biobased nanostructural materials: new opportunities for the forest products industry?
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Biobased Nanostructural Materials: New Opportunities for the Forest Products Industry?. Joseph J. Bozell Forest Products Center – Biomass Chemistry Laboratories University of Tennessee Knoxville, TN 37996 [email protected]. Presentation Topics. Renewables and the biorefinery - PowerPoint PPT PresentationTRANSCRIPT
Biobased Nanostructural Materials: New Opportunities for the Forest
Products Industry?
Joseph J. Bozell
Forest Products Center – Biomass Chemistry LaboratoriesUniversity of Tennessee
Knoxville, TN [email protected]
Presentation TopicsPresentation Topics
• Renewables and the biorefinery
• A few examples of carbohydrate nanotechnology opportunities
• Self assembling carbohydrate based bolaforms and their interaction with cellulose
Inputs (Supply)Butadiene
Polylactic acidPentanes, pentene
BTXSuccinic acid
PhenolicsEthanol
Organic acidsFurfuralPolyols
ResorcinolLevulinic acidLevoglucosanPeracetic acid
TetrahydrofuranAnthraquinone
Sorbitolothers
Outputs (Conversion)
StarchCellulose
LigninOther Carbohydrates
Oils
Building blocks(Separation)
The Biorefinery as a Unifying ConceptThe Biorefinery as a Unifying Concept
CornSwitchgrass
PotatoesSorghumSoybeans
Apple pomaceJerusalem artichoke
GuayuleBeet molasses
Sugar caneWood
Residues
Forest Products MatrixForest Products Matrix
Forest (renewable)
resource
Timber products,plywood, OSB, etc.
KraftCellulose
Black liquorAlkali
extraction CelluloseHemicelluloseBlack liquor
Advanced fractionation Cellulose
HemicelluloseLigninSugars
Extractives
Woodprocessing
Wood as wood;relative value low
Wood for paperand fuel; relative value
low to mid
Wood for paper, fuel, and commodities; relative
value low to mid
Wood for chemicals;relative value mid
to high
Conventional
Emerging
Strategic Goals for the Use of Renewable Feedstocks and Biorefinery Development
• Dramatically reduce, or even end, dependence on foreign oil (a displacement and energy component)
• Spur the creation of a domestic bioindustry (an enabling and economic component)
Integration of chemicals with fuels will simultaneously address both
goals.
Impacts of Product Integration with Fuels
Scenario 1: Fossil Fuel and
PDO
Scenario 2: Independent
BioPDO and EtOH
Scenario 3: Integrated Corn
Biorefinery
Economic:Pretax Return
11% 3% 20%
Environment: Total Energy
Down 72% vs scenario 1
Petroleum Down 90% vs scenario 1
Natural gas Down 54% vs scenario 1
R. Dorsch and R. Miller, World Congress on Industrial Biotechnology and Bioprocessing, April 2004, Orlando, FL
What Product Should We Make?What Product Should We Make?
• The DOE “Top 12” products from sugars:
Technology development will have more impact than pre-identification of products with both fundamental
and applied research needed!
Succinic, fumaric, and malic acids 2.5-Furandicarboxylic acid 3-Hydroxypropionic acid
Aspartic acid Glucaric acid Glutamic acid I taconic acid Levulinic acid
3-Hydroxybutyrolactone Glycerol Sorbitol
Xylitol/ arabinitol
Available at http://www.nrel.gov/docs/fy04osti/35523.pdf
• Biomass as a feedstock for products is an issue of current high interest to a wide range of industrial segments.
• Develop technology to make inexpensive building blocks of defined carbon number and businesses will develop.
• Lignin product development is important.
