Dynamic Disorder Research Articles

Predictors of psychopathology response in atypical anorexia nervosa following inpatient treatment: A propensity score matching study of weight suppression and weight loss speed.

This study examines weight suppression (WS) and weight loss speed (WLS) in atypical anorexia nervosa (AN) and its implications for treatment outcomes, compared to people with AN and bulimia nervosa (BN). A mixed cross-sectional and prospective design was employed, assessing WS and WLS in people with atypical AN, AN, and BN. Participants were matched for age, gender, age of onset, and disorder duration. Clinical measurements and eating disorders questionnaire (EDE-Q) scores were employed to evaluate the response to treatment. Individuals with atypical individuals exhibited WS patterns similar to AN, distinct from BN. Rapid WLS predicted clinical responses in atypical AN and BN, underscoring its treatment relevance. Atypical AN showed higher eating psychopathology scores than AN or BN, emphasizing the need for a reframed diagnosis. Understanding atypical AN's connection to restrictive behaviors and weight loss informs screening, assessment, and treatment practices. Recognition of atypical AN's severity and adoption of tailored approaches are essential for recovery. This study highlights the significance of WS and WLS in atypical AN treatment outcomes, offering insights into clinical practice and care. The proposal to reframe atypical AN as a restrictive eating disorder emphasizes its clinical relevance. The phenomenon of weight suppression, involving the discrepancy between past highest weight and current weight, has garnered attention due to cultural pressures emphasizing fitness and appearance. This study focuses on its implications in atypical anorexia nervosa, aiming to uncover the relationship between WS, its speed, and treatment outcomes. The investigation contributes insights into tailored interventions for atypical anorexia nervosa and enriches the understanding of this complex disorder's dynamics.

Nuclear quantum effects in the acetylene:ammonia plastic co-crystal.

Organic molecular solids can exhibit rich phase diagrams. In addition to structurally unique phases, translational and rotational degrees of freedom can melt at different state points, giving rise to partially disordered solid phases. The structural and dynamic disorder in these materials can have a significant impact on the physical properties of the organic solid, necessitating a thorough understanding of disorder at the atomic scale. When these disordered phases form at low temperatures, especially in crystals with light nuclei, the prediction of material properties can be complicated by the importance of nuclear quantum effects. As an example, we investigate nuclear quantum effects on the structure and dynamics of the orientationally disordered, translationally ordered plastic phase of the acetylene:ammonia (1:1) co-crystal that is expected to exist on the surface of Saturn's moon Titan. Titan's low surface temperature (∼90K) suggests that the quantum mechanical behavior of nuclei may be important in this and other molecular solids in these environments. By using neural network potentials combined with ring polymer molecular dynamics simulations, we show that nuclear quantum effects increase orientational disorder and rotational dynamics within the acetylene:ammonia (1:1) co-crystal by weakening hydrogen bonds. Our results suggest that nuclear quantum effects are important to accurately model molecular solids and their physical properties in low-temperature environments.

Morphology, dynamic disorder, and charge transport in an indoloindole-based hole-transporting material from a multi-level theoretical approach.

The exponential effort in the design of hole-transporting materials (HTMs) during the last decade has been motivated by their key role as p-type semiconductors for (opto)electronics. Although structure-property relationships have been successfully rationalized to decipher optimal site substitutions, aliphatic chain lengths or efficient aromatic cores for enhanced charge conduction, the impact of molecular shape, material morphology and dynamic disorder has been generally overlooked. In this work, we characterize by means of a multi-level theoretical approach the charge transport properties of a novel planar small-molecule HTM based on the indoloindole aromatic core (IDIDF), and compare it with spherical spiro-OMeTAD. Hybrid DFT calculations predict moderate band dispersions in IDIDF associated to the main transport direction characterized by π-π stacked molecules, both between the indoloindole cores and the thiophene groups. Strongly coupled dimers show relevant non-covalent interactions (NCI), indicating that NCI surfaces are a necessary but not exclusive requirement for large electronic couplings. We evidence remarkable differences in the site energy standard deviation and electronic coupling distributions between the conduction paths of IDIDF and spiro-OMeTAD. Despite the spherical vs. planar shape, theoretical calculations predict in the static crystal strong direction-dependent charge transport in the two HTMs, with ca. one-order-of-magnitude higher mobility (μ) for IDIDF. The dynamical disorder promoted by finite temperature effects in the crystal leads to a reduction in the hole transport properties in both HTMs, with maximum μ values of 2.42 and 4.2 × 10-2 cm2 V-1 s-1 for IDIDF and spiro-OMeTAD, respectively, as well as a significant increase in the transport anisotropy in the latter. Finally, the impact of the material amorphousness in the hole mobility is analysed by modelling a fully random distribution of HTM molecules. An average (lower-bound) mobility of 1.1 × 10-3 and 4.9 × 10-5 cm2 V-1 s-1 is predicted for planar IDIDF and spherical spiro-OMeTAD, respectively, in good accord with the experimental data registered in thin-film devices. Our results demonstrate the strong influence of molecular shape, dynamic structural fluctuations and crystal morphology on the charge transport, and pose indoloindole-based HTMs as promising materials for organic electronics and photovoltaics.

