CN111690406B - Preparation method and application of optical property-adjustable molybdenum oxide quantum dots - Google Patents
Preparation method and application of optical property-adjustable molybdenum oxide quantum dots Download PDFInfo
- Publication number
- CN111690406B CN111690406B CN202010657370.8A CN202010657370A CN111690406B CN 111690406 B CN111690406 B CN 111690406B CN 202010657370 A CN202010657370 A CN 202010657370A CN 111690406 B CN111690406 B CN 111690406B
- Authority
- CN
- China
- Prior art keywords
- molybdenum oxide
- oxide quantum
- quantum dots
- concentration
- permanganate
- 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.)
- Active
Links
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 230000003287 optical effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 claims abstract description 39
- 229960000830 captopril Drugs 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 18
- 239000012086 standard solution Substances 0.000 claims description 16
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 108010024636 Glutathione Proteins 0.000 claims description 7
- 229960003180 glutathione Drugs 0.000 claims description 7
- 239000002096 quantum dot Substances 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- HDFXRQJQZBPDLF-UHFFFAOYSA-L disodium hydrogen carbonate Chemical compound [Na+].[Na+].OC([O-])=O.OC([O-])=O HDFXRQJQZBPDLF-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- 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"
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biophysics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a preparation method and application of molybdenum oxide quantum dots with adjustable optical properties. The preparation method has the characteristics of rapidness and high efficiency, the particle size of the synthesized molybdenum oxide quantum dots can be controlled by controlling the microwave heating time, so that the emission wavelength of the molybdenum oxide quantum dots can be regulated, nitrogen and phosphorus elements are doped, the edge emission trap of the nano material is increased, the fluorescence emission of the nano material is expanded to a longer green light wavelength region, the molybdenum oxide quantum dots with green emission wavelength are obtained, the contents of permanganate and captopril can be detected sensitively and efficiently with low cost, and the application field of the molybdenum oxide quantum dots is expanded.
Description
Technical Field
The invention relates to the technical field of combination of nano materials and analytical chemistry, in particular to a preparation method and application of molybdenum oxide quantum dots with adjustable optical properties.
Background
Molybdenum oxide (MoO) x ) As a typical Transition Metal Oxide (TMO) material, the nano material becomes an exciting new material with excellent physical and chemical properties, in particular MoO x In the Near Infrared (NIR) and visible regionPromising tunable Localized Surface Plasmon Resonance (LSPR) has been expanding its range of applications due to its light collection capability on the nanometer scale. The application development of the method in the fields of catalysis, single molecule spectrum, photothermal therapy, photochromism and the like is promoted. On the other hand, when MoO x Is less than 10nm (MoO) x QDs), which exhibits excellent photoluminescence characteristics due to the influence of quantum confinement and edge effects. Due to MoO x QDs have special quantum size effect, surface effect, high reactivity and high stability of nanometer material defects, moO x QDs are considered suitable materials for optical probes. However, moO in almost all reports x QDs all exhibit strong blue emission, which may hinder their application in the fields of solar cells, light emitting devices, and biosensing. Therefore, development and preparation of MoO with long-wave luminescence x The QDs method is beneficial to improving the utilization value of the QDs and has high social requirements.
To date, fluorescent MoO's have been prepared x Methods of QDs can be divided into two categories: the top-down method comprises a microwave ultrasonic stripping method and an oxidation reaction; bottom-up processes include solvothermal processes. For the top-down approach, moO x QDs is from MoO 3 Powder or bulk MoS 2 Prepared by disintegration, the preparation process usually involves reagents harmful to the environment, and the size and the shape of the obtained nano material are often uncontrollable. The bottom-up method uses solvent heat as energy and utilizes end-capping molecules to obtain stable and excellent water-soluble MoO x QDs, however, generally have problems of high temperature, long time consumption, and the like. Thus, the development of rapid synthesis of water-soluble MoO with controllable size x The QDs method is of great significance to expand its application range.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of an optical property-adjustable molybdenum oxide quantum dot, so as to solve the problems that the size and the shape of a molybdenum oxide material prepared by the prior art are not controllable and do not have long-wave luminescence characteristics.
