CN105713602A - Preparation method and application of fluorescence copper nanocluster probe - Google Patents
Preparation method and application of fluorescence copper nanocluster probe Download PDFInfo
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- CN105713602A CN105713602A CN201610040451.7A CN201610040451A CN105713602A CN 105713602 A CN105713602 A CN 105713602A CN 201610040451 A CN201610040451 A CN 201610040451A CN 105713602 A CN105713602 A CN 105713602A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
Abstract
The invention provides a preparation method and application of a fluorescence copper nanocluster probe and belongs to fluorescence nano materials. The pH-responsive fluorescence copper nanocluster probe which is even in size and good in stability is prepared by using silk fibroin as the template and protecting agent and using a one-pot method in an alkaline environment. The preparation method is low in cost, simple to operate, wide in raw material source, easy in raw material obtaining and good in repeatability. The prepared fluorescence copper nanocluster probe is good in water solubility, high in stability and applicable to detection of pH in actual water samples.
Description
Technical field
The present invention relates to fluorescent nano material preparing technical field, the preparation method being specifically related to a kind of fluorescence copper nanocluster probe, and the application that prepared probe is in detection pH.
Background technology
Metal nanometer cluster, is a kind of metallic core extra small nanoparticle of being smaller in size than 2nm.Recent years, fluorescence intensity is high, and the metal nanometer cluster of good stability, is used for detecting number of types of object as novel fluorescence nanocluster probe by intensive report.One obvious characteristic of metal nanometer cluster is its strong luminescence generated by light, and has good light stability, big Stokes shift and high emission effciency, thus causes researcher interest widely.Relative to Jin Heyin, copper is less expensive.Therefore, copper nanocluster is increasingly becoming the important component part in metal nano material, and is widely used in the research fields such as chemical analysis, bio-sensing, bio-imaging, ion detection.
Biomacromolecule is peptide and protein such as, has good biocompatibility, self possesses multiple biological function, it is easy to accomplish the functionalization of copper nanocluster, is also commonly used for the good template of synthesis fluorescence copper nanocluster probe.Document (Ultrasensitiveandwide-rangepHsensorbasedontheBSA-cappedC unanoclustersfabricatedbyfastsynthesisthroughtheuseofhyd rogenperoxideadditive, X.Q.Liao, R.Y.Li, X.H.Long, Z.J.Li, RSCAdv., 2015,5,48835-48841), with a kind of business-like common protein----bovine serum albumin, add hydrogen peroxide, synthesize the copper nanocluster of high luminescence, the pH of different buffer solution is had response, it is possible to complete the detection of pH in actual water sample.But, the method building-up process is a bit loaded down with trivial details, relatively costly, and therefore we are simple in the urgent need to one synthesis, new method with low cost.
Summary of the invention
Present invention aim at the preparation method providing a kind of fluorescence copper nanocluster probe, the method is simple to operate, and reaction condition is gentle, and gained fluorescence copper nanocluster probe particle diameter is less, good dispersion, can be used in actual water sample the detection of pH.
For achieving the above object, the preparation method of a kind of fluorescence copper nanocluster probe provided by the invention, step includes:
(1) Bombyx bombycis is cut into 1-2cm2Small pieces, Bombyx bombycis small pieces are placed in 0.01-0.03mol/L sodium carbonate liquor, at 90-110 DEG C heat degumming 0.5-2h, prepare fibroin albumen；
(2) fibroin albumen deionized water step (1) obtained cleans 2-4 time, at CaCl2: water: in the mixed solution of ethanol=1:8:2, heats 1-3h at 70-90 DEG C, makes fibroin albumen dissolve；
(3) silk fibroin protein solution obtained to step (2) is cooled to room temperature, filters, and dialyse 48h, is placed in 4 DEG C of refrigerators standby；
(4) silk fibroin protein solution that step (3) obtains is measured, it is stirred continuously down, adding 8-15mmol/L copper nitrate in silk fibroin protein solution, continue stirring and make both fully mix, the volume ratio of silk fibroin water solution and copper nitrate solution is 1-4:1；
(5) adding 25 μ L concentration in the mixed solution obtained to step (4) is the sodium hydroxide solution of 1mol/L, continues stirring 2-10h at 25-95 DEG C；
(6) mixed solution step (5) obtained, through centrifugal, finally gives fluorescence copper nanocluster probe solution.
