CN108998012A - A kind of blue luminescence quantum dot and preparation method thereof and copper ion detection application - Google Patents

A kind of blue luminescence quantum dot and preparation method thereof and copper ion detection application Download PDF

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CN108998012A
CN108998012A CN201810936227.5A CN201810936227A CN108998012A CN 108998012 A CN108998012 A CN 108998012A CN 201810936227 A CN201810936227 A CN 201810936227A CN 108998012 A CN108998012 A CN 108998012A
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quantum dot
methanol
cds
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黄赛朋
成杰伟
薛伟明
李文帅
温惠云
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Northwest University
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Abstract

A kind of blue luminescence quantum dot disclosed by the invention and its preparation method and application, belongs to technical field of nano material.Preparation method: 1) using citric acid as carbon source, using the polyethyene diamine dendritic with amino as nitrogen source, carbon quantum dot presoma is made using decocting method；2) using ethylenediamine as decorating molecule, methyl acrylate is link molecule, is modified carbon quantum dot presoma, and blue luminescence quantum dot is made.The preparation method highway route design is reasonable, easy to operate, reproducible, low for equipment requirements；Blue luminescence quantum dot good water solubility obtained, stability are high, and fluorescence property is excellent, be capable of specificity for detecting copper ion.

Description

A kind of blue luminescence quantum dot and preparation method thereof and copper ion detection application
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of blue luminescence quantum dot and preparation method thereof and answer With.
Background technique
The vital movement of any living matter all be unable to do without water in the Nature.But with the rapid development of society, the mankind The problem of increasingly enhancing the dependence of water resource, causing water pollution by the improper processing of trade waste, causes people's height to be closed Note.Since heavy metal is easily enriched in organism and is transmitted with biological chain, thus to the ecological environment and life and health of the mankind Bring huge threat.Since tin, copper, lead, zinc, mercury, chromium etc. have significant bio-toxicity, and these heavy metals pass through micro- life The effect of object can be converted to the substance bigger to bio-toxicity.Therefore, they have been put into the blacklist of control pollutant.Generation National governments of boundary and united nations environment protective tissue etc. have put into effect relevant regulation, to the content of beary metal in drinking water and food Strictly limited.China has also carried out specific regulation to drinking water and content of heavy metal in foods: in Drinking Water The maximum limitation of chromium is 0.05mgL-1, and the maximum limitation of aluminium is 0.2mgL-1, and the maximum limitation of copper is 1mgL-1.Grain The limit content of copper is 10mgkg-1 in food, and the limit content of lead is 0.2mgkg-1, and the limit content of chromium is 0.2mg kg-1.The content of lead must not exceed 0.2mgkg-1 in poultry meat, and the content of chromium must not exceed 0.1mgkg-1, and copper contains Amount must not exceed 10mgkg-1.Meanwhile according to the United Nations's hygienic environment-protecting organization prescribed, copper in drinking water ion concentration must not surpass Cross 10 μm of olL-1
Copper is the metal that the mankind have found earliest and the most popular metal of the mankind, be widely used in agricultural and In industrial products, such as: reagent, pesticide, plasticizer, emulsifier and coating.Meanwhile copper is in terms of adjusting organism physiological activity Also it plays an important role.On the one hand, suitable copper plays a part of can not be substituted to normal physiological activity in vivo. In body, many enzymes for participating in physiological activities have the participation of copper, for example, ascorbic acid oxidase, superoxide dismutase, Ascorbic acid oxidase etc., it is inseparable with electron transmission redox reaction in bioconversion.Meanwhile the generation of many enzymes It thanks and is also closely related with copper.In vivo, copper ion plays a crucial role absorption, the transport of ferro element.Copper coin The shortage of element can inhibit the synthesis of hemoglobin in organism, cause content of hemoglobin to reduce, lead to Functional Anemia；Together When, copper ion also has a certain impact to endocrine system and nervous system.The shortage of copper is to covellite egg in nerve fiber The activity of white, superoxide dismutase, cytochrome oxidase etc. has important influence, and the symptom clinically showed is main There are Wilson disease (Wilson disease), Alzheimer's disease (Alzheimer disease), parkinson's syndrome (Parkinsonism), central nervous system sick (Central Nervous System Disease) etc.；Meanwhile copper bone and The physiological activity of cartilage and its connective tissue also has vital influence, and copper shortage can produce the bone growth of children It is raw to influence.On the other hand, copper too high levels can also generate certain harm in body.It is aobvious according to World Health Organization's research Show, the amount safe for ingestion of baby, children and the daily copper of teenager are respectively 80,40 and 30 μ gkg-1.Meanwhile according to China Nutrition Society (Chinese Nutrition Society) report, adult should be 210 to the amount safe for ingestion of copper daily~ 300mg；Likewise, the name United States Food nutrition committee (National Nutritional Foods Association) Recommendation recognizes to should be 115~310mg to the amount safe for ingestion of copper daily.It is shown according to correlative study, copper content is more than in body The limit will generate haemolysis.Long-term Excess free enthalpy copper can cause memory loss, nausea, dysfunction of liver and liver enlargement etc..
Copper ion traditional detection method has the precipitation method, development process, fluorescence probe method, metal quantum point method etc., but these sides All there is the problems such as sensitivity is low and accuracy is inadequate in method, be difficult to detect micro copper ion in organism；Fluorescence probe simultaneously Method and metal quantum point method bring bio-toxicity greatly limit its on-line checking and application.Therefore, exploitation it is highly sensitive and The low copper ion detection method of bio-toxicity realizes the detection of micro copper ion, it is expected to realize because copper ion accumulation causes disease Early diagnosis.
In recent years, with the development of nano material, carbon quantum dot as a kind of novel fluorescent nano material increasingly by To the concern of researchers.Currently, mainly doing passivator by organic solvent, to fill up the defect on carbon quantum dot surface glimmering to improve The quantum yield of light carbon quantum dot.However, it is complex to select organic solvent to do passivator subsequent processing.Therefore, vast research Person seeks more cheap simpler method to improve carbon quantum dot fluorescence quantum yield.Due to the radius phase of N atom and C atom Closely, therefore, nitrating is carried out to it in the process of preparation carbon quantum dot handle the nitrogen-doped carbon quantum dot that will be had excellent performance (N-CDs)。
Currently, reported nitrogen source mainly has ethylenediamine, amino acid, dendrimer etc..But these nitrogen substance conducts Raw material is entrained in carbon quantum dot surface after splitting molecule again by violent reaction.Since the amino on carbon quantum dot surface can CDs fluorescence is caused to be quenched to capture copper ion formation cupric ammine complex and be covered on carbon quantum dot surface.However, making The standby most of amino of carbon quantum dot process can be oxidized, split or recombinate, and prepared carbon quantum dot amino amount is caused to reduce So that the sensitivity decrease of copper ion detection.