The invention also provides the application of the optical property-adjustable molybdenum oxide quantum dots in detection of the concentrations of permanganate and captopril, and the contents of the permanganate and the captopril can be detected with low cost and high sensitivity.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of optical property adjustable molybdenum oxide quantum dots comprises the following steps:
will H 3 P(Mo 3 O 10 ) 4 ·xH 2 Adding O, glutathione and ammonia water into water, fully mixing under an ultrasonic condition to obtain a mixed solution, transferring the mixed solution into a microwave reaction kettle, carrying out microwave heating to 150-190 ℃, reacting for 2-60 min, naturally cooling, centrifuging to remove large particles, and dialyzing to remove unreacted substances to obtain the molybdenum oxide quantum dots with adjustable optical properties.
Preferably, the mixed solution is transferred to a microwave reaction kettle to be heated to 160-180 ℃ by microwave, and the reaction time is 4-40 min.
Preferably, said H 3 P(Mo 3 O 10 ) 4 ·xH 2 The molar ratio of O, glutathione to ammonia water is 1 (40-42) to (645-655). Wherein, the H 3 P(Mo 3 O 10 ) 4 ·xH 2 The molar ratio of O, glutathione and ammonia is further preferably 1.
Preferably, H in the mixed solution 3 P(Mo 3 O 10 ) 4 ·xH 2 The mass-volume ratio of O to water is 1mg: (725-1000) mL. Wherein, H in the mixed solution 3 P(Mo 3 O 10 ) 4 ·xH 2 The mass-to-volume ratio of O to water is further preferably 1mg:925mL.
The invention provides a method for measuring the concentration of permanganate by using optical property adjustable molybdenum oxide quantum dots, which is applied to measuring the concentration of permanganate and comprises the following steps:
and (3) drawing a permanganate standard curve: mixing the molybdenum oxide quantum dots with a series of permanganate standard solutions with concentration gradients, and buffering and dissolving the mixture by using carbonateFixing the volume to the same volume, measuring fluorescence intensity of the solution at excitation wavelength of 430nm and emission wavelength of 500nm, and measuring relative fluorescence intensity (I) with permanganate concentration as abscissa 0 -I)/I is a standard curve plotted on the ordinate; wherein, I 0 When the concentration of the permanganate is zero, the fluorescence intensity of the molybdenum oxide quantum dots is obtained, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dots and the permanganate with different concentrations coexist.
Preferably, the molar ratio of the molybdenum oxide to the permanganate standard solution is (1000-10): 1, and the carbonate is Na 2 CO 3 Or K 2 CO 3 The pH value of the carbonate buffer solution is 7-11.
Preferably, the concentration of the permanganate standard solution is 0. Mu.M, 0.08. Mu.M, 0.1. Mu.M, 0.5. Mu.M, 1. Mu.M, 3. Mu.M, 5. Mu.M, 7. Mu.M, 9. Mu.M, 15. Mu.M, 21. Mu.M, 23. Mu.M, 25. Mu.M, 27. Mu.M, 29. Mu.M, 31. Mu.M, 37. Mu.M, 39. Mu.M, 50. Mu.M, 70. Mu.M, 80. Mu.M, 90. Mu.M, 100. Mu.M, respectively.
Preferably, the regression equation of the standard curve is y =0.05967+0.05279x (0.08-25 μ M), R 2 =0.9973, wherein y is (I) 0 -I)/I, x is the permanganate concentration in μ M and R is the correlation coefficient.
