in quest of a systematic ramework - … · alchemy (331 b.c. – nomenclature 18th century) -...

1

© D.A. Tomalia, National Dendrimer & Nanotechnology Center, Central Michigan University, 2009.

IN QUEST OF A SYSTEMATIC FRAMEWORK

FOR UNIFYING AND DEFINING NANOSCIENCE

Donald A. Tomalia

Department of Chemistry National Dendrimer & Nanotechnology Center

Central Michigan University Mt. Pleasant, MI 48859

A 19th Century Paradigm for Traditional Chemistry

A 21st Century Paradigm for Nanoscience

John Dalton

(1808)

Atoms Compound Atoms

John Dalton

(1808)

Atoms Compound Atoms

J. Dalton (1808)

D. Mendeleev Periodic Table (1869)

Atoms form chemical bonds Atoms bond with discrete

valencies, stoichiometries Atoms bond with discrete

directionality Atoms exhibit periodic

properties o

ms Bond with Discrete Stoichio

2


Historical Background:[1-3] Alchemy (331 B.C. – 18th Century) -

chemistry chaos, empirical chemistry recipes, not a true science.

L.-J. Proust (1788) - reactive modules,

whole integer relationships in reactions/assemblies.

A.L. Lavoisier (1789) - chemical evidence

for reactive modules- atoms/elements (Traite Elementaire de Chemie.

J. Dalton (1808) - First example of atom

mimicry, wood spheroids (first CPK models), table of chemical elements, compound atoms, first chemical symbols/chemical language (front page).

Atoms: Form chemical bonds Bond with discrete valencies and

stoichiometries Bond with discrete directionality Exhibit systematic property trends

J. Berzelius (1832) - first universal

chemical language based on chemical symbols, isomerism, etc. [4]

Others: S. Cannizzaro (1860), J. Newland

(1865) “Law of octaves”, etc.– observed many mini-periodic property patterns associated with the elements.

Pre-Mendeleev: Elemental physical

properties depend on mass (size); Chemical properties depend on valency.

Mendeleev’s Dream: A 19th Century Concept (1808-1869) Mendeleev attempted to rationalize mini periodic patterns. This led to systematic framework for all atomic elements (Mendeleev’s Periodic Table). [5]

19th and 20th Century Chemists/Physicists A traditional chemistry system and nomenclature evolves -–“central paradigm.” A 20th Century overview of the Periodic Table: Based on observed periodic patterns and 20th century insights the atomic elements may be viewed to exhibit general trends and Critical Atomic Design Parameters (CADP’s)[6,7] as described in Figure 1.

Figure 1.

Tomalia’s Dream: A 21st Century Concept (1985-1990) Reported first synthesis of complete

dendrimer family (i.e., PAMAM’s) [8] and their use as precise, systematic nanoscale building blocks for construction of new mega polymers called “Starburst Polymers”.

Subsequent dendrimer studies provided insights into the importance of “critical structure control parameters” involved at the atomic CADP, small molecule CMDP, and nanoscale CNDP levels; namely: (a) size, (b) shape, (c) surface chemistry, (d) flexibility /rigidity, (e) architecture/ topology, (f) elemental composition. Performing iterative reaction sequences (i.e., aufbau steps) according to dendritic growth principles transferred CADP->CMDP>CNDP and produced precise, synthetic nanoscale macromolecules with structure control equivalent to precise biological macromolecules such as proteins, DNA and RNA.[5]

3


All summed up in Angew. Chem. Abstract-(1990) – ISI citations: >2100. [6] Abstract

Starburst dendrimers are three-dimensional, highly ordered oligomeric and polymeric compounds formed by reiterative reaction sequences starting from small molecules—“initiator cores” such as ammonia or pentaerythritol. Protecting group strategies are crucial in these syntheses, which proceed via discrete “Aufbau” stages referred to as generations. Critical molecular design parameters (CMDPs) such as size, shape, and surface chemistry may be controlled by reactions and synthetic building blocks used. Starburst dendrimers can mimic certain properties of micelles and liposomes and even those of biomolecules and the still more complicated, but highly organized, building blocks of biological systems. Numerous applications of these compounds are conceivable, particularly in mimicking the functions of large biomolecules as drug carriers and immunogens. This new branch of “supramolecular chemistry” should spark new developments in both organic and macromolecular chemistry.[6]

Figure 2.[6]

Further Elaboration/Expansion of the “The Dream” (1994-2009):

Questions asked: “Could traditional chemistry 1st principles

be used to define a central paradigm for synthetic nanoscale chemistry?”

