CN102874785B - Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method - Google Patents
Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method Download PDFInfo
- Publication number
- CN102874785B CN102874785B CN201210387362.1A CN201210387362A CN102874785B CN 102874785 B CN102874785 B CN 102874785B CN 201210387362 A CN201210387362 A CN 201210387362A CN 102874785 B CN102874785 B CN 102874785B
- Authority
- CN
- China
- Prior art keywords
- zirconium phosphate
- aie
- ultrasonic
- ion exchange
- zrp
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of preparation of an inorganic and organic hybrid material with a fluorescence property and particularly relates to an ion exchange method for preparing an aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material. Cation groups containing water-soluble AIE molecules are intercalated into the material by an ion exchange intercalation mode by using zirconium phosphate with a laminar structure as a framework element and organic amine as a pre-swelling agent, so that the inorganic and organic hybrid material with the strong fluorescence can be obtained. The method is suitable for various laminar zirconium phosphate materials which contain the AIE water soluble molecules of the cation groups and have the anion framework structures. The interlamellar spacing and the luminance of the zirconium phosphate can be effectively controlled by changing the varieties and the adding amounts of the AIE molecules or the pre-swelling agents, so that the material can be widely applied to the fields of medicine delivery, bioimaging, explosive detection and the like.
Description
Technical field
The invention belongs to the Inorganic-organic Hybrid Material preparing technical field with photoluminescent property, be specifically related to a kind of layered zirconium phosphate material that adopts ion-exchange techniques to prepare aggregation inducing luminophore (AIE) functionalization, make advantage that the material that obtains not only had an inorganic layer plate structure simultaneously but also there is the special photoluminescent property of AIE molecule, thereby represented good application prospect in fields such as drug delivery, bio-imaging, explosive detection.
Technical background
Inorganic-organic Hybrid Material has been widely used in the fields such as catalysis, separation, organic and inorganic host-guest chemistry, functional materials as a kind of matrix material of novelty.Wherein the inorganic materials of organic fluorescence molecular modification has represented good character at aspects such as cell imaging, drug delivery, biological detection.But traditional fluorescence molecule has stronger fluorescence as rhodamine, fluorescein etc. in dilute solution, and there is the even phenomenon of cancellation (aggregation caused quenching of fluorescent weakening at immobilization or while assembling, ACQ), this has limited the further application of this type of functional material to a certain extent.
Calendar year 2001, it is found that the special fluorescence molecule of a class, and it is not luminous in the time of solution state, and in the time of solid-state or state of aggregation, present stronger fluorescence, it is luminous (aggregation induced emission, the AIE) phenomenon of aggregation inducing (Chem.Commun.2001,1740).Wherein, Internal Rotations of Molecules is limited is the major cause that Enhancement of Fluorescence occurs.Since this quasi-molecule is in the news, represent good using value in fields such as detection, cell imaging and organic photoelectric diodes.
Zirconium phosphate (ZrP) and derivative thereof are the layered inorganic materials that a class has cation exchange capacity (CEC), have the advantage such as thermostability and chemical stability that composition is single, synthetic simply, higher, are the good matrixes of preparing Pillared Comepound.In previous work, our mode by rear grafting by immobilized AIE molecule in mesoporous SBA-15 material (Chem.Commun.2011,47,11077-11079; Chem.Commun.2012,48,7167-7169), make material aspect drug delivery and explosive detection, represent good character.At present synthetic about the pillared zirconium phosphate material of AIE molecule, does not also have relevant report.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of simple and fast, prepare the layered zirconium phosphate material of AIE radical functino by the method for ion-exchange.It is to have the zirconium phosphate of laminate structure as skeleton primitive, adopting organic amine is pre-support agent, mode by ion-exchange intercalation is inserted into the cation group that contains water-soluble AIE molecule in material, thereby obtains having the Inorganic-organic Hybrid Material compared with hyperfluorescenceZeng Yongminggaoyingguang.
