CN105885843B - A kind of up-conversion luminescent material of visual quick detection - Google Patents
A kind of up-conversion luminescent material of visual quick detection Download PDFInfo
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- CN105885843B CN105885843B CN201610238316.3A CN201610238316A CN105885843B CN 105885843 B CN105885843 B CN 105885843B CN 201610238316 A CN201610238316 A CN 201610238316A CN 105885843 B CN105885843 B CN 105885843B
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- luminescent material
- nanogold
- fluorescence quantum
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- 239000000463 material Substances 0.000 title claims abstract description 182
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 55
- 230000000007 visual effect Effects 0.000 title claims abstract description 27
- 238000001514 detection method Methods 0.000 title claims abstract description 20
- 239000008187 granular material Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 39
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000000975 bioactive effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 238000003745 diagnosis Methods 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 239000000020 Nitrocellulose Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 230000000740 bleeding effect Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920001220 nitrocellulos Polymers 0.000 claims description 10
- 238000003780 insertion Methods 0.000 claims description 9
- 230000037431 insertion Effects 0.000 claims description 9
- 238000013508 migration Methods 0.000 claims description 9
- 230000005012 migration Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 5
- 229910009523 YCl3 Inorganic materials 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- -1 octadecylene Chemical group 0.000 claims description 4
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 210000004204 blood vessel Anatomy 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims 1
- 239000003643 water by type Substances 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007877 drug screening Methods 0.000 description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012800 visualization Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012631 diagnostic technique Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
-
- 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"
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
Abstract
A kind of up-conversion luminescent material of visual quick detection, it includes upper forwarding luminescent material and nanogold material granule, it is characterised in that：Upper forwarding luminescent material is uniformly wrapped in up-conversion luminescent material surface with nanogold material granule strong bonded, nanogold material granule；Either upper forwarding luminescent material and fluorescence quantum material granule strong bonded or upper forwarding luminescent material and fluorescence quantum material granule strong bonded；And globulate is wrapped up by surface modification, then be connected with bioactive molecule, prepare by vision institute qualitative recognition, by the marking particle thing of instrumentation quantitative measurment.
Description
Technical field
The invention belongs to bielement nano up-conversion luminescent material composite chromatography method field of biological detection application.
Technical background
In vitro quick diagnosis in existing biomarker technology, be widely used for medical diagnosis, food inspection,
The fields such as residues of pesticides, environmental protection judgement.Such as：Nanogold particle material marking is widely used in various biological diagnosises, and its is excellent
Point is can be with simple and fast vision qualitative recognition, and its is insufficient, and place is that quantitative judgement accuracy is relatively low.Fluorescence method diagnostic techniques can be with
Qualitative, quantitative, but its Ultraluminescence background noise is more, and resolution error is larger, and quantitative error is big.Although up-conversion fluorescence technology
Solve noiseless background and can be largely used to qualitative, quantitative in the biological diagnosis of chromatography kit, but its is qualitative complete
The full special testing instrument for relying on complex and expensive, reduces service efficiency, is unable to reach timely visual purpose.Upper conversion hair
Luminescent material is also required to auxiliary with combinations such as magnetic material, nano silver material, organic fluorescent dye, nanogold and magnetic materials and set
Standby to realize detection, this has widely in Chinese patent 201210236102.4,201310045670.0,200610104760.2
Disclose, their deficiencies, which are effectively to simplify, is applied to chromatography detection technique field.
A kind of quick visualization detection side based on bielement nano up-conversion luminescent material composite of the present invention
Method, nano gold mark is carried out in upper forwarding light particle surface by the method for chemical synthesis, obtains the upper forwarding of nano gold mark
Luminescent material, the material technically have fast in biomolecular labeling and detection, nano biological sensor and nano biological chip etc.
The visual advantage of speed simultaneously but also with it is highly sensitive, can qualitative, quantitative, stably, inexpensively, it is accurate the advantages that, present invention investment amount
Small, product cost is low, and technical advantage is completely obvious, and simple production process, is advantageous to mass production.
