CN105255487A - Amino alcohol functional CDs (carbon dots), preparation method and application of amino alcohol functional CDs in copper ion measurement - Google Patents
Amino alcohol functional CDs (carbon dots), preparation method and application of amino alcohol functional CDs in copper ion measurement Download PDFInfo
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Abstract
The invention discloses a preparation method of amino alcohol functional CDs (carbon dots) and an application of the amino alcohol functional CDs in double-signal copper ion measurement. The preparation method comprises steps as follows: carbon source preparation, CD preparation, fluorescence detection and ultraviolet visible detection. According to the method, preparation and surface modification are combined, L-phenylalaninol is adopted as the carbon source for the first time, fluorescence detection of the copper ions is performed through the biuret reaction of amino alcohol and the copper ions under the alkaline condition for the first time, bluish violet is produced, rapid detection of the copper ions in water is realized, behaviors of a water production enterprise are regularized, and development of the water quality safety career of China is promoted.
Description
Technical field
The invention belongs to technical field of analysis and detection, be specifically related to the preparation method of carbon point and the application of fluorescence property thereof in carbon nanomaterial.
Background technology
Carbon-based nano point is a kind of novel zero dimension carbonaceous Nano-Materials, comprise graphene quantum dot (graphenequantumdots, GQDs), fluorescent carbon nanometer tube (fluorescentcarbonnanotubes, and carbon point (carbondots, CDs) etc. CNTs).CDs is the spherical carbon nano-particles of Discrete-time quasi that a kind of diameter is less than 10nm, its typical core-shell structure comprise containing carboxyl or other chemical functional groups shell and inside is unformed or the core of crystalline graphite.Compared with organic dye or conventional semiconductors quantum dot, CDs has many advantages, powerful luminescent properties, highly water-soluble, biocompatibility and hypotoxicity, resistance to photobleaching, the strong unreactiveness of such as visible-range, is easy to synthesis and finishing etc.In recent years, CDs is widely used in every field, as bio-imaging, sensor, photochemical catalysis, photoelectronics etc.Fluoroscopic examination metal ion is wherein one of most important application, can the quantitative assay of simple realization metal ion by the change observing fluorescence intensity, without the need to expensive instrument and complex operations.
Cupric ion is outside iron ions and zine ion, and in human body, the 3rd abundant transiting state metal ion, is plant, animal, comprises the essential trace element of the mankind, in environmental area, biological and chemical system, play vital effect.In body, the shortage of cupric ion can affect related enzyme activity, T suppression cell metabolism, cause hematological manifestation, and the cupric ion of long-term exposure high density can cause liver or injury of the kidney, and multiple encephalopathy such as alzheimer disease, Parkinsonism is also relevant to cupric ion.Cupric ion is classified as priority pollutant by Environmental Protection Agency (U.S.EnvironmentalProtectionAgency, EPA), and the limitation in its tap water is 1.3ppm (about 20 μm of olL
-1), the mean concns of normal group blood cupric ion is 100-150 μ gdL
-1(15.7-23.6 μm of olL
-1).Therefore, causing toxic action for controlling cupric ion pollution with it, being badly in need of setting up simple green, reliably responsive cupric ion detection method.
The carbon point of existing a lot of finishing is used for the detection of cupric ion, but without the rare report of carbon point of finishing.Herein, adopt L-phenylalaninol as sole carbon source, prepare amino alcohol functionalized carbon point by a step hydrothermal carbonization.Compared with preparing nano-sensor with two traditional steps, the strategy of this " integrated preparation-modification " is more effectively simple.Adopt L-phenylalaninol as carbon source, have the following advantages: containing phenyl ring in (1) its structure, there is higher carbon containing degree; (2) amino in L-phenylalaninol structure makes the carbon point synthesized be N-doping carbon point, ensure that it does not need surface passivation can obtain higher quantum yield; (3) compared with L-Phe, not containing carboxyl in L-phenylalaninol.By deoxygenation abundant before hydrothermal carbonization, obviously can reduce the carboxyl on the carbon point surface of preparation, avoid the sequestering action of carboxyl and other ions, improve the selectivity to cupric ion; (4) in the basic conditions, amino alcohol can produce biuret reaction with cupric ion, produces bluish voilet mixture and causes carbon point assemble and quenching of fluorescence occurs.Dual signal change in this kind of sensing system may be used for fluorescence and the colorimetric sensing of cupric ion, provides correction to the issuable false signal in single signal sensing system.Therefore the sensing system prepared herein has prospect very much as the detection platform of cupric ion.
