CN107254307A - A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application - Google Patents
A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application Download PDFInfo
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- CN107254307A CN107254307A CN201710440531.6A CN201710440531A CN107254307A CN 107254307 A CN107254307 A CN 107254307A CN 201710440531 A CN201710440531 A CN 201710440531A CN 107254307 A CN107254307 A CN 107254307A
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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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- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The present invention relates to a kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application, the fluorescence vesica is by Ag6It is dissolved into formation fluorescence vesica in polar organic solvent.The fluorescence vesica of the present invention is adding Fe3+Fluorescent quenching afterwards, fluorescence can be recovered by continuously adding reducing agent DL dithiothreitol (DTT)s, not only act as the effect of double check, and can be used for multiple times to detect Fe3+.The silver nanoclusters fluorescence vesica preparation method of the present invention is simple, with low cost；Detection means simple and fast, it is easy to observe；It may be reused.
Description
Technical field
The present invention relates to a kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application, belong to new material
Field.
Background technology
Ferro element is required trace element in human body, and total content is about 4~5g.Hemoglobin in red blood cell is transport
The carrier of oxygen, and iron is the constituent of hemoglobin, it is combined with oxygen, transports each part of body, for people
Breathing oxidation, to provide energy, obtains nutrition；Iron can also promote development, increase the resistance to disease, and regulation tissue is exhaled
Inhale, prevent fatigue, constitute ferroheme, prevention and treatment anaemia because of caused by iron deficiency makes skin recover good color.So
And, excessive iron is stored in vivo there is also potential illeffects, causes iron poisoning, this and a variety of diseases, such as heart and liver
Dirty disease, diabetes and some tumours are relevant.In addition, in water if there is excessive ferro element can influence the color of water, smell, taste
Deng, or even special industry such as weaving, papermaking and food industry can be influenceed.Therefore study it is a kind of easily and fast, simply, be easy to see
The method for the detection iron examined is necessary, and has very big application prospect.
Fluorescent material is often selected as fluorescence probe to detect noxious material.Its principle is tested substance and fluorescent material
Between occur interaction then influence fluorescent material luminous situation, so as to reach the purpose of detection.Metal nanometre cluster due to
There is the pi-pi accumulation effect between ligand metal electric charge transfer, metal-metal effect, ligand-ligand in it, with unique hair
Optical phenomenon, therefore metal nanometre cluster can detect harmful toxic matter as fluorescence probe.
Silver nanoclusters cause the favor of people in the industry due to its property and raw material sources extensively, on silver nanoparticle
The patent document of cluster also has many reports, such as：Chinese patent document CN104227016A (application numbers：201410494598.4)
The method for disclosing the silver nanoclusters that there is hyperfluorescence to launch for a kind of quick preparation, it is characterized in that, by volume, take 14.75 parts
Redistilled water is in container, in thermostat water bath, and 2.0 parts of AgNO are sequentially added under stirring condition3Solution, 0.25 part of NaBH4
Solution and 3.0 parts of amino black 10B, stir 3-90min at 30-80 DEG C, you can obtain the silver nanoclusters launched with hyperfluorescence.
Again for example：Chinese patent document CN103878386A (application numbers：201410120530.X) disclose one kind and prepare fluorescence silver and receive
The method of rice cluster, it is related to a kind of method for preparing fluorescence silver nanoclusters, and preparation method is as follows：First, by a certain amount of silver salt and
Enuatrol is distributed in aqueous solvent respectively；2nd, two kinds of solution are mixed and constant temperature magnetic force is put into after its is uniform for a period of time
Heat a period of time on agitator；Three：Solution after reaction is filtered, solid matter is removed, obtains fluorescence silver nanoclusters, i.e.,
Complete.
But, the exploration of synthetic method and the research of solid state properties are only limited to for silver nanoclusters report at present, for
The application study of the Assembling Behavior and aggregation of silver nanoclusters in the solution is rarely reported.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection
Fe3+Application.
