CN105255487B - 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, and in particular to the preparation method and its fluorescence of carbon point in carbon nanomaterial
The application of performance.
Background technology
Carbon-based nano point is a kind of new zero dimension carbonaceous Nano-Materials, including graphene quantum dot (graphene
Quantum dots, GQDs), fluorescent carbon nanometer tube (fluorescent carbon nanotubes, CNTs) and carbon point
(carbon dots, CDs) etc..CDs is a kind of discrete torispherical carbon nano-particles of diameter less than 10nm, its typical shell core knot
Structure is comprising the shell containing carboxyl or other chemical functional groups and an inside be unformed or core of crystalline graphite.With organic dyestuff
Or conventional semiconductors quantum dot is compared, CDs has many advantages, the powerful luminescent properties of such as visible-range, highly-water-soluble, life
The thing compatibility and hypotoxicity, resistance to photobleaching, strong chemical inertness, it is readily synthesized with surface modification etc..In recent years, CDs by
It is widely used in every field, such as bio-imaging, sensor, photocatalysis, optoelectronics.Fluoroscopic examination metal ion is wherein
It is most important application one of, by observe fluorescence intensity change can simple realization metal ion quantitative determination, without the need for costliness
Instrument and complex operations.
Copper ion is the 3rd abundant transiting state metal ion in human body outside iron ions and zinc ion, is plant, moves
Thing, including the essential trace element of the mankind, in environmental area, biological and chemical system vital effect is played.In vivo
The shortage of copper ion can affect related enzyme activity, suppress cellular metabolism, causes hematological manifestation, and expose the copper of high concentration for a long time
Ion can cause liver or injury of kidney, and various brain diseasess such as alzheimer disease, parkinson also with copper ion
It is related.Environmental Protection Agency (U.S.Environmental Protection Agency, EPA) is classified as copper ion preferentially
Pollutant, the limitation in its drinking water is 1.3ppm (about 20 μm of ol L-1), the mean concentration of normal group blood copper ion is 100-
150μg dL-1(15.7-23.6μmol L-1).Therefore, it is that the pollution of control copper ion causes toxic action with it, is badly in need of setting up letter
Single green, reliable sensitive copper ion detection method.
The carbon point of existing many surface modifications is used for the detection of copper ion, but the rare report of carbon point without surface modification.
Herein, amino alcohol functionalized carbon point is prepared by a step hydrothermal carbonization as sole carbon source using L- phenylalaninols.With tradition
Two steps prepare nano-sensor and compare, this " integrated preparation-modification " it is tactful simpler effectively.Using L- phenylalaninols
As carbon source, with advantages below：(1) phenyl ring is contained in its structure, with higher carbon containing degree；(2) L- phenylalaninols structure
In amino to cause the carbon point for synthesizing be N- doped carbons point, it is ensured that it does not need surface passivation that higher quantum is obtained and produces
Rate；(3) compared with L-phenylalanine, carboxyl is not contained in L- phenylalaninols.By the abundant deoxygenation before hydrothermal carbonization, can substantially subtract
The carboxyl on few carbon point surface for preparing, it is to avoid carboxyl and the chelation of other ions, improves the selectivity to copper ion；(4)
In the basic conditions, amino alcohol can with copper ion produce biuret reaction, produce bluish violet complex and cause carbon point assemble and
Generation fluorescent quenching.Dual signal change in a kind of this sensing system can be used for the fluorescence and colorimetric sensing of copper ion, right
Issuable spurious signal in single signal sensing system provides correction.Therefore sensing system produced herein is used as copper ion
Detection platform have very much prospect.
The content of the invention
It is an object of the invention to provide a kind of fluorescent carbon point, the carbon point preparation process is simple, good water solubility, luminescent properties are steady
It is fixed, with wide absorption spectrum and narrow fluorescence emission spectrum.
It is another object of the present invention to overcome the deficiencies in the prior art, there is provided a kind of amino alcohol functionalized carbon point preparation method
And determine the application in copper ion, the method preparation of combined with fluorescent carbon point first and surface modification, fluorescence sense in dual signal
The copper ion constructed first based on biuret reaction with colorimetric sensing is detected, realized to qualitative point of copper ion fast quantification in water body
Analysis.Be conducive to the behavior of specification water body manufacturing enterprise, promote the development of China's water quality safety cause.