Summary of the invention
The object of this invention is to provide a kind of fluorescent carbon point, this carbon point preparation technology is simple, and good water solubility, stable luminescent property, has wide absorption spectrum and narrow fluorescence emission spectrum.
Another object of the present invention overcomes the deficiencies in the prior art, a kind of amino alcohol functionalized carbon point preparation method is provided and measures the application in cupric ion in dual signal, the cupric ion that the method preparation of combined with fluorescent carbon point first and finishing, fluorescence sense and colorimetric sensing are constructed first based on biuret reaction detects, and realizes cupric ion fast quantification qualitative analysis in water body.Be conducive to the behavior of specification water body manufacturing enterprise, promote the development of China's water quality safety cause.
The object of the invention is to realize in the following manner:
A kind of amino alcohol functionalized carbon point, this amino alcohol functionalized carbon point is prepared by following steps:
A) L-phenylalaninol is dissolved in deionized water, is adjusted to pH7.5-10.0 by NaOH solution, and the ultrasonic L-of making phenylalaninol is uniformly dispersed and obtains suspension; Wherein, every 0.05gL-phenylalaninol powder adds deionized water 6-12mL;
B) after suspension being carried out nitrogen deoxygenation 10-50min, at 150-200 DEG C of temperature, heat 4-14h, then be cooled to room temperature, then redissolve with deionized water, obtain carbon point solution;
C) by carbon point solution centrifugal, get supernatant liquor, then purify 24h with the molecular weight dialysis tubing retained as 500D, obtain amino alcohol functionalized carbon point.
Step a) described in the concentration of NaOH solution be 0.1molL
-1.
Step a) described in ultrasonic time be 0.2-1h.
Step b) in suspension be placed in teflon-lined autoclave carry out nitrogen deoxygenation.
Step c) in centrifugal rotational speed be 10000-13000rpm, centrifugation time is 10-30min.
The preparation method of above-mentioned amino alcohol functionalized carbon point comprises the following steps:
A) L-phenylalaninol is dissolved in deionized water, is adjusted to pH7.5-10.0 by NaOH solution, and the ultrasonic L-of making phenylalaninol is uniformly dispersed and obtains suspension; Wherein, every 0.05gL-phenylalaninol powder adds deionized water 6-12mL;
B) after suspension being carried out nitrogen deoxygenation 10-50min, at 150-200 DEG C of temperature, heat 4-14h, then be cooled to room temperature, then redissolve with deionized water, obtain carbon point solution; The amount of deionized water that this redissolution uses can add deionized water 6-12mL according to every 0.05gL-phenylalaninol powder;
C) by carbon point solution centrifugal, get supernatant liquor, then purify 24h with the molecular weight dialysis tubing retained as 500D, obtain amino alcohol functionalized carbon point.
Above-mentioned amino alcohol functionalized carbon point preparation method specifically comprises the following steps:
A) 0.05gL-phenylalaninol is dissolved in 6-12mL deionized water, uses 0.1molL
-1naOH solution be adjusted to alkalescence (pH7.5-10.0), ultrasonic 0.2-1h makes L-phenylalaninol be uniformly dispersed and obtains suspension.
B) be placed in by suspension in teflon-lined autoclave, nitrogen deoxygenation 10-50min, 150-200 DEG C of heating 4-14h, be cooled to room temperature, 6-12mL deionized water redissolves, and obtains carbon point solution.Step b) in carbon point strength of solution can be 2.85mgmL
-1.
