In Quest of a Systematic Framework For Unifying and ...In Quest of a Systematic Framework For...
Transcript of In Quest of a Systematic Framework For Unifying and ...In Quest of a Systematic Framework For...
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 48859 USA
NSF Grantees Conference
December 7-9, 2009
©The National Dendrimer & Nanotechnolgy Center, CMU
Newly Established
Ph.D. Program –(2008)
Nanotechnology/
Science of Advanced
Materials
National Dendrimer and Nanotechnology Center
Central Michigan University
Mt. Pleasant, MI 48859
Fullerenes
Nanoscale
Sizes, Shapes,
Physico/Chemical
Surfaces
Colloidal
Silica
RNA/DNANanotubes
ProteinsDendrimers
Colloidal
MetalsViruses
Fullerenes
Nanoscale
Sizes, Shapes,
Physico/Chemical
Surfaces
Colloidal
Silica
RNA/DNANanotubes
ProteinsDendrimers
Colloidal
Metals
Colloidal
MetalsViruses
Nano-Modules
Nano-Compounds
Megamers
Dendronized QD’s
IgG-
Dendrimer
Hybrids
Fullerene-Dendrimer
Hybrids
-S-S-
-S-S--S
-S- -S-S--S-S-
-S-S--S
-S- -S-S-
OH
OH
OH
OH
OH
OH
OHHOHO
HO
HO
HO
HO OHOH
OH
OHOH
HO
HO
HO
HO
HOHO
PP
P
PP
P
P
P
QD
II QD
Dendrimers Quantum Dots Fullerenes Nanotubes
II QD
Dendrimers Quantum Dots Fullerenes Nanotubes
GySiO2GyGyGySiO2GySiO2GyGyGySiO2
Nanotube-Dendrimer
Hybrids
HIV-Virus/Dendrimer
Hybrids
DNA-Dendron
Hybrids
Silica-Dendrimer
Hybrids
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
Expected Nano-Periodic Tables
Reported Nano-Compounds
Proposed
Nano-Element Categories
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins VirusesViruses RNA/DNANano-latexesNano-latexes
Cross-linked
Polymeric
Micelles
Cross-linked
Polymeric
Micelles
Soft Matter-Nano Elements
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
Hard Matter-Nano Elements
Carbon
Nanotubes
Carbon
Nanotubes
1-S 2-S 3-S 4-S 5-S 6-S
1-H 2-H 3-H 4-H 5-H 6-H
Reported Nano-Periodic Patterns
http://www.nsf.gov/crssprgm/nano/GC_Charact
08_Tomalia_nsf9_29_08.pdf
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.
I. Introduction
Background and Historical
picometer
10-1
10-10
10-11
10-12
(trillions)
10-2
10-3
10-4
10-5
10-6
10-7
10-9
100
Macroscale
Microscale
Atoms
Molecular
Structures
Nanostructures
AssembliesAtom Periodicity
Nanoscale
Picoscale
Brief
Historical Overview
19th/20th Century
Chemists/Physicists
D. Mendeleev (1869)
R. Feynman (1959)
A. Lavoisier (1789)
J. Dalton (1808)
Alchemy Pre-1789
Nano-Alchemy (1959-Present)
First Systematic,
Synthetic Nano-
structure
Platform
Dendrimers
(early 1980s)
John Dalton
(1808)
Atoms Compound Atoms
• Atoms Form Chemical
Bonds
• Atoms Bond with Discrete
Stoichiometries, Valency
and Combining Weights
• Atoms Bond with
Discrete Directionality
• Atoms Exhibit Periodic
Properties
Traditional Chemistry – “Central Dogma”First Principles
Atom Mimicry:
(a) Core-Shell Architecture (b) Outer Shell Reactivity
He Ne Ar Kr XeHe Ne Ar Kr Xe
Picoscale Matter
(Atoms)