The invention has the advantages that：It is highly sensitive, can qualitative, quantitative, stably, inexpensively, accurately.It can be widely applied to tachysynthesis
The fields such as analysis, medical diagnosis on disease, drug screening, micro-imaging, genomics research, food and environment measuring, colloid gold particle
Take on a red color to purple and change, be advantageous to operator's Visual Observations Observations.
The content of the invention
A kind of up-conversion luminescent material of visual quick detection, it includes upper forwarding luminescent material and nanogold material granule,
It is characterized in that：Upper forwarding luminescent material and nanogold material granule strong bonded, nanogold material granule, which is uniformly wrapped in, to be turned
Change luminescent material surface；Either upper forwarding luminescent material and fluorescence quantum material granule strong bonded or upper forwarding luminescent material
With fluorescence quantum material granule strong bonded；And globulate is wrapped up by surface modification, then be connected with bioactive molecule,
Prepare by vision institute qualitative recognition, by the marking particle thing of instrumentation quantitative measurment.
The up-conversion luminescent material of visual quick detection, it includes upper forwarding luminescent material and nanogold material granule, or
Upper forwarding luminescent material and perovskite fluorescence quantum material granule, or upper forwarding luminescent material and carbon fluorescence quantum material
Grain.By upper forwarding luminescent material and nanogold material granule, perovskite fluorescence quantum material granule or carbon fluorescence quantum material
Particle strong bonded, then be connected with bioactive molecule, using nitrocellulose filter as carrier, nanogold material granule is wrapped up
Up-conversion luminescent material particle, the up-conversion luminescent material particle or carbon fluorescence volume of perovskite fluorescence quantum material granule parcel
The up-conversion luminescent material particle insertion of son point material granule parcel therebetween, using the capillary action of microporous barrier, is added dropwise
The liquid of film bar another end slowly to other end bleeding, is combined by antigen-antibody, drives luminescent material grains migration, Visual Observations Observations
Qualitative red color is presented in nanogold, and qualitative yellow color, carbon fluorescence quantum material is presented in perovskite fluorescence quantum material granule
Expect that qualitative reddish black color or orange-yellow is presented in particle.Prepare it is by vision institute qualitative recognition, by instrumentation quantitative measurment
Marking particle thing.
Nanogold colloid in the present invention is prepared with silication nucleocapsid knot with upper forwarding luminescent material by sol-gel process
Structure polymer, upper forwarding luminescent material is distributed in fresh ultra-pure water the constant temperature in water-bath and stirred, nanogold is added drop-wise to molten
Stir, be aged in liquid, washing, dry after obtain having spherical nucleocapsid surface parcel nanogold particle upper conversion hair
Luminescent material.Nanogold material in the present invention is to prepare nanogold colloid by reducing agent of trisodium citrate, and gold chloride is water-soluble
Liquid prepares nanogold particle with trisodium citrate as heating and stirring in oil bath in round-bottomed flask；Aqueous solution of chloraurate is
It is dissolved in by high-purity chlorauride in ultra-pure water.
The synthetic method of upper forwarding luminescent material in the present invention is with YCl3,YbCl3,ErCl3And TmCl3Anhydrous chemical combination
Thing is raw material, is then dissolved by heating using octadecylene and oleic acid as solvent；Separately take NaOH and NH4F is using absolute methanol as stirring solvent
Dissolving；In N2Under protection, heating is reacted, and the isothermal reaction time is that room temperature centrifugation is cooled to after 1 hour, cleaning, finally
Dried in vacuum drying chamber, that is, obtain required ball shaped nano up-conversion luminescent material.
In the present invention using nitrocellulose filter as carrier, nanogold material granule parcel up-conversion luminescent material particle
Therebetween, using the capillary action of microporous barrier, the liquid in film bar another end is added dropwise slowly to other end bleeding, by anti-in insertion
Original antibody combines, and drives luminescent material grains migration, and Visual Observations Observations nanogold is presented qualitative red color, reuses instrumentation
Light is forwarded in quantitative measurment.