The invention also provides a method for measuring captopril concentration by utilizing the optical property adjustable molybdenum oxide quantum dots, and the method for measuring the captopril concentration by utilizing the molybdenum oxide quantum dots comprises the following steps:
drawing a captopril standard curve: uniformly mixing a potassium permanganate solution, the molybdenum oxide quantum dots and a series of captopril standard solutions with concentration gradients to obtain a mixed solution, fixing the volume to the same volume by using a carbonate buffer solution, measuring the fluorescence intensity of the solution with the fixed volume at an excitation wavelength of 430nm and an emission wavelength of 500nm, and taking the captopril concentration as a horizontal coordinate and measuring the relative fluorescence intensity (I-I) 0 )/I 0 Drawing a standard curve for the ordinate; wherein, I 0 When the captopril concentration is zero, the fluorescence intensity of a molybdenum oxide quantum dot-potassium permanganate system is zero, and I is the fluorescence intensity corresponding to the co-existence of the molybdenum oxide quantum dot-potassium permanganate system and captopril with different concentrationsLight intensity.
Preferably, the molar ratio of the potassium permanganate to the molybdenum oxide to the captopril standard solution is 1 2 CO 3 Or K 2 CO 3 The pH value of the carbonate buffer solution is 7-11.
Preferably, the captopril standard solution has a concentration of 0. Mu.M, 0.1. Mu.M, 0.3. Mu.M, 0.5. Mu.M, 0.8. Mu.M, 1. Mu.M, 3. Mu.M, 5. Mu.M, 7. Mu.M, 11. Mu.M, 13. Mu.M, 15. Mu.M, 17. Mu.M, 21. Mu.M, 23. Mu.M, 25. Mu.M, 27. Mu.M, 31. Mu.M, respectively; the regression equation of the standard curve is y =0.02912+0.05921x (0.1-31 mu M), R 2 =0.9961, wherein y is (I-I) 0 )/I 0 X is captopril concentration in μ M, and R is a correlation coefficient.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes a microwave-assisted method to synthesize and prepare nitrogen-phosphorus-doped MoO x The QDs method can rapidly heat the reaction medium, and researches show that the particle size of the synthesized molybdenum oxide quantum dots can be controlled by controlling the microwave heating time, so that the emission wavelength of the molybdenum oxide quantum dots can be regulated and controlled; and compared with the traditional hydrothermal method, the method has the characteristics of rapidness and high efficiency.
2. The molybdenum oxide quantum dots prepared by the method are doped with nitrogen and phosphorus elements, so that the edge emission trap of the nano material is increased, the fluorescence emission of the nano material is expanded to a longer green light wavelength region, and the molybdenum oxide quantum dots with green emission wavelength are obtained.
3. The method can detect the contents of permanganate and captopril with low cost, sensitivity and high efficiency, is favorable for enriching and developing the rapid detection methods of the permanganate and captopril, and expands the application field of the molybdenum oxide quantum dots.
Drawings
FIG. 1 is a process schematic of the synthesis method of the present invention.
FIG. 2 is an electron microscope image of the nano material synthesized by the present invention under microwave irradiation for 5 min.
FIG. 3 is an electron microscope image of the nano material synthesized by the present invention under microwave irradiation for 15 min.
FIG. 4 is a graph showing the fluorescence intensity of permanganate concentrations measured using the present invention.
FIG. 5 is a graph showing the fluorescence intensity of captopril at various concentrations detected using the present invention.
FIG. 6 is a three-dimensional fluorescence spectrum of the nanomaterial synthesized by the present invention under microwave irradiation for 5 min.
FIG. 7 is a three-dimensional fluorescence spectrum of the nano-material synthesized by the present invention under microwave irradiation for 15 min.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
1. Preparation method of optical property-adjustable molybdenum oxide quantum dots
Referring to fig. 1, the synthesis method of the present invention comprises the following steps: h is to be 3 P(Mo 3 O 10 ) 4 ·xH 2 Adding O, glutathione and ammonia water into water, and fully mixing under an ultrasonic condition to obtain a mixed solution; then transferring the mixed solution into a microwave reaction kettle for microwave heating to 150-190 ℃ for 2-60 min; naturally cooling, centrifuging to remove large particles, dialyzing to remove unreacted substances to obtain the molybdenum oxide quantum dots with adjustable optical properties.
