Sequence-Mandated, Distinct Assembly of Giant Molecules

Article abstract of DOI:10.1002/anie.201709354

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank–Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence-mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly.

Full text of DOI:10.1002/anie.201709354

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Sequence Mandated, Distinct Assembly of Giant Molecules
Authors: Wei Zhang, Xinlin Lu, Jialin Mao, Chih-Hao Hsu, Gaoyan Mu,
Mingjun Huang, Qingyun Guo, Hao Liu, Chrys Wesdemiotis,
Tao Li, Wen-Bin Zhang, Yiwen Li, and Stephen Z. D. Cheng
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709354
Angew. Chem. 10.1002/ange.201709354
Link to VoR: http://dx.doi.org/10.1002/anie.201709354
http://dx.doi.org/10.1002/ange.201709354

10.1002/anie.201709354
Angewandte Chemie International Edition
COMMUNICATION
Sequence Mandated, Distinct Assembly of Giant Molecules
Wei Zhang,a Xinlin Lu,a Jialin Mao,b Chih-Hao Hsu,a Gaoyan Mu,a Mingjun Huang,a Qingyun Guo,a Hao
Liu,a Chrys Wesdemiotis,a,b Tao Li,c Wen-Bin Zhang,d* Yiwen Lie* and Stephen Z.D. Chenga*
Abstract: Although controlling primary structures is by itself an enormous
challenge for synthetic polymers, the potential of sequence control for
tailoring hierarchical structures remains to be exploited, especially in the
creation of new and unconventional phases. Herein, we design and
synthesize a series of model amphiphilic chain-like giant molecules by
interconnecting both hydrophobic and hydrophilic molecular nanoparticles
in precisely defined sequence and composition to investigate their
intriguing sequence-dependent phase structures. Not only has
pathways. Thus, precisely controlled collective and cooperative
interactions have been increasingly recognized as the key process to
form hierarchical structures with feature sizes of only a few
nanometers.[6] In this case, oligomers/polymers with nano-sized
“macro-monomers”[7] is an effective approach to build phase-
separated nanostructures with the most significant impact of sequence.
The imposing challenge that we are facing is not only to achieve a
macromolecule with precisely defined sequences and sizes, but also to
compositional variation changed the self-assembled supramolecular phases, design and control their self-assembled structures and develop desired
but also specific sequences are found to induce unconventional phase
formation, including Frank-Kasper phases. The formation mechanism has
been attributed to the conformational change driven by the collective
hydrogen bonding and the sequence-mandated topology of the molecules.
These results support that sequence-control in synthetic polymers can have
dramatic impacts on the polymer properties and self-assembly.
properties. Recent advances of “click” chemistries and other efficient
transformations allow scientists to achieve macromolecules with high
structural precision and controlled heterogeneity. On the other hand,
the supramolecular structures are modularly assembled from a set of
building blocks and thus, the topology and interaction of each building
block are critically important to the final assembled structures. They, in
turn, must be accurately determined by the composition and sequence
of the macromolecule. Aiming at such an enormous task, we begin by
rationally designing a series of model amphiphilic giant molecules (so-
called “giant” relative to their small-molecule counterparts)[8] as for
the study of sequence-phase relationships and the role of sequences in
the formation unconventional phases in soft matters.[9] More
specifically, these giant molecules here refer to precise
macromolecules build-up by molecular nanoparticle building blocks.
We have previously investigated the effects of composition and
topology on the self-assembly of giant molecules.[4b, 6c, 9d, 10] However,
the importance of sequence has not been systematically explored in
terms of their impact on phase formation.
