Air–Liquid Interfacial Self-Assembly of Conjugated Block Copolymers into Ordered Nanowire Arrays

Cativo, Ma. Helen M.; Kim, David K.; Riggleman, Robert A.; Yager, Kevin G.; Nonnenmann, Stephen S.; Chao, Huikuan; Bonnell, Dawn A.; Black, Charles T.; Kagan, Cherie R.; Park, Soo‐Young

doi:10.1021/nn505871b

Cited by 54 publications

(67 citation statements)

References 56 publications

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“…The resulting nanostructures show colloidal stability due to the presence of the solvent swollen corona and have been exploited for a variety of uses including the delivery of therapeutic cargoes in nanomedicine2, as additives for friction reduction3, fillers for composite reinforcement4 or for the formation of nanoscopic arrays using optical tweezers5. However, although recent advances have described examples of fibre-like micelles with novel photophysical characteristics67, their assembly into complex semiconducting particles, bundles and branched superstructures891011, and their fabrication of coaxial nanowires with quantum dots1213, ordered two-dimensional assemblies at interfaces14 and solar cells15, the evaluation of their potential as functional electroactive materials in devices is virtually unexplored1415; specifically, uniform samples of low length dispersity have not been investigated.…”

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confidence: 99%

Uniform electroactive fibre-like micelle nanowires for organic electronics

et al. 2017

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Micelles formed by the self-assembly of block copolymers in selective solvents have attracted widespread attention and have uses in a wide variety of fields, whereas applications based on their electronic properties are virtually unexplored. Herein we describe studies of solution-processable, low-dispersity, electroactive fibre-like micelles of controlled length from π-conjugated diblock copolymers containing a crystalline regioregular poly(3-hexylthiophene) core and a solubilizing, amorphous regiosymmetric poly(3-hexylthiophene) or polystyrene corona. Tunnelling atomic force microscopy measurements demonstrate that the individual fibres exhibit appreciable conductivity. The fibres were subsequently incorporated as the active layer in field-effect transistors. The resulting charge carrier mobility strongly depends on both the degree of polymerization of the core-forming block and the fibre length, and is independent of corona composition. The use of uniform, colloidally stable electroactive fibre-like micelles based on common π-conjugated block copolymers highlights their significant potential to provide fundamental insight into charge carrier processes in devices, and to enable future electronic applications.

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confidence: 99%

Uniform electroactive fibre-like micelle nanowires for organic electronics

et al. 2017

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“…[6][7][8] Some small synthetic molecules also undergo supramolecular polymerization to yield hydrogels that assemble and disassemble in response to external stimuli, 9,10 and are being developed for applications in controlled drug delivery 11,12 and tissue engineering. [13][14][15] Synthetic supramolecular polymers are also being exploited in nanofabrication, for the development of nanowires [16][17][18][19] or as components of artificial molecular machines. 20 For such applications, what is required are molecules that, like their biological counterparts, polymerize and de-polymerize in response to small environmental changes.…”

Section: Introductionmentioning

confidence: 99%

Modulation of the cooperativity in the assembly of multistranded supramolecular polymers

Campanella

Lopez-Fontal

Milanesi

et al. 2017

Phys. Chem. Chem. Phys.

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It is highly desirable that supramolecular polymers self-assemble following small changes in the environment. The degree of responsiveness depends on the degree of cooperativity at play during the assembly. Undertanding how to modulate and quantify cooperativity is therefore highly desirable for the study and design of responsive polymers. Here we show that the cooperative assembly of a porphyrin-based, double-stranded polymer is triggered by changes in building blocks and in salt concentration. We develop a model that accounts for this responsiveness by assuming the binding of the salt countercations to the double-stranded polymer. Using our assembly model we generate plots that show the increase in concentration of polymer versus the normalized concentration of monomer. These plots are ideally suited to appreciate changes in cooperativity, and show that, for our system, these changes are consistent with the increase in polymer length observed experimentally. Unexpectedly, we find that polymer stability increases when cooperativity decreases. We attribute this behaviour to the fact that increasing salt concentration stabilizes the overall polymer more than the nucleus. In other words, the cooperativity factor , defined as the ratio between the growth constant Kg and the nucleation constant Kn decreases as the overall stability of the polymer increases. Using our model to simulate the data, we generate cooperativity plots to explore changes in cooperativity for multistranded polymers. We find that, for the same pairwise association constants, the cooperativity sharply increases with the number of strands in the polymer. We attribute this dependence to the fact that the larger the number of strands, the larger is the nucleus necessary to trigger polymer growth. We show therefore that the cooperativty factor  does not properly account for the cooperativity behaviour of multistranded polymers, or any supramolecular polymer with a nucleus composed of more than 2 building blocks, and propose the use of the corrected cooperativity factor m. Finally, we show that multistranded polymers display highly cooperative polymerisation with pairwise association constants as low as 10 M -1 between the building blocks, which should simplify the design of responsive supramolecular polymers.

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“…[ 36 ] Additionally, due to the rigid nature of the PBLG blocks, the tendency for the ordered packing of rod blocks could promote the formation of well‐aligned nanostructures during self‐assembly. [ 30,37 ]…”

Section: Methodsmentioning

confidence: 99%

2D Chiral Stripe Nanopatterns Self‐Assembled from Rod‐Coil Block Copolymers on Microstripes

Tang

Cai

et al. 2020

Macromol. Rapid Commun.

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Chiral nanoarchitectures usually possess unique and intriguing properties. However, the construction of 2D chiral nanopatterns through polymer self‐assembly is a challenge. Reported herein is the formation of chiral stripe nanopatterns through surface self‐assembly of polypeptide‐based rod‐coil block copolymers on microstripes. The nanostripes align oblique to the boundary of the microstripes, resulting in the chirality of the nanopatterns. The chirality of the nanopatterns is closely related to the width of the microstripes, i.e., a narrower width results in higher chirality. Besides, the chiral sense of the nanopatterns can be regulated by the chirality of the polypeptide blocks. This work demonstrates the transmission of chirality from polymer to nanoarchitecture on a confined surface, which can guide the preparation of nanopatterns with tuned chiral features.

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Air–Liquid Interfacial Self-Assembly of Conjugated Block Copolymers into Ordered Nanowire Arrays

Cited by 54 publications

References 56 publications

Uniform electroactive fibre-like micelle nanowires for organic electronics

Uniform electroactive fibre-like micelle nanowires for organic electronics

Modulation of the cooperativity in the assembly of multistranded supramolecular polymers

2D Chiral Stripe Nanopatterns Self‐Assembled from Rod‐Coil Block Copolymers on Microstripes

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