CN108414486A - A kind of preparation method and application of water soluble fluorescence palladium nanocluster - Google Patents
A kind of preparation method and application of water soluble fluorescence palladium nanocluster Download PDFInfo
- Publication number
- CN108414486A CN108414486A CN201810186139.8A CN201810186139A CN108414486A CN 108414486 A CN108414486 A CN 108414486A CN 201810186139 A CN201810186139 A CN 201810186139A CN 108414486 A CN108414486 A CN 108414486A
- Authority
- CN
- China
- Prior art keywords
- palladium
- fluorescence
- preparation
- nanocluster
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 26
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 102000001554 Hemoglobins Human genes 0.000 claims abstract description 15
- 108010054147 Hemoglobins Proteins 0.000 claims abstract description 15
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 229930182817 methionine Natural products 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 7
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 4
- GKBFFPJHOLVCHW-WCCKRBBISA-N azanium;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [NH4+].CSCC[C@H](N)C([O-])=O GKBFFPJHOLVCHW-WCCKRBBISA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000001514 detection method Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 238000001917 fluorescence detection Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 235000015097 nutrients Nutrition 0.000 abstract 1
- 238000012876 topography Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000002211 L-ascorbic acid Substances 0.000 description 6
- 235000000069 L-ascorbic acid Nutrition 0.000 description 6
- 239000013558 reference substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- MURGITYSBWUQTI-UHFFFAOYSA-N fluorescin Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC=C(O)C=C2OC2=CC(O)=CC=C21 MURGITYSBWUQTI-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- IYHCHGIBRATNMX-RGMNGODLSA-N C(=O)O.C(CC)N[C@@H](CCO)C(=O)O Chemical compound C(=O)O.C(CC)N[C@@H](CCO)C(=O)O IYHCHGIBRATNMX-RGMNGODLSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- MUSLHCJRTRQOSP-UHFFFAOYSA-N rhodamine 101 Chemical compound [O-]C(=O)C1=CC=CC=C1C(C1=CC=2CCCN3CCCC(C=23)=C1O1)=C2C1=C(CCC1)C3=[N+]1CCCC3=C2 MUSLHCJRTRQOSP-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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"
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of preparation method and applications of water soluble fluorescence palladium nanocluster, this method is metal precursor using tetrachloro-palladium acid ammonium, methionine is stabilizer, and ascorbic acid is reducing agent, passes through water-soluble palladium nanocluster of the water bath heating synthesis with blue-green fluorescent.Stabilizer used in the present invention, reducing agent are the indispensable nutrient of human body, and nontoxic, environmentally protective, preparation condition is mild, easy to control.The fluorescence palladium nanocluster of the present invention has that size is small, distribution is uniform, has good stability, the characteristic that strong antijamming capability, surface topography are consistent, the fluorescence palladium nanocluster has excellent capabilities of fluorescence detection, it is very sensitive to the hemoglobin of low concentration, it can be in 0.25~3.5 μm of ol/L to its linear response, reach 50 μM by detection limit known to three times signal-to-noise ratio computation, there is potential application prospect in biomolecule detection field.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation method of water soluble fluorescence palladium nanocluster
And water soluble fluorescence palladium nanocluster is in the application in fluoroscopic examination field.
Background technology
Metal nanometer cluster is one kind by several novel fluorescence nano materials formed to hundreds of metallic atoms, size
Close to Fermi's wavelength of electronics, specific energy level separation can be generated, and emit fluorescence under the excitation of certain wavelength light, had
There are some to be similar to the property of molecule, also have the feature that nano material often has, but is not the simple linear of the two property
Interpolation or extension.Compared to fluorescent nano probes such as organic dye molecule, fluorescin, nano particle, semiconductor-quantum-points
Speech, metal nanometer cluster show the properties such as different physics, optics, electricity due to its unique electronic structure, it are made to receive
It is concerned in rice investigation of materials.Various metal nanometer clusters are synthesized by changing ligand or biological support, in biochemical sensitive, life
The fields such as substance markers, fluorescence imaging, catalysis and unimolecule photoelectric device have a wide range of applications.