Elements Exhibiting
Noble Gas
Configurations
Electron shell levels: 1 2 3 4 5Electron shell levels: 1 2 3 4 5
Saturation values (n): 2 10 18 36 54Saturation values (n): 2 10 18 36 54
Atomic weights: 4.00 20.17 39.94 83.80 131.30Atomic weights: 4.00 20.17 39.94 83.80 131.30
Shell Components
n (Electrons)
.064 nm .138 nm .194 nm .220nm .260 nmDiameters: .064 nm .138 nm .194 nm .220nm .260 nmDiameters:
Hard Nano-Matter
(Gold Nanoclusters)
Full-Shell
“Magic Number”
Clusters
Atom shell levels: 1 2 3 4 5Atom shell levels: 1 2 3 4 5
Saturation values (n): 12 54 146 308 560Saturation values (n): 12 54 146 308 560
Nano-cluster weights: 2560 10833 28953 60861 110495Nano-cluster weights: 2560 10833 28953 60861 110495
Shell Components
n (Au Atoms)
.864 nm 1.44 nm 2.02 nm 2.59 nm 3.17 nmDiameters: .864 nm 1.44 nm 2.02 nm 2.59 nm 3.17 nmDiameters:
1.58 nm
G=1
2.2 nm
G=2
3.10 nm
G=3
4.0 nm
G=4
5.3 nm
G=51 nm
G=0
Core
Soft Nano-Matter
(Dendrimers)
Saturated
Monomer
Shells
Shell Components
n (Monomers) Saturation values (n): 9 21 45 93 189Saturation values (n): 9 21 45 93 189
Nanostructure weights: 144 2414 5154 10632 21591Nanostructure weights: 144 2414 5154 10632 21591
Monomer shell levels: G=1 G=2 G=3 G=4 G=5Monomer shell levels: G=1 G=2 G=3 G=4 G=5
1.58 nm 2.2 nm 3.10 nm 4.0 nm 5.3 nmDiameters: 1.58 nm 2.2 nm 3.10 nm 4.0 nm 5.3 nmDiameters:
Comparison of Atoms with Hard and Soft Nanoparticles
D.A. Tomalia, J. of Nanoparticle Research, 11. 1251-1310 (2009)
Self-Assembly of PAMAM Dendrimers (G9) (Atom Mimicry)
D.A. Tomalia, et al., Pure and Applied Chem., 72, 2343 (2000).
C C CC C
C
C C C C C
r1 = radius of core dendrimer
r2 = radius of shell dendrimer
Nmax= Total theoretical number of shell-like
spheroids with radius r2 that can be ideally
parked around core spheroid with radius r1
Mansfield-Tomalia-Rakesh Equation
When: r1/r2 > 1.20
I
r2
r1III
r2
r1
D.A. Tomalia, et al., J. Chem. Phys. 105 (8), 3245 (1996).
Nmax =2
3
r1
r2+ 1
2
Nmax =2
3
r1
r2+ 1
2
Spheroidal Valency Defined by Nano-Sterics
(b) (c)(a)
12 Gold Nano-Clusters
Nano-Element Valency :[H-1] type; [Cubic-(Ag)n ]
M. Rycenga, J. M. McLellan, Y. Xia; Adv. Mater.,(2008), 20, 2416-2420
[Metals]0 = H2 , Cl2, O2
CH4
-(CH2)-n=3,4
=
=
=
= 2-D Assembly
= 3-D Assembly
picometer
10-1
10-8
10-10
10-11
10-12
(trillions)
10-2
10-3
10-4
10-5
10-6
10-7
10-9
100
Macroscale
Microscale
Atoms
Molecular
Structures
Nanostructures
Assemblies
Atom PeriodicityNanoscale
Picoscale
Critical Hierarchical Design Parameters
Size
Shape
Surface
Chemistry
Flexibility
Architecture
(Symmetry)
(CNDP)
(CMDP)
(CADP)
Atom Mimicry
Conservation of Hierarchical Design
Parameters?
(AtomMolecular Nano Structures)
Conservation of Hierarchical Design Parameters?
(CADP CMDP CNDP)
Rudiementary Atomic Element Property
Patterns
Observed before Mendeleev
Physical Properties:
• Dependent on element mass (i.e., At. wt.)