Term explanation：
Ag6：It is a kind of silver nanoclusters of six core, due to the π-π effects between part, part is acted on to the electric charge transfer of metal
And metal-metal effect, Ag6With certain luminosity.
Technical scheme is as follows：
A kind of silver nanoclusters fluorescence vesica, is by Ag6It is dissolved into formation fluorescence vesica in polar organic solvent.
, according to the invention it is preferred to, described polar organic solvent is dimethyl sulfoxide (DMSO), ethylene glycol, methanol or acetonitrile.
, according to the invention it is preferred to, described Ag6It is 10~70 μm of olL in the molar concentration of polar organic solvent-1。
, according to the invention it is preferred to, described Ag6It is prepared as follows obtaining：
By silver nitrate (AgNO3) aqueous solution and 2- mercaptonicotinic acids (H2Mna) aqueous solution is mixed, ultrasonically treated, is precipitated；
Ammoniacal liquor is added dropwise into precipitation, solution is obtained, slow solvent flashing dries it, obtains Ag6。
According to the present invention, the preparation method of above-mentioned silver nanoclusters fluorescence vesica, including step are as follows：
(1)Ag6The synthesis of molecule
By silver nitrate (AgNO3) aqueous solution and 2- mercaptonicotinic acids (H2Mna) aqueous solution is mixed, ultrasonically treated, is precipitated；
Ammoniacal liquor is added dropwise into precipitation, solution is obtained, solvent flashing dries it, obtains Ag6；
(2) preparation of silver nanoclusters fluorescence vesica
By Ag6It is dissolved into polar organic solvent, ultrasonic dissolution, produces silver nanoclusters fluorescence vesica.
Preparation in accordance with the present invention, it is preferred that AgNO in step (1)3The concentration of the aqueous solution is 0.1~1molL-1,H20.1~1molL of concentration of the mna aqueous solution-1；AgNO3And H2Mna mol ratio is 1：(0.8~1.2), it is further excellent
Select 1：1；
It is preferred that, ultrasonically treated supersonic frequency is 30~50kHz, and ultrasonic power is 140~160W, and ultrasonic time is 10
~30 minutes.
Preparation in accordance with the present invention, it is preferred that the mass concentration of ammoniacal liquor is 20~30% in step (1)；Ammoniacal liquor
Addition is untill precipitation is dissolved completely.Obtained solution is yellow clear solution.
, according to the invention it is preferred to, the polar organic solvent described in step (2) is dimethyl sulfoxide (DMSO), ethylene glycol, methanol
Or acetonitrile；
It is preferred that, Ag6It is 10~70 μm of olL in the molar concentration of polar organic solvent-1；
It is preferred that, the supersonic frequency of ultrasonic dissolution is 30~50kHz, and ultrasonic power is 140~160W, and ultrasonic time is 5
~10s.After ultrasonic dissolution of the present invention is complete 20~30h is stood at 18~25 DEG C.
According to the present invention, above-mentioned silver nanoclusters fluorescence vesica is in Fe3+Application in detection.
The principle of the present invention：
Ag6In the solvent of appropriate polarity, amphipathic, its peripheral mna is shown2-In carboxylic acid with ion be parent it is molten
Agent, middle galactic nucleus and mna2-In other parts in addition to carboxylate radical be solvophobic, mna2-Between exist π-π work
With, therefore, Ag6Amphipathic and π-π between molecule, which are acted on, causes Ag6It can assemble to form vesica.Simultaneously part to metal it
Between electro transfer effect, the π-π effects between ligand-ligand make vesica show the characteristic of fluorescence.When adding, certain is specific
Metal ion when, metal ion and Ag6Between exist competition absorb energy relation so that Ag6Enough energy can not be absorbed
Amount, so as to can not launch fluorescence, serves the effect of detection special metal ion.
In the present invention, Ag6The solvent of dissolving carries out creation Sexual behavior mode by many experiments and obtained.If being dissolved in water
In, then Ag6Vesica is not become, without fluorescent effect；For the less solvent of polarity (such as：Normal heptane), Ag6Do not dissolve then, more
Vesica is not become.
