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Opto-nanomechanical spectroscopic material characterization

Nature Nanotechnology volume 10, pages 870–877 (2015)Cite this article

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Abstract

The non-destructive, simultaneous chemical and physical characterization of materials at the nanoscale is an essential and highly sought-after capability. However, a combination of limitations imposed by Abbe diffraction, diffuse scattering, unknown subsurface, electromagnetic fluctuations and Brownian noise, for example, have made achieving this goal challenging. Here, we report a hybrid approach for nanoscale material characterization based on generalized nanomechanical force microscopy in conjunction with infrared photoacoustic spectroscopy. As an application, we tackle the outstanding problem of spatially and spectrally resolving plant cell walls. Nanoscale characterization of plant cell walls and the effect of complex phenotype treatments on biomass are challenging but necessary in the search for sustainable and renewable bioenergy. We present results that reveal both the morphological and compositional substructures of the cell walls. The measured biomolecular traits are in agreement with the lower-resolution chemical maps obtained with infrared and confocal Raman micro-spectroscopies of the same samples. These results should prove relevant in other fields such as cancer research, nanotoxicity, and energy storage and production, where morphological, chemical and subsurface studies of nanocomposites, nanoparticle uptake by cells and nanoscale quality control are in demand.

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Figure 1: Biomass study at various chemical processing stages involved in biofuel production.
Figure 2: Experimental set-up of HPFM.
Figure 3: HPFM characterization of biomass revealing nanoscale features.
Figure 4: Nanoscale characterization of chemical processing.
Figure 5: Broadband nanospectroscopy with HPFM.

References

  1. Garcia, R. & Herruzo, E. T. The emergence of multifrequency force microscopy. Nature Nanotech. 7, 217–226 (2012).

    Article  CAS  Google Scholar 

  2. Tetard, L., Passian, A. & Thundat, T. New modes for subsurface atomic force microscopy through nanomechanical coupling. Nature Nanotech. 5, 105–109 (2010).

    Article  CAS  Google Scholar 

  3. Marquardt, F. & Girvin, S. Optomechanics. Physics 2, 40 (2009).

    Article  Google Scholar 

  4. Lucas, M. & Riedo, E. Combining scanning probe microscopy with optical spectroscopy for applications in biology and materials science. Rev. Sci. Instrum. 83, 061101 (2012).

    Article  Google Scholar 

  5. Dazzi, A., Prazeres, R., Glotin, F. & Ortega, J. M. Local infrared microspectroscopy with subwavelength spatial resolution with an atomic force microscope tip used as a photothermal sensor. Opt. Lett. 30, 2388–2390 (2005).

    Article  CAS  Google Scholar 

  6. García, R., Magerle, R. & Perez, R. Nanoscale compositional mapping with gentle forces. Nature Mater. 6, 405–411 (2007).

    Article  Google Scholar 

  7. Herruzo, E. T., Perrino, A. & García, R. Fast nanomechanical spectroscopy of soft matter. Nature Commun. 5, 3126 (2014).

    Article  Google Scholar 

  8. Davison, B. H. The increasing importance and capabilities of biomass characterization. Ind. Biotechnol. 8, 189–190 (2012).

    Article  Google Scholar 

  9. Haisch, C. Photoacoustic spectroscopy for analytical measurements. Meas. Sci. Technol. 23, 012001 (2012).

    Article  Google Scholar 

  10. Foston, M. & Ragauskas, A. J. Biomass characterization: recent progress in understanding biomass recalcitrance. Ind. Biotechnol. 8, 191–208 (2012).

    Article  CAS  Google Scholar 

  11. Kac˘uráková, M., Capek, P., Sasinková, V., Wellner, N. & Ebringerová, A. FT-IR study of plant cell wall model compounds: pectic polysaccharides and hemicelluloses. Carbohydr. Pol. 43, 195–203 (2000).

    Article  Google Scholar 

  12. Studer, M. H. et al. Lignin content in natural Populus variants affects sugar release. Proc. Natl Acad. Sci. USA 108, 6300–6305 (2011).

    Article  CAS  Google Scholar 

  13. Galazka, J. M. & Cate, J. H. D. Improving the bioconversion of plant biomass to biofuels: a multidisciplinary approach. Energy Environ. Sci. 4, 3329 (2011).

    Article  CAS  Google Scholar 

  14. Lynd, L. R. et al. How biotech can transform biofuels. Nature Biotechnol. 26, 169–172 (2008).

    Article  CAS  Google Scholar 

  15. Davison, B. H., Keller, M. & Fowler, V. S. The goals and research of the BioEnergy Sciences Center (BESC): developing cost-effective and sustainable means of producing biofuels by overcoming biomass recalcitrance. Bioenerg. Res. 2, 177–178 (2009).

    Article  Google Scholar 

  16. Ding, S.-Y. et al. How does plant cell wall nanoscale architecture correlated with enzymatic digestibility? Science 338, 1055–1060 (2012).