The purpose of the present invention is achieved in the following ways：
A kind of amino alcohol functionalized carbon point, the amino alcohol functionalized carbon point is through the following steps that prepare：
A) L- phenylalaninols are dissolved in deionized water, are adjusted to pH 7.5-10.0 with NaOH solution, and ultrasound makes L- phenylpropyl alcohol ammonia
Alcohol is uniformly dispersed and obtains suspension；Wherein, deionized water 6-12mL is added per 0.05g L- phenylalaninols powder；
B) suspension is carried out after nitrogen deoxygenation 10-50min, 4-14h being heated at a temperature of 150-200 DEG C, is cooled to
Room temperature, then deionized water redissolution, obtain carbon dots solution；
C) carbon dots solution is centrifuged, takes supernatant, then purify 24h with the bag filter that molecular weight retention is 500D, obtain ammonia
Base alcohol functionalized carbon point.
The concentration of the NaOH solution described in step a) is 0.1mol L-1。
Ultrasonic time described in step a) is 0.2-1h.
Suspension is placed in teflon-lined autoclave in step b) carry out nitrogen deoxygenation.
Centrifugal rotational speed is 10000-13000rpm in step c), and centrifugation time is 10-30min.
The preparation method of above-mentioned amino alcohol functionalized carbon point is comprised the following steps：
A) L- phenylalaninols are dissolved in deionized water, are adjusted to pH 7.5-10.0 with NaOH solution, and ultrasound makes L- phenylpropyl alcohol ammonia
Alcohol is uniformly dispersed and obtains suspension；Wherein, deionized water 6-12mL is added per 0.05g L- phenylalaninols powder；
B) suspension is carried out after nitrogen deoxygenation 10-50min, 4-14h being heated at a temperature of 150-200 DEG C, is cooled to
Room temperature, then deionized water redissolution, obtain carbon dots solution；The amount of deionized water that the redissolution is used can be according to every 0.05g L- phenylpropyl alcohols
Ammonia alcohol powder adds deionized water 6-12mL；
C) carbon dots solution is centrifuged, takes supernatant, then purify 24h with the bag filter that molecular weight retention is 500D, obtain ammonia
Base alcohol functionalized carbon point.
Above-mentioned amino alcohol functionalized carbon point preparation method specifically includes following steps：
A) 0.05g L- phenylalaninols are dissolved in 6-12mL deionized waters, use 0.1mol L-1NaOH solution adjust to alkalescence
(pH 7.5-10.0), ultrasonic 0.2-1h makes L- phenylalaninols be uniformly dispersed and obtains suspension.
B) suspension is placed in teflon-lined autoclave, nitrogen deoxygenation 10-50min, 150-200 DEG C of heating
4-14h, is cooled to room temperature, and 6-12mL deionized waters redissolve, and obtain carbon dots solution.Carbon dots solution concentration can be in step b)
2.85mg mL-1。
C) carbon dots solution 10000-13000rpm is centrifuged into 10-30min, takes supernatant, remove big precipitate, molecular weight cuts
It is left the bag filter purification 24h of 500D, the carbon point room temperature preservation of purification.
Amino alcohol functionalized carbon point of the present invention can be applied in the fluorescence sense of copper ion, using when carbon point and phosphorus
Phthalate buffer (PBS) mixes.Preferably phosphate buffer concentration is 0.01mol L-1, pH is 8.0-11.0.Fluorescence sense mistake
Cheng Zhong, carbon point consumption is 100-300 μ L, and PBS consumptions are 600-800 μ L.Fluorescence sense process carbon point mixes with PBS, adds copper
The response time is 200-600s after ion.
