Muscle‐Like Supramolecular Polymers with Dual Motion Patterns

Chemistry - A European Journal, Год журнала: 2023, Номер 29(40)

Опубликована: Май 10, 2023

Benefiting from the features like polymeric linear structures, stimuli-responsiveness and dynamic adaptiveness, supramolecular polymers (SPs) are favored as exploiting muscle-like materials, allowing for imitating muscle functions. However, a substantial part of these materials barely owned an unitary motion orientation while it was obviously known that movements involved distinct orientations. Herein, M1 holding structure 44-membered macrocycle with two aldehyde groups designed, meanwhile, M2 comprising secondary ammonium ions, 3,5-di-tert-butylphenyl well alkyl chains fabricated, which could be assembled to generate SPs based on host-guest interactions large ions. underwent vertical compression upon addition N2 H4 owing forming covalent bonds, notably, mechanically interlocked structures were also generated. Afterwards, vertically compressed experienced horizontal shrinkage when tetrabutylammonium chloride contributed due destruction interactions.

Язык: Английский

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Assessment of the quantum valence molecular machine for a rotaxanic complex

Fullerenes Nanotubes and Carbon Nanostructures, Год журнала: 2024, Номер unknown, С. 1 - 15

Опубликована: Окт. 9, 2024

Rotaxanic type molecular machines are very intensively investigated because of their potential for the development nanotechnology. We have applied consecrated HSAB principle ("hard likes hard and soft soft") to a small rotaxanes series pH-switchable determining which resulted interlocked system is more favorable be further consider functionalized as machine also we found quantum structural models in inter-conversion dynamics terms frontier orbitals chemical reactivity. The obtained results strengthen previous studies.

Язык: Английский

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Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie, Год журнала: 2024, Номер 136(23)

Опубликована: Апрель 3, 2024

Abstract Over the last two decades ratchet mechanisms have transformed understanding and design of stochastic molecular systems—biological, chemical physical—in a move away from mechanical macroscopic analogies that dominated thinking regarding dynamics in 1990s early 2000s (e.g. pistons, springs, etc), to more scale‐relevant concepts underpin out‐of‐equilibrium research sciences today. Ratcheting has established nanotechnology as frontier for energy transduction metabolism, enabled reverse engineering biomolecular machinery, delivering insights into how molecules ‘walk’ track‐based synthesisers operate, acceleration reactions enables be transduced by catalysts (both motor proteins synthetic catalysts), dynamic systems can driven equilibrium through catalysis. The recognition biology, their invention systems, is proving significant areas diverse supramolecular chemistry, covalent DNA nanotechnology, polymer materials science, heterogeneous catalysis, endergonic synthesis, origin life, many other branches science. Put simply, give chemistry direction. Kinetic asymmetry, key feature ratcheting, counterpart structural asymmetry (i.e. chirality). Given ubiquity processes significance behaviour function it surely just fundamentally important. This Review charts recognition, development ratchets, focussing particularly on role which they were originally envisaged elements machinery. Different kinetically asymmetric are compared, consequences discussed. These archetypal examples demonstrate inexorably equilibrium, rather than relax towards it.

Язык: Английский

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Beyond Single‐Cycle Autonomous Molecular Machines: Light‐Powered Shuttling in a Multi‐Cycle Reaction Network

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Авг. 17, 2024

Abstract Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular in which kinetic asymmetry has been quantified well described simple single‐cycle networks. Here, we report on a unique light‐driven [2]rotaxane enables the autonomous operation of machine with multi‐cycle network. Unlike prior systems, present one exploits photoactive macrocycle, features different photoreactivity depending binding sites at it resides. Furthermore, E Z isomerization reverses relative affinity macrocycle for two axle, resulting Building most recent theoretical advancements, this work quantifies network first time. Our findings represent simplest rotaxane capable shuttling developed so far and offer general strategy generate quantify beyond systems.

Язык: Английский

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Feedback driven autonomous cycles of assembly and disassembly from minimal building blocks

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 18, 2024

The construction of complex systems by simple chemicals that can display emergent network dynamics might contribute to our understanding behavior from organic reactions. Here we design single amino acid/dipeptide-based exhibit multiple periodic changes (dis)assembly under non-equilibrium conditions in closed system, importantly the absence evolved biocatalysts. two-component based building block exploits pH driven non-covalent assembly and time-delayed accelerated catalysis self-assembled state install orthogonal feedback loops with a batch reactants. Mathematical modelling reaction establishes oscillations are transient for this structure helps predict relative contribution loop ability system such oscillation. Such autonomous purely synthetic molecules starting point enable active materials properties. study formed Here, built on minimal blocks, authors describe utilizing controlled pH-driven assembly.

Язык: Английский

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