CN112175605A - Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof - Google Patents
Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof Download PDFInfo
- Publication number
- CN112175605A CN112175605A CN202011075548.4A CN202011075548A CN112175605A CN 112175605 A CN112175605 A CN 112175605A CN 202011075548 A CN202011075548 A CN 202011075548A CN 112175605 A CN112175605 A CN 112175605A
- Authority
- CN
- China
- Prior art keywords
- ncs
- probe
- magnetic
- dual
- 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.)
- Granted
Links
- 239000000523 sample Substances 0.000 title claims abstract description 89
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 38
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 152
- 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 abstract description 46
- YTGJWQPHMWSCST-UHFFFAOYSA-N Tiopronin Chemical compound CC(S)C(=O)NCC(O)=O YTGJWQPHMWSCST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 108010058907 Tiopronin Proteins 0.000 claims abstract description 41
- 229960004402 tiopronin Drugs 0.000 claims abstract description 41
- 238000001514 detection method Methods 0.000 claims abstract description 31
- 238000002595 magnetic resonance imaging Methods 0.000 claims abstract description 27
- 229960003180 glutathione Drugs 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 9
- 108010024636 Glutathione Proteins 0.000 claims abstract description 8
- 239000003814 drug Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 45
- 239000012498 ultrapure water Substances 0.000 claims description 27
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000002902 bimodal effect Effects 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000005298 paramagnetic effect Effects 0.000 abstract description 7
- 229940079593 drug Drugs 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 16
- 239000007850 fluorescent dye Substances 0.000 description 13
- 239000012086 standard solution Substances 0.000 description 13
- 229910000510 noble metal Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 238000003384 imaging method Methods 0.000 description 10
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 108010054147 Hemoglobins Proteins 0.000 description 8
- 102000001554 Hemoglobins Human genes 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 230000005284 excitation Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010836 blood and blood product Substances 0.000 description 2
- 229940125691 blood product Drugs 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 108010036302 hemoglobin AS Proteins 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- C09K11/60—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing iron, cobalt or nickel
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Power Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses a near-infrared fluorescence magnetic Fe NCs dual-mode probe and a synthetic method and application thereof. The valence state of the iron element in the magnetic Fe NCs dual-mode probe is 0, the particle size of the iron element is 5nm, and the iron nano cluster prepared by the stabilizer glutathione to iron ion molar ratio of 1:0.3073 has excellent near-infrared fluorescence emission capability, can effectively avoid interference of biological autofluorescence in a sample, and can be used for high-sensitivity detection of drug molecule tiopronin in a complex detection system. In addition, the probe also has stronger paramagnetic property and can generate light under the action of an external magnetic fieldBright T1The image signal is weighted and is gradually enhanced along with the increase of the probe concentration, and the method has wide application prospect in the aspect of magnetic resonance imaging.
Description
The invention is supported by a national science fund surface project (No. 21375095), a Tianjin City science fund youth project (No. 17JCQNJC05800), an Tianjin teacher university's key laboratory of inorganic-organic hybrid functional material chemical education department, ' a Tianjin City functional molecular structure and performance key laboratory ' open fund project and a Tianjin teacher university ' future thousand-people plan ' project (WLQR 201914).
Technical Field
The invention belongs to the technical field of chemical synthesis and biological analysis and detection, and relates to a magnetic iron nanocluster with near-infrared fluorescence emission capability and a simple, green and rapid synthesis method thereof.
Background
Metal Nanoclusters (NCs), a nano-luminescent material emerging in recent years, have a particle size close to the fermi wavelength, which not only enables excellent fluorescent properties, but also exhibits properties possessed by molecules such as high water solubility, high dispersibility, and fluorescence tunability. Compared with traditional luminescent materials such as organic fluorescent dye, semiconductor quantum dots and rare earth up-conversion fluorescent materials, the metal nanocluster has smaller particle size and better biocompatibility while maintaining excellent fluorescence property and sensing property of the nano fluorescent probe, so that the metal nanocluster is widely applied in relevant fields such as biomedicine and environmental science, and becomes a hot research and development direction which is concerned in the technical field of domestic and foreign analysis and detection at present. According to different preparation raw materials of the metal nano-cluster fluorescent probe, the metal nano-cluster fluorescent probe can be divided into a noble metal nano-cluster and a common transition metal nano-cluster. The noble metal nanoclusters mainly comprise gold nanoclusters (Au NCs), silver nanoclusters (Ag NCs) and platinum nanoclusters (Pt NCs), and the noble metal nanocluster fluorescent probes are long in development history, so that preparation technologies and processes related to the noble metal nanoclusters are relatively mature, the preparation and application difficulty is low, however, expensive noble metals such as gold and silver are used as preparation raw materials, the preparation and use cost is high, the noble metal nanocluster fluorescent probes are only limited to be applied in small quantities in basic scientific research and laboratory analysis so far, and the large-scale application of the noble metal nanocluster fluorescent probes in practical production such as clinical detection and industrial analysis is greatly limited.