Natural polymers, such as deoxyribonucleic acids, ribonucleic acid,
and proteins, accomplish highly sophisticated functions to sustain life
with a small set of simple building blocks arranged in precisely defined
composition, length, sequence and stereochemistry. Their properties
and performances are in fact mandated by the information encoded in
polymer sequences. The importance of sequence has also been
demonstrated in some bio-resembling polymers, such as peptides,
peptoids and nucleic acids,[1] which inspired the next generation
sequence-controlled synthetic polymers. Recently, with contributions
from Lutz, Du Prez, Haddleton, Liu and others, tremendous progress
has been made on the synthetic methodologies.[2] Although the
synthesis of sequence-controlled polymers at a similar level of precision
to natural polymers is an enormous endeavor by itself,[3] it remains to
be demonstrated how sequence could dictate molecular topology and
assembly toward different structures and functions in synthetic
Herein, the rational design of model compounds was based on
linearly-like configured, monodisperse giant molecules with
consecutively connected polyhedral oligomeric silsesquioxane (POSS)
molecular nanoparticles (NP). For simplicity, only two types of
repeating units were employed: the hydrophobic BPOSS (~1 kDa with 7
sec-butyl groups) and the hydrophilic DPOSS (~1.5 kDa with 14 hydroxyl
groups). Each POSS NP is a building block, which can be viewed as a
“macromonomer” or a “precise block of polymer”. The detailed
molecular structures are illustrated in Figure 1. We believe that the
collective interaction between different macromonomers could enable
efficient construction of novel nanostructures, thus the attachment of
large-sized NPs will make the sequence effect even more pronounced.
This series of amphiphilic giant molecules could thus serve as a good
platform to understand the sequence effect in synthetic
macromolecules. From chemistry point of view, tuning exact number
of nanoparticles with precise chemical structures to build the giant
molecules eliminates the batch to batch variations in conventional
polymers due to polydispersity.[11] We could also precisely manipulate
their connecting sequence to achieve different “sequence isomers” in
a way similar to playing with “Lego” blocks. From physics point of view,
they have large enough immiscibility to induce nanophase separation
between different NPs. The thermodynamic driving force is the strong
collective hydrogen bonding formed via dense hydroxyl groups on the
peripheries of DPOSS cages among giant molecules. The hydrophobic
BPOSS NPs are nanophase separated from DPOSS NPs (χ > 0.3, see SI
for calculation[12]). Due to the incompatibility of these two kinds of
nanoparticles, BPOSS NPs tend to stay away from DPOSS NPs.[10a]
4]
polymer.[2c, While assembly of most synthetic macromolecules is
driven by interaction of monomers,[5] the minute differences between
individual monomers are often insufficient to discriminate assembly
[a]
W. Zhang, X. Lu, C. Hsu, G. Mu, M. Huang, Q. Guo, H. Liu, Prof. C.
Wesdemiotis, Prof. S.Z.D. Cheng
Department of Polymer Science, College of Polymer Science and
Polymer Engineering, The University of Akron, Akron, Ohio, 44325-
3909, United States E-mail: scheng@uakron.edu (S.Z.D.C)
Prof. C. Wesdemiotis
Department of Chemistry, The University of Akron, Akron, Ohio,
44325-3601, United States
[b]
[c]
[d]
T. Li.
X-ray Science Division, Advanced Photon Source, Argonne National
Laboratory, Argonne, Illinois, 60439, United States
Prof. W.B. Zhang
Key Laboratory of Polymer Chemistry and Physics of the Ministry of
Education, College of Chemistry and Molecular Engineering, Center
for Soft Matter Science and Engineering, Peking University, Beijing
100871, China Email: wenbin@pku.edu.cn (W.B.Z.)
Prof. Y. Li
[e]
College of Polymer Science and Engineering, State Key Laboratory
of Polymer Materials Engineering, Sichuan University, Chengdu
610065, China Email: ywli@scu.edu.cn (Y.L.)
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201709354
Angewandte Chemie International Edition
COMMUNICATION
Notably, their selective interactions dominate the formation of building
blocks via macromolecular packing arrangements, and become the
most important factor in determining their assembled structures. The
building blocks are thus constructed by a core of DPOSS NPs aggregated
together and covered with a thick shell formed by BPOSS NPs. It should
be noted that stereochemistry refers another important parameter in
natural polymers. However, this factor is not the focus of the current
study and thus are not further discussed in this paper.
Figure 2. MALDI-TOF spectra of DBn (n = 1-5). All the samples show peaks of [M·Ag]+
corresponding to the calculated molecular weights.
