1 Versatile Synthesis Strategy for Carboxylic Acid-functionalized Upconverting Nanophosphors as...
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Versatile Synthesis Strategy for Carboxylic Acid-functionalized Upconverting Nanop
hosphors as Biological Labels
Zhigang Chen, Huili Chen, He Hu, Mengxiao Yu, Fuyou Li,* Qiang Zhang,Zhiguo Zhou, Tao Yi, and Chunhui Huang*
J. AM. CHEM. SOC. 2008, 130, 3023-3029
演講者:洪柏楷
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Outline Phosphors Synthesis of Oleic Acid-Capped UCNPs Converting Hydrophobic UCNPs into Hydrop
hilic Preparation of Streptavidin-Functionalized UC
NPs Detection of DNA
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Phosphors
Downconverting phosphors
Upconverting phosphors
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Downconversion fluorescent materials
1. Organic dyes
2. Semiconductor nanocrystal
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Up-converting rare-earth nanophosphors (UCNPs)
1. sharp absorption and emission lines2. high quantum yields 3. long lifetimes4. photostability
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oleic acid
2,6-diaminohexanoic acid (Lysine)
1-ethyl-3-(3-dimethylaminopropyl) carbodiimidehydrochloride (EDC)
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Hydroxy-2,5-dioxopyrrolidine-3-sulfonicacid sodium salt (Sulfo-NHS)
4-Morpholineethanesulfonic acid (MES)
2-Amino-2-hydroxymethyl-propane-1,3-diol (Tris)
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Synthesis of Oleic Acid-Capped UCNPs
Ln: 78 mol% Y + 20 mol%Yb + 2 mol%Er
NaOH + water + ethanol + oleic acid rare-earth chloride (LnCl3)
transfer to autoclave 160 °C 8 h
cyclohexane + ethanol
oleic acid-capped UCNPs
1.0 M NaF
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NaYF4: 20 mol%Yb, 2 mol % Er
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Converting Hydrophobic UCNPs into Hydrophilic
UCNP + cyclohexane + tert-butanol + water 5 wt % K2CO3 aqueous solution
KMnO4 + NaIO4 (Lemieux-von Rudloff reagent) 40 °C 48 h.
wash with deionized water acetone ethanol.
HCl (50 mL) pH 4-530 min
washed twice with deionized water
hydrophilic UCNPs
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Oxidized NaYF4:Yb,Er
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TEM
oxidized NaYF4:Yb,ErNaYF4:Yb,Er
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TEM
NaYF4:Yb, Tm oxidized NaYF4:Yb, Tm
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TEM
NaYF4:Yb, Ho oxidized NaYF4:Yb, Ho
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EDXA spectra
NaYF4:Yb,Er
oxidized NaYF4:Yb,Er
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XRD pattern
* cubic phase
▼ hexagonal phaseoxidized NaYF4:Yb,Er
NaYF4:Yb,Er
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1H NMR Spectra
undoped NaYF4
oxidized NaYF4
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FTIR spectra
NaYF4:Yb,Er
oxidized NaYF4:Yb,Er
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Thermogravimetric analysis (TGA)
oxidized NaYF4:Yb,Er
NaYF4:Yb,Er11.32 %
7.55 %
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Oxidized NaYF4:Yb,Er
water DMF DMSO
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Dynamic light scattering analysis
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Luminescence
continuous-wave excitation at 980 nm
red filter green filter
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Luminescence spectra
(A) NaYF4:Yb,Er
(B) Oxidized
NaYF4:Yb,Er
2H11/2 to 4I15/2
4S3/2 to 4I15/2 4F9/2 to 4I15/2
(I540 /I654 ) decrease
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Luminescence spectra
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Energy level diagram
Leyu Wang ; Yadong Li Chem. Mater. 2007, 19, 727-734
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Luminescence spectra
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Preparation of Streptavidin-Functionalized UCNPs
oxidized NaYF4:Yb,Er + EDC + sulfo-NHS + MES buffer 8 h
water
PBS buffer solutioncontaining streptavidin 4 °C 48 h
Lysine water
Streptavidin-Functionalized
UCNPs
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Streptavidin-Functionalized UCNPs
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Oligonucleotide
5' -(biotin)-GATGAGTATTGATGC-3 ' (as Capture-DNA)
5' -CGAATAGTTCCATTG-(TAMRA)-3 ' (as Report-DNA)
5 '-CAATGGAACTATTCG GCATCAATACTCATC-3 ' (as Target-DNA)
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DNA nanosensors based on UCNPs
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TARMA-labeled reporter DNA
absorptionemissionoxidized NaYF4: Yb, Er
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Detection of DNA
streptavidin-functionalized UCNPs + Report-DNA + Capture-DNA + buffered solution.
37 °C for 20 min
Target-DNA
980 nm
luminescencespectrum
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Luminescence spectra
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DNA nanosensors based on UCNPs
Fluorescence resonant energy transfer
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Conclusions We have demonstrated a new, efficient and versatile procedure for converti
ng hydrophobic UCNPs into water-soluble and carboxylic acid-functionalized derivatives by directly oxidizing oleic acid ligands to azelaic acid.
This procedure is not limited to hydrophobic UCNPs,and it can easily be applied to other hydrophobic nanoparticles (including rare earth, semiconductor and metal nanoparticles) where only surface ligands can be oxidized.
The presence of free carboxylic acid groups on the surface of azelaic acid-capped UCNPs allows further conjugation with various biomolecules, and streptavidin-functionalized UCNPs derived from azelaic acid-capped precursors provides a novel approach for detecting and/or binding to a broad range of biotinylated proteins or antibodies .