CN105713602B - A kind of preparation method and application of fluorescence copper nanocluster probe - Google Patents
A kind of preparation method and application of fluorescence copper nanocluster probe Download PDFInfo
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Abstract
The invention provides a kind of preparation method and application of fluorescence copper nanocluster probe, belong to fluorescent nano material.Probe is using fibroin albumen as template and protective agent, in alkaline environment, utilizes the fluorescence copper nanocluster probe that " one kettle way " is made uniform in size, stability is good, is responded to pH；This method cost is relatively low, simple to operate, and raw material is easy to get extensively, has good repeatability；And obtained fluorescence copper nanocluster probe good water solubility, stability are strong, can be applied to the detection of pH in actual water sample.
Description
Technical field
The present invention relates to fluorescent nano material preparing technical field, and in particular to a kind of system of fluorescence copper nanocluster probe
Preparation Method, and application of the prepared probe in pH is detected.
Background technology
Metal nanometer cluster, it is the extra small nano-particle that a kind of metallic core size is less than 2nm.Recent years, fluorescence are strong
Degree is high, and the good metal nanometer cluster of stability is used as novel fluorescence nanocluster probe by intensive report, for detecting a lot
The object of species.One obvious characteristic of metal nanometer cluster is its strong luminescence generated by light, and stable with good light
Property, big Stokes shift and high emission effciency, thus cause the extensive interest of researcher.Come relative to Jin Heyin
Say, copper is less expensive.Therefore, copper nanocluster is increasingly becoming the important component in metal nano material, and is widely used in
The research fields such as chemical analysis, bio-sensing, bio-imaging, ion detection.
Large biological molecule such as peptide and protein, there is good biocompatibility, itself possess a variety of biological functions, easily
In the functionalization for realizing copper nanocluster, also it is commonly used for synthesizing the good template of fluorescence copper nanocluster probe.Document (Ultra
sensitive and wide-range pH sensor based on the BSA-capped Cu nanoclusters
fabricated by fast synthesis through the use of hydrogen peroxide additive,
X.Q.Liao, R.Y.Li, X.H.Long, Z.J.Li, RSC Adv., 2015,5,48835-48841), with it is a kind of it is commercialized often
See protein ----bovine serum albumin(BSA), hydrogen peroxide is added, high luminous copper nanocluster has been synthesized, to different cushioning liquid
PH have response, the detection to pH in actual water sample can be completed.But this method building-up process is a bit cumbersome, cost is higher,
Therefore we synthesize simple, the cheap new method of cost there is an urgent need to one kind.
The content of the invention
Present invention aims at a kind of preparation method of fluorescence copper nanocluster probe is provided, this method is simple to operate, instead
Mild condition is answered, gained fluorescence copper nanocluster probe particle diameter is smaller, good dispersion, can be used for the detection of pH in actual water sample.
To achieve the above object, a kind of preparation method of fluorescence copper nanocluster probe provided by the invention, step include：
(1) silk cocoon is cut into 1-2cm2Small pieces, silk cocoon small pieces are placed in 0.01-0.03mol/L sodium carbonate liquors,
Degumming 0.5-2h is heated at 90-110 DEG C, fibroin albumen is made；
(2) fibroin albumen that step (1) obtains is cleaned 2-4 times with deionized water, in CaCl2:Water:Ethanol=1:8:2
Mixed solution in, heat 1-3h at 70-90 DEG C, dissolve fibroin albumen；
(3) silk fibroin protein solution obtained to step (2) is cooled to room temperature, filtering, and dialyse 48h, is placed in standby in 4 DEG C of refrigerators
With；
(4) silk fibroin protein solution that step (3) obtains is measured, is stirred continuously down, 8- is added into silk fibroin protein solution
15mmol/L copper nitrates, continuing stirring makes both fully mix, and the volume ratio of silk fibroin water solution and copper nitrate solution is 1-
4:1；
(5) sodium hydroxide solution that 25 μ L concentration are 1mol/L is added in the mixed solution obtained to step (4), in 25-
Continue to stir 2-10h at 95 DEG C；
(6) mixed solution that step (5) obtains is finally given into fluorescence copper nanocluster probe solution by centrifugation.
The concentration of sodium carbonate liquor is preferably 0.02mol/L in step (1).
Silk cocoon small pieces preferably heat 1h with sodium carbonate liquor at 100 DEG C in step (1).