Example (b): will H 3 P(Mo 3 O 10 ) 4 ·xH 2 O, glutathione and ammonia were mixed well in water at a molar ratio of 1 3 P(Mo 3 O 10 ) 4 ·xH 2 925mL of water is needed to be added into O, the solution is fully mixed under ultrasonic, and then the mixture is transferred into a microwave reaction kettle to be heated and reacted for 5-40 min at 160-180 ℃, so as to obtain the molybdenum oxide quantum dots with different particle sizes, as shown in figure 2. After natural cooling, the mixture is centrifuged for 8min at 14000r/min for 2 times to remove large particles. Dialysis was then performed for 72h in a dialysis bag with a molecular cut-off of 1kD to remove unreacted materials.
Table 1 examples 1-4 molybdenum oxide quantum dots of different particle sizes were obtained under different heating conditions
Note: -indicates that the item was not detected.
As can be seen from Table 1, the molybdenum oxide quantum dots with different particle sizes can be obtained by changing the heating reaction time, and the emission wavelengths are also different. It can be found from the combination of fig. 2 and fig. 3 that when the microwave heating time is 15min, the particle size of the obtained molybdenum oxide quantum dot is 2.4 ± 0.7nm, and as can be seen from fig. 7, the fluorescence of the obtained molybdenum oxide quantum dot is blue. When the microwave heating time is shortened to 5min, the particle size of the molybdenum oxide quantum dots is obviously changed to reach 4.9 +/-1.2 nm by combining and comparing the graph 2 with the graph 3, the particle size of the molybdenum oxide quantum dots is increased due to the shortening of the microwave heating time, and at the moment, the fluorescence of the molybdenum oxide quantum dots is changed into green light with longer wavelength by combining the graph 6, so that the emission wavelength of the green light is regulated.
According to the invention, the particle size of the molybdenum oxide quantum dots is controlled by adjusting the microwave heating time, so that the fluorescent property of the molybdenum oxide quantum dots is regulated, the green-emitting molybdenum oxide quantum dots are obtained, the fluorescent influence of a blue background can be effectively avoided, and the application range of the green-emitting molybdenum oxide quantum dots is widened.
2. Method for measuring permanganate concentration by using optical property adjustable molybdenum oxide quantum dots
13 μ L of the raw solution molybdenum oxide quantum dots prepared in example 1 and 100 μ L of a series of concentration gradient permanganate standard solutions were taken and added into a colorimetric tube, and the volume was adjusted to 2mL with 0.025M sodium carbonate-carbonic acid buffer solution with pH =10.0, wherein the permanganate standard solution concentrations were 0 μ M,0.08 μ M,0.1 μ M,0.5 μ M,1 μ M,3 μ M,5 μ M,7 μ M,9 μ M,15 μ M,21 μ M,23 μ M,25 μ M,27 μ M,29 μ M,31 μ M,37 μ M,39 μ M,50 μ M,70 μ M,80 μ M,90 μ M, and 100 μ M, respectively. Measuring fluorescence intensity of the solution with constant volume at excitation wavelength of 430nm and emission wavelength of 500nm, and relative fluorescence intensity (I) with permanganate concentration as abscissa 0 The permanganate standard curve is plotted on the ordinate in the form of-I)/I as shown in FIG. 4.
Wherein, I 0 Is high in manganeseWhen the concentration of the acid salt is zero, the fluorescence intensity of the molybdenum oxide quantum dots, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dots and the permanganate with different concentrations coexist.
As can be seen in fig. 4, the fluorescence intensity of the molybdenum oxide quantum dots decreased with the increase of the permanganate concentration, which indicates that the molybdenum oxide quantum dots can be used for the measurement of permanganate.
When the concentration of the permanganate is in the range of 0.08-25 mu M, the regression equation of the standard curve is y =0.0246+0.0616x 2 =0.9973; wherein y is (I) 0 -I)/I, x is the permanganate concentration in μ M and R is the correlation coefficient.