Chemical Properties:
• Dependent on element valency
InertSize
Reactive Surface Chemistry
Shape
Critical Atomic Design Parameters (CADP’s)
Flexibility/Polarizabilty
Critical Nanoscale Design Parameters (CNDP’s)
ISI Citations
2126
decimeter (dm)
picometer
10-1
10-8
10-10
10-11
10-12
(trillions)
(tens)
10-2
10-3
10-4
10-5
10-6
10-7
10-9
100
Nanoscale Atom Mimicry
Hard Nanoparticle
CategoriesSoft Nanoparticle
Categories
Nano-elements
Using Traditional Principles and Rationale for Defining
(Elemental) Atoms and Compounds
Physico-Chemical
Properties
Functional/Application
Properties
Nano-compounds
Nano-periodic Property Patterns
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
Hard Particle Nano-Element Categories
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins VirusesViruses RNA/DNANano-latexesNano-latexes
Polymeric
Micelles
Soft Particle Nano-Element Categories
S-1 S-2 S-3 S-4 S-5 S-6
Macroscale
Microscale
Atoms
Molecular
Structures
Nanostructures
Assemblies
Nano-Periodicity
Atom PeriodicityNanoscale
Picoscale
Critical Hierarchical Design Parameters
Size
Shape
Surface
Chemistry
Flexibility
Architecture
(Symmetry)
(CNDP)
(CMDP)
(CADP)
Atom Mimicry
II.Proposed Nanomaterials Classification Roadmap
Nano-Element (Module) Categories(Selection Criteria)
1. Exhibit Well-Defined Monodispersity:
(>90% monodisperse as a function of size and/or mass)
2.Well-Defined Nanostructures, Assemblies or
Particles that Mimic / Behave Like Atoms:
(They react, assemble and exhibit controlled Critical Nanoscale
Design Parameter (CNDP) properties as a unit.)
3. Exhibit Well-Defined Stoichiometries and Mass
Combining Ratios
4. Exhibit Nano-Periodic Property Patterns
S.Y. Park, C. Mirkin et al., Nature, 451, 553-556 (2008).
Monodispersity Criteria:
Atom-Like, 3-D Nano-cluster Super Lattices
>90% monodisperse
gold nanoclusters
required to obtain
well defined X-ray
patterns
Metals Non-Metals
Soft MatterHard Matter
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins
Viral
Capsids RNA/DNANano-latexesNano-latexesPolymeric
Micelles
Polymeric
Micelles
SOFT PARTICLE NANO-ELEMENT CATEGORIES
S-1 S-2 S-3 S-4 S-5 S-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
Nanomaterials Classification Roadmap
Well-Defined Materials
Atom Mimicry
Category I
Nanoparticles
Undefined MaterialsUndefined Materials
Category IIAtom-Based Structures/Assemblies
Nano-compounds
Nano-elements
Hard
Nanoparticles
Soft
Nanoparticles
Physico-Chemical
• Size
• Shape
• Surface Chemistry
• Interior Features
• Flexibility/Polarizability
• Architecture
Functional/Applications
• Photonic
• Magnetic
• Toxicology
• Electronic
• Catalysis
• Imaging
Nano-periodic Properites
Diameters: 1-100 nm
Mass: 104-1010 daltons
# of Atoms: 103-109
Topology: 0-D and 1-D
Nanoclusters
Gold
Palladium
Silver, etc.