Fibroin albumen after the degumming obtained in step (2) is cleaned preferably 3 times with deionized water, in CaCl2:Water：Ethanol
=1:8:In 2 mixed solution, 2h preferably is heated at 80 DEG C, makes its dissolving.
The bag filter that it is 8000-14000Da with molecular cut off that dialysis, which is, in step (3).
The concentration of copper nitrate solution in step (4) is preferably 10mmol/L.
The volume ratio of silk fibroin water solution and copper nitrate solution in step (4) is preferably 3:1.
In step (5), preferably 6h is stirred at 55 DEG C.
Centrifugation is to centrifuge 10min with 13000r/min rotating speeds in step (6).
The pH that fluorescence copper nanocluster probe prepared by the inventive method can be used in detection actual water sample.
Compared with prior art, the advantage of the invention is that：
(1) using fibroin albumen as template, raw material is easy to get extensively, green, and preparation method is simple, and cost is cheap.
(2) fluorescence copper nanocluster probe has good blue luminescent properties made from, uses it for building actual water
PH sensing system is detected in sample, the interference of other metal ions can be avoided.Fluorescence copper nanocluster prepared by the present invention is visited
Pin can detect the pH in actual water sample.
(3) fluorescence copper nanocluster probe size is small made from, photostability is strong, toxic side effect is small, good water solubility, fluorescence
Intensity is high, has broad application prospects in fields such as bio-imaging, biomarkers.
Brief description of the drawings
Fig. 1 is the mechanism of action schematic diagram of fluorescence copper nanocluster probe prepared by the present invention
Fig. 2 is that to prepare fluorescence copper nanocluster probe solution be respectively that 365nm is ultraviolet in fluorescent lamp (1) and wavelength to the present invention
Photo under lamp (2) irradiation
Fig. 3 prepares fluorescence-ultraviolet figure of fluorescence copper nanocluster probe solution for the present invention, and a is that ultraviolet-visible is inhaled in figure
Spectrogram is received, b is fluorescence spectra
Fig. 4 is that fluorescence copper nanocluster probe solution prepared by the present invention adds different metal ions and pH=10.05
The change of fluorescence peak intensity during BR cushioning liquid
Fluorescence copper nanocluster probe solution prepared by Fig. 5 present invention with ionic strength (concentration of sodium chloride) change its
The change of fluorescence peak intensity
The fluorescence intensity of fluorescence copper nanocluster probe solution prepared by Fig. 6 present invention in BR cushioning liquid with pH change
Change
Linear pass between fluorescence copper nanocluster probe solution prepared by Fig. 7 present invention and different pH BR cushioning liquid
System
The fluorescence intensity of fluorescence copper nanocluster probe solution prepared by Fig. 8 present invention in HEPES-NaOH cushioning liquid
With pH change
Between fluorescence copper nanocluster probe solution prepared by Fig. 9 present invention and different pH HEPES-NaOH cushioning liquid
Linear relationship
The fluorescence intensity of fluorescence copper nanocluster probe solution prepared by Figure 10 present invention in Tris-HCl cushioning liquid
With pH change
Between fluorescence copper nanocluster probe solution prepared by Figure 11 present invention and different pH Tris-HCl cushioning liquid
Linear relationship
Embodiment
The present invention is using fibroin albumen as template, and in alkaline environment, fluorescence copper nanocluster is prepared by " one kettle way "
Probe solution, and for the detection of pH in actual water sample.Below by embodiment combination accompanying drawing, the invention will be further described.
Embodiment 1
Preparation using fibroin albumen as the fluorescence copper nanocluster probe of template：
(1) degumming silkworm cocoons prepare fibroin albumen：Silk cocoon is cut into 1-2cm2Small pieces, silk cocoon small pieces are placed in 0.02mol/
In L sodium carbonate liquors, 1h is heated at 100 DEG C；
(2) fibroin albumen after the degumming for obtaining step (1) is cleaned 3 times with deionized water, in CaCl2:Water:Ethanol=
1:8:In 2 mixed solution, 2h is heated at 80 DEG C, makes its dissolving；
(3) silk fibroin protein solution obtained to step (2) is cooled to room temperature, filtering, and dialyse 48h, is placed in standby in 4 DEG C of refrigerators
With；
(4) silk fibroin protein solution that step (3) obtains is measured, is stirred continuously down, is added into silk fibroin protein solution
10mmol/L copper nitrates, continuing stirring makes both fully mix, and the volume ratio of silk fibroin water solution and copper nitrate solution is 3:
1；
(5) sodium hydroxide solution that 25 μ L concentration are 1mol/L is added in the mixed solution obtained to step (4), at 55 DEG C
Under continue stir 6h；
(6) solution for obtaining step (5) centrifuges 10min with 13000r/min rotating speeds, finally gives fluorescence copper nanoclusters
Aggregate probe solution.
