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
jbozell@utk.edu
 Presentation Topics

Renewables and the biorefinery

A few examples of carbohydrate

nanotechnology opportunities

Self assembling carbohydrate

based bolaforms and their
interaction with cellulose
 The Biorefinery as a Unifying Concept

Outputs (Conversion)
Inputs (Supply)
Butadiene
Building blocks Polylactic acid
(Separation) Pentanes, pentene
Corn BTX
Switchgrass Succinic acid
Potatoes Phenolics
Sorghum Starch Ethanol
Soybeans Organic acids
Cellulose
Apple pomace Furfural
Jerusalem artichoke Lignin
Polyols
Guayule Other Carbohydrates Resorcinol
Beet molasses Oils Levulinic acid
Sugar cane Levoglucosan
Wood Peracetic acid
Residues Tetrahydrofuran
Anthraquinone
Sorbitol
others
 Forest Products Matrix

Wood
processing
Timber products, Wood as wood;
plywood, OSB, etc. relative value low
Conventional
Kraft
Wood for paper
Cellulose
and fuel; relative value
Forest Black liquor
low to mid
(renewable) Alkali
resource extraction
Cellulose Wood for paper, fuel,
Hemicellulose and commodities; relative
Black liquor value low to mid

Emerging
Advanced
fractionation Cellulose
Hemicellulose Wood for chemicals;
Lignin relative value mid
Sugars to high
Extractives
 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: Scenario 2: Scenario 3:

Fossil Fuel and Independent Integrated Corn
PDO BioPDO and EtOH Biorefinery
Economic: 11% 3% 20%
Pretax Return

Environment: Down 72% vs

Total Energy 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?

The DOE Top 12 products from sugars:

Succinic, fumaric, and malic acids

2.5-Fur andicarboxylic acid
Biomass as a feedstock for products is an
3-Hydroxypropionic a cid issue of current high interest to a wide
Aspartic acid range of industrial segments.
Glucaric acid Develop technology to make
Glutamic acid inexpensive building blocks of defined
Itaconic acid carbon number and businesses will
Levulinic a cid develop.
Lignin product development is important.
3-Hydroxybutyrolactone
Glycerol
Sorbitol
Xylitol/arabinitol

Technology development will have more impact than

pre-identification of products with both fundamental
and applied research needed!
Available at http://www.nrel.gov/docs/fy04osti/35523.pdf
 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?

Woody
biomass
Lignin based aromatic
chemicals

Sugar/cellulose based
chemicals

lignin sugars Balance point?

Biobased
Pulp and paper fuels
products
2005: Nanotechnology for
the Forest Products Industry
What Will The Forest Products Biorefinery Look
Like?

Woody
biomass
Lignin based aromatic
chemicals

Sugar/cellulose based
chemicals

lignin sugars Balance point?

Biobased
Pulp and paper fuels
products
Natural Polymers as Templates

Review: H. Sieber, Mat. Sci. Engineering 2005, 412, 43

 Artificial Fossils from Cellulose Templates

ZrO2 - Chem. Comm. 05/795

catalysts
Au/TiO2 - Chem. Comm. 04/1008 Chem. Mater. 05/17/3513
photocatalysts SnO2, gas sensing

ITO - J. Mat. Chem. 06/16/292

Ag - Chem. Comm. 05/795 electronics
 Cellulose/CaCO3 Nanocomposites as Artificial
Bone

J. Biomater. Sci. Polym. Ed. 06/17/435

Biomaterials 06/27/4661

Organized polymers can template

CaCO3
Bacterial cellulose forms a fine, QuickTime and a
TIFF (Uncompressed) decompressor

highly organized template

are needed to see this picture.

Acid functionalization promotes

biomineralization
Biological and Polymer Applications

Medical diagnostics,
biochips, biosensors
Nanomolar sensitivity for
detection of biotin-
containing species
Cellulose provides a new
set of support properties
Angew. Chem. Int. Ed. 06/45/2883

AFM PVA/cellulose composites

Magnetic alignment of
cellulose nanofibers
Improved mechanical
properties
Appl. Phys. A 07/87/641
 Bolaforms As Self Assembling Systems