Potential Market Impact of Nanotechnology
• NSF: $1 trillion by 2015• BCC research (www.bccresearch.com):
– $9.4 billion (2005)– $10.5 billion (2006)– $25.2 billion (2011)
• UK estimate: $1.275 trillion by 2010 (www.uktradeinvest.gov.uk)• Draper Fisher Jarvetson: $600 billion by 2012
What Will The Forest Products Biorefinery Look Like?
lignin sugars
Woodybiomass
Pulp and paperproducts
Lignin based aromaticchemicals
Sugar/cellulose basedchemicals
Biobasedfuels
Balance point?
2005: “Nanotechnology for the Forest Products Industry”
What Will The Forest Products Biorefinery Look Like?
lignin sugars
Woodybiomass
Pulp and paperproducts
Lignin based aromaticchemicals
Sugar/cellulose basedchemicals
Biobasedfuels
Balance point?
Natural Polymers as Templates
Review: H. Sieber, Mat. Sci. Engineering 2005, 412, 43
“Artificial Fossils” from Cellulose Templates
Au/TiO2 - Chem. Comm. 04/1008photocatalysts
Ag - Chem. Comm. 05/795
Chem. Mater. 05/17/3513SnO2, gas sensing
ZrO2 - Chem. Comm. 05/795catalysts
ITO - J. Mat. Chem. 06/16/292electronics
Cellulose/CaCO3 Nanocomposites as Artificial Bone
Biomaterials 06/27/4661
J. Biomater. Sci. Polym. Ed. 06/17/435
QuickTime™ and aTIFF (Uncompressed) decompressor
are needed to see this picture.
• Organized polymers can template CaCO3
• Bacterial cellulose forms a fine, highly organized template
• Acid functionalization promotes biomineralization
Biological and Polymer Applications
Angew. Chem. Int. Ed. 06/45/2883
Appl. Phys. A 07/87/641
• Medical diagnostics, biochips, biosensors
• Nanomolar sensitivity for detection of biotin-containing species
• Cellulose provides a new set of support properties
• PVA/cellulose composites• Magnetic alignment of
cellulose nanofibers• Improved mechanical
properties
AFM
Bolaforms As Self Assembling Systems
O
O O
HOOH
HOOH
OH
OH
OH
OH
O
polar polar
bolaform (Sp. "bola")
O
OO
OH
OH
HOHO
HO
HOHO O COOH
A naturally occurring sophorolipid from Candida bombicola
Langmuir 2004 , 20, 7926
N
N
MeMe
HHH
HMe
Me
BrEt3N NEt3Br18
HOOC
COOH Me
COOH
MeMe
OMe HO NH
OH
OH
OH
OHCH2 NH OH
OH
OH
OH
OH
6
Carbohydrate and glycal based bolaforms
O
OAcAcOAcO
OAc
Br
1) NaN3 O
OAcAcOAcO
OAcNH2
O
OHHOHO
OHNH
O O
O
HO OHOH
HOHN
2) H2, Pt
1) ClC(O)(CH2)nC(O)Cl
n
O
AcOAcO
OAcO
RO
ROOR
O
OR
ORRO
n
glycal (triacetylglucal) glycal bolaamphiphile
e. g., Shimizu and Masuda, J ACS 1997, 119, 2812
Carbohydrate based bolaforms
Glycal based bolaforms
2) NaOMe
Glycal Based Bolaform Research SchematicGlycal Based Bolaform Research Schematic
O
ORRO
OR
O
RO
OR
O
OR
OR
covalent linkages
membrane supported bioactive moleculesbiomimetic lipid/enzyme systems
infection control - hospitalsbiosensors, detectors
bioactive filtersair quality
highly defined catalyst systemscellular recognition, carbohydrate
oligomers
covalently stabilized monolayer membraneslong lived catalyst supports
structurally defined catalystselectronic devices
new nanostructurespredictable macromolecular arraysmacroporous Si catalyst templates
glycals
Ferrier chemistry
organometallictransformations
O
RO
OR
R
organometallictransformations
new methods of functionalizationnew structural/electronic units in sugars
glycal based bolaforms bolaform based monolayer membranes
new carbohydrate based bolaformschain length variation
chain structure variation: stereochemistry,branching, heteroatoms
structure shapepredictive models?