These monodisperse giant molecules (with molecular weight as
high as >7k) exhibit single lines which are accurate to the atomic level
based on matrix assisted laser desorption/ionization-time of flight
(MALDI-TOF) mass spectra as shown in Figure 2. The general synthetic
illustration is shown in Figure 1B and the detailed routes and
characterizations (1H, 13C NMR and other MS spectra) are outlined in
supporting information (SI).
These amphiphilic giant molecules exhibit versatile ordered
supramolecular phases with sub-10 nm feature sizes typically after
thermal annealing for 2 hours at about 150 C. When BPOSS cage does
not crystallize, multiple hydrophilic DPOSS cages start aggregating
together via the collective hydrogen bonding which forms one
nanophase, and push out the rest hydrophobic BPOSS cages to organize
into the other phase.
Figure 1. A. Illustration of chain-like giant molecules with precisely controlled
sequences and compositions built up by both hydrophilic and hydrophobic (D and B)
POSS NPs. (x and y are the number of BPOSS nanoparticles on the left and right side of
the DPOSS in the linear-like giant molecules. n is the total number of the BPOSS NPs.)
B. illustration of general synthetic strategy for these molecules.
For DB (n = 1, x = 0 in Figure 1), it has no sequence isomer. With
more or less commensurate size of the two NPs, an alternating layered
structure is expected from this molecule. A small angle X-ray scattering
(SAXS) pattern shows multiple peaks of equal q interval, indicating a
lamellar (LAM) lattice with layer spacing of 6.81 nm (Figure 3A(i)). The
lamellar structure is also confirmed by the bright field (BF) TEM image
in real space (Figure 3A(ii)).
Therefore, there are two dimensions to tune their structures and
properties–composition and sequence. In detail, the local
conformation of individual giant molecules would be relatively
extended in the tails when x = 0 in Figure 1. We speculate that as the
number of hydrophobic BPOSS (n) increases, it becomes increasingly
difficult to force the BPOSS NPs to line up within the cross-section area
of one DPOSS NP due to the progressively elevated entropic penalty.
This would possibly lead to phase structures evolving from LAM → HEX
→ BCC, like many asymmetric block copolymers. When x ≠ 0 in Figure
1, the local conformation of individual molecules would be in distinct
folded states with respect to the DPOSS NP in the tails by specific design
of DPOSS position in the chain sequence. From left to right along the
horizontal lines (as x increases) in Figure 1, the tail conformation
changes from non-folded to asymmetric, and finally to
symmetric/close-to-symmetric folded conformations with changing
the NP sequence at designated composition. We hypothesize that the
sequence effect in the molecules could induce folded conformation
driven by the collective hydrogen bonding among the hydrophilic
molecular NPs and influenced by the sequence-mandated topology of
the hydrophobic NPs, finally determining the interfacial areas of the
two phases at designate composition. This would result in different
“fan-angles”, “cone-angles” of the whole molecules, which could affect
the aggregation numbers or even possibly induce phase
transformations.
For DB2 (n = 2, x = 0), a double gyroid (DG) lattice (with a space
Ia3d
group of
) can be observed based on characteristic q ratio of
diffractions of √6:√8 in the SAXS pattern (Figure 3B(i)). In this DG lattice,
two BPOSS cages are sequentially and linearly-like tethered on the
DPOSS cage, and the aggregated DPOSS cages via collective hydrogen
bonding are imbedded in the BPOSS matrix (Figure 3B(ii)). However, by
moving the DPOSS cage to the second position (x = 1), the sequence
isomer BDB adopts a symmetric folded conformation with unbalanced
interface between DPOSS and two BPOSS cages. The SAXS pattern of
BDB exhibits scattering vector q ratio of 1: √ 3: √4 in Figure 3C(i),
indicating the formation of a hexagonal packed cylindrical (HEX)
structure. The real space image observed via BF TEM is shown in Figure
3C(iv). The average fan angles (α) for each molecule can be estimated
in BDB to be about 30o (Table 1, for detailed calculation, see SI).