The mechanism of action schematic diagram of the fluorescence copper nanocluster probe of preparation is shown in Fig. 1.
The fluorescence copper nanocluster probe solution of the preparation photograph in the case where fluorescent lamp and wavelength are 365nm ultra violet lamps respectively
Piece is shown in Fig. 2, and 1 is picture of the fluorescence copper nanocluster probe solution under daylight light irradiation in figure, and color is lilac, and 2 be ripple
Picture under a length of 365nm ultra violet lamps, color are blueness.
In addition, fluorescence-ultraviolet figure of the fluorescence copper nanocluster probe solution prepared is shown in Fig. 3, wherein fluorogram (b) shows
The fluorescence copper nanocluster probe of preparation is under the conditions of fixed excitation wavelength is 326nm, and emission peak positions are in 420nm or so.
Embodiment 2
The influence experiment of the fluorescence peak intensity for the fluorescence copper nanocluster probe solution that metal ion is prepared to embodiment 1：
With pH=7 BR cushioning liquid and Pb (NO3)2、Mg(NO3)2、Mn(NO3)2、Fe(NO3)3、Zn(NO3)2、Cd
(NO3)2、Cu(NO3)2、Hg(NO3)2、KNO3、Ca(NO3)2、NaNO3、Ni(NO3)2、Al(NO3)3、Cr(NO3)3、Co(NO3)2Point
It is 100 μm of olL not to be configured to concentration of metal ions-1Solution, the fluorescence copper nanoclusters for respectively preparing 0.1mL embodiments 1
Aggregate probe solution is added in the above-mentioned solution containing different metal ions of 0.9mL.The fluorescence copper for taking 0.1mL embodiments 1 to prepare again
Nanocluster probe solution is added in 0.9mL pH=10.05 BR cushioning liquid, and fixed excitation wavelength is 326nm, in room
Temperature is lower to carry out fluorescence spectrum detection, according to 420nm or so fluorescence peak intensity, detects metal ion and pH to fluorescence copper nanoclusters
The influence of the fluorescence peak intensity of aggregate probe solution.
Fig. 4 is shown in the influence of metal ion and pH to the fluorescence peak intensity of fluorescence copper nanocluster probe solution：Swash in 326nm
Give, from the glimmering of the fluorescence intensity of the fluorescence copper nanocluster probe solution of metal ion and the BR bufferings containing pH=10.05
The fluorescence peak intensity F of light copper nanocluster probe solution is drawn：The fluorescence copper nanocluster probe of pH=10.05 BR bufferings is molten
Liquid change is maximum, and the change of other metal ions is relatively small, illustrates fluorescence copper nanocluster probe solution energy prepared by the present invention
Enough qualitative detection pH.
Embodiment 3
The influence experiment of the fluorescence peak intensity for the fluorescence copper nanocluster probe solution that ionic strength is prepared to embodiment 1：
Fluorescence copper nanocluster probe solution prepared by 100 μ L embodiments 1 is added to 900 μ L BR cushioning liquid (pH=
7.0) in, fixed excitation wavelength is 326nm, the sodium chloride solution (0.04-0.22mol/L) of various concentrations is added, according to 420nm
The fluorescence peak intensity of left and right, influence of the detection ionic strength to the fluorescence peak intensity of fluorescence copper nanocluster probe solution.
Fig. 5 is shown in influence of the ionic strength to the fluorescence peak intensity of fluorescence copper nanocluster probe solution：Excited in 326nm
Under, fluorescence copper nanocluster probe solution is in the range of the sodium chloride solution (0.04-0.22mol/L) of various concentrations, fluorescence peak
Intensity is basically unchanged, and illustrates that the anti-ion interference of fluorescence copper nanocluster probe solution prepared by the present invention is strong.