Based on the presumed conservation and communication of critical atomic design parameters (CADPs) from atomic to the molecular and nanoscale level—

“Could one expect to see analogies of atomic element (atom mimicry), compound formation and periodic property patterns for well-defined nanoscale modules (i.e., collections of 103 -109 atoms; 104 -1010 daltons) that are 103 larger than atoms?”

Published work to answer these questions: 1. Adv. Materials (1994) - Atom mimicry at

the nanoscale level observed for dendrimers--modular reactivity/nano-compound formation.[7]

2. Progress in Polymer Sci. (2005) - Quantized nanoscale building blocks/modules.[8]

3. NSF Workshop (2007) entitled: “Periodic Patterns, Relationships and Categories of Well Defined Nanoscale Building Blocks”.[9]

4. J. Nanoparticle Research (2009) - “In Quest of a System for Unifying and Defining Nanoscience”.[10]

5. Soft Matter (2009, in press) - “Dendrons/Dendrimers: Quantized, Nano-Element Like Building Blocks for Soft-Soft and Soft Hard Nano-Compound Synthesis.”[11]

4


Fulfillment of “The Dream”: (a) Atom mimicry principles are exhibited by

all presently known categories of “well-defined nanomaterials” (i.e., soft and hard matter).

Figure 3.

Figure 4.

Figure 5.[12]

(b) A Nanomaterials Classification

Roadmap has been proposed for all well-defined soft and hard nanoparticles (i.e., 0-D/1-D). Based on “atom mimicry” and other traditional chemistry 1st principles

(i.e., conservation of structure controlled CMDPs/CNDPs), six categories of soft particle nano-elements and six categories of hard particle nano-elements have been proposed.[10]

Figure 6.

Figure 7.

Figure 8.[13]

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:

Nanomaterials Classification Roadmap

Well-Defined Materials

Atom Mimicry

Category I

Nanoparticles

Undefined MaterialsUndefined Materials

Category IIAtom-Based Structures/Assemblies

Nano-compounds/Assemblies

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 Properties

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

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

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

Polymeric

Micelles ProteinsProteinsViral

Capsids

Viral

Capsids

Silica

(Nanoparticles)

Silica

(Nanoparticles)


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


Capsids

Viral

Capsids

Dendrimers

Dendrons

Dendrimers

Dendrons

Nano-

latexes

Nano-

latexes

DNA/RNADNA/RNA

Polymeric

Micelles

Polymeric

Micelles

ProteinsProteins

Viral

Capsids

5


Figure 9.

(c) Many documented literature examples attest to the formation of nano-compounds/assemblies which exhibit well-defined stoichiometries and mass combining ratios (Figs. 10-13).

Figure 10.

Figure 11.[14]

Figure 12.

Figure 13.[15]

(d) Many documented literature examples

describe well-defined “nano-periodic property patterns” for both soft and hard particle nano-elements, as well as their compounds/assemblies (Fig. 14).

Figure 14.[15]

(e) V. Percec, et al.[16] have reported first examples of “nano-periodic tables” that predict self-assembled dendrimers expected from soft nanoparticle [S-1] type dendron nano-elements based on their structure controlled: (a) sizes, (b) shapes and (c) surface chemistries (Figs. 15-16).