Upper forwarding luminescent material and perovskite fluorescence quantum material granule in the present invention, it is characterised in that：Upper forwarding light
Material and fluorescence quantum material granule strong bonded, and wrapped up by surface modification, then be connected with antigen-antibody, prepare
By vision identify qualitatively, quantitative biological diagnosis reagent marking particle thing is measured by instrumentation.Calcium titanium in the present invention
Ore deposit fluorescence quantum material is using bromination methylamine as presoma, using hexamethylene as solvent, is prepared using lead iodide as matrix.
Nitrocellulose filter in the present invention is carrier, the up-conversion luminescent material particle of perovskite fluorescence quantum material granule parcel
Therebetween, using the capillary action of microporous barrier, the liquid in film bar another end is added dropwise slowly to other end bleeding, by anti-in insertion
Original antibody combines, and drives luminescent material grains migration, and qualitative yellow face is presented in Visual Observations Observations perovskite fluorescence quantum material granule
Color, reuse and forward light in instrumentation quantitative measurment.
Upper forwarding luminescent material and carbon fluorescence quantum material granule in the present invention, it is characterised in that：Upper forwarding luminescent material
With fluorescence quantum material granule strong bonded, and wrapped up by surface modification, then be connected with antigen-antibody, prepare by regarding
Feel identify qualitatively, quantitative biological diagnosis reagent marking particle thing is measured by instrumentation.Carbon fluorescent quantum in the present invention
Point material is using ascorbic acid as carbon source, and the concentration of aqueous ascorbic acid is 5%, micro- with a step using PEG-200 as presoma
Ripple method prepares carbon fluorescence quantum material.Nitrocellulose filter in the present invention is carrier, carbon fluorescence quantum material granule bag
Therebetween, using the capillary action of microporous barrier, the liquid in film bar another end is added dropwise in the up-conversion luminescent material particle insertion wrapped up in
Slowly to other end bleeding, combined by antigen-antibody, drive luminescent material grains migration, Visual Observations Observations carbon fluorescence quantum material
Expect that qualitative reddish black color or orange-yellow is presented in particle, reuse and forward light in instrumentation quantitative measurment.
Specific implementation method
A kind of up-conversion luminescent material of visual quick detection, it includes upper forwarding luminescent material and nanogold material granule,
It is characterized in that：Upper forwarding luminescent material and nanogold material granule strong bonded, nanogold material granule, which is uniformly wrapped in, to be turned
Luminescent material surface is changed, and globulate is wrapped up by surface modification, then is connected with bioactive molecule, is prepared by vision institute
Qualitative recognition, marking particle thing by instrumentation quantitative measurment.The synthetic method of upper forwarding luminescent material in the present invention is
With YCl3,YbCl3,ErCl3And TmCl3Anhydrous compound be placed in three-necked flask for raw material, then using octadecylene and oleic acid as
Solvent dissolves by heating, and it is 160 to dissolve by heating temperatureoC；Separately take NaOH and NH4F is placed in single-necked flask, using absolute methanol as solvent
Stirring and dissolving；Then methanol solution is added in three-necked flask, in N2Under protection, heating is reacted, the temperature of heating response
Spend for 300oC, with 20-40oC is that gradient is heated, and each mass ratio participated in needed for reactive material is YCl3：YbCl3：
ErCl3：TmCl3：NaOH：NH4F=30：10:5:1:15:10；The isothermal reaction time is that room temperature centrifugation is cooled to after 1 hour, clearly
Wash, most after being dried in vacuum drying chamber, that is, obtain required ball shaped nano up-conversion luminescent material.
