Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Active and Unidirectional Acceleration of Biaryl Rotation by a Molecular Motor.

ABSTRACT: Light-driven molecular motors possess immense potential as central driving units for future nanotechnology. Integration into larger molecular setups and transduction of their mechanical motions represents the current frontier of research. Herein we report on an integrated molecular machine setup allowing the transmission of potential energy from a motor unit onto a remote receiving entity. The setup consists of a motor unit connected covalently to a distant and sterically encumbered biaryl receiver. By action of the motor unit, single-bond rotation of the receiver is strongly accelerated and forced to proceed unidirectionally. The transmitted potential energy is directly measured as the extent to which energy degeneration is lifted in the thermal atropisomerization of this biaryl. Energy degeneracy is reduced by more than 1.5 kcal mol^-1 , and rate accelerations of several orders of magnitude in terms of the rate constants are achieved.

SUBMITTER: Uhl E

PROVIDER: S-EPMC7154650 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Active and Unidirectional Acceleration of Biaryl Rotation by a Molecular Motor.

Uhl Edgar E Mayer Peter P Dube Henry H

Angewandte Chemie (International ed. in English) 20200220 14

Light-driven molecular motors possess immense potential as central driving units for future nanotechnology. Integration into larger molecular setups and transduction of their mechanical motions represents the current frontier of research. Herein we report on an integrated molecular machine setup allowing the transmission of potential energy from a motor unit onto a remote receiving entity. The setup consists of a motor unit connected covalently to a distant and sterically encumbered biaryl recei ...[more]

PMID: 31943681

Similar Datasets

Corrigendum: Active and Unidirectional Acceleration of Biaryl Rotation by a Molecular Motor.

Project description: Not available

| S-EPMC8097618 | biostudies-literature

Green light powered molecular state motor enabling eight-shaped unidirectional rotation.

Project description:Molecular motors convert external energy into directional motions at the nano-scales. To date unidirectional circular rotations and linear motions have been realized but more complex directional trajectories remain unexplored on the molecular level. In this work we present a molecular motor powered by green light allowing to produce an eight-shaped geometry change during its unidirectional rotation around the central molecular axis. Motor motion proceeds in four different steps, which alternate between light powered double bond isomerizations and thermal hula-twist isomerizations. The result is a fixed sequence of populating four different isomers in a fully unidirectional trajectory possessing one crossing point. This motor system opens up unexplored avenues for the construction and mechanisms of molecular machines and will therefore not only significantly expand the toolbox of responsive molecular devices but also enable very different applications in the field of miniaturized technology than currently possible.

| S-EPMC6773862 | biostudies-other

Chirality-Specific Unidirectional Rotation of Molecular Motors on Cu(111).

Project description:Molecular motors have chemical properties that enable unidirectional motion, thus breaking microscopic reversibility. They are well studied in solution, but much less is known regarding their behavior on solid surfaces. Here, single motor molecules adsorbed on a Cu(111) surface are excited by voltages pulses from an STM tip, which leads to their rotation around a fixed pivot point. Comparison with calculations shows that this axis results from a chemical bond of a sulfur atom in the chemical structure and a metal atom of the surface. While statistics show approximately equal rotations in both directions, clockwise and anticlockwise, a detailed study reveals that these motions are enantiomer-specific. Hence, the rotation direction of each individual molecule depends on its chirality, which can be determined from STM images. At first glance, these dynamics could be assigned to the activation of the motor molecule, but our results show that this is unlikely as the molecule remains in the same conformation after rotation. Additionally, a control molecule, although it lacks unidirectional rotation in solution, also shows unidirectional rotation for each enantiomer. Hence, it seems that the unidirectional rotation is not specifically related to the motor property of the molecule. The calculated energy barriers for motion show that the propeller-like motor activity requires higher energy than the simple rotation of the molecule as a rigid object, which is therefore preferred.

| S-EPMC9979643 | biostudies-literature

Defining Unidirectional Motions and Structural Reconfiguration in a Macrocyclic Molecular Motor.

Project description:The construction of sophisticated molecular machines requires not only precise control of energy fueled motions but their integration into larger functional architectures. Macrocyclization of molecular motors is a way to harness the intrinsic directionality of their rotation and use them to actively power different processes at the nano-scale. An effective concept in this regard uses a defined fragment of the molecular motor as a revolving door within the macrocycle. In this way, motor motions can be transmitted to distant structural entities, other rotations can be actively accelerated, or mechanical molecular threading events can be realized. In this work, a dual macrocyclization approach is presented, which not only allows to supersize the revolving door element but also structurally reconfigure the macrocycle in which the revolving door rotates. Unique possibilities for a multi-level precision control over integrated directional motions are thus opened up without deteriorating the functionality of the molecular machine.

| S-EPMC10288507 | biostudies-literature

Unidirectional rotation of micromotors on water powered by pH-controlled disassembly of chiral molecular crystals.

