Self-assembly of ultralong polyion nanoladders facilitated by ionic recognition and molecular stiffness

Article abstract of DOI:10.1021/ja410443n

It is hard to obtain spatially ordered nanostructures via the polyion complexation process due to the inherent flexibility of polymers and isotropicity of ionic interactions. Here we report the formation of polyion assemblies with well-defined, periodical

Full text of DOI:10.1021/ja410443n

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Article
Self-assembly of Ultralong Polyion Nano-Ladders
Facilitated by Ionic Recognition and Molecular Stiffness
Limin Xu, Lingxiang Jiang, Markus Drechsler, Yu Sun, Zhirong Liu, Jianbin
Huang, Ben Zhong Tang, Zhibo Li, Martien A. Cohen Stuart, and Yun Yan
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja410443n • Publication Date (Web): 13 Jan 2014
Downloaded from http://pubs.acs.org on January 18, 2014
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Self-assembly of Ultralong Polyion Nano-Ladders Facilitated by Ionic
Recognition and Molecular Stiffness
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Limin Xu,1 Lingxiang Jiang,1 Markus Drechsler,2 Yu Sun,1 Zhirong Liu,1 Jianbin Huang,*,1 Ben
Zhong Tang,*,3 Zhibo Li,4 Martien A. Cohen Stuart,5 and Yun Yan*,1
1Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural
Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking
University, Beijing 100871, China
2Bayreuth Institute of Macromolecular Research (BIMF) ꢀ TEM, University of Bayreuth, Dꢀ95440,
Bayreuth, Germany
3Department of Chemistry, The Hong Kong University of Science & Technology, Clear Water Bay,
Kowloon, Hong Kong, China
4 State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy
of Sciences, Beijing, 100190, China
5Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703
HB Wageningen, The Netherlands
*Corresponding Authors:
yunyan@pku.edu.cn (Y.Y.), jbhuang@pku.edu.cn (J.B.H)), tangbenz@ust.hk (B.Z.T.).
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Abstract: It is hard to obtain spatially ordered nanostructures via the polyion complexation process
due to the inherent flexibility of polymers and isotropicity of ionic interactions. Here we report the
formation of polyion assemblies with wellꢀdefined, periodically regular internal structure by imparting
the proper stiffness to the molecular tile. A stiff bisligand TPEꢀC4ꢀL2 was designed which is able to
form a negatively charged supramolecular polyelectrolyte with transition metal ions. This
supramolecular polyelectrolyte slowly selfꢀassembled into polydispersed flat sheets with cocoonꢀlike
patterns. Upon the addition of an oppositely charged ordinary polyelectrolyte, the polydispersed
cocoons immediately transformed into ultralong, uniform nanoꢀladders as a result of matched ionic
density recognition. The supramolecular polyelectrolytes assembled sideꢀbyꢀside and the negative
charges aligned in an array. This structure forced the positively charged polymers to lie along the
negative charges so that the perpendicular arrangement of the oppositely charged chains was
achieved. Such precise charge recognition will provide insight into the design of advanced materials
with hierarchical selfꢀassembled structures.
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Key words: Selfꢀassembly; Polyion Complex; Supramolecular Assembly
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Introduction
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Ionic interaction1ꢀ5 has emerged as an important driving force for the fabrication of ionic
selfꢀassembly.6ꢀ10 Well known examples are the polyion assemblies formed in water by pairs of
oppositely charged polyelectrolytes,11ꢀ13 which can be forced into films14ꢀ16 and capsules17ꢀ21 with
appropriate protocols, or made into micelles2,22ꢀ27 and vesicles28ꢀ30 by endꢀattaching uncharged water
soluble blocks to (at least one of) the polyelectrolytes. This is also the case when one of the
polyelectrolyte was replaced by reversible or ‘soft’ coordination polymers, namely, supramolecular
chains in which organic bisligands and transition metal ions alternate in a regular fashion.31ꢀ34 By
proper choice of the bisligands, one can even obtain supramolecular polyelectrolytes,35ꢀ39 which in turn
can form polyion assemblies just like ordinary polyelectrolytes.40ꢀ43 Usually, polyion assemblies
formed with covalent polylectrolytes26,44 or coordination polymers45ꢀ51 have internally random
structures, since the polymers are flexible and the ionic interactions are isotropic between the flexible
chains.