Summary of the invention
In order to overcome the problems of the above-mentioned prior art, the purpose of the present invention is to provide a kind of blue luminescence quantum dots And its preparation method and application, the preparation method highway route design is reasonable, and it is easy to operate, it is reproducible, it is low for equipment requirements；It is made Blue luminescence quantum dot good water solubility, stability is high, and fluorescence property is excellent, be capable of specificity for detecting copper ion.
The present invention is to be achieved through the following technical solutions:
1) using citric acid as carbon source, using the polyethyene diamine dendritic with amino as nitrogen source, using decoction legal system Obtain carbon quantum dot presoma；
2) using ethylenediamine as decorating molecule, methyl acrylate is link molecule, is modified carbon quantum dot presoma, is made Obtain blue luminescence quantum dot.
Preferably, carbon quantum dot presoma is prepared using decocting method in step 1), comprising the following steps:
1.1) citric acid: the polyethyene diamine dendritic with amino: water=1g:0.5g:5mL amount ratio is pressed, Citric acid and polyethyene diamine dendritic are dispersed in water, 2h is handled in 200 DEG C of decoctions, brown solution is made；
1.2) to brown solution centrifugal treating, supernatant is collected, supernatant is successively through filtering with microporous membrane, dialysis and drying Carbon quantum dot presoma is made in processing.
It is further preferred that supernatant uses 0.22 μm of syringe membrane filtration, then will be filtered molten in step 1.2) The carbon quantum dot presoma that average grain diameter is 4.4nm is made in the bag filter dialysis treatment 8h of liquid 10000Da.
Preferably, in step 2), using ethylenediamine as decorating molecule, methyl acrylate is link molecule, before carbon quantum dot It drives body to be modified, concrete operations include:
2.1) by carbon quantum dot presoma with methanol extraction for several times, collect methanol extraction liquid, be added dropwise into methanol extraction liquid Methyl acrylate, reacts for 24 hours at 30 DEG C, the solution revolving after reaction is removed methanol, and washed for several times with methanol；
2.2) methanol: ethylenediamine=10:16 volume ratio is pressed, methanol is added into the solution after washing and second is added dropwise dropwise Diamines reacts for 24 hours at 30 DEG C；Solution revolving after reaction is removed into methanol, and is washed for several times with methanol, it is molten that yellow is made Liquid；By the dialysis of resulting yellow solution, freeze-drying process, blue luminescence quantum dot is made.
Preferably, the polyethyene diamine dendritic with amino specific the preparation method is as follows:
Step 1: after stirring ethylenediamine and methanol by the volume ratio of 4:10, acrylic acid is added dropwise into the solution Methyl esters reacts for 24 hours at 30 DEG C；The volume ratio of methyl acrylate and ethylenediamine is 1:4；
Step 2: the solution revolving after step 1 reaction being removed into methanol, again with methanol is washed for several times, then to after washing Methanol and ultrasonic disperse are added in solution, then ethylenediamine is added dropwise into the solution after dispersion, is reacted for 24 hours at 30 DEG C；Methanol with The volume ratio of ethylenediamine is 10:(3~10)；
Step 3: the solution revolving after step 2 reaction being removed into methanol, again with methanol is washed for several times, and yellow oily liquid is obtained Body is generation dendrimer 1G-PAMAM；
Step 4: after stirring generation dendrimer 1G-PAMAM and methanol by the volume ratio of 4:10, to this Methyl acrylate is added dropwise in solution, reacts 36h at 35 DEG C；The quality of methyl acrylate and generation dendrimer 1G-PAMAM Than for 1:4；
Step 5: the solution revolving after step 4 reaction being removed into methanol, again with methanol is washed for several times, then to after washing Methanol and ultrasonic disperse are added in solution, then generation dendrimer 1G-PAMAM is added dropwise into the solution after dispersion, in 35 DEG C Lower reaction 48h；The volume ratio of methanol and generation dendrimer 1G-PAMAM are 20:(3~10)；
Step 6: the solution revolving after step 5 reaction being removed into methanol, again with methanol is washed for several times, two generation dendrimers 2G-PAMAM；
Generation dendrimer 1G-PAMAM and two generation dendrimer 2G-PAMAM is being capable of having as nitrogen source The polyethyene diamine dendritic of amino.
The invention also discloses blue luminescence quantum dot obtained with the aforedescribed process is adopted, which is put down Equal partial size is 25.3nm, and surface charge is+94.4mV.
The invention also discloses the applications using above-mentioned blue luminescence quantum dot as copper ion detection fluorescence probe.
Preferably, the blue luminescence quantum dot is 0.01 μm of olL to the detectable concentration section of copper ion-1~600 μ mol·L-1。
Preferably, blue luminescence quantum dot can specificity detect intracellular copper ion.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention, using the polyethyene diamine dendritic by moditied processing as nitrogen source, passes through using citric acid as carbon source Decocting method obtains unmodified carbon quantum dot presoma (bare-CDs).Using ethylenediamine as decorating molecule, methyl acrylate is Connection molecule forms amination carbon dots on carbon quantum dot presoma surface for ethylene diamine-modified by amide reaction, blue is made Fluorescence quantum NH2- CDs, blue luminescence quantum dot NH2- CDs emits blue-fluorescence under luminoscope or laser co-focusing instrument, Meet copper ion fluorescent quenching.Its pattern and structure are characterized by dynamic light scattering particle size instrument and transmission electron microscope, by red External spectrum instrument (FT-IR) characterizes its surface functional group, prepared bare-CDs and NH2The average grain diameter of-CDs is distinguished For 4.4nm and 25.3nm, surface charge is respectively+40.1mV and+94.4mV, passes through IR Characterization, NH2- CDs exists respectively 1654cm-1And 1706cm-1There is the characteristic peak of amido bond in place, illustrates that ethylenediamine is successfully grafted on the surface bare-CDs.