In order to better solve the problem of high cost and difficult popularization of the noble metal nano-cluster fluorescent probe in practical application, in recent years, technologists develop two common transition metal nano-cluster fluorescent probes, namely copper nano-clusters (Cu NCs) and iron nano-clusters (Fe NCs), successively. Because the two transition metal nanoclusters are cheap and easily available in preparation raw materials, heating is not needed in the preparation process, and the reaction time is short, the preparation cost and the use cost are greatly reduced compared with those of the traditional noble metal nanocluster fluorescent probe, the preparation method is very beneficial to large-scale popularization in practical production application, and the preparation method has a wide application prospect.
Among the transition metal nanocluster fluorescent probes, fluorescent Fe NCs also have many unique advantages compared to Cu NCs fluorescent probes that have been widely reported in recent years. Firstly, as for raw materials, the price of iron is obviously lower than that of copper, so that the cost of the Fe NCs probe is much lower than that of the Cu NCs probe, and the Fe NCs probe has more cost advantage in practical production application such as analysis and detection. And secondly, Fe NCs have longer fluorescence emission wavelength than Cu NCs, so that interference of biological autofluorescence in a biological sample is avoided, and the sensitivity and accuracy of analysis and detection are improved. More importantly, both the noble metal nanoclusters and the Cu NCs only have fluorescence emission performance and do not have any magnetic performance, the nanoclusters can only be used as a fluorescence probe but not as a fluorescence/magnetic resonance dual-mode probe, and the simultaneous output of a fluorescence signal and a magnetic resonance signal cannot be realized. If a fluorescence/magnetic resonance bimodal nanoprobe is prepared based on the metal nanoclusters, other nanoparticles (such as Fe) with magnetic signal response must be additionally coupled3O4Etc.), not only additional preparation processes are added, but also the preparation cost is increased. However, the iron element is magnetic, and Fe NCs prepared by using the iron element as a matrix have not only light emission properties but also magnetic properties. If the probe is developed into a fluorescence/magnetic resonance bimodal sensing probe, two signals can be simultaneously transmittedOutput, realize a material dual-purpose, practice thrift the application cost. Therefore, the Fe NCs probe undoubtedly has great technical progress as compared with the noble metal nanocluster probe and the Cu NCs probe.
Currently, fluorescent Fe NCs probes are rarely reported in domestic and foreign technical literature because iron element belongs to a metal before hydrogen, and reduction of iron element from cations to 0-valent Fe NCs in a solution is more difficult than reduction of metal elements after hydrogen such as gold, silver and copper, and the prepared Fe NCs are also very easy to be oxidized again, so that the product is difficult to store under conventional conditions. At present, only 3 documents are reported internationally for preparing fluorescent Fe NCs, which are: n. goswamine et al., Nanoscale, 2014, 6, 1848-. Since the preparation of Fe NCs is very difficult, in order to avoid the re-oxidation of the prepared Fe NCs, the above three documents all use hemoglobin (Hb) as an iron source and a preparation template, and they extract iron ions in hemoglobin to the surface of hemoglobin by using piperidine and reduce the iron ions to iron atoms by using a corresponding reducing agent, thereby preparing a yellow to orange (emission wavelength of 580-600 nm) emitting Fe NCs fluorescent probe. The preparation method has the following defects: firstly, whether noble metal nanoclusters or Cu NCs are adopted, metal elements in the nanoclusters are all from metal inorganic salt raw materials, and in the Fe NCs prepared by the method, iron elements are from blood products, namely hemoglobin. As is well known, the price of metal inorganic salt is far lower than that of blood products, and the method adopting hemoglobin as a main raw material for preparing Fe NCs undoubtedly increases the preparation and application cost of the Fe NCs. Secondly, the fluorescence emission capability of the metal nanocluster comes from the transition of excited electrons in metal atoms, the more metal atoms grow and combine on the template molecule, the more the number of electrons excited to generate the transition, and correspondingly, the stronger the fluorescence emission capability of the nanocluster. Generally, 10-100 metal atoms will grow on the surface of one template molecule of the fluorescent metal nanocluster. In the preparation method, hemoglobin is both an iron source and a template, one hemoglobin molecule only contains one iron ion, and if Fe NCs are prepared by the method, only one metal atom can grow on the surface of one template molecule, so that the luminous efficiency of the Fe NCs probe is greatly restricted. Meanwhile, the preparation method cannot directly reduce iron ions in hemoglobin, and the iron ions are extracted from the hemoglobin to the surface by using piperidine firstly. Piperidine is a toxic reagent and belongs to an easily prepared toxic chemical, is strictly controlled, and is used as a necessary reagent for preparing Fe NCs, so that great safety and economic risks are faced, and large-scale popularization in actual production is not facilitated.
