observations of self assembled bolaform amphiphiles on cellulose
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2007 International Conference on Nanotechnology for the Forest Products Industry. Observations of Self Assembled Bolaform Amphiphiles on Cellulose. Sunkyu Park 1 , Joseph J. Bozell 1 , Josef Oberwinkler 2 June 14, 2007 1 Forest Products Center, University of Tennessee - PowerPoint PPT PresentationTRANSCRIPT
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Observations of Self Assembled
Bolaform Amphiphiles on
Cellulose
Sunkyu Park 1, Joseph J. Bozell 1, Josef Oberwinkler 2
June 14, 20071 Forest Products Center, University of Tennessee
2 Salzburg University of Applied Sciences, Salzburg, Austria
2007 International Conference
on Nanotechnology for the Forest Products Industry
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3 Summary
2 Interaction Between Cellulose and Bolaforms
1What are Bolaform Amphiphiles?
1. Interaction on Cellulose
Surface
2. Interaction with Cellulose
Matrix
Presentation Contents
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What are Bolaform What are Bolaform
Amphiphiles?Amphiphiles?
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Bolaform Amphiphiles
Figure from Fuhrhop and Wang, Chem. Rev. 2004, 104, 2901-2937
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Bolaforms as Self Assembling Systems
Figures from T. Shimizu, Macromol. Rapid Commun. 2002, 23, 311
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Ferrier Bolaform Synthesis
Final product
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Other Types of Bolaform Amphiphiles
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Materials Used in this Study
Symmetric and C12 Bolaform Amphiphiles
Cellulose
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Cellulose and Bolaform Cellulose and Bolaform AmphiphilesAmphiphiles
(1) Interaction (1) Interaction onon Cellulose Cellulose SurfaceSurface
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• Materials– Cellulose: Microcrystalline cellulose (Avicel)
• Pretreatments– MeOH exchange ×3– DMAc exchange ×3
– Solvent• 8% LiCl in DMAc (N,N-dimethylacetamide)
– Solution• Cellulose + Bolaforms + LiCl/DMAc
• Methods– A drop on glass-slide– Drying– Polarized optical microscope
xx
Materials and Methods
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Cellulose Film in Absence of Bolaforms
200µm
Cellulose film without bolaforms in LiCl/N,N-dimethylacetamide
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Individualstructures
Bolaform Crystallization in Absence of Cellulose
200µm
Bolaforms without cellulosein LiCl/N,N-
dimethylacetamide
50µm
200µm 200µm
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Bolaform Crystallization in Presence of Cellulose
200µm
Edge of drop
Bolaforms with cellulosein LiCl/N,N-
dimethylacetamide
200µm
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Bolaform Crystallization Process
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200µm
200µm 200µm
200µm
Different Crystal Structures
200µm
200µm
Without cellulose
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FT-IR Imaging Characterization (1)
Image scanning
4000~650 cm-1 Image map at 2918 cm-1
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FT-IR Imaging Characterization (2)
Multivariate analysis of cellulose-bolaforms pellets using statistics package
(Unscrambler)
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Bolaform concentration mapping
FT-IR Imaging Characterization (3)
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MeOH Washing
• MeOH washing– All bolaform crystals were immediately dissolved in
MeOH
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Cellulose Film in Absence of Bolaforms
Solution:
Dissolved cellulose, LiCl/DMAc
Gel-type cellulose pad:
Cellulose pad, LiCl/ some DMAc, H2O
Formation mechanism
• Evaporation of DMAc
• Solidification of dissolved cellulose by H2O
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Cellulose Film in Presence of Bolaforms
Formation mechanism
• Evaporation of DMAc
• Solidification of dissolved cellulose by H2O
• Individual bolaform crystal formation
• Deposition of individual bolaform crystals
(cellulose is acting as nucleating sites)
Solution:
Dissolved cellulose, LiCl/DMAc, Dissolved bolaforms
Gel-type cellulose pad:
Cellulose pad, LiCl/ some DMAc, H2O, Bolaform crystals
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Cellulose as a Template for Assembly
Kondo et al, PNAS 2002, 99, 14008Kondo, 2007, Chap. 16 in Cellulose: Molecular and Structural Biology
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200µm
200µm 200µm