The layered zirconium phosphate material that the method is applicable to all kinds of AIE water soluble molecules that contain cation group and has anion frame structure.By changing AIE molecule or supportting in advance the kind of agent and add-on can be controlled the luminosity such as interlamellar spacing and fluorescence color and intensity of zirconium phosphate effectively, make material in drug delivery, bio-imaging, the fields such as explosive detection have good application prospect.
The inventive method step is as follows:
(1) be dispersed in 10～20mL deionized water ultrasonic 0.4～1.0g ZrP, then add 0.07～0.3g organic amine, continue ultrasonic 0.3～1h; After centrifugation (rotating speed is 8000～11000rpm, and the time is 15～30min), repeatedly wash solid product with deionized water, be then fully dried and obtain white presoma;
(2) weigh the presoma that obtains of 30～60mg step (1), ultrasonic it is distributed in 10～20mL deionized water completely, obtain the suspension liquid of presoma; Water-soluble 10～107mg AIE molecule is joined in 30～50mL deionized water, ultrasonic it is dissolved completely, then this solution is joined in presoma suspension liquid, under 10～50 ℃ of conditions, fully mix 0.5～36h, obtain uniform faint yellow suspension liquid;
(3) (rotating speed is 8000～11000rpm by centrifugal the suspension liquid of step (2), time is 15～30min), and repeatedly wash solid product with deionized water, to wash away the AIE molecule of not participating in reaction, obtain the layered zirconium phosphate material of AIE radical functino after dry.
Zirconium phosphate described in above-mentioned steps is the one in α-ZrP, θ-ZrP, γ-ZrP; Organic amine is the one in methylamine, propylamine, butylamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH.Water miscible AIE molecule is the one having in the quaternary ammonium salt of following general structure, the integer that wherein n is 2～5.
As optimization experiment scope of the present invention, well-mixed mode be ultrasonic, stir, vibration in one.
The mode of first passage ion-exchange of the present invention is prepared the layered zirconium phosphate material of AIE radical functino, and it has following advantage:
1. the ion exchange method that the present invention proposes is prepared the layered zirconium phosphate material of AIE radical functino, without using more expensive tensio-active agent to zirconium phosphate material pore-creating, as cetyl trimethylammonium bromide, P123, F127 etc., and the synthetic method of raw material zirconium phosphate is simple, water dispersible good, Stability Analysis of Structures, be easy to regulate size and the interlamellar spacing of material.
2. the ion exchange method that the present invention proposes is prepared the layered zirconium phosphate material of AIE radical functino, and the AIE molecule of employing is cheap, be easy to preparation, reduced production cost.
3. the ion exchange method that the present invention proposes is prepared the layered zirconium phosphate material of AIE radical functino, and working method is simple, and generated time is shorter, has reduced the process of removed template method.Be easy to regulate amount and the kind of AIE molecule in interposed layer simultaneously, thereby change fluorescence intensity and the luminous peak position of matrix material.
Accompanying drawing explanation:
Fig. 1: be the XRD spectra of the embodiment of the present invention 1 raw material α-ZrP;
Fig. 2: be the scanning electron microscope picture of the embodiment of the present invention 1 raw material α-ZrP;
Fig. 3: be the XRD spectra of α-ZrP material after the embodiment of the present invention 1 butylamine reaming;
Fig. 4: be the scanning electron microscope picture of α-ZrP material after the embodiment of the present invention 1 butylamine reaming;
Fig. 5: the XRD spectra of α-ZrP material after the TPEN intercalation obtaining for the embodiment of the present invention 1;
Fig. 6: the scanning electron microscope picture of α-ZrP material after the TPEN intercalation obtaining for the embodiment of the present invention 1;
Fig. 7: the transmission electron microscope picture of α-ZrP material after the TPEN intercalation obtaining for the embodiment of the present invention 1;
Fig. 8: the nitrogen adsorption desorption curve of α-ZrP material after the TPEN intercalation obtaining for the embodiment of the present invention 1;
Fig. 9: the fluorogram of α-ZrP material in the aqueous solution after the TPEN intercalation obtaining for the embodiment of the present invention 1.