Super-small (grain size is less than 2nm) preparation of luminescent metal cluster is always a very attractive research class
Topic.Researchers prepare gold nano cluster and silver with different IPs size under conditions of different ligands and reducing agent,
Copper, platinum nanoclusters, and ripe is gradually tended to the research of such nanocluster, and about the synthesis of fluorescence palladium nanocluster and
Property Quality Research report it is relatively fewer.And the preparation of traditional palladium nanocluster has qualitatively difficult a, organic reagent used
With certain toxicity, there is different degrees of stimulation to human eye, skin and respiratory tract.
Invention content
In view of the deficienciess of the prior art, that the technical problem to be solved in the present invention is to provide a kind of preparation conditions is mild,
Easily-controlled operation, the preparation method of environmentally protective water soluble fluorescence palladium nanocluster and water soluble fluorescence palladium nanocluster
Application in fluoroscopic examination field.
To achieve the goals above, the present invention is to realize by the following technical solutions：A kind of water soluble fluorescence palladium is received
Rice cluster preparation method, includes the following steps：
A. tetrachloro-palladium acid ammonium-methionine solution is prepared；
B. it is added sodium hydroxide solution into step a acquired solutions, mixing is to get to metal-stabilizer under water bath condition
The mixed solution of compound；
C. it is added reducing agent in step b acquired solutions, continues water-bath to get to fluorescence palladium nanocluster；
Preferably, the preparation method of tetrachloro-palladium acid ammonium-methionine solution described in step a is：By tetrachloro-palladium acid ammonium salt solution
It is uniformly mixed with methionine solution；
It is furthermore preferred that a concentration of 2.5mmol/L of tetrachloro-palladium acid ammonium salt solution in step a, dosage 12mL；Methionine solution
A concentration of 0.06~0.14mol/L, dosage 24mL；
Preferably, in step b sodium hydrate aqueous solution a concentration of 0.4~0.8mol/L；
It is furthermore preferred that in the step b sodium hydrate aqueous solution a concentration of 0.6mol/L, dosage 3.6mL；
Preferably, the time that water-bath described in step b mixes is 30min, and temperature is 40~70 DEG C；
Preferably, reducing agent described in step c is ascorbic acid, a concentration of 0~0.2mol/L；
It is furthermore preferred that in the step c ascorbic acid a concentration of 0.14mol/L, dosage 9mL；
Preferably, in step c, water-bath temperature is 40~70 DEG C, and the time is 4~10h.
Further, the water soluble fluorescence palladium nanocluster that prepared by the present invention is in fluoroscopic examination low concentration hemoglobin
Using.
Benefit of the present invention
The present invention is used as metal precursor using water-soluble good tetrachloro-palladium acid ammonium, low using toxicity, with good
The formic acid propylhomoserin of good biocompatibility is stabilizer, uses more mild, environmental protection ascorbic acid for reducing agent.
Preparation process of the present invention is simple, easy to control.
Water soluble fluorescence Metal Palladium nanocluster size produced by the present invention is small, distribution is uniform, can be in 365nm ultraviolet lamps
Under send out blue-green fluorescent, quantum yield is about 5.47%.
Palladium nanocluster size distribution produced by the present invention is uniform, and stability is good.
Palladium nanocluster strong antijamming capability produced by the present invention, possesses excellent capabilities of fluorescence detection, to biomolecule
The hemoglobin of low concentration is very sensitive, it is made to be had potential application in biomolecule detection field.
Description of the drawings
Fig. 1 is the fluorescence excitation spectrum and emission spectra of the embodiment of the present invention 5；
Fig. 2 is the high-resolution-ration transmission electric-lens figure of the embodiment of the present invention 5；
Fig. 3 is the atomic force microscopy diagram of the embodiment of the present invention 5；
Fig. 4 is response of the palladium nanocluster fluorescent emission intensity of the embodiment of the present invention 10 to various concentration hemoglobin
Figure；
Fig. 5 is linear response section of the palladium nanocluster fluorescent emission intensity to hemoglobin of the embodiment of the present invention 10
Fitted figure.