The present invention outstanding feature and beneficial effect be：
1st, Ag in the present invention6It is multi-metal cluster compound, belongs to new inorganic material, structure is novel, unique；Using super
The method of molecular self-assembling, can induce Ag under given conditions6Self aggregation formation vesica.Ag6The supermolecule vesica of formation retains
Photoluminescent property under solid state.
2nd, the present invention can prepare fluorescence vesica in multi-solvents, and fluorescence color is different with the species of solvent
And change.
3rd, fluorescence vesica of the invention is to Fe3+Detection there is high selectivity, sensitivity.And it is easy to detect, using portable
Formula uviol lamp is the change that fluorescence intensity can be observed, simple to operate, it is easy to accomplish.
4th, fluorescence vesica prepared by the present invention is adding Fe3+Fluorescent quenching, continuously adds reducing agent DL- dithiothreitol (DTT)s afterwards
Fluorescence can be recovered, not only act as the effect of double check, and can be used for multiple times to detect Fe3+。
Material characteristics set forth in the present invention are tested using the following method：
1st, transmission electron microscope (TEM).The pattern of fluorescence vesica can be observed by TEM.
2nd, high resolution transmission electron microscopy (HR-TEM).The fine structure of fluorescence vesica can be observed by HR-TEM.
3rd, fluorescence spectrum.Pass through the fluorescence intensity of sepectrophotofluorometer test sample.
4th, UV-vis spectroscopy spectrum.Can be with the absorption curve of determination sample by UV-vis spectroscopy spectrum.
Brief description of the drawings
Fig. 1 is the substance A g synthesized by the embodiment of the present invention 16Molecular structure.
Fig. 2 is the TEM figures of prepared silver nanoclusters fluorescence vesica different multiplying in the embodiment of the present invention 1.
Fig. 3 schemes for the TEM of silver nanoclusters fluorescence vesica made from the embodiment of the present invention 2,3,4.Wherein：(a) it is embodiment
2, (b) is embodiment 3, and (c) is embodiment 4.Illustration therein is the image under bigger enlargement ratio, and scale is 20nm.
Fig. 4 is the optical photograph of silver nanoclusters fluorescence vesica sample prepared by 1-4 of the embodiment of the present invention.Wherein：(a) to be real
Example 2 is applied, (b) is embodiment 1, and (c) is embodiment 3, and (d) is embodiment 4.
Fig. 5 is the fluorescence spectra of silver nanoclusters fluorescence vesica prepared by 1-4 of the embodiment of the present invention.
Fig. 6 is addition same concentrations (2mmol L in experimental example 1 of the present invention-1) dissimilar metals ion is in of the invention real
Apply after the silver nanoclusters fluorescence vesica prepared in example 1, sample is the optical photograph under 365nm ultra violet lamp in wavelength.
Fig. 7 is addition same concentrations (2mmol L in experimental example 1 of the present invention-1) dissimilar metals ion is in of the invention real
Apply the fluorescence spectra of the silver nanoclusters fluorescence vesica of the preparation of example 1.
(I) and addition metal after metal ion are added in the silver nanoclusters fluorescence vesica that Fig. 8 is prepared for the embodiment of the present invention 1
(I before ion0) fluorescence intensity ratio at wavelength 485nm block diagram (left side).Continue the silver prepared to the embodiment of the present invention 1
Fe is added in the system that other kinds of metal ion is added in nanocluster fluorescence vesica3+Afterwards, (the I/I at 485nm0) ratio
Block diagram (right side).
Fig. 9 is addition various concentrations Fe in experimental example 2 of the present invention3+The fluorescence vesica prepared in the embodiment of the present invention 1
Fluorescence spectra.
Figure 10 is addition various concentrations Fe in experimental example 2 of the present invention3+(I) is in addition Fe afterwards3+Before (I0) at wavelength 485nm
Fluorescence intensity ratio change curve.