DB3 (n = 3, x = 0) and its isomer BDB2 (n = 3, x = 1) both exhibit HEX
structures (Figure 3C), yet with different lattice sizes (6.79 and 6.58 nm).
Among them, each BDB2 molecule possesses an asymmetric folded
conformation in the assembly, while DB3 does not. Therefore, BDB2
sample contains a larger fan angle, less number of molecules per unit
length of the cylinder (10 molecules per DPOSS cage thickness, α ~36o,
Table 1, see SI for calculation) compared to the DB3 (12 molecules per
This article is protected by copyright. All rights reserved.

10.1002/anie.201709354
Angewandte Chemie International Edition
COMMUNICATION
DPOSS cage thickness, α ~30o), which leads to a smaller lattice size of
BDB2 (6.58 nm) than that of DB3 (6.79 nm, Table 1).
soft matters, the formation of F-K A15 phase is probably due to the
deformable and squishable nature and volume exchange of the
spherical building blocks. Thermodynamically, the A15 phase possesses
a better sphericity of building blocks,[16] and a lower interfacial tension
with higher stretching energy compared with those in BCC.[17] When we
move the DPOSS cage from the chain end to the second position, BDB3
(n = 4, x = 1) starts to adopt the folded conformation. However, with
the asymmetric number of BPOSS cages on both side of the DPOSS cage,
this might generate “surface defects” at the spherical building blocks of
BDB3. In this case, the supramolecular structure of BDB3 is identified to
be a dodecagonal quasicrystal (DQC), as illustrated by the characteristic
SAXS pattern (the 00002, 12100, 10102, and 12101 diffractions in
Figure 3D(ii)). More than one representative tiling patterns of 32.4.3.4,
33.42, 44 and 36 could be observed in the BF TEM image in Figure 3D(v),
illustrating that the structure losses the translational symmetry along
the a*b*-plane.[9d, 14a] For B2DB2 (n = 4, x = 2), the sequence change
resulted in a shorter but symmetric BPOSS tails, it forms an A15 phase
again. In this A15 structure, each molecule adopts the folded
conformation in the assembly and possesses a larger cone angle (~38,
Table 1, see SI for calculation), a smaller average number of molecules
in one spherical building block (μ = 36, Table 1, see SI for calculation)
and thus, a smaller lattice spacing (a = 13.5 nm) compared to the DB4
case (with a cone angle 33, μ = 47, a = 14.8 nm).
When BPOSS cage number exceeds three, the incommensurate
volumes between DPOSS and BPOSS cages become increasingly large.
This may cause the molecules to form a cone-like shape to
accommodate this volume difference, the shape of building blocks
must be spherical, leading to further assemble into spherical phases.
For example, in traditional diblock copolymer systems, BCC structures
are usually observed in cases with spherical building blocks.
Interestingly enough, however, DB4 (n = 4, x = 0) shows an
Oh3
Pm3n
unanticipated Frank-Kasper (F-K) A15 phase (space group
(
))
with characteristic q ratio of √2:√4:√5:√6 in the SAXS patterns as
shown in Figure 3D(i) and a representative tiling number of 44 in the BF
TEM images along the [001] zone in Figure 3D(iv).[10a] Note that F-K
phases were originally found in many metal alloys which possess
topological close packing combining the Frank lattice (distorted
icosahedral with coordination number, CN, of 12) and the Kasper
polyhedra (with CN of 14, 15, or 16).[13] Some F-K phases were also
recently found in soft materials, such as dendrimers, block copolymers
etc.[9a, 9b, 9d, 14] The A15 is one of three basic phases in the series of F-K
phases with two types of slightly different sizes of the spherical building
blocks in a ratio of 1:3.[15] Its crystal structure (space group
Oh3
Pm3n
(
))
involves both the Frank lattice (CN: 12) and the Kasper polyhedra (CN:
14). Although the F-K phase formation mechanism remains elusive in
Figure 3. SAXS patterns, TEM images and packing models of giant molecules. (A). DB forms a LAM phase. (B) DB2 forms a DG phase. (C). BDB, DB3, and BDB2 adopt fan-shapes and
form HEX phases. (D). DB4, BDB3, and B2DB2 adopt cone-shapes and form A15, DQC and A15 phases, respectively. The inset in (v) is the Fourier filtered image. (E). DB5, BDB4, and
B2DB3 adopt cone-shape and form BCC, σ and A15 phases, respectively. The inset in (v) is the Fourier filtered image.