C) by the centrifugal 10-30min of carbon point solution 10000-13000rpm, get supernatant liquor, remove large throw out, molecular weight retains the dialysis tubing purifying 24h into 500D, the carbon point room temperature preservation of purifying.
Amino alcohol functionalized carbon point of the present invention can be applied in the fluorescence sense of cupric ion, and during application, carbon point mixes with phosphate buffered saline buffer (PBS).Preferably phosphate buffer concentration is 0.01molL
-1, pH is 8.0-11.0.In fluorescence sense process, carbon point consumption is 100-300 μ L, and PBS consumption is 600-800 μ L.Fluorescence sense process carbon point mixes with PBS, and after adding cupric ion, the reaction times is 200-600s.
Amino alcohol functionalized carbon point of the present invention can application in the ultraviolet transducing of cupric ion, and during application, carbon point mixes with NaOH solution, and the concentration of preferred NaOH solution is 0.1molL
-1.Preferred ultraviolet transducing process carbon point and NaOH solution mass concentration ratio are 1:2-2:1.Ultraviolet transducing process carbon point mixes with NaOH solution, and after adding cupric ion, the reaction times is 200-600s.
The application that above-mentioned amino alcohol functionalized carbon point measures in cupric ion in dual signal specifically comprises the following steps:
1) cupric ion fluorescence sense: mixed with PBS by carbon point obtained above, rocked at room temperature builds alkaline environment, and add different concns cupric ion, control group adds aliquots of deionized water, and reaction 200-600s, measures fluorescence and calculate quenching of fluorescence rate.
2) cupric ion ultraviolet transducing: mixed with NaOH solution by carbon point obtained above, rocked at room temperature builds alkaline environment, adds different concns cupric ion, observes the bluish voilet complex compound of the formation of biuret reaction.NaOH solution, its concentration is 0.1molL
-1.
Realize fluorescence of the present invention-visible dual signal by following methods to detect:
Fluorescence detection method and condition:
Come that (it is F that experimental group adds the fluorescence intensity after cupric ion, and the fluorescence intensity that control group adds equal-volume deionized water is F herein with the difference of experimental group and control group fluorescence intensity and the ratio of control group fluorescence intensity
0, quenching of fluorescence rate R=(F
0-F)/F
0) show the effect of cupric ion quenching of fluorescence.R is larger, and show that the carbon point that cupric ion combines under certain condition is more, quencher efficiency is higher.Excitation wavelength is 340nm, and sweep velocity is 1200nmmin
-1, Photomultiplier tube voltage is 700V, and exciting slit and launching slit width is 5nm.
Ultraviolet detection method and condition:
Carbon point (preparing according to embodiment 1 method) and NaOH solution (0.1molL
-1) mixing, jolting is evenly to form alkaline environment.The cupric ion adding different concns obtains a series of concentration in system.Rocked at room temperature is even, observes the formation of biuret reaction bluish voilet mixture after reaction for some time, and gained solution centrifugal is got supernatant liquor carries out ultraviolet determination, and determined wavelength is 540nm.
Sample determination: select lake water and tap water two kinds of water samples.Before sample determination, need carry out simple pre-treatment to lake water, remove solid impurity in lake water with 0.45 μm of filter membrane suction filtration, tap water is without the need to any pre-treatment.Get carbon point and the 800 μ LPBS solution (0.01molL of 100 μ L purifying
-1, pH=10.5) and mixing, jolting is evenly with after forming alkaline environment, and add 100 μ L water samples, control group adds 100 μ L deionized waters, by the concentration of the fluorescence detection method mensuration Determined Copper in Aqueous Solution in above-mentioned after reaction 500s.