Aiming at the defects of the prior art, the invention provides a preparation method of a fast, efficient, green and low-cost near-infrared fluorescence magnetic Fe NCs (Fe NCs) bimodal probe. The method uses reduced Glutathione (GSH) as a preparation template and a protective agent, takes ferrous chloride inorganic salt as an iron source, and takes sodium borohydride as a reducing agent in aqueous solution to reduce ferrous ions with the valence of +2 into iron atoms with the valence of 0, thereby preparing the Fe NCs with near infrared fluorescence emission performance and paramagnetic performance. The preparation template GSH adopted by the method is a bioactive small molecule (tripeptide) which is widely existed in animals and plants, has wide source and low price, and the rich sulfhydryl group can combine a plurality of iron atoms, thereby ensuring the fluorescence emission efficiency of the prepared Fe NCs. According to the method, sodium borohydride replaces a hydrazine hydrate reducing agent commonly used in the traditional metal nano-cluster synthesis method, toxic reagents such as piperidine are not needed, the preparation process is green, environment-friendly and efficient, and the time is only 15 minutes. The finally formed Fe NCs have stable performance, long preservation time and excellent magnetic resonance response performance, can realize the simultaneous output of fluorescent and magnetic resonance bimodal signals, and has obvious technical progress and wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a simple aqueous phase room temperature synthesis method of water-soluble non-toxic Fe NCs, the Fe NCs prepared by the method have excellent near infrared fluorescence emission capability and excellent paramagnetic property, can simultaneously have the response capability of two detection signals of fluorescence and Magnetic Resonance Imaging (MRI), namely the response capability of a bimodal signal, and has good application prospect in the aspects of drug molecule detection, MRI imaging application and the like.
In order to realize the purpose, the invention discloses a near-infrared fluorescence magnetic Fe NCs dual-mode probe, which is characterized in that: the valence state of the iron element in the magnetic Fe NCs dual-mode probe is 0, the particle size of the iron element is 5nm, and the molar ratio of Glutathione (GSH) serving as a stabilizer to iron ions is 1: 0.3073;
the Fe NCs probe has near-infrared fluorescence emission capability, the maximum excitation wavelength of the Fe NCs probe is 515nm, and the maximum emission wavelength of the Fe NCs probe is 702 nm; and the Fe NCs probe has fluorescent property and obvious paramagnetic property.
The invention further discloses a synthesis method of the near-infrared fluorescence magnetic Fe NCs dual-mode probe, which is characterized by comprising the following steps:
(1) weighing 0.1000g of reduced Glutathione (GSH) and dissolving in 15mL of high-purity water;
(2) weighing ferrous chloride tetrahydrate (FeCl)2·4H2O) 0.1988g, dissolving in 10mL of high-purity water to form 0.1M ferrous chloride aqueous solution, transferring 1mL of the liquid, adding into GSH solution, and stirring for 20 min;
(3) and adding 0.0190g of sodium borohydride under the stirring condition, fully reacting for 15 min, and changing the color of the solution from colorless to light yellow to obtain the Fe NCs probe solution with both magnetism and near-infrared fluorescence emission capability.
The invention further discloses an application of the near-infrared fluorescence magnetic Fe NCs dual-mode probe in the aspect of high-sensitivity detection of medicine molecule tiopronin, and the method comprises the following steps: preparing a detection system by using a certain volume of Fe NCs probe solution, a tiopronin standard solution and high-purity water, determining the quenching quantity (delta F) of a target substance tiopronin on a fluorescence signal of the Fe NCs probe by using the detection system containing the tiopronin standard solutions with different concentrations as a vertical coordinate, drawing a standard curve by using the concentration of the tiopronin standard solution as a horizontal coordinate, determining the concentration of the tiopronin in a sample according to the standard curve, wherein the linear range of the method for detecting the tiopronin is 0.1-0.6M; the detection limit is: 3.7 mM.