phase 1 - establish baselines
phase 2 - bolaform properties and self assembly
phase 3 - stabilization of membranes, bioactive systems
approximate timephases of work
current progress
self assembly
Ferrier Bolaform Synthesis
NaOMe, MeOH
O
AcO
OAc
OAc
HO OH3 - 5% I2
THF
O
AcO
OAcO
OAc
OO
O
AcO
OAcO OH
O
AcO
OAc
O
AcO
OAcO O O
OAc
OAc
O
HO
OHO O O
OH
OH
O
AcOOAc
O
AcO
OAc
OAc
OAc
OAc
O
AcOOAc
OAc
OAcOAc
O
HOOH
OH
OH Ac2O
MontmorilloniteK10
30% HBr/HOAc
EDC, 0o
O
AcOOAc
OAc
Br Zn, NMI
EtOAc, rfx
O
AcOOAc
O
AcOOAc
OAc
BrOAc
93%
61% over two steps
67% overtwo steps
xylal
galactal
Starting glycals
O
AcOOAc
OAcO OH
OHHOOH
OH1) LReO3 (??)
2) Ac2Oeventual biobased
source?
Bolaform Synthesis Summary
O O O O
HO
OH
OH
OH
O O
HO
OH
OO
OH
OH
n
8 8
O
AcO
OAc
OAc
O O
AcO
OAcOH
O O
HO
OH
R
12
1) cat. I2, THF
Alcohol Ferrier reaction Zemplen deacetylation
90%
76%
57%
50%
2) NaOMe
HO CH2 OHn
29% (1:1) 85%
O
AcO
OAc
OAc8 78%
O
AcO
OAcO
8
Grubbs'catalyst
47%5:1 E/Z
Bolaform (major isomer)
ROH
n=12n=18
n=10n=8n=4 83% 66%
90%81%
Glycal
O
AcO
OAc
OAc
O
AcO
OAc
OAc
HO CH2 OH12 20%
O
AcOOAc
HO CH2 OH12
50% (3 isomers)
O O O O
HO
OH
OH
OH
12
O O O O
HO
OH
OH
OH
12
O O O O
HO OH12
OH I2
O
AcO
OAc
OAc
TEM Images of Nanostructures
O HN
O
O
NH
NH2
OH
HOHO OH
Shimizu et al, Adv. Mater. 2005, 17, 2732
Thompson, Kim (Purdue), Dunlap, Tice
O
HO
OHO O O
OH
OH
500 nm
500 nm
Hypothetical Assembly Process
T. Shimizu, Macromol. Rapid Commun. 2002, 23, 311
OOO H
OHO H
HO
RR
OHOH
OHOH
OO
OH
O HHO
RR
OH
O
O
OH
O
R
R
OH
H
O H
O
O
OH
O
R
R
O H
HO H
Glycal analog Parallel Antiparallel
T. Shimizu, Carb. Res. 2000, 326, 56
O
OHHO
HO
OH
NH
O O
O
HOOH
OH
HO
HNn
X-ray Structures of Bolaform Crystals
Glucal; ,-diastereomer
Glucal; ,-diastereomer
Galactal, ,-diastereomer
ON
N OHO
OHOH
OHOH
OH
HO
OH O
O
Masuda, Shimizu, Carb. Res. 2000, 326, 56
Comparative Hydrogen Bonding Networks
O OHHOOHO OH
O O
ON N O
HO OHOH
OHOHOH
HOOH O
O
Disaccharide Bolaform Headgroups
O
OO
O
OO
OH
OHHOHO
OHOH
HO OH
OHHO
OH OH
OHOHHO
OH
1) Ac2O, HBr/HOAc
2) HBr/HOAc3) Zn/CuSO4/NaOAc/H2O/HOAc
OO
O
OOAcAcO
AcOOAc
OAcAcO
OAc OAc
OOAc
AcO
OOAc
AcO
O
OO
OHHOHO
OH
OHOHHO
OH
lactose
maltose
cellobiose
O
OO
OHHOHO OH
OHHOxylobiose
lactal, 50%
maltal, ~50%
OO
OHHO
OH OH
OOH
O(CH2)12O OO
HO OH
OHHO
OHO
1) HO(CH2)12OHI2, THF
2) NaOMe,MeOH
Koreeda, et al
