CN110079297A - A method of blue-fluorescence copper nano-cluster is synthesized using 6- sulfydryl-beta cyclodextrin - Google Patents
A method of blue-fluorescence copper nano-cluster is synthesized using 6- sulfydryl-beta cyclodextrin Download PDFInfo
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Abstract
The invention discloses a kind of using 6- sulfydryl-beta cyclodextrin synthesis blue-fluorescence copper nano-cluster method, belongs to fluorescence copper nano-cluster technical field.At room temperature, single (6- sulfydryl -6- the deoxidation)-beta-cyclodextrin of general is added in copper sulphate and reacts in the case where stirring rate is 500~600rmp to solution is colourless obtains solution A to the present invention；Sodium hydroxide solution is added in solution A to obtain reaction system and react in the case where stirring rate is 500~600rmp to colourless to obtain solution B；Solution B is placed in 60~270min of reaction under the conditions of temperature is 55~85 DEG C and obtains dark brown solution to get to blue-fluorescence copper nanocluster CuNCs@6-SH-CD.The present invention, which is utilized, synthesizes copper nano-cluster by reducing agent and coating agent of sulfydryl-beta cyclodextrin, and synthetic method is simple.
Description
Technical field
The present invention relates to a kind of using 6- sulfydryl-beta cyclodextrin synthesis blue-fluorescence copper nano-cluster method, and it is glimmering to belong to blue
Light copper nano-cluster technical field.
Background technique
Noble metal nanocluster has a wider excitation band, relatively narrow transmitting band, and higher quantum yield is adjustable photic
It shines.
At present the synthetic method of copper nano-cluster (CuNCs) have stirring synthetic method, microwave assisting method, sonochemistry synthetic method,
Microemulsion method etc., but these methods there are it is time-consuming, complicated, be related to that toxic organic reagent, quantum yield are low, stability is poor etc. and lack
Point；The method of copper nano-cluster (CuNCs) is synthesized easily using different molecular template such as protein, DNA, small thio ligands etc.
Be oxidized, size it is difficult to control.
In the prior art the shortcomings that copper nano-cluster:
(1) since the Nature comparison of copper is active, it is relatively difficult to synthesize copper nano-cluster that is stable, fluorescing；
The synthesis step of copper nano-cluster is relatively cumbersome at present, and condition is harsh, and there are many disadvantages in preparation process, such as time-consuming, molten
Xie Du is low, and energy consumption is big, and quantum yield is low etc.；Since the Nature comparison of copper is active, even if by complicated synthesis process, it is prepared
Products therefrom oxidation resistance is also poor afterwards, and photoluminescent property is unstable.
(2) be coated in the stabilizer on metal nanometre cluster surface property the photoluminescent property of metal nanometre cluster is also played it is very heavy
The effect wanted, currently used stabilizer have oligonucleotide, peptide and protein, thiol class substance etc., these substances are often
Without selectivity, to be applied to certain restrictions.
Summary of the invention
The technical issues of for copper nano-cluster in the prior art, the present invention provide a kind of utilization 6- sulfydryl-beta cyclodextrin synthesis
The method of blue-fluorescence copper nano-cluster, the present invention, which is utilized, synthesizes copper nano-cluster by reducing agent and coating agent of sulfydryl-beta cyclodextrin,
Synthetic method is simple.
A method of blue-fluorescence copper nano-cluster is synthesized using 6- sulfydryl-beta cyclodextrin, the specific steps are as follows:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 500~600rmp to solution is colourless to obtain solution A；
(2) in the solution A of step (1) be added sodium hydroxide solution obtain reaction system and stirring rate be 500~
Reaction obtains solution B to colourless under 600rmp；
(3) solution B of step (2) is placed under the conditions of temperature is 55~85 DEG C to obtain dark-brown molten by 60~270min of reaction
Liquid to get arrive blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The molar ratio of copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is 1:10~1:13 in the step (1)；
The concentration of sodium hydroxide solution is 0.12~0.24mol/L in step (2) reaction system；
At 379nm, maximum emission wavelength exists the maximum excitation wavelength of the copper nano-cluster CuNCs@6-SH- β-CD
At 463nm.
6-SH- β-CD is used as coating agent and reducing agent simultaneously in entire reaction system, and NaOH is 6-SH- β-CD reduction
CuSO4Alkaline environment is provided, when the concentration of NaOH in reaction system is 0.04~0.2mol/L, NaOH concentration is higher, forms copper
The fluorescence intensity of nano-cluster is stronger, but excessively high concentration also easily makes nanoparticle aggregation；High temperature provides energy for entire reaction system
Amount, when temperature is 55~85 DEG C, temperature more high-energy is higher, and the fluorescence intensity of the copper nano-cluster of synthesis is stronger, and excessively high temperature
Degree can also make nanoparticle aggregation, so that fluorescence intensity be made to weaken.
