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Award Detail

Awardee:UNIVERSITY OF WISCONSIN SYSTEM
Doing Business As Name:University of Wisconsin-Madison
PD/PI:
  • Pupa Gilbert
  • (608) 262-2281
  • pupa@physics.wisc.edu
Award Date:06/06/2011
Estimated Total Award Amount: $ 450,000
Funds Obligated to Date: $ 450,000
  • FY 2012=$150,000
  • FY 2011=$150,000
  • FY 2013=$150,000
Start Date:08/01/2011
End Date:07/31/2014
Transaction Type:Grant
Agency:NSF
Awarding Agency Code:4900
Funding Agency Code:4900
CFDA Number:47.049
Primary Program Source:040100 NSF RESEARCH & RELATED ACTIVIT
Award Title or Description:Structure of Mollusk Shells at Different Length-Scales
Federal Award ID Number:1105167
DUNS ID:161202122
Parent DUNS ID:041188822
Program:BIOMATERIALS PROGRAM
Program Officer:
  • Aleksandr Simonian
  • (703) 292-2191
  • asimonia@nsf.gov

Awardee Location

Street:21 North Park Street
City:MADISON
State:WI
ZIP:53715-1218
County:Madison
Country:US
Awardee Cong. District:02

Primary Place of Performance

Organization Name:University of Wisconsin-Madison
Street:21 North Park Street
City:MADISON
State:WI
ZIP:53715-1218
County:Madison
Country:US
Cong. District:02

Abstract at Time of Award

ID: MPS/DMR/BMAT(7623) 1105167 PI: Gilbert, Pupa ORG: University of Wisconsin Title: Structure of mollusk shells at different length-scales INTELLECTUAL MERIT: The complex structures of mollusk shells will be analyzed with unprecedented resolution, and on a large scale, using new spectromicroscopy methods developed with the previous NSF grant and which are now available to many other synchrotron users around the world. The mollusks produce a variety of mineralized shells that are presumably adapted to specific functions. The PI will study the processes leading to the formation of complex shell structures, and correlate these observations with the physical parameters (e.g. depth, pressure, temperature) of the environments in which the mollusks live. This will provide insights into the evolution of mollusk shells, how they adapted to different environments, and possibly provide new tools to for measurement of environmental parameters. Beyond this, a full understanding of how mollusk shells are constructed can serve as a guide for biomimetic manufacture of strong, tough composites. BROADER IMPACTS: The methods developed with the previous NSF grant have now been established, and are available to hundreds of other spectromicroscopy users around the world. The PI has also developed software to process the spectromicroscopy data, which is distributed free-of charge to the community on http://home.physics.wisc.edu/gilbert/. The experiments proposed here will yield detailed microcrystal and nanocrystal architectures and the formation mechanisms of tough biominerals, and may therefore inspire the engineering of new synthetic materials with improved performances for medical implants or micro-mechanical machines. One graduate and one undergraduate student per year will be involved in the proposed experiments. Women and underrepresented minority students will be actively recruited. Four major outreach activities will be performed, including: (1) Development of instructional modules on biomineralization within the framework of the Wisconsin Center for the Integration of Research, Teaching, and Learning (CIRTL). These will be actively disseminated through CIRTL for use by high school teachers and college educators for their own classes. (2) Presentations to about 3000 people/year from the general public at the UW-Madison Physics Fair. (3) The PI and her students will continue to provide lectures and lab experiments to African American students within the PEOPLE program every summer. (4) The PI has given and will continue to give invited talks at the American Association of Physics Teachers (AAPT) annual meeting, during which she has and will disseminate teaching tools, modules, and slides to the teachers, to teach the fascination of biominerals to high school and college students.

Publications Produced as a Result of this Research

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Johnson, C. J. Gilbert, P.U.P.A. Abrecht, M. Baldwin, K. L. Russell, R E. Pedersen, J. A. Aiken, J. M. McKenzie, D. "Low copper and high manganese levels in prion protein plaques" Viruses, v.5, 2013, p.654-662.

Kabalah-Amitai, Lee Mayzel, Boaz Kauffmann, Yaron Fitch, Andrew N. Bloch, Leonid Gilbert, Pupa U. P. A. Pokroy, Boaz "Vaterite crystals contain two interspersed crystal sructures" Science, v.340, 2013, p.454-457. doi:10.1126/science.1232139 

Gong, Y. U. T. Killian, C. E. Olson, I. C. Appathurai, N. P. Amasino, A. L. Martin, M. C. Holt, L. J. Wilt, F. H. Gilbert, P. U. P. A. "Phase transitions in biogenic amorphous calcium carbonate" Proc Natl Acad Sci USA, v.109, 2012, p.6088-6093. doi:10.1073/pnas.1118085109 

Konicek, A. R. Grierson, D. S. Sumant, A. V. Friedmann, T. A. Sullivan, J. P. Gilbert, P. U. P. A. Sawyer, W. G. Carpick, R. W. "Influence of surface passivation on the friction and wear behavior of ultrananocrystalline diamond and tetrahedral amorphous carbon thin films" Physical Review B, v.85, 2012, p.155448.

