In Quest of a Systematic Framework For Unifying and Defining Nanoscience

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1 In Quest of a Systematic Framework For Unifying and Defining Nanoscience Donald A. Tomalia, Ph.D. Director, The National Dendrimer and Nanotechnology Center Central Michigan University Mt. Pleasant, MI USA The National Dendrimer & Nanotechnolgy Center, CMU

2 National Dendrimer and Nanotechnology Center Central Michigan University Mt. Pleasant, MI Periodic Patterns, Relationships and Categories of Well-Defined Nanoscale Building Blocks Report on a National Science Foundation Workshop Central Michigan University September 24-25, 2007 Epected Nano-Periodic Tables Reported Nano-Periodic Patterns Reported Nano-Compounds Proposed Nano-Element Categories Nano-Compounds Dendronized QD s Nano-Modules HIV-Virus/Dendrimer Hybrids Colloidal Metals Viruses Megamers IgG- Dendrimers Proteins Dendrimer Hybrids Nanoscale Sizes, Shapes, Physico/Chemical Surfaces Nanotubes Nanotube-Dendrimer RNA/DNA DNA-Dendron Hybrids Hybrids Colloidal Fullerenes Silica Fullerene-Dendrimer Hybrids Silica-Dendrimer Hybrids 08_Tomalia_nsf9_29_08.pdf Newly Established Ph.D. Program (2008) Nanotechnology/ Science of Advanced Materials

3 The Concept A systematic framework is proposed for unifying and defining nanoscience. This systematic framework is based on the same first principles initiated by Lavoisier, Dalton, Mendeleev and others that led to a periodic system and central paradigm for traditional elemental atom and small molecule chemistry.

4 Traditional Chemistry 1 st Priniciples? Atom Periodicity Pico-Modules (Atomic Elements) Picoscale Collections of Protons, Neutrons and Electrons Nano- Periodicity Nano-Modules (Nano-Element Categories) Nanoscale Collections of Atoms, Monomers, or Small Molecule Modules 6 Nucleus He Ne Bottom-up Structure Controlled Synthesis Atom Mimicry Ar Kr Xe Rn N Electrons Required to Saturate Shell Atomic Number Atomic Weights 1 nm Bucky Ball (C 60 ) Nano-Objects.064 nm He.138 nm Ne.194 nm Ar.220nm Kr.260 nm Xe.290 nm Rn 1 nm G= nm G=1 2.2 nm G= nm G=3 4.0 nm G=4 5.3 nm G=5 6.1 nm G=6 Dendrimers

5 The spirit of this perspective is not to disrupt any natural physico-chemical laws, but to encourage new and different thinking. This is a works in progress! Much more remains to be done. Donald A. Tomalia J. Nanoparticle Res., 11, ,(2009)

6 Outline I. Background/Historical (a) First Principles of Traditional Atom/Small Molecule Chemistry (b) Heuristic Atom Mimicry (c) Conservation of Hierarchical Design Parameters (CADP CMDP CNDP)? (d) Breaking Hierarchical Symmetry - P.W. Anderson the whole becomes not only more than, but very different from the sum of its parts II. Proposed Nanomaterials Classification Roadmap III. Nano-Element (Module) Categories IV. Nano-Elements Nano-Compounds/Assemblies V. Nano-Periodic Property Patterns VI. Conclusions - The Future

7 I. Introduction Background and Historical

8 Macroscale 10-2 Brief Historical Overview Microscale 10-6 Nanostructures Assemblies Molecular Structures R. Feynman (1959) 19 th /20 th Century Chemists/Physicists Nanoscale Picoscale Nano-Alchemy (1959-Present) Atom Periodicity Atoms Alchemy A. Lavoisier (1789) J. Dalton (1808) Pre picometer (trillions) D. Mendeleev (1869)

9 Critical Atomic Design Parameters (CADP s) Reactive Surface Chemistry Size Electronegativity Inert Fleibility/Polarizabilty Shape