Beneficial effects of the present invention:
The present invention, which is utilized, synthesizes copper nano-cluster by reducing agent and coating agent of sulfydryl-beta cyclodextrin, and synthetic method is simple.
Detailed description of the invention
Fig. 1 is the fluorescence excitation-emission spectrogram of 1 bronze medal nano-cluster of embodiment；
Fig. 2 is the UV-vis abosrption spectrogram of 1 bronze medal nano-cluster of embodiment；
Fig. 3 is that the TEM of 1 bronze medal nano-cluster of embodiment schemes；
Fig. 4 is the x-ray photoelectron spectroscopy figure of 1 bronze medal nano-cluster of embodiment；
Fig. 5 is the fluorescent emission intensity figure of 1~11 nano-cluster of embodiment.
Fig. 6 is the fluorescent emission intensity figure of 5~8 bronze medal nano-cluster of embodiment；
Fig. 7 is the fluorescent emission intensity figure of 9~11 bronze medal nano-cluster of embodiment.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:10；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 85 DEG C under the conditions of reaction 120min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster as shown in Figure 1, as can be known from Fig. 1, blue-fluorescence
The maximum excitation wavelength of copper nano-cluster is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not as shown in Fig. 2, as can be known from Fig. 2, UV absorption has
Apparent absorption peak, therefore copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes as shown in figure 3, as can be known from Fig. 3, the partial size of copper nano-cluster be about 3nm and
In dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is as shown in figure 4, as can be known from Fig. 4, in conjunction with can be
Fitting peak at 952.73eV, 952.00eV is Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can be in 932.85eV, 932.23eV
The fitting peak at place is Cu (I) 2p3/2 or Cu (0) 2p3/2, the satellites of bivalent cupric ion does not occur in 943Ev or so, therefore
The valence state of copper is Cu (0) or Cu (I)；
Embodiment 2: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 580rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 580rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 55 DEG C under the conditions of reaction 270min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is as shown in figure 4, as can be known from Fig. 4, in conjunction with can be
Fitting peak at 952.73eV, 952.00eV is Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can be in 932.85eV, 932.23eV
The fitting peak at place is Cu (I) 2p3/2 or Cu (0) 2p3/2, the satellites of bivalent cupric ion does not occur in 943Ev or so, therefore
The valence state of copper is Cu (0) or Cu (I)；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 3: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 550rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:12；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 75 DEG C under the conditions of reaction 140min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 4: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 500rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:13；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 550rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 85 DEG C under the conditions of reaction 120min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 5: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 500rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.12mol/L in reaction system；
(3) solution B of step (2) is placed in reaction 60min under the conditions of temperature is 85 DEG C and obtains dark brown solution to get arriving
Blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 6: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 550rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.16mol/L in reaction system；
(3) solution B of step (2) is placed in reaction 80min under the conditions of temperature is 75 DEG C and obtains dark brown solution to get arriving
Blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 7: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 85 DEG C under the conditions of reaction 100min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 8: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.24mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 85 DEG C under the conditions of reaction 120min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 9: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 95 DEG C under the conditions of reaction 150min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 10: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 85 DEG C under the conditions of reaction 120min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)。
Embodiment 11: a method of blue-fluorescence copper nano-cluster being synthesized using 6- sulfydryl-beta cyclodextrin, specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and in stirring speed
Rate is to react under 600rmp to solution is colourless to obtain solution A；Wherein copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin
Molar ratio is 1:11；
(2) sodium hydroxide solution is added in the solution A of step (1) to obtain reaction system and be 600rmp in stirring rate
Lower reaction obtains solution B to colourless；Wherein the concentration of sodium hydroxide solution is 0.2mol/L in reaction system；
(3) by the solution B of step (2) be placed in temperature be 75 DEG C under the conditions of reaction 120min obtain dark brown solution to get
