to embodiments, specific operating process and detailed embodiment are logical It crosses embodiment to provide, single protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10mL is added, It is added in autoclave, is put into 150 DEG C of baking oven pyroreaction 4 hours;
Step 2, cooling obtains brown solution after reaction, passes through centrifugation, 0.22 μm of filter filtering, then in 500- It dialyses 3 days in 1000D bag filter, obtaining brown color liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brownish-yellow powder by step 3, that is, is purpose carbon Nanoparticle, sending blue-fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using quinine sulfate as standard) is 5.8%.
Embodiment 2
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10mL is added, It is added in autoclave, is put into 200 DEG C of baking oven pyroreaction 4 hours;
Step 2, cooling obtains brown solution after reaction, passes through centrifugation, 0.22 μm of filter filtering, then in 500- It dialyses 3 days in 1000D bag filter, obtaining brown color liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brownish-yellow powder by step 3, that is, is purpose carbon Nanoparticle, sending blue-fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using quinine sulfate as standard) is 12.9%.
Embodiment 3
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10mL is added, It is added in autoclave, is put into 250 DEG C of baking oven pyroreaction 4 hours;
Step 2, cooling obtains brown solution after reaction, passes through centrifugation, 0.22 μm of filter filtering, then in 500- It dialyses 3 days in 1000D bag filter, obtaining brown color liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brownish-yellow powder by step 3, i.e., receives for purpose carbon Rice corpuscles, sending blue-fluorescence soluble in water;
Step 4 obtains fluorescent carbon nano-particles, relative quantity after being freeze-dried above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using quinine sulfate as standard) is 6.8%.
Embodiment 4
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10mL is added, It is added in autoclave, is put into 200 DEG C of baking oven pyroreaction 3 hours;
Step 2, cooling obtains brown solution after reaction, passes through centrifugation, 0.22 μm of filter filtering, then in 500- It dialyses 3 days in 1000D bag filter, obtaining brown color liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brownish-yellow powder by step 3, that is, is purpose carbon Nanoparticle, sending blue-fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using quinine sulfate as standard) is 10.9%.
Embodiment 5
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10ml is added, It is added in autoclave, is put into 200 DEG C of baking oven pyroreaction 5 hours;
Step 2, cooling obtains brown solution after reaction, passes through centrifugation, 0.22 μm of filter filtering, then in 500- It dialyses 3 days in 1000D bag filter, obtaining brown color liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brownish-yellow powder by step 3, that is, is purpose carbon Nanoparticle, sending blue-fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using quinine sulfate as standard) is 7.2%.
Embodiment 6
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10mL is added Then the stirring of 1g NaOH solid, which is added, dissolves it sufficiently, is added in autoclave, is put into 200 DEG C of pyroreactions 4 of baking oven Hour;
Step 2, cooling obtains dark brown solution after reaction, and by centrifugation, then 0.22 μm of filter filtering exists It dialyses 3 days in 500-1000D bag filter, obtaining brown liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brown ceramic powder by step 3, i.e., receives for purpose carbon Rice corpuscles, sending green fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using rhodamine 6G as standard) is 4.8%.
Embodiment 7
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10mL is added Then the stirring of 2g NaOH solid, which is added, dissolves it sufficiently, is added in autoclave, is put into 200 DEG C of pyroreactions 4 of baking oven Hour;
Step 2, cooling obtains dark brown solution after reaction, and by centrifugation, then 0.22 μm of filter filtering exists It dialyses 3 days in 500-1000D bag filter, obtaining brown liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brown ceramic powder by step 3, i.e., receives for purpose carbon Rice corpuscles, sending green fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using rhodamine 6G as standard) is 8.9%.
Embodiment 8
Step 1 dries fresh cloves petal, is ground into powder, weighs 1g in small beaker and deionized water 10ml is added Then the stirring of 3g NaOH solid, which is added, dissolves it sufficiently, is added in autoclave, is put into 200 DEG C of pyroreactions 4 of baking oven Hour;
Step 2, cooling obtains dark brown solution after reaction, and by centrifugation, then 0.22 μm of filter filtering exists It dialyses 3 days in 500-1000D bag filter, obtaining brown liquid is pure carbon nano-particles solution;
Carbon nano-particles solution vacuum freezedrying in step 2 is obtained brown ceramic powder by step 3, i.e., receives for purpose carbon Rice corpuscles, sending green fluorescence soluble in water;
Step 4 will obtain fluorescent carbon nano-particles, relative quantity after the freeze-drying of above-mentioned fluorescent carbon nano-particles aqueous solution Sub- yield (using rhodamine 6G as standard) is 6.5%.
Embodiment 9
The obtained pure carbon nano-particles of embodiment 1-5 are subjected to fluorescence spectrum test, if Figure 1A, B are embodiment 1-5 Fluorogram.The obtained pure carbon nano-particles of embodiment 6-8 are subjected to fluorescence spectrum test, if Fig. 1 C is embodiment 6- 8 fluorescence spectra.