Perhydroxyl radical, carboxylated carbon dots and EDTA confirmatory experiment, illustrate to promote NH2The main original that-CDs fluorescence is quenched Because of the Cu in the amino capture solution on its surface2+And it is formed caused by cupric ammine complex.Using ultraviolet-visible spectrophotometer (UV-Vis) and sepectrophotofluorometer (PL) carries out optical property research to it, PL and UV-vis map shows that Cu2+ can make NH2-CDs fluorescence is quenched, to Cu2+Detection interval be 0.01~600 μm of olL-1, detectable limit is 0.01 μm of olL-1.It is tested by specificity, NH2- CDs can be used as specificity efficient detection Cu2+Fluorescence probe.Meanwhile with MCF-7, HepG-2 and L-929 cell is that model probes into NH2The cytotoxicity of-CDs, and using laser confocal microscope to intracellular glimmering Light imaging behavior is observed, and experimental result is shown, Cu2+There are energy obvious quenching NH2The fluorescence of-CDs is adding copper ion outside When, fluorescence intracellular is quenched, and quenching time 16s illustrates NH2- CDs can be realized to Cu in cell2+Quick detection.
Detailed description of the invention
Fig. 1 is preparation and the detection copper ion flow diagram of blue luminescence quantum dot of the invention；
Fig. 2A is the transmission electron microscope picture and grain size distribution of carbon quantum dot presoma bare-CDs；
Fig. 2 B is blue quantum dot NH2The transmission electron microscope picture and grain size distribution of-CDs；
Fig. 2 C is bare-CDs and NH2The surface charge of-CDs；
Fig. 2 D is bare-CDs and NH2The infrared spectrum of-CDs；
Fig. 3 A is NH2- CDs fluorescence intensity is with concentration variation relation figure；
Fig. 3 B is NH2- CDs emits map under different wave length excitation；
Fig. 4 is 100 μ gml-1NH2- CDs ultravioletvisible absorption map, fluorescence excitation and transmitting map；
Fig. 5 is 100 μ gml-1NH2- CDs is in various concentration Cu2+Middle fluorogram；
Fig. 6 is 100 μ gml-1NH2- CDs is 10 μm of olL in concentration-1Different metal ions (A) and amino acid (B) are molten Fluorescence intensity in liquid；
Fig. 7 is that concentration is 100 μ gmL-1Hydroxylating carbon dots (A) and carboxylated carbon dots (B) in 10 μm of olmL-1It is different Fluorescence intensity in metal ion；
Fig. 8 is NH2Fluorescence intensity of-the CDs in buffer (A) and various concentration NaCl solution (B)；
Fig. 9 is (A) 100 μ gmL-1NH2- CDs detects Cu in different pH solution2+Fluorescence intensity figure；(B)NH2-CDs It is 0,400 μm of olL in concentration-1Cu2+And 400 μm of olL-1Cu2+With 400 μm of olL-1Fluorescence intensity figure in EDTA solution；
Figure 10 is the NH of various concentration2- CDs is to HepG-2, the influence of MCF-7 and L-929 cytotoxicity；
Figure 11 is HepG-2 and NH2- CDs co-culture 4h after with Cu2+Laser co-focusing figure is descended in different time points；
Under Figure 12 laser co-focusing, 100 μ g/ml NH2- CDs is to various concentration copper ion in MCF-7 and HepG-2 cell The fluorescence response of (250nM, 10 μM and 100 μM).
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
The preparation of 1 carbon quantum dot of embodiment
The polyethyene diamine dendritic with amino used in the present invention as nitrogen source can choose commercially available production Product also can choose and voluntarily prepare.
Referring to Fig. 1, blue luminescence quantum dot NH of the invention2The preparation method of-CDs, comprising the following steps:
The preparation of step 1:G-PAMAM
1) it is separately added into 4mL ethylenediamine and 10mL methanol into round-bottomed flask and stirs 5min.To above-mentioned solution after stirring In 16mL methyl acrylate be added dropwise dropwise and reacted for 24 hours at 30 DEG C；
2) it to remove methanol at 30 DEG C with Rotary Evaporators after reaction, and is washed three times with methanol to remove largely Methyl acrylate.10mL methanol is added in acquired solution after to above-mentioned revolving and is uniformly dispersed with ultrasound.Again to dispersion 16mL ethylenediamine is added dropwise in solution afterwards dropwise, and at 30 DEG C the reaction was continued for 24 hours；
3) methanol is removed at 30 DEG C with Rotary Evaporators after reaction, and washed three times with methanol to remove largely Ethylenediamine obtains yellow oily liquid i.e. generation dendrimer (1G-PAMAM) after processing.
4) it is separately added into 4mL generation dendrimer 1G-PAMAM and 10mL methanol into round-bottomed flask and stirs 5min, 16mL methyl acrylate is added dropwise dropwise into above-mentioned solution after stirring and is reacted for 24 hours at 30 DEG C；
5) it to remove methanol at 30 DEG C with Rotary Evaporators after reaction, and is washed three times with methanol to remove largely Methyl acrylate.10mL methanol is added in acquired solution after to above-mentioned revolving and is uniformly dispersed with ultrasound；
6) 16mL generation dendrimer 1G-PAMAM is added dropwise dropwise into the solution after dispersion again, and continues at 30 DEG C Reaction for 24 hours, removes methanol at 30 DEG C with Rotary Evaporators after reaction, and two generation dendrimer 2G-PAMAM are made, set It is saved in 4 DEG C of refrigerators.
Generation dendrimer 1G-PAMAM and two generation dendrimer 2G-PAMAM can be used as of the invention with ammonia The polyethyene diamine dendritic of base, nitrogen source needed for reaction is provided.
Step 2: hydro-thermal decocting method prepares carbon dots
Accurately weigh 1g citric acid, the 2G-PAMAM of 0.5g step 1 preparation is in a round bottom flask and that 5mL pure water is added is super Sound is dispersed.200 DEG C of setting electric heating cover temperature obtain brown liquid to above-mentioned solution heating 2h.By gained brown solution in 10000rpm centrifugation is in supercentrifuge to remove the substance being carbonized in heating process.And resulting supernatant will be centrifuged and used 0.22 μm of syringe membrane filtration obtains the carbon quantum dot presoma (bare-CDs) compared with small particle.Filtered solution is placed in Molecular weight is that 8h is dialysed in 1000Da bag filter to remove unreacted citric acid and 2G-PAMAM.By bare-CDs after purification Solution freeze-drying process obtains solid bare-CDs, and places it in drier.