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)

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


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--S-S-

-S-S--S

-S- -S-S--S-S-

-S-S--S

-S- -S-S--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

6


Figure 15.[17]

Figure 16.[16]

Figure 17.[10]

Primary

Dendron/Dendrimer

Structures

Tertiary

Dendrimer

Structures

Quaternary

Dendrimer

Assemblies

Size Shape Surface Chemistry

Self

Assembly

7


Systematic Nano-periodicConcept overview (Figs. 17-18): By using first principles and step logic

that led to the “central dogma” for traditional chemistry, the criteria of nanoscale atom mimicry was applied to Category I-type, well-defined nanoparticles.

This produced 12 nano-element categories which were classified into six hard particle [H (1-6)] and six soft particle [S (1-6)] nano-element categories.

Chemically bonding or assembling these hard and soft nano-elements leads to hard:hard, soft:hard or soft:soft type nano-compound/assembly categories, many of which have been reported in the literature .

Based on discrete, quantized features associated with the proposed nano-elements and their compounds/assemblies, an abundance of nano-periodic property patterns related to their intrinsic physico-chemical and functional/application properties have been observed and reported in the literature.

The first example of nano-periodic tables based on this concept have been reported by V. Percec, et al.[16] for prediction of tertiary/quaternary self assembly structures for [S-1] type dendrons based on size, shape and surface chemistry.

Prologue: “Science will continue to advance regardless of disputes over priorities. However, confusion and disagreement over common scientific language and standards can plunge a discipline into chaos. Such was the case for 19th century traditional chemistry before Mendeleyev’s Periodic Table of the Elements.” “Mendeleleyev’s Dream- The Quest for the Elements”- P. Strathern[3]

Figure 18.[10]

The Future: This proposed concept must be viewed as a nano-periodic system with many defining dimensions. This new complexity will undoubtedly require more than a single nano-periodic table to capture such a broad range of designable features and information. The daunting challenge will be to consolidate these emerging nano-periodic property patterns into major trends and areas much as pre-Mendeleelev scientists did in the 19th century with the expectation that this effort will crystallize into a grand perspective and system of understanding. Accomplishing this objective will provide a powerful means for predicting new nano-properties/behavior as well as an effective system for anticipating new nano-materials yet to be discovered, while defining important and critical risk/benefit boundaries in the field of nanoscience. Finally this concept embraces the emergence of the new field of “well-defined synthetic nanochemistry” as described in Figure 19.

Figure 19.

8


References 1. Pullman B: The Atom in the History of

Human Thought. New York: Oxford

University Press; 1998.

2. Scerri ER: The Periodic Table. New York:

Oxford University Press; 2007.

3. Strathern P: Mendeleyev's Dream. New York:

The Berkley Publishing Group; 2000.

4. Berzelius J: J Fortsch Phys Wissensch 1832,

11:44.

5. Rosen BM, Wilson CJ, Wilson DA, Peterca M,

Imam MR, Percec V: Dendron-mediated self-

assembly, disassembly, and self-organization

of complex systems. Chem Rev 2009,

109:6275-6540.

6. Tomalia DA, Naylor AM, Goddard III WA:

Starburst dendrimers: molecular level

control of size, shape, surface chemistry,

topology and flexibility from atoms to

macroscopic matter. Angew Chem Int Ed Engl

1990, 29(2):138-175.

7. Tomalia DA: Starburst/cascade dendrimers:

fundamental building blocks for a new

nanoscopic chemistry set. Adv Mater 1994,

6:529-539.

8. Tomalia DA: Birth of a new macromolecular

architecture: dendrimers as quantized

building blocks for nanoscale synthetic

polymer chemistry. Prog Polym Sci 2005,

30:294-324.

9. Tomalia DA: Periodic patterns, relationships

and categories of well-defined nanoscale

building blocks

(http://www.nsf.gov/crssprgm/nano/GC_Cha

ract08_Tomalia_nsf9_29_08.pdf). National

Science Foundation Final Workshop Report

2008:1-156.

10. Tomalia DA: In quest of a systematic

framework for unifying and defining

nanoscience. J Nanopart Res 2009, 11:1251-

1310.

11. Tomalia DA: Dendrons/Dendrimer:

quantized, nano-element like building blocks

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