Steering Committee Meeting / 24.5 - Nc State Universityojrojas/Lignocell/Report May 2013.pdf ·...

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LIGNOCELLVALUE-ADDED MATERIALS AND FUNCTIONAL STRUCTURES FROM LIGNOCELLULOSICS

Steering Committee Meeting / 24.5.2013

Scientific Report

(see also budget info at the end)

http://www4.ncsu.edu/~ojrojas/Lignocell.htm

Lignocell: Instrument to develop knowledge in lignocellulose science and engineering

Students: • Temporal: Learn from core competences and apply

their skills in proposed Lignocell subjects• Permanent: Long-term learning to become top-notch

scientists

Mentors:To provide ideas, guidance and to connect people

Industry: Opportunity to “steer” work in strategic areas in an open, scientifically-driven effort

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http://www4.ncsu.edu/~ojrojas/Lignocell.htm

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Laura TaajamaaAalto, FIN

Dr. Arcot LokanathanAalto, FIN

Nan

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tech

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logy

Dr. Cristina CastroUPB, Colombia

Bac

teri

al

cellu

lose

Angelica GrandonU. Concepcion, Chile

Sap

on

ins

Thin

film

s

Aff

iliat

ed M

em

ber

s

Dr. Mariko AgoTokushima Bunri, Japan

Nan

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tech

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logy

Elec

tro

-sp

inn

ing

Co

lloid

s an

d In

terf

ace

s G

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p

Prof. O. Rojas

Dr. Raquel MartinINIA, Spain

Ch

emic

al E

ng.

2013

Lignin &

Biopolymer StructuresCellulose

nanocrystals

Cellulose nanofibrils

Composites, Fibers, Additives , Hydro- and Aero-gels

Plant and microorganism Biopolymers

João V. WirbitzkiUNICAMP, Brazil

NC State University

Aalto University

Depts. Forest Biomaterials &

Chemical & Biomolecular

Engineering

Fatima Vargas

Bicomponentfilms

Electro-SpinningPorous

structures

NFCQCM

degradationEnzymes

SPRChitosan

FilmsBiomolecule

binding

NFCLignin

Mechanicalproperties

Soy proteinsCMC

Nano-particles

Click chem.Click chem.Conductive

fibers

Lignin-cellulose blendsEnzyme activity

ElisabetQuintana

UPC

Laura Taajamaa

Aalto

HannesOrelmaAalto

Dr. Maria S. Peresin

VTT

XiaomengLiu

Singenta

Ingrid Hoeger

NCSU/FPL

Dr. IlariFilponnen

Aalto

Raquel Martin

Complutense

Justin ZoppeAalto

Stimuli-responsive

CNCs

Ana FerrerUniv.

Cordoba

NFC from EFB

Raquel Martin

INIA

Enzyme inhibition

TiinaNypeloNCSU

Magnetic CNCs

Cristina Castro

Univ. Pontificia

Julio Arboleda

NCSU

Bacterial cellulose

Soy proteins aerogels

Bio coupling

OriolCusola

UPC

LignoCell

2010to

2012

http://www.facebook.com/photo.php?pid=3023429&id=666131894&op=1&view=global&subj=1354236973

http://www.flags.net/ARGE.htm

http://www.flags.net/CHIN.htm

http://www.flags.net/VENZ.htm

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LignoCell

2012to

2013Dr. Arcot

LokanathanAalto, FIN

Nan

o-

tech

no

logy

Laura TaajamaaAalto

5

Subjects1. Introduction and general report

(Orlando Rojas)2. Hydrolysis of bicomponent films

(Raquel Martin / OR)3. Hydrolysis of SEW nanofibers & BC

(Luis Morales)4. Novel methods in NFC production

(Carlos Carrillo / OR)5. SEW fibers, NFC and nanopaper

(Ester Rojo)6. NFC aerogels with SPs

(Julio Arboleda/OR)7. NFLC aerogels

(Mariko Ago/OR)8. Laccase-mediated coupling

(Oriol Cusola / OR)9. Carbon nanodots

(Kaoliina Junka / OR)10. CNC modeling

(Henry Bock)11. Surface chemistries

(Ilari Filpponen)12. Asymmetric CNC modification

(Arcot Lokanathan)Laura Taajamaa in Maternity Leave

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Laura Taajamaa in Maternity Leave













(Arcot Lokanathan)

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1. Hoeger, I.C., Gleisner, R., Negron, J., Rojas, O.J., Zhu, J.Y., Bark Beetle-killed Lodgepole Pine for the Production of Submicron Lignocellulose Fibrils, Accepted Journal Forest Science (2013)

2. Zhang, Y., Nypelö, T., Salas, C., Arboleda, J., Hoeger, I., Rojas, O.J.CelluloseNanofibrils: From Strong Materials to Bioactive Surfaces, Accepted Journal of Renewable Resources (2013)

3. Goli, K., Gera, N. Liu, X., Rao, B., Rojas, O.J., Genzer, J., Generation and properties of antibacterial coatings based on electrostatic attachment of silver nanoparticles to protein-coated polypropylene fiber, Accepted ACS Applied Materials & Interfaces, (2013)

4. Garcia-Ubasart, J., Vidal, T., Torres, A.L., Rojas, O.J. Laccase-mediated coupling of nonpolar chains for the hydrophobization of lignocellulose, Biomacromolecules, Accepted DOI: 10.1021/bm400291s (2013)

5. Song, J., Rojas, O.J., Approaching Superhydrophobicity Based on cellulosic materials: A Review, Nordic P&P Research Journal, Accepted (2013)

6. Hubbe, M.A., Rojas, O.J., Fingas, M., Gupta, B.S.,Cellulosic Substrates for Removal of Pollutants from Aqueous Systems: A Review. 3. Spilled Oil and Emulsified Organic Liquids, Bioresources , 8(2): 3038-3097 (2013)

7. Martín-Sampedro, R., Rahikainen, J.L., Johansson, L-S., Marjamaa, K., Laine, J., Kruus, K., Rojas, O.J., Preferential adsorption and activity of monocomponent cellulases on lignocellulose thin films with varying lignin content, Biomacromolecules, 14: 1231–1239 (2013)

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8. Taajamaa, L., Rojas, O.J., Laine, J., Yliniemi, K., Kontturi, E. Protein-assisted 2D assembly of gold nanoparticles on a polysaccharide surface, Chemical Communications, 59: 1318-1320 (2013).

9. Ago, M., Jakes, J., Rojas, O.J. Thermo-Mechanical Properties of Lignin-based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals, Biomacromolecules, accepted

10. Zhang, Y., Islam, N., Carbonell, R.G., Rojas, O.J. Specific binding and detection of IgGby bioactive short peptides immobilized on supported copolymer layers, Analytical Chemistry, 2013, 85 (2): 1106–1113 (2013).

11. Salas, C.; Rojas, O.J.; Lucia, L.A.; Hubbe, M.A., Genzer, J., On the surface interactions of proteins with lignin, ACS Applied Materials & Interfaces, 5: 199-206 (2013)

12. Rahikainena, J., Martin-Sampedro, R., Heikkinena, H., Rovioa, S., Marjamaaa, K., Tamminena, T., Rojas, O.J., Kruus, K., Inhibitory effect of lignin during cellulose bioconversion: the effect of lignin chemistry on non-productive enzyme adsorption, Bioresource Technology, 133, 270–278 (2013)

13. Hoeger, I.C., Nair, S.S., Ragauskas, A.J., Yulin Deng, Y., Rojas,O.J., Zhu, J.Y., Mechanical Deconstruction of Lignocellulose Cell Walls and their Enzymatic Saccharification, Cellulose, 20: 807-818 (2013).

14. Junka, K., Filpponen, I., Johansson, L-S., Kontturi, E., Rojas, O.J., Laine, J., A method for the heterogeneous modification of nanofibrillar cellulose in aqueous media, Carbohydrate Polymers, Accepted doi:10.1016/j.carbpol.2012.11.063.

15. Park, J., Meng, J., Lim, K.H., Rojas, O.J., Park, S. Transformation of lignocellulosic biomass during torrefaction, Journal of Analytical and Applied Pyrolysis, 100: 199–206(2013). 10

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16. Abdelgawad, A.M., Hudson, S.M., Rojas, O.J. Antimicrobial wound dressing microfiber mats from multicomponent (chitosan/silver-NPs/polyvinyl alcohol) systems, Carbohydrate Polymers, Accepted CARBPOL-D-12-01631R1

17. Martin-Sampedro, R., Filpponen, I.; Hoeger, I.C., Zhu, J.Y., Laine, J., Rojas, O.J., Rapid and Complete Enzyme Hydrolysis of Lignocellulosic Nanofibrils, ACS Macro Letters, 1, 1321-1325 (2012)

18. Goli, K, Rojas, O.J., Genzer, J. Formation and antifouling properties of amphiphiliccoatings on polypropylene fibers, Biomacromolecules, 13, 3769-3779 (2012).

19. Orelma, H., Filpponen, I., Johansson, L-S., Österberg, M., Rojas, O.J., Laine, J. Surface functionalized nanofibrillar cellulose (NFC) film as a platform for rapid immunoassays and diagnostics, Biointerphases, 7, 61 (2012).

20. Hoeger, I.C., Filpponen, I., Martin-Sampedro, R., Johansson, L-S., Österberg, M., Laine, J., Kelley, S., Rojas, O.J. Bi-component lignocellulose thin films to study the role of surface lignin in cellulolytic reactions, Biomacromolecules, 13, 3228–3240 (2012).

21. Ago, M., Jakes, J.E., Johansson, L-S., Park, S., Rojas, O.J. Interfacial Properties of Lignin-based Electrospun Nanofibers and Films Reinforced with Cellulose Nanocrystals, ACS Applied Materials and Interfaces, 4(12): 6849-6856 (2012).

