Third Workshop on Future Directions of Solid State Chemistry The Status of Solid State Chemistry and its Impact in the P

1. 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)

2. Robert Hooke: solid state chemistry and physics (1665)

3. 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

4. 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….

5. 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?

6. The role of SSC in other disciplines • Today’s 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 • magnetic materials • quantum dots

7. 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

8. Studtite and Metastudtite [(UO2)(O2)(H2O)2](H2O)2 An actinyl peroxide with linked polyhedra c Burns & Hughes (2003): Am. Mineral.

9. 56 (4) 43 (6) 57 (9) 204 (70) 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.

10. Solid state chemistry and biology Skeleton of hexactinellid sponge Euplectella sp. Aizenberg, et al., Science2005,309, 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)

11. Solid-state chemistry and biology (clinical) • Bioactive glasses: SiO2–CaO–P2O5–MO (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

12. 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?

13. 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

14. Kidney stone formation Therapies for stone prevention more desirable Need to understand critical events at the fundamental level

15. Solid-state chemistry and disease ~ 97% mineral ~ 3% organic

16. 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

17. COD vs. COM

18. 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

19. 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

20. COM (100) COM (100) stacks in a stone COD (101) Non-specific binding www.herringlab.com COD vs. COM: pathological activity • COM (100) and COD (101) most prominent faces in vivo • Aggregation and attachment critical processes

21. 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)?

22. 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

23. 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., PNAS2003, 100, 2180.

24.  : P212121  P21 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

26. 25 mm 25 mm 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)