10 Conservation of Hierarchical Design Parameters? (CADP CMDP CNDP)

11 Critical Nanoscale Design Parameters (CNDP s) ISI Citations 2135 (CADP CMDP CNDP)

12 Dendrimer Chemstry Over-view

13 Outer Shell Modular Reactivity (Picometer to Nanometer Dimensions) Atom Mimicry Atoms Dendrimers Core Shell Tecto(dendrimers) Dimensions nm 1 15 nm nm Valency (Reactivity) (Core Shell) Architecture Induced Reactivity (Unfilled Shells) Z * Z * Unfilled Outer Electron Shell Z * * Z N 1 2 Z y (e.g., fluorine) Unfilled Shell () Unfilled Outer Branch Cell Shell I 1 y 2 Unfilled Shell () G G G Unfilled Outside Dendrimer Shell G G G G G y G y Unfilled Shell () Functional Components Directing Valency Missing One Electron (y) in Outer Shell () Penultimate to Saturated Noble Gas Configuration Missing One Terminal Branch Cell in Outer Shell () Eposing Functionality (y) Missing One Dendrimer Shell Reagent Eposing Functionality (y) Chemical Bond Formation Leading to Saturated Outer Shell: Atoms, Dendrimers, Core-Shell Tecto(dendrimers) Z * * Z Z * Z * Z N 1 y 2 I 1 2 y G G G G G G G y G G y D.A. Tomalia, et al., PNAS, 99 (8) (2002). D.A. Tomalia, Prog. Polym. Sci., 30, , (2005).

14 Traditional Chemistry Central Dogma First Principles John Dalton (1808) Atoms Atoms Form Chemical Bonds Atoms Bond with Discrete Stoichiometries, Valency and Combining Weights Atoms Bond with Discrete Directionality Atoms Ehibit Periodic Properties Compound Atoms

15 First Systematic, Synthetic Nanostructure Platform Dendrimers (early 1980s)

16 Atom Mimicry: Core-Shell Architectures Atomic ( nm) Dendrimeric (1-20 nm) Principal Electron Shells (Periods) Nucleus He Ne Ar Kr Xe Rn Principal Monomer Shells (Generations) Core G=0 G=1 G=2 G=3 G=4 G=5 G=6 N. Bohr (1922) N Electrons Required to Saturate Shell Atomic Number Core , , , ,633 21,591 43,507 Monomers Required to Saturate Shell Dendrimeric Number (Degree of Polymerization) F. Aston (1922) Atomic Weights Picoscale Structures 1 nm Bucky Ball (C 60 ) Molecular Weights Nanoscale Structures.064 nm He.138 nm Ne.194 nm Ar.220nm Kr.260 nm Xe.290 nm Rn 1 nm G= nm G=1 2.2 nm G= nm G=3 4.0 nm G=4 5.3 nm G=5 6.1 nm G=6

17 Size Control (Diameters) In Dendrimers C.L. Jackson, H.D. Chanzy, F.P. Booy, B.J. Drake, D.A. Tomalia, B.J. Bauer, E.J. Amis, Macromolecules, 31(18), 6259, (1998). D A. Tomalia, W.A. Goddard, et al., Angew. Chem. Int. Ed. Engl., 29, 136 (1990).

18 Self-Assembly of PAMAM Dendrimers (G9) (Atom Mimicry) C C C C C C C C C C C D.A. Tomalia, et al., Pure and Applied Chem., 72, 2343 (2000).

19 Nano-Element Valency:[H-1] type; [Cubic-(Ag) n ] [Inert Gases] 0 = = H 2, Cl 2, O 2 -(CH 2 )- n=3,4 = = 2-D Assembly CH 4 = = 3-D Assembly M. Rycenga, J. M. McLellan, Y. Xia; Adv. Mater.,(2008), 20,

20 Atom Mimicry: (a) Core-Shell Architecture (b) Outer Shell Reactivity

21 Critical Hierarchical Design Parameters Macroscale Conservation of Hierarchical Design Parameters? (Atom Molecular Nano Structures) 10 Atom Mimicry -4 Architecture (Symmetry) 10-5 Microscale Nanostructures Assemblies (CNDP) Molecular Structures (CMDP) Atoms (CADP) Size Shape Surface Chemistry Fleibility Nanoscale Picoscale Atom Periodicity picometer (trillions)