Amino alcohol functionalized carbon point prepared by present method is for fluoroscopic examination cupric ion, and its detectability (Limitofdetection, LOD) can reach 3.2nmolL
-1(S=3 σ), compared with known references, has wider linearity range (0.01-1,1-100 μm of olL
-1).There is the features such as highly sensitive, selectivity good, response is quick, have good stability, the efficient, sensitive of cupric ion in complex matrices can be realized and detect in real time.In addition, due to the biuret reaction of cupric ion under alkaline condition and amino alcohol uniqueness, can realize that there is 1mmolL
-1the visual detection of detectability.
Beneficial effect of the present invention:
1, the present invention adopt hydrothermal method first with L-phenylalaninol for carbon source, integrated synthesis and finishing, a step prepares amino alcohol functionalized carbon point.Compared with traditional finishing carbon point methods, the amino alcohol functionalized carbon point prepared in the present invention is for synthesize first, and one-step synthesis and modification, simplify preparation method.
2. the carbon point that prepared by the present invention is N doping carbon point, can obtain higher quantum yield without the need to surface passivation.
3., by controlling the time of hydro-thermal carbon point, the carbon point of different quantum yield can be obtained.
4. under alkaline condition, the amino alcohol on cupric ion and carbon point surface produces specific biuret reaction, and carbon point is reunited, and produces quenching of fluorescence.
5., compared with the carbon point amido modified with other, the amino alcohol of the carbon point prepared herein can produce biuret reaction in the basic conditions with cupric ion and form bluish voilet complex compound, can realize cupric ion Visual retrieval.Set up a kind of visual, easy cupric ion detection method.
6. breaking cannot the limitation of effective fluoroscopic examination cupric ion in the basic conditions, has widened the pH scope of cupric ion fluoroscopic examination further.
7. the carbon point selection of preparation is high, and sensitivity is good, has good stability and repeatability.
Accompanying drawing explanation
Fig. 1 is ultraviolet spectrogram and the fluorescence emission spectrogram of amino alcohol functionalized carbon point.
In interior illustration, (a) is carbon point solution under natural light; B () is carbon point solution under 365nm ultraviolet lamp
In figure, 1 is the ultraviolet spectrogram of amino alcohol functionalized carbon point, and 2 is fluorescence emission spectrogram.
Can see the obvious absorption peaks that carbon point has conjugation C=C key π-π * transfer transport to produce at 257nm wavelength from ultraviolet-visible absorption spectroscopy figure, and absorption band edge extends to 400nm, shows the formation of nano-sized carbon.Interior illustration is the photo of carbon point solution respectively under visible ray and UV-light (365nm), and carbon point solution clear, then sends obvious bright blue fluorescence under ultra violet lamp under visible light, proves the successful preparation of carbon point further.
Fig. 2 is the fluorescence emission spectrogram of amino alcohol functionalized carbon point under different excitation wavelength (310-380nm)
From the fluorescence emission spectrogram of carbon point, carbon point under 340nm excitation wavelength gained emission peak at 420nm place, visible region.The different excitation wavelength (310-380nm) of carbon point is excited, finds that carbon point is similar to the fluorescent characteristic that other fluorescent carbon materials also have exciting light dependence.Along with the increase of excitation wavelength, red shift is also with the change of fluorescence intensity gradually for the emmission spectrum of carbon point, and this phenomenon may be launched relevant with electron conjugated structure to the energy trapping of carbon point.
Fig. 3 is the infrared spectrogram of L-phenylalaninol and amino alcohol functionalized carbon point
In figure, (a) is L-phenylalaninol; B () is amino alcohol functionalized carbon point
In infrared spectrogram, a series of L-phenylalaninol and the common characteristic peak of carbon point can be observed, 3000cm
-1and 3500cm
-1place absorption peak correspondence-OH and-NH
2stretching vibration peak; 2922cm
-1and 2854cm
-1place absorption peak correspondence-CH
2-stretching vibration peak; 1574cm
-1and 1446cm
-1place's absorption peak then corresponding phenyl ring C=C stretching vibration peak.In Fig. 3 (a), 1436cm
-1the absorption peak at place is C-N stretching vibration.
Fig. 4 is the Raman spectrogram of amino alcohol functionalized carbon point.