As shown in Fig. 1,3,5: first peak position of raw material α-ZrP appears at 2 θ=11.6 °, show that its interlamellar spacing is
when adopt butylamine pillared as pre-support agent after, first peak position appears at the interlamellar spacing that 2 θ=5.9 ° show pillared rear material and is about 1.5nm.After water miscible TPEN molecule inserts in pillared material, find that first diffraction peak of material continues to move 2 θ=4.3 ° to Small angle, show that the interlamellar spacing of α-ZrP material is extended to 2.1nm after TPEN intercalation.
As shown in Fig. 2,4,6: α-ZrP its pattern before and after intercalation remains unchanged substantially, is still sheet hexagonal structure, show that intercalation process is to the not larger change of the basic pattern of material.
As shown in Figure 7: α-ZrP material of TPEN intercalation has obvious band shape duct, be about 2.1nm by measuring its interlamellar spacing, the result that this and XRD obtain is basically identical.
As shown in Figure 8: show that by nitrogen adsorption desorption test the BET specific surface area of α-ZrP material is 51.9m after TPEN intercalation
2/ g.(deleting former figure nine)
As shown in Figure 9: α-ZrP material of TPEN intercalation evenly spreads to after the aqueous solution, under 360nm ultraviolet excitation, has stronger fluorescence emission peak at 473nm place, show the material transmitting blue light after intercalation.This is to have stronger ionic linkage effect due to water miscible AIE molecule TPEN and α-ZrP, has suppressed the high speed rotating of TPEN molecule, thereby produces stronger fluorescence.
Embodiment
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited to this, can not be interpreted as limiting the scope of the invention.
By synthetic α-ZrP(New J.Chem.2007,31,39-43) centrifugal, ultrasonic dispersion repeatedly, fully washing is to the pH value of its solution between 5～7, and then lyophilize obtains white solid powder, for subsequent use.
Embodiment 1:
By the about 400nm of 0.5g α-ZrP(particle diameter) ultrasonic being scattered in 15mL deionized water, it is fully uniformly dispersed, then add the butylamine of 0.07g, continue after ultrasonic 0.5h, centrifugation (10000rpm, 20min), to neutral, after lyophilize, obtain solid precursors α-ZrPBA with a large amount of deionized water wash.
Weigh 50mg α-ZrPBA, ultrasonic evenly spreading in the 17mL aqueous solution; Then 57.6mgTPEN is added in 33mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of α-ZrP presoma, under 40 ℃ of conditions, continue to stir 24h, obtain uniform faint yellow suspension liquid.With supercentrifuge centrifugal (10000rpm, 20min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 55mg.
Embodiment 2:
Weigh the α-ZrPBA in 35mg embodiment 1, ultrasonic being distributed in the 10mL aqueous solution, adds the TPEN of 10mg in 30mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of α-ZrPBA, under 40 ℃ of conditions, continue to stir 24h, obtain uniform faint yellow suspension liquid.Centrifugation (10000rpm, 20min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 36mg.
Embodiment 3:
Weigh the α-ZrPBA in 50mg embodiment 1, ultrasonic being distributed in the 17mL aqueous solution, adds the TPEN of 90mg in 33mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of α-ZrPBA, under 40 ℃ of conditions, continue to stir 24h, obtain uniform faint yellow suspension liquid.Centrifugation (10000rpm, 20min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 56mg.
Embodiment 4:
Weigh the α-ZrPBA in 50mg embodiment 1, ultrasonic being distributed in the 17mL aqueous solution, by the TPEO(n=2 of 62.4mg) add in 33mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEO is added in the suspension liquid of α-ZrPBA, under 40 ℃ of conditions, continue to stir 36h, obtain uniform faint yellow suspension liquid.Centrifugation (8000rpm, 30min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEO molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 52mg.
Embodiment 5:
400nm by 1g α-ZrP(particle diameter) in the ultrasonic 20mL of being scattered in deionized water, it is uniformly dispersed, then add the butylamine of 0.3g, continue after ultrasonic 0.5h, centrifugation (11000rpm, 15min), to neutral, after lyophilize, obtain solid precursors α-ZrP2BA with a large amount of deionized water wash.
