Third Workshop on Future Directions of Solid State Chemistry

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Third Workshop on Future Directions of Solid
State Chemistry The Status of Solid State
Chemistry and its Impact in the Physical
Sciences Northwestern University May 18 - 20,
2006 Organizers Mercouri G Kanatzidis Kenneth
Poeppelmeier
Subpanel 8 The place of solid state chemistry
within other physical disciplines Peter Burns
(Purdue) Julia Chan (LSU) Anne Meyer (SUNY
Buffalo) Chris Murray (IBM) Art Ramirez
(Lucent) Michael D. Ward (NYU, chair) Lian Yu (U
Wisconsin)
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Robert Hooke solid state chemistry and physics
(1665)
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Some stated objectives for 2006 SSC workshop

• Assess impact of SSC on the physical sciences
  through continuing advances and the many ways of
  interacting across disciplinary boundaries
• Assess how to make the NSF and the scientific
  community more aware of this impact
• Assess the links between SSC and hybrid
  materials, which are inherently
  interdisciplinary
• Assess how SSC impacts other fields with respect
  to understanding and predicting the properties of
  materials, and stimulating the discovery of new
  materials
• Premise greatest opportunities often exist at
  the interdisciplinary boundaries

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NSF-supported interdisciplinary initiatives

• Materials Research Science and Engineering
  Centers (MRSEC)
• Engineering Research Centers (ERC)
• Nano initiative (NSECs, NIRTs)
• Focused research groups (FRGs)
• Integrative Graduate Education and Research
  Traineeship Program (IGERT)
• Industry/University Cooperative Research Centers
  Program (I/UCRC)
• Nanoscale Interdisciplinary Research Teams
  (NIRTs)
• Others.

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Global questions

• How much SSC is embedded within interdisciplinary
  NSF programs?
• What about other agencies (DOE, DOD, etc.)?
• How is solid state chemistry currently impacting
  other disciplines? Is the impact growing? How do
  we measure this? How do we increase the awareness
  of this impact?
• What is the impact of solid state chemistry in
  the context of societal needs that can only be
  addressed through connections to other
  disciplines?
• What are the future growth opportunities for SSC
  in other disciplines?
• How do investigators in different disciplines
  connect, particularly those that extend beyond
  the physical sciences?
• What are the best mechanisms for promoting these
  ventures?
• Are the current funding mechanisms sufficient in
  terms of efficacy and financial support?
• Should new mechanisms be considered?

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The role of SSC in other disciplines

• Todays examples
• Geology
• Biology
• Medicine/Disease
• Pharmacy
• Physics
• Energy
• Organic devices
• Information technology
• Missing, but not to be ignored
• Ordered mesoporous solids and templated synthesis
• Soft Materials
• Hierarchical core-shell structures
• Molecular materials
• metal-organic and hydrogen-bonded networks
• organic conductors and magnetic materials
• Nanomaterials

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Solid-state chemistry and geology

• Minerals Raw materials for technology
• Critical technological, social, and political
  issues (e.g., water, oil)
• Solid state chemistry and environment transport
  of contaminants by groundwater, radionuclide
  release
• Strong overlap with other fields glasses,
  zeolites, cements
• Methodologies of petrologists wider application
  in solid state chemistry
• Geology involves nanoscale processes physics and
  chemistry molecular level concepts
• Mineralogists often expert crystallographers
  familiar with complex inorganic structures

Chernobyl Lava
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Studtite and Metastudtite
(UO2)(O2)(H2O)2(H2O)2
An actinyl peroxide with linked polyhedra
c
Burns Hughes (2003) Am. Mineral.
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Structural Hierarchy of Uranyl Phases
Polymerization of Polyhedra of Higher
Bond-Valence Frequency as of spring, 2005 Total
(Minerals) Relevant to radionuclide release in
geologic nuclear waste repositories (including
parasitic radionuclides neptunium)
Burns (2005) Can. Mineral.
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Solid state chemistry and biology
Skeleton of hexactinellid sponge Euplectella
sp. Aizenberg, et al., Science 2005,309, 275 - 278

• Mechanically robust glass structure with unusual
  periodic features
• Strength attributed to hierarchical structures
  across large range of length scales
• Impact on biology, mechanical engineering,
  nanoscience
• Templating phenomena single crystal magnetic
  nanorods structural scaffolds based on
  composites (calcium carbonate protein)

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Solid-state chemistry and biology (clinical)

• Bioactive glasses SiO2CaOP2O5MO (M Na, Mg,
  etc.)
• Bone-forming activity associated with
• - composition
• - porosity
• - specific surface area
• - crystallinity
• - particle size
• Slow induction period for crystalline apatite
  formation
• Lack of plasticity limits practical applications
• Requirements for bioactive glass
• - can be injected and molded into
  irregularly shaped defects in bones and teeth
• - hardens rapidly
• - promotes rapid formation of biocompatible
  HA layers that promote cellular processes

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Solid-state chemistry new biocompatible cements
Stucky, et al., Adv. Mater. 2006, 18, 1038
molded, 10 min.
extruded, 10 min.