Unraveling the excitonics of light emission from metal-halide perovskite quantum dots.

Metal halide semicondictor perovskites have been under intense investigation for their promise in light absorptive applications like photovoltaics. They have more recently experienced interest for their promise in light emissive applications. A key aspect of perovskites is their glassy, ionic lattice that exhibits dynamical disorder. One possible result of this dynamical disorder is their strong coupling between electronic and lattice degrees of freedom which may confer remarkable properties for light emission such as defect tolerance. How does the system, comprised of excitons, couple to the bath, comprised of lattice modes? How does this system-bath interaction give rise to novel light emissive properties and how do these properties give insight into the nature of these materials? We review recent work from this group in which time-resolved photoluminescence spectroscopy is used to reveal such insights. Based upon a fast time resolution of 3 ps, energy resolution, and temperature dependence, a wide variety of insights are gleaned. These insights include: lattice contributions to the emission linewidths, multiexciton formation, hot carrier cooling, excitonic fine structure, single dot superradiance, and a breakdown of the Condon approximation, all due to complex structural dynamics in these materials.

Structural insights into the disulfide isomerase and chaperone activity of TrbB of the F plasmid type IV secretion system

Bacteria have evolved elaborate mechanisms to thrive in stressful environments. F-like plasmids in gram-negative bacteria encode for a multi-protein Type IV Secretion System (T4SSF) that is functional for bacterial proliferation and adaptation through the process of conjugation. The periplasmic protein TrbB is believed to have a stabilizing chaperone role in the T4SSF assembly, with TrbB exhibiting disulfide isomerase (DI) activity. In the current report, we demonstrate that the deletion of the disordered N-terminus of TrbBWT, resulting in a truncation construct TrbB37-161, does not affect its catalytic in vitro activity compared to the wild-type protein (p = 0.76). Residues W37–K161, which include the active thioredoxin motif, are sufficient for DI activity. The N-terminus of TrbBWT is disordered as indicated by a structural model of GST-TrbBWT based on ColabFold-AlphaFold2 and Small Angle X-Ray Scattering data and 1H–15N Heteronuclear Single Quantum Correlation (HSQC) spectroscopy of the untagged protein. This disordered region likely contributes to the protein's dynamicity; removal of this region results in a more stable protein based on 1H–15N HSQC and Circular Dichroism Spectroscopies. Lastly, size exclusion chromatography analysis of TrbBWT in the presence of TraW, a T4SSF assembly protein predicted to interact with TrbBWT, does not support the inference of a stable complex forming in vitro. This work advances our understanding of TrbB's structure and function, explores the role of structural disorder in protein dynamics in the context of a T4SSF accessory protein, and highlights the importance of redox-assisted protein folding in the T4SSF.

Thermal behaviors during lithium diffusion in Li0.4WO3 bronze studied by elastic and quasi-elastic neutron scattering.