Weigh 60mg α-ZrP2BA, ultrasonic being distributed in the 10mL aqueous solution, then adds 107mg TPEN in 50mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of α-ZrP2BA, under 10 ℃ of conditions, continue to stir 24h, obtain uniform faint yellow suspension liquid.Centrifugation (11000rpm, 15min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 67mg.
Embodiment 6:
Weigh the α-ZrP2BA in 50mg embodiment 5, ultrasonic being distributed in the 17mL aqueous solution, then adds 57.6mg TPEN in 33mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of α-ZrP2BA, room temperature continues ultrasonic 0.5h, obtains uniform faint yellow suspension liquid.Centrifugation (11000rpm, 15min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 52mg.
Embodiment 7:
150nm by 0.5g α-ZrP(particle diameter) in the ultrasonic 10mL of being scattered in deionized water, it is fully uniformly dispersed, then add the butylamine of 0.14g, continue after ultrasonic 0.3h, centrifugation (11000rpm, 20min), to neutral, after lyophilize, obtain solid precursors nano-α-ZrPBA with a large amount of deionized water wash.
Weigh 50mg nano-α-ZrPBA, ultrasonic being distributed in the 20mL aqueous solution, then adds 14.4mgTPEN in 30mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of nano-α-ZrPBA, under 50 ℃ of conditions, continue to stir 24h, obtain uniform faint yellow suspension liquid.Centrifugation (11000rpm, 20min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 51mg.
Embodiment 8:
400nm by 0.4g α-ZrP(particle diameter) in the ultrasonic 10mL of being scattered in deionized water, it is fully uniformly dispersed, then add the TBAH of 0.08g, continue after ultrasonic 1h, centrifugation (8000rpm, 30min), to neutral, after lyophilize, obtain solid precursors α-ZrPTBA with a large amount of deionized water wash.
Weigh 30mg α-ZrPTBA, ultrasonic being distributed in the 10mL aqueous solution; Then 34.6mg TPEN is added in 30mL deionized water, ultrasonic it is dissolved completely.The aqueous solution of TPEN is added in the suspension liquid of α-ZrPTBA, under 40 ℃ of conditions, continue to stir 36h, obtain uniform faint yellow suspension liquid.With supercentrifuge centrifugal (8000rpm, 30min), and repeatedly wash solid with a large amount of deionized waters, to wash away the TPEN molecule of not participating in reaction, then lyophilize, obtains the layered zirconium phosphate material of AIE radical functino, and quality is 33mg.
Claims (4)
1. ion exchange method is prepared the layered zirconium phosphate material of aggregation inducing luminophore functionalization, and its step is as follows:
(1) be dispersed in 10～20mL deionized water ultrasonic 0.4～1.0g ZrP, then add 0.07～0.3g organic amine, continue ultrasonic 0.3～1h; After centrifugation, repeatedly wash solid product with deionized water, be then fully dried and obtain white presoma;
(2) weigh the presoma that obtains of 30～60mg step (1), ultrasonic it is distributed in 10～20mL deionized water completely, obtain the suspension liquid of presoma; Water-soluble 10～107mg AIE molecule is joined in 30～50mL deionized water, ultrasonic it is dissolved completely, then this solution is joined in presoma suspension liquid, under 10～50 ℃ of conditions, fully mix 0.5～36h, obtain uniform faint yellow suspension liquid;
Wherein, water miscible AIE molecule is the one having in the quaternary ammonium salt of following general structure, the integer that wherein n is 2～5,
(3) by centrifugal the suspension liquid of step (2), and repeatedly wash solid product with deionized water, to wash away the AIE molecule of not participating in reaction, obtain the layered zirconium phosphate material of AIE radical functino after dry.
2. ion exchange method as claimed in claim 1 is prepared the layered zirconium phosphate material of aggregation inducing luminophore functionalization, it is characterized in that: zirconium phosphate is the one in α-ZrP, θ-ZrP, γ-ZrP.