22. Hao-yu, J., Lucia, L.A., Rojas, O.J., Hubbe, M.A., Pawlak, J.J., A Survey of Soy Protein Flour as a Novel Dry Strength Additive for Papermaking Furnishes, Journal of Agricultural and Food Chemistry, 60, 9828-33

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23. Ferrer, A., Filpponen, I., Rodríguez, A., Laine, J., Rojas, O.J. Valorization of Residual Empty Palm Fruit Bunch Fibers (EPFBF) by Microfluidization: Production of Nanofibrillated Cellulose and EPFBF Nanopaper, Bioresource Technology, 125, 249-255 (2012).

24. Ferrer, A., Quintana, E., Filpponen, I., Solala, I., Vidal, V., Rodríguez, R., Laine, J., Rojas, O.J. Effect of Residual Lignin and Heteropolysaccharides in Nanofibrillar Cellulose and Nanopaper, Cellulose, 19, 2179–2193 (2012)

25. Orelma, H., Johansson, L-S., Filpponen, I., Rojas, O.J., Laine, J. Generic Method for Attaching Biomolecules via Avidin-Biotin Complexes Immobilized on Films of Regenerated and Nanofibrillar Cellulose, Biomacromolecules, 13, 2802−2810 (2012)

26. Carrillo,C.A., Saloni, D., Lucia, L.A., Hubbe, M.A., Rojas, O.J. Capillary flooding of wood with microemulsions from Winsor I systems, Journal of Colloids and Interface Science, 381, 171–179 (2012).

27. Csoka, L., Hoeger, I.C., Peralta, P., Peszlen , I., Rojas, O.J. Piezoelectric Effect of Cellulose Nanocrystals Thin Films, ACS Macro Letters, 1, 867–870 (2012)

28. Payne, K., Jackson, C., Aizpurua Gonzalez, C., Rojas, O.J., Hubbe, M., Oil Spills Abatement: Factors Affecting Oil Uptake by Cellulosic Fibers, Environmental Science & Technology, 46:7725-7730 (2012)

29. Vallejos, M.E., Peresin, M.S., Rojas, O.J. All-Cellulose Composite Fibers Obtained by Electrospinning Dispersions of Cellulose Acetate and Cellulose Nanocrystals, Journal of Polymers and the Environment, 20:1075–1083 (2012).

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1. Taajamaa, L., Laine, J., Kontturi. E., Rojas, O.J., Bicomponent fibre mats with adhesive ultra-hydrophobicity tailored with cellulose derivatives J. Mater. Chem., DOI:10.1039/C2JM30572K.

2. Zoppe, J.O., Venditti, R.A., Rojas, O.J. Pickering emulsions stabilized by cellulose nanocrystals grafted with thermo-responsive polymer brushes. Journal of Colloid and Interface Science, 369 202–209 (2012)

3. Goli, K., Rojas, O. J., Ozcam, A., Genzer, J. Generation of functional coatings on hydrophobic surfaces through deposition of denatured proteins followed by grafting from polymerization, Biomacromolecules, In press, DOI: 10.1021/bm300075u

4. Castro, C., Zuluaga, R., Álvarez, C., Putaux, J-L., Caro, G., Rojas, O.J. Mondragon, I., Gañán, P. Bacterial cellulose produced by a novel acid-resistant strain Gluconacetobacter medellensis, Carbohydrate Polymers, In press, DOI: 10.1016/j.carbpol.2012.03.045

5. Ago, M., Okajima, K., Jakes, J.E., Park, S., Rojas, O.J., Lignin-based biomimetic electrospun nanofibers reinforced with cellulose nanocrystals, Biomacromolecules, 13: 918–926 (2012)

6. Salas, Carlos, Rojas, O. J., Lucia, L. Hubbe, M.A., Genzer, J. Adsorption of glycinin and ß-conglycinin on silica and cellulose:surface interactions as a function of denaturation, pH, and electrolytes, Biomacromolecules, 13: 387-396 (2012)

7. Li, Y., Rojas, O.J., Hinestroza, J.P., Boundary Lubrication of PEO-PPO-PEO Triblock Copolymer Physisorbed on Polypropylene, Polyethylene, and Cellulose Surfaces, Ind. Eng. Chem. Res. , 51: 2931-2940 (2012)

8. Liu, X., He, F., Salas, C., Pasquinelli, M., Genzer, J., Rojas, O.J. Experimental and Computational Study of the Effect of Alcohols on the Solution and Adsorption Properties of a Nonionic Symmetric Triblock Copolymer, Journal of Physical Chemistry B, 116: 1289–1298 (2012).

9. Liu, H., Li, Y., Krause, W., Rojas, O.J., Pasquinelli, M. The Soft-Confined Method for Creating Molecular Models Amorphous Polymer Surfaces, The Journal of Physical Chemistry B, 116: 1570–1578 (2012)

10. Li, Y., Rojas, O.J., Hinestroza, J.P., Boundary Lubrication of PEO-PPO-PEO Tri-block Copolymer Physisorbed on Polypropylene, Polyethylene and Cellulose surfaces, Industrial & Engineering Chemistry Research

11. Liu, H., Li, Y., Krause, W., Pasquinelli, M., Rojas, O.J. Mesoscopic Simulations of the Phase Behavior of Aqueous EO19PO29EO19 Solutions Confined and Sheared by Hydrophobic and Hydrophilic Surfaces, ACS Applied Materials & Interfaces, 4: 87-95(2012)

12. Orelma, O., Filpponen, I., Johansson, L-S, Laine, J., Rojas, O.J. Modification of Cellulose Films by Adsorption of CMC and Chitosan for Controlled Attachment of Biomolecules Biomacromolecules, 12(12): 4311–4318(2011).

13. Taajamaa, L., Rojas, O.J., Laine, J, Kontturi. E. Phase-specific pore growth in ultrathin bicomponent films from cellulose-based polysaccharides, Soft Matter, 7: 10386-10394 (2011)

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14. Hoeger, I., Rojas, O.J., Efimenko, K., Velev, O.D., Kelley, S.S. Ultrathin film coatings of aligned cellulose nanocrystals from a convective-shear assembly system and their surface mechanical properties Soft Matter, 7 (5), 1957-1967 (2011)

15. Csoka, L., Hoeger, I., Peralta, P., Peszlen, I., Rojas, O.J. Dielectrophoresis of cellulose nanocrystals and their alignment in ultrathin films by electric field-assisted shear assembly, Journal of Colloid and Interface Science, 363(1):206-12 (2011).

16. Spence, K.L., Venditti, R.A., Rojas, O.J., Pawlak, J.J., Hubbe, M.A., Water Vapor Barrier Properties of Microfibrillated Cellulose Films, Bioresources, 6(4):4370-4388 (2011).

17. Zoppe, J.O., Österberg, M., Venditti, R.A., Laine, J., Rojas, O.J. Surface Interaction Forces of Cellulose Nanocrystals Grafted with Thermo-responsive Polymer Brushes, Biomacromolecules, 12 (7): 2788–2796 (2011).

18. Liu, X., Vesterinen A-H., Genzer, J., Seppälä, J.V., Rojas, O.J. Adsorption of PEO−PPO−PEO Triblock Copolymers with End-Capped Cationic Chains of Poly(2-dimethylaminoethyl methacrylate), Langmuir, 27 (16), 9769–9780 (2011).

19. Martin-Sampedro, R., Capanema, E.A., Hoeger, I., Villar, J.C., Rojas, O.J. Lignin Changes after Steam Explosion and Laccase-Mediator Treatment of Eucalyptus Wood Chips, Journal of Agricultural and Food Chemistry, 59 (16): 8761–8769 (2011).

20. Li, Y., Liu, H., Song, J., Rojas, O.J., Hinestroza, J.P., Adsorption and Association of a Symmetric PEO-PPO-PEO Triblock Copolymer on Polypropylene, Polyethylene, and Cellulose Surfaces, ACS Applied Materials and Interfaces, 3 (7): 2349–2357 (2011)

21. Wu, N., Hubbe, M.A., Rojas, O.J., Park, S., Permeation of a Cationic Polyelectrolyte into Meso-porous Silica. Part 3, Colloids and Surfaces A, 381, 1-6 (2011).

22. Liu, X., Kiran, K., Genzer, J., Rojas, O.J. Multilayers of Weak Polyelectrolytes of Low and High Molecular Mass Assembled on Polypropylene and Self-assembled Hydrophobic Surfaces, Langmuir 27 (8), 4541–4550 (2011)

23. Spence, K.L., Venditti, R.A., Rojas, O.J., Habibi, Y., Pawlak, J.P. A comparative study of energy consumption and physical properties of microfibrillated cellulose produced by different processing methods, Cellulose, 18:1097–1111 (2011).

24. Wang, Z., Hauser, P., Rojas, O.J., Multilayers of low-charge-density polyelectrolytes on thin films of carboxymethylated and cationic cellulose, Journal of Adhesion Science and Technology, 25 (6-7), 643-660 (2011)

25. Álvarez, C., Rojano, B., Almaza, O.,Rojas, O.J., Gañán, P., Self-bonding boards from plantain fiber bundles after enzymatic treatment, Journal of Polymers and the Environment, 19(1), 182-188 (2011).

26. Silva, D.J., Rojas, O.J., Hubbe, M.A., Park, S.W. Enzymatic treatment as a pre-step to remove cellulose films in from sensors, Macromolecular Symposia, 299/300, 107–112 (2011). 14

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1. Rojas, O.J., Nanoparticles and Nanostructures from Direct- and Self- Assembly of Components Cleaved from Fiber Cell

Walls, XXI International Materials Research Congress (MRS), Cancun, Mexico, August 12-16, 2012

2. Rojas, O.J., Nypelo, T., Ago, M., Zhang, Y., Taajamaa, L., Orelma, H., Filpponen, I. Laine, J. Cellulose as Tunable

Material in Nanotechnologies: Thin Films of Cellulose and Cellulose Derivatives with Designed Properties by Surface

Modification, 3rd International Cellulose Conference, Sapporo, Japan, October 10-12, 2012.

3. Filpponen, I., Lokanathan, A., Rojas, O.J., Laine, J. Click chemistry reactions on the reducing end groups of cellulose

nanocrystals, 3rd International Cellulose Conference, Sapporo, Japan, October 10-12, 2012.

