CN108548801A - Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion - Google Patents
Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion Download PDFInfo
- Publication number
- CN108548801A CN108548801A CN201810226358.4A CN201810226358A CN108548801A CN 108548801 A CN108548801 A CN 108548801A CN 201810226358 A CN201810226358 A CN 201810226358A CN 108548801 A CN108548801 A CN 108548801A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- carbon quantum
- copper ion
- metalloporphyrin
- fluorescence
- 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
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"
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Inorganic Chemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of application of metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion, detect copper ion using fluorescence analysis, the metalloporphyrin framework encapsulation carbon quantum dot is used as the Ratiometric fluorescent probe of copper ion.Cu2+Addition the fluorescence intensity of metalloporphyrin frame can be caused to weaken, and the fluorescence intensity of carbon quantum dot is constant, and the addition of other metal ions cannot cause and Cu2+Similar change in fluorescence overcomes the influence of existing fluorescence probe concentration and environment, it can be achieved that highly selective fluorogenic quantitative detection to copper ion.
Description
Technical field
The present invention relates to application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion.
Background technology
Copper is that transition elements is most important to human health.This element generates many to life together with certain protein
Vital enzyme.Copper is also the micronutrient of all known life forms, it has from bon e formation and cellular respiration to knot
Form the multiple functions such as tissue development.But if being not added with regulation and control, copper can cause cellular homeostasis disorderly, so as to cause serious
Neurodegenerative disease.In addition, due to Cu2+Being widely used in agricultural and industry, Cu-W ore deposit and its potential toxicity pair
The influence of the mankind is still a challenging problem in the whole world.Therefore, exploitation is a kind of reliable, sensitive and highly selective
Fluorescence probe detection water in content of copper ion health and environmental protection are had a very big significance.
Fluorescence analysis is to generate the characteristic of fluorescence and its determining for intensity progress substance under ultraviolet light using substance
The method of property and quantitative analysis.The Cu of fluorescence is not emitted for itself2+For, design a kind of highly selective identification Cu2+It is glimmering
Light probe is to realize Cu2+The key of fluorescence analysis.The Ratiometric fluorescent probe at least emission peak with 2 different wave lengths, utilizes 2
The intensity rate of fluorescence emission peak realizes the detection to object at a different wave length.Compared with common fluorescent probe, ratio
Type fluorescence probe can eliminate the error that the factors such as the environment residing for probe molecule concentration and probe molecule are brought.
Invention content
It is an object of the invention to the present situations according to above-mentioned background technology, provide a kind of metalloporphyrin framework encapsulation carbon amounts
Application of the son point in detecting copper ion.
In order to solve the above technical problem, the present invention provides the following technical solutions：
Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion, using fluorescence analysis detection copper from
Son, the metalloporphyrin framework encapsulation carbon quantum dot are used as the Ratiometric fluorescent probe of copper ion.
Preferably, the step of fluorescence analysis detection copper ion includes：
(1) metalloporphyrin framework encapsulation carbon quantum dot is mixed with the buffer solution of pH=7, obtains probe solution；
(2) copper ion sample solution is added into probe solution, detects fluorescence signal.
Preferably, the pH buffer solutions are the HEPES buffer solutions of pH=7.2.
Preferably, when detecting fluorescence signal：The a length of 390nm of excitation light wave detects 446nm, at 654nm and 715nm wavelength
Emission peak fluorescence intensity.
A kind of method of metalloporphyrin framework encapsulation carbon quantum dot, includes the following steps：
(1) N,N-dimethylformamide is added in zirconium chloride, (4- carboxyl phenyls) porphyrins of 5,10,15,20- tetra- and benzoic acid
In solvent, mixing obtains precursor solution；
(2) carbon quantum dot, mixing are added into the precursor solution of step (1), metalloporphyrin frame is obtained by the reaction in heating
The carbon quantum dot of encapsulation.
Preferably, the mass ratio of the zirconium chloride and 5,10,15,20- tetra- (4- carboxyl phenyls) porphyrins is 3:1；5,10,
The mass ratio of (4- carboxyl phenyls) porphyrins of 15,20- tetra- and benzoic acid is 1:20~1:40, the amount of benzoic acid is very few to preparation
The size of MOF is influenced.