Amino alcohol functionalized carbon point of the present invention can in the application in the ultraviolet transducing of copper ion, using when carbon point with
NaOH solution mixes, and the concentration of preferred NaOH solution is 0.1mol L-1.It is preferred that ultraviolet transducing process carbon point and NaOH solution quality
Concentration ratio is 1:2-2:1.Ultraviolet transducing process carbon point mixes with NaOH solution, adds the response time after copper ion to be 200-
600s。
Above-mentioned amino alcohol functionalized carbon point determines the application in copper ion and specifically includes following steps in dual signal：
1) copper ion fluorescence sense：Carbon point obtained above is mixed with PBS, rocked at room temperature builds alkaline environment, added
Variable concentrations copper ion, matched group adds aliquots of deionized water, reacts 200-600s, determines fluorescence and calculates fluorescent quenching rate.
2) copper ion ultraviolet transducing：Carbon point obtained above is mixed with NaOH solution, rocked at room temperature builds alkaline environment,
Variable concentrations copper ion is added, the bluish violet complex of the formation of biuret reaction is observed.NaOH solution, its concentration is 0.1mol
L-1。
Fluorescence of the present invention-visible dual signal detection can be realized by the following method：
Fluorescence detection method and condition：
Carry out (experimental group addition with the ratio of matched group fluorescence intensity with the difference of experimental group and matched group fluorescence intensity herein
Fluorescence intensity after copper ion is F, and it is F that matched group adds the fluorescence intensity of equal-volume deionized water0, fluorescent quenching rate R=(F0-
F)/F0) show the effect of copper ion fluorescent quenching.R is bigger, shows that the carbon point that copper ion is combined under the conditions of certain is more, quenching effect
Rate is higher.Excitation wavelength is 340nm, and scanning speed is 1200nm min-1, Photomultiplier tube voltage is 700V, exciting slit and
Transmite slit width is 5nm.
Ultraviolet detection method and condition：
Carbon point (preparing according to the method for embodiment 1) and NaOH solution (0.1mol L-1) mixing, shaking is uniformly with formation
Alkaline environment.The copper ion for adding variable concentrations obtains a series of concentration in system.Rocked at room temperature is uniform, after reaction a period of time
The formation of observation biuret reaction bluish violet complex, and resulting solution centrifuging and taking supernatant is carried out into ultraviolet determination, detect ripple
A length of 540nm.
Sample determination：Select two kinds of water samples of lake water and tap water.Before sample determination, simple pre- place need to be carried out to lake water
Reason, with 0.45 μm of filter membrane sucking filtration solid impurity in lake water is removed, and tap water is without the need for any pretreatment.Take the carbon point of 100 μ L purification
With 800 μ L PBS solutions (0.01mol L-1, pH=10.5) mixing, shaking uniformly with formed alkaline environment after, add 100 μ L water
Sample, matched group adds 100 μ L deionized waters, to react and determine Determined Copper in Aqueous Solution by the fluorescence detection method in above-mentioned after 500s
Concentration.
Amino alcohol functionalized carbon point prepared by this method is used for fluoroscopic examination copper ion, its test limit (Limit of
Detection, LOD) can reach 3.2nmol L-1(S=3 σ), compared with known references, with the broader range of linearity (0.01-
1,1-100μmol L-1).With sensitivity height, good selectivity, response quickly, have good stability the features such as, be capable of achieving complexity base
Efficient, the sensitive and real-time detection of copper ion in matter.Further, since the copper ion biuret unique with amino alcohol under alkalescence condition
Reaction, is capable of achieving have 1mmol L-1Test limit visual detection.
Beneficial effects of the present invention：
1st, the present invention adopt hydro-thermal method first with L- phenylalaninols as carbon source, integrated synthesis and surface modification, step preparation
Amino alcohol functionalized carbon point.Compared with traditional surface modification carbon point methods, the amino alcohol functionalized carbon point prepared in the present invention
To synthesize first, one-step synthesis with modification, simplify preparation method.
2. the carbon point that prepared by the present invention is N doped carbons point, and higher quantum yield is obtained without the need for surface passivation.
3., by the time of control hydro-thermal carbon point, the carbon point of different quantum yields is obtained.
4., there is carbon point in copper ion and the biuret reaction of the amino alcohol generation specificity on carbon point surface under alkalescence condition
Reunite, produce fluorescent quenching.
