Biomass Fundamentals
Modules 18: Higher Order Functionality in Biomass:
Nanotechnology
A capstone course for
BioSUCCEED:
Bioproducts Sustainability: a University Cooperative
Center of Excellence in EDucation
The USDA Higher Education Challenge Grants program gratefully
acknowledged for support
This course would not be possible without
support from:
USDA
Higher Education Challenge (HEC) Grants Program
www.csrees.usda.gov/funding/rfas/hep_challenge.html
Article of Interest
• “Optically Transparent Composites
Reinforced with Plant Fiber-Based
Nanofibers”
• Iwamoto, S.; Nakagaito, A.N.; Yano, H.;
Nogi, M. Appl. Phys. A. 2005, 81, 11091112.
America’s Forests
•
•
736 million acres (2/3 of original)
• 2/3 East of the Mississippi River
• Growth to Harvest is over 2:1
• Benefits
•Carbon Sequestration
•Water – quality & quantity (2/3 of fresh water)
•Animal Habitat
•Recreation
•Open Space
•Renewable forest products
Threats to America’s Forests
• Catastrophic Forest Fire
(182 million acres at risk
nation-wide)
• Insects & Disease
• Fragmentation
• Parcelization (Conversion
to non-forest uses)
• Invasive Species
Forest Products
0
200
150
100
50
Czech Rep
Spain
New Zealand
Poland
South Africa
Australia
Japan
Chile
India
France
Germany
Malaysia
Finland
Indonesia
Sweden
Russian Fed
Brazil
China
Canada
USA
Millions of Cubic
Meters
Percent
of Total
World
Producti
on
Portugal
Belarus
Romania
Turkey
Austria
US #1 Producer of Wood as a
Material
450
100
400
90
350
80
300
70
250
60
50
40
30
20
10
0
U.S. Forest Products Consumption
(production plus net imports)
600
Net Imports
M illion tons, dry weight
500
Paper& paperboard
Composites production
400
L umber & miscellaneous
0.9% per year increase
300
1.9% per year increase
200
Paper/paperboard increases most
100
0
1960
1970
1980
1990
2000
2010
2020
2030
2040
2050
US Forest Products Sector
•
•
•
•
•
$243 Billion per year to the US Economy
Employment – 1.1 million
7% of US manufacturing base
In top 10 in manufacturing in 46 of 50 states
Converts 300 million tons of timber per year for
products
• US consumption about 225 million tons per year
• Post-consumer recovery of paper & paperboard
is 50%
Why Nanotechnology &
Wood/Lignocellulose?
• One of the most abundant biological raw materialsubiquitous
• Nano-fibrilar structure
• Self-assembly—controlled
• Lignocellulose as a nanomaterial and its interact with
other nanomaterials is largely unexplored
• Capacity to be made multifunctional
• New analytical techniques adapted to biomaterials are
beginning to allow us to see new possibilities
• Cornerstone/support for advancing the carbohydrate
renewable, sustainable economy
Cellulose Synthesis Proteins: Natures Molecular
Assembly Machines
Glucose
molecules
Plant cell
wall
Cellulose
nanofibers
6 Cellulose producing proteins forming a ‘rosette’
SEM of rosette,
Candace
Haigler, NCSU
Cellulose Synthesis and Material Production:
Nature Working Across a Length Scale >1010!
Cellulose nanofiber bundles
~28nm
6 Assembly
proteins
(rosette)
which
produces
cellulose
nanofibers
www.ita.doc.gov/td/forestprod/
jupiter.phys.ttu.edu/corner/1999/dec99.pdf
Candace Haigler and Larry Blanton, Cellulose:
“You're surrounded by it, but did you know it was
there?”
Nanotechnology in the Forest
Products Sector
• 1st forest products sector road mapping
workshop held October 18 – 20, 2004
• Roadmap document– expected February 2005
• Build support for forest products sector
nanotechnology research agenda & priorities
• Industry
• Government
• Academia
• Increase linkages with nanotechnology
research community
Vision Statement from Workshop
To sustainably meet the needs of
present and future generations for
wood-based materials and products
by applying nanotechnology science
and engineering to efficiently and
effectively capture the entire range
of values that wood-based
lignocellulosic materials are capable
of providing.