• Plastic but rapid setting cement from mesoporous
  bioactive glass in ammonium phosphate solution
• Fully set cement retains geometrical shape and
  mechanical strength
• Induces accelerated in vitro calcium-deficient
  hydroxyapatite nanocrystals (Ca10(PO4)6(OH)2)
  during setting (30 minutes)
• Mesoporosity surface composition regulation
  of Ca2 superior in vivo bone-forming?

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Solid-state chemistry and bioactive surfaces
Generic surfaces with hydrolytic stability and
physiologic activity Schwartz, et al., Langmuir,
2004, 20, 5501
Human osteoblast cells on Si-3 after 1.5 hours
actin filaments (red) focal adhesions (green)
Generic IgG antibody surfaces with immobilized
monoclonal antibodies bind specific cell lines

• Solid monolayer films with reactive tails
• AFM 1.8 nm thick, roughness 0.4 nm
• Adhesion of osteoblasts, fibroblasts, tumor cell
  lines.
• Also two different Chinese hamster ovary (CHO)
  cell lines with RGD-binding ?5?1 and ?v?3
  integrins

CHO?4 adhered specifically to an anti-?4-integrin
antibody
CHO?5 cells adhered specifically to an
anti-?5-integrin antibody
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Kidney stone formation
Therapies for stone prevention more
desirable Need to understand critical events at
the fundamental level
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Solid-state chemistry and disease
97 mineral 3 organic
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Stages of stone formation

• Calcium oxalate monohydrate (COM) aggregates and
  adheres to epithelial cells
• Calcium oxalate dihydrate (COD) protective
• Crystal aggregation/attachment influenced by
  urinary macromolecules

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COD vs. COM
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Adhesion force measurements COD vs. COM
Sheng, et al., Proc. Nat. Acad. Sci. 2005, 102,
267 Sheng, et al., J. Amer. Soc. Nephrol. 2005,
16, 1904
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COD and COM crystal surfaces
0.0542 Ca2/Å2
0.0429 Ca2/Å2
0.0333 Ca2/Å2
0.0439 Ca2/Å2
0.0225 Ca2/Å2
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COD vs. COM pathological activity

• COM (100) and COD (101) most prominent faces in
  vivo
• Aggregation and attachment critical processes

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Solid-state chemistry and biology (clinical)

• Metals, metal alloys, ceramics, non-absorbable
  polymers the "stuff" of devices implants
• The role of SSC in tissue engineering needs to be
  better defined
• Complex interactions with proteins and cells need
  to be defined at a fundamental level
• Are the effects of nanosized features on
  interactions due to size alone
• Or can biology sense different crystal
  structures (e.g. atomic spacing, surface
  structure and composition)
• What tools are needed to explore and predict
  these responses?
• Increased support for biologically oriented
  approaches in solid-state materials?
• Scientists, engineers, and clinicians must bridge
  a culture gap for interdisciplinary
  interactions
• NSF vs. NIH (or (NSF NIH)?

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Solid state chemistry and pharmaceuticals

• Solid state properties of pharmaceuticals crucial
  for bioavailability
• Polymorphism difficult to control important for
  FDA certification and patent protection
• Solid state transformations impact stability
  (shelf life)
• Disappearing polymorphs
• Challenge Selective crystallization of
  polymorphs and enantiomorphs
• 100 billion impact
• Other specialty chemicals

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Pharmaceutical polymorphism
Ritonavir (Norvir, Abbot Labs)

• 1996 introduced as protease inhibitor
• Not bioavailable as solid form
• Oral liquid or semi-solid capsules
• 1998 Failed dissolution test
• Conformational polymorph
• Form I undersaturated
• Form II 400 supersaturated
• Cold storage not possible
• Reformulated as Form II ()
• Now 5 polymorphs total
• Regulating crystal growth imperative!

Chemburkar, et al., Org Proc. Res. Dev. 2000, 4,
413. Bauer, et al., Pharm. Res. 2001, 18,
859. Law, et al., J. Pharm. Sci. 2001, 90,
1015. Morrisette, et al., PNAS 2003, 100, 2180.
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Solid state chemistry and pharmaceuticals
Yu, J. Am. Chem. Soc. 2003, 125, 6380
Spherulites crystallized from D-mannitol melt.

• Methods for reliable prediction of polymorphs
  needed
• High-throughput screening
• Amorphous phases emerging
• Crystallization one of the largest unit
  operations
• Need to elucidate crystallization processes at
  the fundamental level

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Calcium oxalate solvates COM COD
CaOx Monohydrate (symptomatic)
CaOx Dihydrate (protective)
polyD
P21/c (a 6.290 Å, b 14.580 Å, c 10.116 Å, b
109.46o)
I4/m (a b 12.371 Å, c 7.357 Å, a b g
90o)