22 Mass Control Comparison Atoms versus Dendrimers Atomic Weight Ideal PD.=1.000 Dendrimer Mass Ideal PD.=1.000 Hg (1.53:1) Ne Gen. PD. s G4= 1.05 Cu G3= 1.03 Ne G2= 1.01 Cd (1.29:1) G1= Li ( 1:1) Atomic Number: Atomic Number: Shell Number: Shell Number: He 1 He Ne Ar Kr Xe Rn Ne Ar 3 Kr 4 Xe 5 Rn 6 (Monomer Shells) Generations: J.C. Hummelen, J.L.J. van Dongen and E.W. Meijer, Chem. Eur. J. 1997, 3,

23 Shape Control in Dendrimers Shape and Size Control as a Function of Core and Generation Shape Control as a Function of Generational Amplification A.M. Naylor, W. A. Goddard III, G.E. Kiefer and D.A. Tomalia, J. Am. Chem. Soc., 111, , (1989).

24 Surface Chemistry Control with Dendrimers Valency Diversity of Functionality # of Terminal Groups (Z) Z= N c N b G P. Antoni, Y. Hed, A. Nordberg, D. Nystrom., H. von Holst, A. Hult and M. Malkoch, Angew. Chem. Int. Ed., 2009, 48, D.A. Tomalia, Prog. Polym.Sci., 30, , (2005).

25 Critical Hierarchical Design Parameters 10 0 decimeter (dm) Macroscale (tens) Atom Mimicry Architecture (Symmetry) 10-5 Microscale Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Nano-Periodicity Nanoscale Atom Mimicry Hard Nanoparticle Categories Hard Particle Nano-Element Categories Metal Oide (Nanocrystals) Silica (Nanoparticles) Physico-Chemical Properties Fullerenes Nano-elements Carbon Nanotubes H-1 H-2 H-3 H-4 H-5 H-6 Dendrimers Dendrons Nano-compounds Nano-periodic Property Patterns Soft Nanoparticle Categories Soft Particle Nano-Element Categories Nano-latees Polymeric Micelles Proteins Functional/Application Properties Viruses RNA/DNA S-1 S-2 S-3 S-4 S-5 S-6 Nanostructures Assemblies (CNDP) Molecular Structures (CMDP) Atoms (CADP) Size Shape Surface Chemistry Fleibility Nanoscale Picoscale Atom Periodicity picometer (trillions)

26 II. Proposed Nanomaterials Classification Roadmap

27 Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Dendrimers Dendrons Nanolatees Polymeric Micelles Proteins Viruses DNA/RNA Nanomaterials Classification Roadmap Atom-Based Structures/Assemblies Diameters: nm Mass: daltons # of Atoms: Topology: 0-D and 1-D Category II Undefined Materials Hard Nanoparticles Category I Well-Defined Materials Atom Mimicry Nano-elements Soft Nanoparticles Insulators Metals (M ) Conductors Semi-Conductors Metal-Non Metal (Groups 4A-7A Compounds) Semi- Metals Non- Metals Non-Metal Organic Structures Nanostructures/Particles Nanoclusters Gold Palladium Silver, etc. Nano-Crystals Metal Chalcogenides Metal Oides Amorphous Nanoparticles Silca Nanoparticles Rigid Carbon Allotropes 0-D Fullerenes 1-D Carbon Nanotubes Dendrons/ Dendrimers Synthetic Nanolatees Polymeric Micelles Proteins Biological Viruses DNA/RNA H-1 H-2 H-3 H-4 H-5 H-6 S-1 S-2 S-3 S-4 S-5 S-6 Nano-compounds Hard Particle Nano-compounds Soft/Hard Particle Nano-compounds Soft Particle Nano-compounds Nano- Elements Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Nano- Elements Dendrimers Dendrons Nano- Elements Nanolatees Polymeric Micelles Proteins Viruses DNA/RNA Metal (M ) (Nanoclusters) H-1:H-1 H-2:H-1 H-3:H-1 H-4:H-1 H-5:H-1 H-6:H-1 S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1 Dendrimers Dendrons S-1:S-1 S-2:S-1 S-3:S-1 S-4:S-1 S-5:S-1 S-6:S-1 Metal (Chalcogenide) (Nanocrystals) H-2:H-2 H-3:H-2 H-4:H-2 H-5:H-2 H-6:H-2 S-1:H-2 S-2:H-2 S-3:H-2 S-4:H-2 S-5:H-2 S-6:H-2 Nanolatees S-2:S-2 S-3:S-2 S-4:S-2 S-5:S-2 S-6:S-2 Metal Oide (Nanocrystals) H-2:H-3 H-3:H-3 H-4:H-3 H-5:H-3 H-6:H-3 S-1:H-3 S-2:H-3 S-3:H-3 S-4:H-3 S-5:H-3 S-6:H-3 Polymeric Micelles S-2:S-3 S-3:S-3 S-4:S-3 S-5:S-3 S-6:S-3 Silica (Nanoparticles) H-2:H-4 H-3:H-4 H-4:H-4 H-5:H-4 H-6:H-4 S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4 Proteins S-2:S-4 S-3:S-4 S-4:S-4 S-5:S-4 S-6:S-4 Fullerenes H-2:H-5 H-3:H-5 H-4:H-5 H-5:H-5 H-6:H-5 S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5 Viruses S-2:S-5 S-3:S-5 S-4:S-5 S-5:S-5 S-6:S-5 Carbon Nanotubes H-2:H-6 H-3:H-6 4-H:H-6 H-5:H-6 H-6:H-6 S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6 DNA/RNA S-2:S-6 S-3:S-6 S-4:S-6 S-5:S-6 S-6:S-6 Physico-Chemical Size Shape Surface Chemistry Nano-periodic Properites Interior Features Fleibility/Polarizability Architecture Photonic Magnetic Toicology Functional/Applications Electronic Catalysis Imaging

