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, 1109-1112.

America’s ForestsAmerica’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

US #1 Producer of Wood as a Material

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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 materials-ubiquitous

• 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 Cellulose

nanofibers

6 Cellulose producing proteins forming a ‘rosette’

Plant cell wall

Jeffrey M. Catchmark, Penn State University and NSF NNIN

SEM of rosette, Candace

Haigler, NCSU

Cellulose nanofiber bundles

6 Assembly proteins (rosette) which produces cellulose nanofibers

Candace Haigler and Larry Blanton, Cellulose: “You're surrounded by it, but did you know it was there?”

jupiter.phys.ttu.edu/corner/1999/dec99.pdf www.ita.doc.gov/td/forestprod/

Cellulose Synthesis and Material Production: Nature Working Across a Length Scale >1010!

~28nm

Source: Jeffery Catchmark , Penn State University

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 BiopolymerNano-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 morphology.

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 propertiesTailoredMultifunctionalRenewableRecyclable Biodegradable

Directed Design of BiopolymerNano-composites

• NeedControl

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 nanostructuresHigh Surface areaMatrix for other materialsEasily reconfigured into other shapes and

formsPotential 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, duringcardiopulmonary bypass surgery and other invasive procedures

Detection With Ion-Channel Biosensors

• Rapid method, more so than QCM – more acceptable clinically

• Displacement assay• Disruption of signal-

producing 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• 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

BIOSENSOR

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 lectin-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 analyte/probe molecule of interest, the emission of the acceptor is turned “off” and only free donor emission is observed

A emission

D emission

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)