3. ion exchange method as claimed in claim 1 is prepared the layered zirconium phosphate material of aggregation inducing luminophore functionalization, it is characterized in that: organic amine is the one in methylamine, propylamine, butylamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH.
4. ion exchange method as claimed in claim 1 is prepared the layered zirconium phosphate material of aggregation inducing luminophore functionalization, it is characterized in that: in step (2) fully hybrid mode be ultrasonic, stir, one in vibration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210387362.1A CN102874785B (en) | 2012-10-12 | 2012-10-12 | Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210387362.1A CN102874785B (en) | 2012-10-12 | 2012-10-12 | Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102874785A CN102874785A (en) | 2013-01-16 |
| CN102874785B true CN102874785B (en) | 2014-06-11 |
Family
ID=47476350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210387362.1A Expired - Fee Related CN102874785B (en) | 2012-10-12 | 2012-10-12 | Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102874785B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2910618A1 (en) | 2014-02-24 | 2015-08-26 | Centre National De La Recherche Scientifique | Luminescent hybrid nanomaterials with aggregation induced emission |
| CN107001927B (en) * | 2014-11-21 | 2019-09-17 | 香港科技大学 | For bacterium imaging, kill, the AIE illuminophore and its production method of photodynamic therapy and antibiotic-screening |
| CN105199384B (en) * | 2015-09-21 | 2017-10-27 | 四川天策聚材科技有限公司 | Fire-retardant benzoxazine nano composite material of transparent type and preparation method thereof |
| CN105368016B (en) * | 2015-11-30 | 2017-07-04 | 东华大学 | A kind of preparation method of PET organophosphors hydridization α ZrP composites |
| CN105369387B (en) * | 2015-11-30 | 2017-10-31 | 东华大学 | A kind of preparation method of PET organophosphors hydridization α ZrP complex fiber materials |
| CN106939163B (en) * | 2017-03-13 | 2019-04-09 | 吉林大学 | A kind of preparation method of the fluorescent functional organic clay of height water dispersible |
| CN106957650A (en) * | 2017-03-22 | 2017-07-18 | 深圳市华星光电技术有限公司 | A kind of preparation method for modifying quantum dot and modification quantum dot film |
| CN110760304A (en) * | 2019-10-27 | 2020-02-07 | 浙江理工大学 | Preparation method of tetra (hydroxyphenyl) zirconium porphyrin-AIE fluorescent molecule composite photosensitive sensing material |
| CN113716540B (en) * | 2021-08-25 | 2024-03-01 | 西安工业大学 | Preparation method of nano zirconium phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214947A (en) * | 2008-01-18 | 2008-07-09 | 中国科学技术大学 | Method for preparing carbon nano-tube by catalyzing and carbonizing polymer and /or asphalt |
| CN101926358A (en) * | 2009-12-18 | 2010-12-29 | 暨南大学 | Quaternary phosphonium salt pillared layered zirconium phosphate material, and preparation method and application thereof |
| CN102897737A (en) * | 2012-09-24 | 2013-01-30 | 常州大学 | Method for preparation of pillared zirconium phosphate material by self-assembly technology |
-
2012
- 2012-10-12 CN CN201210387362.1A patent/CN102874785B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214947A (en) * | 2008-01-18 | 2008-07-09 | 中国科学技术大学 | Method for preparing carbon nano-tube by catalyzing and carbonizing polymer and /or asphalt |
| CN101926358A (en) * | 2009-12-18 | 2010-12-29 | 暨南大学 | Quaternary phosphonium salt pillared layered zirconium phosphate material, and preparation method and application thereof |
| CN102897737A (en) * | 2012-09-24 | 2013-01-30 | 常州大学 | Method for preparation of pillared zirconium phosphate material by self-assembly technology |
Non-Patent Citations (4)
| Title |
|---|
| Challa V. Kumar等.Supramolecular Assemblies of Tris(2,2"-bipyridine)ruthenium(II) Bound to Hydrophobically Modified a-Zirconium Phosphate: Photophysical Studies.《J. Phys. Chem.》.1995,第99卷(第49期), |