Olson, I. C. Blonsky, A. Z. Tamura, N. Kunz, M. Gilbert, P. U. P. A. "Crystal nucleation and near-epitaxial growth in nacre" J Struct Biol, v.184, 2013, p.454-457.

Yang, L. Killian, C. E. Kunz, M. Tamura, N. Gilbert, P. U. P. A. "Biomineral nanoparticles are space-filling" RSC-Nanoscale, v.3, 2011, p.603-609.

IC Olson, R Kozdon, JW Valley, and PUPA Gilbert "Mollusk Shell Nacre Ultrastructure Correlates with Environmental Temperature and Pressure" J. Am. Chem. Soc., v.134, 2012, p.7351-7358. doi:10.1021/ja210808s 

Olson, I. C.;Kozdon, R.;Valley, J. W.;Gilbert, P. U. P. A.; "Mollusk shell nacre ultrastructure correlates with environmental temperature and pressure" J Am Chem Soc, v.134, 2012, p.735173.

Gilbert, P. U. P. A.;Young, A.;Coppersmith, S. N.; "Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using x-ray absorption spectroscopy" Proc Natl Acad Sci USA, v.108, 2011, p.11350-113.

Gilbert, P. U. P. A.;Wilt, F. H.; "Molecular aspects of biomineralization of the echinoderm endoskeleton" Molecular Biomineralization, v., 2011, p.199-223.

Killian, C. E. Metzler, R. A Gong, Y. U. T. Churchill, T. H. Olson, I. C. Trubetskoy, V. Christensen, M. B. Fournelle, J. H. De Carlo, F. Cohen, S. Mahamid, J. Wilt, F. H. Scholl, A. Young, A. Doran, A. Coppersmith, S. N. Gilbert, P. U. P. A. "Self-sharpening mechanism of the sea urchin tooth" Adv Funct Mater, v.21, 2011, p.682?690. doi:10.1002/adfm.201001546 

Olson, I. C. Gilbert, P. U. P. A. "Aragonite crystal orientation in mollusk shell nacre may depend on temperature. The angle spread of crystalline aragonite tablets records the water temperature at which nacre was deposited by Pinctada margaritifera." Faraday Discuss, v.159, 2012, p.421-432. doi:10.1039/C2FD20047C 

Gong, Y. U. T.;Killian, C. E.;Olson, I. C.;Appathurai, N. P.;Amasino, A. L.;Martin, M. C.;Holt, L. J.;Wilt, F. H.;Gilbert, P. U. P. A.; "Phase transitions in biogenic amorphous calcium carbonate" Proc Natl Acad Sci USA, v.109, 2012, p.6088-6093.

Yang, L.;Killian, C. E.;Kunz, M.;Tamura, N.;Gilbert, P. U. P. A.; "Biomineral nanoparticles are space-filling" RSC-Nanoscale, v.3, 2011, p.603-609.

Gilbert, P. U. P. A. Young, A. Coppersmith, S. N. "Measurement of c-axis angular orientation in calcite (CaCO3) nanocrystals using x-ray absorption spectroscopy" Proc Natl Acad Sci USA, v.108, 2011, p.11350-113. doi:10.1073/pnas.1107917108 

YUT Gong, CE Killian, IC Olson, NP Appathurai, AL Amasino, MC Martin, LJ Holt, FH Wilt, PUPA Gilbert "Phase Transitions in Biogenic Amorphous Calcium Carbonate" Procs. Natl. Acad. Sci. USA, v.109, 2012, p.6088-6093. doi:10.1073/pnas.1118085109 

Olson, I. C. Kozdon, R. Valley, J. W. Gilbert, P. U. P. A. "Mollusk shell nacre ultrastructure correlates with environmental temperature and pressure" J Am Chem Soc, v.134, 2012, p.7351?7358. doi:dx.doi.org/10.1021/ja210808s 

RSK Lam, RA Metzler, PUPA Gilbert, E Beniash "Anisotropy of Chemical Bonds in Collagen Molecules Studied by X-ray Absorption Near-Edge Structure (XANES) Spectroscopy" ACS Chemical Biology, v.7, 2012, p.476-480. doi:10.1021/cb200260d 

AR Konicek, DS Grierson, AV Sumant, TA Friedmann, JP Sullivan, PUPA Gilbert, WG Sawyer, RW Carpick "Influence of surface passivation on the friction and wear behavior of ultrananocrystalline diamond and tetrahedral amorphous carbon thin films" Physical Review B, v.85, 2012, p.155448. doi:10.1103/PhysRevB.85.155448 

Konicek, A. R.;Grierson, D. S.;Sumant, A. V.;Friedmann, T. A.;Sullivan, J. P.;Gilbert, P. U. P. A.;Sawyer, W. G.;Carpick, R. W.; "Influence of surface passivation on the friction and wear behavior of ultrananocrystalline diamond and tetrahedral amorphous carbon thin films" Physical Review B, v.85, 2012, p.155448.