The Raman spectrum of carbon point is 1343 and 1592cm
-1place's appearance two obvious absorption peaks, respectively corresponding D peak and G peak, the carbon atom vibration of dangling bonds on the terminal surface that D peak results from disordered graphite or glass carbon, the E of G peak then corresponding graphite
2gvibration modes, with sp in graphite two-dimensional hexagonal lattice
2hydbridized carbon atoms vibration is relevant, the vibration in reflection molecule in aromatic structure plane between C-C.Strength ratio (the I at usual D peak and G peak
d/ I
g) weigh unordered degree and the sp of carbon
3/ sp
2ratio.As seen from the figure, the I of carbon point
d/ I
gvalue is about 1.096, may be relevant with the textural defect of the carbon point produced in the pyrolytic process of L-phenylalaninol, as sp
2oxygen-containing functional group (C-O, C=O) on hydbridized carbon atoms site, and produce lattice vacancy and sp
3hydbridized carbon atoms.
Fig. 5 is that interference metal ion and cupric ion quenching of fluorescence efficiency comparative scheme.
Embodiment
Medicine and reagent: copper sulfate (CuSO
4the new precious Fine Chemical Works in Shanghai), sodium hydroxide (NaOH) (Chemical Reagent Co., Ltd., Sinopharm Group), L-phenylalaninol (L-phenylalaninol), Quinine Sulphate Di HC (Quininesulfate), dialysis membrane (MWCO:500) (in Aladdin reagent Co., Ltd), SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
42H
2o, Nanjing Chemistry Reagent Co., Ltd.), Sodium phosphate dibasic (Na
2hPO
412H
2o, Shanghai Ling Feng chemical reagent company limited), experimental water is redistilled water, 0.01molL
-1na
2hPO
412H
2o and 0.01molL
-1naH
2pO
42H
2the phosphate buffer soln (phosphatebufferedsolution, PBS) of the different pH of O solution preparation.
Below by way of specific embodiment, the present invention is described, but the present invention is not merely defined in these embodiments.
Embodiment 1
(1) preparation of carbon point: first 0.05gL-phenylalaninol is dispersed in 6mL deionized water, uses 0.1molL
-1naOH solution regulates pH to 7.5, ultrasonic 20min to make, and L-phenylalaninol is dispersed obtains suspension.Subsequently, suspension is transferred in teflon-lined autoclave, after nitrogen deoxygenation 10min, and 150 DEG C of heating (i.e. hydrothermal carbonization) 6h.Be cooled to room temperature, add 8mL deionized water and redissolve, obtain carbon point solution.The centrifugal 20min of solution 10000rpm is to remove large throw out, and centrifugal gained supernatant liquor molecular weight retains the dialysis tubing dialysis 24h of 500D, carbon point (the i.e. amino alcohol functionalized carbon point) room temperature preservation of purifying.
(2) fluorescence sense process: the carbon point 200 μ L getting purifying, with 600 μ L0.01molL
-1pBS solution (pH=8.5) mixing, jolting is evenly to form alkaline environment.
When measuring, add copper ion solution or copper water sample, rocked at room temperature is even, and carry out fluorometric assay after reaction 200s, excitation wavelength is 340nm.
(3) ultraviolet transducing process: the carbon point 100 μ L getting purifying, with 0.1molL
-1naOH solution mixes, and jolting is evenly to form alkaline environment.The two mass concentration ratio is 1:1.
When measuring, add copper ion solution or copper water sample, rocked at room temperature is even, observes the formation of biuret reaction bluish voilet mixture and carry out ultraviolet determination after reaction 200s.