Embodiment 10
By the highest carbon nano-particles of blue-fluorescence quantum yield, i.e. carbon nano-particles obtained in embodiment 2 carry out purple External spectrum measurement, fluorescence excitation spectrum, emission spectra measurement, such as Fig. 2;By the highest carbon nano-particles of green fluorescence quantum yield, i.e., Carbon nano-particles obtained in embodiment 7 carry out ultraviolet spectroscopy, fluorescence excitation spectrum, emission spectra measurement, such as Fig. 3.It will implement Fluorescent emission spectrogram of the carbon nano-particles solution under different excitation wavelengths in example 2 is measured, such as Fig. 4 A, in good transmitted wave It grows in 450nm or so, belongs to blue light scope;By fluorescence of the carbon nano-particles solution under different excitation wavelengths in embodiment 2 Transmitting spectrogram is measured, as Fig. 4 B belongs to green light scope in good launch wavelength in 520nm or so.
High-purity carbon nano-particles will be obtained in embodiment 2 and embodiment 7 carries out infrared, TEM/HRTEM, XPS, XRD characterization, It is respectively less than 10nm as Fig. 5-8 obtains the high-purity carbon nano particle diameter that the present invention obtains, the carbon nano-particles of blue light-emitting contain carboxylic Base, hydroxyl and amino groups, the carbon nano-particles of green light contain the groups such as carboxyl, hydroxyl, and two kinds of carbon nano-particles contain There is group slightly to distinguish.
Embodiment 11
Example 2 prepare fluorescent carbon nano-particles aqueous solution (2.8mg/mL) be placed in fluorescence cuvette, respectively plus 17 kinds of common metal ion solutions (300mM) are sufficiently mixed uniformly, emission spectrum (λ ex=are scanned in Fluorescence Spectrometer 340nm, λ em=445nm), and record the fluorescence intensity after each ion is added, as shown in Figure 9 B, the carbon nanometer of embodiment 2 Particle is to Fe3+There are good selectivity, i.e. Fe3+The blue-fluorescence of the carbon nano-particles in embodiment 2 can be made to be quenched.In order to Carbon nano-particles are calculated to Fe3+Detection range, Example 2 prepare fluorescent carbon nano-particles aqueous solution (2.8mg/mL) set In fluorescence cuvette, it is separately added into the Fe of various concentration from low to high3+Solution is sufficiently mixed uniformly, measures in various concentration Fe3+The fluorescence of fluorescent carbon nano-particles in lower embodiment 2, as Fig. 9 A, Cong Tuzhong are then obtained to Fe3+Detection be limited to it is reachable 3.69×10-7Mol/L detects range of linearity 0-150mol/L.And the fluorescent carbon nano-particles of the green light in embodiment 7 do not have There is good selection to certain metal ion species, such as Fig. 9 C.
Embodiment 12
Fluorescent carbon nano-particles aqueous solution (2.8mg/mL) prepared by Example 2 is placed in fluorescence cuvette, passes through benefit With various concentration Fe3+C can be made in titration(Fe3+)With the linear relationship of fluorescence intensity, so as to measure in actual water sample (from In water) Fe3+Content, institute's measured value and the result that inductively coupled plasma spectrum generator (ICP) measures are almost the same, see Table 1, the method for determining us have reliability.
Embodiment 13
The carbon nano-particles (1.6mg/mL) of the green light prepared in embodiment 7 are placed in fluorescence cuvette, are added not With its fluorescence is measured in the solution (1.89-11.92) of pH, it is sufficiently mixed uniformly, emission spectrum (λ is scanned in Fluorescence Spectrometer Ex=450nm, λ em=520nm), and record and be added to the fluorescence intensity after each pH, as shown in Figure 10 A, in 1.89- Linear in 8.95 ranges, i.e. pH is bigger, and fluorescence is stronger, and fluorescence is unaffected after 1.89 and 8.95 different repeated transformations, such as schemes 10B illustrates that the fluorescent carbon nano-particles of green light prepared by embodiment 7 have good sensitivity to pH.
Embodiment 14
The carbon nano-particles (1.6mg/mL) of the green light prepared in embodiment 7 are placed in fluorescence cuvette, are added not With its fluorescence is measured in the solution (1.89-8.95) of pH, the linear relationship of pH value of solution and fluorescence intensity is obtained, so as to measure PH in unknown real solution, institute's measured value and business pH analyzer measured value are very close to being shown in Table 2.
Embodiment 15
Luminous carbon nano-particles different in embodiment 2,7 are subjected to cytotoxicity test, prepare various concentration respectively Carbon nano-particles solution (0-50mg/mL) acts on human breast cancer cell line Bcap-37, i.e., analyze by routine MTT experiment The luminous carbon nano-particles of the difference prepared in embodiment 2,7 out are to cytotoxicity very little, such as Figure 11.