Specific implementation mode
Following embodiment is only being expanded on further and illustrate to the present invention, rather than limiting the scope of the invention.Under
Face is further elaborated on the present invention with reference to embodiment, it should be appreciated to those skilled in the art that the present invention is not limited to this
A little embodiments and the preparation method used.Moreover, those skilled in the art's description according to the present invention can to the present invention into
Row equivalent replacement, combination, improvement or modification, but these are intended to be included in the scope of the present invention
Embodiment 1
Figure is please referred to, the present invention provides a kind of technical solution：A kind of preparation method of water soluble fluorescence palladium nanocluster,
It is characterized in that, preparation method includes the following steps：
A. by 12mL, the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, the methionine solution mixing of 0.07mol/L
Uniformly；
B. 3.6mL, 0.4mol/L sodium hydroxide solutions, under 40 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL distilled water is added in step b acquired solutions, continuation reacts 8h in 40 DEG C of water-baths, obtains achromaticity and clarification
Solution.
Embodiment 2
A. by 12mL, the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, the methionine solution mixing of 0.07mol/L
Uniformly；
B. 3.6mL, 0.4mol/L sodium hydroxide solutions, under 40 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL is added in step b acquired solutions, 0.14mol/L ascorbic acid reducing agents continue anti-in 40 DEG C of water-baths
8h is answered, the clear water soluble fluorescence palladium nanocluster of yellow is obtained.
Embodiment 3
A. by 12mL, the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, the methionine solution mixing of 0.07mol/L
Uniformly；
B. 3.6mL, 0.4mol/L sodium hydroxide solutions, under 40 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL is added in step b acquired solutions, 0.2mol/L ascorbic acid reducing agents continue anti-in 40 DEG C of water-baths
8h is answered, the clear water soluble fluorescence palladium nanocluster of yellow is obtained.
Embodiment 4
A. by 12mL, the methionine solution mixing of the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, 0.1mol/L is equal
It is even；
B. 3.6mL, 0.6mol/L sodium hydroxide solutions, under 60 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL distilled water is added in step b acquired solutions, continuation is reacted 5.5h in 60 DEG C of water-baths, obtained colourless clear
Clear solution.
Embodiment 5
A. by 12mL, the methionine solution mixing of the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, 0.1mol/L is equal
It is even；
B. 3.6mL, 0.6mol/L sodium hydroxide solutions, under 60 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL is added in step b acquired solutions, 0.14mol/L ascorbic acid reducing agents continue anti-in 60 DEG C of water-baths
5.5h is answered, the clear water soluble fluorescence palladium nanocluster of yellow is obtained.
Fluorescence excitation spectrum and emission spectra test are carried out to water soluble fluorescence palladium nanocluster obtained by the present embodiment, as a result as schemed
Shown in 1.
As shown in Figure 1, the excitation peak of palladium nanocluster is located at 420nm or so, and emission peak is located at 500nm or so, thus demonstrate,proves
Bright, transmitting is blue-green fluorescent and Stokes shift is only 80nm, in metal nanometer cluster, is less than this of 150nm
The luminescence generated by light of lentor displacement generally results from the band-to-band transition of electronics, according to formulaPalladium can be calculated
The quantum yield of nanocluster is about 5.47%.
Wherein A is the absorbance in excitation wave strong point metal cluster；
ArFor in the absorbance of excitation wave strong point reference substance；
I is the integrated fluorescence intensities of metal cluster；
IrFor the integrated fluorescence intensities of reference substance；
N is the solvent refractive index of metal cluster；
nrFor the solvent refractive index of reference substance；
Q is the photoluminescence quantum yield of metal cluster；
QrFor the photoluminescence quantum yield of reference substance；
The reference substance of the present invention is Rhodamine 101.