Figure 11 be in experimental example 3 of the present invention into silver nanoclusters fluorescence vesica made from embodiment 1 addition 2mmol L-1Fe3 +, then add the optical photograph of the sample variation of DL- dithiothreitol (DTT)s.Wherein：(a) it is silver nanoclusters made from embodiment 1
Fluorescence vesica, (b) is that silver nanoclusters fluorescence vesica addition concentration is 2mmol L-1Fe3+, (c) is addition Fe3+After add
4mmol L-1DL- dithiothreitol (DTT)s.(a), left side is the photo under fluorescent lamp in (b), (c), and right side is wavelength 365nm's
Photo under uviol lamp.
Figure 12 be in experimental example 3 of the present invention into silver nanoclusters fluorescence vesica made from embodiment 1 addition 2mmol L-1Fe3 +After add after different amounts of DL- dithiothreitol (DTT)s, the fluorescence spectra of sample.
Figure 13 is that 2mmol L are added into silver nanoclusters fluorescence vesica made from embodiment 1 in experimental example 3-1Fe3+Afterwards again
Add (I) and addition DL- dithiothreitol (DTT)s (I after different amounts of DL- dithiothreitol (DTT)s0) before wavelength be 485nm at fluorescence
The ratio change curve of intensity.
Figure 14 is the silver nanoclusters fluorescence vesica of the preparation of embodiment 1 in experimental example 3 of the present invention and added thereto successively
2mmolL-1Fe3+With the uv absorption spectra after DL- dithiothreitol (DTT)s.
Embodiment
The present invention is further elaborated with reference to specific embodiments and the drawings, but not limited to this.
Raw materials used in embodiment is convenient source, commercial products, wherein：AgNO3Buy close europeanized in Tianjin section
Learn reagent Co., Ltd, H2Mna is bought in Sigma-Aldrich, and various metal salts are that nitrate buys close in Tianjin section
Europe chemical reagent Co., Ltd, solvent is bought in Chemical Reagent Co., Ltd., Sinopharm Group, using preceding without processing, is directly made
With.
Embodiment 1
A kind of preparation method of silver nanoclusters fluorescence vesica, including step are as follows：
(1)Ag6The synthesis of molecule
The accurate AgNO for weighing 1mmol (167mg)3With 1mmol (155mg) H2Mna solids add 6mL in round-bottomed flask
Water dissolving, at room temperature, ultrasonically treated 20 minutes (160W, 40kHz) is precipitated.Ammoniacal liquor is added dropwise into precipitation
(25wt%, 8 drops), obtain the settled solution of yellow.Slow solvent flashing dries it, obtains Ag6。
(2) preparation of silver nanoclusters fluorescence vesica
Weigh 1.674mg Ag6It is dissolved into 20mL ethylene glycol, ultrasonic 10s dissolves it, it is quiet in 20 DEG C of insulating boxs
24h is put, is produced.
The Ag that the present embodiment is obtained6Molecular structure it is as shown in Figure 1.Ag as shown in Figure 16It is a kind of silver nanoparticle of six core
Cluster.
The TEM figures that the present embodiment obtains silver nanoclusters fluorescence vesica different multiplying are as shown in Figure 2.As shown in Figure 2, silver nanoparticle
Cluster fluorescence vesica is rendered as vesica state.
Embodiment 2
A kind of preparation method of silver nanoclusters fluorescence vesica, including step are as follows：
(1)Ag6The synthesis of molecule
The accurate AgNO for weighing 2mmol (334mg)3With 2mmol (310mg) H2Mna solids add 6mL in round-bottomed flask
Water dissolving, at room temperature, ultrasonically treated 20 minutes (160W, 40kHz) is precipitated.Ammoniacal liquor is added dropwise into precipitation
(25wt%, 16 drops), obtain the settled solution of yellow.Slow solvent flashing dries it, obtains Ag6。
(2) preparation of silver nanoclusters fluorescence vesica
Weigh 1.674mg Ag6It is dissolved into 20mL dimethyl sulfoxide (DMSO)s, ultrasonic 10s dissolves it, then at 20 DEG C of insulating boxs
Middle standing 24h, is produced.
The present embodiment obtains the TEM figures of silver nanoclusters fluorescence vesica as shown in Fig. 3 (a).