5. compared with other amido modified carbon points, the amino alcohol of carbon point produced herein can be with copper ion in alkalescence condition
Lower generation biuret reaction forms bluish violet complex, is capable of achieving copper ion Visual retrieval.Set up a kind of visualization, easy
Copper ion detection method.
6. broken cannot effective fluoroscopic examination copper ion in the basic conditions limitation, further widened copper ion glimmering
The pH scopes of light detection.
7. the carbon point selection for preparing is high, and sensitivity is good, with preferable stability and repeatability.
Description of the drawings
Fig. 1 is the ultraviolet spectrogram and fluorescence emission spectrogram of compound of amino alcohol functionalized carbon point.
It is (a) carbon dots solution under natural light in interior illustration；B () is carbon dots solution under 365nm uviol lamps
In figure, 1 is the ultraviolet spectrogram of amino alcohol functionalized carbon point, and 2 is fluorescence emission spectrogram of compound.
Can see that carbon point has conjugation C=C key π-π * electronics to turn at 257nm wavelength from ultraviolet-visible absorption spectroscopy figure
The obvious absorption peaks for producing are moved, and absorbs belt edge and extend to 400nm, show the formation of nano-sized carbon.Interior illustration is carbon dots solution
Photo under visible ray and ultraviolet light (365nm) respectively, carbon dots solution clear under visible light, under ultra violet lamp
Obvious bright blue fluorescence is then sent, the successful preparation of carbon point is further proved.
Fig. 2 is fluorescence emission spectrogram of compound of the amino alcohol functionalized carbon point under different excitation wavelengths (310-380nm)
From the fluorescence emission spectrogram of compound of carbon point, carbon point emission peak obtained by under 340nm excitation wavelengths is in visible region
At 420nm.Carbon point is excited with different excitation wavelengths (310-380nm), finds carbon point similar to other fluorescence carbon materials
Material also has the fluorescent characteristic that exciting light is relied on.With the increase of excitation wavelength, the gradually red shift and adjoint of the emission spectrum of carbon point
The change of fluorescence intensity, this phenomenon may be related to the transmitting of the energy trapping of carbon point and electron conjugated structure.
Fig. 3 is the infrared spectrogram of L- phenylalaninols and amino alcohol functionalized carbon point
In figure, (a) it is L- phenylalaninols；B () is amino alcohol functionalized carbon point
In infrared spectrogram, it can be observed that a series of common characteristic peak of L- phenylalaninols and carbon point, 3000cm-1With
3500cm-1Place absworption peak correspondence-OH and-NH2Stretching vibration peak；2922cm-1And 2854cm-1Place absworption peak correspondence-CH2- flexible
Vibration peak；1574cm-1And 1446cm-1Place's absworption peak then corresponds to phenyl ring C=C stretching vibration peaks.In Fig. 3 (a), 1436cm-1Place
Absworption peak be C-N stretching vibrations.
Fig. 4 is the Raman spectrogram of amino alcohol functionalized carbon point.
The Raman spectrum of carbon point is 1343 and 1592cm-1There are two obvious absworption peaks in place, and D peaks and G peaks are corresponded to respectively,
D peaks result from the carbon atom vibration of dangling bonds on the terminal surface of disordered graphite or glass carbon, and G peaks then correspond to the E of graphite2gVibration mould
Sp in formula, with graphite two-dimensional hexagonal lattice2Hydbridized carbon atoms vibration is related, in reflection molecule in aromatic structure plane between C-C
Vibration.Generally with D peaks and the strength ratio (I at G peaksD/IG) weighing the unordered degree and sp of carbon3/sp2Ratio.As seen from the figure,
The I of carbon pointD/IGValue about 1.096, may be relevant with the fault of construction of the carbon point produced in the pyrolytic process of L- phenylalaninols, such as
sp2Oxygen-containing functional group (C-O, C=O) on hydbridized carbon atoms site, and the lattice vacancy and sp of generation3Hydbridized carbon atoms.