Step 3:NH2The preparation of-CDs
Bare-CDs prepared by step 2 is transferred in round-bottomed flask three times and by extract liquor with methanol extraction.It measures 16mL methyl acrylate and being added dropwise in extract liquor dropwise reacts for 24 hours at 30 DEG C.To after reaction, by the solution after reaction Methanol is evaporated off in 30 DEG C of backspins, and is washed three times with methanol to remove unreacted methyl acrylate.To after above-mentioned washing 10mL methanol is added in solution and 16mL ethylenediamine is added dropwise dropwise and is reacted for 24 hours at 30 DEG C.After the reaction was completed, 30 DEG C of backspins are evaporated off Methanol is removed, and is washed three times with methanol to remove unreacted ethylenediamine.Resulting yellow solution is transferred to molecular cut off It is the 8h that dialyses in the bag filter of 1000Da to remove unreacted ethylenediamine and methyl acrylate.By NH after purification2- CDs is molten Liquid is freeze-dried and obtained drying solid is placed in drier.
The characterization of 2 carbon quantum dot of embodiment
1, average grain diameter and Zeta potential characterization
Bare-CDs and NH is measured using ZEN3600 type Malvern dynamic light scattering particle size instrument2Two samples of-CDs are put down Equal partial size and Zeta potential, tested media is water, and test temperature is 25 DEG C.
2, TEM microscopic appearance and structural characterization
Take a small amount of bare-CDs and NH22mL anhydrous methanol is added simultaneously into centrifuge tube respectively in 5mL centrifuge tube in-CDs Ultrasonic disperse 5min uniformly drips sample on 400 mesh copper mesh, is added using Tecnai G2F20 Flied emission transmission electron microscope in 80KV Observing samples pattern under fast voltage.It is red using transmission electron microscope (TEM), dynamic light scattering particle size instrument (DLS) and Fourier External spectrum instrument (FT-IR) has carried out microscopic appearance observation to bare-CDs the and NH2-CDs sample of preparation.
As shown in Fig. 2A, it can be seen that using hydro-thermal decocting method preparation bare-CDs have regular spherical shape, particle it Between monodispersity it is good, size uniformity.It is scanned to obtain bare-CDs's by Malvern dynamic light scattering particle size instrument Average grain diameter is 4.4nm.Using ethylenediamine as coating material, bare-CDs table is grafted on amido bond by methyl acrylate Face makes bare-CDs amination obtain NH2-CDs.As shown in Fig. 2 B, NH2- CDs average grain diameter increases to 25.3nm.Pass through TEM Figure is as can be seen that NH2Monodispersity is good between-CDs, and size uniformity, there is no agglomerations.Meanwhile it can be with by Fig. 2 C Find out, the Zeta potential of bare-CDs is+40.1mV, NH2The Zeta potential of-CDs is+94.4mV.This is because 2G-PAMAM Carbon dots are constructed by decocting method as nitrogen source, the amino on 2G-PAMAM promotes bare-CDs rich in a large amount of amino, to make Bare-CDs shows positive charge.And ethylenediamine is dressing agent, being grafted on the surface bare-CDs by methyl acrylate makes the number of amino Amount increases, therefore NH2The Zeta potential of-CDs increases 54.3mV compared with bare-CDs.
3, FT-IR is characterized
Take bare-CDs and NH2Sample, pressing potassium bromide troche is lyophilized in-CDs.Using 27 type determination of infrared spectroscopy of Tensor Infrared absorption pattern, scanning range are 500~4000cm-1.Test result is as shown in Figure 2 D, can by the infared spectrum of bare-CDs To find out, 3332cm-1And 1560cm-1Place respectively bare-CDs surface amino groups N-H stretching vibration peak and flexural vibrations peak, 1148cm-1Place is the flexural vibrations peak of C-N, 1328cm-1Place is the flexural vibrations peak of-OH, 1483cm-1Place is-OH on carboxyl Flexural vibrations peak.After ethylenediamine is connect by methyl acrylate grafts on the surface bare-CDs with amido bond.In 1654cm-1Place is aobvious Reveal the flexural vibrations peak of amido bond N-H, 1706cm-1Place shows the C-N flexural vibrations peak of amido bond.In addition to this, 3075cm-1Place is-NH2Stretching vibration peak, peak become it is wider, illustrate by it is ethylene diamine-modified afterwards carbon dots amination degree It is higher.And 1560cm-1Place and 1406cm-1Place is respectively the N-H flexural vibrations peak of surface amino groups and the flexural vibrations peak of-OH.
4, photoluminescent property
Prepare certain density bare-CDs, NH2- CDs, 2G-PAMAM solution, using fluorescent spectrophotometer assay its Fluorescence pattern, scanning range are 200~700nm.As a result as shown in Figure 3A, it can be seen that NH2The fluorescence intensity of-CDs is dense with it Spend positive correlation.Work as NH2The concentration of-CDs is less than 18 μ gmL-1When, NH2- CDs fluorescence intensity with its concentration increase and It sharply increases.But when its concentration is greater than 18 μ gmL-1When, with NH2The concentration of-CDs increases, and fluorescence intensity, which increases, to be become It is slow.Due to during detecting copper ion, NH2The concentration of-CDs has the influence of conspicuousness to the sensitivity of detection.Work as NH2-CDs When concentration is smaller, the error as caused by instrument signal to noise ratio accounts for leading factor.Work as NH2When-CDs concentration is larger, although can be by instrument It influences to eliminate brought by device signal-to-noise ratio, but its higher concentration can then reduce the sensitivity of detection.Therefore, according to testing repeatedly Determine NH2The detectable concentration of-CDs is 100 μ gmL-1。
Fig. 3 B is NH2- CDs its fluorescent emission map under different wave length excitation.As seen from the figure, it is excited in different wave length Under, NH2- CDs launch wavelength does not have biggish change.But fluorescence intensity corresponding to launch wavelength is with excitation wavelength First increase and reduces afterwards.This is because, the NH after ethylene diamine-modified2Its partial size of-CDs increases to 25nm relative to bare-CDs.When Quantum effect is weakened after the partial size of carbon quantum dot is greater than 10nm, and dependence is not presented in launch wavelength and excitation wavelength.Cause This, synthesized NH2- CDs has more stable spectroscopic properties.
