element periodic property patterns have been shown to be dependent on their
intrinsic CADPs (Fig. 16) and are routinely utilized for predictive purposes in
traditional small-molecule chemistry, it was hoped that similar relationships and
behavior would be observed at the nanoscale level.
Recently, first steps toward the fulfillment of this expectation have been realized
by publication of the first “Mendeleev-like nano-periodic tables” for predicting the
self-assembly modes of soft nano-element modules. More specifically, the selfassembly properties of soft nano-elements such as amphiphilic dendrons (i.e., [S-1]
nano-elements) were systematically investigated by Percec, Rosen and colleagues
[151]. They reported a prediction accuracy for resulting self-assembled structures
of 85–90% based on the a priori use of dendron CNDPs. These issues will be
described later in Section 6.6.3.
6.3 Atom Mimicry: Nanoscale Superatoms
and Atom Equivalents
6.3.1 Quantized Aufbau Components: Electrons, Atoms,
and Monomer Units
The selection process for various category I-type, hard and soft particle nanoelements (Fig. 18) was based on certain heuristic or experimentally demonstrated
atom mimicry features. Earlier general atom mimicry comparisons were made
based on the similarity of core–shell architecture exhibited by atoms and
dendrimers [10, 11]; however, more detailed working examples that include (inorganic) hard metal nanoclusters are as illustrated in Fig. 19. In descending order,
analogous (i.e., heuristic) aufbau components (i.e., electron, Au atoms, and
β-alanine monomer units) leading to core–shell picoscale (atoms) and nanoscale
hard matter (Au nanoclusters) and soft matter (dendrimers), respectively, are
compared. This comparison illustrates aufbau component mimicry and quantized
features required to produce core–shell-type structures at two diverse hierarchical
dimensional levels. Well-defined sizes, atomic/molecular masses, and outer-shell
saturation values (n) are inextricably connected to specific electron shell, atom
shell, or monomer shell (generation) levels in each case. Such atom mimicry is
clearly demonstrated for hard nanoparticle gold clusters and soft nanoparticle
dendrimers. Similar architectural motif patterns may be observed to a lesser or
greater degree in the pervasive core–shell taxonomy observed for all proposed
nano-element categories, as described elsewhere [137, 138].
Seminal work by Schmid [152, 153] and Rao [154] has shown that fundamental
core–shell metal nanoclusters (i.e., Au and Pd) with magic numbers of metal atoms
(i.e., 13, 55, 147, 309, 561, and 1,415) corresponding to closed atom shells 1, 2, 3, 4,
5, and 7, respectively, do indeed exist. As noted by Schmid, they are substantially
more robust when ligand-stabilized [155]. Furthermore, they can be prepared
Twenty-First Century Polymer Science After Staudinger: The Emergence of. . .
357
intrinsic CADPs (Fig. 16) and are routinely utilized for predictive purposes in
traditional small-molecule chemistry, it was hoped that similar relationships and
behavior would be observed at the nanoscale level.
Recently, first steps toward the fulfillment of this expectation have been realized
by publication of the first “Mendeleev-like nano-periodic tables” for predicting the
self-assembly modes of soft nano-element modules. More specifically, the selfassembly properties of soft nano-elements such as amphiphilic dendrons (i.e., [S-1]
nano-elements) were systematically investigated by Percec, Rosen and colleagues
[151]. They reported a prediction accuracy for resulting self-assembled structures
of 85–90% based on the a priori use of dendron CNDPs. These issues will be
described later in Section 6.6.3.
6.3 Atom Mimicry: Nanoscale Superatoms
and Atom Equivalents
6.3.1 Quantized Aufbau Components: Electrons, Atoms,
and Monomer Units
The selection process for various category I-type, hard and soft particle nanoelements (Fig. 18) was based on certain heuristic or experimentally demonstrated
atom mimicry features. Earlier general atom mimicry comparisons were made
based on the similarity of core–shell architecture exhibited by atoms and
dendrimers [10, 11]; however, more detailed working examples that include (inorganic) hard metal nanoclusters are as illustrated in Fig. 19. In descending order,
analogous (i.e., heuristic) aufbau components (i.e., electron, Au atoms, and
β-alanine monomer units) leading to core–shell picoscale (atoms) and nanoscale
hard matter (Au nanoclusters) and soft matter (dendrimers), respectively, are
compared. This comparison illustrates aufbau component mimicry and quantized
features required to produce core–shell-type structures at two diverse hierarchical
dimensional levels. Well-defined sizes, atomic/molecular masses, and outer-shell
saturation values (n) are inextricably connected to specific electron shell, atom
shell, or monomer shell (generation) levels in each case. Such atom mimicry is
clearly demonstrated for hard nanoparticle gold clusters and soft nanoparticle
dendrimers. Similar architectural motif patterns may be observed to a lesser or
greater degree in the pervasive core–shell taxonomy observed for all proposed
nano-element categories, as described elsewhere [137, 138].
Seminal work by Schmid [152, 153] and Rao [154] has shown that fundamental
core–shell metal nanoclusters (i.e., Au and Pd) with magic numbers of metal atoms
(i.e., 13, 55, 147, 309, 561, and 1,415) corresponding to closed atom shells 1, 2, 3, 4,
5, and 7, respectively, do indeed exist. As noted by Schmid, they are substantially
more robust when ligand-stabilized [155]. Furthermore, they can be prepared
Twenty-First Century Polymer Science After Staudinger: The Emergence of. . .
357