Chemical Stabilization and Bioactive MaterialsChemical Stabilization and Bioactive Materials
Patterning:Hesse and Kondo, Carb. Polym. 2005, 60, 457;Kondo et al, PNAS 2002, 99, 14008
OO O
OO
O OOH
OH
OH
OHHOHO HO
OHHO
HO O O
OH
OH
OO O
O
OO O
O
O
O
OHHO
HO HO
OHHO
O
O
O
OOHHO
O
HO OH
OOHHO
S S S S SSM M
cellulose fiber
cellulosefunctionalization
templated complexation and fiber ordering (self assembly)
microbial cellulose
bioactive molecules (M)
Bolaform Crystal Formation in Presence Bolaform Crystal Formation in Presence of Celluloseof Cellulose
No avicel, 20% bolain DMAc/LiCl
4% avicel, 20% bola(based on avicel) in DMAc/LiCl
2% avicel, 20% bola in DMAc/LiCl, edge of drop. Note transition from crystals to greater structure. Trunk and branches
200µm
200µm
200µm
200µm
SEM of Cellulose Films
No bolaform added
AFM Images of Bola/Cellulose FilmAFM Images of Bola/Cellulose Film4% avicel in DMAc/LiCl 4% avicel in DMAc/LiCl, 5% bola
Alignment of Carbohydrates
O
OO
OHHO
HO
O
O
HOOH
OH
OO
O
H
H
H
H
OO
O
H
H OO
OO
OO
O
H
H
OO
O
H
H
O
OO
HOOH
OH
O
O
OHHO
HO
H
H
Hypothetical organization of cellobiose
Organization/self assembly intonanostructures Maintenance of
H-bonding network
Additional stabilizationthrough -bonding and
alignment of hydrophobicchains?
OO
OOH
HOHO
O
O
HOOH
OH
OO
O
H
H
H
H
OOO
H
H O O
O O
O O
O
H
H
O OO
H
H
OO
OHO
OHOH
O
O
OHHO
HO
H
H
OO
OOH
HOHO
O
O
HOOH
OH
OO
O
H
H
H
H
OOO
H
H O O
O O
O O
O
H
H
O OO
H
H
OO
OHO
OHOH
O
O
OHHO
HO
H
H
OO
OOH
HOHO
O
O
HOOH
OH
OO
O
H
H
H
H
OOO
H
H O O
O O
O O
O
H
H
O OO
H
H
OO
OHO
OHOH
O
O
OHHO
HO
H
H
OO
OOH
HOHO
O
O
HOOH
OH
OO
O
H
H
H
H
OOO
H
H O O
O O
O O
O
H
H
O OO
H
H
OO
OHO
OHOH
O
O
OHHO
HO
H
H
Conclusions and AcknowledgementsConclusions and Acknowledgements
• Renewable sources of carbon offer unique opportunities for the production of chemicals, fuels and materials.
• The forest biorefinery of the future must integrate new product opportunities with their traditional product lines
• Carbohydrate based bolaforms could offer an entry into the rapidly growing field of nanostructural materials, but more work is needed to control the process
• Interaction of bolaforms with natural polymers may lead to new families of uniquely patterned materials
• Thanks! To Thomas Elder, David Thompson, John Dunlap, Sebastien Vidal, Joseph Bullock
Funding:• USDA/NRI