Polycrystalline Li0.4WO3 bronze has been synthesized by solid state reaction carried out in a silica tube at 10-7 MPa and 973 K. The sample is characterized by temperature-dependent neutron elastic and quasielastic scatterings. The room-temperature neutron powder data Rietveld refinement confirmed the space group Im3̄ along with lithium occupancy found predominantly at the 6b crystallographic site. Upon increasing temperature above 300 K lithium at 6b site decreases and at 2a site increases, suggesting Li+ cation diffusion between these two sites demonstrated by quasielastic neutron scattering as well. The lattice thermal expansion anomaly is observed between 380 K and 450 K, which is explained in terms of lithium dynamic disorder (non-equilibrium) as complemented by elastic and quasielastic neutron scatterings. DFT calculations with different lithium distributions at two different crystallographic sites guide to understand the lattice expansion anomaly. The lattice thermal expansion is modeled using Grüneisen first-order approximation, where the Debye-Einstein-Anharmonicity approach provides the temperature-dependent vibrational energy. The DFT-calculated phonon density of states and bulk modulus help extract the characteristic Debye and Einstein frequencies.

A minimal kinetic model for the interpretation of complex catalysis in single enzyme molecules.

Multi-exponential waiting-time distribution and randomness parameter greater than unity ascribe dynamic disorder in single-enzyme catalysis corroborated to the interplay of transforming conformers [English et al., Nat. Chem. Biol., 2006, 2, 87]. The associated multi-state model of enzymatic turnovers with statically heterogeneous catalytic rates misdescribes the non-linear uprising of the randomness parameter from unity in relation to the attributes of the fall-offs of the waiting-time distribution at different substrate concentrations. To resolve this crucial issue, we first employ a comprehensive stochastic reaction scenario and further rationalize and work out the minimal indispensable dynamic-disorder model that ensures the foregoing relationship upon comparison with the data. We elucidate that specific disregard for the transition rate coefficients in the multi-state model on account of the especially slow conformational transitions is the underlying reason for not achieving interrelation between the observables.

Impact of static and dynamic disorder effects on the charge transport properties of merocyanine single crystals

Static and dynamic disorder effects impact the charge transport properties of merocyanine single crystals. While thermal disorder enhances the hole transfer rates, polarization phenomena lower the hole mobility and modify the transport topology.

Spin dynamics phenomena of a cerium(III) double-decker complex induced by intramolecular electron transfer.

Switchable spin dynamic properties in single-molecule magnets (SMMs) via an applied stimulus have applications in single-molecule devices. Many SMMs containing heavy lanthanoid ions with strong uniaxial magnetic anisotropy have been reported to exhibit SMM characteristics in the absence of an external magnetic field. On the other hand, SMMs containing light lanthanoid cerium(III) (Ce3+) ions exhibit field-induced slow magnetic relaxation. We investigated the chemical conversion of a diamagnetic Ce4+ ion (4f0) to a paramagnetic Ce3+ ion (4f1) in Ce-phthalocyaninato double-decker complexes (TBA+[Ce(obPc)2]- (1) and TBA+[Ce(Pc)2]- (2)) which exhibit field-induced SMM behaviour due to a 4f1 system. The phthalocyaninato ligands with electron-donating substituents (obPc2- = 2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato) in 1 have a significant effect on the valence state of the Ce ion, which is reflected in its magnetic properties due to the mixed valence state of the Ce ion. Given that Ce double-decker complexes with π-conjugated ligands undergo intramolecular electron transfer (IET) to the Ce ion mixed valence state, characterised by a mixture of 4f0 and 4f1 configurations, we examined the dynamic disorder inherent in IET influencing magnetic relaxation.

Solvent-assisted mechanochemical crystallization of the metal-free perovskite solid solution (H2dabco, H2hmta)NH4(BF4)3.

All-proportional solid solutions of the metal-free perovskite (H2dabco1-y, H2hmtay)(NH4)(BF4)3 ((d,h)-BF4) were crystallized via a mechanochemical method. Their molecular dynamics depend on the ratio y with a compositional boundary at y = 0.43, where H2dabco2+ was deduced to be at a dynamic disorder state, even below phase transition temperature to a plastic crystalline phase seen at y = 0.

Complex relaxation of trapped spin-states in spin crossover materials.