H-1
Nano-Crystals
Metal-Non Metal
(Groups 4A-7A Compounds)
Amorphous
Nanoparticles
Silca
Nanoparticles
H-4
Non-
Metals
Rigid Carbon Allotropes
1-D Carbon
Nanotubes
H-6
0-D
Fullerenes
H-5
Metal
Chalcogenides
H-2
Metal Oxides
H-3
Conductors Semi-Conductors
Semi-
MetalsMetals
(M°)
Synthetic
Dendrons/
Dendrimers
S-1
Nanolatexes
S-2
Polymeric
Micelles
S-3
Nanostructures/Particles
DNA/RNA
S-6
Biological
Viruses
S-5
Proteins
S-4
Insulators
Non-Metal
Organic Structures
Soft/Hard Particle Nano-compounds
Nano-
Elements
S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1
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
S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4
S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5
S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6
Soft/Hard Particle Nano-compounds
Nano-
Elements
S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1
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
S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4
S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5
S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6
Dendrimers
Dendrons
Dendrimers
Dendrons
Metal (M°)
(Nanoclusters)
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal
(Chalcogenide)
(Nanocrystals)
Nano-
latexes
Nano-
latexes DNA/RNADNA/RNA
Metal Oxide
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Carbon
Nanotubes
Carbon
Nanotubes
Polymeric
Micelles ProteinsProteins VirusesViruses
Silica
(Nanoparticles)
Silica
(Nanoparticles)
FullerenesFullerenes
Soft Particle Nano-compounds
Nano-
Elements
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
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
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
Soft Particle Nano-compounds
Nano-
Elements
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
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
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
Dendrimers
Dendrons
Dendrimers
Dendrons
Nano-
latexes
Nano-
latexesDNA/RNADNA/RNA
Polymeric
Micelles ProteinsProteins VirusesViruses
Dendrimers
Dendrons
Dendrimers
Dendrons
Nano-
latexes
Nano-
latexes
DNA/RNADNA/RNA
Polymeric
Micelles
ProteinsProteins
VirusesViruses
Hard Particle Nano-compounds
Nano-
Elements
H-1:H-1 H-2:H-1 H-3:H-1 H-4:H-1 H-5:H-1 H-6:H-1
H-2:H-2 H-3:H-2 H-4:H-2 H-5:H-2 H-6:H-2
H-2:H-3 H-3:H-3 H-4:H-3 H-5:H-3 H-6:H-3
H-2:H-4 H-3:H-4 H-4:H-4 H-5:H-4 H-6:H-4
H-2:H-5 H-3:H-5 H-4:H-5 H-5:H-5 H-6:H-5
H-2:H-6 H-3:H-6 4-H:H-6 H-5:H-6 H-6:H-6
Hard Particle Nano-compounds
Nano-
Elements
H-1:H-1 H-2:H-1 H-3:H-1 H-4:H-1 H-5:H-1 H-6:H-1
H-2:H-2 H-3:H-2 H-4:H-2 H-5:H-2 H-6:H-2
H-2:H-3 H-3:H-3 H-4:H-3 H-5:H-3 H-6:H-3
H-2:H-4 H-3:H-4 H-4:H-4 H-5:H-4 H-6:H-4
H-2:H-5 H-3:H-5 H-4:H-5 H-5:H-5 H-6:H-5
H-2:H-6 H-3:H-6 4-H:H-6 H-5:H-6 H-6:H-6
Metal (M°)
(Nanoclusters)
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Carbon
Nanotubes
Carbon
Nanotubes
Silica
(Nanoparticles)
Silica
(Nanoparticles)
FullerenesFullerenes
Metal (M°)
(Nanoclusters)
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Metal Oxide
(Nanocrystals)Carbon
Nanotubes
Carbon
NanotubesSilica
(Nanoparticles)
Silica
(Nanoparticles)FullerenesFullerenes
Nanomaterials Classification Roadmap
J. of Nanoparticle Research, 11, 1251-1310 (2009).
NanomaterialsSize: 1-100 nm
# Atoms: 103-109 atoms
Mass: 104-1010 daltons
Undefined
Statistically Polydisperse
a) size
b) mass
Hard Nanoparticle
Categories
Soft Nanoparticle
Categories
Category I Category II
Well Defined
Monodisperse
a) size
b) mass
Atom Mimicry
J. of Nanoparticle Research, 11, 1251-1310 (2009).
Abbreviated Nanomaterials Classification Roadmap
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins
Viral
Capsids RNA/DNANano-latexesNano-latexesPolymeric
Micelles
Polymeric
Micelles
SOFT PARTICLE NANO-ELEMENT CATEGORIES
S-1 S-2 S-3 S-4 S-5 S-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
Dendrimers
DendronsProteins Viral
CapsidsRNA/DNANano-latexes
Polymeric
Micelles
SOFT PARTICLE NANO-ELEMENT CATEGORIES
S-1 S-2 S-3 S-4 S-5 S-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
S. Maruyama, Y. Yamaguchi, Chemical
Physics Letters, 286, 343-349 (1998).
J.P. Wilcoxon, et al., Chem. Soc. Rev.