The invention also discloses the application of the near infrared fluorescence magnetic Fe NCs dual-mode probe in the aspect of Magnetic Resonance Imaging (MRI), and the method comprises the following steps: taking the Fe NCs probe solution with different concentrations, and carrying out T treatment in a clinical medical MRI imaging system1Weighted imaging was performed in the mode in which the T of the Fe NCs probe increased with increasing concentration1The MRI signal of the weighted mode is continuously enhanced, the MRI image is brighter and brighter, and the probe can effectively enhance the T of water1The MRI images are weighted.
The invention is described in more detail below:
a near-infrared fluorescence magnetic Fe NCs bimodal detection probe is characterized in that: glutathione (GSH) and Fe atom (FeCl as iron source) as protective agents for the Fe NCs probe2·4H2Calculated as O) is 1:0.3073, respectively; the particle size of the Fe NCs probe is about 5nm, the Fe NCs probe can emit fluorescence in a near infrared region under the excitation of visible light, the maximum excitation wavelength of the Fe NCs probe is 515nm, the maximum emission wavelength of the Fe NCs probe is 702nm, and the Fe NCs probe has obvious T1Weighted-mode Magnetic Resonance (MRI) signal response (i.e., MRI images become brighter as probe concentration increases).
The synthesis method of the near-infrared fluorescence magnetic Fe NCs dual-mode probe is characterized by comprising the following steps of:
(1) weighing 0.1000g of GSH, and dissolving in 15mL of high-purity water;
(2) weighing 0.1988 gFeCl2·4H2O, dissolved in 10mL of high-purity water to form FeCl with the concentration of 0.1M2Transferring 1mL of the liquid into the GSH solution, and fully stirring for 20 min;
(3) and adding 0.0190g of sodium borohydride under the stirring condition, fully reacting for 15 min, and changing the color of the solution from colorless to light yellow to obtain the near-infrared fluorescent magnetic Fe NCs probe solution.
The invention further discloses application of the near-infrared fluorescence magnetic Fe NCs bimodal probe in high-sensitivity detection of a drug molecule tiopronin. The method specifically comprises the steps of preparing a detection system by using a certain volume of Fe NCs probe solution, tiopronin standard solution and high-purity water, measuring the quenching quantity (delta F) of a target substance tiopronin to a fluorescence signal of the Fe NCs probe by using the detection system containing the tiopronin standard solution with different concentrations as a vertical coordinate, drawing a standard curve by using the concentration of the tiopronin standard solution as a horizontal coordinate, and measuring the concentration of the tiopronin in a sample according to the standard curve.
In the detection method, linear equations Δ F =415.50648x +27.89188 are obtained, and Δ F = F0-F,F0Equal to the fluorescence intensity without tiopronin, F is the fluorescence intensity after tiopronin addition, and x is the tiopronin concentration.
In the above detection method, the linear range of detection is 0.1-0.6M, and the detection limit is 3.7 mM.
In the detection method, 3.55mL of high-purity water, 0.25mL of Fe NCs dispersion system and 0.20mL of tiopronin solution are adopted.
In the detection method, the fluorescence intensity of the tiopronin solution is detected after the tiopronin solution is added into the high-purity water and Fe NCs dispersion system for 90 min.
The invention further discloses an application of the near-infrared fluorescence magnetic Fe NCs bimodal probe in Magnetic Resonance Imaging (MRI). In particular to taking the Fe NCs probe solution with different concentrations and carrying out T in a clinical medical MRI imaging system1Weighted imaging was performed in the mode in which the T of the Fe NCs probe increased with increasing concentration1The MRI signal of the weighted mode is continuously enhanced, and the MRI image is brighter and brighter.
A typical example of the present invention:
a method for synthesizing a near-infrared fluorescent magnetic Fe NCs dual-mode probe comprises the following steps:
step 1: GSH and FeCl2·4H2Dissolving O in high-purity water respectively to obtain stock mother liquor; wherein 0.1000g GSH is dissolved in 15mL of high purity water; 0.1988g FeCl2·4H2O was dissolved in 10mL of high purity water.
Step 2: FeCl is added2Dropwise adding the stock solution into the GSH solution, and fully stirring at room temperature; specifically, 1mL of FeCl prepared in step 1 is removed2The solution was added dropwise to the GSH solution and stirred well for 20 min.