Embodiment 2
(1) preparation of carbon point: first 0.05gL-phenylalaninol is dispersed in 8mL deionized water, uses 0.1molL
-1naOH solution regulates pH to 8.5.Ultrasonic 30min makes that L-phenylalaninol is dispersed obtains suspension.Subsequently, suspension is transferred in teflon-lined autoclave, after nitrogen deoxygenation 30min, and 160 DEG C of heating (i.e. hydrothermal carbonization) 8h.Be cooled to room temperature, add 10mL deionized water and redissolve, obtain carbon point solution.The centrifugal 30min of solution 10000rpm is to remove large throw out.For being further purified carbon point, centrifugal gained supernatant liquor molecular weight retains the dialysis tubing dialysis 24h of 500D.Carbon point (the i.e. amino alcohol functionalized carbon point) room temperature preservation of purifying.
(2) fluorescence sense process: the carbon point 200 μ L getting purifying, with 700 μ L0.01molL
-1pBS solution (pH=9.0) mixing, jolting is evenly to form alkaline environment.
When measuring, add copper ion solution or copper water sample.Rocked at room temperature is even, and carry out fluorometric assay after reaction 300s, excitation wavelength is 340nm.
(3) ultraviolet transducing process: the carbon point 150 μ L getting purifying, with 0.1molL
-1naOH solution mixes, and jolting is evenly to form alkaline environment.The two mass concentration ratio is 1.5:1.
When measuring, add copper ion solution or copper water sample, rocked at room temperature is even, observes the formation of biuret reaction bluish voilet mixture and carry out ultraviolet determination after reaction 300s.
Embodiment 3
(1) preparation of carbon point: first 0.05gL-phenylalaninol is dispersed in 10mL deionized water, uses 0.1molL
-1naOH solution regulates pH to 9.5.Ultrasonic 40min makes L-phenylalaninol dispersed.Subsequently, suspension is transferred in teflon-lined autoclave, after nitrogen deoxygenation 40min, and 170 DEG C of heating (i.e. hydrothermal carbonization) 8h.Be cooled to room temperature, add 12mL deionized water and redissolve, obtain carbon point solution.The centrifugal 20min of solution 13000rpm is to remove large throw out.For being further purified carbon point, centrifugal gained supernatant liquor molecular weight retains the dialysis tubing dialysis 24h of 500D.Carbon point (the i.e. amino alcohol functionalized carbon point) room temperature preservation of purifying.
(2) fluorescence sense process: the carbon point 200 μ L getting purifying, with 800 μ L0.01molL
-1pBS solution (pH=9.5) mixing, jolting is evenly to form alkaline environment.
When measuring, add copper ion solution or copper water sample.Rocked at room temperature is even, and carry out fluorometric assay after reaction 400s, excitation wavelength is 340nm.
(3) ultraviolet transducing process: the carbon point 200 μ L getting purifying, with 0.1molL
-1naOH solution mixes, and jolting is evenly to form alkaline environment.The two mass concentration ratio is 2:1.
When measuring, add copper ion solution or copper water sample, rocked at room temperature is even, observes the formation of biuret reaction bluish voilet mixture and carry out ultraviolet determination after reaction 400s.
Embodiment 4
(1) preparation of carbon point: first 0.05gL-phenylalaninol is dispersed in 12mL deionized water, uses 0.1molL
-1naOH solution regulates pH to 10.0.Ultrasonic 50min makes L-phenylalaninol dispersed.Subsequently, suspension is transferred in teflon-lined autoclave, 180 DEG C of heating (i.e. hydrothermal carbonization) 12h after nitrogen deoxygenation 50min.Be cooled to room temperature, add 10mL deionized water and redissolve, obtain carbon point solution.The centrifugal 30min of solution 13000rpm is to remove large throw out.For being further purified carbon point, centrifugal gained supernatant liquor molecular weight retains the dialysis tubing dialysis 24h of 500D.Carbon point (the i.e. amino alcohol functionalized carbon point) room temperature preservation of purifying.
(2) fluorescence sense process: the carbon point 100 μ L getting purifying, with 700 μ L0.01molL
-1pBS solution (pH=10.0) mixing, jolting is evenly to form alkaline environment.
When measuring, add copper ion solution or copper water sample, rocked at room temperature is even, and carry out fluorometric assay after reaction 500s, excitation wavelength is 340nm.