    Article  CAS  Google Scholar 

  17. Fernandes, A. N. et al. Nanostructure of cellulose microfibrils in spruce wood. Proc. Natl Acad. Sci. USA 108, E1195–E1203 (2011).

    Article  Google Scholar 

  18. Himmel, M. E. Biomass Recalcitrance (Blackwell, 2008).

    Book  Google Scholar 

  19. Fahlen, J. & Salmen, L. Pore and matrix distribution in the fiber wall revealed by atomic force microscopy and image analysis. Biomacromolecules 6, 433–438 (2005).

    Article  CAS  Google Scholar 

  20. Grethlein, H. E. The effect of pore size distribution on the rate of enzymatic hydrolysis of cellulosic substrates. Nature Biotechnol. 3, 155–160 (1985).

    Article  CAS  Google Scholar 

  21. Jung, S., Foston, M., Sullards, M. C. & Ragauskas, A. J. Surface characterization of dilute acid pretreated Populus deltoides by ToF-SIMS. Energy & Fuels 24, 1347–1357 (2010).

    Article  CAS  Google Scholar 

  22. Tetard, L. et al. Virtual resonance and frequency difference generation by van der Waals interaction. Phys. Rev. Lett. 106, 180801 (2011).

    Article  CAS  Google Scholar 

  23. Kalluri, U. C. & Keller, M. Bioenergy research: a new paradigm in multidisciplinary research. J. R. Soc. Interface 7, 1391–1401 (2010).

    Article  Google Scholar 

  24. Sannigrahi, P., Ragauskas, A. & Tuskan, G. A. Poplar as a feedstock for biofuels: a review of compositional characteristics. Biofuels Bioprod. Bioref. 4, 209–226 (2010).

    Article  CAS  Google Scholar 

  25. Schenzel, K., Fischer, S. & Brendler, E. New method for determining the degree of cellulose I crystallinity by means of FT Raman spectroscopy. Cellulose 12, 223–231 (2005).

    Article  CAS  Google Scholar 

  26. Tetard, L. et al. Imaging nanoparticles in cells by nanomechanical holography. Nature Nanotech. 3, 501–505 (2008).

    Article  CAS  Google Scholar 

  27. Plodinec, M. et al. The nanomechanical signature of breast cancer. Nature Nanotech. 7, 757–765 (2012).

    Article  CAS  Google Scholar 

  28. Coffey, D. C., Reid, O. G. & Ginger, D. S. Imaging local photocurrents in polymer/fullerene solar cells with photoconductive atomic force microscopy. Nano Lett. 7, 738–744 (2007).

    Article  CAS  Google Scholar 

  29. Leopold, J., Gunther, H. & Leopold, R. New developments in fast 3D-surface quality control. Measurement 33, 179–187 (2003).

    Article  Google Scholar 

  30. Solar, M. I. & Buehler, M. J. Composite materials: taking a leaf from nature's book. Nature Nanotech. 7, 417–419 (2012).

    Article  CAS  Google Scholar 

  31. Sato, Y. et al. Strong coupling between distant photonic nanocavities and its dynamic control. Nature Photon. 6, 56–61 (2012).

    Article  CAS  Google Scholar 

  32. Stinaff, E. A. et al. Optical signatures of coupled quantum dots. Science 311, 636–639 (2006).

    Article  CAS  Google Scholar 

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Acknowledgements

This work was sponsored by the BioEnergy Science Center (BESC) of the Oak Ridge National Laboratory (ORNL). L.T. acknowledges partial support from ORNL's Wigner Fellowship Program. The authors thank the BESC scientists S. Jung and A. Ragauskas at Georgia Institute of Technology for providing the samples and M. Davis and R. Sykes at the National Renewable Energy Laboratory (NREL) for providing the Populus stems that were used for cross-sectioning. BESC is a US Department of Energy (DOE) Bioenergy Research Center supported by the Office of Biological and Environmental Research in the DOE Office of Science. ORNL is managed by UT-Battelle, LLC, for the US DOE under contract DE-AC05-00OR22725.

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Author notes

  1. L. Tetard

    Present address: Present address: Nanoscience Technology Center, Orlando, Florida 32826, USA,

Authors and Affiliations

  1. Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    L. Tetard, A. Passian, R. H. Farahi & B. H. Davison

  2. Department of Physics, University of Tennessee, Knoxville, 37996-1200, Tennessee, USA

    A. Passian

  3. Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, 37996, Tennessee, USA

    A. Passian, R. H. Farahi & B. H. Davison

  4. Department of Chemical and Materials Engineering, University of Alberta, Edmonton, T6G 2V4, Alberta, Canada

    T. Thundat

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  1. L. Tetard
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Contributions

All authors contributed to the manuscript. A.P. and R.H.F. performed the revisions, new measurements and data analysis. B.H.D. provided plant biological expertise.

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Correspondence to A. Passian.

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The authors declare no competing financial interests.

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Tetard, L., Passian, A., Farahi, R. et al. Opto-nanomechanical spectroscopic material characterization. Nature Nanotech 10, 870–877 (2015). https://doi.org/10.1038/nnano.2015.168

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