High-resolution-ration transmission electric-lens test is carried out to the water soluble fluorescence palladium nanocluster obtained by the present embodiment, as a result such as Fig. 2
It is shown.
As shown in Figure 2, the water soluble fluorescence palladium nanocluster grain size that prepared by the present invention is small and is evenly distributed, and average diameter is about
For 1.91nm, random spherical shape is showed, apparent clustering phenomena does not occur.Thus it proves, fluorescence palladium of the invention is received
Rice cluster has good dispersion performance.
Atomic force microscope test equally is carried out to the present embodiment, the results are shown in Figure 3.
From the figure 3, it may be seen that water soluble fluorescence palladium nanocluster typical case's Terrain Elevation is less than 2.5nm, and it is evenly distributed, thus demonstrate,proves
Bright, the present invention has successfully prepared the fluorescence palladium nanocluster of super-small.
Embodiment 6
A. by 12mL, the methionine solution mixing of the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, 0.1mol/L is equal
It is even；
B. 3.6mL, 0.6mol/L sodium hydroxide solutions, under 70 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL is added in step b acquired solutions, 0.2mol/L ascorbic acid reducing agents continue anti-in 70 DEG C of water-baths
4.5h is answered, the clear water soluble fluorescence palladium nanocluster of yellow is obtained.
Embodiment 7
A. by 12mL, the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, the methionine solution mixing of 0.12mol/L
Uniformly；
B. 3.6mL, 0.8mol/L sodium hydroxide solutions, under 70 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL distilled water is added in step b acquired solutions, continuation is reacted 4.5h in 70 DEG C of water-baths, obtained colourless clear
Clear solution.
Embodiment 8
A. by 12mL, the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, the methionine solution mixing of 0.12mol/L
Uniformly；
B. 3.6mL, 0.8mol/L sodium hydroxide solutions, under 70 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL is added in step b acquired solutions, 0.14mol/L ascorbic acid reducing agents continue anti-in 70 DEG C of water-baths
4.5h is answered, the clear water soluble fluorescence palladium nanocluster of yellow is obtained.
Embodiment 9
A. by 12mL, the tetrachloro-palladium acid ammonium salt solution and 24mL of 2.5mmol/L, the methionine solution mixing of 0.12mol/L
Uniformly；
B. 3.6mL, 0.8mol/L sodium hydroxide solutions, under 70 DEG C of water bath condition are added into step a acquired solutions
Mix 30min, you can obtain the mixed solution of metal-stabilizer compound；
C. 9mL is added in step b acquired solutions, 0.2mol/L ascorbic acid reducing agents continue anti-in 70 DEG C of water-baths
4.5h is answered, the clear water soluble fluorescence palladium nanocluster of yellow is obtained.
Embodiment 10
The haemoglobin aqueous solution of one group of various concentration is prepared respectively, prepares solution concentration range in 0.1~200 μm of ol/L
Between
The palladium nanocluster for taking one group of 1.9mL institutes the present embodiment 5 to prepare, the hemoglobin for being separately added into various concentration are water-soluble
100 μ L of liquid test response of the palladium nanocluster fluorescent emission intensity to various concentration hemoglobin, as a result such as by fluorescence spectrum
Shown in Fig. 4；And it finds the fluorescent emission intensity of palladium nanocluster there are linear response section, warps with the concentration that is added hemoglobin
Fitting, the results are shown in Figure 5.
As shown in Figure 4, the fluorescent emission intensity of gradually increasing with hemoglobin concentration, palladium nanocluster gradually subtracts
It is weak.Thus illustrate, fluorescence palladium nanocluster of the invention possesses excellent capabilities of fluorescence detection, to the hemoglobin ten of low concentration
Divide sensitivity, may be used as the fluorescence probe of detection hemoglobin.