Nanogold colloid in the present invention is prepared with silication nucleocapsid knot with upper forwarding luminescent material by sol-gel process
Structure polymer, upper forwarding luminescent material is distributed in fresh ultra-pure water the constant temperature in water-bath and stirred, nanogold is added drop-wise to molten
In liquid stir, be aged, washing, dry after i.e. obtain the nanogold particle up-conversion luminescent material with spherical nucleocapsid.This
Nanogold material is to prepare gold colloid by reducing agent of trisodium citrate in invention, and aqueous solution of chloraurate is molten by high-purity chlorauride
For solution in ultra-pure water, the concentration of aqueous solution of chloraurate is 0.01%, and the concentration of trisodium citrate is 1%, by aqueous solution of chloraurate with
Trisodium citrate prepares nanogold particle as heating and stirring in oil bath in round-bottomed flask；The temperature control of oil bath reaction
For 90 ± 5oWithin C, the time of isothermal reaction is 30 minutes.
In the present invention using nitrocellulose filter as carrier, nanogold material granule parcel up-conversion luminescent material particle
Therebetween, using the capillary action of microporous barrier, the liquid in film bar another end is added dropwise slowly to other end bleeding, by anti-in insertion
Original antibody combines, and drives luminescent material grains migration, and Visual Observations Observations nanogold is presented qualitative red color, reuses instrumentation
Light is forwarded in quantitative measurment.Nitrocellulose filter in the present invention is carrier, perovskite fluorescence quantum material granule parcel
Up-conversion luminescent material particle is embedded in therebetween, using the capillary action of microporous barrier, be added dropwise film bar another end liquid slowly
To other end bleeding, combined by antigen-antibody, drive luminescent material grains migration, Visual Observations Observations perovskite fluorescence quantum material
Expect that qualitative yellow color is presented in particle, reuse and forward light in instrumentation quantitative measurment.Nitrocellulose filter in the present invention is
Carrier, the up-conversion luminescent material particle insertion of carbon fluorescence quantum material granule parcel utilize the blood capillary of microporous barrier therebetween
Pipe acts on, and the liquid in film bar another end is added dropwise slowly to other end bleeding, is combined by antigen-antibody, drives luminescent material grains
Migration, Visual Observations Observations carbon fluorescence quantum material granule are presented qualitative reddish black color or orange-yellow, reuse instrumentation and determine
Light is forwarded on measurement.
Nanogold colloid in the present invention, perovskite fluorescence quantum material or carbon fluorescence quantum material and upper forwarding finish
Material is prepared out with silication core shell structure polymer by sol-gel process method, and upper forwarding luminescent material is distributed into fresh surpass
Constant temperature stirs in water-bath in pure water, and the dispersion liquid concentration control of upper forwarding luminescent material is 15% -20%, nanogold colloid, calcium titanium
The dispersion liquid concentration of ore deposit fluorescence quantum material or carbon fluorescence quantum material is controlled 0.5% -2%, by nanogold colloid, calcium
Titanium ore fluorescence quantum material or carbon fluorescence quantum material, which are added drop-wise in solution, to be stirred, is aged, washing, being had after drying
There is the up-conversion luminescent material of spherical nucleocapsid knot.Bath temperature is 50 ± 5oC, reaction time are 2 hours, and digestion time is 1 small
When, drying temperature 80oC。
Upper forwarding luminescent material and perovskite fluorescence quantum material granule in the present invention, it is characterised in that：Upper forwarding light
Material and fluorescence quantum material granule strong bonded, and wrapped up by surface modification, then be connected with antigen-antibody, prepare
By vision identify qualitatively, quantitative biological diagnosis reagent marking particle thing is measured by instrumentation.Calcium titanium in the present invention
Ore deposit fluorescence quantum material is using bromination methylamine as presoma, using hexamethylene as solvent, is prepared using lead iodide as matrix.
