CN103666461A - Iridium complex organic fluorescent nanoparticles and preparation method thereof - Google Patents
Iridium complex organic fluorescent nanoparticles and preparation method thereof Download PDFInfo
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- CN103666461A CN103666461A CN201410005612.XA CN201410005612A CN103666461A CN 103666461 A CN103666461 A CN 103666461A CN 201410005612 A CN201410005612 A CN 201410005612A CN 103666461 A CN103666461 A CN 103666461A
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Abstract
The invention discloses a kind of iridium complex organic fluorescent nanoparticles and a preparation method thereof. The structural formula of the iridium complex organic fluorescent nanoparticles is R2Ir(Mu-Cl)2R2@PEO-b-P4VP, wherein R2Ir(Mu-Cl)2R2 is dichloro-bridged, R is dfppy, ppy or pq, PEO-b-P4VP is polyglycol-b-poly(4-vinylpyridine), the iridium complex organic fluorescent nanoparticles have a spherical morphology, and the grain size is 50nm to 150nm. The nanoparticles have excellent luminescent properties, can emit fluorescent light from blue light to red light and have significant potential application value in the field of luminescent organic nanomaterials; the preparation method of the iridium complex organic fluorescent nanoparticles has the advantages of simpleness in operation, mild conditions, low equipment requirement, no pollution and the like.
Description
Technical field
The present invention relates to organic nano material field, be specifically related to class complex of iridium organic fluorescence nanoparticle and preparation method thereof.
Background technology
Small-sized due to nanoparticle, suitable with biomacromolecule, such as enzyme, polynucleotide, antibody etc.And than cell, size has reduced 100 to 10000 times, therefore these nano particles can enter cell, and with cell surface or inside and bio-molecular interaction, this early detection that is study of disease, Precise Diagnosis and particular treatment provide potential application platform.At present, nanoparticle is mainly used in the aspects such as medicine and gene delivery, bio-sensing, bio-imaging in biological field.
At title complexs such as iridium, platinum, rhenium, ruthenium and osmium of photochemistry field phosphorescence heavy metal complex, due to its remarkable optical physics and spectrochemical property, it has had lot of documents report at aspects such as photocatalyst, Optochemical sensor, photochemistry biomarkers.Yet as the phosphor material of superior performance, the research of phosphorescence heavy metal complex aspect organic fluorescence nano material is relatively less.The present invention has not only synthesized three kinds of phosphorescent metal complex of iridium, and conventional amphiphilic block copolymer in medicament preparation is incorporated into the preparation system of fluorescent nano particles, obtained the good organic nano material of this biocompatibility, increase on the one hand the stability of fluorescent material in water, contributed on the one hand in addition the stable transfer in its organism.
Summary of the invention
The object of the invention is to prepare a class complex of iridium organic fluorescence nanoparticle.
The present invention also provides the preparation method of above-mentioned nanoparticle.
One class complex of iridium organic fluorescence nanoparticle, is characterized in that, its structural formula is:
R
2ir (μ-Cl)
2r
2@PEO-b-P4VP, wherein R
2ir (μ-Cl)
2r
2for dichloro bridge, R is dfppy(2-fluorophenyl pyridine), ppy(2-phenylpyridine) or pq(2-phenylquinoline), PEO-b-P4VP is polyoxyethylene glycol-b-poly 4 vinyl pyridine, and described complex of iridium organic fluorescence nanoparticle has spherical morphology, and particle diameter is at 50～150nm.
That is, the concrete structure formula of three kinds of dichloro bridges is respectively:
The preparation method of above-mentioned complex of iridium organic fluorescence nanoparticle comprises the following steps:
For 1:1～3:1, take in molar ratio the dichloro bridge R of complex of iridium
2ir (μ-Cl)
2r
2with PEO-b-P4VP and be dissolved in DMF, stir after spending the night and dialyse with deionized water; The concentration of the dichloro bridge of complex of iridium in DMF is 3～10mmol/L.
Described R
2ir (μ-Cl)
2r
2preparation method comprise the steps:
Under nitrogen protection, get the IrCl that mol ratio is 1:2～1:5
33H
2o and R, adding volume ratio is the cellosolvo of 1:1～5:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 60 ℃～135 ℃, stirs after 1～45 hour, preferably after 10～20 hours, cooling, filter, washing, R is dfppy, ppy or pq.