28 Criteria for Nano-Element Categories Discrete Collections of Atoms (N): (a) N = atoms, (b) mass: daltons, (c) at least one dimension is: nm Discrete Reactive/Passive Nano-Modules (units) with Well Defined: (a) valency, (b) stoichiometries, (c) combining mass ratios -> to form nano-compounds Well Defined Chemical/Physical Features (CNDPs) (a) size, (b) shape, (c) surface chemistry, (d) fleibility (polarizabilty) Robust Enough for Routine Analytical Characterization

29 Monodispersity Criteria: Atom-Like, 3-D Nano-cluster Super Lattices Required >90% monodisperse gold nanoclusters to obtain well defined X-ray patterns S.Y. Park, C. Mirkin et al., Nature, 451, (2008).

30 Hard Matter Metals Soft Matter Non-Metals Inorganic Organic HARD PARTICLE NANO-ELEMENT CATEGORIES SOFT PARTICLE NANO-ELEMENT CATEGORIES Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Dendrimers Dendrons Nano-latees Polymeric Micelles Proteins Viral Capsids RNA/DNA

31 Nano-Element Categories (Inorganic) HARD PARTICLE NANO-ELEMENT CATEGORIES (1-D) Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes (Provisional) H-1 H-2 H-3 H-4 H-5 H-6 (Organic) SOFT PARTICLE NANO-ELEMENT CATEGORIES (1-D) Dendrimers Dendrons Nano-latees Polymeric Micelles Proteins Viral Capsids RNA/DNA S-1 S-2 S-3 S-4 S-5 S-6

32 Abbreviated Nanomaterials Classification Roadmap Nanomaterials Size: nm # Atoms: atoms Mass: daltons Category I Well Defined Monodisperse a) size b) mass Hard Nanoparticle Categories Atom Mimicry Category II Undefined Statistically Polydisperse a) size b) mass Soft Nanoparticle Categories HARD PARTICLE NANO-ELEMENT CATEGORIES SOFT PARTICLE NANO-ELEMENT CATEGORIES Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Dendrimers Dendrons Nano-latees Polymeric Micelles Proteins Viral Capsids RNA/DNA J. of Nanoparticle Research, 11, (2009).

33 III. Proposed Nano-Element Categories

34 Nano-Element Categories HARD PARTICLE NANO-ELEMENT CATEGORIES Metal (M ) (Nanoclusters) H-1 Metal (Chalcogenide) (Nanocrystals) H-2 (1-D) Metal Oide Silica Carbon Fullerenes (Nanocrystals) (Nanoparticles) Nanotubes (Provisional) H-3 H-4 H-5 H-6 SOFT PARTICLE NANO-ELEMENT CATEGORIES Dendrimers Dendrons Nano-latees Polymeric Micelles Proteins Viral Capsids (1-D) RNA/DNA S-1 S-2 S-3 S-4 S-5 S-6 (Synthetic Polymers) (Biological Polymers)