(3) ultraviolet transducing process: the carbon point 250 μ L getting purifying, with 0.1molL
-1naOH solution mixes, and jolting is evenly to form alkaline environment.The two mass concentration ratio is 1:2.
When measuring, add copper ion solution or copper water sample, rocked at room temperature is even, observes the formation of biuret reaction bluish voilet mixture and carry out ultraviolet determination after reaction 500s.
The sign of the amino alcohol functionalized carbon point prepared according to embodiment 1 method is shown in Fig. 1-4.
The selectivity assessment of fluoroscopic examination cupric ion
Investigate other common metal ion (Na
+, K
+, Ca
2+, Mg
2+, Fe
2+, Fe
3+) impact on Copper Ion.Iron ion is selected to be all 20 μm of olL mutually with ferrous ion concentration and copper ion concentration
-1, other concentration of metal ions are 100 μm of olL
-1, measure the fluorescence intensity of metal ion solution and blank solution by above-mentioned fluorometry respectively, calculate quenching of fluorescence efficiency.The results are shown in Figure 5, show these metal ions and all can not produce significantly interference to this experiment, describe the detection of amino alcohol functionalized carbon point to cupric ion and there is good selectivity.
Sample determination methodology (carbon is pressed according to the preparation of embodiment method)
1. typical curve and detectability
Preparation system copper ion concentration is 0 μm of olL
-1-500 μm of olL
-1serial solution, carry out fluorometric assay.Result shows, copper ion concentration is at 0.01-1 μm of olL
-1with 1-100 μm of olL
-1with system quenching of fluorescence degree ((F in scope
0-F)/F
0) in good linear relationship.Equation of linear regression is (F
0-F)/F
0=0.067C+0.0039 and (F
0-F)/F
0=0.0018C+0.0727, relation conefficient is respectively 0.9926 and 0.9942.LOD is obtained as 3.2nmolL by 3 times of blank signal standard deviations (S=3 σ) estimation
-1(wherein σ is the standard deviation of mensuration 20 blank solutions).
2. stability and repeatability
Get 5 batches and parallelly prepare carbon point, measure respectively, its relative standard deviation (Relativestandarddeviation, RSD) is 3.31%.Get with a collection of carbon point replication 20 times, fluorescence intensity does not change substantially.Carbon point is preserved one month at ambient temperature, and its fluorescence intensity declines 14.3%.Above-mentioned experimental result shows that the fluorescent detection system based on amino alcohol functionalized carbon point is comparatively stable, measures repeatability excellent, can ensure the accuracy of detected result and the practicality of detection method.
3. actual sample analysis
Selection lake water and from the beginning water sample, investigate feasibility and practicality that present method measures cupric ion in water body.Carry out sample determination by cupric ion fluorescence sense method, and in water sample, add basic, normal, high 3 concentration (10,100,1000nmolL
-1) cupric ion carry out average recovery test (n=3), result is as table 1.The rate of recovery of cupric ion is in 91.3% ~ 102.1% scope, and RSD is less than 6.0%, proves that the detection method of this fluorescence sense has good preci-sion and accuracy, can realize the mensuration of micro-trace copper ion in actual water sample.
The assay of table 1 Determined Copper in Aqueous Solution
Claims (10)
1. an amino alcohol functionalized carbon point, is characterized in that this amino alcohol functionalized carbon point is prepared by following steps:
A) L-phenylalaninol is dissolved in deionized water, is adjusted to pH7.5-10.0 by NaOH solution, and the ultrasonic L-of making phenylalaninol is uniformly dispersed and obtains suspension; Wherein, every 0.05gL-phenylalaninol powder adds deionized water 6-12mL;
B) after suspension being carried out nitrogen deoxygenation 10-50min, at 150-200 DEG C of temperature, heat 4-14h, then be cooled to room temperature, then redissolve with deionized water, obtain carbon point solution;
C) by carbon point solution centrifugal, get supernatant liquor, then purify 24h with the molecular weight dialysis tubing retained as 500D, obtain amino alcohol functionalized carbon point.