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On the other hand, endeavors in creating hierarchical selfꢀassembled structures from basic
molecular tiles are increasingly directed toward advanced materials. Since the pioneering work by
Lehn 52and de Gennes,53 supramolecular selfꢀassembly has been verified as a marvelous approach to
exotic selfꢀassemblies. For instances, complex shapes were made by controlled assembly of
singleꢀstrand DNA,54 inorganic vesicles were found upon dispersing polyoxametalate (POM) solids
in acetone,55,56 and multicompartment micelles were created using properly designed block
copolymers.57ꢀ60 However, so far manipulation of structural hierarchy has not been achieved in
polyion assemblies, because the ionic interactions usually are not sufficient to produce ordered
structures.
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In this work we show that precise alignment of polyelectrolyte chains inside polyion assemblies
can be achieved by imparting proper stiffness to the molecular tiles. The stiff bisligand TPEꢀC4ꢀL2
(Scheme 1a) and transition metal ions (Ni2+, Zn2+, Ca2+, etc.) can form a negatively charged
supramolecular polyelectrolyte which alone can slowly selfꢀassemble into polydispersed flat
cocoonꢀlike sheets. Upon the addition of a properly designed positively charged block
polyelectrolyte PMVP41ꢀbꢀPEO205(Scheme 1b ), the polydispersed cocoons immediately transformed
into uniform ultraꢀlong nanoꢀladders as a result of matched charge density. The negatively charged
coordination supramolecular polymer chains aligned parallel to each other and were perpendicularly
interconnected by the positively charged block of PMVP41ꢀbꢀPEO205 to form an ordered gridꢀlike
structure (Scheme 1c). To the best of our knowledge, this is the first time to obtain the spatially
ordered arrangement of the polyion chains upon the charge attraction.
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(a)
(b)
O
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OK
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O
N
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(c)
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Scheme 1.Structure of (a) TPEꢀC4ꢀL2, (b) PMVP41ꢀbꢀPEO205 and (c) schematic representation of the
structures formed by TPEꢀC4ꢀL2 and metal ions without and with polymer; the PE0205 block is
illustrated as the yellow shell that covers the ultralong nanoꢀladders.
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The synthesis of the bisligand TPEꢀC4ꢀL2 is given in supporting information. The TPE group is
wellꢀknown for its aggregationꢀinduced emission,61 which acts as a reporter group in this work.
Without the presence of metal ions, the solution of TPEꢀC4ꢀL2 exhibited negligible fluorescence,
indicating no aggregation of TPEꢀC4ꢀL2. Upon addition of transition metal ions at a stoichiometric
ratio, the dilute solution didn’t exhibit noticeable fluorescence firstly, but the fluorescence increased
slightly over time (Figure 1a) due to the slow aggregation of TPEꢀC4ꢀL2. Both TEM (Figure 1b) and
cryoꢀTEM (Figure S4) images revealed the formation of flat, cocoonꢀlike sheets. The presence of
regularly separated dark and light lines indicated that metal ions have aligned in an array. This
indicates the formation of coordination polymer chains with alternatively arranged metal ions and
TEPꢀC4ꢀL2. In Figure 2a we show the molecular modeling of one repeating unit of this arrangement
with Chem Hyper 8.0. The details of such molecular alignment will be discussed further in the
following text.
200
TPE-C4-L2
TPE-C4-L2/Ni
(a)
TPE-C4-L2/Ni, 50 min
TPE-C4-L2/Ni, 4 h
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TPE-C4-L2/Ni, 12 h
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Wavelength (nm)
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Figure 1. (a) Fluorescence intensity and (b) TEM image of TPEꢀC4ꢀL2/Ni=1/1 solution. ([Ni2+] =
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0.5mM)
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Wavelength(nm)
Figure 2. (a) Hyper Chem 8.0 simulation of the πꢀπ stacking between the TPE groups in the
sideꢀbyꢀside alignment of TPEꢀC4ꢀL2/metal system. The distance between two neighboring
coordinating centers (or the butyl chains) is 9.37 Å. The extending length of the TPEꢀC4ꢀL2 is 35.56
Å. (b) Fluorescence spectra of different solutions. The inset images are the photos of the solution of (1)
TPEꢀC4ꢀL2/Ni, (2) TPEꢀC4ꢀL2/PMVP41ꢀbꢀPEO205, and (3) TPEꢀC4ꢀL2 /Ni /PMVP41ꢀbꢀPEO205
irradiated at 365 nm.