A diverse range of relaxation dynamics of trapped spin-states are observed in spin crossover (SCO) materials, including exponential, sigmoidal, stretched exponential, multi-step, and mixed kinetics. We reproduce and explain this full range of relaxation behaviours using a semi-empirical, semi-classical model that combines crystal field theory with elastic inter-molecular interactions. We show that frustrated intermolecular interactions, which are responsible for multistep thermal transitions, also lead to multiple energetically competitive ordered phases, even in systems that contain only one crystallographically distinct SCO site. This rugged free energy landscape leads to dynamic disorder and thence the complex dynamics widely observed in SCO materials. Similar mechanisms are vital for understanding dynamics of more complex materials from proteins to quantum materials.

(Invited) Achieving Stable Black-CsPbI3 Thin-Films for Opto-Electronic Applications

Halide perovskite materials, particularly CsPbI3, have emerged as promising candidates for optoelectronic applications, including solar cells, due to their favorable bandgap of ~1.7 eV for tandem solar cells with silicon-based counterparts. However, their widespread adoption is hindered by their instability and reactivity under ambient conditions, especially to moisture and oxygen. The black phase CsPbI3 polymorphs (α, β, and γ) are only stable at elevated temperatures, and at room temperature (RT), they transform to a yellow, nonperovskite phase (δ) with a wider bandgap of ~2.8 eV, leading to a loss of device performance. To address this challenge, various approaches have been explored to increase the stability of the black phase of CsPbI3 thin films under ambient conditions.[1]One approach is based on interface engineering to induce crystal strain, which increases the stabilization time of the black phase. Thin films of CsPbI3 are prepared on substrates with different thermal expansion coefficients, leading to interfacial strain when quenched from high temperatures (> 320 °C) to RT. This interfacial strain increases the stability of the black phase from a few seconds in bulk polycrystalline samples to a few minutes in thin films, as shown in Fig. 1(a).[2] Additionally, black phase stabilization has been enhanced to a few hours by introducing minimal amounts (< 5%) of dopant elements in the Pb site of CsPbI3, which modifies the texture and generates microstrain in the polycrystalline perovskite films (see Fig. 1(b)).[3] The dopants locally disrupt the normal bonding arrangement and manipulate strains/distortions, and structural relaxation around the dopants is mediated by dynamic disorder and the relatively soft elastic constants of halide perovskite, resulting in the stabilization of the required crystallographic phase.Furthermore, annealing of CsPbI3 thin films in the presence of oxygen has been explored as another approach to increase the stability of the black phase (stable for a few days). Heating the films under oxygen leads to surface oxidation and the formation of Pb-O bonds, resulting in the gathering of Pb and O atoms and the formation of lead oxide. The replacement of I atoms in the inorganic frameworks by O atoms tends to form volatile iodine (I2), but PbI2 is typically detected as the dominant product of degradation during heating in a dry air environment (Fig. 1(c)).[4] The oxidation products on the surface could potentially serve as a protective layer to inhibit further oxidation.Another highly effective approach to enhance the stability of the black phase CsPbI3 in perovskite thin films and devices is through the implementation of coarse photolithography to embed a PbI2-based interfacial microstructure.[5] The resulting films, adorned with a tessellating microgrid ((Fig. 1(d))), display remarkable resistance to moisture-induced decay and demonstrate prolonged stability of the black phase, persisting beyond 2.5 years even in dry environments. This remarkable stability can be attributed to the significant increase in the phase transition energy barrier and the effective limitation of potential yellow phase formation to structurally isolated domains within the microgrid.In summary, our laboratory has effectively implemented various methods to enhance the durability of black phase CsPbI3 thin films when exposed to ambient conditions. These methods comprise inducing interfacial strain, introducing bulk strain through doping, embedding interfacial microstructures, and surface oxidation. These techniques have demonstrated encouraging outcomes in maintaining the black phase of CsPbI3 for extended durations, ranging from a few minutes to several months, and exhibit significant potential for the advancement of practical applications of CsPbI3-based perovskite solar cells. Further exploration and advancement in this direction are anticipated to contribute to achieving long-lasting and efficient perovskite devices.[1] Acc. Mater. Res., 2020, 1, 1, 3–15[2] Science, 2019, 365, 679-684[3] J. Am. Chem. Soc., 2021, 143, 28, 10500–10508[4] unpublished results[5] Nature Commun., 2022, 13, 7513. Figure 1

Temperature Dependent EXAFS to Address Functional Mechanisms in Battery Materials