O O
HO
OH
O O OH OH
HO
OH OH OH

OH
O
Me N Me HO O COOH
HO
Me H HO O O
BrEt3N NEt3Br HO A naturally occurring sophorolipid from
H H 18
HO Candida bombicola
N OH
Me H Langmuir 2004, 20, 7926
Me
Me
COOH
HOOC
OH OH OH OH
OMe
HO OH
NH CH2 NH
COOH Me OH OH 6 OH OH
Carbohydrate and glycal based bolaforms

Carbohydrate based bolaforms

OAc OAc
O 1) NaN3 O 1) ClC(O)(CH2)nC(O)Cl
AcO NH2
AcO
AcO AcO 2) NaOMe
OAc 2) H2, Pt OAc
Br
OH HO
O O
HO NH HN OH
HO n OH
OH O O HO

e. g., Shimizu and Masuda, JACS 1997, 119, 2812

Glycal based bolaforms

OAc RO OR
O O OR RO O
AcO
AcO OR n RO

glycal (triacetylglucal) glycal bolaamphiphile

 Glycal Based Bolaform Research Schematic

ne w carb ohydrate ba sed bola forms

chain len gth va riati on
chain stru ctu re varia tion : stereochem istry,
bra nch ing, heteroatoms covalen t li nka ges

covalen tly stabil ized m onol ayer me mbran es

OR OR OR lo ng l ived cata lyst s uppo rts
Fe rrier chem istry structurall y defi ned catalysts
O O O el ectronic de vi ces
se lf a ssem bly
ne w nano structure s
RO pre dictabl e ma crom olecula r arrays
org anom etal lic RO OR ma crop orous Si cata lyst templ ates
OR tra nsfo rmati ons

gl ycals gl ycal base d bo lafo rms bo lafo rm ba sed mono layer m embra nes

predictive models?
org anom etal lic OR structure shape
tra nsfo rmati ons
O

RO R me mbran e su pported b ioactive mole cul es

bi omim etic li pid/enzyme s ys tems
ne w meth ods of function alization in fection co ntrol - ho spitals
ne w structura l/el ectronic un its in s ugars bi osen sors, detectors
bi oactive filte rs
ai r qua lity
hi ghly d efin ed cata lyst s ys tems
current progress cellu lar re cog niti on, carb ohydrate
ol igom ers

phase 1 - establish baselines

approximate time
phases of work phase 2 - bolaform properties and self assembly

phase 3 - stabilization of membranes, bioactive systems

 Ferrier Bolaform Synthesis
OAc OAc OAc
3 - 5% I2 O OH
O O HO

AcO THF AcO O

OAc O

OAc
O OAc
OAc OAc
O O AcO O O
OH O O
OAc
AcO AcO

OH
OH
NaOMe, MeOH O O
O O
OH
HO

Starting glycals

O OH Ac2O O OAc 30% HBr/HOAc O Br Zn, NMI O

61% over
Montmorillonite two steps
HO OH AcO OAc EDC, 0o AcO OAc EtOAc, rfx AcO
K10
OH OAc OAc OAc
93% xylal
OAc OAc OAc
O OAc O Br O
67% over
two steps
AcO OAc AcO OAc AcO
OAc OAc OAc
OH OAc galactal
O OH 1) LReO3 (??) O
eventual biobased
source?
HO OH 2) Ac2O AcO
OH OAc
Bolaform Synthesis Summary

OAc OH
O 1) cat. I2, THF O O
R
ROH
AcO 2) NaOMe HO
OAc

Glycal Alcohol Bolaform (major isomer) Ferrier reaction Zemplen deacetylation

OAc n=4 83% 66%
OH OH
O
O O O O n=8 90%
HO CH2 OH
n n n=10 81%
AcO
OAc HO OH n=12 90% 57%
n=18 29% (1:1) 85%
OAc OAc OH OH
O O O OH O O O O
12 76% 50%
12
AcO AcO HO OH
OAc
OAc
OH OH
O
O O O O
HO CH2 OH 12 20%
AcO 12
HO OH
OAc
O O O O O
HO CH2 OH 12 50% (3 isomers)
AcO 12
HO OH
OAc
OAc
OH
O OAc OH
Grubbs'
I2 O O catalyst O O
OH O O
AcO 8 8 8
8 78% OH
OAc AcO 47%
HO
5:1 E/Z
TEM Images of Nanostructures