Surprisingly, as soon as a neutralꢀcationic diblock copolymer polyꢀNꢀmethylꢀ2ꢀvinyl pyridinium
iodideꢀbꢀpoly (ethylene oxide), PMVP41ꢀbꢀPEO205 (Scheme 1b), was added at charge stoichiometry,
the significant enhancement of the fluorescence was detected (Figure 2b), indicating the strong
aggregation of the TPE moieties. The solution also appeared bluish and the light scattering intensity
increased 30ꢀfold (Table S1). Both were likely due to the presence of large aggregates in the solution.
In Figure 3 we showed the cryoꢀTEM micrographs of the polyion complexes formed by the
coordination polymer and PMVP41ꢀbꢀPEO205 mixed at charge stoichiometry. Flexible, ribbonꢀlike
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structures with length over 1 ꢁm were shown in Figure 3a. Moreover, strikingly fine ‘ladder’ꢀlike
periodic structure of thin dark stripes normal to the ribbon long axis was clearly shown in the
zoomedꢀin pictures (Figures 3b and c). It is amazing that the wellꢀordered periodic structures are
uniform in the whole system, and the length of the ladders persists up to a few micrometers. The
average width of the ladders is around 10.7 nm which features these structures ‘nanoꢀladders’. The
nanoꢀladders are thin and sometimes twisted, as shown in Figure 3c. At places where two
nanoꢀladders overlap (indicated by the arrow), the overlay of the dark lines can be easily identified
(Figure 3c), suggesting the thickness of the nanoꢀladders is within the focusing depth of the
cryoꢀTEM.
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The dark/light periodicity measured from the Fourier analysis was determined to be about 3.6 nm
(inset in Figure 3b), which agrees well with the fully extended length of the TPEꢀC4ꢀL2 obtained
from molecular simulations by Chem Hyper 8 (Figure 2a). This indicates that the ‘nanoꢀladders’
(dark lines) are the sideꢀbyꢀside aligned coordination polymers as illustrated in Scheme 1c.
Compared with the cocoonꢀlike structures in the solutions without the presence of PMVP41ꢀbꢀPEO205,
it is clear that neutralization of the negative charges at the coordination center promoted the striking
parallel alignment of the coordination polymer chains to such a large length scale.
Charge density of the coordination polymers and of PMVP41ꢀbꢀPEO205 was analyzed to
understand the molecular arrangement in the nanoꢀladders. The negative charge density
perpendicular to the long axis of the ribbons is two negative elementary charges per 9.37Å (Figure
2a). The charge density of PMVP41 block is one elementary positive charge per 2.3Å, or four positive
charges per 9.2 Å (Supporting information). The complete charge neutralization could be achieved if
two arrays of coordination centers (metal ions) interact with one PMVP41 block. Therefore the
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PMVP41 blocks would be sandwiched between two sheets of coordination polymers (Scheme 1c). The
fully extended length of the PMVP41 block is around 9.5 nm which coincides with the width of the
long nanoꢀladders (10.7 nm), possibly indicating the fully extended chain configuration of the
PMVP41 block inside the polyion complex and supporting the structural model proposed in Scheme 1c.
The model in Scheme 1c clearly demonstrates that the molecular stiffness at atomic level in the
ligand has been successfully amplified to macroscopic level.
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Figure 3. CryoꢀTEM images of the aggregates formed in the TPEꢀC4ꢀL2/Ni/PMVP41ꢀbꢀPEO205
mixed system. Panels (a)–(c) are the images obtained at different magnifications. The insets in (b)
are the illustration of the nanoꢀladders (left) and the FFT analysis (right) of them, respectively.
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These nanoꢀladders are stabilized against further aggregation by the PEO205 blocks. Although the
presence of PEO205 blocks is not directly visible in cryoꢀTEM because they are well solvated, their
presence can be indicated by the lack of bundling of the ladders. The PEO205 blocks would form a
very thin layer surrounding the ladders in solutions. This can provide steric repulsions to prevent the
ladders from further bundling. The presence of PEO blocks on the surface of the nanoꢀladders was
also verified by the AFM measurements. As showed in Figure 4, the stripes cannot be observed in
the AFM images, and the height measurements suggest that the presence of mountains up to 10 nm
on each ribbon. These mountains should be the dried PEO coils which act as a thick corona shell
surrounding the ladders. For the same reason, the stripes cannot be observed either with normal TEM
(Figure S5), just because the ladders were deeply buried under the dried thick PEO coils.