This article is protected by copyright. All rights reserved.

10.1002/anie.201709354
Angewandte Chemie International Edition
COMMUNICATION
By further increasing the number of BPOSS cages to five, the long
BPOSS tail length in DB5 (n = 5, x = 0) would impose higher entropy
penalty if it remains in an extended chain conformation. It is found to
form a BCC structures (space group of Im3m) with a = 9.86 nm as shown
in Figure 3E(i) and (iv). While for BDB4 (n = 5, x =1) with asymmetric
folded conformation, the resulting SAXS pattern shows a set of peaks
that can be assigned as a  lattice (space group of P42/mnm) with
tetragonal unit cell parameter a = b = 25.4 nm, c = 13.4 nm as shown in
Figure 3E(ii) and (v). In σ phase, there are two spherical building blocks
with different sizes in equal number ratio, which are packed in a way
combining the Frank Lattice (CN: 12) and two types of Kasper polyhedra
(CN: 14 and 15).[9a, 14b] For B2DB3 (n = 5, x = 2) with close to symmetric
conformation and shortened BPOSS chain length (only 3), it possesses
an A15 lattice with a = 12.9 nm (Figure 3E). Detailed supramolecular
lattice parameters for all these self-assembled structures are listed in
Table 1.
folded conformation. Namely, the sequence variation first transcripts
into the disparity in macromolecular topology, which, in turn, translates
into the distinct molecular packing, leading to different ordered
supramolecular lattices. The incommensurate cross-section areas
between hydrophilic and hydrophobic components lead to curved
interfaces to stabilize the supramolecular lattices. In addition, the
deformability and squeezability of the spherical building blocks are also
mainly attributed to the rearrangement and relocation of the BPOSS
cages after the folded conformation and the confined packing of each
giant molecule in the assembly. Note that no matter how these BPOSS
cages pack in the thick shell of the spherical aggregates, their density
must remain constant (measured to be ~1.2 g/cm3). In comparison to
previous cases with F-K phases formed by block copolymers, our results
highlight the ability to tune phase structures with precise composition
and sequence.
In summary, we have specifically designed this library of chain-like
giant molecules with precisely defined sequences and compositions.
This system contains a pair of interactions: collective hydrogen bonding
and nanophase separation, namely, the hydrogen bonding and
hydrophilic/hydrophobic interactions. Starting from DPOSS
nanoparticle located at one end of the chain and increasing the number
of hydrophobic BPOSS, these chain-like giant molecules create lattices
from LAM, DG, to HEX, F-K A15 and BCC structures. By moving the
DPOSS nanoparticle toward the center of the chain, a series of
sequence isomers with identical composition was prepared. The
distinct locations of DPOSS mandate the folded conformation of giant
molecules into different conformations, which further results in
different supramolecular lattices including F-K A15,  as well as DQC
structures. As designed, the molecules with symmetric/asymmetric
folded conformation significantly affect the ordered lattice structure
formations within this window of unconventional phases. This work has
demonstrated the importance of primary structure, especially
molecular sequence, in mandating molecular topologies to affect their
self-assembly behaviors in these linear-like POSS-based giant molecules.
We envision that the building blocks are not limited as POSS
nanoparticles and could also include other functional motifs (e.g.
optical, electric, magnetic). Tremendous interesting materials could be
constructed by incorporating more complicated precise sequence with
multiple cooperative/competing interactions or functionalities.
Inspired by this work and general rule in giant molecules, to
systematically develop macromolecules with precision at molecular
weight scale as well as at the sequence scale, a new field of synthetic
polymeric materials would be opening.
Table 1. Supramolecular structure analysis of giant molecules.