Embodiment 4
Fluorescence intensity of the fluorescence copper nanocluster probe solution in BR cushioning liquid prepared by embodiment 1 with pH change
Experiment：
The BR bufferings that the μ L of fluorescence copper nanocluster probe solution 100 prepared by Example 1 are added to 900 μ L differences pH are molten
In liquid, fixed excitation wavelength be 326nm, at room temperature progress fluorescence spectrum detection, according to 420nm or so fluorescence peak intensity,
Detect the influence of different pH BR cushioning liquid to the fluorescence peak intensity of fluorescence copper nanocluster probe solution.
Fig. 6 is shown in influence of the different pH BR cushioning liquid to the fluorescence peak intensity of fluorescence copper nanocluster probe solution：
326nm is excited down, and fluorescence copper nanocluster probe solution gradually increases adding different pH BR cushioning liquid, fluorescence peak intensity
By force；Wherein pH value is 1.82,2.27,3.05,4.00,5.03,6.08,7.00,8.06,9.07,10.05,11.02 respectively,
12.00 BR cushioning liquid illustrates this hair to the fluorescence spectra of fluorescence copper nanocluster probe solution fluorescence peak intensity effect
The fluorescence copper nanocluster probe solution of bright preparation can realize the detection to different pH.
In addition, the BR changed from different pH of the fluorescence peak intensity of fluorescence copper nanocluster probe solution prepared by the present invention
Cushioning liquid is linear, as shown in fig. 7, with the growth of pH value, fluorescence peak intensity gradually strengthens, the R of linear equation2=
0.9992。
Embodiment 5
Fluorescence intensity of the fluorescence copper nanocluster probe solution in HEPES-NaOH cushioning liquid prepared by embodiment 1 with
PH change experiment：
The μ L of fluorescence copper nanocluster probe solution 100 prepared by Example 1 are added to 900 μ L differences pH HEPES-
In NaOH cushioning liquid, fixed excitation wavelength is 326nm, fluorescence spectrum detection is carried out at room temperature, according to the glimmering of 420nm or so
Photopeak intensity, different pH HEPES-NaOH cushioning liquid is detected to the fluorescence peak intensity of fluorescence copper nanocluster probe solution
Influence.
Influence of the different pH HEPES-NaOH cushioning liquid to the fluorescence peak intensity of fluorescence copper nanocluster probe solution
See Fig. 8：In the case where 326nm is excited, fluorescence copper nanocluster probe solution is adding different pH HEPES-NaOH cushioning liquid, glimmering
Photopeak intensity gradually strengthens；Wherein pH value is 6.80,7.05,7.25,7.64,7.98,8.18 HEPES-NaOH bufferings respectively
Solution illustrates fluorescence copper prepared by the present invention to the fluorescence spectra of fluorescence copper nanocluster probe solution fluorescence peak intensity effect
Nanocluster probe solution can realize the detection to different pH.
In addition, the change of the fluorescence peak intensity of fluorescence copper nanocluster probe solution prepared by the present invention is from different pH's
HEPES-NaOH cushioning liquid is linear, as shown in figure 9, with the growth of pH value, fluorescence peak intensity gradually strengthens, linearly
The R of equation2=0.9946.
Embodiment 6
The fluorescence intensity of fluorescence copper nanocluster probe solution prepared by embodiment 1 in Tris-HCl cushioning liquid is with pH
Change experiment：
The μ L of fluorescence copper nanocluster probe solution 100 prepared by Example 1 are added to 900 μ L differences pH Tris-HCl
In cushioning liquid, fixed excitation wavelength is 326nm, fluorescence spectrum detection is carried out at room temperature, according to 420nm or so fluorescence peak
Intensity, detect the influence of different pH Tris-HCl cushioning liquid to the fluorescence peak intensity of fluorescence copper nanocluster probe solution.
Influence of the different pH Tris-HCl cushioning liquid to the fluorescence peak intensity of fluorescence copper nanocluster probe solution is shown in
Figure 10：In the case where 326nm is excited, fluorescence copper nanocluster probe solution is adding different pH Tris-HCl cushioning liquid, fluorescence
Peak intensity gradually strengthens；Wherein pH value is 6.95,7.24,7.56,7.99,8.68,9.00 Tris-HCl cushioning liquid respectively
To the fluorescence spectra of fluorescence copper nanocluster probe solution fluorescence peak intensity effect, illustrate fluorescence copper nanometer prepared by the present invention
Cluster probe solution can realize the detection to different pH.