The amount of carbon quantum dot is very few to make the fluorescent emission of carbon quantum dot in probe too weak, observing effect unobvious.It is excellent
The mass ratio of selection of land, described 5,10,15,20- tetra- (4- carboxyl phenyls) porphyrins and carbon quantum dot is 20:1~40:1.
Preferably, the reaction temperature of step (2) is 120 DEG C, and the time is for 24 hours.
Carbon quantum dot can be obtained by solvent-thermal method by citric acid and reacting ethylenediamine.The synthesis of carbon quantum dot of the present invention is simultaneously
It is not limited to the method.
Solvent-thermal method prepare carbon quantum dot process include：The mixed aqueous solution of citric acid and ethylenediamine is placed in sealing
In reaction kettle, carbon quantum dot is obtained within 5 hours in 200 DEG C of reactions,
Cu2+Addition the fluorescence intensity of metalloporphyrin frame (hereinafter referred to as porphyrin MOF) can be caused to weaken, and carbon quantum dot
Fluorescence intensity it is constant；Fluorescence spectrometry is the result shows that the addition of other metal ions cannot cause and Cu2+Similar fluorescence
Variation, fluorescence intensity are held essentially constant, and thus highly selective identification copper ion, realizes the quantitative detection of copper ion.
The carbon quantum dot that this technology is encapsulated using porphyrin MOF utilizes fluorescence as a kind of novel Ratiometric fluorescent probe
The quantitative detection of copper ion is realized in the variation of signal, and this method is not only simple, quick, easy to operate, but also porphyrin MOF encapsulation
Fluorescence probe of the carbon quantum dot as double transmittings, eliminates background interference, and strong interference immunity detects sensitiveer.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings：
The fluorescence emission spectrogram of compound of the carbon quantum dot of Fig. 1 porphyrins MOF encapsulation.
The probe solution of Fig. 2 present invention is in detection Cu2+During selectively test.
The probe solution of Fig. 3 present invention is in Cu2+The variation diagram of fluorescence intensity in the range of a concentration of 0-40 μM.
The probe solution of Fig. 4 present invention is in Cu2+In the range of a concentration of 0-10nM, the ratio of I (654nm)/I (446nm)
With Cu2+The linear relationship collection of illustrative plates of concentration.
The probe solution of Fig. 5 present invention is in Cu2+In the range of a concentration of 0-40 μM, the ratio of I (654nm)/I (446nm)
With Cu2+The relation map of concentration.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1 synthesizes the carbon quantum dot Ratiometric fluorescent probe of porphyrin MOF encapsulation
1) synthesis of 5,10,15,20- tetra- (4- carboxylate methyl ester bases phenyl) porphyrin (TCPP-OMe)：First pass through vacuum distillation
It is new to steam pyrroles.16.5g p formylbenzoic acids methyl esters (0.1mol) and 100mL propionic acid are added in 500mL three neck round bottom flask,
128 DEG C are quickly heated with stirring in oil bath pan to reflux.Then pyrroles and propionic acid are added dropwise in 30min with constant pressure funnel
Mixed solution (3.1mL pyrroles, 10mL propionic acid), after being added dropwise to complete, continue back flow reaction 1h.It is added after being cooled to room temperature
100mL absolute ethyl alcohols, are put into cool overnight in -4 DEG C of refrigerator, are filtered with Buchner funnel, and filter cake is washed with absolute ethyl alcohol,
Crude product is obtained, is dried in vacuo at 40 DEG C, darkviolet crystalline solid product, silica gel column chromatography post separation, first with dichloro are obtained
Methane (CH2Cl2) it is eluant, eluent after the removal of the first green color bars, then with dichloromethane：Ethyl acetate=20:1 is eluant, eluent,
The first colour band of purple is collected, is spin-dried for obtaining product TCPP-OMe.
2) synthesis of (4- carboxyl phenyls) porphyrins of 5,10,15,20- tetra- (TCPP)：It is added in 250mL three neck round bottom flask
0.58g (0.2mmol) TCPP-OMe and 25mL methanol (CH3OH), 25mL tetrahydrofurans (THF), while being added 20mL's 40%
Potassium hydroxide (KOH) solution starts back flow reaction 1h at 65 DEG C.Natural cooling cools down, and waits for that after reaction, reaction solution being used
It is 5-6 that concentrated hydrochloric acid, which adjusts pH value,.THF is used later:CH2Cl2=1:1 mixed extractant solvent 2-3 times takes organic phase revolving dry, then
It is put in 40 DEG C of vacuum drying chamber and dries to get purple brick-red target product TCPP.