4. Martín-Sampedro, R., Rahikainen, J., Hoeger, I., Marjamaa, K., Kruus, K., Filponnen, I., Laine, J., Rojas, O.J., 4th Effects

of Lignin on the Hydrolysis of Cellulose by Pure and Multicomponent Enzymes, International Conference on Pulping,

Papermaking and Biotechnology (ICPPB’12), Nanjing, China, November 7-9, 2012

5. Ago, M., Silveira, J., Taajamaa, L., Jakes, J.E., Kontturi, K., Bittencourt, E., Laine, J., Rojas, O.J., Electrospun Micro-

and Nano- Fibers from Multicomponent Lignocellulose Systems: Functional Materials with Special Surface, Mechanical

and Thermal Properties, International Conference on Pulping, Papermaking and Biotechnology (ICPPB’12), Nanjing,

China, November 7-9, 2012

6. Hubbe, M.A., Payne, K.C., Jackson, C.D., Aizpurua, C.E., Rojas, O.J. Application of Cellulosic Fiber Materials for The

Remediation of Petroleum Spills in Water, International Conference on Pulping, Papermaking and Biotechnology

(ICPPB’12), Nanjing, China, November 7-9, 2012.

7. Filpponen, I., Laine, J., Rojas, O.J. Click chemistry for producing lignin-based novel materials, International Conference

on Pulping, Papermaking and Biotechnology (ICPPB’12), Nanjing, China, November 7-9, 2012.

8. Carrillo, C., Rojas, O.J. High water content microemulsions as a novel method for wood pretreatment and extraction,

12th European Workshop on Lignocellulosics and Pulp, Espoo, Finland, August 27-30, 2012.

9. Silveira, J.V.W., Millas, A.L.G., Tessarolli, L.F., Ago, M., Rojas, O.J., Bittencourt, E., Produção de Fibras Eletrofiadas a

Partir de Acetato de Celulose e Lignina, XIX Brazilian Congress in Chemical Engineering (COBEQ 2012), Búzios, RJ,

Brazil, September 9-12, 2012

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245th ACS Meeting, April 7-11, 2013 | New Orleans, Louisiana

1. In situ self-assembly and hydrophobization of Gluconacetobacter bacterial cellulose,Cristina Castro, Robin Zuluaga,

Jean-Luc Putaux, Marlon Osorio, Gloria Caro, Orlando Rojas, Piedad Gañán

2. Short peptide-conjugated copolymer based biosensor for specific binding of immunoglobulin G, Yanxia Zhang, Orlando

Rojas, Nafisa Islam, Ruben Carbonell

3. Lignin nano- and microparticles for coating and interfacial stabilization, Tiina Nypelo, Mariko Ago, Shuai Li, Orlando

Rojas

4. Effect of composition and formulation variables in biomass flooding capacity by o/w microemulsions, Carlos A Carrillo,

Daniel Saloni, Orlando J Rojas

5. Phase behavior and properties of the oil-in-water emulsions stabilized by carboxymethylated and acetylated lignins,

Shuai Li, Maryam Mazloumpour, Professor Julie Willoughby, Professor Orlando J Rojas

6. Magnetic cellulose nanocrystals: Demonstration and properties of organic-inorganic hybrid system, Tiina Nypelo, Carlos

Rodriguez-Abreu, José Rivas, Michael Dickey, Orlando Rojas

7. Surface modification of hydrophobic substrates by soy protein adsorption, Carlos L. Salas, Orlando J. Rojas, Jan

Genzer, Martin A. Hubbe, Lucian Lucia

8. Cellulose acetate/lignin-based electrospun fibers, Joao V. W. Silveira, Ana L. G. Millas, Mariko Ago, Orlando J. Rojas,

Edison Bittencourt

9. Mechanical deconstruction of lignocellulose cell walls and production of nanopaper, Ingrid C Hoeger, Orlando J Rojas,

Junyong-FS Zhu

10.Effects of lignin and hemicelluloses on the enzymatic hydrolysis of nanofibrillated softwood lignocellulose after SO2-

ethanol-water (SEW) fractionation, Luis O Morales, Mikhail Iakovlev, Jenni Rahikainen, Leena-Sisko Johansson, Raquel

Martin, Janne Laine, Adriaan van Heiningen, Orlando Rojas

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245th ACS Meeting, April 7-11, 2013 | New Orleans, Louisiana

12. Influence of the deconstruction of the cell wall in the enzymatic saccharification of softwoods, Ingrid C Hoeger, Sandeep

S Nair, Professor Arthur J Ragauskas, Professor Yulin Deng, Professor Orlando J Rojas, Junyong-FS Zhu

13.Asymmetric thiolation of cellulose nanocrystals using reductive amination of reducing ends, Lokanathan R Arcot, Jani

Seitsonen, Antti Nykänen, Leena S Johansson, Joseph Campbell, Janne Ruokolainen, Olli Ikkala, Orlando Rojas, Janne

Laine

14.Protein-assisted 2D assembly of gold nanoparticles on an ultrathin cellulose film, Laura Taajamaa, Orlando J Rojas,

Janne Laine, Eero Kontturi

15.Synthesis and characterization of soy protein-nanocellulose composite aerogels, Julio C Arboleda, Orlando J Rojas,

Lucian A Lucia, Janne Laine

16. Surface functionalized nanofibrillar cellulose (NFC) film as a platform for immunoassays and diagnostics, Ilari

Filpponen, Hannes Orelma, Leena-Sisko Johansson, Monika Österberg, Orlando Rojas, Janne Laine

17.Novel Pretreatment in the Manufacture of Nanofibrillated Cellulose via Microfluidization , Carlos A Carrillo, Janne Laine,

Orlando J Rojas

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Orals:1. Nanoparticles and Nanostructures from Direct- and Self- Assembly of Components Cleaved from

Fiber Cell Walls, Orlando Rojas, North Carolina State & Aalto University2. 2-Dimensional Nanoscale Structures from Cellulosic Materials, Eero Kontturi, Aalto University3. Super-Strong Soy Protein/Nanocellulose Composite Aerogels, Julio Arboleda, North Carolina State

University4. Surface Assembly of Chemically Reactive Polysaccharides on Nanocellulose, Janne Laine, Aalto

University5. Magnetic Cellulose Nanocrystal Hybrid, Tiina Nypelö, North Carolina State University6. ZnO-Bacterial Cellulose Nanocrystal Composite and its Potential as Energy Harvesting Material,

Levente Csoka, University of West Hungary7. Surface Functionalized Nanofibrillar Cellulose (NFC) Film as a Platform for Immunoassays and

Diagnostics, Ilari Filpponen, Aalto University8. Nanofibrillated Cellulose as Carrier for Short Peptides Assemblies for Human IgG Detection and

Affinity Separation, Yanxia zhang, North Carolina State University9. Self-Assembly of Cellulose Fibrils/SiO2 Nanoparticles During Synthesis by Gluconacetobacter

Bacteria- Robin Zuluaga Gallego, Pontificia Bolivariana University

Posters:1. Reinforcing Nanocellulose Isolated from Banana Rachis and Corn Husk-Robin Zuluaga Gallego,

Pontificia Bolivariana University2. Hydrophobization of Cellulosic Substrates by Creating Surface Nanostructures Using Enzymatic

Methods-Oriol Cusola, Universitat Politècnica de Catalunya UPC-BarcelonaTech 19













(Arcot Lokanathan)

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EndoglucanaseExoglucanases

(CBH-II)Exoglucanases

(CBH-I)

β-glucosidases

Crystalline cellulose Amorphous cellulose Crystalline cellulose

Trichoderma cellulase enzymes

Enzyme Conc (%)

CBH I 50-60

CBH II 15-18

EG I 12-15

EG II 9-11

EG III 0-3

EG V 0-3

Tolan, 2002 Clean Techn Environ Policy 3, 339-345

LigninLignin

Inhibition of Enzymatic Hydrolysis by Residual Lignins From Softwood – Study of Enzyme Binding and Inactivation of Linin-Rich Surface

Rahikainen, J.; Mikander, S.; Marjamaa, K.; Tamminen, T.; Lappas, A.; Viikari, L.; Kruss, K.

Biotechnology and Bioengineering2011, 108 (12): 2823-2834

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Vibrating quartz crystal

V~

Substrate

Adsorption

Water phase

Ampli-

tude

Time Circuit off

Q-Sense E4

QCM: Electromechanical techniqueDynamics of the adsorption: Changes in resonance frequency

Resonator: quartz crystals

Quartz Crystal Microbalance (QCM)

HIDROLYSIS OF NFC FILMS

Birch Pulp NFC NFC filmsFluidization Spin Coating

% Lignin Pulp NFC

Unbleached 2.6 2.8

Bleached 0.3 0.1

1.67g/lSonication

Centrifugation

Supernatant

PEI Adsorption

Silica Sensor0

0.5

1

1.5

2

2.5

3

3.5

4

200 250 300 350 400

Adsorb

ance

Wavelength (nm)

Lignin in Supernatant

Unbleached

Bleached

Spin Coating3000rpm1min

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25

Enzymatic hydrolysis

0 1 2 3 4 5

-140

-120

-100

-80

-60

-40

-20

0

20

40

60

0 1 2 3 4 5

-140

-120

-100

-80

-60

-40

-20

0

20

40

60

f 3(H

z)

Time (min)

Unbleached

Bleached

Time (min)

40oC, pH 5, NS50013 (0.15mg/ml, 0.06FPU/ml)

Complete and fast hydrolysis of NFC

Adsorption rate: Unbleached ≈ Bleached

Minimum frequency: Unbleached ≈ Bleached

Hydrolysis rate: Unbleached > Bleached

Maximum frequency: Unbleached > Bleached

Acetylated lignin in Chloroform

CTA or TMSC in Choloroform

HYDROLYSIS OF CELLULOSE-LIGNIN FILMS

Deacetylation (AcL and CTA) (NH4OH atmosphere at room T for 3 days

followed by washing with water)

3

Blend CTA / AcL or TMSC / AcL(conc. of the major component fixed at 5 g/l )