In addition, the change of the fluorescence peak intensity of fluorescence copper nanocluster probe solution prepared by the present invention is from different pH's
Tris-HCl cushioning liquid is linear, and as shown in figure 11, with the growth of pH value, fluorescence peak intensity gradually strengthens, linearly
The R of equation2=0.9843.
Embodiment 7
Fluorescence copper nanocluster probe solution prepared by embodiment 1 is used for the test experience of pH in actual water sample：
Respectively with commercialized pH meter (pHa) with embodiment 1 prepare fluorescence copper nanocluster probe solution (pHb) detection
The originally pH of water sample and lake water sample, to calculate both relative deviations, as shown in table 1.
Table 1 is that commercialized pH meter is used for pH in actual water sample with fluorescence copper nanocluster probe solution prepared by the present invention
Detection
Claims (10)
1. a kind of preparation method of fluorescence copper nanocluster probe, it is characterised in that step includes：
(1) silk cocoon is cut into 1-2cm2Small pieces, silk cocoon small pieces are placed in 0.01-0.03mol/L sodium carbonate liquors, in 90-
Degumming 0.5-2h is heated at 110 DEG C, fibroin albumen is made；
(2) fibroin albumen that step (1) obtains is cleaned 2-4 times with deionized water, in CaCl2:Water:Ethanol=1:8:2 mixing
In solution, 1-3h is heated at 70-90 DEG C, dissolves fibroin albumen；
(3) silk fibroin protein solution obtained to step (2) is cooled to room temperature, filtering, and dialyse 48h, is placed in standby in 4 DEG C of refrigerators；
(4) silk fibroin protein solution that step (3) obtains is measured, is stirred continuously down, 8-15mmol/ is added into silk fibroin protein solution
L copper nitrate solutions, continuing stirring makes both fully mix, and the volume ratio of silk fibroin protein solution and copper nitrate solution is 1-4:1；
(5) sodium hydroxide solution that 25 μ L concentration are 1mol/L is added in the mixed solution obtained to step (4), at 25-95 DEG C
Under continue stir 2-10h；
(6) mixed solution that step (5) obtains is finally given into fluorescence copper nanocluster probe solution by centrifugation.
A kind of 2. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(1) concentration of sodium carbonate liquor is 0.02mol/L in.
A kind of 3. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(1) silk cocoon small pieces heat 1h with sodium carbonate liquor at 100 DEG C in.
A kind of 4. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(2) fibroin albumen after the degumming obtained in is cleaned 3 times with deionized water, in CaCl2:Water：Ethanol=1:8:2 mixed solution
In, 2h is heated at 80 DEG C, makes its dissolving.
A kind of 5. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(3) dialysis is that the bag filter for being 8000-14000Da with molecular cut off is dialysed in.
A kind of 6. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(4) concentration of the copper nitrate solution in is 10mmol/L.
A kind of 7. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(4) volume ratio of silk fibroin protein solution and copper nitrate solution in is 3:1.
A kind of 8. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(5) in, 6h is stirred at 55 DEG C.
A kind of 9. preparation method of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that described step
(6) centrifugation is to centrifuge 10min with 13000r/min rotating speeds in.
10. the application of fluorescence copper nanocluster probe prepared by the either method as described in claim 1-9 in pH detections.
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| CN107782704B (en) * | 2016-08-29 | 2020-06-23 | 天津师范大学 | Folic acid detection method based on near-infrared fluorescent probe copper nanocluster |
| CN106520114B (en) * | 2016-09-20 | 2018-10-16 | 山西大学 | A kind of preparation method and application of fluorescence gold nano cluster probe |
| CN108329904B (en) * | 2018-01-25 | 2020-05-08 | 暨南大学 | Cysteamine modified copper nanocluster solution fluorescent probe and preparation and application thereof |
| CN109794618A (en) * | 2019-01-15 | 2019-05-24 | 南通纺织丝绸产业技术研究院 | The preparation of the copper nano-cluster of sericin package and fluorescence probe |
| CN111420707B (en) * | 2020-05-07 | 2023-02-28 | 西南大学 | Preparation of silk fibroin-iridium dioxide multifunctional composite nanocluster |
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