35, 1161-1194 (2006).
Nano-Element Categories
(1-D)
(1-D)
S-1
H-3 H-4 H-5 H-6
S-2 S-3 S-4 S-5 S-6
(Provisional)
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins
Viral
Capsids RNA/DNANano-latexesNano-latexesPolymeric
Micelles
Polymeric
Micelles
SOFT PARTICLE NANO-ELEMENT CATEGORIES
S-1 S-2 S-3 S-4 S-5 S-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
(Synthetic Polymers) (Biological Polymers)
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6H-2H-1
SOFT PARTICLE NANO-COMPOUNDS
Nano-
Elements
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
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
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
SOFT PARTICLE NANO-COMPOUNDS
Nano-
Elements
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
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
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
Dendrimers
Dendrons
Dendrimers
Dendrons
Nano-
latexes
Nano-
latexesDNA/RNADNA/RNA
Polymeric
Micelles
Polymeric
Micelles ProteinsProteinsViral
Capsids
Dendrimers
Dendrons
Dendrimers
Dendrons
Nano-
latexes
Nano-
latexes
DNA/RNADNA/RNA
Polymeric
Micelles
Polymeric
Micelles
ProteinsProteins
Viral
Capsids
-S-S-
-S-S--S
-S- -S-S--S-S-
-S-S--S
-S- -S-S-
Soft Nanoparticle Compounds
Dendrimer-Cluster
Compounds
Tomalia, et al.
Adv. Mater. (2000)
IgG-Dendrimer
Compounds
(Stratus®)
Siemens
Germany
DNA-Dendrimer
Compounds
(Superfect®)
Qiagen, Ger.
HIV-Virus-
Dendrimer
Compounds
(VivaGel®)
Starpharma, AU
Tobacco Mosaic
Virus Compound
Viral Capsid-RNA [S-5:S-6] Core-Shell Type,
Nano-Compound
Diameter: 18 nm
Length: 300 nm
Helical Symmetry
Subunits: 158 amino acids
ss-RNA: 6400 nucleotide
units
Tobacco Mosaic
Virus
P.J.G. Butler, A. Klug, Sci. Amer. 239 (5) 62-69, (1978).
Nano-Compound
Stoichiometry:
2130x-Protein Subunits [S-5];
1x-ss-RNA [S-6]
[S-6]
[S-5]
OH
OH
OH
OH
OH
OH
OHHOHO
HO
HO
HO
HO OHOH
OH
OHOH
HO
HO
HO
HO
HOHO
PP
P
PP
P
P
P
QD
GySiO2GyGyGySiO2
Soft/Hard Matter Nano-Compounds
Nano-
Elements
S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1
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
S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4
S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5
S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6
Soft/Hard Matter Nano-Compounds
Nano-
Elements
S-1:H-1 S-2:H-1 S-3:H-1 S-4:H-1 S-5:H-1 S-6:H-1
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
S-1:H-4 S-2:H-4 S-3:H-4 S-4:H-4 S-5:H-4 S-6:H-4
S-1:H-5 S-2:H-5 S-3:H-5 S-4:H-5 S-5:H-5 S-6:H-5
S-1:H-6 S-2:H-6 S-3:H-6 S-4:H-6 S-5:H-6 S-6:H-6
Dendrimers
Dendrons
Dendrimers
Dendrons
Metal (M°)
(Nanoclusters)
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal
(Chalcogenide)
(Nanocrystals)
Nano-
latexes
Nano-
latexes DNA/RNADNA/RNA
Metal Oxide
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Carbon
Nanotubes
Carbon
Nanotubes
Cross-linked
Polymeric
Micelles
Cross-linked
Polymeric
Micelles
ProteinsProteins VirusesViruses
Silica
(Nanoparticles)
Silica
(Nanoparticles)
FullerenesFullerenes
Soft/Hard Nanoparticle Compounds
Mirkin, et al.
Nature, (2008)Wiesner, et al.,
Chem. Mater.
(2007)
Tomalia et.al.
J. Luminescence
(2005)
Jensen, et al.
Nano Lett. (2005) Rotello, et al.