Embodiment 3
A kind of preparation method of silver nanoclusters fluorescence vesica, including step are as follows：
(1)Ag6The synthesis of molecule
The accurate AgNO for weighing 1mmol (167mg)3With 1mmol (155mg) H2Mna solids add 6mL in round-bottomed flask
Water dissolving, at room temperature, ultrasonically treated 20 minutes (160W, 40kHz) is precipitated.Ammoniacal liquor is added dropwise into precipitation
(25wt%, 8 drops), obtain the settled solution of yellow.Slow solvent flashing dries it, obtains Ag6。
(2) preparation of silver nanoclusters fluorescence vesica
Weigh 0.6696mg Ag6It is dissolved into 20mL methanol, ultrasonic 10s dissolves it, it is quiet in 20 DEG C of insulating boxs
24h is put, is produced.
The present embodiment obtains the TEM figures of silver nanoclusters fluorescence vesica as shown in Fig. 3 (b).
Embodiment 4
A kind of preparation method of silver nanoclusters fluorescence vesica, including step are as follows：
(1)Ag6The synthesis of molecule
The accurate AgNO for weighing 1mmol (167mg)3With 1mmol (155mg) H2Mna solids add 6mL in round-bottomed flask
Water dissolving, at room temperature, ultrasonically treated 20 minutes (160W, 40kHz) is precipitated.Ammoniacal liquor is added dropwise into precipitation
(25wt%, 8 drops), obtain the settled solution of yellow.Slow solvent flashing dries it, obtains Ag6。
(2) preparation of silver nanoclusters fluorescence vesica
Weigh 0.6696mg Ag6It is dissolved into 40mL acetonitriles, ultrasonic 10s dissolves it, it is quiet in 20 DEG C of insulating boxs
24h is put, is produced.
The present embodiment obtains the TEM figures of silver nanoclusters fluorescence vesica as shown in Fig. 3 (c).
Experimental example 1
20 μ L concentration are pipetted for 200mmolL-1Metal ion (Ba2+,Zn2+,Pb2+,Ni2+,Mg2+,Na+,Cu2+,Co2 +,Cd2+,Fe3+) ethylene glycol solution in 2mL embodiment 1 prepare silver nanoclusters fluorescence vesica in, vortex 10s mixes it
Uniformly, 2 hours are stood, sample, optical photograph (the moon of metal ion as shown in Figure 6 is observed in the case where wavelength is 365nm uviol lamp
Ion is all nitrate anion).
Silver nanoclusters fluorescence vesica and the sample added after different types of metal ion are transferred to quartz cuvette respectively
In ware, using the launching light spectrogram of sepectrophotofluorometer test sample, as shown in Figure 7.Added in silver nanoclusters fluorescence vesica
(I) is with adding (I before metal ion after metal ion0) fluorescence intensity ratio at wavelength 485nm block diagram such as Fig. 8 (left side)
It is shown.
Ag6Molecule is because part is to metal electric charge transfer, the π-π effects between part, after aggregation forms vesica according to
So remain original luminosity.From Fig. 7,8, after metal ion is added, it can be found that only Fe3+It can make completely
Fluorescent quenching, the addition of other metal ions is smaller to fluorescence intensity.Illustrate that silver nanoclusters fluorescence vesica prepared by the present invention exists
Detect Fe3+Aspect has high selectivity.The phenomenon can be observed using hand-held ultraviolet lamp and fluorescence spectrum, and testing result is held
Easily observe, be easy to determine.
Experimental example 2
Pipette different amounts of Fe3+Ethylene glycol solution in 2mL embodiment 1 prepare silver nanoclusters fluorescence vesica in, make
Its concentration is by 1 to 1333 μm of ol L-1, vortex 10s make its be well mixed, stand 2 hours.Various concentrations Fe will be added3+Sample
It is transferred in quartz colorimetric utensil, using the launching light spectrogram of sepectrophotofluorometer test sample, as a result as shown in Figure 9.Yin Na
Fe is added in rice cluster fluorescence vesica3+(I) is with adding Fe afterwards3+Before (I0) fluorescence intensity ratio value changes curve at wavelength 485nm
As shown in Figure 10.