Fig. 5 is that interference metal ion is schemed with copper ion fluorescent quenching efficiency comparative.
Specific embodiment
Medicine and reagent：Copper sulfate (CuSO4, the new treasured Fine Chemical Works in Shanghai), sodium hydroxide (NaOH) (Chinese medicines group
Learn reagent company limited), L- phenylalaninols (L-phenylalaninol), quinine sulfate (Quinine sulfate), dialyzer
(MWCO:500) (Co., Ltd in Aladdin reagent), sodium dihydrogen phosphate (NaH2PO4·2H2O, the limited public affairs of Nanjing chemical reagent
Department), disodium hydrogen phosphate (Na2HPO4·12H2O, Shanghai Ling Feng chemical reagent company limited), experimental water is redistilled water,
0.01mol·L-1 Na2HPO4·12H2O and 0.01molL-1 NaH2PO4·2H2O solution is prepared the phosphate of difference pH and is delayed
Rush solution (phosphate buffered solution, PBS).
Below by way of the specific embodiment explanation present invention, but the present invention is not merely defined in these embodiments.
Embodiment 1
(1) preparation of carbon point：0.05g L- phenylalaninols are dispersed in first in 6mL deionized waters, use 0.1mol L-1
NaOH solution adjusts pH to 7.5, and ultrasonic 20min makes that L- phenylalaninols are dispersed to obtain suspension.Subsequently, suspension is transferred to
In teflon-lined autoclave, after nitrogen deoxygenation 10min, 150 DEG C of heating (i.e. hydrothermal carbonization) 6h.It is cooled to room temperature,
Add 8mL deionized waters to redissolve, obtain carbon dots solution.Solution 10000rpm is centrifuged 20min to remove big precipitate, centrifugation gained
Supernatant molecular weight retains the bag filter dialysis 24h of 500D, carbon point (the i.e. amino alcohol functionalized carbon point) room temperature preservation of purification.
(2) fluorescence sense process：The μ L of carbon point 200 of purification are taken, with 600 μ L 0.01mol L-1PBS solution (pH=
8.5) mix, shake uniformly to form alkaline environment.
When being measured, copper ion solution or copper water sample are added, rocked at room temperature is uniform, after reaction 200s fluorescence survey is carried out
Fixed, excitation wavelength is 340nm.
(3) ultraviolet transducing process：The μ L of carbon point 100 of purification are taken, with 0.1mol L-1NaOH solution mix, shaking uniformly with
Form alkaline environment.The two mass concentration ratio is 1:1.
When being measured, copper ion solution or copper water sample are added, rocked at room temperature is uniform, after reaction 200s biuret is observed
The formation of reaction bluish violet complex simultaneously carries out ultraviolet determination.
Embodiment 2
(1) preparation of carbon point：0.05g L- phenylalaninols are dispersed in first in 8mL deionized waters, use 0.1mol L-1
NaOH solution adjusts pH to 8.5.Ultrasonic 30min makes that L- phenylalaninols are dispersed to obtain suspension.Subsequently, suspension is transferred to
In teflon-lined autoclave, after nitrogen deoxygenation 30min, 160 DEG C of heating (i.e. hydrothermal carbonization) 8h.It is cooled to room temperature,
Add 10mL deionized waters to redissolve, obtain carbon dots solution.Solution 10000rpm is centrifuged 30min to remove big precipitate.To enter one
Step purified carbon point, centrifugation gained supernatant molecular weight retains the bag filter dialysis 24h of 500D.Carbon point (the i.e. amino alcohol of purification
Functionalized carbon point) room temperature preservation.
(2) fluorescence sense process：The μ L of carbon point 200 of purification are taken, with 700 μ L 0.01mol L-1PBS solution (pH=
9.0) mix, shake uniformly to form alkaline environment.
When being measured, copper ion solution or copper water sample are added.Rocked at room temperature is uniform, and after reaction 300s fluorescence survey is carried out
Fixed, excitation wavelength is 340nm.
(3) ultraviolet transducing process：The μ L of carbon point 150 of purification are taken, with 0.1mol L-1NaOH solution mix, shaking uniformly with
Form alkaline environment.The two mass concentration ratio is 1.5:1.