3) synthesis of carbon quantum dot：Citric acid solid powder 0.425g is weighed, 530 μ L of ethylenediamine solution, Yi Jizheng are measured
Citric acid is mixed with distilled water, then ethylenediamine solution is added in mixed liquor by distilled water 10ml, and glass bar is used in combination to stir to equal
It is even, the mixed solution of three is transferred in the autoclave of polytetrafluoroethyllining lining, then autoclave is put into Muffle furnace and is added
Heat continues 5 hours to 200 DEG C, after reaction, allows reactant cooled to room temperature, will obtain brownish black, transparent
Product, at this point, again the dialysis bag dialysis 48 hours of obtained product, the molecular weight of dialysis bag is 1000, after dialysis to obtain the final product
To the carbon dots solution in yellow.Powdered carbon dots are obtained after drying.
4) porphyrin MOF encapsulates the synthesis of carbon quantum dot：Weigh 0.24g ZrCl4, 0.08g TCPP and 2.4g benzoic acid is molten
Solution ultrasound 15min in 7.5ml DMF, then before 0.5ml carbon quantum dots (4mg/ml) aqueous solution is added to above-mentioned porphyrin MOF
It drives in liquid solution, the mixed solution will be finally transferred in the autoclave of sealing by stirring at normal temperature 2h.By reaction under high pressure
Kettle is put into baking oven, controlling reaction temperature be 120 DEG C, hydro-thermal reaction for 24 hours after, take out reaction kettle be cooled to room temperature, then by from
The heart collects aubergine solid, and being dried in vacuo 5h at 60 DEG C after being used in combination DMF and acetone to wash for several times obtains the carbon amounts of porphyrin MOF encapsulation
Sub- point (CQDs PCN) aubergine powder.
It configures porphyrin MOF and encapsulates carbon quantum dot aqueous solution, a concentration of 1mg/mL preserves solution under conditions of 4 DEG C
It is spare.Porphyrin MOF porphyrins MOF encapsulation carbon quantum dot excites at 390nm, and maximum hair is obtained at 446nm, 654nm, 715nm
Peak is penetrated, as shown in Figure 1.
Embodiment 2 detects Cu2+
Above-mentioned porphyrin MOF encapsulation carbon quantum dot aqueous solutions are mixed with HEPES buffer solutions (pH 7.2,20mM) first equal
It is even, it is configured to the probe solution of 50mg/L, takes 2mL probe solutions in the quartz colorimetric utensil of four sides light transmission.
Then a series of copper ion solution of concentration is added, detects the Cu of various concentration respectively2+To fluorescence probe signal
It influences.The slit width of Fluorescence Spectrometer is set as 10nm, and a length of 390nm of excitation light wave is arranged, and detects 446nm, 654nm,
Emission peak fluorescence intensity at 715nm wavelength.
Fig. 2 is fluorescence response of the probe solution to different metal ions, it can be seen that porphyrin MOF encapsulates carbon quantum dot pair
Copper ion has good selectivity.
Cu2+Addition the fluorescence intensity (I) of porphyrin MOF can be caused to weaken, and with Cu2+The increase of concentration, fluorescence probe
Signal strength weakens therewith, and the fluorescence intensity of carbon quantum dot is constant, and the results are shown in Figure 3, the ratio of I (654nm)/I (446nm)
Value and Cu2+Concentration is in good linear relationship, and for detection limit down to 3.7nM, corresponding linearity curve is as shown in Figure 4.
Fig. 5 is probe solution in Cu2+In the range of a concentration of 0-40 μM, the ratio and Cu of I (654nm)/I (446nm)2+
The relation map of concentration.
Concentration unit mol/L of the present invention indicates that corresponding nM indicates nmol/L with M, μM expression μm ol/L, mM expression
mmol/L。
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (10)
1. application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion detects copper ion using fluorescence analysis,
It is characterized in that, the metalloporphyrin framework encapsulation carbon quantum dot is used as the Ratiometric fluorescent probe of copper ion.