200µm
Different Crystal Structures
200µm
200µm
Without cellulose
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Control of Bolaform Crystallization
Formation mechanism
• Evaporation of DMAc
• Solidification of dissolved cellulose by H2O
• Individual bolaform crystal formation
• Deposition of individual bolaform crystals
Morphology of bolaform crystals in solvent
Template conditions of cellulose gel
Air flow
Cellulose concentration
Bolaforms concentration
Relative humidity
Temperature… more
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MeOH Washing
(2) 0 min, 1st drop(1) 0 min (3) 15 min, 2nd drop
(4) 30min, 3rd drop
200µm
(5) 45 min, 4th drop
(6) 60 min, 5th drop
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(7) 75min, 6th drop (8) 90 min, 7th drop
(9) After 95 min
90 min, before 7th drop
Bolaform Re-crystallization
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Cellulose and Bolaform Cellulose and Bolaform AmphiphilesAmphiphiles
(2) Interaction (2) Interaction withwith Cellulose Cellulose MatrixMatrix
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• Materials– Cellulose: Microcrystalline cellulose (Avicel)
• Pretreatments– MeOH exchange ×3– DMAc exchange ×3
– Solvent• 8% LiCl in DMAc (N,N-dimethylacetamide)
– Solution• Cellulose + Bolaforms + LiCl/DMAc
• Methods– Slow casting in Petri-dish– Washing with H2O– Drying at 60°C (restrained drying)– AFM, SEM, NMR, Sorption test
Materials and Methods
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Cellulose-bolaform Film Preparation (1)
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Cellulose-bolaform Film Preparation (2)
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FT-IR: Multivariate Analysis
Multivariate analysis of bolaform-incorporated cellulose films
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Film Surface: (1) AFM Images
Cellulose in DMAc/LiCl Bolaform/ Cellulose in DMAc/LiCl
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Film Surface: (2) SEM Images
Cellulose Film Cellulose-Bolaform Film
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Wide Angle X-ray Diffraction
X-ray source: CuKα (0.1542nm)
45kV and 0.66mA
Beam time: 30min
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(110)/(020)
(103)(004)
(110)¯
Avicel
0% Bolaform Film
Bolaform powder
Diffraction Patterns for Powders/ Films
5% Bolaform Film
15% Bolaform Film
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1D Integrated WAXD Profiles
Bolaform powder
Avicel powder
Amorphous cellulose powder
Cellulose film(bolaforms 0%)
Cellulose film(bolaforms 5%)
Cellulose film(bolaforms 15%)
5 10 15 20 25 30 35 40
2 theta, degree
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Structural Information for Cellulose Films
• Crystallinity index, CI
• Crystal size, L
cos
kL
,%( )
Area of crystalline peaksCI
Area of crystalline amorphous peaks
k: Scherrer constant, 0.94
λ: x-ray wavelength
β: full-width at half-maximum
θ: Bragg angle
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Bolaformconcentration,
%
Crystallinity
index, %
Crystal size,nm
R2 a) F b)
0% 35.5 2.36 0.9975 7038
1% 37.9 2.24 0.9982 8683
3% 36.7 2.24 0.9958 3587
5% 37.9 2.18 0.9943 2597
15% 39.1 2.18 0.9955 2303
Structural Information: Crystallinity, Crystal Size
a) and b) are regression coefficients during the curve fitting procedure
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Low Resolution NMR
• Experimental Parameters– CPMG procedures
– τau 0.05 ms
– 256 echoes– 750 scans– 5 second recycle delay
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NMR Relaxation Time
1.0
1.2
1.4
1.6
1.8
Cellulose 2%,Bolaform 0%
Cellulose 2%,Bolaform 5%
Cellulose 4%,Bolaform 0%
Cellulose 4%,Bolaform 5%
Rel
axat
ion
Tim
e, T
2 in
ms
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SummarySummary
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Summary
• Bolaform amphiphiles were successfully synthesized and the interactions with cellulose were studies.
• Highly-ordered self assembly of bolaform amphiphiles were observed on cellulose template, while individual self-assembled structures were found in the absence of cellulose.
• Bolaform-incorporated cellulose film showed higher relaxation time, which might be attributed to the interaction between cellulose hydroxyl groups and bolaform molecules.
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• Thomas Elder– USDA-Forest Service– Southern Research Station– Pineville, LA
• Nicole Labbé– Forest Products Center– The University of Tennessee
• John R. Dunlap– Program in Microscopy– The University of Tennessee
Acknowledgements
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