And step 3: adding 0.0190g of sodium borohydride into the reaction system obtained in the step 2, fully reacting for 15 min, and obtaining a Fe NCs probe solution when the color of the reaction solution is changed from colorless to light yellow;
and 4, step 4: and (4) centrifuging the Fe NCs probe solution obtained in the step (3) at the rotating speed of 8000 r/min, washing the solution with absolute ethyl alcohol and high-purity water for three times, and drying the solution for 12 hours at the temperature of 60 ℃ in a vacuum environment to obtain a Fe NCs solid product.
Another typical example of the present invention:
step 1: 1.6319 g of tiopronin is weighed and dissolved in 10mL of high-purity water to prepare 1M of tiopronin high-standard solution for storage and standby.
Step 2: accurately transferring the tiopronin high-standard solution prepared in the step 1 with different volumes into a 10mL colorimetric tube, diluting the tiopronin high-standard solution with high-purity water to prepare the tiopronin standard solution with the concentration of 0.1M, 0.2M, 0.3M, 0.4M and 0.6M in sequence, and storing the tiopronin standard solution for later use.
And step 3: and (3) accurately transferring 0.20mL of the tiopronin standard solution with each concentration prepared in the step (2) into 5mL centrifuge tubes respectively, adding 0.25mL of Fe NCs probe solution and 3.55mL of high-purity water into each centrifuge tube, uniformly mixing, and measuring the fluorescence intensity of the mixed solution in each centrifuge tube after 90 min.
And 4, step 4: adding 0.25mL of Fe NCs solution into a 5mL centrifuge tube, adding 3.75 mL of high-purity water, mixing, standing for 90min, measuring the fluorescence intensity and marking as F0Calculating the fluorescence intensity and F of each detection solution in the step 30And (3) marking as delta F, drawing a standard curve by taking the delta F as an ordinate and the concentration of the tiopronin standard solution as an abscissa, and obtaining a linear equation of delta F =415.50648x +27.89188, and the linear equation of delta F = F0-F,F0Equal to the fluorescence intensity without tiopronin, F is the fluorescence intensity after tiopronin addition, and x is the tiopronin concentration.
Yet another exemplary embodiment of the present invention
Step 1: and transferring Fe NCs probe solutions with different volumes, adding high-purity water to dilute the Fe NCs probe solutions to 0.0045M, 0.00225M, 0.001125M and 0.0009M respectively, and storing the Fe NCs probe solutions for later use.
Step 2: accurate movementTaking 2 mL of the solution to be tested prepared in the step 1 and pure water (for comparison), respectively moving the solution and the pure water into different hole sites of a detection plate, and carrying out T-test in a clinical medical MRI imaging system1And carrying out weighted imaging in the mode, and observing the image brightness of the sample in each hole site.
Compared with the prior art, the near-infrared fluorescence magnetic Fe NCs dual-mode probe and the synthesis method thereof disclosed by the invention have the beneficial effects that:
(1) the Fe NCs prepared by the invention have the advantages of stable optical property, small particle size of synthetic materials, good fluorescence property and the like, the synthetic method is simple and rapid, and complex processes such as heating, pH adjustment, functional modification and the like are not needed in the synthetic process.
(2) The Fe NCs probe has a fluorescence emission wavelength of 702nm, is positioned in a near infrared region, has a good fluorescence emission peak shape and high fluorescence intensity, and has good paramagnetism.
(3) The preparation method of the Fe NCs is novel and is not easily interfered by other reasons such as pH, temperature and the like. The sodium borohydride is used as a reducing agent, so that the method is environment-friendly, does not generate by-products harmful to the environment, has high reaction speed, can finish the reaction within 15 min at the fastest speed, is simple in preservation method, and has stable fluorescence and magnetic resonance properties.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of an Fe NCs probe, illustrating that the Fe NCs have a small particle size and are uniform in size;
FIG. 2 is a fluorescence excitation spectrum and an emission spectrum of the Fe NCs probe, showing that the maximum excitation wavelength is 515nm and the maximum emission wavelength is 702 nm;
FIG. 3 is a standard curve diagram of the detection of tiopronin by Fe NCs probe;
FIG. 4 shows T values of pure water and Fe NCs probe aqueous solutions of different concentrations1The MRI images are weighted, which shows that the probe has paramagnetic property and MRI response capability and can enhance the MRI signal of water.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise defined, all technical means used in the present invention are the same as those of ordinary skill in the artKnown methods are known. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. All the reagents used were analytically pure, and the reagents and manufacturers used were as follows: GSH was purchased from shanghai source, leaf biotechnology limited; sodium borohydride was purchased from Tianjin Guangfu Fine chemical research institute; FeCl2·4H2O was purchased from kyo illinokay technologies ltd. Poly-reduced glutathione, sodium borohydride, ferrous chloride tetrahydrate are commercially available.
