Cooperative and Synchronized Rotation in Motorized Porous Frameworks: Impact on Local and Global Transport Properties of Confined Fluids

<div>Molecules in gas and liquid states, as well as in solution, exhibit significant and random Brownian motion. Molecules in the solid-state, although strongly immobilized, can still exhibit significant intramolecular dynamics. However, in most framework materials, these intramolecular dynamics are driven by temperature, and therefore are neither controlled nor spatially or temporarily aligned. In recent years, several examples of molecular machines that allow for a stimuli-responsive control of dynamical motion, such as rotation, have been reported.</div><div><br></div><div>In this contribution, we investigate the local and global properties of a Lennard-Jones (LJ) fluid surrounding a molecular motor and consider the influence of cooperative and non-directional rotation for a molecular motor-containing pore system. This study uses classical molecular dynamics simulations to describe a minimal model, which was developed to resemble known molecular motors. The properties of an LJ liquid surrounding an isolated molecular mo-tor remain mostly unaffected by the introduced rotation. We then considered an arrangement of motors within a one-dimensional pore. Changes in diffusivity for pore sizes approaching the length of the rotor were observed, resulting from rotation of the motors. We also considered the influence of cooperative motor directionality on the directional transport properties of this con-fined fluid. Importantly, we discovered that specific unidirectional rotation of altitudinal motors can produce directed diffusion.</div><div><br></div><div>This study provides an essential insight into molecular machine-containing frameworks, highlighting the specific structural arrangements that can produce directional mass transport.</div>

Cooperative and Synchronized Rotation in Motorized Porous Frameworks: Impact on Local and Global Transport Properties of Confined Fluids

<div>Molecules in gas and liquid states, as well as in solution, exhibit significant and random Brownian motion. Molecules in the solid-state, although strongly immobilized, can still exhibit significant intramolecular dynamics. However, in most framework materials, these intramolecular dynamics are driven by temperature, and therefore are neither controlled nor spatially or temporarily aligned. In recent years, several examples of molecular machines that allow for a stimuli-responsive control of dynamical motion, such as rotation, have been reported.</div><div><br></div><div>In this contribution, we investigate the local and global properties of a Lennard-Jones (LJ) fluid surrounding a molecular motor and consider the influence of cooperative and non-directional rotation for a molecular motor-containing pore system. This study uses classical molecular dynamics simulations to describe a minimal model, which was developed to resemble known molecular motors. The properties of an LJ liquid surrounding an isolated molecular mo-tor remain mostly unaffected by the introduced rotation. We then considered an arrangement of motors within a one-dimensional pore. Changes in diffusivity for pore sizes approaching the length of the rotor were observed, resulting from rotation of the motors. We also considered the influence of cooperative motor directionality on the directional transport properties of this con-fined fluid. Importantly, we discovered that specific unidirectional rotation of altitudinal motors can produce directed diffusion.</div><div><br></div><div>This study provides an essential insight into molecular machine-containing frameworks, highlighting the specific structural arrangements that can produce directional mass transport.</div>

Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions

Statistical models provide a powerful and useful class of approximations for calculating reaction rates by bypassing the need for detailed, and often difficult, dynamical considerations. Such approaches invariably invoke specific assumptions about the extent of intramolecular vibrational energy flow in the system. However, the nature of the transition to the statistical regime as a function of the molecular parameters is far from being completely understood. Here, we use tools from nonlinear dynamics to study the transition to statisticality in a model unimolecular reaction by explicitly visualizing the high dimensional classical phase space. We identify generic features in the phase space involving the intersection of two or more independent anharmonic resonances and show that the presence of correlated, but chaotic, intramolecular dynamics near such junctions leads to nonstatisticality. Interestingly, akin to the stability of asteroids in the Solar System, molecules can stay protected from dissociation at the junctions for several picoseconds due to the phenomenon of stable chaos.

Effects of generation number, spacer length and temperature on the structure and intramolecular dynamics of siloxane dendrimer melts: molecular dynamics simulations

The structure and properties of two homologous series of polysiloxane dendrimer melts are studied by extensive atomistic molecular dynamics simulations.

HspB1 phosphorylation regulates its intramolecular dynamics and mechanosensitive molecular chaperone interaction with filamin C

Mechanical force–induced conformational changes in proteins underpin a variety of physiological functions, typified in muscle contractile machinery. Mutations in the actin-binding protein filamin C (FLNC) are linked to musculoskeletal pathologies characterized by altered biomechanical properties and sometimes aggregates. HspB1, an abundant molecular chaperone, is prevalent in striated muscle where it is phosphorylated in response to cues including mechanical stress. We report the interaction and up-regulation of both proteins in three mouse models of biomechanical stress, with HspB1 being phosphorylated and FLNC being localized to load-bearing sites. We show how phosphorylation leads to increased exposure of the residues surrounding the HspB1 phosphosite, facilitating their binding to a compact multidomain region of FLNC proposed to have mechanosensing functions. Steered unfolding of FLNC reveals that its extension trajectory is modulated by the phosphorylated region of HspB1. This may represent a posttranslationally regulated chaperone-client protection mechanism targeting over-extension during mechanical stress.