Project description:Biological and synthetic molecular motors, fueled by various physical and chemical means, can perform asymmetric linear and rotary motions that are inherently related to their asymmetric shapes. Here, we describe silver-organic micro-complexes of random shapes that exhibit macroscopic unidirectional rotation on water surface through the asymmetric release of cinchonine or cinchonidine chiral molecules from their crystallites asymmetrically adsorbed on the complex surfaces. Computational modeling indicates that the motor rotation is driven by a pH-controlled asymmetric jet-like Coulombic ejection of chiral molecules upon their protonation in water. The motor is capable of towing very large cargo, and its rotation can be accelerated by adding reducing agents to the water.

| S-EPMC10198998 | biostudies-literature

Sunlight-powered kHz rotation of a hemithioindigo-based molecular motor.

Project description:Photodriven molecular motors are able to convert light energy into directional motion and hold great promise as miniaturized powering units for future nanomachines. In the current state of the art, considerable efforts have still to be made to increase the efficiency of energy transduction and devise systems that allow operation in ambient and non-damaging conditions with high rates of directional motions. The need for ultraviolet light to induce the motion of virtually all available light-driven motors especially hampers the broad applicability of these systems. We describe here a hemithioindigo-based molecular motor, which is powered exclusively by nondestructive visible light (up to 500 nm) and rotates completely directionally with kHz frequency at 20 °C. This is the fastest directional motion of a synthetic system driven by visible light to date permitting materials and biocompatible irradiation conditions to establish similarly high speeds as natural molecular motors.

| S-EPMC4598625 | biostudies-literature

Steric Effects on the Thermal Processes of Hemithioindigo Based Molecular Motor Rotation.

Project description:Tuning the thermal behavior of light driven molecular motors is fundamentally important for their future rational design. In many molecular motors thermal ratcheting steps are comprised of helicity inversions, energetically stabilizing the initial photoproducts. In this work we investigated a series of five hemithioindigo (HTI) based molecular motors to reveal the influence of steric hindrance in close proximity to the rotation axle on this process. Applying a high yielding synthetic procedure, we synthesized constitutional isomeric derivatives to distinguish between substitution effects at the aromatic and aliphatic position on the rotor fragment. The kinetics of thermal helix inversions were elucidated using low temperature 1 H NMR spectroscopy and an in situ irradiation technique. In combination with a detailed theoretical description, a comparative analysis of substituent effects on the thermal helix inversions of the rotation cycle is now possible. Such deeper understanding of the rotational cycle of HTI molecular motors is essential for speed regulation and future applications of visible light triggered nanomachines.

| S-EPMC8361725 | biostudies-literature

Light-Gated Rotation in a Molecular Motor Functionalized with a Dithienylethene Switch.

Project description:A multiphotochromic hybrid system is presented in which a light-driven overcrowded alkene-based molecular rotary motor is connected to a dithienylethene photoswitch. Ring closing of the dithienylethene moiety, using an irradiation wavelength different from the wavelength applied to operate the molecular motor, results in inhibition of the rotary motion as is demonstrated by detailed 1 H-NMR and UV/Vis experiments. For the first time, a light-gated molecular motor is thus obtained. Furthermore, the excitation wavelength of the molecular motor is red-shifted from the UV into the visible-light region upon attachment of the dithienylethene switch.

| S-EPMC6099277 | biostudies-literature

The Influence of Strain on the Rotation of an Artificial Molecular Motor.

Project description:In artificial small-molecule machines, molecular motors can be used to perform work on coupled systems by applying a mechanical load-such as strain-that allows for energy transduction. Here, we report how ring strain influences the rotation of a rotary molecular motor. Bridging the two halves of the motor with alkyl tethers of varying sizes yields macrocycles that constrain the motor's movement. Increasing the ring size by two methylene increments increases the mobility of the motor stepwise and allows for fine-tuning of strain in the system. Small macrocycles (8-14 methylene units) only undergo a photochemical E/Z isomerization. Larger macrocycles (16-22 methylene units) can perform a full rotational cycle, but thermal helix inversion is strongly dependent on the ring size. This study provides systematic and quantitative insight into the behavior of molecular motors under a mechanical load, paving the way for the development of complex coupled nanomachinery.

| S-EPMC9544085 | biostudies-literature

Active Mechanical Threading by a Molecular Motor.

Project description:Molecular motors transform external energy input into directional motions and offer exquisite precision for nano-scale manipulations. To make full use of molecular motor capacities, their directional motions need to be transmitted and used for powering downstream molecular events. Here we present a macrocyclic molecular motor structure able to perform repetitive molecular threading of a flexible tetraethylene glycol chain through the macrocycle. This mechanical threading event is actively powered by the motor and leads to a direct translation of the unidirectional motor rotation into unidirectional translation motion (chain versus ring). The mechanism of the active mechanical threading is elucidated and the actual threading step is identified as a combined helix inversion and threading event. The established molecular machine function resembles the crucial step of macroscopic weaving or sewing processes and therefore offers a first entry point to a "molecular knitting" counterpart.

| S-EPMC9314141 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data