3. Method for measuring captopril concentration by using optical property-adjustable molybdenum oxide quantum dots
A series of captopril standard solutions with concentration gradients and 100 μ L of 1mM potassium permanganate solution were added into a colorimetric cylinder, 13 μ L of the raw solution molybdenum oxide quantum dots prepared in example 1 were added and mixed, and then the mixture was made to volume of 2mL with 0.025m sodium carbonate-carbonic acid buffer solution with ph = 10.0. Wherein, the standard solution concentration of captopril is 0 μ M,0.1 μ M,0.3 μ M,0.5 μ M,0.8 μ M,1 μ M,3 μ M,5 μ M,7 μ M,11 μ M,13 μ M,15 μ M,17 μ M,21 μ M,23 μ M,25 μ M,27 μ M,31 μ M. Measuring fluorescence intensity of the solution with constant volume at excitation wavelength of 430nm and emission wavelength of 500nm, and taking captopril concentration as abscissa and relative fluorescence intensity (I-I) 0 )/I 0 The captopril standard curve is plotted on the ordinate as shown in figure 5.
Wherein, I 0 When the captopril concentration is zero, the fluorescence intensity of a molybdenum oxide quantum dot-potassium permanganate system is obtained, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dot-potassium permanganate system and captopril with different concentrations coexist.
As can be seen in fig. 5, the fluorescence intensity of the molybdenum oxide quantum dot-permanganate system increases with the increase of captopril concentration, which indicates that the molybdenum oxide quantum dot-permanganate system can be used for captopril determination.
When the captopril concentration is in the range of 0.1-31 μ M, the standard curve regression equation is y =0.02912+0.05921x,R 2 =0.9961; wherein y is (I-I) 0 )/I 0 X is captopril concentration in μ M, and R is a correlation coefficient.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (9)
1. A preparation method of optical property adjustable molybdenum oxide quantum dots is characterized by comprising the following steps:
h is to be 3 P(Mo 3 O 10 ) 4 •xH 2 Adding O, glutathione and ammonia water into water, fully mixing under an ultrasonic condition to obtain a mixed solution, transferring the mixed solution into a microwave reaction kettle, heating the mixed solution to 150-190 ℃ by microwave, reacting for 2-60min, naturally cooling, centrifuging to remove large particles, and dialyzing to remove unreacted substances to obtain the molybdenum oxide quantum dots with adjustable optical properties;
said H 3 P(Mo 3 O 10 ) 4 •xH 2 The molar ratio of O, glutathione to ammonia water is 1 (40 to 42) to (645 to 655).
2. The method for preparing the optical property-adjustable molybdenum oxide quantum dot according to claim 1, wherein H in the mixed solution 3 P(Mo 3 O 10 ) 4 •xH 2 The mass-volume ratio of O to water is 1mg: (725 to 1000) mL.
3. The method for measuring the concentration of permanganate by using the molybdenum oxide quantum dots with adjustable optical properties is characterized in that the method for measuring the concentration of permanganate by using the molybdenum oxide quantum dots according to any one of claims 1 to 2 comprises the following steps:
and (3) drawing a permanganate standard curve: subjecting the molybdenum oxide quantum dots to a series of concentration gradientsMixing the permanganate standard solutions, diluting to the same volume with carbonate buffer solution, measuring fluorescence intensity of the solution with constant volume at excitation wavelength of 430nm and emission wavelength of 500nm, and measuring relative fluorescence intensity (I) with permanganate concentration as abscissa 0 -I)/I is a standard curve plotted on the ordinate; wherein, I 0 When the concentration of the permanganate is zero, the fluorescence intensity of the molybdenum oxide quantum dots is obtained, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dots and the permanganate with different concentrations coexist.
4. The method for measuring the concentration of permanganate by using the optical property-adjustable molybdenum oxide quantum dots according to claim 3, wherein the molar ratio of the molybdenum oxide quantum dots to the permanganate standard solution is (1000 to 10): 1, and the carbonate is Na 2 CO 3 Or K 2 CO 3 The pH value of the carbonate buffer solution is 7 to 11.