1

Spin coating on silicon wafers(at 4000 rpm for 1 min)

2

1:0 10:1 5:1 1:1 1:5 0:1

Cellulose / Lignin films

(Ce/L)

NH4OH (30%)

Films

Deacetylation (AcL) (NH4OH atmosphere at room T for 1 days

followed by washing with water)

3

Desilylation (TMSC) (HCl atmosphere at room T and vacuum for 2

min followed by washing with water)

4

HCl (10%)

Films

CTA /AcL TMSC /AcL

23.5.2013

14

Deacetylation68h NH4OH atm

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

1:010:1

5:11:1

1:50:1

After deacetylation

Deacetylation68h NH4OH atm

Cellulose (Ce/L 1:0)

61o CTA

Lignin (Ce/L 0:1)

71o Ac. Lignin

26o Cellulose 76o Lignin

Contact angle

Commercial enzymes mixture

Lignin inhibition: higher lignincontent lower hydrolysis rate

40oC, pH 5, NS50013 (7,5mg/ml, 3 FPU/ml)

23.5.2013

15

Enzy

mat

ictr

eatm

ent

Cellulose Blend ratio 10:1 Blend ratio 5:1 Blend ratio 1:1

Enzymatic hydrolysis using QCM-D: enzymes mixture

Roughness increase:

Cellulose hydrolysis

Enzyme adsorption

Aft

er H

ydro

lysi

sB

efo

re H

ydro

lysi

s

EndoglucanaseExoglucanases (CBH-II)

Exoglucanases

(CBH-I)

Trichoderma cellulase enzymes

Enzyme Conc (%)

CBH I 50-60

CBH II 15-18

EG I 12-15

EG II 9-11

EG III 0-3

EG V 0-3

Monocomponents enzymes

Cellobiohydrolase or exoglucanase

Endoglucanase

23.5.2013

16

0 50 100 150 200 250 300 350 400-200

-160

-120

-80

-40

0

40

f 3(H

z)

Time (min)

Enzyme

injection

Buffer

rinsing

Ce/L 1:0

Ce/L 5:1

Ce/L 1:1

Ce/L 0:1

CBH-I adsorbs more on lignin than on cellulose.

Lignin reduce the hydrolysis rate (compare Ce/L 1:0 to 5:1) until complete inhibition for 1:1.

0 5 10 15 20 25 30 35 40-30

-20

-10

0

10

20

30

f 3(H

z)

Time (min)

Enzyme

injection

Stop

injection

Ce/L 1:0

Ce/L 5:1

Ce/L 1:1Ce/L 0:1

CBH I

40oC, pH 5, CBH I (0,25 mg/ml)

0 50 100 150 200 250 300

-140

-120

-100

-80

-60

-40

-20

0

20

40

60

Ce/L 1:1

f 3(H

z)

Time (min)

Buffer

rinsing

Enzyme

injection

Ce/L 0:1

Ce/L 1:0

Ce/L 5:1

EG-I are adsorbed on both lignin and cellulose

Lignin reduce the hydrolysis rate of cellulose (compare Ce/L 1:0 to 5:1 and 1:1) until almost complete inhibition.

More EG-I can be adsorbed on lignin after 20 minutes

0 5 10 15 20 25 30 35 40-30

-20

-10

0

10

20

30

40

50

f 3(H

z)

Time (min)

Stop

injection

Enzyme

injection

Ce/L 1:0

Ce/L 5:1

Ce/L 1:1

Ce/L 0:1

EG I

40oC, pH 5, EG I (0,25 mg/ml)

23.5.2013

17

After long adsorption stage Inhibition of hydrolysis in cellulose films Overcrowding

The dense binding of enzyme molecules hinder each other from accessing the cellulose with their catalytic domains (Suchy et al. Langmuir 2011, 27, 8879-8828)

0 50 100 150 200 250 300 350

-20

0

20

40

60

80

f 3(H

z)

Time (min)

Enzyme

injection

Stop

injection

Buffer

rinsing

Ce/L 0:1

Ce/L 1:1

Ce/L 5:1

Ce/L 1:0

Enzymatic hydrolysis using EG I Overcrowding

Roughness increase:

Cellulose hydrolysis

Enzyme adsorption

Aft

er C

BH

I (0

.5m

g/m

l)

Roughness 3.31 nm Roughness 3.56nm Roughness 2.62nm Roughness 0.947 nm

Bef

ore

hyd

roly

sis

Roughness 1.81 nm Roughness 1.67 nm Roughness 1.49 nm Roughness 0.443 nm

Ce/L 1:0 Ce/L 0:1Ce/L 5:1 Ce/L 1:1

1µ

m

Aft

er E

G I

(0

.5m

g/m

l)

Roughness 3.04 nm Roughness 3.19 nm Roughness 2.45 nm Roughness 0.931 nm

23.5.2013

18

Roughness 0.443 nm

Ce/L 0:1

Roughness 0.947 nm

Roughness 0.931 nm

Bef

ore

hyd

roly

sis

Aft

er C

BH

I (0

.5m

g/m

l)A

fter

EG

I (

0.5

mg

/ml)

Cellulases immobilized on PIII-treated polystyrene(PIII=Plasma immersion ion implatation)Increase in roughness from 0.5 to 0.9 nm

Hirsh et al. Langmuir 2010, 26 (17), 14380-14388

Enzyme adsorption on lignin film

Individual enzyme molecules: size 10-15nm

5nm

Roughness 0.443 nm

Ce/L 0:1

Roughness 0.947 nm

Roughness 0.931 nm

Bef

ore

hyd

roly

sis

Aft

er C

BH

I (0

.5m

g/m

l)A

fter

EG

I (

0.5

mg

/ml)

Enzyme adsorption on lignin film

5nm

23.5.2013

19

CONCLUSIONS

Fast enzymatic hydrolysis of NFC compared to other substrates

Thin bicomponent film of cellulose/lignin where successfully developed from TMSC or CTA and acetylated lignin.

Inhibition of enzymatic hydrolysis was observed in bicomponentfilms with enzyme mixtures and with both monocomponentenzymes studied

Both CBH I and EG I are adsorbed on cellulose and lignin. CBH I has higher affinity for cellulose and EG I for lignin.

Lignin inhibition is due to both irreversible enzyme adsorption and physical blocking.

For EG I, inhibition due to overcrowding was observed.

Effects of lignin and hemicelluloses on the

enzymatic hydrolysis of nanofibrillated softwood

lignocellulose after

SO2-ethanol-water fractionation













(Arcot Lokanathan)

23.5.2013

20

SO2-ethanol-water (SEW) process

SEW fractionation

(pulping)

Evaporation and

conditioning

Fermentation and

separation

Butanol

Acetone/Isopropanol

Ethanol

Make-up Ethanol

+ SO2

Biomass/

wood

Lignosulfonates

Ethanol

+ SO2

Glucose

Hemicellulose

monosugars,

lignosulfonates

Enzymatic

hydrolysisRecycled fibres

Solid

residue

(pulp)

”Organosolv” lignin

Dissolving/

papermaking

pulp

Aims

Study the fundamental features of hemicelluloses and

lignin contribution to the enzymatic hydrolysis of

nanofibrillated lignocellulose (NFLC) obtained from

Norway spruce after SEW fractionation

23.5.2013

21

SEW fibers used (Norway spruce)

SEW fibers 1 2 3 4 5 6

Temperature (C) 135 165 135 135 135 135

SO2 % 12 12 12 3 6 12

Fractionation time (min) 160 22.5 80 380 140 50

Total lignin (%) 1.7 2 4.1 4.8 5.9 13

Cellulose (%) 91 90 85 94 90 76

Hemicelluloses (%) 8 3.8 11.4 6.8 10.3 12

Glucan 1.1 0.4 1.5 0.9 1.4 1.7

Xylan 2.3 1.6 3.2 2.0 2.8 2.3

Mannan 4.4 1.7 6.3 3.7 5.8 4.4

No major differences in nanofibrilar morphology of NFLC from different SEW treatments

1 2 3 4 5 6

Microfluidization (1.5 % fiber suspensions, 10 passes,

constant shear rate, 55 Mpa)

SEW

pulp

19 nm 18 nm 14 nm 20 nm 14 nm 15 nm Rq

1 2 3 4 5 6

NFLC

23.5.2013

22

NFLC substrates for enzymatic hydrolysis

PAHBAH, QCM-D

Hyd

roly

sis

1.67 g/L NFLC homogenized

& centrifuged (10400 rpm, 45

min, 25 C)

Course material

Supernatant

(Fine material)

I

II

PAHBAH

PAHBAH (p-hydroxybenzoic acid hydrazine method): Reducing sugars in suspension

QCM-D (Quartz Crystal Microbalance with Dissipation): Model films

Hydrolysis with Celluclast 1.5L: Course (I) and Fine NFLC (II)

20 FPU/g substrate, T= 40ºC, 24 h, pH 5,

50 mM sodium actetate, PAHBAH method

23.5.2013

23

Celluclast 1.5 L + Novozyme 188

T= 40ºC, pH 5, 50 mM sodium actetate,

PAHBAH method

Hydrolysis of NFLC’s fine material (II) (low lignin content case)

Enzyme binding and hydrolysis parameters estimated with Boltzman sigmoidal eqn.

Binding Hydrolysis

NFLC -Mmax (Hz) W50 (min) 1/T (min-1) B (%) V50 (min) 1/C (min-1)

1 86.7 1.2 3.1 131.8 1.9 1.5

2 88.6 0.9 3.7 103.5 1.8 1.4

Films treated with Celluclast 1.5 L +

Novozyme 188 (1 %), continuous enzyme

injection for 15 min at 100 µl/min

Hydrolysis of NFLC’s fine material (II) (moderate lignin content case)

Celluclast 1.5 L + Novozyme 188

T= 40ºC, pH 5, 50 mM sodium actetate,

PAHBAH method




Enzyme binding and hydrolysis parameters estimated with Boltzman sigmoidal Eqn.