To blue-fluorescence copper nanocluster CuNCs@6-SH-CD；
The fluorescence excitation-emission spectrogram of the present embodiment copper nano-cluster it is found that the copper nano-cluster of blue-fluorescence maximum excitation
Wavelength is at 379nm, and maximum emission wavelength is at 463nm；
The UV-vis abosrption spectrogram of the present embodiment copper nano-cluster is not it is found that UV absorption has apparent absorption peak, therefore
Copper nano-cluster rather than copper nano-particle, are presented blue-fluorescence under the ultraviolet light irradiation of 365nm；
The TEM of the present embodiment copper nano-cluster schemes it is found that the partial size of copper nano-cluster is about 3nm and in dispersity；
The present embodiment copper nano-cluster is colourless under natural light, is blue under the ultraviolet lamp of 365nm；
The x-ray photoelectron spectroscopy figure of the present embodiment copper nano-cluster is it is found that in conjunction with can be at 952.73eV, 952.00eV
Fitting peak be Cu (I) 2p1/2 or Cu (0) 2p1/2, in conjunction with can fitting peak 932.85eV, 932.23eV at be Cu (I)
There are not the satellites of bivalent cupric ion in 943Ev or so in 2p3/2 or Cu (0) 2p3/2, thus the valence state of copper be Cu (0) or
Cu(Ⅰ)；
The fluorescent emission intensity figure of Examples 1 to 4 copper nano-cluster is shown in Fig. 5, and as can be seen from Figure 5,6-SH- β-CD is entirely reacting
Coating agent and reducing agent are used as in system simultaneously, as CuSO in reaction system4It is 1:10~1:13 with 6-SH- β-CD molar ratio
When, the fluorescence intensity of the copper nano-cluster of generation first increases to be reduced again, and in 1:11 condition, the fluorescence intensity of copper nano-cluster reaches maximum；
The fluorescent emission intensity figure of 5~8 bronze medal nano-cluster of embodiment is shown in Fig. 6, as can be seen from Figure 6, NaOH be 6-SH- β-CD also
Former CuSO4Alkaline environment is provided, when the concentration of NaOH in reaction system is 0.12~0.24mol/L, NaOH concentration is higher, shape
Fluorescence intensity at copper nano-cluster is stronger, but excessively high concentration also easily makes nanoparticle aggregation, and in 0.2mol/L condition, copper is received
The fluorescence intensity of rice cluster reaches maximum；
The fluorescent emission intensity figure of 9~11 bronze medal nano-cluster of embodiment is shown in Fig. 7, and as can be seen from Figure 7, high temperature is entire reaction system
Energy is provided, when temperature is 75~95 DEG C, the fluorescence intensity of the copper nano-cluster of generation first increases to be reduced again, in 85 DEG C of conditions
The fluorescence intensity of copper nano-cluster reaches maximum.
Claims (3)
1. a kind of utilize 6- sulfydryl-beta cyclodextrin synthesis blue-fluorescence copper nano-cluster method, which is characterized in that specific steps are such as
Under:
(1) at room temperature, single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is added in copper sulphate and is in stirring rate
Reaction obtains solution A to solution is colourless under 500~600rmp；
(2) in the solution A of step (1) be added sodium hydroxide solution obtain reaction system and stirring rate be 500~
Reaction obtains solution B to colourless under 600rmp；
(3) solution B of step (2) is placed in 60~270min of reaction under the conditions of temperature is 55~85 DEG C and obtains dark brown solution,
Obtain blue-fluorescence copper nanocluster CuNCs 6-SH-CD.
2. according to claim 1 using 6- sulfydryl-beta cyclodextrin synthesis blue-fluorescence copper nano-cluster method, feature exists
In: the molar ratio of copper sulphate and single (6- sulfydryl -6- deoxidation)-beta-cyclodextrin is 1:10~1:13 in step (1).
3. according to claim 1 using 6- sulfydryl-beta cyclodextrin synthesis blue-fluorescence copper nano-cluster method, feature exists
In: the concentration of sodium hydroxide solution is 0.12~0.24mol/L in step (2) reaction system.
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| CN111187614A (en) * | 2020-01-17 | 2020-05-22 | 常州大学 | Silicon quantum dot/cyclodextrin copper fluorescent cluster and preparation method thereof and application of fluorescent cluster in detection of sulfhydryl compound |
| CN112113943A (en) * | 2020-09-22 | 2020-12-22 | 江南大学 | Method for detecting paraquat |
| CN113801650A (en) * | 2021-08-26 | 2021-12-17 | 桂林电子科技大学 | Sulfydryl beta-cyclodextrin-gold nanocluster and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187614A (en) * | 2020-01-17 | 2020-05-22 | 常州大学 | Silicon quantum dot/cyclodextrin copper fluorescent cluster and preparation method thereof and application of fluorescent cluster in detection of sulfhydryl compound |
| CN111187614B (en) * | 2020-01-17 | 2022-10-28 | 常州大学 | Silicon quantum dot/cyclodextrin copper fluorescent cluster and preparation method thereof and application of fluorescent cluster in detection of sulfhydryl compound |
| CN112113943A (en) * | 2020-09-22 | 2020-12-22 | 江南大学 | Method for detecting paraquat |
| CN113801650A (en) * | 2021-08-26 | 2021-12-17 | 桂林电子科技大学 | Sulfydryl beta-cyclodextrin-gold nanocluster and preparation method and application thereof |
| CN113801650B (en) * | 2021-08-26 | 2023-07-14 | 桂林电子科技大学 | Sulfhydryl beta-cyclodextrin-gold nanocluster and preparation method and application thereof |
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