When being measured, copper ion solution or copper water sample are added, rocked at room temperature is uniform, after reaction 300s biuret is observed
The formation of reaction bluish violet complex simultaneously carries out ultraviolet determination.
Embodiment 3
(1) preparation of carbon point：0.05g L- phenylalaninols are dispersed in first in 10mL deionized waters, use 0.1mol L-1
NaOH solution adjusts pH to 9.5.Ultrasonic 40min makes L- phenylalaninols dispersed.Subsequently, suspension is transferred to politef
In the autoclave of liner, after nitrogen deoxygenation 40min, 170 DEG C of heating (i.e. hydrothermal carbonization) 8h.Room temperature is cooled to, adds 12mL to go
Ionized water redissolves, and obtains carbon dots solution.Solution 13000rpm is centrifuged 20min to remove big precipitate.To be further purified carbon point,
Centrifugation gained supernatant molecular weight retains the bag filter dialysis 24h of 500D.The carbon point (i.e. amino alcohol functionalized carbon point) of purification
Room temperature preservation.
(2) fluorescence sense process：The μ L of carbon point 200 of purification are taken, with 800 μ L 0.01mol L-1PBS solution (pH=
9.5) mix, shake uniformly to form alkaline environment.
When being measured, copper ion solution or copper water sample are added.Rocked at room temperature is uniform, and after reaction 400s fluorescence survey is carried out
Fixed, excitation wavelength is 340nm.
(3) ultraviolet transducing process：The μ L of carbon point 200 of purification are taken, with 0.1mol L-1NaOH solution mix, shaking uniformly with
Form alkaline environment.The two mass concentration ratio is 2:1.
When being measured, copper ion solution or copper water sample are added, rocked at room temperature is uniform, after reaction 400s biuret is observed
The formation of reaction bluish violet complex simultaneously carries out ultraviolet determination.
Embodiment 4
(1) preparation of carbon point：0.05g L- phenylalaninols are dispersed in first in 12mL deionized waters, use 0.1mol L-1
NaOH solution adjusts pH to 10.0.Ultrasonic 50min makes L- phenylalaninols dispersed.Subsequently, suspension is transferred to polytetrafluoroethyl-ne
In the autoclave of alkene liner, 180 DEG C of heating (i.e. hydrothermal carbonization) 12h after nitrogen deoxygenation 50min.Room temperature is cooled to, 10mL is added
Deionized water redissolves, and obtains carbon dots solution.Solution 13000rpm is centrifuged 30min to remove big precipitate.To be further purified carbon
Point, centrifugation gained supernatant molecular weight retains the bag filter dialysis 24h of 500D.Carbon point (the i.e. amino alcohol functionalized carbon of purification
Point) room temperature preservation.
(2) fluorescence sense process：The μ L of carbon point 100 of purification are taken, with 700 μ L 0.01mol L-1PBS solution (pH=
10.0) mix, shake uniformly to form alkaline environment.
When being measured, copper ion solution or copper water sample are added, rocked at room temperature is uniform, after reaction 500s fluorescence survey is carried out
Fixed, excitation wavelength is 340nm.
(3) ultraviolet transducing process：The μ L of carbon point 250 of purification are taken, with 0.1mol L-1NaOH solution mix, shaking uniformly with
Form alkaline environment.The two mass concentration ratio is 1:2.
When being measured, copper ion solution or copper water sample are added, rocked at room temperature is uniform, after reaction 500s biuret is observed
The formation of reaction bluish violet complex simultaneously carries out ultraviolet determination.
The sign of the amino alcohol functionalized carbon point prepared according to the method for embodiment 1 is shown in Fig. 1-4.
The selectivity assessment of fluoroscopic examination copper ion
Other common metal ions (Na is investigated+,K+,Ca2+,Mg2+,Fe2+,Fe3+) impact to Copper Ion.Choosing
Select iron ion and ferrous ion concentration and be mutually all 20 μm of ol L with copper ion concentration-1, other concentration of metal ions are 100 μm of ol
L-1, the fluorescence intensity of metal ion solution and blank solution is determined respectively by above-mentioned fluorimetry, calculate fluorescent quenching effect
Rate.As a result see Fig. 5, show that these metal ions will not produce significantly interference to the experiment, illustrate amino alcohol functionalization
Detection of the carbon point to copper ion has preferable selectivity.