Binding Hydrolysis


3 24.3 0.3 11.1 33.2 0.4 6.4

4 22.6 0.4 11.5 17.8 0.8 2.0

23.5.2013

24

Hydrolysis of NFLC’s fine material (II) (lignin content case)

Celluclast 1.5 L + Novozyme 188, T= 40ºC,

pH 5, 50 mM sodium actetate, PAHBAH

method




Binding Hydrolysis


5 51.6 0.5 4.2 54.9 1.9 1.1

6 26.1 0.2 9.1 15.7 1.3 1.9

Enzyme binding and hydrolysis parameters estimated with Boltzman sigmoidal Eqn.

Conclusions

SEW provides feedstocks of different chemical composition that can

be used for bioconversion

Hemicelluloses enhance the enzymatic hydrolysis of small particle

size NFLC

Lignin has a negative effect on the enzymatic hydrolysis of NFLC

23.5.2013

25

Work with bacterial cellulose (BC)Hannes Orelma, Luis Morales

Pure cellulose with unique mechanical properties

(high crystallinity and water holding capacity,

mechanical strength, biocompatibility)

Scaffold for tissue engenieering, wound healing,

acoustic materials and electronic paper,

nanocomposites, aerogels, drug delivery

(Klemm et al. (2011) Angewandte Chemie International Edition 50 (24): 5438-5466

Modify BC tubes produced on silicone

tubes

- Adsorption of dibenzylcyclooctyne (DBCO)

modified with carboxymethyl cellulose (CMC)

DBCO-CMC

In-situ modification of BC tubes

- Produced on silicone tubes under the presence

of CMC in the culture media

Modified bacterial cellulose tubes for synthetic blood vessels and filtration applications

Aims of the study:

23.5.2013

26

Charge and water retention values (WRV) of in-situ CMC-modified BC

BC-CMC membranes washed with 0.1 M NaOH at 60 ºC for 4 hours. Charge

measurements were done by standard SCAN-CM 65:02 Total acidic group content

Addition of CMC increases the charge repulsion between protein

residues and fibrils causing lower protein content

SEM images

BC

BC-CMC

Surface Cross section

23.5.2013

27













(Arcot Lokanathan)

Tasks:

1. Application of an oil in water microemulsion as a pulp pretreatment for

NFC manufacture

2. Microemulsification of NFC in a reverse microemulsion

3. ASA emulsification using cationic NFC as emulsifier

23.5.2013

28

250 nm

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)

Energy Consumption (x106 J)

EDA Microemulsion

Aqueous EDA

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)


Urea Microemulsion

Aqueous Urea

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)


Urea Microemulsion

Aqueous Urea

20µm

20µm

20µm

20µm

Microemulsions:Oil / surfactant : co-surfactant / aq. urea

Oil / surfactant : co-surfactant / aq. ethylene diamine (EDA)

Dispersion of

fibers in the

microemulsion

EquilibrationCentrifugation

and washing

Pulp pretreatment

Fibrillation

20000

rpm for

15min

Disperse pulp

in water

2000 Bar

200 µm – 100

µm

7 passes

Bleached

Birch pulp

Eucalyptus

pulp

(kappa = 27)

MicroemulsionsNanofibrillated Cellulose

Nanopaper Preparation

Properties Applications Properties Applications

High strength

High stiffness

Low weight

High aspect ratio

Biodegradable

Renewable

Composites

Paper and

paperboard

Absorbent products

Viscosity modifier

Oil recovery

Emulsion stabilizer

Coatings

Thermodynamically stable

Ultra-low interfacial tension

Dissolve water and oil

Wet hydrophilic and

hydrophobic surfaces

High interfacial area

Drug delivery

Personal care products

Pesticides

Reaction media

Enhanced oil recovery

• Defibrillation is improved and

energy consumption is reduced by

using microemulsions.

• Marked improvement in the case of

unbleached fibers

• Unbleached fibers produce stiffer

and denser nanopaper

Prepare NFC

dispersions

(0,1% NFC)

Filter using a

membrane

(P)

Dry at 80 ºC

overnight

Unbleached fibersBleached fibersBleached fibers

Bleached fibers

EDA Microemulsion

Bleached fibers

Urea Microemulsion

Unbleached fibers

Urea Microemulsion

Unbleached fibers

Aqueous Urea

Bleached fibers

Aqueous Urea

Bleached fibers

Urea Microemulsion

ʎ = 48nm

TS = 35 MPa

ʎ = 35 nm

TS = 20 MPa

ʎ = 23 nm

TS = 85 MPa

ʎ = 34 nm

TS = 63 MPa

Compared to aqueous

systems smaller fibril

diameters are obtained

by using microemulsions

Energy reduction of 32

and 50% for bleached

and unbleached fibers,

respectively

Better fiber packing in

nanopaper when using

urea microemulsion

compared to EDA

Nanopaper from

unbleached pulp have

higher stiffness and

density

HydrophilicGroup

(polar)

Hydrophobic Group (non-

polar)

Sodium dodecyl sulfate (SDS)

Anionic

1µm

Application of an oil in water microemulsion as a pulp

pretreatment for NFC manufacture

WRV was measured as a quantification of the degree of fibrillation.

• NFC’s from microemulsion pretreatment present larger values for WRV compared to the aqueous solutions.

• Pretreatment using Urea gives NFC with larger WRV’s than the pretreatment using EDA.

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)


Urea Microemulsion

Aqueous Urea

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)


EDA Microemulsion

Aqueous EDA

20%

increment18%

increment

http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=aSUhhVVv4uf-KM&tbnid=X6i5MXCBh2kQcM:&ved=0CAUQjRw&url=http://chemistry.about.com/od/factsstructures/ig/Chemical-Structures---S/Sodium-Dodecyl-Sulfate.htm&ei=KEkcUYnhHoSC8ASSz4GgCg&bvm=bv.42452523,d.eWU&psig=AFQjCNHzewt2_tM6wc5HYTR_XeMTI62o8w&ust=1360894618894885

23.5.2013

29



Fully bleached Birch pulp Eucalyptus pulp (Kappa = 27)

• The difference in WRV’s between the pulp pretreated with aqueous solution of the chemical and the pulp

pretreated with the microemulsion is larger when lignin is present.

• WRV’s for the fully bleached pulp are larger than the values for the pulp with lignin.

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)


Urea Microemulsion

Aqueous Urea

0.0 0.5 1.0 1.5 2.00

250

500

750

1000

1250

1500

1750

2000

WR

V (

%)


Urea Microemulsion

Aqueous Urea

20%

increment55%

increment



1 Pass 3 Pass 7 Pass

Aqueus Urea

Urea ME

EDA ME

23.5.2013

30



Preparation of nanopapers with the NFC obtained

Prepare

dispersions of the

NFC

(0,1% NFC)

Filter using a 5 µm

membrane

(0,5 Bar)

Dry at 80 ºC overnight

Aqueous UreaUrea ME EDA ME

Urea ME Aqueous Urea

NFC from Birch

(Fully bleached)

NFC from Eucalyptus

(Kappa = 27)

Microemulsification of NFC in a reverse microemulsion

Systems used:

o NFC (1,4%)/Span80:Triton X-100:n-pentanol/Octane

o NFC (1,4%)/Span80:Triton X-100:n-pentanol/Limonene

Ternary diagrams

Prepare the surfactant

mixture

Span80:Triton X-100:n-

pentanol

(1:1:1 by weight)

Prepare mixtures of

the surfactant and the

oil from 10% to 90% by

weight

Wait for equilibrium

to be reached and

determine the

number and type of phases

Titrate the mixtures

from the previous step

with the NFC

Microemulsification

Solubilize the

surfactants and co-

surfactant in the oil

phase

Mix at 400 rpm for

5 minutes

Add the required

amount of NFC

23.5.2013

31

0 20 40 60 80 100

0

20

40

60

80

100 0

20

40

60

80

100

NFC

Surfactant

Octane

Span 80 : Triton X-100 : n-pentanol (1:1:1)

(1.4 wt. %)


NFC (1,4%)/Span80:Triton X-100:n-pentanol/Octane

1 phase

ME

2 phases

0 20 40 60 80 100

0

20

40

60

80

100 0

20

40

60

80

100

NFC

Surfactant

Limonene

Span 80 : Triton X-100 : n-pentanol (1:1:1)

(1.4 wt. %)

NFC (1,4%)/Span80:Triton X-100:n-pentanol/Limonene

2 phases

1 phase

ME

• Larger microemulsion region when using limonene as the oil phase


ME with NFC (WOR = 0,25)

NFC = 0,28%Pure ME

NFC in water

NFC = 0,28%

23.5.2013

32


1 10 100 1000 100000.000

0.025

0.050

0.075

0.100

0.125

Vis

co

sity [P

a*s

]

Shear rate [1/s]

Aq 0.14% NFC

ME 0.14% NFC

1 10 100 1000 100000.000

0.025

0.050

0.075

0.100

0.125

Vis

co

sity [P

a*s

]

Shear rate [1/s]

Aq 0.21% NFC

ME 0.21% NFC

1 10 100 1000 100000.000

0.025

0.050

0.075

0.100

0.125

Vis

co

sity [P

a*s

]

Shear rate [1/s]

Aq 0.28% NFC

ME 0.28% NFC

Emulsification of ASA with cationic NFC as stabilizer

NFC (% wt.) 0 0,010 0,025 0,075 0,100 0,125 0,150 0,175 0,200 0,225

Stability Unstable Unstable Unstable Unstable Stable Stable Stable Stable Stable Stable

Drop size (µm) -- -- -- -- 5,3 3,2 3,8 4,7 5,1

Viscosity -- -- -- -- Moderate Moderate Moderate Moderate High High

Protocol for emulsification

• Disperse the cationic NFC in water to the desired concentration.

• Add the ASA to the NFC dispersion

• Emulsify the system using the homogenizer Polytron PT2000 for 2 min with the speed selector in

position 1 (~2000rpm)

The values in the red square seems to be the best conditions for emulsification of the ASA

The stability of the emulsion comes from the increment in the viscosity of the continuous phase when the

NFC is increased.