2. application according to claim 1, it is characterised in that：Fluorescence analysis detect copper ion the step of include：
(1) metalloporphyrin framework encapsulation carbon quantum dot is mixed with pH buffer solutions, obtains probe solution；
(2) copper ion sample solution is added into probe solution, detects fluorescence signal.
3. application according to claim 2, it is characterised in that：The HEPES bufferings that the pH buffer solutions are pH=7.2 are molten
Liquid.
4. application according to claim 2, it is characterised in that：When detecting fluorescence signal：The a length of 390nm of excitation light wave, inspection
Survey 446nm, the emission peak fluorescence intensity at 654nm and 715nm wavelength.
5. application according to claim 1, it is characterised in that：The metalloporphyrin frame is zirconium-porphyrin frame object.
6. a kind of method of metalloporphyrin framework encapsulation carbon quantum dot, includes the following steps：
(1) N,N-dimethylformamide solvent is added in zirconium chloride, (4- carboxyl phenyls) porphyrins of 5,10,15,20- tetra- and benzoic acid
In, mixing obtains precursor solution；
(2) carbon quantum dot, mixing are added into the precursor solution of step (1), metalloporphyrin framework encapsulation is obtained by the reaction in heating
Carbon quantum dot.
7. according to the method described in claim 6, it is characterized in that：The zirconium chloride and (the 4- carboxyl benzene of 5,10,15,20- tetra-
Base) porphyrin mass ratio be 3:The mass ratio of 1,5,10,15,20- tetra- (4- carboxyl phenyls) porphyrin and benzoic acid is 1:20~1:
40。
8. the method described according to claim 6 or 7, it is characterised in that：The 5,10,15,20- tetra- (4- carboxyl phenyls) porphyrin
Mass ratio with carbon quantum dot is 20:1~40:1.
9. according to the method described in claim 6, it is characterized in that：The reaction temperature of step (2) is 120 DEG C, and the time is for 24 hours.
10. a kind of metalloporphyrin framework encapsulation carbon quantum dot prepared according to claim 6 the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810226358.4A CN108548801A (en) | 2018-03-19 | 2018-03-19 | Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810226358.4A CN108548801A (en) | 2018-03-19 | 2018-03-19 | Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108548801A true CN108548801A (en) | 2018-09-18 |
Family
ID=63516617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810226358.4A Pending CN108548801A (en) | 2018-03-19 | 2018-03-19 | Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108548801A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468130A (en) * | 2018-12-27 | 2019-03-15 | 武汉工程大学 | A kind of preparation method of metal-doped fluorescent carbon quantum dot |
| CN110018144A (en) * | 2019-04-17 | 2019-07-16 | 南京理工大学 | Inorganic ions electrochemiluminescdetection detection method based on ZnTCPP@MOF |
| CN110229662A (en) * | 2019-07-09 | 2019-09-13 | 长春工业大学 | A kind of preparation method of carbon quantum dot and metal organic framework composite material |
| CN110669498A (en) * | 2019-09-25 | 2020-01-10 | 浙江理工大学 | Preparation method of tetraphenylzirconium porphyrin-AIE fluorescent molecule composite photosensitive sensing material |
| CN112225261A (en) * | 2019-07-15 | 2021-01-15 | 武汉中原长江科技发展有限公司 | Lithium-rich manganese-based positive electrode material carbonate precursor and preparation method and application thereof |
| CN113072936A (en) * | 2021-04-01 | 2021-07-06 | 上海大学 | Fluorescent probe based on carbon quantum dot-porphyrin assembly system and preparation method and application thereof |
| CN113218923A (en) * | 2021-03-26 | 2021-08-06 | 南京林业大学 | Carbon quantum dot ratio fluorescence sensor and preparation method and application thereof |
| CN113406052A (en) * | 2021-06-18 | 2021-09-17 | 长江大学 | Method for detecting phosphate ions |
| CN114106825A (en) * | 2021-12-17 | 2022-03-01 | 陕西工业职业技术学院 | Sulfur-phosphorus co-doped carbon point @ Zr-MOFs based on sesame straw and preparation method and application thereof |