In step (1), the concentration of sodium carbonate liquor is preferably 0.02mol/L.
In step (1), Bombyx bombycis small pieces heat 1h with sodium carbonate liquor at 100 DEG C.
Fibroin albumen deionized water after the degumming obtained in step (2) cleans preferably 3 times, at CaCl2: water: in the mixed solution of ethanol=1:8:2, it is preferable that heat 2h at 80 DEG C so that it is dissolve.
Dialysis is to be the bag filter of 8000-14000Da with molecular cut off in step (3).
The concentration of the copper nitrate solution in step (4) is preferably 10mmol/L.
The volume ratio of the silk fibroin water solution in step (4) and copper nitrate solution is preferably 3:1.
In step (5), it is preferable that stir 6h at 55 DEG C.
Centrifugal in step (6) is with the centrifugal 10min of 13000r/min rotating speed.
Fluorescence copper nanocluster probe prepared by the inventive method can be used for the pH detecting in actual water sample.
Compared with prior art, it is an advantage of the current invention that:
(1) with fibroin albumen for template, raw material is extensively easy to get, environmental protection, and preparation method is simple, with low cost.
(2) the fluorescence copper nanocluster probe prepared has good blue luminescent properties, uses it for and builds the sensing system detecting pH in actual water sample, it is possible to avoids the interference of other metal ion.Fluorescence copper nanocluster probe prepared by the present invention can detect the pH in actual water sample.
(3) the fluorescence copper nanocluster probe size prepared is little, light stability is strong, toxic and side effects is little, good water solubility, and fluorescence intensity is high, has broad application prospects in the field such as bio-imaging, biomarker.
Accompanying drawing explanation
Fig. 1 is the mechanism of action schematic diagram of fluorescence copper nanocluster probe prepared by the present invention
Fig. 2 is that the present invention prepares fluorescence copper nanocluster probe solution respectively at the photo that daylight lamp (1) and wavelength are under 365nm uviol lamp (2) irradiation
Fig. 3 is that to prepare in the fluorescence of fluorescence copper nanocluster probe solution-ultraviolet figure, figure that a is uv-visible absorption spectra figure, b be fluorescence spectrum figure to the present invention
Fig. 4 be the fluorescence copper nanocluster probe solution prepared of the present invention add different metal ion and pH=10.05 BR buffer solution time fluorescence peak intensity change
Fluorescence copper nanocluster probe solution prepared by Fig. 5 present invention is with the change changing its fluorescence peak intensity of ionic strength (concentration of sodium chloride)
Fluorescence copper nanocluster probe solution prepared by Fig. 6 present invention fluorescence intensity in BR buffer solution is with the change of pH
Linear relationship between fluorescence copper nanocluster probe solution and the BR buffer solution of different pH prepared by Fig. 7 present invention
Fluorescence copper nanocluster probe solution prepared by Fig. 8 present invention fluorescence intensity in HEPES-NaOH buffer solution is with the change of pH
Linear relationship between fluorescence copper nanocluster probe solution and the HEPES-NaOH buffer solution of different pH prepared by Fig. 9 present invention
Fluorescence copper nanocluster probe solution prepared by Figure 10 present invention fluorescence intensity in Tris-HCl buffer solution is with the change of pH
Linear relationship between fluorescence copper nanocluster probe solution and the Tris-HCl buffer solution of different pH prepared by Figure 11 present invention
Detailed description of the invention
The present invention is with fibroin albumen for template, in alkaline environment, prepares fluorescence copper nanocluster probe solution by " one kettle way ", and for the detection of pH in actual water sample.In conjunction with accompanying drawing, the invention will be further described by the examples below.
