Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

doi:10.1038/ncomms7234

Cited by 126 publications

(236 citation statements)

References 51 publications

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“…The short-range aromatic contribution to self-assembly (Δ E stack ) was calculated as the number of stably stacked groups in the assemblies multiplied by the stacking interaction energies of CHE, PHE, NAP and ANT groups 47 respectively (see SI for details), according to the same approach adopted recently to quantify the role of hydrogen bonding in supramolecular polymers. 48 The remaining part of the tail-tail self-assembly energy (Δ E tail ) was assumed to be imputable to hydrophobic effect (Δ E hyd ). This analysis provides qualitative insight on the type of interactions in the self-assembly and on their modulation in response to temperature change.…”

Section: Resultsmentioning

confidence: 99%

Role of Aromatic Interactions in Temperature-Sensitive Amphiphilic Supramolecular Assemblies

et al. 2016

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Aromatic interactions were found to greatly influence the temperature-dependent dynamic behavior within supramolecular assemblies. Using an amphiphilic dendron, we systematically changed the hydrophobic groups introducing increasing levels of aromaticity while keeping the hydrophilic part constant. We show that the supramolecular assemblies become less sensitive to temperature changes when aromatic interactions in the aggregate are increased. Conversely, the absence of aromaticity in the hydrophobic moieties produces temperature-sensitive aggregates. These results show that subtle molecular-level interactions can be utilized to control temperature-sensitive behavior in the nanoscale. These findings open up new design strategies to rationally tune stimuli-responsive supramolecular assemblies on multiple spatiotemporal scales.

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Section: Resultsmentioning

confidence: 99%

Role of Aromatic Interactions in Temperature-Sensitive Amphiphilic Supramolecular Assemblies

et al. 2016

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“…Atomic (1) incorporating (S)-stereocenters in its hydrophilic moiety and its achiral counterpart (2). Notably, the chirality of building blocks has been proven to influence equilibrium dynamics of supramolecular assemblies dramatically (40). Upon irradiation with UV light (λ = 365 nm), the building block undergoes trans-to-cis isomerization (not all possible conformations are displayed on this scheme).…”

Section: Resultsmentioning

confidence: 99%

Molecular photoswitches mediating the strain-driven disassembly of supramolecular tubules

Fredy

Méndez‐Ardoy

Kwangmettatam

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Chemists have created molecular machines and switches with specific mechanical responses that were typically demonstrated in solution, where mechanically relevant motion is dissipated in the Brownian storm. The next challenge consists of designing specific mechanisms through which the action of individual molecules is transmitted to a supramolecular architecture, with a sense of directionality. Cellular microtubules are capable of meeting such a challenge. While their capacity to generate pushing forces by ratcheting growth is well known, conversely these versatile machines can also pull microscopic objects apart through a burst of their rigid tubular structure. One essential feature of this disassembling mechanism is the accumulation of strain in the tubules, which develops when tubulin dimers change shape, triggered by a hydrolysis event. We envision a strategy toward supramolecular machines generating directional pulling forces by harnessing the mechanically purposeful motion of molecular switches in supramolecular tubules. Here, we report on wholly synthetic, water-soluble, and chiral tubules that incorporate photoswitchable building blocks in their supramolecular architecture. Under illumination, these tubules display a nonlinear operation mode, by which light is transformed into units of strain by the shape changes of individual switches, until a threshold is reached and the tubules unleash the strain energy. The operation of this wholly synthetic and stripped-down system compares to the conformational wave by which cellular microtubules disassemble. Additionally, atomistic simulations provide molecular insight into how strain accumulates to induce destabilization. Our findings pave the way toward supramolecular machines that would photogenerate pulling forces, at the nanoscale and beyond.artificial molecular switches | supramolecular polymers | supramolecular machines | light

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“…Initially BTA has attracted a lot of interest due to structure-related strong intermolecular interaction and the resultant formation of supramolecular polymers in solution, the ability to create gels as well as rigid nanofibers. [31][32][33][34] The ferroelectric behavior, however, is a relatively new finding. [9,35] Fitié et al were first to probe BTA homologues with 18, 10, and 6 carbons-long alkyl chain (BTA-C18, BTA-C10, and BTA-C6).…”

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confidence: 99%

Tuning the Ferroelectric Properties of Trialkylbenzene‐1,3,5‐tricarboxamide (BTA)

Urbanavičiūtė

Meng

Cornelissen

et al. 2017

Adv Elect Materials

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This study demonstrates how simple structural modification of a prototypical organic ferroelectric molecule can be used to tune its key ferroelectric properties. In particular, it is found that shortening the alkyl chain length of trialkylbenzene-1,3,5-tricarboxamide (BTA) from C18H37 to C6H13 causes an increase in depolarization activation energy (approximate to 1.1-1.55 eV), coercive field (approximate to 25-40 V mu m(-1)), and remnant polarization (approximate to 20-70 mC m(-2)). As the polarization enhancement far exceeds the geometrically expected factor, these observations are attributed to an increase in the intercolumnar interaction. The combination of the mentioned characteristics results in a record polarization retention time of close to three months at room temperature for capacitor devices of the material having the shortest alkyl chain. The long retention and the remnant polarization that is as high as that of P(VDF:TrFE) distinguish the BTA-C6 material from other small molecular organic ferroelectrics and make it a perspective choice for applications that require cheap, flexible, and lightweight ferroelectrics.

Funding Agencies|NWO Nano program; Vetenskapsradet; Swedish Government Strategic Research Area in Materials Science on Functional Materials at the Linkping University (Faculty Grant SFO Mat LiU) [2009 00971]

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Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

Cited by 126 publications

References 51 publications

Role of Aromatic Interactions in Temperature-Sensitive Amphiphilic Supramolecular Assemblies

Role of Aromatic Interactions in Temperature-Sensitive Amphiphilic Supramolecular Assemblies

Molecular photoswitches mediating the strain-driven disassembly of supramolecular tubules

Tuning the Ferroelectric Properties of Trialkylbenzene‐1,3,5‐tricarboxamide (BTA)

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