Example 1
The preparation of the near-infrared fluorescent magnetic Fe NCs is carried out at room temperature according to the following steps:
(1) weighing 0.1000g of GSH and dissolving in 15mL of high-purity water;
(2) 0.1988g of FeCl were weighed2·4H2O, dissolved in 10mL of high-purity water to form FeCl with the concentration of 0.1M2Transferring 1mL of the aqueous solution into a prepared GSH solution, and fully stirring for 20 min;
(3) and adding 0.0190g of sodium borohydride solid into the reaction mixed solution under the stirring condition, and fully reacting for 15 min under the stirring condition to obtain a final product solution, wherein the color of the reaction solution is changed from colorless to light yellow.
Example 2
(1) Preparation of Fe NCs reference example 1;
(2) transmission Electron Microscopy (TEM) characterization of Fe NCs:
dispersing the prepared Fe NCs into high-purity water, uniformly dripping the Fe NCs on a special copper net, airing to prepare an observation sample, and observing the appearance of the Fe NCs by using a field emission transmission electron microscope. As shown in FIG. 1, the Fe NCs are approximately spherical in morphology and uniformly dispersed, and have small particle size (about 5 nm) and uniform distribution.
Example 3
(1) Preparation of Fe NCs reference example 1;
(2) measurement of fluorescence excitation spectrum and emission spectrum of Fe NCs:
the prepared Fe NCs are dispersed in high-purity water, and a fluorescence excitation spectrum and an emission spectrum of the Fe NCs sample are measured by a fluorescence spectrophotometer, as shown in FIG. 2, the maximum excitation wavelength of the Fe NCs is 515nm, and under the excitation of the maximum excitation wavelength, the fluorescence emission wavelength is 702nm and is positioned in a near infrared region, which indicates that the Fe NCs have good near infrared fluorescence emission capability.
Example 4
(1) Preparation of Fe NCs reference example 1;
(2) the application of the Fe NCs probe in the aspect of detecting the medicine molecule tiopronin is as follows:
respectively taking 2 empty centrifuge tubes, numbering (1) and (2), respectively transferring 3.55mL of high-purity water into the centrifuge tubes, transferring 250 μ L of Fe NCs probe solution into the centrifuge tubes, mixing uniformly, and continuing to addAdding 200 mu L of high-purity water into the centrifugal tube serving as a blank control group, adding 200 mu L of tiopronin solution into the centrifugal tube, reacting for 90min to quench fluorescence, and detecting fluorescence emission intensity by using a fluorescence photometer, so that the detection of the tiopronin solution can be realized.
Example 5
(1) Preparation of Fe NCs reference example 1;
(2) the application of the Fe NCs probe in the aspect of detecting the medicine molecule tiopronin is as follows:
adding 3.55mL of high-purity water into a 5mL centrifuge tube, transferring 250 μ L of Fe NCs probe solution, adding into the centrifuge tube, mixing uniformly, adding 200 μ L of tiopronin solutions with different concentrations respectively, reacting for 90min, detecting the fluorescence emission intensity, and performing parallel determination for three times. According to the quenching degree of the Tiopronin with different concentrations on the fluorescence of the Fe NCs probe, the linear relation (shown in figure 3) between the fluorescence quenching amount (delta F) and the concentration of the Tiopronin solution is obtained, and the Tiopronin is quantitatively detected according to the linear relation, wherein the linear range of the detection is 0.1-0.6M, and the detection limit is 3.7 mM.
Example 6
(1) Preparation of Fe NCs reference example 1;
(2) paramagnetic characterization of Fe NCs and their use at T1Application of weighted MRI imaging:
drying and weighing the prepared Fe NCs probe, dissolving in high-purity water again to obtain standard probe solutions (numbered 1-5) with concentrations of 0.0045M, 0.00225M, 0.001125M and 0.0009M in sequence, transferring 2 mL of the solution to be detected and pure water (numbered 6) for comparison, transferring into different holes of an MRI image detection plate, and performing T-shaped fluorescence quantitative fluorescence1And carrying out weighted imaging in the mode, and observing the image brightness of the sample in each hole site. As shown in FIG. 4, T of the Fe NCs1The weighted magnetic resonance image becomes bright obviously along with the increase of the probe concentration, which indicates that the Fe NCs probe has good paramagnetic property and T1Weighted MRI response capability (T is generated if ferromagnetic material is used)2Weighted signal, i.e., MRI images become darker as probe concentration increases). In addition, the MRI signal of the Fe NCs probe solution in the hole sites 1-5 is obviously stronger than that of pure water in the hole site 6, which shows that the Fe NCs probe can effectively enhance the MRI signal of a substance without MRI signal response performance like water, and has wide application prospect in MRI imaging.