Molecules
DB
Phase
LAM
DG
a (nm)[a]
6.81
r (nm)[b]
-
μ[c]
-
α or θ d
-
DB2
6.34
-
-
-
BDB
HEX
HEX
HEX
A15
DQC
A15
BCC

6.30
3.64
3.92
3.80
4.59
-
12
12
10
47
-
30o
30o
36o
33o
-
DB3
6.79
BDB2
DB4
6.58
14.8
BDB3
B2DB2
DB5
-
13.5
4.19
4.86
4.09
4.00
36
45
28
26
38o
34o
43.6o
45.2o
9.87
BDB4
B2DB3
25.42×13.4
12.9
A15
[a] Dimensions of the phase: lamellar periodicities, inter-column
distances of HEX lattice, lattice dimensions of A15, BCC and

lattices. [b] dimensions of the motif: radiuses plates in HEX, radiuses
of spheres in A15, BCC and  lattices. [c] number of molecules per
spherical building block. [d] fan-angle (α) or cone angle (θ).
How to understand these experimental observations and what are
the general implications? If we exam the first left column in Figure 1, it
is evident that this series of samples only represent the compositional
variation without alternating the sequences. With increasing the
volume fraction of the BPOSS cages from ~1/2 to 5/6, the
supramolecular structure evolves from LAM to DG to HEX to A15 and
finally, to BCC phases. This phase sequence with the volume fraction
has been reported experimentally,[9d] and predicted theoretically.[18] It
is very interesting that phase structures also change with identical
volume fraction but distinct sequences. For example, in the first line of
DB5 series in Figure 1, with moving the DPOSS cage from x = 0 to x = 3,
the phase structure changes from BCC to  and to A15 phases (also see
the second row of DB4 series). The rationale for the phase structure
changes in this series of chain-like giant molecules is probably due to
the effect of overall macromolecular topologies dominated by the
Experimental Section
The detailed synthetic routes, characterization methods, samples preparation
and other data are described in the Supporting Information.
Acknowledgements
This work was supported by NSF (DMR-1408872 to S.Z.D.C) and NSFC
(51603133 to Y. L, 21674003, 91427304 to W.-B. Z.).
Keywords: sequence • polymer • supramolecular structure • POSS •
Frank-Kasper phase
This article is protected by copyright. All rights reserved.

10.1002/anie.201709354
Angewandte Chemie International Edition
COMMUNICATION
[7]
[8]
S. Alexandris, A. Franczyk, G. Papamokos, B. Marciniec, K. Matyjaszewski,
K. Koynov, M. Mezger, G. Floudas, Macromolecules 2015, 48, 3376-3385.
M. J. Boerakker, J. M. Hannink, P. H. H. Bomans, P. M. Frederik, R. J. M.
Nolte, E. M. Meijer, N. A. J. M. Sommerdijk, Angew. Chem. Int. Ed. 2002,
41, 4239-4241.
a) G. Ungar, Y. Liu, X. Zeng, V. Percec, W.-D. Cho, Science 2003, 299,
1208-1211; b) K. Kim, M. W. Schulze, A. Arora, R. M. Lewis, M. A.
Hillmyer, K. D. Dorfman, F. S. Bates, Science 2017, 356, 520-523; c) M.
Peterca, M. R. Imam, S. D. Hudson, B. E. Partridge, D. Sahoo, P. A.
Heiney, M. L. Klein, V. Percec, ACS Nano 2016, 10, 10480-10488; d) K.
Yue, M. Huang, R. L. Marson, J. He, J. Huang, Z. Zhou, J. Wang, C. Liu, X.
Yan, K. Wu, Z. Guo, H. Liu, W. Zhang, P. Ni, C. Wesdemiotis, W.-B. Zhang,
S. C. Glotzer, S. Z. D. Cheng, Proc. Natl. Acad. Sci. U.S.A. 2016, 113,
14195-14200.
a) M. Huang, C.-H. Hsu, J. Wang, S. Mei, X. Dong, Y. Li, M. Li, H. Liu, W.