23.5.2013

33













(Arcot Lokanathan)

f

1

1

COMPLUTENSE UNIVERSITY OF MADRID, SPAIN – Department of Chemical Engineering

• Study: “Phenolic composites reinforced with cellulosic fibres”

• Application: Automotive sector

Background

SPANISH RESEARCH COUNCIL, SPAIN – Institute of Polymer Science and Technology

• Study: “Photo-curing of polymers”

• Application: Coating in roofing slates

UNIVERSITY OF BATH, UK – Department of Mechanical Engineering

• Study: “Creep behavior of thixotropic adhesives using DMTA”

• Application: Reparation/reinforcement of timber structures

23.5.2013

34

Cellulosic fibers

Reinforcement

Phenolic resin

MatrixBIO-BASED REINFORCED

COMPOSITESAdhesion

Summary of my thesis, motivation

Directive 2000/53/CE for end of life vehicle in the EU

“… by 2015, 95 % of the components of all the automobiles

must present recyclable materials…”

Define the problem

FIBERSHydrophilic

MATRIXHydrophobic, but even with hydrophilic MATRIX

H2O

H2O

FIBERS

VoidsCuring

INTERFACE:Contact region between matrix-reinforcement

It ensures stress transfer between the two phases

¿Solution? Treatment of the fibers NaOH

Silanes as coupling agents

¿Problem? Lack of adhesion

http://images.google.es/imgres?imgurl=http://earthobservatory.nasa.gov/Newsroom/NewImages/Images/PacificVapor_M2002119.jpg&imgrefurl=http://www.meteored.com/ram/263/imagen-curiosa-rara/&usg=__eDX-l_iE-bxX9IZ0Dgk7u5HvSpk=&h=645&w=540&sz=140&hl=es&start=2&tbnid=FLQiDQ1XTIF2bM:&tbnh=137&tbnw=115&prev=/images?q=vapor&gbv=2&hl=es

http://images.google.es/imgres?imgurl=http://imagenes.solostocksargentina.com.ar/resina-termoplastica--insumos-metalograficos-216625z0.jpg&imgrefurl=http://www.solostocksargentina.com.ar/resina-termoplastica-insumos-metalograficos-oferta-216625&usg=__2015S81csVhnDRum6Hg4RROLMyI=&h=500&w=282&sz=15&hl=es&start=24&sig2=qPfuYruXLhKEnR76hoRsiw&tbnid=XL2JJVP15adiyM:&tbnh=130&tbnw=73&prev=/images?q=resina+fen%C3%B3lica&gbv=2&ndsp=20&hl=es&sa=N&start=20&ei=ZXdLSuPAMIfc-QbLn6XfBQ

23.5.2013

35

COMPOSITE MATERIALS

Study of the effect on the properties of the composites:

‐ Treatment of the fibers

‐ Fiber loading

PHENOLIC MATRIX

Selection of the optimal conditions:

‐ Formulation

‐ Curing

‐ Drying

CELLULOSIC FIBERS

Modification of the fibers to improve fiber-matrix adhesion:

‐ Alkali treatment‐ Silanes as coupling agents

Specific objectives

Work in Aalto / motivation

NFC, NFLC

Reinforcement

Soybean oil resin

Matrix

Adhesion

Substrate of Printed Circuit Boards (electronic applications)Matrix: Epoxy (petroleum-based) Soybean oil

Reinforcement: E-glass (high energy requires) NFCOthers: Coupling agents (chemicals) Lignin (NFLC)

Lignin, NFLC

BIOCOMPOSITES

Lignin is awesome!

23.5.2013

36

Preliminary results

4 % L 14 % L0 % L

Mechanical properties

Barrier properties (water, oxygen) Interactions with water (contact angle, rate of water uptake, water absorbency)

Effect of lignin content on the properties of nanopapers

0 % Lignin 4 % Lignin 14 % Lignin

Density (g/cm3) 1.24 ± 0.03 1.18 ± 0.05 1.20 ± 0.02

Tensile Strength, MPa 164 ± 17 156 ± 17 116 ± 7

Tensile Index, kN/g 1942 ± 565 1625 ± 134 1306 ± 80

Breaking Strain, % 2.88 ± 0.12 2.83 ± 0.35 1.71 ± 0.25

Elastic modulus, GPa 14.3 ± 0.5 13.4 ± 0.9 12.2 ± 0.2

TEA, kJ/m2 161 ± 18 154 ± 34 66 ± 15

TEA, J/g 1904 ± 269 1598 ± 319 737 ± 167 0

50

100

150

200

0 1 2 3

Stre

ss (

MP

a)

Strain (%)

0% L

4% L

14% L

4 % L 14 % L0 % L

52.1° 65.7° 65.8°

Preliminary results

Effect of lignin content on the properties of nanopapers: Mechanical properties

4 %

14 %

0 %

100

200

300

4

8

12

16

A B C D E F G H I J K L0

3

6

9

12

Str

ength

(M

Pa)

Modulu

s (

GP

a)

Str

ain

(%

)

Softwood Hardw. Non-w.

A

A : Present work

B-L : Literature values- L

+ L

23.5.2013

37

Synthesis and characterization of soy protein-nanocellulose

composite aerogels













(Arcot Lokanathan)

USA crop value (2011) $35.7 billionUSA exports (2011) $21.5 billionMain use Soy oil Protein for human food 5%

American Soybean Association, Soy Stats 2011 World Agricultural Supply and Demand Estimates, 2012United Soybean Board, 2012

Relevance of soy bean

Soybean production is a world-scale business and generates large amounts of residual proteins

74

23.5.2013

38

Pro-Fam 955. Isolated Soy Protein. Data Sheet. ADM. 2009

Soy proteins-chemical diversity

Aromatic10.1%

Hydrophobic34.3%

Nucleophilic10.4%

Hydroxyl9.2% Other (small)

8.4%

Acids/Esters30.7%

Cationic16.5%

75

It is a porous material resulting from removing the solvent from a regular gel

What is an aerogel?

Aerogels are extensively used for aerospace applications, such as insulation for launch vehicles or for planetary entry, descent, and landing systems

In 1997 silica aerogels were used for the first time in the Mars Pathfinder mission

Meador, et Al. Applied Materials & Interfaces. 2012. 4, 536-544

Mech. strength between 5 – 9MPa

76

23.5.2013

39

Because of their high specific surface area and low density aerogels can be used in different applications

Aerogels

Thermal isolation

Non wovens

Filters

Packaging

Absorption Surface chemistry and catalysis

Packaging

77

Not every gel can be dried to form an aerogel

Aerogels

Even freeze drying induces stress and collapse

Only ”strong” materials can form aerogels by freeze drying

Gelatin collapses by freeze drying

Capillary forces in conventional drying

78

23.5.2013

40

Soy proteins alone tend to form brittle structures. Reinforcement with cellulose nano fibers (CNF) was studied

Cellulose Nano Fibers (CNF) reinforcement

CNFs can form aerogels by themselves, in this work the synergistic effect of both materials is studied

79

Under certain conditions (T and pH) Soy Protein (SP) denatures forming a viscous gel. The gel can be frozen and dried to form an aerogel

Aerogels from soy proteins

T: 70 CHCl 0.09 N1 h10% SP

SP – NFC Mixtures8% Solids

Slow Freezing

80

23.5.2013

41

Now Before

If not freezing is used the material flow out of the containers.

Procedure used successfully for CNF alone

If the freezing is too fast the material experience a fast expansion and it may break

Channels may be formed following temperature gradients

Munch, 2008

In presence of soy proteins conventional techniques are not adequate

Vacuum drying Fast freezing Directional freezing

81

82

23.5.2013

42

Surface area of CNF aerogels is 10 times lower compared with fast freezing processes

Surface area decreases when SP is added

SP Increment

Surface Area (BET)

83

The samples were weighted after drying and then left in a room in controlled conditions (23 °C, 50% relative humidity). The water uptake was followed

Equilibrium moisture is very similar in aerogels with different protein content

Water uptake from air

84

23.5.2013

43

Aerogels do not collapse under stress of 5 MPa

Stress required for 18% deformation

Mechanical properties

are similar for aerogels with reinforcing CNF of 33% or higher

Compression tests

CNF works as reinforcing agent

85

Water sorption is modulated by the composition

Hexane sorption is fast in all cases

Wat

er s

orp

tio

nH

exan

e so

rpti

on

Wicking tests

86

23.5.2013

44

Gels with higher SP content absorb more water

Excellent aerogel integrity (water and hexane)

SP Increment

Absorption by immersion

Water

Hexane

87

• Soy protein aerogels were produced by freeze drying

• Slow drying: avoids channel formation

• CNF reinforcing effect

• Soy protein decreases the rate of water uptake by the aerogels.

• Tunable water loading capacity

Conclusions

88

23.5.2013

45







(Julio Arboleda/OR)7. NFLC aerogels/foams






(Arcot Lokanathan)

Development of Bio-based

porous material and lignin

functionalization

NFC for porous material; high strength, high aspect ratio will allow to form rigid networks though interfibrils bondingsincluding physical entanglement and hydrogen bonds.

Amylopectin;Highly branched polysaccharide, semicrystal, Low cost, biodegradability, and renewal

In this study, NFC from EFB origin (provided from Dr. Ana Ferrer) with various content of lignin was used for the composited with amylopectin to investigate

-effect of lignin content on morphology and physical properties.-effect of compositions of NFC and amylopetin

Porous materials forInsulation, cushioning protection, catalysis, membrane, biomedical, construction materials

Water reservation

Tissue engineering

Cushioning protection

catalysis

NFLC/amylopectin biocomposite

Development of Bio-based porous material

23.5.2013

46

NFLC: Three different EFB pulp grades were produced after sulfur-free chemical treatments:

Composition of NFC-N or NFC-F and Amylopectin (w/w)

Table 1. EFB pulp chemical composition in weight percent (data rounded off to the first significant figure). Short notation N, M and F are used for NaOH-AQ, Milox and FoOH, respectively

Pulp type α-Cellulose Hemicellulose Holocellulose LigninEthanol

extractivesAsh

NaOH-AQ: N 81.8 15.9 97.7 2.3 2.5 1.0

Milox: M 63.4 22.1 85.5 6.2 5.1 1.6

FoOH: F 75.8 6.2 82 9 8.6 1.7

NFC-N ; at -20 oC

NFC-F; at -10 oC

Amylopectin soluble in liquid (water)

NFC

Freeze dry

Freezing temperature

wet gel aerogel

Air (void)

SolidSkeleton

NFCamylopect

insolid content

wt%

NFC-N(-200C)

100 0 1.675 25 2.0

50 50 3.1

25 75 6

0 100 5

NFC-F(-10 OC)

100 0 5

75 25 5

50 50 5

25 75 5

0 100 5

-Regeneration (crystallization) of amylopectin-Ice nucleatingThese factors can be influenced on the structure.