35 Comparison of Atoms with Hard and Soft Nanoparticles Picoscale Matter (Atoms) Shell Components n (Electrons) Elements Ehibiting Noble Gas Configurations He Ne Ar Kr Xe Electron shell levels: Diameters:.064 nm.138 nm.194 nm.220nm.260 nm Saturation values (n): Atomic weights: Hard Nano-Matter (Gold Nanoclusters) Shell Components n (Au Atoms) Full-Shell Magic Number Clusters Atom shell levels: Diameters:.864 nm 1.44 nm 2.02 nm 2.59 nm 3.17 nm Saturation values (n): Nano-cluster weights: Soft Nano-Matter (Dendrimers) Saturated Monomer Shells Monomer shell levels: G=1 G=2 G=3 G=4 G=5 Shell Components n (Monomers) Saturation values (n): Diameters: 1.58 nm 2.2 nm 3.10 nm 4.0 nm 5.3 nm Nanostructure weights: D.A. Tomalia, J. of Nanoparticle Research, (2009)

36 IV. Nano-Elements to Nano-Compounds and Assemblies

37 Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Dendrimers Dendrons Nanolatees Polymeric Micelles Proteins Viruses DNA/RNA Nanomaterials Classification Roadmap Atom-Based Structures/Assemblies Diameters: nm Mass: daltons # of Atoms: Topology: 0-D and 1-D Category II Undefined Materials Hard Nanoparticles Category I Well-Defined Materials Atom Mimicry Nano-elements Soft Nanoparticles Insulators Metals (M ) Conductors Semi-Conductors Metal-Non Metal (Groups 4A-7A Compounds) Semi- Metals Non- Metals Non-Metal Organic Structures Nanostructures/Particles Nanoclusters Gold Palladium Silver, etc. Nano-Crystals Metal Chalcogenides Metal Oides Amorphous Nanoparticles Silca Nanoparticles Rigid Carbon Allotropes 0-D Fullerenes 1-D Carbon Nanotubes Dendrons/ Dendrimers Synthetic Nanolatees Polymeric Micelles Proteins Biological Viruses DNA/RNA H-1 H-2 H-3 H-4 H-5 H-6 S-1 S-2 S-3 S-4 S-5 S-6 Nano-compounds Hard Particle Nano-compounds Soft/Hard Particle Nano-compounds Soft Particle Nano-compounds Nano- Elements Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Nano- Elements Dendrimers Dendrons Nano- Elements Nanolatees Polymeric Micelles Proteins Viruses DNA/RNA Metal (M ) (Nanoclusters) H-1:H-1 H-2:H-1 H-3:H-1 H-4:H-1 H-5:H-1 H-6:H-1 S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1 Dendrimers Dendrons S-1:S-1 S-2:S-1 S-3:S-1 S-4:S-1 S-5:S-1 S-6:S-1 Metal (Chalcogenide) (Nanocrystals) H-2:H-2 H-3:H-2 H-4:H-2 H-5:H-2 H-6:H-2 S-1:H-2 S-2:H-2 S-3:H-2 S-4:H-2 S-5:H-2 S-6:H-2 Nanolatees S-2:S-2 S-3:S-2 S-4:S-2 S-5:S-2 S-6:S-2 Metal Oide (Nanocrystals) H-2:H-3 H-3:H-3 H-4:H-3 H-5:H-3 H-6:H-3 S-1:H-3 S-2:H-3 S-3:H-3 S-4:H-3 S-5:H-3 S-6:H-3 Polymeric Micelles S-2:S-3 S-3:S-3 S-4:S-3 S-5:S-3 S-6:S-3 Silica (Nanoparticles) H-2:H-4 H-3:H-4 H-4:H-4 H-5:H-4 H-6:H-4 S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4 Proteins S-2:S-4 S-3:S-4 S-4:S-4 S-5:S-4 S-6:S-4 Fullerenes H-2:H-5 H-3:H-5 H-4:H-5 H-5:H-5 H-6:H-5 S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5 Viruses S-2:S-5 S-3:S-5 S-4:S-5 S-5:S-5 S-6:S-5 Carbon Nanotubes H-2:H-6 H-3:H-6 4-H:H-6 H-5:H-6 H-6:H-6 S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6 DNA/RNA S-2:S-6 S-3:S-6 S-4:S-6 S-5:S-6 S-6:S-6 Physico-Chemical Size Shape Surface Chemistry Nano-periodic Properites Interior Features Fleibility/Polarizability Architecture Photonic Magnetic Toicology Functional/Applications Electronic Catalysis Imaging