| Supramolecular Assemblies of Tris(2,2"-bipyridine)ruthenium(II) Bound to Hydrophobically Modified a-Zirconium Phosphate: Photophysical Studies;Challa V. Kumar等;《J. Phys. Chem.》;19951231;第99卷(第49期);第17633页的实验部分 * |
| 张双等.聚集诱导发光机理研究.《化学进展》.2011,第23卷(第4期),623-636. |
| 聚集诱导发光机理研究;张双等;《化学进展》;20110430;第23卷(第4期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102874785A (en) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102874785B (en) | Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method | |
| Xu et al. | A smartphone-integrated method for visual detection of tetracycline | |
| Zhang et al. | CH3NH3PbBr3 perovskite nanocrystals encapsulated in lanthanide metal–organic frameworks as a photoluminescence converter for anti-counterfeiting | |
| Liu et al. | Metal–organic framework-based fluorescent sensing of tetracycline-type antibiotics applicable to environmental and food analysis | |
| Li et al. | A 3D hierarchical dual-metal–organic framework heterostructure up-regulating the pre-concentration effect for ultrasensitive fluorescence detection of tetracycline antibiotics | |
| CN103638944B (en) | A kind of magnetic coupling catalyst A g/HNTs/Fe 3o 4preparation method | |
| CN105820585A (en) | Preparation of mesoporous molecular imprinting fluorescent probe and detection of tetracycline antibiotics by mesoporous molecular imprinting fluorescent probe | |
| DE102020132495B3 (en) | Particles composed of an organic polymer core, a first inorganic oxide shell containing a magnetic material, and a mesoporous second inorganic shell | |
| DE102020132480B3 (en) | Molecularly imprinted fluorescent polymers for direct detection of glyphosate, its degradation products and metabolites | |
| US12054404B2 (en) | Preparation method and application of clay/tannic acid/metal ion composite material for efficient adsorption of antibiotics | |
| Robby et al. | Recyclable metal nanoparticle-immobilized polymer dot on montmorillonite for alkaline phosphatase-based colorimetric sensor with photothermal ablation of Bacteria | |
| CN107771791A (en) | A kind of lignosulfonates mesoporous SiO 2 nanosphere and preparation method thereof | |
| CN104479679B (en) | A kind of NaYF4: Yb3+/ Er3+@Ag nano composite material and preparation method and application | |
| Wei et al. | Ionic liquid-sensitized molecularly imprinted polymers based on heteroatom co-doped quantum dots functionalized graphene for sensitive detection of λ-cyhalothrin | |
| CN105199710A (en) | Fluorescent mesoporous silica composite nanoparticles and preparing method thereof | |
| CN103205257A (en) | Novel synthesis method for multilayer protection hyperstable water-soluble single fluorescent quantum dot and fluorescent microsphere | |
| CN105642233A (en) | Method for preparing CMC/GO compound hydrogel microspheres by virtue of continuous method | |
| Wang et al. | Thiadiazole-functionalized metal-organic frameworks multifunction-architectonics for dual-target sensing of ethylamine and gossypol | |
| Zhou et al. | Tetracycline generated red luminescence based on a novel lanthanide functionalized layered double hydroxide nanoplatform | |
| CN105936669B (en) | One kind being based on the porous super-molecule assembling body and preparation method thereof of cucurbit [8] urea | |
| Wu et al. | Bimodal counterpropagating-responsive sensing material for the detection of histamine | |
| Zhu et al. | Efficient adsorption and photocatalytic degradation of dyes by AgI‐Bi2MoO6/Vermiculite composite under visible Light | |
| Qian et al. | Highly sensitive and selective novel core–shell molecularly imprinted polymer based on NaYF4: Yb 3+, Er 3+ upconversion fluorescent nanorods | |
| Chua et al. | Recent advances in aggregation-induced emission (AIE)-based chemosensors for the detection of organic small molecules | |
| Yue et al. | Fluorometric sensing of pH values using green-emitting black phosphorus quantum dots |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140611 Termination date: 20151012 |
|
| EXPY | Termination of patent right or utility model |