Pulp typeα-

CelluloseHemicellulose Holocellulose Lignin

Ethanol

extractivesAsh

1 NaOH-AQ: N 81.8 15.9 97.7 2.3 2.5 1.0

2 Milox: M 63.4 22.1 85.5 6.2 5.1 1.6

3 FoOH: F 75.8 6.2 82 9 8.6 1.7

4NFC (bleaced, from birch), prepared by Anu

--* -- -- -- -- --

NFLCs for biofoam with amylopectin

Preparation of NFC; Mechanical treatment1.5 wt% suspensions in D. I. waterMicrofluidaizer; 5passes

Chemical compositions of NFCs used for composite biofoam

Amylopectin (AP)from waxy corn

AP solution (water)NFC

Freeze dry

wet gel biofoam

Air (void)

SolidSkeleton

* -- Not measured

23.5.2013

47

NFC AP solid contentwt%

Densitymg/cm3

NFC-N(-200C)

100 0 1.6 26

75 25 2.0 45

50 50 3.1 50

25 75 6 118

0 100 5 98

NFC-M(-10 OC)-01, -02

100 0 3

75 25 3

50 50 3

25 75 3

0 100 3

NFC-F(-10 OC)

-01 (solid,5wt%),

-02 (3wt%)

100 0 5 or 3 82

75 25 5 or 3 67

50 50 5 or 3 57

25 75 5 or 3 49

0 100 5 or 3 53

NFC-01, -02(-10 OC)

100 0 3 360

75 25 3 61

50 50 3 56

25 75 3 34

0 100 3 36

NFC/AP (w/w)

100/0 75/25 50/50 25/75 0/100

AP

Weight ratio and densiy of biofoams with various types of NFC and AP

NFC

Preparation of biofoam NFLC and AP

Water adsorption test

NFLC-N /Amylopectin and NFLC-F/Amylopectin composites after freeze-drying

NFC/Amylopectin (w/w)

100/0 75/25 50/50 25/75 0/100

NFLC

NFLC-N

NFLC-F

amylopectin

-20 oC

-10 oC

•Density of the composite was increased with increasing of NFC content.

Density of the composites with various NFLC-F amount •Two different NFLC and amylopectin composites were

prepared by freeze-drying with various compositions.

0 20 40 60 80 1000.00

0.02

0.04

0.06

0.08

0.10

NFC-F, wt%

den

sity

, g/c

m3

0

2

4

6

8

10

solid

, wt%

•Lower temperature (-20 oC) for freeze-dry was found less defects on the morphology, especially NFLC dominant composition.

•How dose freezing temperature affect on the structure? Amylopectin crystallizing + ice nucleating

23.5.2013

48

NFC/AP

NFC-F/AP 99 mg/g

67 mg/g 64 mg/g55 mg/g53 mg/g

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0 50 100 150 200 250

0.00

0.02

0.04

0.06

0.08

0.10

wat

er r

egai

n, g

/g

25

NFC, 0

50

75

100

25

wat

er r

egai

n, g

/g

time, min

NFC, 0

50

75

100

30 mg/g

27 mg/g

22 mg/g

20 mg/g

11 mg/g

Water regain (4h)Condition: NaCl aq. Sat (22 oC)

Water adsoption test on biofoams

Water adsorption of NFLCs/AP bio foam was increased with increasing AP ratio in the biofoam.

NFLC-F containing 9 % lignin and AP biofoams showed higher water adsorption than NFLC (bleached)/AP biofoams.

Both NFC0 (AP100) in foams of NFLC and NFLC-F were supposed to be similar, but they were different in the value of water regain. Need to check the procedure of preparation of biofoam.

23.5.2013

49

New lignin based nancomposite material with Click reaction

Lignin beadsCrosslink withEpichlorohydr

in

Surface modification(alkynylation) of lignin beads

Clickchemistry for alkynyl lignin and starch-N3

suspension polymerisation Lignin beads Click reactionalkynyl lignin

Cross linking in situ

Scheme for lignin click reaction

Oil phase: 1,2-dichroloethane:, 8ml (10% Span80 (w/v))

Water phase: lignin (20 wt%)/2M NaOH, 0.52g

1-BuOH, 0.9 ml

Epichlorohydrin, 100 ml

50 oC, 24h

preciptation with HCl

Washed with water until pH7

production

AFM observation

Lignin as macromonomer reaction (polymerization) in suspension

20 ×20 mm2 5 ×5 mm2

23.5.2013

50

Lignin was used as macromonomer for polymerization in suspension condition

Particle morphology was observed after reaction













(Arcot Lokanathan)

Laccase-mediated

coupling of

nonpolar chains

for the

hydrophobization

of lignocellulose

23.5.2013

51

Laccase

+

HB-C12

101

ethyl 3,4,5-trihydroxybenzoate

(HB-C2, r1)

propyl 3,4,5-

trihydroxybenzoate

(HB-C3, r2)

octyl 3,4,5-trihydroxybenzoate

(HB-C8, r3)

dodecyl 3,4,5-trihydroxybenzoate

(HB-C12, r4)

β-sitosterol (r5)

α-tocopherol (r6)

4-[4-(trifluoromethyl)phenoxy]phenol (r7)

3-methylbutyl 2-hydroxybenzoate (r8)

2,4,6-tris(1-phenylethyl)phenol (r9)

102

23.5.2013

52

Laccase

+

(1)

(2)

103

Change in third overtone QCM frequency of a model film of cellulose as function of

time. After equilibration in the background buffer solution (first 5 minutes) solutions

of Lac, HB-C12 or Lac/HB-C12 were injected, as indicated. At about 63 min time

rinsing with buffer solutions was carried out. 104

23.5.2013

53

105

106

23.5.2013

54

107

108

23.5.2013

55













(Arcot Lokanathan)

• Carbon nanodots + NFC

• Carbon nanodots

– Photoluminescence both in solution and the solid state

– non-toxic

– interest in biosensing applications utilizing the photoluminescence properties of CNDs

J. Mater. Chem., 2012, 22,24230-24253

110

23.5.2013

56

111

112

23.5.2013

57

113

Covalent attachment of carbon

nanodots on carboxymethylated NFC

• Carboxymethylated NFC is spin-coated on PEI-coated

QCM-D sensor

• The stabilized surface (pH 4.5; 10 mM buffer) is

EDC/NHS treated for 20 minutes

• The carbon nanodots are added (20 minutes; pH 4.5;

10mM NaAc/HAC buffer)

• The surface is rinsed with buffer (15 min) and with

NaHCO3 (pH 8.5; 10 mM; 15 min) to remove any solely

electrostatically bound particles• The surface is rinsed with buffer (pH 4.5; 10 mM)

114

23.5.2013

58

115

116

23.5.2013

59

117

118

23.5.2013

60

119

Next step: bulk modifications of NFC

• Procedure: Activation of NFC + attachment of carbon

nanodots + dialysis

• Different dosages of carbon nanodots

• Three different degrees of activation: charge properties

of the resulting gel, FTIR, elemental analysis

• Fluorescense properties: microscopy imaging, UV-vis• Biosensing application

120

23.5.2013

61

The unusual

interactions

between

polymer grafted

cellulose

nanocrystal

aggregates













(Arcot Lokanathan)

The unusual interactions between polymer grafted cellulose nanocrystal aggregates.

Local densities of beads of the grafted molecules in the plane perpendicular

to the long axis if the CNA as a colour map (as indicated in the figure) for

molecules with 8 beads (left) and 22 beads (right). The green square

indicates the nanocrystal.122

23.5.2013

62

Interaction-induced deformation of the polymer coronas of pairs of CNAs (difference

between the local density of the deformed system and an undisturbed system. Red indicates

density increase and blue density decrease. Note also that only the molecules grafted to one

CNA are used for the comparison. Compared are face-to-face configurations for three different

distances: (a) 47, (b) 40 and (c) 25 and one edge-to-edge conformation at a CNA/CNA distance

of 25. The grey lines indicate the centre between the CNA. The plots reflect the increasing

deformation with decreasing distance and the greater confinement in the face-to-face

arrangement compared to the edge-to-edge configuration.

123

Force per unit length of nanocrystal generated by steric repulsion between

grafted molecules of 8 beads length (top) and 22 beads length (bottom) as a

function of the distance between the CNA centres. Compared are the face-to-

face conformation: blue and red to the edge to- edge conformation yellow and

green. In both cases a crossover from stronger edge-to-edge forces to

stronger face-to-face forces can be observed.

124

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63

Synthetic modifications of

lignin & cellulose

nanocrystals (CNCs) towards click chemistry

reactions













(Arcot Lokanathan)

Lignin - natural and renewable raw material

Most important by-product of the paper

industry and between 40 and 50 million tons

per year are produced worldwide mainly as a

non-commercialized waste product

Possible feedstock for producing fine

chemicals that traditionally require the use of

petroleum-based chemicals

Lignin is highly functionalized (hydroxyl

and carboxyl moieties) which allows the use

of various chemistries for modifying the

properties of core lignin polymer.

23.5.2013

64

Modification of Lignin – CDI Coupling Followed by Click Chemistry

CDI (carbonyldiimidazole) cross linking agent can be used for

OH- or COOH-funtionalization

CDI

Click

-CH (terminal),

3300 cm-1

Amide,

1646 cm-

1

15

20

25

30

35

40

45

50

55

60

65

70

75

%T

500 1000 1500 2000 2500 3000 3500 4000

W avenumbers (cm-1)

Azide

2120 cm-1

FTIR of modified lignins

Azide-modified lignin Alkyne-modified lignin

23.5.2013

65

Modification of cellulose reducing end groups (REGs)?