38 Hard Nanoparticles Gold Nano-Clusters Soft Nanoparticles Dendrimers Z = Generations Surface Groups (Z) Total # of Aufbau Monomers MW M w /M n (Gold Nano-Cluster) Nano-Compounds (Dendrimer) Nano-Compounds DNA Connector C. Mirkin et al., J. Am. Chem. Soc,120, 12674, (1998). D.A.Tomalia, et al., Adv. Mater.,12,(11), 796, (2000).

39 Nano-Compound Morphologies B. Xu, et al., Accounts of Chemical Res., 42 (8) 1097 (2009)

40 Soft Nanoparticle Compounds Dendrimer-Cluster Compounds Tomalia, et al. Adv. Mater. (2000) Nanolatees -S-S- -S-S- -S-S- -S-S- -S-S- Dendrimers Dendrons Nanolatees Dendrimers Dendrons Nano- Elements Polymeric Micelles Proteins Viral Capsids DNA/RNA S-1:S-1 S-2:S-1 S-3:S-1 S-4:S-1 S-5:S-1 S-6:S-1 S-2:S-2 S-3:S-2 S-4:S-2 S-5:S-2 S-6:S-2 DNA-Dendrimer Compounds (Superfect ) Qiagen, Ger. IgG-Dendrimer Compounds (Stratus ) Siemens Germany Polymeric Micelles Proteins S-2:S-3 S-3:S-3 S-4:S-3 S-5:S-3 S-6:S-3 S-2:S-4 S-3:S-4 S-4:S-4 S-5:S-4 S-6:S-4 Tobacco Mosaic Virus Compound Viral Capsids DNA/RNA S-2:S-5 S-3:S-5 S-4:S-5 S-5:S-5 S-6:S-5 S-2:S-6 S-3:S-6 S-4:S-6 S-5:S-6 S-6:S-6 HIV-Virus- Dendrimer Compounds (VivaGel ) Starpharma, AU

41 Self-Assembly of Nanoscale Wedges Protein Sub-Units Viral Capsids Dendrons Dendrimers First Demonstration of Quasi-Equivalence with Synthetic Nanostructures J.G. Rudick, V. Percec, Accounts of Chemical Research, 41,(12), (2008)

42 ss-rna:protein Sub-unit [S-6:(S-4)2130] Core-Shell Nano-Compound Tobacco Mosaic Virus Nano-Compound Stoichiometry: 2130-Protein Subunits [S-4]; 1-ssRNA [S-6] Shell Diameter: 18 nm Length: 300 nm Helical Symmetry [S-4] Subunits: 2130; 158 amino acids/sub-unit Core [S-6] ss-rna: 1; 6400 nucleotide units/ss-rna P.J.G. Butler, A. Klug, Sci. Amer. 239 (5) 62-69, (1978); (Nobel-!982)

43 Spheroidal Valency Defined by Nano-Sterics r 1 = radius of core dendrimer r 2 = radius of shell dendrimer N ma = Total theoretical number of shell-like spheroids with radius r 2 that can be ideally parked around core spheroid with radius r Gold Nano-Clusters Mansfield-Tomalia-Rakesh Equation N 2! ma = "3 r r 2 2 D.A. Tomalia, et al., J. Chem. Phys. 105 (8), 3245 (1996). When: r 1 /r 2 > 1.20

44 Core-Shell Tecto(dendrimers): Saturated Shell Models Dendrimers (1) Self Assembly (Equilibration) Core Reagent -(NH 2 ) n + -(CO 2 H) m Shell Reagent (Ecess) (2) Covalent Bond Formation Core Shell Tecto(dendrimers) -(CO 2 H) m Non-autoreactive S. Uppuluri, D.R. Swanson, L.T. Piehler, J. Li, G.L. Hagnauer, D.A. Tomalia Adv. Mater. 2000, 12(11)

45 Structure Controlled (Fleibility) Compressibility of Dendrimers G9 [G9] n G7/G5 D.A. Tomalia, et al., Langmuir, 18, (2002).