5. The method for measuring the concentration of permanganate in the optical property adjustable molybdenum oxide quantum dots according to claim 3, wherein the concentrations of the permanganate standard solutions are 0 μ M,0.08 μ M,0.1 μ M,0.5 μ M,1 μ M,3 μ M,5 μ M,7 μ M,9 μ M,15 μ M,21 μ M,23 μ M,25 μ M,27 μ M,29 μ M,31 μ M,37 μ M,39 μ M,50 μ M,70 μ M,80 μ M,90 μ M and 100 μ M respectively.
6. The method for measuring the concentration of permanganate in the optical property-adjustable molybdenum oxide quantum dots according to claim 3, wherein the regression equation of the standard curve is y =0.05967+0.05279x (0.08-25 μ M), R 2 =0.9973, wherein y is (I 0 -I)/IX is the permanganate concentration in μ M and R is the correlation coefficient.
7. A method for measuring captopril concentration by using optical property adjustable molybdenum oxide quantum dots, which is characterized in that the method for measuring the captopril concentration by using the molybdenum oxide quantum dots according to any one of claims 1 to 2 comprises the following steps:
drawing a captopril standard curve: uniformly mixing a potassium permanganate solution, the molybdenum oxide quantum dots and a series of captopril standard solutions with concentration gradients to obtain a mixed solution, fixing the volume to the same volume by using a carbonate buffer solution, measuring the fluorescence intensity of the solution with the fixed volume at an excitation wavelength of 430nm and an emission wavelength of 500nm, and taking the captopril concentration as a horizontal coordinate and measuring the relative fluorescence intensity (a)I-I 0 )/I 0 Drawing a standard curve for the ordinate; wherein the content of the first and second substances,I 0 when the captopril concentration is zero, the fluorescence intensity of the molybdenum oxide quantum dot-potassium permanganate system,Iis the corresponding fluorescence intensity when a molybdenum oxide quantum dot-potassium permanganate system and captopril with different concentrations coexist.
8. The method for measuring captopril concentration by using the optical property-adjustable molybdenum oxide quantum dots as claimed in claim 7, wherein the molar ratio of the potassium permanganate, the molybdenum oxide quantum dots and the captopril standard solution is 1 (0.002 to 0.6), the carbonate is Na 2 CO 3 Or K 2 CO 3 And the pH value of the carbonate buffer solution is 7 to 11.
9. The method for determining captopril concentration by using the optical property-adjustable molybdenum oxide quantum dots, as claimed in claim 7, wherein the captopril standard solution has a concentration of 0 μ M,0.1 μ M,0.3 μ M,0.5 μ M,0.8 μ M,1 μ M,3 μ M,5 μ M,7 μ M,11 μ M,13 μ M,15 μ M,17 μ M,21 μ M,23 μ M,25 μ M,27 μ M,31 μ M; the regression equation of the standard curve is y =0.02912+0.05921x (0.1-31 μ M), R 2 =0.9961, wherein y is (I-I 0 )/I 0 X is captopril concentration in μ M, and R is a correlation coefficient.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010657370.8A CN111690406B (en) | 2020-07-09 | 2020-07-09 | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010657370.8A CN111690406B (en) | 2020-07-09 | 2020-07-09 | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111690406A CN111690406A (en) | 2020-09-22 |
CN111690406B true CN111690406B (en) | 2022-12-23 |
Family
ID=72485758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010657370.8A Active CN111690406B (en) | 2020-07-09 | 2020-07-09 | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111690406B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112326647A (en) * | 2020-11-05 | 2021-02-05 | 西南科技大学 | Phosphorus content detection reagent based on molybdenum trioxide and preparation method and detection method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108408778A (en) * | 2018-04-18 | 2018-08-17 | 长江师范学院 | A kind of preparation method and application of molybdenum oxide |
-
2020
- 2020-07-09 CN CN202010657370.8A patent/CN111690406B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108408778A (en) * | 2018-04-18 | 2018-08-17 | 长江师范学院 | A kind of preparation method and application of molybdenum oxide |
