Stereodivergent Anion Binding Catalysis with Molecular Motors

Dorel, Ruth; Feringa, Ben L.

doi:10.1002/ange.201913054

Cited by 20 publications

(13 citation statements)

References 70 publications

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“…[78][79] The ability to conformationally respond to external stimuli may offer yet another level of sophistication in catalysts design. 80,81 Investigation of metal ion binding properties and potential effects on self-assembly is currently ongoing in our laboratories.…”

Section: Discussionmentioning

confidence: 99%

Increasing the Functional Group Diversity in Helical β-Peptoids: Achievement of Solvent- and pH-Dependent Folding

Wellhöfer¹,

Beck²,

Frydenvang³

et al. 2020

Preprint

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We report the synthesis of a series of bis-functionalized <i>b</i>-peptoid oligomers of the hexamer length. This was achieved by synthesizing and incorporating protected amino- or azido-functionalized chiral building blocks into precursor oligomers by a trimer segment coupling strategy. The resulting hexamers were readily elaborated to provide target compounds displaying amino groups, carboxy groups, hydroxy groups, or triazolo-pyridines, which should enable metal ion binding. Analysis of the novel hexamers by CD spectroscopy and HSQC NMR spectroscopy revealed robust helical folding propensity in acetonitrile. CD analysis showed solvent-dependent degree of helical content in the structural ensembles when adding different ratios of protic solvents including aqueous buffer. These studies were enabled by the substantial increase in solubility compared to previously analyzed <i>b</i>-peptoid oligomers. This also allowed for investigation of the effect of pH on folding propensity of the amino- and carboxy-functionalized oligomers, respectively. Interestingly, we could demonstrate a reversible effect of sequentially adding acid and base, resulting in a switching between compositions of folded ensembles with varying helical content. We envision that the present discoveries can form the basis for the development of functional peptidomimetic materials responsive to external stimuli.

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Section: Discussionmentioning

confidence: 99%

Increasing the Functional Group Diversity in Helical β-Peptoids: Achievement of Solvent- and pH-Dependent Folding

Wellhöfer¹,

Beck²,

Frydenvang³

et al. 2020

Preprint

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“…The reverse process was driven by irradiation at 365 nm. Some other recent examples have proved the general feasibility of this (supra-)molecular approach for the construction of photoresponsive guest release systems, 49 polymers, 50 vesicles, 35 catalysts, 28,51 and biomacromolecules. 29,52,53 However, the macroscopic functions of supramolecular materials constructed through this strategy are mostly limited to light-switchable disassembly/reassembly 34,35,50,54,55 and modulation of molecular recognition.…”

Section: Molecular Design Guidelinesmentioning

confidence: 98%

“…29,52,53 However, the macroscopic functions of supramolecular materials constructed through this strategy are mostly limited to light-switchable disassembly/reassembly 34,35,50,54,55 and modulation of molecular recognition. 28,[51][52][53] The visible response (output) to the light stimulus (input) is often lacking in terms of both macroscopic signal-most of the primary assemblies are invisible unless detected by electron microscopy-and practicability, as solvents are needed to stabilize the microscopic colloids and retain the operational abilities of the molecular motors. On the basis of the several reported systems, 34,35,50,54 it can be concluded that a simple design based on the primary assemblies is not enough to enable effective signal delivery from the molecular level to the macroscopic dimensions.…”

Section: Molecular Design Guidelinesmentioning

confidence: 99%

Bottom-Up: Can Supramolecular Tools Deliver Responsiveness from Molecular Motors to Macroscopic Materials?

Zhang

Tian

et al. 2020

Matter

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Motion is omnipresent, as is obvious from the artificial machines in the macro-world and the biomolecular motors in living systems, controlling dynamic behavior along many length scales. With the emergence of molecular machines in the past decades, a major step has been made toward responsive materials and dynamic molecular systems. Photochemical rotary molecular motors hold a unique position, as embedding nanoscale motors in macroscopic materials enables light-driven responsive and adaptive properties. Although the synthesis and engineering of discrete molecular motors in the solution phase are well understood, the design and construction of motorized smart materials that operate at the supramolecular and macroscopic levels provide several fundamental challenges. This Review highlights emerging methodologies that take advantage of the supramolecular toolbox for the bottom-up assembly of responsive materials. Illustrative examples include muscle-like actuators, motor-based metal-organic frameworks, and motorized liquid crystal films and droplets. Emphasis is on how the lightresponsive behavior and motion of rotary molecular motors can be communicated, delivered, and amplified to result in a specific dynamic output ranging from the nanoscale and molecular level all the way to the macroscopic scale and materials level. Furthermore, general guidelines for the supramolecular amplification of molecular motion and challenges and perspectives for the development of future motorized smart materials are presented.

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“…It can perform photochemical and thermal isomerizations between three isomers with distinct anion binding affinities. , This kind of receptor can serve as a molecular motor with unidirectional rotation governed by anionic chirality . It can also serve as an anion binding catalyst . In addition, they reported a photoswitchable anion receptor with two isomers based on stiff-stilbene and found strong binding affinities of acetate and phosphate to the Z isomer …”

Section: Introductionmentioning

confidence: 99%

Azopyrazole-Based Photoswitchable Anion Receptor for Dihydrogen Phosphate Transport

Yang

et al. 2020

J. Phys. Chem. A

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Small-molecule anion carriers are potential reagents used in the treatment of diseases caused by dysregulated anion transport. Photoswitchable anion receptors, which can be reversibly switched between isomers by light and thereby cause reversible changes in anion binding affinity, have been receiving enormous interest. Here, based on the well-known photoswitch 1-N-methyl-3-phenylazopyrazole (3pzH), we designed a novel tetramethylamide-3pzH (3pzH_TA) photoswitchable receptor that achieves highly efficient and durable anion transportation. It enables high photoisomerization ratios of E → Z (>98%) and Z → E (97%) with a thermal half-life two times longer than that of 3pzH. We further demonstrated the high sensitivity of 3pzH_TA toward H 2 PO 4 − anion and revealed the key role of hydrogen bonds between H 2 PO 4 − and Z isomer in the strength of anion binding. Our findings open up a new strategy for the rational design and understanding of new types of photoswitchable anion receptors.

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Stereodivergent Anion Binding Catalysis with Molecular Motors

Cited by 20 publications

References 70 publications

Increasing the Functional Group Diversity in Helical β-Peptoids: Achievement of Solvent- and pH-Dependent Folding

Increasing the Functional Group Diversity in Helical β-Peptoids: Achievement of Solvent- and pH-Dependent Folding

Bottom-Up: Can Supramolecular Tools Deliver Responsiveness from Molecular Motors to Macroscopic Materials?

Azopyrazole-Based Photoswitchable Anion Receptor for Dihydrogen Phosphate Transport

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