| CN114225911A (en) * | 2021-12-17 | 2022-03-25 | 陕西工业职业技术学院 | Nitrogen-phosphorus co-doped carbon dot @ ZIF-8 based on potatoes as well as preparation method and application thereof |
| CN115594856A (en) * | 2021-11-30 | 2023-01-13 | 青岛大学（Cn） | Preparation method and application of ratiometric fluorescent probe |
| CN116003814A (en) * | 2022-12-23 | 2023-04-25 | 天津科技大学 | Preparation method of porphin-based metal organic framework material and application of porphin-based metal organic framework material in detection of F ions |
| CN116120578A (en) * | 2023-02-02 | 2023-05-16 | 江苏大学 | Molecularly imprinted photoelectrochemical sensor constructed based on CDs@PCN-224 nanocomposite and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107179301A (en) * | 2017-04-24 | 2017-09-19 | 西北师范大学 | Application of the zirconium porphyrin metal organic framework material as fluorescence probe in detection phosphoric acid hydrogen radical ion |
-
2018
- 2018-03-19 CN CN201810226358.4A patent/CN108548801A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107179301A (en) * | 2017-04-24 | 2017-09-19 | 西北师范大学 | Application of the zirconium porphyrin metal organic framework material as fluorescence probe in detection phosphoric acid hydrogen radical ion |
Non-Patent Citations (3)
| Title |
|---|
| LINLIN LU等: "Hydrophobic-carbon-dot-based dual-emission micelle for ratiometric fluorescence biosensing and imaging of Cu2+ in liver cells", 《BIOSENSORS AND BIOELECTRONICS》 * |
| XIAOMEI LIN等: "Encapsulation of Strongly Fluorescent Carbon Quantum Dots in Metal-Organic Frameworks for Enhancing Chemical Sensing", 《ANALYTICAL CHEMISTRY》 * |
| 张卫军等: "卟啉枝接联吡啶用于高选择性铜离子荧光传感器的研究", 《化 学 传 感 器》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468130A (en) * | 2018-12-27 | 2019-03-15 | 武汉工程大学 | A kind of preparation method of metal-doped fluorescent carbon quantum dot |
| CN109468130B (en) * | 2018-12-27 | 2021-12-03 | 武汉工程大学 | Preparation method of metal-doped fluorescent carbon quantum dots |
| CN110018144A (en) * | 2019-04-17 | 2019-07-16 | 南京理工大学 | Inorganic ions electrochemiluminescdetection detection method based on ZnTCPP@MOF |
| CN110229662A (en) * | 2019-07-09 | 2019-09-13 | 长春工业大学 | A kind of preparation method of carbon quantum dot and metal organic framework composite material |
| CN112225261A (en) * | 2019-07-15 | 2021-01-15 | 武汉中原长江科技发展有限公司 | Lithium-rich manganese-based positive electrode material carbonate precursor and preparation method and application thereof |
| CN112225261B (en) * | 2019-07-15 | 2022-12-13 | 武汉中原长江科技发展有限公司 | Lithium-rich manganese-based positive electrode material carbonate precursor and preparation method and application thereof |
| CN110669498A (en) * | 2019-09-25 | 2020-01-10 | 浙江理工大学 | Preparation method of tetraphenylzirconium porphyrin-AIE fluorescent molecule composite photosensitive sensing material |
| CN113218923A (en) * | 2021-03-26 | 2021-08-06 | 南京林业大学 | Carbon quantum dot ratio fluorescence sensor and preparation method and application thereof |
| CN113218923B (en) * | 2021-03-26 | 2023-03-07 | 南京林业大学 | Carbon quantum dot ratio fluorescence sensor and preparation method and application thereof |
| CN113072936B (en) * | 2021-04-01 | 2022-11-04 | 上海大学 | Fluorescent probe based on carbon quantum dot-porphyrin assembly system and preparation method and application thereof |
| CN113072936A (en) * | 2021-04-01 | 2021-07-06 | 上海大学 | Fluorescent probe based on carbon quantum dot-porphyrin assembly system and preparation method and application thereof |
| CN113406052B (en) * | 2021-06-18 | 2022-11-29 | 长江大学 | Method for detecting phosphate ions |
| CN113406052A (en) * | 2021-06-18 | 2021-09-17 | 长江大学 | Method for detecting phosphate ions |
| CN115594856A (en) * | 2021-11-30 | 2023-01-13 | 青岛大学（Cn） | Preparation method and application of ratiometric fluorescent probe |
| CN115594856B (en) * | 2021-11-30 | 2023-06-23 | 青岛大学 | Preparation method and application of ratio fluorescent probe |
| CN114225911A (en) * | 2021-12-17 | 2022-03-25 | 陕西工业职业技术学院 | Nitrogen-phosphorus co-doped carbon dot @ ZIF-8 based on potatoes as well as preparation method and application thereof |