Claims (4)
1. A near-infrared fluorescence magnetic Fe NCs dual-mode probe is characterized in that: the valence state of the iron element in the magnetic Fe NCs dual-mode probe is 0, the particle size of the iron element is 5nm, and the molar ratio of glutathione serving as a stabilizer to iron ions is 1: 0.3073.
2. The synthesis method of the near-infrared fluorescence magnetic Fe NCs dual-mode probe as claimed in claim 1, which is characterized by comprising the following steps:
(1) weighing 0.1000g of reduced Glutathione (GSH) and dissolving in 15mL of high-purity water;
(2) weighing four waterIron (FeCl) chloride2·4H2O) 0.1988g, dissolving in 10mL of high-purity water to form 0.1M ferrous chloride aqueous solution, transferring 1mL of the liquid, adding into GSH solution, and stirring for 20 min;
(3) and adding 0.0190g of sodium borohydride under the stirring condition, fully reacting for 15 min, and changing the color of the solution from colorless to light yellow to obtain the Fe NCs probe solution with both magnetism and near-infrared fluorescence emission capability.
3. The application of the near-infrared fluorescent magnetic Fe NCs dual-mode probe in claim 1 in the aspect of high-sensitivity detection of medicine tiopronin.
4. Use of the near-infrared fluorescent magnetic Fe NCs bimodal probe of claim 1 in Magnetic Resonance Imaging (MRI).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011075548.4A CN112175605B (en) | 2020-10-10 | 2020-10-10 | Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011075548.4A CN112175605B (en) | 2020-10-10 | 2020-10-10 | Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112175605A true CN112175605A (en) | 2021-01-05 |
CN112175605B CN112175605B (en) | 2022-10-21 |
Family
ID=73947919
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011075548.4A Active CN112175605B (en) | 2020-10-10 | 2020-10-10 | Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112175605B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113072930A (en) * | 2021-03-24 | 2021-07-06 | 山西大学 | Preparation method of green fluorescent iron-based nanoparticles |
CN116496786A (en) * | 2023-07-01 | 2023-07-28 | 北京建工环境修复股份有限公司 | Gadolinium nanocluster fluorescent probe and application thereof in environment detection |
CN116514901A (en) * | 2023-07-04 | 2023-08-01 | 北京建工环境修复股份有限公司 | Double-response fluorescent iron nanocluster probe and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111157506A (en) * | 2020-01-17 | 2020-05-15 | 天津师范大学 | Integrated fluorescent test paper for detecting thioglycollic acid in real time and application |
-
2020
- 2020-10-10 CN CN202011075548.4A patent/CN112175605B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111157506A (en) * | 2020-01-17 | 2020-05-15 | 天津师范大学 | Integrated fluorescent test paper for detecting thioglycollic acid in real time and application |
Non-Patent Citations (5)
Title |
---|
AKHILA JOSE: "Multifunctional fluorescent iron quantum clusters for non-invasive radiofrequency ablationof cancer cells", 《COLLOIDS AND SURFACES B: BIOINTERFACES》, vol. 165, 27 February 2018 (2018-02-27), pages 371 - 380, XP085369116, DOI: 10.1016/j.colsurfb.2018.02.058 * |
HONG HUANG: "One-pot green synthesis of highly fluorescent glutathione-stabilized stabilizedcopper nanoclusters for Fe3+sensing", 《SENSORS AND ACTUATORS B》, vol. 241, 19 October 2016 (2016-10-19), pages 292 - 297, XP029864110, DOI: 10.1016/j.snb.2016.10.086 * |
LU TIAN: "Multi-talented applications for cell imaging, tumor cells recognition,patterning, staining and temperature sensing by using egg white-encapsulated gold nanoclusters", 《SENSORS AND ACTUATORS B》, vol. 240, 26 August 2016 (2016-08-26), pages 114 - 124, XP029818986, DOI: 10.1016/j.snb.2016.08.147 * |
NIRMAL GOSWAMI: "Luminescent iron clusters in solution", 《NANOSCALE》, vol. 6, 27 November 2013 (2013-11-27), pages 1848 - 1854 * |
张菲: "铜纳米簇荧光探针高灵敏定量检测谷丙转氨酶", 《吉林师范大学学报( 自然科学版)》, vol. 41, 28 February 2020 (2020-02-28), pages 84 - 89 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113072930A (en) * | 2021-03-24 | 2021-07-06 | 山西大学 | Preparation method of green fluorescent iron-based nanoparticles |
CN113072930B (en) * | 2021-03-24 | 2022-05-31 | 山西大学 | Preparation method of green fluorescent iron-based nanoparticles |