Upper forwarding luminescent material and carbon fluorescence quantum material granule in the present invention, it is characterised in that：Upper forwarding luminescent material
With fluorescence quantum material granule strong bonded, and wrapped up by surface modification, then be connected with antigen-antibody, prepare by regarding
Feel identify qualitatively, quantitative biological diagnosis reagent marking particle thing is measured by instrumentation.Carbon fluorescent quantum in the present invention
Point material is using ascorbic acid as carbon source, and the concentration of aqueous ascorbic acid is 5%, micro- with a step using PEG-200 as presoma
Ripple method prepares carbon fluorescence quantum material.
Advantage of the present invention
1st, quick visualization：Change because colloid gold particle takes on a red color to purple, when nano Au particle and different antibodies phase
After combining to form stable compound, the light absorbs of certain wavelength can be had an impact, the meeting under white light or monochromatic irradiation
Certain specific color is presented, it is labelled to give the different tissues cell of antibody binding, is advantageous to directly observe.
2nd, it is highly sensitive, can qualitative, quantitative it is stable, accurate：On turn luminescence technology（UPT）It can be widely applied to tachysynthesis point
The fields such as analysis, medical diagnosis on disease, drug screening, genomics research, food and environment measuring.
3rd, simple production process, mass production is advantageous to：The present invention is by by nanogold colloid and upper forwarding luminescent material
Pass through Sol-Gel（Sol-gel process）Method is prepared out with core shell structure polymer, simple production process, is advantageous to mass
Production.
Specific embodiment
Embodiment 1
YCl is weighed respectively3：6.013g；YbCl3：2.006g；ErCl3：1.011g；TmCl3：0.201g is placed in three-necked flask
It is interior, it is then respectively adding 100ml oleic acid 200ml octadecylenes；Add condensing reflux, react whole logical nitrogen protection, then start to add
Heat of solution, initial temperature are set to 40oC, then with 20oC is that gradient is warming up to 160 successivelyoConstant temperature is stirred to grain dissolution after C, most
After be cooled to room temperature.Separately take NaOH：3.012g；NH4F：2.012g is placed in single-necked flask, adds 100ml absolute methanols, stirring
Dissolving.
Then methanol solution is slowly dropped in three-necked flask with 2ml/min speed, and be stirred continuously, is completely dispersed
After set temperature as 200oC Evaporation of methanol 40min, then with 20oC is that gradient is warming up to 300 successivelyoConstant temperature stirring reaction 1 is small after C
When, solution is cooled to after room temperature after terminating and carries out centrifuge washing with absolute ethyl alcohol and hexamethylene mixed solution by reaction, is washed till
Grain is white, is finally placed in 80oRequired upper forwarding luminescent material is obtained after being dried in C vacuum drying chambers.
Take 0.1% aqueous solution of chloraurate 10ml in flask and add 90ml ultra-pure waters dilution, then add 1% lemon
Three sodium solution 30ml of acid are added in flask and agitating and heating reaction, and the temperature control of reaction is 90oWithin C, isothermal reaction when
Between be 30min, reaction terminate after take out cooling after can obtain nano Au colloid body.
Take 1mmol bromination methylamines respectively, 1mmol lead iodides, 0.2ml normal octanes, 5ml oleic acid, 50mlTHF is placed in beaker
In, then carry out supersound process 30min, as persursor material；Separately 50ml hexamethylenes are taken to take 5ml forerunner in being stirred in flask
Body is added in hexamethylene and is stirred continuously with 0.1ml/min speed, and solution is carried out into rotation after the completion of reaction is evaporated, finally
Drying is to perovskite fluorescence quantum material.5.0g ascorbic acid is taken in beaker, 100ml ultra-pure waters is added and then stirs
20min, then add 100mlPEG-200 and continue to stir 30min, take out washing after last microwave 30min, drying can obtain
To carbon fluorescence quantum material.