46 OH Soft/Hard Nanoparticle Compounds HO HO HO HO HO HO HO HO HO HO HO P P P HO P QD P OH P P P OH OH OH OH Tomalia et.al. J. Luminescence (2005) OH OH OH OH OH OH Metal (M ) (Nanoclusters) Dendrimers Dendrons Nano- Elements Nanolatees Cross-linked Polymeric Micelles Proteins Viruses DNA/RNA S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1 SiO G y 2 Wiesner, et al., Chem. Mater. (2007) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) S-1:H-2 S-2:H-2 S-3:H-2 S-4:H-2 S-5:H-2 S-6:H-2 S-1:H-3 S-2:H-3 S-3:H-3 S-4:H-3 S-5:H-3 S-6:H-3 Mirkin, et al. Nature, (2008) S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4 Jensen, et al. Nano Lett. (2005) Silica (Nanoparticles) S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5 Rotello, et al. J.A.C.S. (2005) Fullerenes Carbon Nanotubes S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6 X. Tu, et al., Nature (2009)

47 Gold Nanocluster: DNA - [H-1:S-6]; Heterodimer Type Nano-Compound Series P. Alivisatos, et al, Angew. Chem. Int. Ed., 38 (12) (1999).

48 Core-Shell Architecture of Dendrimer-Fullerene Nano-Compound G=4 PAMAM -(NH 2 ) h, 25 (pyridine) Dendrimer Core Yield: 89% Fullerene Shell Proposed Reaction Mechanism [S-1:H-5] Nano-Compound Nano-Compound Stoichiometry: 1-[G4];(PAMAM) 32-C 60 A.W. Jensen, D. Mohanty, D.A. Tomalia, et al. Nano Letters, 5(6), (2005).

49 Barrel Shaped, SWNT:DNA -[H-6:S-6]; Core-Shell Type Nano-Compound Series SWNT; [S-6] DNA; [S-6] Nano-Compound Synthesis, Yields and Purities Core-Shell; [H-6:S-6] Type Nano-Compounds X. Tu, S. Manohar, A Jagota and M. Zheng, Nature, 2009, 460, 250

50 Using Traditional First Principles Nanoscale Atom Mimicry Hard Nanoparticle Categories Nano-elements Soft Nanoparticle Categories HARD PARTICLE NANO-ELEMENT CATEGORIES SOFT PARTICLE NANO-ELEMENT CATEGORIES Metal (M ) (Nanoclusters) Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Fullerenes Carbon Nanotubes Dendrimers Dendrons Nano-latees Polymeric Micelles Proteins Viral Capsids RNA/DNA Nano-compounds Nano-Periodic Property Patterns Intrinsic Properties Functional/Application Properties D.A. Tomalia, J. of Nanoparticle Research, (2009)

51 Nano-Periodic Property Patterns for a Series of [H-6:S-6] Nano-Compounds SWNT; [H-6] DNA; [S-6] Optical Absorption Spectra versus SWNT (n,m) Chirality X. Tu, S. Manohar, A Jagota and M. Zheng, Nature, 2009, 460, 250

52 V. Nano-Periodic Property Patterns

53 Comparison of Atoms with Hard and Soft Nanoparticles Picoscale Matter (Atoms) Shell Components n (Electrons) Elements Ehibiting Noble Gas Configurations He Ne Ar Kr Xe Electron shell levels: Diameters:.064 nm.138 nm.194 nm.220nm.260 nm Saturation values (n): Atomic weights: Hard Nano-Matter (Gold Nanoclusters) Shell Components n (Au Atoms) Full-Shell Magic Number Clusters Atom shell levels: Diameters:.864 nm 1.44 nm 2.02 nm 2.59 nm 3.17 nm Saturation values (n): Nano-cluster weights: Soft Nano-Matter (Dendrimers) Saturated Monomer Shells Monomer shell levels: G=1 G=2 G=3 G=4 G=5 Shell Components n (Monomers) Saturation values (n): Diameters: 1.58 nm 2.2 nm 3.10 nm 4.0 nm 5.3 nm Nanostructure weights: D.A. Tomalia, J. of Nanoparticle Research, (2009)

54 Gold Cluster- [H-1];Type Nano-Elements (Melting Points vs. Nano Sizes) Melting Points Shells: Total Atoms: K.J. Klabunde, Nanoscale Materials in Chemistry, J. Wiley & Sons, NY, 2001.