The present invention relates to organic nano science and technology field, three kinds of complex of iridium organic fluorescence nanoparticles and preparation method thereof are disclosed, and can be to its water-soluble improvement by single stage method, its structure is suc as formula shown in I, there is remarkable optical property, can send the fluorescence between 550～650nm, in light function organic nano material field, there is great potential using value.This nano material is to be formed by chemically crosslinked effect by the dichloro bridge of three kinds of complex of iridium and a kind of diblock copolymer PEO-b-P4VP.There is simple to operate, mild condition, low for equipment requirements, the advantage such as pollution not.
Accompanying drawing explanation
Fig. 1 is the FESEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 1.
Fig. 2 is the TEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 1.
Fig. 3 is the FESEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 2.
Fig. 4 is the TEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 2.
Fig. 5 is the FESEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 3.
Fig. 6 is the TEM electromicroscopic photograph of the complex of iridium organic fluorescence nanoparticle in embodiment 3.
Fig. 7 is the fluorescence spectrum figure of the complex of iridium organic fluorescence nanoparticle in embodiment 1,2,3.
Specific embodiment
Just the present invention will be further described for embodiment, is not used for limiting the present invention.
(1) prepare dichloro bridge (dfppy)
2ir (μ-Cl)
2(dfppy)
2: under nitrogen protection, get the IrCl that mol ratio is 2:5
33H
2o and dfppy, adding volume ratio is the cellosolvo of 3:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 110 ℃, stirs after 24 hours, cooling, filters washing.
(2) preparation (dfppy)
2ir (μ-Cl)
2(dfppy)
2@PEO-b-P4VP: the dichloro bridge (dfppy) of complex of iridium
2ir (μ-Cl)
2(dfppy)
2with the mol ratio of PEO-b-P4VP be 12:1; The concentration of the dichloro bridge of complex of iridium in DMF is 4.5mmol/L; Stirring is dialysed one day with deionized water after spending the night.
The result of the present embodiment, as shown in the FESEM Electronic Speculum of Fig. 1, is all spherical morphology, and size is 50～100nm.
Fig. 2 is the TEM Electronic Speculum result of the present embodiment.
(1) prepare dichloro bridge (ppy)
2ir (μ-Cl)
2(ppy)
2: under nitrogen protection, get the IrCl that mol ratio is 1:3
33H
2o and polypyrrole, adding volume ratio is the cellosolvo of 3:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 110 ℃, stirs after 24 hours, cooling, filters washing.
(2) preparation (ppy)
2ir (μ-Cl)
2(ppy)
2@PEO-b-P4VP:
The dichloro bridge (ppy) of complex of iridium
2ir (μ-Cl)
2(ppy)
2with the mol ratio of PEO-b-P4VP be 12:1; The concentration of the dichloro bridge of complex of iridium in DMF is 4.5mmol/L; Stirring is dialysed one day with deionized water after spending the night.
As shown in Figure 3, major part is spherical morphology to the FESEM Electronic Speculum figure of the present embodiment products obtained therefrom, size 50～100nm.
Fig. 4 is the TEM Electronic Speculum result of the present embodiment.
(1) prepare dichloro bridge (pq)
2ir (μ-Cl)
2(pq)
2: under nitrogen protection, get the IrCl that mol ratio is 1:3
33H
2o and pq, adding volume ratio is the cellosolvo of 3:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 110 ℃, stirs after 24 hours, cooling, filters washing.
(2) preparation (pq)
2ir (μ-Cl)
2(pq)
2@PEO-b-P4VP: the dichloro bridge (pq) of complex of iridium
2ir (μ-Cl)
2(pq)
2with the mol ratio of PEO-b-P4VP be 12:1; The concentration of the dichloro bridge of complex of iridium in DMSO is 4.5mmol/L; Stirring is dialysed one day with deionized water after spending the night.
As shown in Figure 5, major part is spherical pattern to the FESEM Electronic Speculum figure of the present embodiment products obtained therefrom, size 100～150nm.
Fig. 6 is the TEM Electronic Speculum result of the present embodiment.
As shown in Figure 7, embodiment 1, under 360nm exciting light, sends 627nm red fluorescence to the complex of iridium organic fluorescence nanoparticle fluorescence spectrum figure of embodiment 1～3.Embodiment 2, under 360nm exciting light, sends 565nm fluorescent orange.Embodiment 3, under 360nm exciting light, sends 582nm light green fluorescence.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So every, do not depart from the equivalence completing under principles of this disclosure or revise, all falling into the scope of protection of the invention.
