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


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


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


Hard Particle Nano-Element Categories

Carbon

Nanotubes

Carbon

Nanotubes

H-1 H-2 H-3 H-4 H-5 H-6

Dendrimers

Dendrons

Dendrimers


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


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)


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


Viral


Micelles

Polymeric

Micelles


S-1 S-2 S-3 S-4 S-5 S-6

Metal (M°)

(Nanoclusters)

Metal

(Chalcogenide)

(Nanocrystals)

Metal Oxide

(Nanocrystals)

Silica



Carbon

Nanotubes

Carbon

Nanotubes

H-1 H-2 H-3 H-4 H-5 H-6

Dendrimers

DendronsProteins Viral

CapsidsRNA/DNANano-latexes

Polymeric

Micelles


S-1 S-2 S-3 S-4 S-5 S-6

Metal (M°)

(Nanoclusters)

Metal

(Chalcogenide)

(Nanocrystals)

Metal Oxide

(Nanocrystals)

Silica



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


Viral


Micelles

Polymeric

Micelles


S-1 S-2 S-3 S-4 S-5 S-6

Metal (M°)

(Nanoclusters)

Metal

(Chalcogenide)

(Nanocrystals)

Metal Oxide

(Nanocrystals)

Silica



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



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



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



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

http://www.discoverymagazine.com/image/selart/d0104a.jpg

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)


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


Hard Nanoparticle

Categories

Soft Nanoparticle

Categories

Nano-elements

Intrinsic

Properties


Properties

Nano-compounds

Nano-Periodic Property Patterns

Using Traditional “First Principles”

Dendrimers

Dendrons

Dendrimers


Viral


Micelles

Polymeric

Micelles


S-1 S-2 S-3 S-4 S-5 S-6

Metal (M°)

(Nanoclusters)

Metal

(Chalcogenide)

(Nanocrystals)

Metal Oxide

(Nanocrystals)

Silica



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


Hard Nanoparticle

CategoriesSoft Nanoparticle

Categories

Nano-elements

Using Traditional Principles and Rationale for Defining

(Elemental) Atoms and Compounds

Physico-Chemical

Properties


Properties

Nano-compounds

Nano-periodic Property Patterns

Metal (M°)

(Nanoclusters)

Metal

(Chalcogenide)

(Nanocrystals)

Metal Oxide

(Nanocrystals)

Silica


Hard Particle Nano-Element Categories

Carbon

Nanotubes

Carbon

Nanotubes

H-1 H-2 H-3 H-4 H-5 H-6

Dendrimers

Dendrons

Dendrimers


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

in quest of a systematic framework for unifying and ...in quest of a systematic framework for...

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