| CN114106825A (en) * | 2021-12-17 | 2022-03-01 | 陕西工业职业技术学院 | Sulfur-phosphorus co-doped carbon point @ Zr-MOFs based on sesame straw and preparation method and application thereof |
| CN116003814A (en) * | 2022-12-23 | 2023-04-25 | 天津科技大学 | Preparation method of porphin-based metal organic framework material and application of porphin-based metal organic framework material in detection of F ions |
| CN116120578A (en) * | 2023-02-02 | 2023-05-16 | 江苏大学 | Molecularly imprinted photoelectrochemical sensor constructed based on CDs@PCN-224 nanocomposite and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108548801A (en) | Application of the metalloporphyrin framework encapsulation carbon quantum dot in detecting copper ion | |
| CN107179301A (en) | Application of the zirconium porphyrin metal organic framework material as fluorescence probe in detection phosphoric acid hydrogen radical ion | |
| Zhang et al. | Photoluminescent and electrochemiluminescent dual-signaling probe for bio-thiols based on a ruthenium (II) complex | |
| CN105694857B (en) | A kind of Mitochondrially targeted nitrosyl hydrogen molecule fluorescence probe and its preparation method and application | |
| CN105623648B (en) | One kind is based on the sour cyanines colorimetric probe of the asymmetric side of benzindole and anil, preparation method and application | |
| CN109722059B (en) | Purine skeleton-based no-wash aggregation-induced cell membrane targeted staining reagent and preparation method and application thereof | |
| CN110156688A (en) | A kind of targeting endoplasmic reticulum detects polar fluorescence probe and its application | |
| CN108864056A (en) | Near infrared fluorescent compound and its preparation method and application with AIE performance | |
| CN101118236A (en) | Near-infrared fluorescent detecting probe for detecting charged hydrogen in cell, synthetic method and use thereof | |
| Shen et al. | Red emission cysteine probe with high selectivity based on fluorescent protein chromophores and turn-on fluorescence in cell cultures | |
| Zhang et al. | Red emissive fluorescent probe for the rapid detection of selenocysteine | |
| CN106008510B (en) | For detecting Hg2+Aggregation-induced emission type fluorescent optical sensor and its preparation method and application | |
| CN110092773B (en) | Xanthene derivative and preparation method and application thereof | |
| CN109942508B (en) | Ratio type carbon monoxide fluorescent probe and preparation method and application thereof | |
| Fan et al. | Highly specific esterase activated AIE plus ESIPT probe for sensitive ratiometric detection of carbaryl | |
| CN111675674A (en) | AIE molecule and synthetic method thereof | |
| Guo et al. | A novel two-channel ratio fluorescent probe for monitoring intracellular pH fluctuations | |
| CN111217799A (en) | Indole salt-coumarin derivative and synthesis method and application thereof | |
| CN107043372B (en) | A kind of flavones fluorescence probe of targetted mitochondria and the preparation method and application thereof | |
| Zheng et al. | Development of fast-response turn-on phosphorescent probes for biothiols based on ruthenium (II) complexes | |
| Zhang et al. | A novel aggregation‐induced emission fluorescent probe with large Stokes shift for sensitive detection of pH changes in live cells | |
| CN105884650A (en) | Nitrile-group-containing azulene-styrene derivatives adopted as near infrared fluorescence probe as well as preparation method and application of nitrile-group-containing azulene-styrene derivative | |
| Jia et al. | A fast-responsive fluorescent turn-on probe for nitroreductase imaging in living cells | |
| CN110950877B (en) | Double-detection fluorescent probe, preparation method and application thereof in detection of hydrogen sulfide and copper ions | |
| CN110669350B (en) | Piperidyl BODIPY red-light fluorescent dye and preparation method and application thereof |
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 |
Application publication date: 20180918 |
|
| RJ01 | Rejection of invention patent application after publication |