2. amino alcohol functionalized carbon point according to claim 1, is characterized in that the concentration of the NaOH solution described in step a) is 0.1molL
-1.
3. amino alcohol functionalized carbon point according to claim 1, is characterized in that the ultrasonic time described in step a) is 0.2-1h.
4. amino alcohol functionalized carbon point according to claim 1, is characterized in that suspension to be placed in teflon-lined autoclave to carry out nitrogen deoxygenation.
5. amino alcohol functionalized carbon point according to claim 1, is characterized in that step c) in centrifugal rotational speed be 10000-13000rpm, centrifugation time is 10-30min.
6. a preparation method for amino alcohol functionalized carbon point according to claim 1, is characterized in that the method comprises the following steps:
A) L-phenylalaninol is dissolved in deionized water, is adjusted to pH7.5-10.0 by NaOH solution, and the ultrasonic L-of making phenylalaninol is uniformly dispersed and obtains suspension; Wherein, every 0.05gL-phenylalaninol powder adds deionized water 6-12mL;
B) after suspension being carried out nitrogen deoxygenation 10-50min, at 150-200 DEG C of temperature, heat 4-14h, then be cooled to room temperature, then redissolve with deionized water, obtain carbon point solution;
C) by carbon point solution centrifugal, get supernatant liquor, then purify 24h with the molecular weight dialysis tubing retained as 500D, obtain amino alcohol functionalized carbon point.
7. the application of amino alcohol functionalized carbon point according to claim 1 in the fluorescence sense of cupric ion.
8. application according to claim 7, is characterized in that carbon point mixes with phosphate buffered saline buffer.
9. the application of amino alcohol functionalized carbon point according to claim 1 in the ultraviolet transducing of cupric ion.
10. application according to claim 9, is characterized in that carbon point mixes with NaOH solution, and the concentration of preferred NaOH solution is 0.1molL
-1.
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| CN106629677A (en) * | 2016-11-16 | 2017-05-10 | 江南大学 | Preparation method of functionalized graphene quantum dots producing ultrasensitive fluorescence response to Fe<3+> |
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| CN106629677A (en) * | 2016-11-16 | 2017-05-10 | 江南大学 | Preparation method of functionalized graphene quantum dots producing ultrasensitive fluorescence response to Fe<3+> |
| CN110927128A (en) * | 2018-09-20 | 2020-03-27 | Tcl集团股份有限公司 | Detection method of free zinc ions |
| CN110927128B (en) * | 2018-09-20 | 2021-08-06 | Tcl科技集团股份有限公司 | Detection method of free zinc ions |
| 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 |
| CN112574742A (en) * | 2020-11-13 | 2021-03-30 | 南京医科大学 | Dipyridyl methyl amine carbon quantum dot and synthesis method and application thereof |
| CN112574742B (en) * | 2020-11-13 | 2022-01-04 | 南京医科大学 | Dipyridyl methyl amine carbon quantum dot and synthesis method and application thereof |
| CN113000051A (en) * | 2021-02-26 | 2021-06-22 | 上海大学材料基因组工程(萍乡)研究院 | Method for generating high-temperature-resistant catalyst on surface of cordierite carrier |
| CN115465853A (en) * | 2022-09-07 | 2022-12-13 | 西华大学 | Orange light carbon dot based on citric acid and chiral 2-amino-1, 2-diphenylethanol and preparation method and application thereof |
| CN116463046A (en) * | 2023-06-19 | 2023-07-21 | 山东孚日宣威新材料科技有限公司 | Functional carbon-point polyurethane urea composite marine anti-corrosion coating with self-repairing performance and preparation method thereof |
| CN116463046B (en) * | 2023-06-19 | 2023-08-25 | 山东孚日宣威新材料科技有限公司 | Functional carbon-point polyurethane urea composite marine anti-corrosion coating with self-repairing performance and preparation method thereof |
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