Increasing the contribution of renewable energy sources is necessary to meet the fast increase of global energy needs and match the CO2 reduction targets. In order to address these challenges, intensive research efforts are ongoing both in energy harvesting and storage technologies such as solar panels, fuel cells, supercapacitors and batteries. The latter are required to match the energy demand and supply; in fact, batteries are by far the most ubiquitous energy storage technology currently employed.Synchrotron x-ray spectroscopies have played a key role in the continuous development and breakthroughs in battery science, thanks to their capability to provide accurate information on electronic structure of the redox active element, local structure, and morphological information. In particular, X-ray absorption spectroscopy (XAS) is more and more employed for addressing battery materials [1]. Generally, XAS studies on battery materials are performed at a single temperature as a function of charge, to access information on the electrochemical behavior and charge transfer mechanism during the intercalation or deintercalation process. However, the fact that the charging/discharging process is expected to have direct influence on the bond length characteristics, strength and disorder, it is important to perform temperature dependence measurements to find a realistic correlation between the local structure and the battery characteristics. Indeed, temperature-dependent studies quantitatively allow to discriminate in between static and dynamic disorder, and to have direct access to the local force constant between the atom pairs. Here the interest of performing temperature dependent extended X-ray absorption fine structure (EXAFS) studies is highlighted by exploiting several examples. In Li and Mn-rich NMC cathodes temperature-dependent EXAFS investigation revealed the evolution of the lattice rigidity which directly affects the reversible anionic redox contribution [2-3]. Similar studies on Ti based MXene-type [4], NaxCoO2 [5], and V2O5 [6] electrode materials underline the importance of the local atomic correlations as limiting factor in the ion diffusion in battery materials.

Conformational Dynamics in Proteins: Entangled Slow Fluctuations and Nonequilibrium Reaction Events.

Proteins exhibit conformational fluctuations and changes over various time scales, ranging from rapid picosecond-scale local atomic motions to slower microsecond-scale global conformational transformations. In the presence of these intricate fluctuations, chemical reactions occur and functions emerge. These conformational fluctuations of proteins are not merely stochastic random motions but possess distinct spatiotemporal characteristics. Moreover, chemical reactions do not always proceed along a single reaction coordinate in a quasi-equilibrium manner. Therefore, it is essential to understand spatiotemporal conformational fluctuations of proteins and the conformational change processes associated with reactions. In this Perspective, we shed light on the complex dynamics of proteins and their role in enzyme catalysis by presenting recent results regarding dynamic couplings and disorder in the conformational dynamics of proteins and rare but rapid enzymatic reaction events obtained from molecular dynamics simulations.

Targeted four-dimensional computerized tomography scans for elbow disorders: a literature review and refinement of existing technique with two exemplar cases

Background4D-CTs or motion CTs in elbow disorders have several potential advantages over conventional static imaging such as a reduction of misdiagnoses, a more targeted surgical approach, better patient understanding of their condition and potentially faster operative times. However, the radiation dose is higher than conventional static CT scans so this should be used judiciously. Our study reviews the current literature for 4D-CTs in dynamic elbow disorders and provides a technical note describing radiation-reduced targeted elbow 4D-CTs (te4D-CT) with two exemplar cases alongside our recommendations for when te4D-CTs are indicated. Methodste4D-CTs are performed in a lateral decubitus elbow above head position. Preliminary static source axial cut CT obtained with subsequent sagittal and axial planes reconstruction and 3D reconstruction obtained, followed by scan performed in motion and reconstructed to 4D Component. te4D-CTs are taken for either flexion and extension (FE) or pronation and supination (PS) motions depending on the clinical pathology suspected following thorough clinical examination. Resultste4D-CT for PS and FE protocol scans had an effective radiation exposure dose of 0.53 and 0.95mSv respectively compared to 1.13-1.83mSv in conventional elbow 4D-CTs. In addition, te4D-CTs have good diagnostic accuracy provided that the FE or PS pathology is identified carefully by the ordering physician. Conclusionte4D-CT using isolated pronation and supination, or flexion and extension protocols does come with a significantly reduced radiation dose and can be of equal clinical yield compared with 4D-CTs.

Dynamic nasopharyngeal collapse in horses: What we know so far.