Claims (5)
1. a class complex of iridium organic fluorescence nanoparticle, is characterized in that, its structural formula is: R
2ir (μ-Cl)
2r
2@PEO-b-P4VP, wherein R
2ir (μ-Cl)
2r
2for dichloro bridge, R is dfppy, ppy or pq, and PEO-b-P4VP is polyoxyethylene glycol-b-poly 4 vinyl pyridine, and described complex of iridium organic fluorescence nanoparticle has spherical morphology, and particle diameter is at 50～150nm.
2. the preparation method of complex of iridium organic fluorescence nanoparticle according to claim 1, is characterized in that, comprises the following steps:
For 1:1～3:1, take in molar ratio the dichloro bridge R of complex of iridium
2ir (μ-Cl)
2r
2with PEO-b-P4VP and be dissolved in DMF, stir after spending the night and dialyse with deionized water.
3. the preparation method of complex of iridium organic fluorescence nanoparticle according to claim 2, is characterized in that, the concentration of the dichloro bridge of complex of iridium in DMF is 3～10mmol/L.
4. according to the preparation method of the complex of iridium organic fluorescence nanoparticle described in claim 2 or 3, it is characterized in that described R
2ir (μ-Cl)
2r
2preparation method comprise the steps:
Under nitrogen protection, get the IrCl that mol ratio is 1:2～1:5
33H
2o and R, adding volume ratio is the cellosolvo of 1:1～5:1 and the mixed solvent of water, and above-mentioned mixing solutions is heated to 60 ℃～135 ℃, stirs after 1～45 hour, cooling, filter, washing, R is dfppy, ppy or pq.
5. the preparation method of complex of iridium organic fluorescence nanoparticle according to claim 4, is characterized in that, churning time is 1～30 hour.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591358A (en) * | 2009-06-30 | 2009-12-02 | 上海师范大学 | A kind of phosphorescent iridium complex that contains isosulfocyanate radical and its production and application |
| WO2012105753A2 (en) * | 2011-02-01 | 2012-08-09 | 부산대학교 산학협력단 | Deep-blue phosphorescent iridium complex using an n-methylimidazolyl triazole ancillary ligand |
| US20130030120A1 (en) * | 2011-07-25 | 2013-01-31 | Zhiqun Lin | Amphiphilic multi-arm copolymers and nanomaterials derived therefrom |
| CN102942920A (en) * | 2012-11-15 | 2013-02-27 | 安徽工业大学 | Iridium complex phosphorescence material with trifluoroacetyl phenyl substituent quinolone as ligand and preparation method thereof |
| WO2013165118A1 (en) * | 2012-04-30 | 2013-11-07 | 율촌화학주식회사 | Novel intermetallic compound, and blue phosphorescent organic light-emitting diode including same |
-
2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591358A (en) * | 2009-06-30 | 2009-12-02 | 上海师范大学 | A kind of phosphorescent iridium complex that contains isosulfocyanate radical and its production and application |
| WO2012105753A2 (en) * | 2011-02-01 | 2012-08-09 | 부산대학교 산학협력단 | Deep-blue phosphorescent iridium complex using an n-methylimidazolyl triazole ancillary ligand |
| US20130030120A1 (en) * | 2011-07-25 | 2013-01-31 | Zhiqun Lin | Amphiphilic multi-arm copolymers and nanomaterials derived therefrom |
| WO2013165118A1 (en) * | 2012-04-30 | 2013-11-07 | 율촌화학주식회사 | Novel intermetallic compound, and blue phosphorescent organic light-emitting diode including same |
| CN102942920A (en) * | 2012-11-15 | 2013-02-27 | 安徽工业大学 | Iridium complex phosphorescence material with trifluoroacetyl phenyl substituent quinolone as ligand and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ILJA K. VOETS ET AL.: "Complex coacervate core micelles", 《ADVANCES IN COLLOID AND INTERFACE SCIENCE》 * |
| STANISLAV N. SIDOROV ET AL.: "Influence of Metalation on the Morphologies of Poly(ethylene oxide)-block-poly(4-vinylpyridine) Block Copolymer Micelles", 《LANGMUIR》 * |
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