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Figure 4. AFM image of the aggregates formed in the TPEꢀC4ꢀL2/Ni/PMVP41ꢀbꢀPEO205 mixture
system. Panels (a) and (b) are the images obtained at different magnifications. Panel (c) is the 3D
image of panel (b). (d) Height distribution of TPEꢀC4ꢀL2/Ni/PMVP41ꢀbꢀPEO205.
Ionic recognition and charge balancing are very crucial to the formation of ultralong nanoꢀladders.
When the coordination polymer was in excess, the negative charges couldn’t be completely balanced
by the positive charges on PMVP41ꢀbꢀPEO205. Subsequently not all cocoons were transformed into
ultralong nanoꢀladders (Figure 5a). This implies that the complete transformation from cocoons into
uniform nanoꢀladders requires complete charge neutralization. On the other hand, as
PMVP41ꢀbꢀPEO205 is in excess, the nanoꢀladders were significantly shortened (Figure 5b). In
addition, if the linear PMVP41ꢀbꢀPEO205 was replaced by a branched polyelectrolyte polyetheneimine
(PEI), only spheres were obtained (Figure 5c and Figure S6) because the branched structure of PEI
doesn’t allow charge density matching between the positive and negative charges.
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O
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N
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OK
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O
KO
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O
OK
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n
Figure 5. (aꢀb): CryoꢀTEM image of the aggregates formed in the TPEꢀC4ꢀL2/Ni/PMVP41ꢀbꢀPEO205
mixture. (a) [ꢀ] = 2[+]; (b) [+] = 2[ꢀ] ([+] = concentration of positive charges carried by PMVP41
block and [ꢀ] = concentration of negative charges carried by TPEꢀC4ꢀL2/Ni); (c) TEM image of
TPEꢀC4ꢀL2/Zn/PEI mixture; (d) CryoꢀTEM image of TPEꢀ(EO)4ꢀL2/ Ni/ PMVP41ꢀbꢀPEO205. The
insets in (cꢀd) are the structure demonstration of PEI and TPEꢀ(EO)4ꢀL2, respectively.
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Finally, the molecular stiffness of the bisligand is also critical to the formation of ultralong
nanoꢀladders. When the butyl group in TPEꢀC4ꢀL2 was replaced with the foldable four ethylene
oxide (EO) group, TPEꢀ(EO)4ꢀL2 (inset in Figure 5d), only spherical structures were formed (Figure
5d) even if the TPE group was preserved. Molecular simulations (Supporting Information) suggest
that the πꢀπ stacking between the TPE groups occurred (Figure 2a) in the system. Although πꢀπ
stacking by its own may drive selfꢀassembly formation,62 only the πꢀπ stacking between the TPE
groups is not enough to lead to the formation of the nanoꢀladders. It should also be clarified that the
change of the spacer length and hydrophilicity aroused by replacing the butyl group with the (EO)4
doesn’t influence our conclusion, either. First of all, the main effect of the (EO)4 group is to make the
chain foldable. Alkyl chains of even longer length always take a stretched conformation in molecular
selfꢀassemblies.63 Secondly, the hydrophobic interaction doesn’t contribute to the sideꢀbyꢀside
alignment of the coordination polymers since the interꢀchain distance is as far as 9.37 Å, which is
much larger than the length scale of hydrophobic interactions.64 Therefore, it is the molecular
stiffness that governs the topology of the selfꢀassembled structures.
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The results presented here are universal for most transition metal ions (nickel, zinc, copper,
calcium, gold, cobalt, iron, barium, strontium, etc.; see Figures S7ꢀS11). We infer that the bisligand
demonstrated here can also be replaced by other properly designed stiff ones. This suggests that
controlled organization of stiff polymers into ordered hierarchical polyion assemblies requires the
concerted effects of molecular stiffness and charge recognition, each of which is necessary to obtain
the precise alignment that we observed in these supramolecular structures. Since ionic interaction is
prevalent in nature and artificial systems, the fabrication of hierarchical structures in polyion
assemblies signifies a new protocol to prepare novel controlled structures. In this strategy, the
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molecular stiffness at atomic level can be amplified into supramolecular stiffness of macroscopic
level. In addition, the precise alignment of metal elements in this work may also provide an approach
that leads to controlled printing in nanoscale.
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Acknowledgments: The authors acknowledge the financial support from the National Natural Science Foundation of
China (Grant No. 21173011, 21273013, 51121091), 973 program (2013CB933800), and Research Grants Council of
Hong Kong (HKUST2/CRF/10).
Supporting Information Available: Materials and methods, syntheses and characterizations. This
information is available free of charge via the Internet at http://pubs.acs.org/.
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