CN116496786A (en) * | 2023-07-01 | 2023-07-28 | 北京建工环境修复股份有限公司 | Gadolinium nanocluster fluorescent probe and application thereof in environment detection |
CN116496786B (en) * | 2023-07-01 | 2023-09-29 | 北京建工环境修复股份有限公司 | Gadolinium nanocluster fluorescent probe and application thereof in environment detection |
CN116514901A (en) * | 2023-07-04 | 2023-08-01 | 北京建工环境修复股份有限公司 | Double-response fluorescent iron nanocluster probe and preparation method and application thereof |
CN116514901B (en) * | 2023-07-04 | 2023-09-29 | 北京建工环境修复股份有限公司 | Double-response fluorescent iron nanocluster probe and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN112175605B (en) | 2022-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112175605B (en) | Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof | |
CN109490269B (en) | Preparation method of dual-emission colorimetric fluorescent nano-microsphere and application of dual-emission colorimetric fluorescent nano-microsphere in bacterial detection | |
CN109266333B (en) | Preparation method and application of fluorescent silver nanocluster probe | |
CN108659815A (en) | Golden copper nanocluster fluorescence probe and preparation method thereof for copper ion detection | |
Lv et al. | Carbon dots doped lanthanide coordination polymers as dual-function fluorescent probe for ratio sensing Fe2+/3+ and ascorbic acid | |
CN112159522B (en) | Water-soluble rhodamine-based fluorescent/colorimetric dual-mode probe and preparation method and application thereof | |
Khan et al. | High biocompatible nitrogen and sulfur Co-doped carbon dots for Hg (II) detection and their long-term biological stability in living cells | |
CN109652065A (en) | A kind of preparation method of gold doping fluorescent carbon quantum dot | |
CN107253961A (en) | It is a kind of can ratio test cysteine water soluble fluorescence sensor preparation and application | |
Feng et al. | Dual-modal light scattering and fluorometric detection of lead ion by stimuli-responsive aggregation of BSA-stabilized copper nanoclusters | |
CN108949171A (en) | A kind of rare earth carbon nano-particles and preparation method thereof and the application based on fluorescence determination of colority pH value | |
CN113999679B (en) | Method for high-sensitivity detection of thiamphenicol based on up-conversion nano material 'off-on' type fluorescent sensor | |
CN109738398B (en) | Method for rapidly and visually detecting heavy metal silver ions through paper sensing | |
CN111590087A (en) | Preparation method of fluorescent gold nanocluster, prepared fluorescent gold nanocluster and application thereof | |
CN115308169A (en) | Ratiometric fluorescent probe based on sulfur quantum dots and copper nanoclusters and application thereof | |
Zhou et al. | Au@ Ag@ ZIF-8 multifunction probe with internally o-phenylenediamine encoding for the colorimetric, fluorescence, and SERS multi-mode optical detection of reactive sulfur species | |
CN111363542B (en) | Full-color fluorescent CaF 2 And use of CaF 2 Prepared furfural molecular imprinting ratio fluorescence sensor and preparation method thereof | |
CN109632752A (en) | The method and detector of various metals ion are identified by fluorescent carbon point | |
CN105670630B (en) | A kind of water-solubility rare-earth dopen Nano crystal and its preparation method and application | |
Huang et al. | Aqueous synthesis of CdTe quantum dots by hydride generation for visual detection of silver on quantum dot immobilized paper | |
CN116285961B (en) | Preparation method of fluorescent nano gold cluster and method for rapidly detecting lead ions by using fluorescent nano gold cluster | |
CN113791056B (en) | Method for detecting ferric ions and glutathione based on HOF-PyTTA fluorescent material | |
CN109053711B (en) | Probe compound for mercury ion detection and preparation method and application thereof | |
Zhao et al. | Metabolic iron detection through divalent metal transporter 1 and ferroportin mediated cocktail fluorogenic probes | |
CN114149798A (en) | Trace element copper ion fluorescence detection nanocrystalline material in blood, preparation method thereof and detection kit |
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 | ||
OL01 | Intention to license declared | ||
OL01 | Intention to license declared |