Embodiment 1
Preparation with the fluorescence copper nanocluster probe that fibroin albumen is template:
(1) degumming silkworm cocoons prepares fibroin albumen: Bombyx bombycis is cut into 1-2cm2Small pieces, Bombyx bombycis small pieces are placed in 0.02mol/L sodium carbonate liquor, at 100 DEG C heat 1h；
(2) the fibroin albumen deionized water after degumming step (1) obtained cleans 3 times, at CaCl2: water: in the mixed solution of ethanol=1:8:2, heats 2h so that it is dissolve at 80 DEG C；
(3) silk fibroin protein solution obtained to step (2) is cooled to room temperature, filters, and dialyse 48h, is placed in 4 DEG C of refrigerators standby；
(4) measuring the silk fibroin protein solution that step (3) obtains, be stirred continuously down, add 10mmol/L copper nitrate in silk fibroin protein solution, continue stirring and make both fully mix, the volume ratio of silk fibroin water solution and copper nitrate solution is 3:1；
(5) adding 25 μ L concentration in the mixed solution obtained to step (4) is the sodium hydroxide solution of 1mol/L, continues stirring 6h at 55 DEG C；
(6) solution step (5) obtained is with the centrifugal 10min of 13000r/min rotating speed, finally gives fluorescence copper nanocluster probe solution.
Fig. 1 is shown in by the mechanism of action schematic diagram of the fluorescence copper nanocluster probe of preparation.
The fluorescence copper nanocluster probe solution of preparation is that Fig. 2 is shown in by the photo under 365nm ultra violet lamp at daylight lamp and wavelength respectively, in figure, 1 is fluorescence copper nanocluster probe solution picture under daylight lamp irradiates, color is lilac, 2 is the picture that wavelength is under 365nm ultra violet lamp, and color is blue.
Additionally, the fluorescence-ultraviolet figure of the fluorescence copper nanocluster probe solution of preparation is shown in Fig. 3, wherein fluorogram (b) shows that the fluorescence copper nanocluster probe of preparation is when fixing excitation wavelength is 326nm, and emission peak positions is at about 420nm.
Embodiment 2
The impact experiment of the fluorescence peak intensity of the fluorescence copper nanocluster probe solution that embodiment 1 is prepared by metal ion:
With the BR buffer solution of pH=7 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)2Being configured to concentration of metal ions respectively is 100 μm of ol L-1Solution, fluorescence copper nanocluster probe solution 0.1mL embodiment 1 prepared respectively joins in the above-mentioned solution containing different metal ion of 0.9mL.The fluorescence copper nanocluster probe solution taking 0.1mL embodiment 1 preparation again joins in the BR buffer solution of 0.9mLpH=10.05, fixing excitation wavelength is 326nm, at room temperature carry out fluorescence spectrum detection, fluorescence peak intensity according to about 420nm, detection metal ion and the pH impact on the fluorescence peak intensity of fluorescence copper nanocluster probe solution.
The impact of the fluorescence peak intensity of fluorescence copper nanocluster probe solution is shown in Fig. 4 by metal ion and pH: under 326nm excites, draw from the fluorescence intensity of fluorescence copper nanocluster probe solution of metal ion with the fluorescence peak intensity F of the fluorescence copper nanocluster probe solution cushioned of the BR containing pH=10.05: the fluorescence copper nanocluster probe solution change of the BR buffering of pH=10.05 is maximum, the change of other metal ions is relatively small, illustrates that fluorescence copper nanocluster probe solution prepared by the present invention can qualitative detection pH.
Embodiment 3
The impact experiment of the fluorescence peak intensity of the fluorescence copper nanocluster probe solution that embodiment 1 is prepared by ionic strength:
The fluorescence copper nanocluster probe solution 100 μ L embodiments 1 prepared joins in 900 μ LBR buffer solution (pH=7.0), fixing excitation wavelength is 326nm, add the sodium chloride solution (0.04-0.22mol/L) of variable concentrations, fluorescence peak intensity according to about 420nm, detects the ionic strength impact on the fluorescence peak intensity of fluorescence copper nanocluster probe solution.
The impact of the fluorescence peak intensity of fluorescence copper nanocluster probe solution is shown in Fig. 5 by ionic strength: under 326nm excites, fluorescence copper nanocluster probe solution is in sodium chloride solution (0.04-0.22mol/L) scope of variable concentrations, fluorescence peak intensity is basically unchanged, and illustrates that the fluorescence copper anti-ion interference of nanocluster probe solution prepared by the present invention is strong.
Embodiment 4
The fluorescence copper nanocluster probe solution of embodiment 1 preparation fluorescence intensity in BR buffer solution is tested with the change of pH:
The fluorescence copper nanocluster probe solution 100 μ L of Example 1 preparation joins in the BR buffer solution of 900 μ L difference pH, fixing excitation wavelength is 326nm, at room temperature carry out fluorescence spectrum detection, fluorescence peak intensity according to about 420nm, the impact on the fluorescence peak intensity of fluorescence copper nanocluster probe solution of the BR buffer solution of the different pH of detection.