As shown in Figure 5, when testing result shows that the concentration range of hemoglobin is 0.25~3.5 μm of ol/L, fluorescence palladium is received
The fluorescence of rice cluster reduces degree and shows certain linear relationship with hemoglobin concentration, obtained coefficient R2For
0.9915.Thus it proves, in relatively low and wider concentration range, fluorescence palladium nanocluster of the invention has hemoglobin
Good detection performance.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention, for this field skill
For art personnel, it is clear that invention is not limited to the details of the above exemplary embodiments, and without departing substantially from the present invention spirit or
In the case of essential characteristic, the present invention can be realized in other specific forms.Therefore, in all respects, should all incite somebody to action
Embodiment regards exemplary as, and is non-limiting, the scope of the present invention by appended claims rather than on state
Bright restriction, it is intended that including all changes that come within the meaning and range of equivalency of the claims in the present invention
It is interior.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (10)
1. a kind of preparation method of water soluble fluorescence palladium nanocluster, which is characterized in that include the following steps：
A. tetrachloro-palladium acid ammonium-methionine solution is prepared；
B. sodium hydroxide solution is added into step a acquired solutions, mixing is to get compound to metal-stabilizer under water bath condition
The mixed solution of object；
C. it is added reducing agent in step b acquired solutions, continues water-bath to get to fluorescence palladium nanocluster.
2. the preparation method of fluorescence palladium nanocluster according to claim 1, which is characterized in that tetrachloro palladium described in step a
The preparation method of sour ammonium-methionine solution is：Tetrachloro-palladium acid ammonium salt solution is uniformly mixed with methionine solution.
3. the preparation method of fluorescence palladium nanocluster according to claim 2, which is characterized in that tetrachloro-palladium acid in step a
Ammonium salt solution a concentration of 2.5mmol/L, dosage 12mL；A concentration of 0.06~0.14mol/L of methionine solution, dosage are
24mL。
4. the preparation method of fluorescence palladium nanocluster according to claim 1, which is characterized in that sodium hydroxide in step b
A concentration of 0.4~0.8mol/L of aqueous solution.
5. the preparation method of fluorescence palladium nanocluster according to claim 4, which is characterized in that hydrogen-oxygen in the step b
Change a concentration of 0.6mol/L, dosage 3.6mL of sodium water solution.
6. the preparation method of fluorescence palladium nanocluster according to claim 1, which is characterized in that water-bath described in step b is mixed
The time of conjunction is 30min, and temperature is 40~70 DEG C.
7. the preparation method of fluorescence palladium nanocluster according to claim 1, which is characterized in that reducing agent described in step c
For ascorbic acid, wherein a concentration of 0~0.2mol/L of ascorbic acid.
8. the preparation method of fluorescence palladium nanocluster according to claim 7, which is characterized in that the ascorbic acid it is dense
Degree is 0.14mol/L, dosage 9mL.
9. the preparation method of fluorescence palladium nanocluster according to claim 1, which is characterized in that in step c, water-bath
Temperature is 40~70 DEG C, and the time is 4~10h.
