Biomass Fundamentals Modules 18 : Higher Order Functionality in Biomass: Nanotechnology

1. Biomass FundamentalsModules 18: Higher Order Functionality in Biomass:Nanotechnology A capstone course for BioSUCCEED: BioproductsSustainability: a University Cooperative Center of Excellence in EDucation The USDA Higher Education Challenge Grants program gratefully acknowledged for support

2. 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

3. 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.

4. 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

5. 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

8. Forest Products

10. US #1 Producer of Wood as a Material Millions of Cubic Meters Percent of Total World Production

12. 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%

13. 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

14. Cellulose Synthesis Proteins: Natures Molecular Assembly Machines Glucose molecules Plant cell wall Cellulose nanofibers SEM of rosette, Candace Haigler, NCSU 6 Cellulose producing proteins forming a ‘rosette’ Jeffrey M. Catchmark, Penn State University and NSF NNIN

15. Cellulose Synthesis and Material Production: Nature Working Across a Length Scale >1010! Cellulose nanofiber bundles 6 Assembly proteins (rosette) which produces cellulose nanofibers ~28nm 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?” Source: Jeffery Catchmark , Penn State University

16. 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

17. 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.

18. 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

19. 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.

20. 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

21. 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

22. Directed Design of BiopolymerNano-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

23. 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

24. Nanotechnology of Related Forest Biomaterials: Heparin Most common disaccharide unit in HEPARIN

25. 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

26. Biosensors for Heparin Real time monitoring is critical, for example, during cardiopulmonary bypass surgery and other invasive procedures

27. 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

28. 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

29. 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

30. 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

31. 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)