Calculating is obtained, and detection line is 24.8 μm of ol L-1, Fe3+And Ag6Action constant be 2.59 × 104M-1.Illustrate this hair
The silver nanoclusters fluorescence vesica of bright preparation is in detection Fe3+Aspect has high sensitivity.
Experimental example 3
2mmol L will be added in silver nanoclusters fluorescence vesica made from embodiment 1-1Fe3+, then add 4mmol L-1
DL- dithiothreitol (DTT)s, respectively with fluorescent lamp and 365nm wavelength uviol lamp under sample variation photo it is as shown in figure 11.Its
In：(a) it is silver nanoclusters fluorescence vesica made from embodiment 1, (b) is that silver nanoclusters fluorescence vesica addition concentration is 2mmol L- 1Fe3+, (c) is addition Fe3+After add 4mmol L-1DL- dithiothreitol (DTT)s.(a), (b), (c) middle left side is under fluorescent lamps
Photo, right side is photo under wavelength 365nm uviol lamp.
2mmol L will be added in silver nanoclusters fluorescence vesica made from embodiment 1-1Fe3+, then pipette different amounts of DL-
(concentration is by 0 to 4.66mmol L for the ethylene glycol solution of dithiothreitol (DTT)-1) be added thereto, vortex 10s is well mixed it, stands
2 hours.Add after different amounts of DL- dithiothreitol (DTT)s, the fluorescence spectra of sample is as shown in figure 12.Add the sulphur threoses of DL- bis-
(I) is with adding DL- dithiothreitol (DTT)s (I after alcohol0) preceding in ratio change curve such as Figure 13 that wavelength is the fluorescence intensity at 485nm
It is shown.Silver nanoclusters fluorescence vesica and add 2mmol L thereto successively prepared by embodiment 1-1Fe3+With DL- dithiothreitol (DTT)s
Uv absorption spectra afterwards is as shown in figure 14.
From Figure 12,13,14, the silver nanoclusters fluorescence vesica that fluorescence is quenched completely adds with DL- dithiothreitol (DTT)s
Enter and start gradually to recover, this is due to that DL- dithiothreitol (DTT)s have strong reproducibility, can make Fe3+It is reduced to Fe2+, ion exists
Absorption intensity at 320nm is decreased obviously, and competition absorbs to be weakened significantly, Ag6More energy can be absorbed so that fluorescence is extensive
It is multiple.Illustrating the silver nanoclusters fluorescence vesica of the present invention can realize to Fe3+With the double check of DL- dithiothreitol (DTT)s, in addition, should
Silver nanoclusters fluorescence vesica can be reused, and be realized to Fe3+Repeated detection.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, not to present invention protection model
The limitation enclosed, on the basis of technical scheme, those skilled in the art need not pay creative work and can do
The various modifications or deformation gone out are still within protection scope of the present invention.
Claims (10)
1. a kind of silver nanoclusters fluorescence vesica, it is characterised in that the fluorescence vesica is by Ag6It is dissolved into shape in polar organic solvent
Into fluorescence vesica.
2. silver nanoclusters fluorescence vesica according to claim 1, it is characterised in that described polar organic solvent is diformazan
Base sulfoxide, ethylene glycol, methanol or acetonitrile.
3. silver nanoclusters fluorescence vesica according to claim 1, it is characterised in that described Ag6In polar organic solvent
Molar concentration is 10~70 μm of olL-1。
4. silver nanoclusters fluorescence vesica according to claim 1, it is characterised in that described Ag6It is prepared as follows
Arrive：
By silver nitrate (AgNO3) aqueous solution and 2- mercaptonicotinic acids (H2Mna) aqueous solution is mixed, ultrasonically treated, is precipitated；Xiang Chen
Ammoniacal liquor is added dropwise in shallow lake, solution is obtained, slow solvent flashing dries it, obtains Ag6。
5. the preparation method of the silver nanoclusters fluorescence vesica described in claim 1, including step are as follows：
(1)Ag6The synthesis of molecule
By silver nitrate (AgNO3) aqueous solution and 2- mercaptonicotinic acids (H2Mna) aqueous solution is mixed, ultrasonically treated, is precipitated；Xiang Chen
Ammoniacal liquor is added dropwise in shallow lake, solution is obtained, solvent flashing dries it, obtains Ag6；
(2) preparation of silver nanoclusters fluorescence vesica
By Ag6It is dissolved into polar organic solvent, ultrasonic dissolution, produces silver nanoclusters fluorescence vesica.