10. application of the fluorescence palladium nanocluster made from claim 1~9 in fluoroscopic examination low concentration hemoglobin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810186139.8A CN108414486A (en) | 2018-03-07 | 2018-03-07 | A kind of preparation method and application of water soluble fluorescence palladium nanocluster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810186139.8A CN108414486A (en) | 2018-03-07 | 2018-03-07 | A kind of preparation method and application of water soluble fluorescence palladium nanocluster |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108414486A true CN108414486A (en) | 2018-08-17 |
Family
ID=63130245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810186139.8A Pending CN108414486A (en) | 2018-03-07 | 2018-03-07 | A kind of preparation method and application of water soluble fluorescence palladium nanocluster |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108414486A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110508828A (en) * | 2019-08-28 | 2019-11-29 | 淮北师范大学 | Preparation method of orange-red fluorescent copper nanoclusters based on L-methionine |
| CN110976906A (en) * | 2019-12-04 | 2020-04-10 | 山西大学 | Fluorescent palladium nanocluster and synthesis method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279375A (en) * | 2008-01-16 | 2008-10-08 | 南京大学 | Preparation method of palladium nanoparticles |
| CN103611946A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Preparation method of gold nanocluster fluorescent materials protected by methionine |
-
2018
- 2018-03-07 CN CN201810186139.8A patent/CN108414486A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279375A (en) * | 2008-01-16 | 2008-10-08 | 南京大学 | Preparation method of palladium nanoparticles |
| CN103611946A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Preparation method of gold nanocluster fluorescent materials protected by methionine |
Non-Patent Citations (1)
| Title |
|---|
| YAN PENG等: "Green Synthesis of Fluorescent Palladium Nanoclusters", 《MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110508828A (en) * | 2019-08-28 | 2019-11-29 | 淮北师范大学 | Preparation method of orange-red fluorescent copper nanoclusters based on L-methionine |
| CN110976906A (en) * | 2019-12-04 | 2020-04-10 | 山西大学 | Fluorescent palladium nanocluster and synthesis method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Andresen et al. | Surface modifications for photon-upconversion-based energy-transfer nanoprobes | |
| Wang et al. | Chemiluminescence of CdTe nanocrystals induced by direct chemical oxidation and its size-dependent and surfactant-sensitized effect | |
| Peng et al. | Color-tunable binuclear (Eu, Tb) nanocomposite powder for the enhanced development of latent fingerprints based on electrostatic interactions | |
| CN1795141B (en) | Manufacturing method and use of metal nanorods | |
| Jin et al. | Photoactivated luminescent CdSe quantum dots as sensitive cyanide probes in aqueous solutions | |
| Sreenivasan et al. | Luminescent nanoparticles and their applications in the life sciences | |
| Loukanov et al. | Photosensitizer-conjugated ultrasmall carbon nanodots as multifunctional fluorescent probes for bioimaging | |
| Liang et al. | Fabrication of near-infrared-emitting CdSeTe/ZnS core/shell quantum dots and their electrogenerated chemiluminescence | |
| Yang et al. | Ag2Te quantum dots with compact surface coatings of multivalent polymers: ambient one-pot aqueous synthesis and the second near-infrared bioimaging | |
| US9352394B2 (en) | Nano aggregates of molecular ultra small clusters of noble metals and a process for the preparation thereof | |
| US20070264719A1 (en) | Partially passivated quantum dots, process for making, and sensors therefrom | |
| Nabil et al. | Quantum dot nanomaterials: preparation, characterization, advanced bio-imaging and therapeutic applications | |
| Liang et al. | High-performance formaldehyde sensing using paper-based fluorescent copper nanoclusters | |
| CN107225255B (en) | A red fluorescent silver nanocluster probe and its preparation method and application | |
| Li et al. | Synthesis of high-quality N-acetyl-L-cysteine-capped CdTe quantum dots by hydrothermal route and the characterization through MALDI-TOF mass spectrometry | |
| KR100861899B1 (en) | Metal microparticle, composition containing the same and process for producing metal microparticle | |
| Wang et al. | Synthesis of highly stable fluorescent Ag nanocluster@ polymer nanoparticles in aqueous solution | |
| Zhu et al. | Ligand-based surface engineering of lanthanide nanoparticles for bioapplications | |
| CN115960603A (en) | A kind of fluorescent sulfur quantum dot and its synthesis method and application | |
| CN113960002B (en) | Detection method of lead ions | |
| Lan et al. | One-pot hydrothermal synthesis of orange fluorescent silver nanoclusters as a general probe for sulfides | |
| CN109181678B (en) | Method for synthesizing green fluorescent gold nanocluster stabilized by mercapto-beta-cyclodextrin and application of green fluorescent gold nanocluster | |
| CN103468260A (en) | pH nanometer sensing material with upconversion luminescence property, and preparation method thereof | |
| CN108414486A (en) | A kind of preparation method and application of water soluble fluorescence palladium nanocluster | |
| Tegafaw et al. | High-Quantum-Yield Ultrasmall Ln2O3 (Ln= Eu, Tb, or Dy) Nanoparticle Colloids in Aqueous Media Obtained via Photosensitization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180817 |