Embodiment 2
Weigh forwarding luminescent material 5g to be placed in beaker, 30ml ultra-pure waters are added, 50oConstant temperature stirs in C water-baths, separately
0.5g nanogold colloids are taken in beaker, 100ml ultra-pure waters is added, is dispersed with stirring, then by nano Au colloid liquid solution with 2ml/
Min speed, which is added drop-wise to, to be turned in luminescent solution and is stirred continuously, and is added dropwise to complete rear constant temperature stirring reaction 2 hours, is then taken out
Still aging 1 hour, finally pour out supernatant and be washed to neutrality after in 80 with ultra-pure wateroDried in C vacuum drying chambers.
Material after drying is taken out and is placed in beaker, 50ml ultra-pure waters are added, 80oConstant temperature stirs in C water-baths, takes
5% sodium silicate aqueous solution 50ml is added drop-wise in solution and is stirred continuously with 2ml/min speed, and isothermal reaction is taken out quiet after 1 hour
Ageing is put, supernatant is finally poured out and is washed to neutrality after in 80 with ultra-pure wateroDried in C vacuum drying chambers.
Embodiment 3
Weigh forwarding luminescent material 10g to be placed in beaker, 100ml ultra-pure waters are added, 50oConstant temperature stirs in C water-baths,
1.0g perovskite fluorescence quantum materials separately are taken in beaker, are added 100ml ultra-pure waters, are dispersed with stirring, it is then that perovskite is glimmering
Light quanta point material solution is added drop-wise to 2ml/min speed to be turned in luminescent solution and is stirred continuously, and is added dropwise to complete rear constant temperature
Stirring reaction 2 hours, then take out still aging 1 hour, finally pour out supernatant with ultra-pure water be washed to it is neutral after in
80oDried in C vacuum drying chambers.
Material after drying is taken out and is placed in beaker, 100ml ultra-pure waters are added, 80oConstant temperature stirs in C water-baths,
5% sodium silicate aqueous solution 100ml is taken to be added drop-wise in solution and be stirred continuously with 2ml/min speed, isothermal reaction takes after 1 hour
Go out it is still aging, finally pour out supernatant with ultra-pure water be washed to neutrality after in 80oDried in C vacuum drying chambers.
Embodiment 4
Weigh forwarding luminescent material 20g to be placed in beaker, 300ml ultra-pure waters are added, 50oConstant temperature stirs in C water-baths,
1.5g carbon fluorescence quantum materials separately are taken in beaker, are added 100ml ultra-pure waters, are dispersed with stirring, then by carbon fluorescence volume
Son point material solution is added drop-wise to 2ml/min speed to be turned in luminescent solution and is stirred continuously, and is added dropwise to complete rear constant temperature stirring
Reaction 2 hours, then takes out still aging 1 hour, finally pours out supernatant and is washed to neutrality after in 80 with ultra-pure wateroC is true
Dried in empty drying box.
Material after drying is taken out and is placed in beaker, 300ml ultra-pure waters are added, 80oConstant temperature stirs in C water-baths,
5% sodium silicate aqueous solution 300ml is taken to be added drop-wise in solution and be stirred continuously with 2ml/min speed, isothermal reaction takes after 1 hour
Go out it is still aging, finally pour out supernatant with ultra-pure water be washed to neutrality after in 80oDried in C vacuum drying chambers.
Make above for preferably embodiment of the invention after illustrating, to one skilled in the art should
It is realized that without departing from the spirit and scope of the present invention, any changes and improvements made for the present invention all exist
In the scope of the present invention.
Claims (9)
1. a kind of up-conversion luminescent material of visual quick detection, it includes upper forwarding luminescent material and nanogold or quanta point material
Particle, it is characterised in that：Upper forwarding luminescent material is uniformly wrapped in nanogold material granule strong bonded, nanogold material granule
Up-conversion luminescent material surface；Or upper forwarding luminescent material firmly wraps up combination with fluorescence quantum material granule；And by surface
Trim wraps up globulate, then is connected with bioactive molecule, prepares by vision institute qualitative recognition, is determined by instrumentation
The marking particle thing of measurement.