Non-Patent Citations (2)
Title |
---|
Facile and rapid synthesis of emission color-tunable molybdenum oxide quantum dots as a versatile probe for fluorescence imaging and environmental monitoring;Haiyan Cao et al.;《Analyst》;20200817;第145卷;第6270-6276页 * |
New Off−On Sensor for Captopril Sensing Based on Photoluminescent MoOx Quantum Dots;Sai Jin Xiao et al.;《ACS Omega》;20170426;第2卷;第1666-1671页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111690406A (en) | 2020-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Carbon dots: synthesis, formation mechanism, fluorescence origin and sensing applications | |
Xu et al. | Low-cost synthesis of carbon nanodots from natural products used as a fluorescent probe for the detection of ferrum (III) ions in lake water | |
He et al. | Microwave-assisted synthesis of water-dispersed CdTe nanocrystals with high luminescent efficiency and narrow size distribution | |
Khani et al. | Synthesis and characterizations of ultra-small ZnS and Zn (1− x) FexS quantum dots in aqueous media and spectroscopic study of their interactions with bovine serum albumin | |
Yan et al. | Microwave-assisted synthesis of BSA-stabilized and HSA-protected gold nanoclusters with red emission | |
CN102071027B (en) | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof | |
CN109679646B (en) | Preparation method of high-stability carbon dot-silicon dioxide composite particles | |
CN103160279A (en) | Functional carbon dots, and preparation and application thereof | |
CN102703081B (en) | Water-soluble rare earth doped gadolinium sodium tetrafluoride fluorescent marked nano-crystal, and preparation method thereof | |
CN108165265B (en) | Water-soluble terbium-doped calcium fluoride nano particle, preparation method and application thereof | |
Wang et al. | Synthesis of CdSe quantum dots using selenium dioxide as selenium source and its interaction with pepsin | |
Du et al. | Microwave-assisted synthesis of highly luminescent glutathione-capped Zn 1− x Cd x Te alloyed quantum dots with excellent biocompatibility | |
CN109423282A (en) | A kind of synthetic method and application of N doping water-solubility fluorescent carbon quantum dot | |
CN104807791A (en) | Method for detecting bisphenol A based on quantum dot-gold nanoparticle self-assembled superstructure | |
CN111690406B (en) | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots | |
Chu et al. | A new fluorescence probe comprising nitrogen-doped graphene quantum dots for the selective and quantitative determination of cerium (iv) | |
Jiao et al. | Controllable Synthesis of Upconversion Nanophosphors toward Scale‐Up Productions | |
Wang et al. | Dual-emission carbon dots achieved by luminescence center modulation within one-pot synthesis for a fluorescent ratiometric probe of pH, Hg 2+, and glutathione | |
CN106701069A (en) | Preparation method of wavelength-controllable long wavelength emitting fluorescent carbon-based nanodots | |
Han et al. | Fluorescent carbon dots directly derived from polyethyleneimine and their application for the detection of Co 2+ | |
Lin et al. | Continuous microflow synthesis of fluorescent phosphorus and nitrogen co-doped carbon quantum dots | |
CN112375561A (en) | Up-conversion fluorescent nanoprobe and application thereof | |
CN106010536A (en) | Method for synthesizing monodisperse rare earth doped up-converted fluorescence nanocrystalline through microwave assistance, and product thereof and application | |
Zhu et al. | Microwave-mediated nonaqueous synthesis of quantum dots at moderate temperature | |
CN117487540A (en) | Microwave-assisted synthesis method and application of nitrogen-iron-manganese co-doped carbon point |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20240226 Address after: 408000, No. 102 Zengyin Avenue, Longqiao Street Office, Fuling District, Chongqing Patentee after: Chongqing Zengcheng Technology Co.,Ltd. Country or region after: China Address before: No. 16, Fuling District, Chongqing, Chongqing Patentee before: YANGTZE NORMAL University Country or region before: China |