Versatile Synthesis Strategy for Carboxylic Acid
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Upconversion

Versatile Synthesis Strategy for Carboxylic Acid-functionalized Upconverting Nanophosphors as Biological Labels

演講者:洪柏楷

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


Outline

Outline

  • Phosphors

  • Synthesis of Oleic Acid-Capped UCNPs

  • Converting Hydrophobic UCNPs into Hydrophilic

  • Preparation of Streptavidin-Functionalized UCNPs

  • Detection of DNA


Phosphors

Phosphors

  • Downconverting phosphors

  • Upconverting phosphors


Downconversion fluorescent materials

Downconversion fluorescent materials

  • 1. Organic dyes

  • 2. Semiconductor nanocrystal


Up converting rare earth nanophosphors ucnps

Up-converting rare-earth nanophosphors (UCNPs)

  • 1. sharp absorption and emission lines

  • 2. high quantum yields

  • 3. long lifetimes

  • 4. photostability


Upconversion

oleic acid

2,6-diaminohexanoic acid (Lysine)

1-ethyl-3-(3-dimethylaminopropyl) carbodiimidehydrochloride (EDC)


Upconversion

Hydroxy-2,5-dioxopyrrolidine-3-

sulfonicacid sodium salt (Sulfo-NHS)

4-Morpholineethanesulfonic acid (MES)

2-Amino-2-hydroxymethyl-propane-1,3-diol (Tris)


Synthesis of oleic acid capped ucnps

Synthesis of Oleic Acid-Capped UCNPs

NaOH + water + ethanol + oleic acid

rare-earth chloride (LnCl3)

1.0 M NaF

transfer to autoclave 160 °C 8 h

cyclohexane + ethanol

oleic acid-capped UCNPs

Ln: 78 mol% Y + 20 mol%Yb + 2 mol%Er


Nayf 4 20 mol yb 2 mol er

NaYF4: 20 mol%Yb, 2 mol % Er


Converting hydrophobic ucnps into hydrophilic

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 4-5

30 min

washed twice with deionized water

hydrophilic UCNPs


Oxidized nayf 4 yb er

Oxidized NaYF4:Yb,Er


Upconversion

TEM

NaYF4:Yb,Er

oxidized NaYF4:Yb,Er


Upconversion

TEM

NaYF4:Yb, Tm

oxidized NaYF4:Yb, Tm


Upconversion

TEM

NaYF4:Yb, Ho

oxidized NaYF4:Yb, Ho


Edxa spectra

EDXA spectra

oxidized NaYF4:Yb,Er

NaYF4:Yb,Er


Xrd pattern

XRD pattern

* cubic phase

▼hexagonal phase

oxidized NaYF4:Yb,Er

NaYF4:Yb,Er


1 h nmr spectra

1H NMR Spectra

oxidized NaYF4

undoped NaYF4


Ftir spectra

FTIR spectra

oxidized NaYF4:Yb,Er

NaYF4:Yb,Er


Thermogravimetric analysis tga

Thermogravimetric analysis (TGA)

7.55 %

oxidized NaYF4:Yb,Er

NaYF4:Yb,Er

11.32 %


Oxidized nayf 4 yb er1

Oxidized NaYF4:Yb,Er

water

DMF

DMSO


Dynamic light scattering analysis

Dynamic light scattering analysis


Luminescence

Luminescence

continuous-wave excitation at 980 nm

red filter

green filter


Luminescence spectra

Luminescence spectra

2H11/2 to 4I15/2

(A) NaYF4:Yb,Er

(B) Oxidized

NaYF4:Yb,Er

4S3/2 to 4I15/2

4F9/2 to 4I15/2

(I540 /I654 ) decrease


Luminescence spectra1

Luminescence spectra


Energy level diagram

Energy level diagram

Leyu Wang ; Yadong Li Chem. Mater. 2007, 19, 727-734


Luminescence spectra2

Luminescence spectra


Preparation of streptavidin functionalized ucnps

Preparation of Streptavidin-Functionalized UCNPs

oxidized NaYF4:Yb,Er + EDC + sulfo-NHS + MES buffer 8 h

water

PBS buffer solution

containing streptavidin 4 °C 48 h

Lysine water

Streptavidin-Functionalized

UCNPs


Streptavidin functionalized ucnps

Streptavidin-Functionalized UCNPs


Oligonucleotide

Oligonucleotide

5'-(biotin)-GATGAGTATTGATGC-3 '

(as Capture-DNA)

5'-CGAATAGTTCCATTG-(TAMRA)-3 '

(as Report-DNA)

5 '-CAATGGAACTATTCG GCATCAATACTCATC-3 '(as Target-DNA)


Dna nanosensors based on ucnps

DNA nanosensors based on UCNPs


Tarma labeled reporter dna

TARMA-labeled reporter DNA

absorption

emission

oxidized NaYF4: Yb, Er


Detection of dna

Detection of DNA

streptavidin-functionalized UCNPs + Report-DNA + Capture-DNA + buffered solution.

Target-DNA

37 °C for 20 min

980 nm

luminescence

spectrum


Luminescence spectra3

Luminescence spectra


Dna nanosensors based on ucnps1

DNA nanosensors based on UCNPs

Fluorescence resonant energy transfer


Conclusions

Conclusions

  • We have demonstrated a new, efficient and versatile procedure for converting 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 .


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