3 carbon dots of embodiment detect copper ion
1, copper ion responsiveness is tested
Due to NH2The amino on the surface-CDs can fast Acquisition solution Cu2+It forms cupric ammine complex and is covered on its surface. According to rate effect in fluorescence, it is formed by cupric ammine complex and is covered on NH2The surface-CDs.At this point, NH2The surface-CDs is formed by Cupric ammine complex can prevent it from receiving external ultraviolet stimulation, or the hair of its fluorescence can be prevented after it receives external irritant It penetrates.Therefore, work as NH2- CDs captures Cu2+The cupric ammine complex being formed on its surface afterwards can change its spectrum behavior.
As a result referring to fig. 4, a c e respectively indicates carbon quantum dot NH in Fig. 42The ultra-violet absorption spectrum of-CDs, excitation spectrum And emission spectrum；B d f respectively indicates NH2- CDs in conjunction with copper ion after ultra-violet absorption spectrum, excitation spectrum and transmitting light Spectrum；G and h is respectively indicated under fluorescent light, carbon quantum dot NH2The fluorescence phenomenon of the front and back in conjunction with copper ion-CDs.It can by Fig. 4 Know, NH2The ultraviolet characteristic absorption peak of-CDs is in 232.2nm.As addition Cu2+Afterwards, NH2The ultraviolet characteristic peak of-CDs is blue shifted to 206.4nm. Meanwhile occurring a new peak at 365nm.This is because amino and Cu2+It is formed caused by cupric ammine complex.By NH2- CDs's Excitation and transmitting map can be seen that.In not copper ions, NH2The excitation of-CDs and launch wavelength be respectively 349nm and 454nm, corresponding intensity are respectively 563.6 and 444.2；NH after addition copper ion2The excitation of-CDs and launch wavelength are constant, right The intensity answered successively is reduced to 100.1 and 85.4.Due to Cu2+With NH2The surface-CDs-NH2Complexing forms cupric ammine complex covering In NH2The surface-CDs.According to fluorescence inner filtering effect, it is formed by complex compound and is covered on NH2The surface-CDs will prevent NH2- CDs connects By burst of ultraviolel and carbon dots emission spectrum is prevented, so as to cause NH2- CDs is in capture Cu2+Its excitation and emissive porwer are certain afterwards It is weakened in degree.As can be seen that prepared NH2- CDs shows blue light under ultraviolet 365nm excitation, as addition Cu2+Afterwards, Fluorescence intensity is substantially reduced under 365nm excitation.
2、Cu2+Linear relationship detection
Accurately weigh the NH of above method preparation2- CDs is simultaneously dissolved in PBS (pH=7.4) buffer, and using by It is 100 μ gmL that grade dilution method, which obtains concentration,-1NH2- CDs mother liquor；Use step by step dilution method with PBS (pH=7.4) buffer it is molten Liquid is that successively compound concentration is 1 μm of olL to solvent-1, 1mmolL-1Cu2+Mother liquor.
With above-mentioned matched Cu2+Liquid is mother liquor, and PBS (pH=7.4) buffer is that compound concentration is 0,0.01 to solvent respectively, 0.05,0.25,0.5,0.75,10,50,100,250,400,600μmol·L-1Cu2+Liquid to be detected.To it is above-mentioned it is to be measured in plus Enter the prepared NH of I2- CDs mother liquor makes NH in prepare liquid2The concentration of-CDs is 10 μ gmL-1.By the solution prepared in glimmering NH is detected under 365nm in light spectrophotometer2The fluorescence intensity of-CDs.
As a result as shown in figure 5, under the conditions of excitation and transmission channel are all 5nm, 100 μ gmL-1NH2- CDs fluorescence intensity It is 468.9.When copper ion concentration is continuously increased in solution, NH2The fluorescence intensity of-CDs also weakens therewith, works as Cu2+Concentration increases To 600 μm of olmL-1When its fluorescence intensity be reduced to 81.9, fluorescence intensity is free from 0.17 times of copper ion.Pass through fitting Curve can be seen that NH2The section that-CDs detects copper ion is 0.01~600 μm of olL-1, fit equation Y=3.4281+ 0.34718X, R2=0.94289, there is wider detection range.By matched curve it can be seen that the probe concentration be 100 μg·mL-1The limit of lower detection copper ion is 0.01 μm of olL-1。
3、NH2- CDs selective enumeration method
1) metal heteroion interference experiment
Use step by step dilution method by solvent compound concentration of PBS (pH=7.4) buffer be 1mmolL-1Heteroion it is female Liquid (M+:Co2+,Mn2+,Ag+,Cs2+,Zn2+,Hg2+,Na+,Fe2+,K+,Mg2+,Ba2+,Ni2+,Ca2+,Fe3+).It is miscellaneous by what is matched Ion mother liquor be diluted with concentration be 10 μm of olL-1Heteroion prepare liquid.The above method is added into above-mentioned prepare liquid The NH of preparation2- CDs mother liquor makes NH in prepare liquid2The concentration of-CDs is 10 μ gmL-1.By the solution prepared in fluorescence spectrophotometer NH is detected under 365nm in photometer2The fluorescence intensity of-CDs.
2) amino acid interference experiment
Use step by step dilution method by solvent compound concentration of PBS (pH=7.4) buffer be 1mmolL-1Amino acid it is female Liquid (L-Pro, L-ALa, L-Lys, L-Met, L-Ser, L-GLy, L-GLu, L-Leu, L-Hyp, L-His, L-Cys).It will be matched Span amino acid mother liquor be diluted with concentration be 10 μm of olL-1Amino acid prepare liquid.On being added into above-mentioned prepare liquid State the NH of method preparation2- CDs mother liquor makes NH in prepare liquid2The concentration of-CDs is 10 μ gmL-1.By the solution prepared in glimmering NH is detected under 365nm in light spectrophotometer2The fluorescence intensity of-CDs.
In order to detect prepared NH2- CDs is only capable of by Cu2+It is quenched, we have selected different types of metal ion and ammonia Base acid verifies it.It is 100 μ gmL as shown in (A) in Fig. 6-1NH2- CDs in different metal ions solution, Fluorescence intensity under 365nm burst of ultraviolel.15 metal ion species detected Cu only2+Ion can make NH2- CDs fluorescence occurs It is quenched.Especially in the periodic table of elements with Cu2+Adjacent Ni2+And Zn2+Ion cannot be such that its fluorescence is quenched.Illustrate institute The NH of synthesis2- CDs has good specificity, can be with the Cu in the detection solution of specificity2+.Fig. 6 (B) is 100 μ gmL- 1NH2The fluorescence intensity figure of-CDs in different aminoacids solution, it can be seen that the addition of amino acid is to NH2The fluorescence intensity of-CDs Without influence.Prepared NH is proved from side2- CDs can be applied to Cu in organism2+Detection.