6. preparation method according to claim 5, it is characterised in that AgNO in step (1)3The concentration of the aqueous solution be 0.1~
1mol·L-1,H20.1~1molL of concentration of the mna aqueous solution-1；AgNO3And H2Mna mol ratio is 1：(0.8~1.2).
7. preparation method according to claim 5, it is characterised in that ultrasonically treated supersonic frequency is 30~50kHz, is surpassed
Acoustical power is 140~160W, and ultrasonic time is 10~30 minutes.
8. preparation method according to claim 5, it is characterised in that in step (1) mass concentration of ammoniacal liquor be 20~
30%.
9. preparation method according to claim 5, it is characterised in that the polar organic solvent described in step (2) is two
Methyl sulfoxide, ethylene glycol, methanol or acetonitrile；
Ag6It is 10~70 μm of olL in the molar concentration of polar organic solvent-1；
The supersonic frequency of ultrasonic dissolution is 30~50kHz, and ultrasonic power is 140~160W, and ultrasonic time is 5~10s.
10. the silver nanoclusters fluorescence vesica described in claim 1 is in Fe3+Application in detection.
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| CN110330512A (en) * | 2019-07-30 | 2019-10-15 | 山东大学 | A kind of ag nano-cluster fluorescence nano stick and preparation method thereof and the application in white light LEDs |
| CN114525125A (en) * | 2022-02-15 | 2022-05-24 | 山东大学 | Water-soluble 'atom accurate' Ag6Nanocluster and macro synthesis method and application thereof |
| CN114958344A (en) * | 2022-05-09 | 2022-08-30 | 曲阜师范大学 | Preparation method of gold nanocluster luminescent hydrogel and application of gold nanocluster luminescent hydrogel in information encryption |
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| CN104914083A (en) * | 2015-06-14 | 2015-09-16 | 湖南科技大学 | Method for simultaneously detecting I<-> and Br<-> by adopting fluorescence silver nanoclusters and application thereof |
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| CN109283168A (en) * | 2018-08-13 | 2019-01-29 | 浙江大学 | A kind of highly sensitive SERS molecular detecting method based on both sexes nano particle |
| CN109283168B (en) * | 2018-08-13 | 2020-07-03 | 浙江大学 | High-sensitivity SERS molecule detection method based on amphoteric nanoparticles |
| CN109856096A (en) * | 2019-01-09 | 2019-06-07 | 贵州大学 | The recognition methods of copper ion and iron ion in a kind of aqueous solution |
| CN109856096B (en) * | 2019-01-09 | 2021-08-24 | 贵州大学 | Method for identifying copper ions and iron ions in aqueous solution |
| CN110330512A (en) * | 2019-07-30 | 2019-10-15 | 山东大学 | A kind of ag nano-cluster fluorescence nano stick and preparation method thereof and the application in white light LEDs |
| CN110330512B (en) * | 2019-07-30 | 2021-05-14 | 山东大学 | Silver nanocluster fluorescent nanorod, preparation method thereof and application thereof in white light LED |
| CN114525125A (en) * | 2022-02-15 | 2022-05-24 | 山东大学 | Water-soluble 'atom accurate' Ag6Nanocluster and macro synthesis method and application thereof |
| CN114958344A (en) * | 2022-05-09 | 2022-08-30 | 曲阜师范大学 | Preparation method of gold nanocluster luminescent hydrogel and application of gold nanocluster luminescent hydrogel in information encryption |
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