Lam, R. S. K.;Metzler, R. A.;Gilbert, P. U. P. A.;Beniash, E.; "Anisotropy of Chemical Bonds in Collagen Molecules Studied by X-ray Absorption Near-Edge Structure (XANES) Spectroscopy" ACS Chemical Biology, v.7, 2012, p.476-480.

Killian, C. E.;Metzler, R. A;Gong, Y. U. T.;Churchill, T. H.;Olson, I. C.;Trubetskoy, V.;Christensen, M. B.;Fournelle, J. H.;De Carlo, F.;Cohen, S.;Mahamid, J.;Wilt, F. H.;Scholl, A.;Young, A.;Doran, A.;Coppersmith, S. N.;Gilbert, P. U. P. A.; "Self-sharpening mechanism of the sea urchin tooth" Adv Funct Mater, v.21, 2011, p.682690.

IC Olson and PUPA Gilbert "Aragonite crystal orientation in mollusk shell nacre may depend on temperature" Faraday Discussions, v.159, 2012, p.421-432. doi:10.1039/C2FD20047C 

PUPA Gilbert "Polarization-dependent Imaging Contrast (PIC) mapping reveals nanocrystal orientation patterns in carbonate biominerals" J. Electr. Spectrosc. and Rel. Phenom. special issue on Photoelectron microscopy, Time-resolved pump-probe PES. Eds. M Kiskinova, A Scholl., v.185, 2012, p.395-405. doi:http://dx.doi.org/10.1016/j.elspec.2012.06.001 

DeVol, Ross T. Metzler, Rebecca A. Kabalah-Amitai, Lee Pokroy, Boaz Politi, Yael Gal, Assaf Addadi, Lia Weiner, Steve Fernandez-Martinez, Alejandro Demichelis, Raffaella Gale, Julian D. Ihli, Johannes Meldrum, Fiona C. Blonsky, Adam Z. Killian, Christophe "Oxygen spectroscopy and Polarization-dependent Imaging Contrast (PIC)-mapping of calcium carbonate minerals and biominerals" The Journal of Physical Chemistry B, v.118, 2014, p.8449-8457. doi:10.1021/jp503700g 

L Kabalah-Amitai, B Mayzel, Y Kauffmann, AN Fitch, L Bloch, PUPA Gilbert, B Pokroy. "Vaterite crystals contain two interspersed crystal structures." Science, v.340, 2013, p.454-457. doi:10.1126/science.1232139 

Lam, R. S. K. Metzler, R. A. Gilbert, P. U. P. A. Beniash, E. "Anisotropy of Chemical Bonds in Collagen Molecules Studied by X-ray Absorption Near-Edge Structure (XANES) Spectroscopy" ACS Chemical Biology, v.7, 2012, p.476-480. doi:10.1021/cb200260d 

Gilbert, P. U. P. A. "Polarization-dependent Imaging Contrast (PIC) mapping reveals nanocrystal orientation patterns in carbonate biominerals" J Electr Spectrosc Rel Phenom, special issue on Photoelectron microscopy, Time-resolved pump-probe PES, v.185, 2012, p.395-405. doi:http://dx.doi.org/10.1016/j.elspec.2012.06.001 

Olson, I. C. Metzler, R. A Tamura, N. Kunz, M. Killian, C. E. Gilbert, P. U. P. A. "Crystal lattice tilting in prismatic calcite" J Struct Biol, v.183, 2013, p.180-190.

CJ Johnson, PUPA Gilbert, M Abrecht, KL Baldwin, RE Russell, JA Pedersen, JM Aiken, D McKenzie "Low copper and high manganese levels in prion protein plaques" Viruses, v.5, 2012, p.654-662. doi:10.3390/v5020654 


Project Outcomes Report

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

We studies seashells and imaged their microscopic structure, that is, we looked at how micro-and nano-crystals are arranged in various parts of seashells. We used PIC-mapping, an imaging method developed by the PI to show the orientation of tiny crystals, down to 20 nanometers, or 20 billionths of a meter. PIC-mapping made us discover new aspects of inner and outer sides of 15 different seashell species. The inner layer is also called mother-of-pearl or nacre, the outer is called the prismatic layer.

 

In nacre from all species the order of nacre tablet orientation increases with growth in shell thickness, but the rates of this gradual ordering differ. The tablet thickness and average width are also characteristic of each species, as is the way co-oriented tablets are stacked on top of one another in vertical columns staggered diagonally

 

In the prismatic layer we found that all species differ in prism size and orientation. We observed for the first time that the crystal orientation tilts gradually, as if forming a curved crystal. This is highly unusual for a crystal, which usually grows straight, at the atomic scale but also macroscopically, with flat faces and straight edges. If the atomic structure of the crystal tilts the crystal grows curved, not straight. Most interestingly, we found the crystals that curved only in the Pinctada species, these are pearl oysters from Japan and French Polynesia. After measuring the hardness of all prismatic layers in all shells, we found that the pearl oysters have the hardest. Therefore, we conclude that it is possible that the observed crystal curving is a hardening mechanism. As far as we know this is the first structure-property relation thus far observed in the prismatic layer of seashells.


Last Modified: 08/03/2014
Modified by: Pupa Gilbert

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