Dynamic nasopharyngeal collapse (NPC) is an obstructive upper airway disease that affects mainly the inspiratory phase of respiration in horses undergoing strenuous exercise. It occurs when the neuromuscular activity of the nasopharynx is overwhelmed by the intense negative pressures generated during exercise. This leads to collapse of at least one of the four components of the nasopharynx which is comprised of the two lateral walls, the dorsal roof and the ventral soft palate. As a result, the airway diameter and thus airflow become compromised. Even small changes in the airway diameter produces profound increases in negative inspiratory pressure, perpetuating the cycle of collapse. Compared to other dynamic upper respiratory tract disorders, the amount of literature on NPC as a disease entity is limited. The exact pathophysiology of NPC is unknown; however, it impacts up to one quarter of high-performance equine athletes presenting for poor performance. There is currently no definitive treatment for this severely performance-limiting condition. Thus, the prognosis for future athletic prognosis is guarded, with most horses being retired from racing or athletic use in general. Further research is warranted in this field to reduce the impact of disease and in turn, reduce the turnover rate and economic loss by enhancing the career longevity of elite equine athletes diagnosed with NPC.

Two In-based Hybrid Compounds with Structural Phase Transitions Caused by Displacement Motion or Dynamic Disorder

Two In-based Hybrid Compounds with Structural Phase Transitions Caused by Displacement Motion or Dynamic Disorder

Interlayer Charge Transport in 2D Lead Halide Perovskites from First Principles.

We report on the implementation of a versatile projection-operator diabatization approach to calculate electronic coupling integrals in layered periodic systems. The approach is applied to model charge transport across the saturated organic spacers in two-dimensional (2D) lead halide perovskites. The calculations yield out-of-plane charge transfer rates that decay exponentially with the increasing length of the alkyl chain, range from a few nanoseconds to milliseconds, and are supportive of a hopping mechanism. Most importantly, we show that the charge carriers strongly couple to distortions of the Pb-I framework and that accounting for the associated nonlocal dynamic disorder increases the thermally averaged interlayer rates by a few orders of magnitude compared to the frozen-ion 0 K-optimized structure. Our formalism provides the first comprehensive insight into the role of the organic spacer cation on vertical transport in 2D lead halide perovskites and can be readily extended to functional π-conjugated spacers, where we expect the improved energy alignment with the inorganic layout to speed up the charge transfer between the semiconducting layers.

Lattice Distortion and Low-Frequency Anharmonic Phonons Suppress Charge Recombination in Lead Halide Perovskites upon Pseudohalide Doping: Time-Domain Ab Initio Analysis.

Perovskite solar cells have witnessed a surge in interest as a promising technology for low-cost, high-efficiency photovoltaics with certified power conversion efficiencies beyond 25%. However, their commercial development is hindered by poor stability and nonradiative losses that restrict their approach to the theoretical efficiency limit. Using ab initio nonadiabatic molecular dynamics, we demonstrate that nonradiative charge recombination is suppressed when the iodide in formamidinium lead iodide (FAPbI3) is partially replaced with pseudohalide anions (SCN-, BF4-, and PF6-). The replacement breaks the symmetry of the system and creates local structural distortion and dynamic disorder, decreasing electron-hole overlap and nonadiabatic electron-vibrational coupling. The charge carrier lifetime is found to increase with increased structural distortion and is the longest for PF6-. This work is fundamentally relevant to the design of high-performance perovskite materials for optoelectronic applications.

Targeting stress granules in neurodegenerative diseases: A focus on biological function and dynamics disorders.

Stress granules (SGs) are membraneless organelles formed by eukaryotic cells in response to stress to promote cell survival through their pleiotropic cytoprotective effects. SGs recruit a variety of components to enhance their physiological function, and play a critical role in the propagation of pathological proteins, a key factor in neurodegeneration. Recent advances indicate that SG dynamic disorders exacerbate neuronal susceptibilityto stress in neurodegenerative diseases (NDs) including Alzheimer's disease (AD), amyotrophic lateral sclerosis (ALS), frontotemporal dementia (FTD), Huntington's disease (HD) and Parkinson's disease (PD). Here, we outline the biological functions of SGs, highlight SG dynamic disorders in NDs, and emphasize therapeutic approaches for enhancing SG dynamics to provide new insights into ND intervention.