J.A.C.S. (2005)
X. Tu, et al.,
Nature (2009)
X. Tu, S. Manohar, A Jagota and M. Zheng, Nature, (2009), 460, 250
Barrel Shaped, SWNT:DNA -[H-6:S-6];
Core-Shell Type Nano-Compound Series
Core-Shell; [H-6:S-6] Type Nano-Compounds
DNA; [S-6]
SWNT; [S-6]
Nano-Compound Synthesis, Yields and Purities
Nano-Periodic Property Patterns for a
Series of [H-6:S-6] Nano-Compounds
Optical Absorption Spectra versus SWNT (n,m) Chirality
X. Tu, S. Manohar, A Jagota and M. Zheng, Nature, 2009, 460, 250
DNA [S-6]SWNT [H-6]
V.Nano-(Periodic) Property Trends
Nanoscale Atom Mimicry
Hard Nanoparticle
Categories
Soft Nanoparticle
Categories
Nano-elements
Intrinsic
Properties
Functional/Application
Properties
Nano-compounds
Nano-Periodic Property Patterns
Using Traditional “First Principles”
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins
Viral
Capsids RNA/DNANano-latexesNano-latexesPolymeric
Micelles
Polymeric
Micelles
SOFT PARTICLE NANO-ELEMENT CATEGORIES
S-1 S-2 S-3 S-4 S-5 S-6
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
HARD PARTICLE NANO-ELEMENT CATEGORIES
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
D.A. Tomalia, J. of Nanoparticle Research, 11. 1251-1310 (2009)
Nano-Periodic Trends of [S-1]-Type Nano-Elements (Dendrons)
J.G. Rudick, V. Percec, Accounts of Chemical Research, 41,(12), 1641-1652 (2008)
First Demonstration of Quasi-Equivalence with Synthetic Nanostructures
(Size, Shape, Surface Chemistry Driven Self Assembly Patterns)
(Tertiary)
Supramolecular
Dendrimers
(Quaternary)
Dendrimer
Assemblies
Percec’s Nano-Periodic Self-Assembly Table
(Primary)
Dendron
Structures
V. Percec, et al., J. Am. Chem. Soc., (in press)
“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, 1251-1310,(2009)
(1 nm)
(100 nm)
Atoms (Elements) (Periodic
Table)
Simple Compounds
(HCl, H2O, NH3, CH4)
Sub-nano Modules
(Aliphatic, Aromatic)
Functional Groups
(-CO2H, -NH2, -OH)
Complex Compounds
(Palytoxin, C60)
Nanoscale Modules
(Proteins, DNA, RNA)
Bio-assemblies
(Viruses, Ribosomes)
Biological Cells
Simple Organisms
(Bacteria)
Organisms
(Plants, Animals)
Complex Organisms
(Humans)
Complexity Staircase
Organic Chemistry
Inorganic Chemistry
Polymer Chemistry
Polypeptide Chemistry
Nanoscale Atom Mimicry
Hard Nanoparticle
CategoriesSoft Nanoparticle
Categories
Nano-elements
Using Traditional Principles and Rationale for Defining
(Elemental) Atoms and Compounds
Physico-Chemical
Properties
Functional/Application
Properties
Nano-compounds
Nano-periodic Property Patterns
Metal (M°)
(Nanoclusters)
Metal
(Chalcogenide)
(Nanocrystals)
Metal Oxide
(Nanocrystals)
Silica
(Nanoparticles)Fullerenes
Hard Particle Nano-Element Categories
Carbon
Nanotubes
Carbon
Nanotubes
H-1 H-2 H-3 H-4 H-5 H-6
Dendrimers
Dendrons
Dendrimers
DendronsProteinsProteins VirusesViruses RNA/DNANano-latexesNano-latexes
Polymeric
Micelles
Soft Particle Nano-Element Categories
S-1 S-2 S-3 S-4 S-5 S-6
Atoms
Monomers
Synthetic
Nano-ChemistryHard/Soft
Nano-Elements
Nano-Periodicity
Quantized Building
Blocks
The Future
Natural Physico-Chemical Laws
We are not advocating
changes in the gospel!
We are merely
proposing some new
hymns--new thinking.
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