Embodiment 16
By the carbon nano-particles aqueous solution (6mg/mL) of the transmitting blue-fluorescence prepared in embodiment 2 for marking human milk gland Cancer MCF-7 cell, such as Figure 12, Figure 12 A are that the carbon nano-particles aqueous solution (6mg/mL) only prepared in embodiment 2 is added to training It supports in the DMEM culture solution in MCF-7 cell, (excitation wavelength is 405nm to the laser confocal imaging of incubation after ten minutes, is connect altogether The launch wavelength range of receipts is 425-480nm), it is very strong to be displayed in blue fluorescence;Figure 12 B-E is that the carbon prepared in embodiment 2 is added Nanoparticle aqueous solution (6mg/mL) is added in the DMEM culture solution in culture MCF-7 cell, is incubated for altogether after ten minutes, immediately Fe is added3+(300mM) in the laser confocal imaging of different time, as time goes by, fluorescence gradually weakens for display;Figure 12 F It is that Fe is added3+In intensity of cellular fluorescence figure in different time periods, show that the carbon nano-particles prepared in embodiment 2 can be in work Fe is detected in cell3+
Embodiment 17
By the carbon nano-particles aqueous solution (5mg/mL) of the transmitting green fluorescence prepared in embodiment 7 for marking human milk gland Cancer MCF-7 cell, such as Figure 13 indicate that the carbon nano-particles aqueous solution (5mg/mL) prepared in embodiment 7 is added to culture MCF-7 In DMEM culture solution in cell, it is incubated for after ten minutes that (excitation wavelength is 405nm, received transmitting altogether in different pH environment Wave-length coverage is 480-545nm) laser confocal imaging, it is very weak to be shown in the lesser acidic environment green fluorescence of pH, and The biggish neutral and mild alkaline conditions green fluorescence of pH is very strong, shows the carbon nano-particles of transmitting green fluorescence prepared by embodiment 7 Acid-base property can be detected in living cells.
Table 1 measures Fe in tap water3+Content (n=3)
Table 2 measures unknown solution pH value
Embodiment above describes preparation method and applications of the invention.The technical staff of the industry should know the present invention It is not restricted to the described embodiments, under the range for not departing from essence of the invention, various changes and improvements may be made to the invention, this In a little changes and improvements are all fallen within the protection scope of the present invention.

Claims (4)

1. a kind of controllable luminous carbon nano-particles, it is characterized in that being made up of following steps:
(1) fresh cloves petal is dried, is ground into powder, weighs 1-2g in small beaker and deionized water 10mL is added, then It is dissolved sufficiently by the way that the stirring of 0-3gNaOH solid is added, and is added in autoclave, is put into 150-250 DEG C of high temperature of baking oven Reaction 3-5 hours;
(2) cooling obtains brown or dark brown solution after reaction, and by centrifugation, then 0.22 μm of filter filtering exists It dialyses 3 days in 500-1000D bag filter, obtains brown color or brown liquid is pure carbon nano-particles solution;
(3) the carbon nano-particles solution vacuum freezedrying in step (2) is obtained into brown color or brown ceramic powder, that is, is purpose carbon Nanoparticle, it is soluble in water to issue strong blue or green fluorescence.
2. a kind of preparation method of controllable luminous carbon nano-particles described in claim 1, it is characterized in that the following steps are included:
(1) fresh cloves petal is dried, is ground into powder, weighs 1-2g in small beaker and deionized water 10mL is added, then It is dissolved sufficiently by the way that the stirring of 0-3g NaOH solid is added, and is added in autoclave, is put into 150-250 DEG C of height of baking oven Temperature reaction 3-5 hours;
(2) cooling obtains brown or dark brown solution after reaction, and by centrifugation, then 0.22 μm of filter filtering exists It dialyses 3 days in 500-1000D bag filter, obtains brown color or brown liquid is pure carbon nano-particles solution;
(3) the carbon nano-particles solution vacuum freezedrying in step (2) is obtained into brown color or brown ceramic powder, that is, is purpose carbon Nanoparticle, it is soluble in water to issue strong blue or green fluorescence.
3. the application of controllable luminous carbon nano-particles described in claim 1, it is characterized in that water-soluble for detecting as fluorescence probe Fe in liquid3+The pH value of concentration and aqueous solution passes through the Fe in live cell fluorescent image checking living cells3+Concentration and work are thin PH value in born of the same parents.
4. the application of controllable luminous carbon nano-particles according to claim 3, it is characterized in that for detecting in aqueous solution Fe3+Fe in concentration and living cells3+When concentration, the additional amount of NaOH solid in preparing the step of shining carbon nano-particles (1) For 0g;For detect aqueous solution pH value and living cells pH value when, prepare shine carbon nano-particles the step of (1) in NaOH The additional amount of solid is 1-3g.
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