500 nm 500 nm

OH
OH
O O
O O
OH
HO

Thompson, Kim (Purdue), Dunlap, Tice

OH O
O H
N NH2
HO N
HO OH H
O

Shimizu et al, Adv. Mater. 2005, 17, 2732

 Hypothetical Assembly Process
OH HO
O O
HO NH HN OH
HO n OH
OH O O HO

T. Shimizu, Macromol. Rapid Commun. 2002, 23, 311

R
O OH
H R T. Shimizu, Carb. Res. 2000, 326, 56
O O OH
HO R
O H OH O
H R
O H O
OH
O
H O
R R O
R H
O O O H O
R
O H H
HO O O
H H H
H O
O
O O
OH

Glycal analog Parallel Antiparallel

X-ray Structures of Bolaform Crystals

Glucal; ,-diastereomer

Glucal; ,-diastereomer

Galactal, ,-diastereomer

OH
OH O
O OH
N O
HO N
OH O
HO
OH Masuda, Shimizu, Carb. Res. 2000, 326, 56
OH
 Comparative Hydrogen Bonding Networks

OH
OH O
O OH
N O
HO N HO
HO HO OH OH
OH O OH O O
OH

O
O
Disaccharide Bolaform Headgroups
OH OH
O HO OH
lactose O OH
HO OH O
OH
OH
O
maltose HO OH
HO O 1) Ac2O, HBr/HOAc
OH
O OH
HO
OH
OH 2) HBr/HOAc
O HO OH
HO O
cellobiose OH 3) Zn/CuSO4/NaOAc/H2O/HOAc
HO OH O
OH
O HO OH
HO O Koreeda, et al
xylobiose OH
HO OH O

OAc OAc
O AcO
O
AcO OAc O
1) HO(CH2)12OH
OAc OH OH HO OH
lactal, 50% I2, THF O O
O O(CH2)12O O
2) NaOMe, HO OH O OH
OAc O HO
O MeOH OH HO
AcO OAc
AcO O
OAc
O
AcO
maltal, ~50%
Chemical Stabilization and Bioactive Materials

HO OH
HO OH
OH O
HO O O O
OH OH O
HO O O O
O HO OH O HO
O O HO O
O O O O
HO O HO OH O O O
OH O HO OH
OH HO OH
O
microbial cellulose O
cellulose
O functionalization

HO OH

M M
bioactive molecules (M) S S S S S S

cellulose fiber

templated complexation and

Patterning: fiber ordering (self assembly)
Hesse and Kondo, Carb. Polym. 2005, 60, 457;
Kondo et al, PNAS 2002, 99, 14008
 Bolaform Crystal Formation in Presence
of Cellulose

200m 200m

No avicel, 20% bola 4% avicel, 20% bola

in DMAc/LiCl (based on avicel) in DMAc/LiCl

200m 200m

2% avicel, 20% bola in DMAc/LiCl, edge of drop. Note

transition from crystals to greater structure. Trunk and branches
 SEM of Cellulose Films

No bolaform added
AFM Images of Bola/Cellulose Film
4% avicel in DMAc/LiCl 4% avicel in DMAc/LiCl, 5% bola
 Alignment of Carbohydrates
H
H O O
O
O O
O O H
H O H O HO
H
O O OH

HO
O HO
O
OH
OH
HO
HO
O
OH O
OH
Hypothetical organization of cellobiose
HO O O
OH H
O H H
O
H O O
O
O
O O H
O
H

H
H O O O
O O
O O H
H O H O
H HO
O O OH
OH HO O OH
HO O HO OH O
O OH HO
HO O O
OH O H
H O H

Organization/self assembly into

H O O O
O
O O H

Maintenance of
O
H

nanostructures H O O O
H

H-bonding network
O O
O O H
H O H O
H HO
O O OH
OH HO O OH
HO O HO OH O
O OH HO
HO O O
OH O H
H O H
H O O O
O
O O O H
H
H
H O O O
O O
O O H
H O H O
H HO
O O OH
OH HO O OH
HO O HO OH O
OH
Additional stabilization
O HO
HO O O
OH O H
H O H
H O O O

through -bonding and

O
O O O H
H

alignment of hydrophobic
H
H O O O
O O
O O H

chains? H O H O
H HO
O O OH
OH HO O OH
HO O HO OH O
O OH HO
HO O O
OH O H
H O H
H O O O
O
O O O H
H
Conclusions 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