Correction: Foroozani Behbahani, A.; Harmandaris, V. Gradient of Segmental Dynamics in Stereoregular Poly(methyl methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets. Polymers 2021, 13, 830

The authors wish to make the following corrections to this paper: [...]

A Dynamically Correlated Network Model for the Collective Dynamics in Glass-Forming Molecular Liquids and Polymers

The non-Arrhenius behavior of segmental dynamics in glass-forming liquids is one of the most profound mysteries in soft matter physics. In this article, we propose a dynamically correlated network (DCN) model to understand the growing behavior of dynamically correlated regions during cooling, which leads to the viscous slowdown of supercooled liquids. The fundamental concept of the model is that the cooperative region of collective motions has a network structure that consists of string-like parts, and networks of various sizes interpenetrate each other. Each segment undergoes dynamical coupling with its neighboring segments via a finite binding energy. Monte Carlo simulations showed that the fractal dimension of the DCNs generated at different temperatures increased and their size distribution became broader with decreasing temperature. The segmental relaxation time was evaluated based on a power law with four different exponents for the activation energy of rearrangement with respect to the DCN size. The results of the present DCN model are consistent with the experimental results for various materials of molecular and polymeric liquids.

Detecting anisotropic segmental dynamics in disordered proteins by cross-correlated spin relaxation

Among the numerous contributions of Geoffrey Bodenhausen to NMR spectroscopy, his developments in the field of spin-relaxation methodology and theory will definitely have a long lasting impact. Starting with his seminal contributions to the excitation of multiple-quantum coherences, he and his group thoroughly investigated the intricate relaxation properties of these “forbidden fruits” and developed experimental techniques to reveal the relevance of previously largely ignored cross-correlated relaxation (CCR) effects, as “the essential is invisible to the eyes”. Here we consider CCR within the challenging context of intrinsically disordered proteins (IDPs) and emphasize its potential and relevance for the studies of structural dynamics of IDPs in the future years to come. Conventionally, dynamics of globularly folded proteins are modeled and understood as deviations from otherwise rigid structures tumbling in solution. However, with increasing protein flexibility, as observed for IDPs, this apparent dichotomy between structure and dynamics becomes blurred. Although complex dynamics and ensemble averaging might impair the extraction of mechanistic details even further, spin relaxation uniquely encodes a protein's structural memory. Due to significant methodological developments, such as high-dimensional non-uniform sampling techniques, spin relaxation in IDPs can now be monitored in unprecedented resolution. Not embedded within a rigid globular fold, conventional 15N spin probes might not suffice to capture the inherently local nature of IDP dynamics. To better describe and understand possible segmental motions of IDPs, we propose an experimental approach to detect the signature of anisotropic segmental dynamics by quantifying cross-correlated spin relaxation of individual 15N1HN and 13C′13Cα spin pairs. By adapting Geoffrey Bodenhausen's symmetrical reconversion principle to obtain zero frequency spectral density values, we can define and demonstrate more sensitive means to characterize anisotropic dynamics in IDPs.

Gradient of Segmental Dynamics in Stereoregular Poly(Methyl Methacrylate) Melts Confined between Pristine or Oxidized Graphene Sheets

Segmental dynamics in unentangled isotactic, syndiotactic, and atactic poly(methyl methacrylate) (i-, a-, and s-PMMA) melts confined between pristine graphene, reduced graphene oxide, RGO, or graphene oxide, GO, sheets is studied at various temperatures, well above glass transition temperature, via atomistic molecular dynamics simulations. The model RGO and GO sheets have different degrees of oxidization. The segmental dynamics is studied through the analysis of backbone torsional motions. In the vicinity of the model nanosheets (distances less than ≈2 nm), the dynamics slows down; the effect becomes significantly stronger with increasing the concentration of the surface functional groups, and hence increasing polymer/surface specific interactions. Upon decreasing temperature, the ratios of the interfacial segmental relaxation times to the respective bulk relaxation times increase, revealing the stronger temperature dependence of the interfacial segmental dynamics relative to the bulk dynamics. This heterogeneity in temperature dependence leads to the shortcoming of the time-temperature superposition principle for describing the segmental dynamics of the model confined melts. The alteration of the segmental dynamics at different distances, d, from the surfaces is described by a temperature shift, ΔTseg(d) (roughly speaking, shift of a characteristic temperature). Next, to a given nanosheet, i-PMMA has a larger value of ΔTseg than a-PMMA and s-PMMA. This trend correlates with the better interfacial packing and longer trains of i-PMMA chains. The backbone torsional autocorrelation functions are shown in the frequency domain and are qualitatively compared to the experimental dielectric loss spectra for the segmental α-relaxation in polymer nanocomposites. The εT″(f) (analogous of dielectric loss, ε″(f), for torsional motion) curves of the model confined melts are broader (toward lower frequencies) and have lower amplitudes relative to the corresponding bulk curves; however, the peak frequencies of the εT″(f) curves are only slightly affected.