3) stability experiment
Use step by step dilution method by solvent of distilled water NH is respectively configured2- CDs concentration is 10 μ gmL-1And NaCl's is dense Degree is respectively 0.1,0.5,0.75,1,1.25,1.5,1.75,2molL-1, and by the solution prepared in fluorescence spectrophotometry NH is detected under 365nm in meter2The fluorescence intensity of-CDs.
Using that concentration is respectively configured by solvent of distilled water for dilution method step by step is 1 μm of olL-1PBS (pH=7.4), Tris-HCl, Tris-HAc, Tris-NaAc, CA-SC, Tris-EDTA and HePes-Tris buffer, and be with this buffer NH is respectively configured in mother liquor2- CDs concentration is 10 μ gmL-1And each buffer concentration is respectively 100nmolL-1Contain NH2-CDs Buffer, and the solution prepared is detected into NH under 365nm in sepectrophotofluorometer2The fluorescence intensity of-CDs.
In order to verify NH2- CDs fluorescent quenching is to capture Cu by the amino on its surface2+One layer of complex compound is formed on surface to draw It rises.Metal heteroion is detected using hydroxylating and carboxylated carbon dots.As a result as shown in Figure 7, it can be seen that identical Under channel width, the fluorescence intensity of hydroxylating and carboxylated CDs are respectively 412 and 550.With prepared NH2- CDs is slightly poor Different, the functional group that reason essentially consists in the surface CDs is the donor of CDs fluorogen electronics, its surface official under burst of ultraviolel It can roll into a ball electronics transfer to fluorescence radiation group.Therefore, CDs surface functional group difference can lead to CDs and generate different fluorescence intensities. On the other hand, Cu2+The fluorescence intensity of two CDs can not be changed, this is because hydroxyl and carboxyl can not capture in solution freely Cu2+, thus can not the surface CDs formed one layer of complex compound cause CDs still can receive the external world ultraviolet stimulation and issue glimmering Light.Since the carbon source of prepared CDs chooses citric acid, citric acid is eliminated as carbon source pair in the identical situation of carbon source Experimental result bring error, this experimental result have absolutely proved addition Cu2+After cause NH2- CDs fluorescence is quenched main Reason is that the amino on its surface captures the Cu in solution2+And its fluorescence is caused to be quenched in one layer of complex compound of its Surface Creation.
In order to further probe into prepared NH2The optical stability of-CDs.This experiment is different types of slow by designing Fliud flushing and the NaCl solution of various concentration probe into probe optical stability.As a result as shown in figure 8, (A) is probe in Fig. 8 In PBS, Tris-HCl, Tris-HAc, Tris-NaAC, CA-SC, Tris-EDTA, the fluorescence in HePes-Tris buffer is strong Degree figure, as can be seen from the figure probe fluorescence intensity deviation in 7 kinds of buffers is little, illustrates prepared NH2- CDs application Range is wide, can be applied in the middle of the copper ion detection of a variety of buffers.(B) is probe in various concentration NaCl solution in Fig. 8 In fluorescence intensity, it can be seen that concentration be 0.1~2molL-1NaCl solution in NH2The fluorescence intensity change of-CDs Less, especially in 0.1molL-1Fluorescence intensity is equal with the fluorescence intensity in PBS buffer solution in NaCl solution.Illustrate this hair Bright prepared NH2- CDs can be applied to Cu in physiological saline2+Detection.
4、NH2- CDs detection mechanism research
Use step by step dilution method by solvent compound concentration of PBS (pH=7.4) buffer be 1mmolL-1Ethylenediamine tetraacetic Acetic acid (EDTA) mother liquor.Sequentially adding 200 μ L concentration is 1mmolL-1Cu2+Mother liquor, 200 μ L EDTA mother liquors, 50 μ L are above-mentioned The NH that method is matched2- CDs mother liquor and 50 μ L ultrapure waters.The solution prepared is examined under 365nm in sepectrophotofluorometer Survey NH2The fluorescence intensity of-CDs.As a result as shown in figure 9, (A) is the NH under condition of different pH in Fig. 92- CDs is to Cu2+Detection Fluorescence intensity profile.As seen from the figure, Cu is being not added2+When NH2- CDs fluorescence intensity in different pH environment is different.In pH < 7 When, fluorescence intensity is reduced with the reduction of pH.In pH > 7, biggish fluctuation does not occur for fluorescence intensity.Mainly due to Prepared NH2- CDs contains on surface a large amount of amino, and in acidic environment, amino is protonated to hinder the jump of electronics It moves.In neutral and alkaline solution, NH2- the NH on the surface-CDs2It is not protonated ,-NH2It can be ultraviolet as electronq donor Electronics is provided to fluorogen under excitation.Meanwhile when pH is between 6~8, NH2- CDs responds copper ion more sensitive.As pH < When 6 and pH > 8, NH2- CDs is to Cu2+Responsiveness sharply decline.This is because in acid system environment, NH2The surface-CDs Amino be protonated hinder amino capture Cu2+, so that its fluorescent quenching can not be made；In alkaline environment, although amino is naked It is exposed at NH2The surface-CDs, but Cu2+Cu (OH) is generated in conjunction with the hydroxyl in solution2Precipitating, and then make NH2- CDs can not be right Cu in aqueous slkali2+It is detected.Due to prepared NH2The section detection pH of-CDs is 6~8.Therefore, prepared probe It can be applied to normal cell and tissue cu in organism2+Detection.
(B) is that EDTA fluorescence restores detection in Fig. 9.As can be seen that addition and Cu in the solution that fluorescent quenching has occurred2+ The edta reagent of isoconcentration, NH2The fluorescence intensity of-CDs is restored.In the NH being quenched2EDTA is added in-CDs, due to EDTA and Cu2+It, can be by NH with more potent complexing power2The surface-CDs is by-NH2The Cu of capture2+Capture comes out, thus broken It is broken NH2The complex layer on the surface-CDs, makes NH2- CDs fluorescence restores.The result illustrates that prepared probe may be reused Remove detection Cu2+。
5, cell experiment
1) cytotoxicity experiment
Selection L-929 is normal cell model, and HepG-2 and MCF-7 are tumor models to NH2- CDs cytotoxicity It is probed into.Under aseptic technique, using the cell of 0.25% trypsin digestion logarithmic growth phase, 2000rpm centrifugation 5min collects cell.It using fresh DMEM culture solution suspension cell and counts, preparing cell suspension makes cell concentration 5 × 103 A mL-1.And enter 5000 cell kinds in 96 orifice plates, every hole is added 100 μ L and cultivates based on incubator culture at 37 DEG C for 24 hours. Compound concentration is 0,2,4,8,10,20,40,60,80,100 μ gmL respectively-1NH2- CDs culture medium solution, and each concentration Design 5 multiple holes.Institute's abacus is respectively provided with blank well, i.e., containing only culture medium in hole.96 orifice plates are replaced with the solution containing drug In original culture medium, culture for 24 hours.It is then 5mgmL with concentration-1MTT solution replace 96 orifice plates in hydroponics 4h, move Except former culture medium, draws 100 μ L DMSO and inject each hole dissolution first a ceremonial jade-ladle, used in libation, absorbance is measured at 490nm using microplate reader.