The impact of the fluorescence peak intensity of fluorescence copper nanocluster probe solution is shown in Fig. 6 by the BR buffer solution of different pH: under 326nm excites, and fluorescence copper nanocluster probe solution is adding the BR buffer solution of different pH, and fluorescence peak intensity strengthens gradually；Wherein pH value is 1.82,2.27,3.05 respectively, 4.00,5.03,6.08,7.00,8.06,9.07,10.05,11.02,12.00 the BR buffer solution fluorescence spectrum figure to fluorescence copper nanocluster probe solution fluorescence peak intensity effect, illustrate that fluorescence copper nanocluster probe solution prepared by the present invention is capable of the detection to different pH.
Additionally, the change of the fluorescence peak intensity of fluorescence copper nanocluster probe solution prepared by the present invention is linear from the BR buffer solution of different pH, as it is shown in fig. 7, along with the growth of pH value, fluorescence peak intensity strengthens gradually, the R of linear equation2=0.9992.
Embodiment 5
The fluorescence copper nanocluster probe solution of embodiment 1 preparation fluorescence intensity in HEPES-NaOH buffer solution is tested with the change of pH:
The fluorescence copper nanocluster probe solution 100 μ L of Example 1 preparation joins in the HEPES-NaOH buffer solution of 900 μ L difference pH, fixing excitation wavelength is 326nm, at room temperature carry out fluorescence spectrum detection, fluorescence peak intensity according to about 420nm, the impact on the fluorescence peak intensity of fluorescence copper nanocluster probe solution of the HEPES-NaOH buffer solution of the different pH of detection.
The impact of the fluorescence peak intensity of fluorescence copper nanocluster probe solution is shown in Fig. 8 by the HEPES-NaOH buffer solution of different pH: under 326nm excites, fluorescence copper nanocluster probe solution is adding the HEPES-NaOH buffer solution of different pH, and fluorescence peak intensity strengthens gradually；Wherein pH value is 6.80,7.05,7.25 respectively, 7.64, the HEPES-NaOH buffer solution of 7.98, the 8.18 fluorescence spectrum figure to fluorescence copper nanocluster probe solution fluorescence peak intensity effect, illustrates that fluorescence copper nanocluster probe solution prepared by the present invention is capable of the detection to different pH.
Additionally, the change of the fluorescence peak intensity of fluorescence copper nanocluster probe solution prepared by the present invention is linear from the HEPES-NaOH buffer solution of different pH, as it is shown in figure 9, along with the growth of pH value, fluorescence peak intensity strengthens gradually, the R of linear equation2=0.9946.
Embodiment 6
The fluorescence copper nanocluster probe solution of embodiment 1 preparation fluorescence intensity in Tris-HCl buffer solution is tested with the change of pH:
The fluorescence copper nanocluster probe solution 100 μ L of Example 1 preparation joins in the Tris-HCl buffer solution of 900 μ L difference pH, fixing excitation wavelength is 326nm, at room temperature carry out fluorescence spectrum detection, fluorescence peak intensity according to about 420nm, the impact on the fluorescence peak intensity of fluorescence copper nanocluster probe solution of the Tris-HCl buffer solution of the different pH of detection.
The impact of the fluorescence peak intensity of fluorescence copper nanocluster probe solution is shown in Figure 10 by the Tris-HCl buffer solution of different pH: under 326nm excites, and fluorescence copper nanocluster probe solution is adding the Tris-HCl buffer solution of different pH, and fluorescence peak intensity strengthens gradually；Wherein pH value is 6.95,7.24,7.56 respectively, 7.99, the Tris-HCl buffer solution of 8.68, the 9.00 fluorescence spectrum figure to fluorescence copper nanocluster probe solution fluorescence peak intensity effect, illustrates that fluorescence copper nanocluster probe solution prepared by the present invention is capable of the detection to different pH.
Additionally, the change of the fluorescence peak intensity of fluorescence copper nanocluster probe solution prepared by the present invention is linear from the Tris-HCl buffer solution of different pH, as shown in figure 11, along with the growth of pH value, fluorescence peak intensity strengthens gradually, the R of linear equation2=0.9843.