Sample determination methodology (carbon is pressed and prepared according to embodiment method)
1. standard curve and test limit
Preparation system copper ion concentration is 0 μm of ol L-1-500μmol L-1Serial solution, carry out fluoremetry.As a result
Show, copper ion concentration is in 0.01-1 μm of ol L-1With 1-100 μm of ol L-1In the range of with system fluorescent quenching degree ((F0-F)/
F0) it is in good linear relationship.Equation of linear regression is (F0-F)/F0=0.067C+0.0039 and (F0-F)/F0=0.0018C+
0.0727, correlation coefficient is respectively 0.9926 and 0.9942.LOD by 3 times of blank signal standard deviations (S=3 σ) estimation obtain for
3.2nmol L-1(wherein σ is the standard deviation for determining 20 blank solutions).
2. stability and repeatability
Take 5 criticize flat rows and prepare carbon point, determine respectively, its relative standard deviation (Relative standard
Deviation, RSD) it is 3.31%.Take with a collection of carbon point replication 20 times, fluorescence intensity does not change substantially.By carbon point
Preserve one month at ambient temperature, its fluorescence intensity declines 14.3%.It is above-mentioned test result indicate that be based on amino alcohol functionalization
The fluorescent detection system of carbon point is relatively stable, determines repeated excellent, ensure that the accuracy and detection method of testing result
Practicality.
3. actual sample analysis
Lake water and originally water sample are selected, feasibility and practicality that this method determines copper ion in water body is investigated.By copper from
Sub- fluorescence sense method carries out sample determination, and basic, normal, high 3 concentration (10,100,1000nmol L are added in water sample-1)
Copper ion carry out average recovery test (n=3), as a result such as table 1.The response rate of copper ion is in 91.3%～102.1% model
In enclosing, RSD is less than 6.0%, it was demonstrated that the detection method of this fluorescence sense has good preci-sion and accuracy, can realize reality
The measure of micro- trace copper ion in the water sample of border.
The assay of the Determined Copper in Aqueous Solution of table 1
Claims (11)
1. a kind of amino alcohol functionalized carbon point, it is characterised in that the amino alcohol functionalized carbon point is through the following steps that prepare
's：
A) L- phenylalaninols are dissolved in deionized water, are adjusted to pH 7.5-10.0 with NaOH solution, and ultrasound makes L- phenylalaninols point
Dissipate and uniformly obtain suspension；Wherein, deionized water 6-12mL is added per 0.05g L- phenylalaninols powder；
B) suspension is carried out after nitrogen deoxygenation 10-50min, 4-14h being heated at a temperature of 150-200 DEG C, is cooled to room temperature,
Again deionized water is redissolved, and obtains carbon dots solution；
C) carbon dots solution is centrifuged, takes supernatant, then purify 24h with the bag filter that molecular weight retention is 500D, obtain amino alcohol
Functionalized carbon point.
2. amino alcohol functionalized carbon point according to claim 1, it is characterised in that the NaOH solution described in step a) it is dense
Spend for 0.1mol L-1。
3. amino alcohol functionalized carbon point according to claim 1, it is characterised in that the ultrasonic time described in step a) is
0.2-1h。
4. amino alcohol functionalized carbon point according to claim 1, it is characterised in that suspension is placed in politef
Nitrogen deoxygenation is carried out in the autoclave of lining.
5. amino alcohol functionalized carbon point according to claim 1, it is characterised in that centrifugal rotational speed is 10000- in step c)
13000rpm, centrifugation time is 10-30min.