Cell survival rate=(ODtreated/ODcontrol) × 100%
Wherein, ODcontrolIt is free from the absorbance in pharmaceutical carrier hole, ODtreatedIt is the absorbance containing pharmaceutical carrier hole.
Figure 10 is respectively NH2- CDs is to HepG-2, the cytotoxicity figure of MCF-7 and L-929 cell.From the thin of three cells In cellular toxicity figure as can be seen that in the 2 μ gmL tested-1~100 μ gmL-1In concentration range, three plants of cell survival rates are equal It is maintained at 95% or more, is illustrated in NH2-Three plants of cytotoxics are acted within the scope of CDs detectable concentration, there is preferable biology Compatibility.
2) cell imaging is tested
Selecting MCF-7 and HepG-2 is that cell model carries out cellular uptake behavior and intracellular copper ion detection research.It is first First prepare the culture medium containing 10% fetal calf serum (FBS), 1% dual anti-(penicillin/streptomycin).By 4 × 105A cell is scattered in It in 8mL culture medium and is separately added into 4 laser co-focusing wares, is cultivated for 24 hours at 37 DEG C of incubator.It is seen under inverted microscope Cellular morphology is examined, is separately added into 2mL NH into 4 laser co-focusing wares when cell state is good2- CDs concentration is 10 μ g mL-1Culture medium solution, discard material liquid after cultivating 4h, after washing 2~3 times with PBS solution, three laser co-focusings thereto The culture medium solution containing various concentration copper ion is added in ware.The culture medium containing copper ion is discarded after impregnating 5min, and After washing 2~3 times with PBS solution, cell is soaked in PBS solution and observes intracellular Fluorescence situation in laser co-focusing.
Process is quenched in order to probe into NH2-CDs fluorescence probe in detection copper ion fluorescence dynamic intracellular.We are by NH2-CDs Certain density copper ion is added in culture dish in laser confocal microscope with after HepG-2 and MCF-7 cell co-cultivation 4h Under be scanned.It as shown in figure 11, is the dynamic scan to HepG-2 cell 23s, under laser co-focusing, carbon quantum dot NH2- CDs and copper ion cohesive process, as binding time extends, fluorescence is gradually quenched.As can be seen that be added in 0s, that is, copper ion Moment still shows clearly blue-fluorescence into the cell.Intracellular blue-fluorescence gradually weakens after reaching 6s, until 20s Intracellular blue-fluorescence, which is quenched, reaches stable.This phenomenon explanation, prepared NH2-CDs can be applied to intracellular copper ion Fast real-time monitoring.It can not be entered in nucleus by nucleus nuclear membrane.
In order to evaluate prepared NH2The application prospect of-CDs fluorescence detection in biology department, Figure 12 are prepared by use NH2- CDs is directly used in Cu in HepG-2 and MCF-7 cell2+Fluorescence detection.Under laser co-focusing, 100 μ g/ml NH2- Fluorescence response of the CDs to various concentration copper ion in MCF-7 and HepG-2 cell (250nM, 10 μM and 100 μM).It can from figure To observe, NH is used2HepG-2 the and MCF-7 cell that-CDs was incubated for shows clearly blue-fluorescence；It is different dense when being added After the copper ion of degree, Cu2+Free diffusing enters into the cell and by NH intracellular2- CDs capture causes fluorescent quenching intracellular.Due to thin Fluorescence probe is there are osmotic pressure inside and outside after birth, and NH2The bio-toxicity of-CDs fluorescence probe is low, and only cell is to its intake foot It is enough, it can accurately realize into the cell to Cu2+Sensitive Detection fluorescence imaging.

Claims (9)

1. a kind of preparation method of blue luminescence quantum dot, which comprises the following steps:
1) using citric acid as carbon source, using the polyethyene diamine dendritic with amino as nitrogen source, carbon is made using decocting method Quantum dot presoma；
2) using ethylenediamine as decorating molecule, methyl acrylate is link molecule, is modified carbon quantum dot presoma, and indigo plant is made Color fluorescence quantum.
2. the preparation method of blue luminescence quantum dot according to claim 1, which is characterized in that using decoction in step 1) Method prepares carbon quantum dot presoma, comprising the following steps:
1.1) citric acid: the polyethyene diamine dendritic with amino: water=1g:0.5g:5mL amount ratio is pressed, by lemon Lemon acid is dispersed in water with polyethyene diamine dendritic, handles 2h in 200 DEG C of decoctions, brown solution is made；
1.2) to brown solution centrifugal treating, collect supernatant, supernatant successively through filtering with microporous membrane, dialysis and it is dry at Carbon quantum dot presoma is made in reason.
3. the preparation method of blue luminescence quantum dot according to claim 2, which is characterized in that in step 1.2), supernatant Liquid uses 0.22 μm of syringe membrane filtration, then by the bag filter dialysis treatment 8h of filtered solution 10000Da, is made flat The carbon quantum dot presoma that equal partial size is 4.4nm.
4. the preparation method of blue luminescence quantum dot according to claim 1, which is characterized in that in step 2), with second two Amine is decorating molecule, and methyl acrylate is link molecule, is modified carbon quantum dot presoma, concrete operations include:
2.1) by carbon quantum dot presoma with methanol extraction for several times, collect methanol extraction liquid, propylene is added dropwise into methanol extraction liquid Sour methyl esters, reacts for 24 hours at 30 DEG C, the solution revolving after reaction is removed methanol, and washed for several times with methanol；
2.2) methanol: ethylenediamine=10:16 volume ratio is pressed, methanol is added into the solution after washing and second two is added dropwise dropwise Amine reacts for 24 hours at 30 DEG C；Solution revolving after reaction is removed into methanol, and is washed for several times with methanol, yellow solution is made； By the dialysis of resulting yellow solution, freeze-drying process, blue luminescence quantum dot is made.