Embodiment 7
The fluorescence copper nanocluster probe solution of embodiment 1 preparation is for the test experience of pH in actual water sample:
Respectively with business-like pH meter (pHa) with embodiment 1 preparation fluorescence copper nanocluster probe solution (pHb) detect the pH of water sample and lake water sample from the beginning, calculate both relative deviations, as shown in table 1.
The fluorescence copper nanocluster probe solution that table 1 is business-like pH meter to be prepared with the present invention is for the detection of pH in actual water sample
Claims (10)
1. the preparation method of a fluorescence copper nanocluster probe, it is characterised in that step includes:
(1) Bombyx bombycis is cut into 1-2cm2Small pieces, Bombyx bombycis small pieces are placed in 0.01-0.03mol/L sodium carbonate liquor, at 90-110 DEG C heat degumming 0.5-2h, prepare fibroin albumen；
(2) fibroin albumen deionized water step (1) obtained cleans 2-4 time, at CaCl2: water: in the mixed solution of ethanol=1:8:2, heats 1-3h at 70-90 DEG C, makes fibroin albumen dissolve；
(3) silk fibroin protein solution obtained to step (2) is cooled to room temperature, filters, and dialyse 48h, is placed in 4 DEG C of refrigerators standby；
(4) silk fibroin protein solution that step (3) obtains is measured, it is stirred continuously down, adding 8-15mmol/L copper nitrate in silk fibroin protein solution, continue stirring and make both fully mix, the volume ratio of silk fibroin water solution and copper nitrate solution is 1-4:1；
(5) adding 25 μ L concentration in the mixed solution obtained to step (4) is the sodium hydroxide solution of 1mol/L, continues stirring 2-10h at 25-95 DEG C；
(6) mixed solution step (5) obtained, through centrifugal, finally gives fluorescence copper nanocluster probe solution.
2. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that in described step (1), the concentration of sodium carbonate liquor is 0.02mol/L.
3. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that in described step (1), Bombyx bombycis small pieces and sodium carbonate liquor heat 1h at 100 DEG C.
4. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that the fibroin albumen deionized water after the degumming obtained in described step (2) cleans 3 times, at CaCl2: water: in the mixed solution of ethanol=1:8:2, heats 2h so that it is dissolve at 80 DEG C.
5. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that in described step (3), dialysis is with the bag filter dialysis that molecular cut off is 8000-14000Da.
6. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that the concentration of the described copper nitrate solution in step (4) is 10mmol/L.
7. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that the volume ratio of the described silk fibroin water solution in step (4) and copper nitrate solution is 3:1.
8. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that in described step (5), stirs 6h at 55 DEG C.
9. the preparation method of a kind of fluorescence copper nanocluster probe as claimed in claim 1, it is characterised in that centrifugal in described step (6) is with the centrifugal 10min of 13000r/min rotating speed.
10. the fluorescence copper nanocluster probe that prepared by either method as described in claim 1-9 application in pH detects.
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| CN111420707A (en) * | 2020-05-07 | 2020-07-17 | 西南大学 | Preparation of silk fibroin-iridium dioxide multifunctional composite nanocluster |
| CN111715890A (en) * | 2020-06-29 | 2020-09-29 | 太原师范学院 | Preparation method, product and application of polyvinylpyrrolidone-copper nanocluster |
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| CN107782704A (en) * | 2016-08-29 | 2018-03-09 | 天津师范大学 | Folic acid detection method based near infrared fluorescent probe copper nano-cluster |
| CN106520114A (en) * | 2016-09-20 | 2017-03-22 | 山西大学 | Preparation method of fluorogold nano-cluster probe and application thereof |
| CN108329904A (en) * | 2018-01-25 | 2018-07-27 | 暨南大学 | A kind of cysteamine modification copper nanocluster solution fluorescence probe and preparation and application |
| 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 |
| CN111420707A (en) * | 2020-05-07 | 2020-07-17 | 西南大学 | Preparation of silk fibroin-iridium dioxide multifunctional composite nanocluster |
| CN111420707B (en) * | 2020-05-07 | 2023-02-28 | 西南大学 | Preparation of silk fibroin-iridium dioxide multifunctional composite nanocluster |
| CN111715890A (en) * | 2020-06-29 | 2020-09-29 | 太原师范学院 | Preparation method, product and application of polyvinylpyrrolidone-copper nanocluster |
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