Zhang, T. Aida, W.-B. Zhang, K. Yue, S. Z. D. Cheng, Science 2015, 348,
424-428; b) X. Feng, R. Zhang, Y. Li, Y.-l. Hong, D. Guo, K. Lang, K.-Y. Wu,
M. Huang, J. Mao, C. Wesdemiotis, Y. Nishiyama, W. Zhang, W. Zhang, T.
Miyoshi, T. Li, S. Z. D. Cheng, ACS Cent. Sci. 2017, 3, 860-867; c) H. Liu, J.
Luo, W. Shan, D. Guo, J. Wang, C.-H. Hsu, M. Huang, W. Zhang, B. Lotz,
W.-B. Zhang, T. Liu, K. Yue, S. Z. D. Cheng, ACS Nano 2016, 10, 6585-
6596; d) X.-M. Wang, Y. Shao, J. Xu, X. Jin, R.-H. Shen, P.-F. Jin, D.-W.
Shen, J. Wang, W. Li, J. He, P. Ni, W.-B. Zhang, Macromolecules 2017, 50,
3943-3953.
J. M. Widin, A. K. Schmitt, A. L. Schmitt, K. Im, M. K. Mahanthappa, J. Am.
Chem. Soc. 2012, 134, 3834-3844.
S. Maheshwari, M. Tsapatsis, F. S. Bates, Macromolecules 2007, 40,
6638-6646.
a) F. C. Frank, J. S. Kasper, Acta Crystallogr. 1958, 11, 184-190; b) F. C.
Frank, J. S. Kasper, Acta Crystallogr. 1959, 12, 483-499.
a) X. Zeng, G. Ungar, Y. Liu, V. Percec, A. E. Dulcey, J. K. Hobbs, Nature
2004, 428, 157-160; b) S. Lee, M. J. Bluemle, F. S. Bates, Science 2010,
330, 349-353.
a) J. M. Sullivan, in Foams and emulsions, Springer, 1999, pp. 379-402; b)
Y. P. Yarmolyuk, P. Kripyakevich, Sov. Phys., Crystallogr. 1974, 19, 334-
337.
[1]
[2]
[3]
a) J. Sun, A. A. Teran, X. Liao, N. P. Balsara, R. N. Zuckermann, J. Am.
Chem. Soc. 2013, 135, 14119-14124; b) C. Leng, H. G. Buss, R. A.
Segalman, Z. Chen, Langmuir 2015, 31, 9306-9311; c) Y. Suzuki, G.
Cardone, D. Restrepo, P. D. Zavattieri, T. S. Baker, F. A. Tezcan, Nature
2016, 533, 369-373; d) R. V. Thaner, Y. Kim, T. I. N. G. Li, R. J. Macfarlane,
S. T. Nguyen, M. Olvera de la Cruz, C. A. Mirkin, Nano Lett. 2015, 15,
5545-5551; e) C.-L. Chen, R. N. Zuckermann, J. J. DeYoreo, ACS Nano
2016, 10, 5314-5320; f) P. A. Korevaar, C. J. Newcomb, E. W. Meijer, S. I.
Stupp, J. Am. Chem. Soc. 2014, 136, 8540-8543.
a) J.-F. Lutz, M. Ouchi, D. R. Liu, M. Sawamoto, Science 2013, 341,
1238149; b) N. Badi, J.-F. Lutz, Chem. Soc. Rev. 2009, 38, 3383-3390; c) R.
K. Roy, A. Meszynska, C. Laure, L. Charles, C. Verchin, J.-F. Lutz, Nat.
Commun. 2015, 6, 7237; d) S. Martens, J. Van den Begin, A. Madder, F. E.
Du Prez, P. Espeel, J. Am. Chem. Soc. 2016, 138, 14182-14185; e) N. G.
Engelis, A. Anastasaki, G. Nurumbetov, N. P. Truong, V. Nikolaou, A.
Shegiwal, M. R. Whittaker, T. P. Davis, D. M. Haddleton, Nat. Chem.