6. the preparation method of the amino alcohol functionalized carbon point described in a kind of claim 1, it is characterised in that the method includes following
Step：
A) L- phenylalaninols are dissolved in deionized water, are adjusted to pH 7.5-10.0 with NaOH solution, and ultrasound makes L- phenylalaninols point
Dissipate and uniformly obtain suspension；Wherein, deionized water 6-12mL is added per 0.05g L- phenylalaninols powder；
B) suspension is carried out after nitrogen deoxygenation 10-50min, 4-14h being heated at a temperature of 150-200 DEG C, is cooled to room temperature,
Again deionized water is redissolved, and obtains carbon dots solution；
C) carbon dots solution is centrifuged, takes supernatant, then purify 24h with the bag filter that molecular weight retention is 500D, obtain amino alcohol
Functionalized carbon point.
7. application of the amino alcohol functionalized carbon point described in claim 1 in the fluorescence sense of copper ion.
8. application according to claim 7, it is characterised in that carbon point mixes with phosphate buffer.
9. application of the amino alcohol functionalized carbon point described in claim 1 in the ultraviolet transducing of copper ion.
10. application according to claim 9, it is characterised in that carbon point mixes with NaOH solution.
11. applications according to claim 10, it is characterised in that the concentration of NaOH solution is 0.1mol L-1。
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| CN109609124B (en) * | 2019-01-14 | 2021-01-26 | 京东方科技集团股份有限公司 | Carbon quantum dot hydrogel and preparation method thereof, and method for detecting copper ions |
| 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 |
| CN115465853B (en) * | 2022-09-07 | 2023-06-20 | 西华大学 | Orange light carbon dot based on citric acid and chiral 2-amino-1, 2-diphenyl ethanol and preparation method and application 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591124A (en) * | 2014-12-10 | 2015-05-06 | 西南交通大学 | Preparation method for fluorescent carbon quantum dot with vitamin as carbon source |
| CN104694117A (en) * | 2013-12-06 | 2015-06-10 | 中国科学院大连化学物理研究所 | Ratio-type fluorescent probe based on carbon dot as well as preparation method and application thereof |
| CN104787744A (en) * | 2014-01-16 | 2015-07-22 | 中国药科大学 | Method for synthesizing carbon quantum dots by using amino acid as precursor and application of carbon quantum dots in detection of metal ion concentration |
| CN104945621A (en) * | 2015-06-23 | 2015-09-30 | 闽南师范大学 | Preparation method of phenylalanine and citric acid composited silicon-doped fluorescent nanometer point |
-
2015
- 2015-10-19 CN CN201510681064.7A patent/CN105255487B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694117A (en) * | 2013-12-06 | 2015-06-10 | 中国科学院大连化学物理研究所 | Ratio-type fluorescent probe based on carbon dot as well as preparation method and application thereof |
| CN104787744A (en) * | 2014-01-16 | 2015-07-22 | 中国药科大学 | Method for synthesizing carbon quantum dots by using amino acid as precursor and application of carbon quantum dots in detection of metal ion concentration |
| CN104591124A (en) * | 2014-12-10 | 2015-05-06 | 西南交通大学 | Preparation method for fluorescent carbon quantum dot with vitamin as carbon source |
| CN104945621A (en) * | 2015-06-23 | 2015-09-30 | 闽南师范大学 | Preparation method of phenylalanine and citric acid composited silicon-doped fluorescent nanometer point |
Non-Patent Citations (4)
| Title |
|---|
| Development of a carbon quantum dots-based fluorescent Cu2+ probe suitable for living cell imaging;Qiang Qu 等;《Chem. Commun.》;20120411;第48卷;5473-5475 * |
| One-pot green synthesis of oxygen-rich nitrogen-doped graphene quantumdotsandtheir potential application in pH-sensitive photoluminescence and detection of mercury(II) ions;Bingfang Shi 等;《Talanta》;20150428;第142卷;131-139 * |
| Polyamine-Functionalized Carbon Quantum Dots as Fluorescent Probes for Selective and Sensitive Detection of Copper Ions;Yongqiang Dong 等;《Anal. Chem.》;20120611;第84卷;6220-6224 * |
| 一步法合成荧光碳纳米粒子及其表征;王颖 等;《沈阳大学学报》;20150630;第27卷(第3期);185-188 * |
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