5. the preparation method of blue luminescence quantum dot described according to claim 1~any one of 4, which is characterized in that institute State polyethyene diamine dendritic specific with amino the preparation method is as follows:
Step 1: after stirring ethylenediamine and methanol by the volume ratio of 4:10, acrylic acid first being added dropwise into the solution Ester reacts for 24 hours at 30 DEG C；The volume ratio of methyl acrylate and ethylenediamine is 1:4；
Step 2: the solution revolving after step 1 reaction being removed into methanol, again with methanol is washed for several times, then to the solution after washing Middle addition methanol and ultrasonic disperse, then ethylenediamine is added dropwise into the solution after dispersion, it is reacted for 24 hours at 30 DEG C；Methanol and second two The volume ratio of amine is 10:(3~10)；
Step 3: the solution revolving after step 2 reaction being removed into methanol, again with methanol is washed for several times, and obtaining yellow oily liquid is Generation dendrimer 1G-PAMAM；
Step 4: after stirring generation dendrimer 1G-PAMAM and methanol by the volume ratio of 4:10, to the solution Middle dropwise addition methyl acrylate, reacts 36h at 35 DEG C；The mass ratio of methyl acrylate and generation dendrimer 1G-PAMAM is 1:4；
Step 5: the solution revolving after step 4 reaction being removed into methanol, again with methanol is washed for several times, then to the solution after washing Middle addition methanol and ultrasonic disperse, then generation dendrimer 1G-PAMAM is added dropwise into the solution after dispersion, it is anti-at 35 DEG C Answer 48h；The volume ratio of methanol and generation dendrimer 1G-PAMAM are 20:(3~10)；
Step 6: the solution revolving after step 5 reaction being removed into methanol, again with methanol is washed for several times, two generation dendrimer 2G- PAMAM；
Generation dendrimer 1G-PAMAM and two generation dendrimer 2G-PAMAM is can be as nitrogen source with amino Polyethyene diamine dendritic.
6. using blue luminescence quantum dot made from method described in any one of Claims 1 to 5, which is characterized in that should The average grain diameter of blue luminescence quantum dot is 25.3nm, and surface charge is+94.4mV.
7. application of the blue luminescence quantum dot as claimed in claim 6 as copper ion detection fluorescence probe.
8. application according to claim 7, which is characterized in that detectable concentration of the blue luminescence quantum dot to copper ion Section is 0.01 μm of olL-1~600 μm of olL-1。
9. application according to claim 7, which is characterized in that blue luminescence quantum dot can specificity detection it is intracellular Copper ion.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109609124A (en) * 2019-01-14 2019-04-12 京东方科技集团股份有限公司 Carbon quantum dot hydrogel and preparation method thereof, the method for detecting copper ion
CN109796973A (en) * 2019-02-21 2019-05-24 中国科学院长春光学精密机械与物理研究所 Solid luminescent carbon nano dot and preparation method and application
CN111422862A (en) * 2020-05-12 2020-07-17 上海理工大学 Method for separating graphene quantum dots by using molecular sieve
CN113652224A (en) * 2021-01-31 2021-11-16 重庆大学 Anti-quenching carbon quantum dot solid compound, anti-blue light film and preparation method thereof
CN115895645A (en) * 2021-09-30 2023-04-04 北京服装学院 Preparation and application of carbon dots by using polyester as precursor
WO2023142891A1 (en) * 2022-01-28 2023-08-03 华东师范大学 Preparation method and application of carbon quantum dots having high fluorescence quantum yield
CN116606648A (en) * 2023-05-22 2023-08-18 辽宁大学 Ethylenediamine doped fluorescent carbon dot, preparation method thereof and application thereof in detecting copper ions in water body

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101430283A (en) * 2008-12-19 2009-05-13 武汉大学 Production method for high-fluorescence quantum yield carbon point
CN107474248A (en) * 2017-08-25 2017-12-15 青岛大学 A kind of big particle diameter dendritic macromole of fluorescence and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101430283A (en) * 2008-12-19 2009-05-13 武汉大学 Production method for high-fluorescence quantum yield carbon point
CN107474248A (en) * 2017-08-25 2017-12-15 青岛大学 A kind of big particle diameter dendritic macromole of fluorescence and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JUNSAI SHEN ET AL.,: ""Nitrogen-doped carbon dots derived from polyamindoamine dendrimer"", 《RSC ADVANCE》 *
崔玉花: ""PAMAM树状大分子的合成及其在纳米材料中的模板作用"", 《万方数据知识服务平台》 *
李敏 等: ""氨基功能化荧光碳量子点的制备及对铜离子的检测"", 《材料导报》 *
杨柳涛 等: "《高分子化学》", 31 December 2015, 四川大学出版社 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109609124A (en) * 2019-01-14 2019-04-12 京东方科技集团股份有限公司 Carbon quantum dot hydrogel and preparation method thereof, the method for detecting copper ion
WO2020147499A1 (en) * 2019-01-14 2020-07-23 京东方科技集团股份有限公司 Carbon quantum dot hydrogel and preparation method therefor, and method for detecting copper ions
CN109796973A (en) * 2019-02-21 2019-05-24 中国科学院长春光学精密机械与物理研究所 Solid luminescent carbon nano dot and preparation method and application
CN109796973B (en) * 2019-02-21 2020-11-03 中国科学院长春光学精密机械与物理研究所 Solid luminescent carbon nanodot and preparation method and application thereof
CN111422862A (en) * 2020-05-12 2020-07-17 上海理工大学 Method for separating graphene quantum dots by using molecular sieve
CN113652224A (en) * 2021-01-31 2021-11-16 重庆大学 Anti-quenching carbon quantum dot solid compound, anti-blue light film and preparation method thereof
CN113652224B (en) * 2021-01-31 2024-02-23 重庆大学 Anti-quenching carbon quantum dot solid compound, blue light prevention film and preparation method thereof
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WO2023142891A1 (en) * 2022-01-28 2023-08-03 华东师范大学 Preparation method and application of carbon quantum dots having high fluorescence quantum yield
CN116606648A (en) * 2023-05-22 2023-08-18 辽宁大学 Ethylenediamine doped fluorescent carbon dot, preparation method thereof and application thereof in detecting copper ions in water body

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