2017, 9, 171-178; f) D. M. Rosenbaum, D. R. Liu, J. Am. Chem. Soc. 2003,
125, 13924-13925.
a) A. Al Ouahabi, L. Charles, J.-F. Lutz, J. Am. Chem. Soc. 2015, 137, 5629-
5635; b) J. C. Barnes, D. J. C. Ehrlich, A. X. Gao, F. A. Leibfarth, Y. Jiang, E.
Zhou, T. F. Jamison, J. A. Johnson, Nat. Chem. 2015, 7, 810-815; c) Y.
Hibi, M. Ouchi, M. Sawamoto, Nat. Commun. 2016, 7, 11064; d) W. R.
Gutekunst, C. J. Hawker, J. Am. Chem. Soc. 2015, 137, 8038-8041; e) S. C.
Solleder, M. A. R. Meier, Angew. Chem. Int. Ed. 2014, 53, 711-714; f) B.
Lewandowski, G. De Bo, J. W. Ward, M. Papmeyer, S. Kuschel, M. J.
Aldegunde, P. M. E. Gramlich, D. Heckmann, S. M. Goldup, D. M.
D’Souza, A. E. Fernandes, D. A. Leigh, Science 2013, 339, 189-193; g) F. A.
Leibfarth, J. A. Johnson, T. F. Jamison, Proc. Natl. Acad. Sci. U.S.A. 2015,
112, 10617-10622.
a) Ufuk S. Gunay, Benoît E. Petit, D. Karamessini, A. Al Ouahabi, J.-A.
Amalian, C. Chendo, M. Bouquey, D. Gigmes, L. Charles, J.-F. Lutz, Chem
2016, 1, 114-126; b) W. Zhang, M. Huang, H. Su, S. Zhang, K. Yue, X.-H.
Dong, X. Li, H. Liu, S. Zhang, C. Wesdemiotis, B. Lotz, W.-B. Zhang, Y. Li, S.
Z. D. Cheng, ACS Cent. Sci. 2016, 2, 48-54; c) M. Porel, D. N. Thornlow, N.
N. Phan, C. A. Alabi, Nat. Chem. 2016, 8, 590-596.
[9]
[10]
[11]
[12]
[13]
[14]
[4]
[15]
[16]
[17]
[18]
S. Lee, C. Leighton, F. S. Bates, Proc. Natl. Acad. Sci. U.S.A. 2014, 111,
17723-17731.
G. M. Grason, B. A. DiDonna, R. D. Kamien, Phys. Rev. Lett. 2003, 91,
058304.
N. Xie, W. Li, F. Qiu, A.-C. Shi, ACS Macro Lett. 2014, 3, 906-910.
[5]
[6]
H.-C. Kim, S.-M. Park, W. D. Hinsberg, Chem. Rev. 2009, 110, 146-177.
a) J.-F. Lutz, J.-M. Lehn, E. W. Meijer, K. Matyjaszewski, Nat. Rev. Mater.
2016, 1, 16024; b) W. Zhang, Y. Chu, G. Mu, S. A. Eghtesadi, Y. Liu, Z.
Zhou, X. Lu, M. A. Kashfipour, R. S. Lillard, K. Yue, T. Liu, S. Z. D. Cheng,
Macromolecules 2017, 50, 5042-5050; c) Y. Chu, W. Zhang, X. Lu, G. Mu,
B. Zhang, Y. Li, S. Z. D. Cheng, T. Liu, Chem. Commun. 2016, 52, 8687-
8690.
This article is protected by copyright. All rights reserved.

10.1002/anie.201709354
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Molecular nanoparticles can
be precisely connected into
chain-like macromolecules as
sequence controlled polymers.
Wei Zhang, Xinlin Lu, Jialin
Mao, Chih-Hao Hsu, Gaoyan
Mu, Mingjun Huang, Qingyun
Guo, Hao Liu, Chrys
Wesdemiotis, Tao Li, Wen-Bin
Zhang, Yiwen Li, Stephen Z.D.
Cheng
The sequence, in addition to
the composition of the
synthetic polymers can be
specifically designed to
mandate their supramolecular
phase structures.
Page No. – Page No.
Sequence Mandated,
Distinct Assembly of Giant
Molecules
This article is protected by copyright. All rights reserved.