Biobased Nanostructural Materials New Opportunities for the Forest by psf35982

VIEWS: 9 PAGES: 30

									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-Furandicarboxylic acid
                                                     •   Biomass as a feedstock for products is an
    3-Hydroxypropionic acid                              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
                                                         develop.
           Levulinic acid
                                                     •   Lignin product development is important.
    3-Hydroxybutyrola ctone
              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




            HO                O                                                              O
                                                                                                          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 car bohydr ate based b olaforms
                                                 chain le ngth va riation
                                       chain structu re varia tio n: stere och emistry,
                                                br anchin g, he te roa to ms                                                                        covalen t linkage s

                                                                                                                                     covalen tly stabilize d mon olayer me mbr ane s
    OR                                     OR                              OR                                                                 lon g live d catalyst supp orts
                     Fer rier chemistry                                                                                                      str uctu rally d efined catalysts
           O                                       O                O            self a ssemb ly                                                   ele ctro nic de vices
                                                                                                                                                  ne w n ano structure s
  RO                                                                                                                                     pr edictable ma cr omo lecular a rrays
                       or gan ome tallic RO                                OR                                                            ma cr opo rous Si catalyst temp late s
           OR         tran sfor mations

    glycals                                     glycal based bo laforms                   bo laform ba se d mon olayer membr ane s

                                                                                predictive models?
 or gan ome tallic            OR
                                                          structure                                         shape
tran sfor mations
                                     O

                            RO             R                                                                                          me mbr ane supp orted b ioactive mo lecules
                                                                                                                                          bio mime tic lip id/enzyme systems
                  ne w methods of fun ction alization                                                                                         infection control - ho sp ita ls
               ne w structural/ele ctro nic u nits in su gar s                                                                                   bio se nsors, de te ctor s
                                                                                                                                                     bio active filter s
                                                                                                                                                        air q uality
                                                                                                                                           hig hly d efined catalyst syste ms
          current progress                                                                                                                cellula r recogn itio n, car boh yd rate
                                                                                                                                                        olig ome rs

                            phase 1 - establ ish baselines
 approximate time
  phases of work                         phase 2 - bol aform properti es and self assembl y


                                                                                            phase 3 - stabili zation of membranes, bioacti ve 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

                200µm                                        200µm




                 No avicel, 20% bola                        4% avicel, 20% bola
                   in DMAc/LiCl                        (based on avicel) in DMAc/LiCl

                200µm                                       200µm




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

                                                                         Additional stabilization
                                                                                                                                                                                                              O                     OH                                        HO
                                                                                                                                                                                  HO                                        O                                                                           O
                                                                                                                                                                                                      OH            O                                                                                 H
                                                                                                                                                                                                                                    H                                                               O   H
                                                                                                                                                                                                                    H                   O O                                                    O

                                                                         through -bonding and                                                                                                                         H
                                                                                                                                                                                                                        O                           O                                      O
                                                                                                                                                                                                                                                                                                              O
                                                                                                                                                                                                                                                                                                               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
re 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
�� USDA/NRI

								
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