2. a kind of up-conversion luminescent material of visual quick detection according to claim 1, by nanogold colloid with upper turn
Luminescent material is prepared with silication core shell structure polymer by sol-gel process, upper forwarding luminescent material is distributed to fresh
Ultra-pure water in water-bath constant temperature stir, by nanogold be added drop-wise in solution stir, be aged, washing, dry after had
There is the nanogold particle up-conversion luminescent material of spherical nucleocapsid.
3. a kind of up-conversion luminescent material of visual quick detection according to claim 1, nanogold material is with lemon
Sour trisodium is that reducing agent prepares nanogold colloid, by aqueous solution of chloraurate and trisodium citrate as in round-bottomed flask in oil bath
Heat and stir to prepare nanogold particle；Aqueous solution of chloraurate is to be dissolved in by high-purity chlorauride in ultra-pure water.
4. a kind of up-conversion luminescent material of visual quick detection according to claim 1, the synthesis of upper forwarding luminescent material
Method is with YCl3,YbCl3,ErCl3And TmCl3Anhydrous compound be raw material, then heated by solvent of octadecylene and oleic acid
Dissolving；Separately take NaOH and NH4F dissolves by stirring solvent of absolute methanol；Then by methanol solution add used in three mouthfuls burning
In bottle, in N2Under protection, heating is reacted, and is cooled to room temperature centrifugation after reacting certain time, cleaning, is most done after vacuum
Dried in dry case, that is, obtain required ball shaped nano up-conversion luminescent material.
A kind of 5. up-conversion luminescent material of visual quick detection according to claim 1, using nitrocellulose filter as load
Body, the up-conversion luminescent material particle insertion of nanogold material granule parcel utilize the capillary action of microporous barrier, drop therebetween
The liquid of film bar another end is added in slowly to other end bleeding, is combined by antigen-antibody, drives luminescent material grains migration, vision
Observe nanogold and qualitative red color is presented, reuse and forward light in instrumentation quantitative measurment.
6. a kind of up-conversion luminescent material of visual quick detection according to claim 1, it includes upper forwarding luminescent material
With perovskite fluorescence quantum material granule, it is characterised in that：Upper forwarding luminescent material is firmly tied with fluorescence quantum material granule
Close, and wrapped up by surface modification, then be connected with antigen-antibody, prepare and identified by vision qualitatively, by instrumentation
Measure quantitative biological diagnosis reagent marking particle thing.
7. a kind of up-conversion luminescent material of visual quick detection according to claim 1, it includes upper forwarding luminescent material
With carbon fluorescence quantum material granule, it is characterised in that：Upper forwarding luminescent material and fluorescence quantum material granule strong bonded, and
Wrapped up by surface modification, then be connected with antigen-antibody, prepare and identified qualitatively, by instrumentation measurement calmly by vision
The biological diagnosis reagent marking particle thing of amount.
A kind of 8. up-conversion luminescent material of visual quick detection according to claim 1, using nitrocellulose filter as load
Body, the up-conversion luminescent material particle insertion of perovskite fluorescence quantum material granule parcel utilize the capillary of microporous barrier therebetween
Blood vessel function, the liquid in film bar another end is added dropwise slowly to other end bleeding, is combined by antigen-antibody, drive luminescent material
Grain migration, Visual Observations Observations perovskite fluorescence quantum material granule are presented qualitative yellow color, reuse instrumentation quantitative measurment
Upper forwarding light.
A kind of 9. up-conversion luminescent material of visual quick detection according to claim 1, using nitrocellulose filter as load
Body, the up-conversion luminescent material particle insertion of carbon fluorescence quantum material granule parcel utilize the capillary of microporous barrier therebetween
Effect, is added dropwise the liquid in film bar another end slowly to other end bleeding, is combined by antigen-antibody, drives luminescent material grains to move
Move, qualitative reddish black color or orange-yellow is presented in Visual Observations Observations carbon fluorescence quantum material granule, reuses instrumentation and quantifies
Light is forwarded in measurement.
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