• The arrangement of individual cellulose chains inside the crystals;

parallel vs. antiparallel (cellulose I vs. cellulose II)

• Derivatization only on the one end of the crystal vs. derivatization on

the both ends of the crystal (regiospecificity)

• Two completely independent chemistries on single CNC surface, where

in one chemistry (end group reactions) proceeds without sterically

hindered reactions on the remainder surface

Parallel: Antiparallel:

129

Synthesis of ”clickable” CNC precursors

Sample N1s S2p Sulfur

(µmol/g)

Nitrogen

(µmol/g)

CNC-thiol

(EDC/NHS)

0.55 0.58 0.34 0.32

CNC-

propargyl

0.61 0 0 0.31

CNC-azide 0.42 0 0 0.26

Note: Calculations are based on the assumption that starting CNCs

contain 0.62% sulfur groups based on the total number of hydroxyl

and sulfur groups

Wilson, W. K. & Padgett, A. A. (1955) Tappi 38, 292-300.

Dong, X. M.; Revol, J. F. & Gray, D. G. (1998). Cellulose, 5, 1, 19-32.130

23.5.2013

66

Fluorescent labeling of CNCs

A photograph of the CNC suspension after the Cu1-catalyzed reaction

with fluorescent dansyl probe (left vial) and CNC suspension after the

reaction with dansyl probe without Cu1 (right vial, negative control)

UV-light (wavelength 366 nm

131

Quartz Crystal Microbalance with Dissipation (QCM-D)

Spin coated CNC model film

(AFM image, 5x5µm2)

Combined mass and

viscoelastic properties

Used in real time adsorption studies

Prepared surfaces can be further analyzed with AFM

Quartz crystal

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67

Quartz Crystal Microbalance Experiments

QCM-D curves of CNC-propargyl/OMe-PEG-N3/Cu 1 (blue line) and

CMC-propargyl/OMe-PEG-N3 (red line). Decreased frequency

denotes increased mass on the substrate.

OMe-PEG-N3 Rinsing

Summary

Lignin was modified with alkyne and azide groups (precursors

for click reaction)

Reducing end groups (REGs) of cellulose nanocrystals were

modified EDC/NHS coupling chemistry (from oxidized REGs)

Modified CNCs were further functionalized with CuAAC

reaction

One of the advantages of presented approach is the

possibility to bring large molecules in the proximity of CNCs

(spacer length)

23.5.2013

68

Future plans

Modify lignin with click counterparts

Prepare and modify cellulose (II) nanocrystals













(Arcot Lokanathan)

Controlling the sorption

behaviour of end functionalized

CNC

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69

Motivation

Smart materials from renewable resources

Requirements for high end applications

- Controlling nano-scale architecture

- Manipulating the self assembly processes

Building blocks for nano-architecture

- Something well defined: structurally and chemically

- Electro-mechanical (Piezoelectric) - Photosensitive, light emitting devices

- Magnetically active - self healing, self cleaning

- pH/thermal responsive - Semiconducting/ Conducting

Meas. Sci. Technol., 2011, 22, 024005

Reducingend

Non-reducingend

Renewable building blocks for nano-architecture

Something well defined: structurally and chemically

23.5.2013

70

Example – Reductive amination at end

STEP 1

Imine formation

Alkaline pH

STEP 2

Reduction

NaBH3(CN)

Neutral pH

NaBH3(CN) : Toxic, work up produces NaCN and other cyanide species

Alternative: NaBH(OAc)3

Topochemical / asymmetric chemical

modification

Where is the proof of ‘END’ only reaction?

Np tagging

23.5.2013

71

(a) (b) (c) (d)

(e) (f) (g) (h)

(i)

(a), (b), (c) – Acetate borohydride pH 5, 7, 9.2

(d), (e), (f) – Cyanobrohydride pH 5, 7, 9.2

(g), (h), (i) – Picoline borane pH 5, 7, 9.2

Scale bar in all images 100nm

AgNp tagged CNC-SH : TEM

How do the modified CNC

interact with Au?

CNC-SH

SSSS S

Gold

Alkane thiol

30°

CNC

23.5.2013

72

Sauerbrey, G Z. Phys.155 (1958) 206

QCM with dissipation

http://www.bu.edu/

Flexible

Higher D

Rigid

Lower D

ΔD

ΔF

Flexible

Higher slope

CNC-SH CNC

SH

Self assembly on Au QCM-D

S SS SS

Gold

• CNC-SH adlayer is far more flexible than CNC adlayer

• CNC-SH adlayer 1mg/ml has higher rigidity relative to 0.1mg/ml

23.5.2013

73

Proving upright orientation- align CNCs

• Evaporation front driven alignment

• Drop casting technique

2 steps

- Chemisorption of CNC-SH

- Evaporating a drop of water

Atomic force microscopy

CNC-SH

adsorbed on Au

CNC-SH adsorbed on Au followed

by drying a drop of water

*All images: 2mm×2mm, Tapping

mode, Air, Force constant : 46 N/m

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74

• Biological cilia mimic

Size selective exclusion of particles

(submitted to Biomacromolecules)

• Inter CNC distance control

Increase and decrease

( to be submitted to Biomacromolecules. )

Other studies related to CNC-SH coatings

Brian Button et al. Science 337, 937 (2012)

Summary of results

– Reducing end thiolation of CNC was sucessful

AgNp tagging (end specific)

– Thiolated CNCs were found to chemisorb on Au

QCM-D (CNC-SH adlayer flexible)

– Chemisorbed CNC-SH could be aligned by drop casting technique

– The inter CNC distance in the chemisorbed CNC-SH adlayer could

be controlled

23.5.2013

75













(Arcot Lokanathan)

Efforts related to Bacterial Cellulose

PVA/BC nanocomposites

+ =

OH

n

Physical linking

Chemical crosslinking

23.5.2013

76

Physical linking

• Cellulose production:

PVA viscosity

• Nanocomposites 10, 22, 30%

cellulose

Chemical crosslinking

• Cellulose production:

Glyoxal (Toxic)

PVA viscosity

• Nanocomposites 0.6, 6, 14%

cellulose

Chemical crosslinking and physical linking

• The transparency of the matrix is not affected

• Increase of 600% and 50% Young's modulus and stress at break

• Thermal stability

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77

b a c

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78

Lotus effect

• Lotus leaf surface is covered with micrometer-

sized structures decorated with nanometer

particles

• Surface composition: epidermal cells of waxy

hydrophobic crystals

• Roughness changes the contact area between the

surface and the liquid drop

Objective: micro- and nano- manufacturing to enable

reproducible construction of hierarchical, multiscale

surface topologies. Image of the surface of a lotus leaf and artificial laser-structured silanized silicon surface*

* Laser structuring of water-repellent biomimetic surfaces. SPIE Newsroom, 2009

+

In-situ assembly

Poly(diallyldimethylammonium chloride), PDDA

Silica nanoparticles, SiO2 NPs

NaCl

Bacterial Cellulose, BC

FOTS

http://wewanttolearn.files.wordpress.com/2011/09/1441_fig1.jpg

23.5.2013

79

Ex-situ assembly

+

Poly(diallyldimethylammonium chloride) (PDDA)

NaCl

Bacterial Cellulose, BC Silica nanoparticles, SiO2 NPs

FOTS

Hydrophobic Treatments

SiO2 NPsPDDA/NaCl –

sodium silicate (SS)FOTS

In BC

In BC - SiO2 NPs X

In BC - SiO2 NPs - FOTS X X

In BC - SiO2 NPs - SS - FOTS X X X

Ex BC

Ex BC - SiO2 NPs X

Ex BC - SiO2 NPs - FOTS X X

Ex BC - SiO2 NPs - SS - FOTS X X X

Trichloro(1H,1H,2H,2H-perfluorooctyl)silane

In-s

itu

Ex-s

itu

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80

Morphology (SEM)

Composition (XRD)

Element Wt% At%CK 31 56.9OK 28 38.3

SiK 0.3 0.24AuM 41 4.6

Matrix Correction ZAF

Element Wt% At%CK 45 59OK 24 24

NaK 23 16SiK 0.4 0.2AuM 6.5 0.5ClK 1.8 0.8

Matrix Correction ZAF

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81

Thermal analysis and inorganic loading

In BC - SiO2 NPs

In BC

In BC - SiO2 NPs

In BC

Ex BC - SiO2 NPs

Ex BC

Ex BC - SiO2 NPs

Ex BC

Water Contact Angle

Water CA (°)

In BC (NaCl) 59 ± 5

In BC (PDDA/NaCl+SiO2) 87 ± 4

In BC (PDDA/NaCl+SiO2) + FOTS 101 ± 3

In BC (PDDA/NaCl+SiO2) + SS+ FOTS 112 ± 3

Ex BC 41 ± 5

Ex BC (PDDA/NaCl+SiO2) 61 ± 5

Ex BC (PDDA/NaCl+SiO2) + FOTS 69 ± 3

Ex BC (PDDA/NaCl+SiO2) + Si + FOTS 71 ± 8

In BC

In BC - SiO2 NPs

In BC - SiO2 NPs - FOTS

In BC - SiO2 NPs - SS - FOTS

In BC

ExBC - SiO2 NPs

Ex BC - SiO2 NPs - FOTS

Ex BC - SiO2 NPs - SS - FOTS

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Conclusions

• A new method to produce hydrophobized bacterial cellulose

• Nanotechnology and bioengineering of bacteria used for in-

situ roughening BC (self-assembled silica NPs) followed by

hydrophobization

• Compared to Ex-situ methods: formation of agglomerates

decreases

• BC - SiO2 NPs - FOTS: WCA of

• Applications: self-cleaning membranes, anti-adhesive

coatings and reinforcing fibers for fluoropolymer matrices

Administration / Budget

164

23.5.2013

83

€

LignoCell Budget

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