Arborescent Amphiphilic Copolymers as Templates for the … · 2013-11-07 · Arborescent...
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Arborescent Amphiphilic Copolymers as Templates for the Preparation of Gold Nanoparticles
Jason DockendorffJason Dockendorff, Mario Gauthier, Mario GauthierDepartment of Chemistry
29th Annual Institute for Polymer Research SymposiumIPR 20
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Outline
1. Focus of Research
2. The Template
3. Results
4. Conclusions & Future WorkIPR 20
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Main Focus
To synthesize a branched polymer template with an inverse micelle morphology for metallic nanoparticle assembly.
Specifically, amphiphilic arborescent copolymers will serve as static scaffolding for metal loading.IP
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Nanoparticle Applications
StabilizedCatalysts
BiologicalLabelling
TEXT TEXT
CellDestruction
Oligonucleotide functionalized nanoparticles exhibit size-dependant light scattering
Functionalized nanoparticles can target then destroy cells when subjected to laser pulses
Applicable to hydrogenation and various coupling reactions
Stable, high turnover, and easy isolation
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Outline
1. Focus and Purpose of Research
2. The Template
3. Results
4. Conclusions & Future WorkIPR 20
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Branched structure obtained from successive grafting reactions
Arborescent Polymers
Linear
- Li, J.; Gauthier, M. Macromolecules 2001, 34, 8918.- Kee, R.A.; Gauthier, M. Macromolecules 1999, 32, 6478.
Functionalization x x x
x xG0
Grafting
*
Copolymers obtained by coupling with a different polymer in the last cycle G1G2
1) Functionalization
2) Grafting
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Synthesis
G0 PS-graft-(P2VP-block-PS)
Θ
Functionalized substrate (G0 PS shown)
Amphiphilic block copolymer (PS-block-P2VP)
amphiphilic arborescent copolymer
PS
P2VP IPR 20
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Polymer loading and reduction
Au0
b
N+
CHH2C
H
b
N
CHH2CbN
CHH2CHAuCl4 -[AuCl4] hydrazine
Other loadable metal salts:– Palladium: Pd(OAC)2
– Platinum: K(PtCl3C2H4)– Rhodium: [Rh(CO)2Cl]2
Selective Reactions
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*Plasma can be used to reduce metal and remove polymer in one step
Plasma
HAuCl4 reduction
Heat
Bare gold nanospheres
Loading and Deposition
Cast on substrate
Polymer stabilized gold nanospheres
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Unique Characteristics
Arborescent Polymer TemplatesArborescent Polymer Templates
Static Structure
SolutionProperties
Activity Tailoring Loading
Versatility
HollowStructure
Size Control
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Agenda
1. Focus and Purpose of Research
2. The Template
3. Results
4. Conclusions & Future WorkIPR 20
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100nm
Preliminary tests
Toluene HAuCl4
PS-b-P2VP
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Arborescent Polymer Loading
PS
P2VP
Gold
G0PS-g-(P2VP-b-PS)IP
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1µm
Polar solvent
Increase the size of PS chains in corona to shield charges
G1PS-g-(P2VP-b-PS)
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PS degree of polymerizationincreased from 65 to 150
G1PS-g-(P2VP-b-PS)
100nm 50nmIP
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100nm
Structure Analysis
Solid Structures: Linear side-chain micelles
Ring Structures: Graft copolymer
Dry
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Structure Analysis
G0
G2
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Purification
“Cloud-point centrifugation”
Addition of a non-solvent to reach cloud point, followed by
centrifugation to isolate graft material.
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Crude Purified
Atomic Force Microscopy
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Chromatography
0
500
1000
1500
2000
2500
12 14 16 18 20 22 24 26
Elution Volume (mL)
DR
I Res
pons
e
PurifiedCrudeBackbone (G1)Side Chains
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Transmission Electron Microscopy
G0 G2IP
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Hydrogen Plasma Etching
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100nm 100nm
Hydrogen Plasma Etching
Reduction and polymer removal(solid state)
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Hydrazine Solution Reduction
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0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
300 350 400 450 500 550 600
Wavelength (nm)
Abs
orba
nce
(arb
itrar
y un
its) Salt
Reduced
UV-Vis Absorbance
(Au+3)
(Au0)
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G1PS-g-(P2VP-b-PS)
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G1PS-g-(P2VP-b-PS)
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PS-g-(P2VP-b-PS)
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Hydrazine Vapour Reduction(Solid State)
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G1PS-g-(P2VP-b-PS)
Reduction by hydrazine vapourIP
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Agenda
1. Focus and Purpose of Research
2. The Template
3. Results
4. Conclusions & Future WorkIPR 20
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Conclusions
• Different arborescent copolymer templates successfully loaded with gold
• Aggregation can be controlled through synthetic procedure and/or solvent changes
• Procedures developed for purification of graft copolymers
• Absorbance fingerprint typical of nanoparticles
• Ring-like structures observed for salt-loaded templates, consistent with hollow metallic nanosphere morphology
• Reduced gold structures rupture in electron beam (evidence for hollowness?)
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Future Work
• Optimization of reduction process to obtain one gold nanoparticle per template molecule.
• Examine and confirm nanoparticle structure and stability.
• Explore use as catalysts after loading with transition metals.IP
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Acknowledgements
Institute for Polymer Research
Lab Colleagues
DWI Institute, RWTH Aachen, Germany
NSERC, OGS, DAAD, Department of ChemistryIPR 20
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Thank you!
Questions?IPR 20
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