55 Dendrimer; [S-1]-Type Nano-Elements (Nano-Periodic Properties of Dendrimers) Surface Area/Head Group (Z) Refractive Inde Density (d) Intrinsic Viscosity (η) G = PAMAM Dendrimer Generation D. A. Tomalia, W.A. Goddard, et al, Angew. Chem. Int. Ed. Engl., 29, 138, (1990).

56 Nano-Periodic Trends of [S-1]-Type Nano-Elements (Dendrons) (Size, Shape, Surface Chemistry Driven Self Assembly Patterns) Size Shape Surface Chemistry Primary Dendron/Dendrimer Structures Self Assembly Tertiary Dendrimer Structures Quaternary Dendrimer Assemblies J.G. Rudick, V. Percec, Accounts of Chemical Research, 41,(12), (2008)

57 Percec s Nano-Periodic Self-Assembly Table (Primary) Dendron Structures (Tertiary) Supramolecular Dendrimers (Quaternary) Dendrimer Assemblies V. Percec, et al., J. Am. Chem. Soc., 131, 17500, (2009).

58 VI. Conclusions - The Future

59 Conclusions First Steps have been taken to unify and define Nanoscience based on traditional chemistry first principles. Hard (Inorganic) and Soft (Organic) Nanoparticle Element Categories have been proposed. Many Nano-Compound/Assembly eamples presently eist in the literature. Synthetic Organic and Inorganic Nano-Chemistries have emerged and are well documented. The first eamples of Nano-Periodic Tables for predicting intrinsic nano physico-chemical properties based on CNDP s have appeared-, V. Percec, et al., J. Am. Chem. Soc., 131,

60 Metal (M ) (Nanoclusters) Hard Nanoparticle Categories Hard Particle Nano-Element Categories Metal (Chalcogenide) (Nanocrystals) Metal Oide (Nanocrystals) Silica (Nanoparticles) Physico-Chemical Properties Nanoscale Atom Mimicry Fullerenes Nano-elements Carbon Nanotubes H-1 H-2 H-3 H-4 H-5 H-6 Nano-Periodicity Dendrimers Dendrons Nano-compounds Nano-periodic Property Patterns Soft Nanoparticle Categories Soft Particle Nano-Element Categories Nano-latees Polymeric Micelles Proteins Functional/Application Properties Viruses RNA/DNA S-1 S-2 S-3 S-4 S-5 S-6 The Future Quantized Building Blocks Synthetic Organic Nano-Chemistry Simple Organisms (Bacteria) Biological Cells Compleity Staircase Comple Organisms (Humans) Organisms (Plants, Animals) Synthetic Inorganic Nano-Chemistry Bio-assemblies (Viruses, Ribosomes) (100 nm) Soft Nano-Elements Nanoscale Modules (Proteins, DNA, RNA) (1 nm) Hard Nano-Elements Monomers Functional Groups (-CO 2 H, -NH 2, -OH) Sub-nano Modules (Aliphatic, Aromatic) Comple Compounds (Palytoin, C 60 ) Polypeptide Chemistry Polymer Chemistry Atoms Simple Compounds (HCl, H 2 O, NH 3, CH 4 ) Atoms (Elements) (Periodic Table) Organic Chemistry Inorganic Chemistry

61 IN QUEST OF A SYSTEMATIC FRAMEWORK FOR UNIFYING AND DEFINING NANOSCIENCE J. Dalton (1808) A 19th Century Paradigm for Traditional Chemistry D. Mendeleev s Periodic Table (1869) A 21st Century Paradigm for Nanoscience

62 Natural Physico-Chemical Laws We are not advocating corruption or changes in the gospel! We are merely proposing some new hymns--new thinking.

63 Acknowledgements Nanotechnology Characterization Laboratory (NCL), National Cancer Institute, National Institute of Health National Science Foundation (NSF) All the Plenary Speakers (NSF-CMU Workshop) (2007) Prof. Jorn Christensen (Univ. of Copenhagen) Dr. M. Roco (NSF) for inspiration and encouragement

64 The spirit of this perspective is not to disrupt any natural physico-chemical laws, but to encourage new and different thinking. This is a works in progress! Much more remains to be done. Donald A. Tomalia J. Nanoparticle Res., 11, ,(2009)

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