Nanotechnology Research Areas
• Use of nanomaterials in current
& new high performance forest
products & processing (films,
sensors, functional materials,
etc.)
• Nanoscale Architecture from
renewable resource
biopolymers (lignocellulose as a
nanomaterial)
• Directed Design of Biopolymer
Nano-composites
Nanotechnology Research Areas
• Growing (self assembly)
lignocellulosic nanomaterials
with unique multifunctional
properties
• Developing & adapting
physical, chemical, optical, and
electrical property
instrumentation and
methodologies used in
nanotechnology and
nanoscience to lignocellulosic
nanofibrillar and cellular
Nanotechnology Opportunities for Current
Products & Processes
• Sensors to monitor processes and product
history
• Revolutionize separations
• Breakthrough surface characteristics
• Incredible bonding
• Dramatic simplification of our processes
• Significant synergy with forest biotechnology
• Significant reduction in the need for energy
• Eliminate the need for water
Nanoscale Architecture from
Renewable Resource Biopolymers
•
•
•
•
Make use of nanofibers
Create novel biopolymers
Create active functional surfaces
Create new class(es) of nanomaterials
 Unique properties
 Tailored
 Multifunctional
 Renewable
 Recyclable
 Biodegradable
Directed Design of Biopolymer
Nano-composites
• Need
 Control
 Size
 Shape
 Crystal ultra-structures/amorphous components
• Understand complexity and surface features of
nanofibrils
• There is a consequence of nano-dimensions on
functional properties
Growing lignocellulosic Nanomaterials
with Unique Multifunctional Properties
• Understand and exploit the architecture &
consolidation (self assembly) of plant cell walls
for producing nanostructures
High Surface area
Matrix for other materials
Easily reconfigured into other shapes and
forms
Potential ability to produce carbon tubules
Nanotechnology of Related Forest
Biomaterials: Heparin
Most common disaccharide unit in HEPARIN
Heparin
• Anticoagulant
• Linear sulfated carbohydrate
• Abundant constituents of extracellular (EC)
matrix
• It modulates may physiological processes
(chemokines, EC matrix proteins, growth
factors) by binding activity
Biosensors for Heparin
Real time monitoring is critical, for example, during
cardiopulmonary bypass surgery and
other invasive procedures
Detection With Ion-Channel
Biosensors
• Rapid method, more so than
QCM – more acceptable
clinically
• Displacement assay
• Disruption of signalproducing analyte such as
Mo(CN)6
• The negatively charged
heparin binds to the
protamin, displacing the
metal anion, and altering the
redox reaction and voltage
potential
Detection with a Fluorescent Biosensor
•
•
•
•
•
•
con A = disaccharide binding unit
Post-photoaffinity-labeling modification
Synthetic guest incorporated and UV-linked
BIOSENSOR
After cleavage, guest released
Fluorophore is covalently attached by a thiol linkage close to binding site
Binding of actual carbohydrate guest changes intensity/frequency of
fluorescence
FRET for Detection!
• Fluorescence Resonance Energy
Transfer technique
• Label a lectin molecule (con A)
with a fluorescent donor (D) close
to binding site while a lectinA emission
bound carbohydrate (e.g., dextran)
has a fluorescent acceptor (A)
• Resonant energy transfer occurs
between D & A leading to A
emission upon excitation of D
• Once D is displaced by
D emission
analyte/probe molecule of
interest, the emission of the
acceptor is turned “off” and only
free donor emission is observed
Carbohydrates as Scaffolds
• These are rigid
components that can serve
as scaffolds for
bionsensors
• Cellulose-antibody films
have been made
• Chitin & chitosan are
excellent matrices for
enzyme sensors – good
permeability to oxygen
and glucose
• Dextran is electrostatically
inert
Homework Questions
• What are the maximum “microfibril”
dimensions possible for transparency in a
commercial application?
• If you wished to do research in
nanotechnology of wood/fiber
composites/plants, draw up a sample
research proposal based on your interests (I
will send you format electronically)