Asymmetric Relaxation Research Articles

Phase Transitions Involving Channel Hydrates of a New Pharmaceutical Compound.

Hydrates are often used as pharmaceutical active pharmaceutical ingredients (API), especially when anhydrates may not be feasible likely due to physicochemical properties concerns. Pharmaceutical hydrates, whereas water is present as crystal adduct, are feasible for drug products as they do not pose any safety concern. Hydrates can impart many different advantages; therefore, they are quite common and preferred solid forms for numerous pharmaceutical materials on market. However, hydrates may involve various phase transitions, which may impact the stability and processability of drug substance. Phase transitions, which include temperature-induced dehydration and moisture-facilitated rehydration are investigated by different solid-state analytical techniques such as powder x-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, polarized light microscopy, and single-crystal x-ray diffraction. This research investigation focuses on the different phase transition behaviors of a newly discovered pharmaceutical compound with three channel hydrates, two of which confirmed by single-crystal analysis. The retention or rearrangement of crystal structures over the transitions are studied. Hydrate 3 exhibits a characteristic feature of channel hydrate that involves symmetric lattice relaxation.Unlike hydrate 3, hydrate 2 results in a potentially new unit cell upon dehydration due to asymmetric lattice relaxation, which converted back to Hydrate 2 in presence of water, a very unique behavior for a channel hydrate, rarely observed, which entails novelty of this research work. The relationship among crystal forms of different hydrates of this new compound is thus established. The current investigation is a vital part of drug product risk assessment for hydrates to avoid any challenges during manufacturing operations and/or stability studies. This investigation was successfully applied in the present study and can be expanded to other newly discovered APIs in future.

Asymmetrical Sc coordination-induced bridging structure and surface relaxation for boosting H2O2 photoactivation in Fenton-like catalysis

A single-atom of the transition metal scandium is introduced into the g-C3N4/MoSe2 heterojunction interfaces to form a single-atom bridging structure (Se–Sc–N) for H2O2 activation in a photo-Fenton-like system.

Asymmetric thermal relaxation in driven systems: Rotations go opposite ways

Asymmetric thermal relaxation in driven systems: Rotations go opposite ways

High-Temperature Dielectric Relaxation and Electric Conduction Mechanisms in a LaCoO3-Modified Na0.5Bi0.5TiO3 System.

This research study examines the high-temperature dielectric relaxation and electric conduction mechanisms in (x)LaCoO3-(1 - x)Na0.5Bi0.5TiO3 samples, where x is 0.05, 0.10, and 0.15. The findings demonstrate that all the samples exhibit two dielectric transitions: first, a frequency-dispersive shoulder at a lower temperature (Ts) around 425-450 K, which is associated with polar nanoregions (PNRs), and second, from ferroelectric to paraelectric transition at the Curie temperature (Tc) approximately between 580 and 650 K. The impedance analysis reveals the negative temperature coefficient of resistance behavior of the specimens. The broad and asymmetric relaxation peaks obtained from modulus spectroscopy demonstrate a wide range of relaxations, suggesting non-Debye-type behavior. Furthermore, the conductivity studies provide insights into understanding the transport phenomena in the samples. The oxygen vacancies resulting from the addition of LaCoO3 into the Na0.5Bi0.5TiO3 ceramics are responsible for the relaxation and conduction processes, and the charge carrier is doubly ionized oxygen ion vacancies. All samples except for LCNBT10 at 1 kHz exhibit a negative magnetodielectric response.

Separation of Micro-Brownian Motion and Side-Group Rotational Motion for Poly(N-isopropylacrylamide) in 1,4-Dioxane Studied by Dielectric Relaxation Spectroscopy

Dielectric relaxation of poly(N-isopropylacrylamide) (PNiPAM) was investigated in 1,4-dioxane as a low-polarity solvent at a concentration between 0 and 20 wt %, temperature between 40 and −35 °C, and a frequency range between 40 Hz and 1.8 GHz. Results suggest that relaxation due to the molecular motion of PNiPAM has two components: relaxation of side-group rotational motion at ∼100 MHz and micro-Brownian motion of PNiPAM chain at ∼1 MHz at room temperature. These processes are described by the sum of two Cole–Cole equations. Furthermore, the relaxation times of these processes showed distinct temperature dependences, as confirmed by activation energies obtained from the Arrhenius plot. In addition, asymmetric relaxation was observed in the MHz region of PNiPAM in various solvents comprising two individual relaxations. This could explain some fundamental aspects of PNiPAM solution properties and provide a deeper understanding of the molecular dynamics of PNiPAM.

Epitaxial ferroelectric memristors integrated with silicon

Neuromorphic computing requires the development of solid-state units able to electrically mimic the behavior of biological neurons and synapses. This can be achieved by developing memristive systems based on ferroelectric oxides. In this work we fabricate and characterize high quality epitaxial BaTiO3-based memristors integrated with silicon. After proving the ferroelectric character of BaTiO3 we tested the memristive response of LaNiO3/BaTiO3/Pt microstructures and found a complex behavior which includes the co-existence of volatile and non-volatile effects, arising from the modulation of the BaTiO3/Pt Schottky interface by the direction of the polarization coupled to oxygen vacancy electromigration to/from the interface. This produces remanent resistance loops with tunable ON/OFF ratio and asymmetric resistance relaxations. These properties might be harnessed for the development of neuromorphic hardware compatible with existing silicon-based technology.

(Invited) Molecular Beam Epitaxy and Dislocation Dynamics of Metamorphic Inassb for Long-Wavelength Infrared Applications

Long-wavelength infrared (IR) III-V based devices have long been of interest for potential applications such as chemical sensing and large format IR imaging. Within the III-V family, only the InAs1-xSbx bulk alloy in composition range 0.45 ≤ x ≤ 0.8, offers the required bandgap energy (Eg ) from 100 to 125 meV at an operating temperature of 80K and below [1]. Over this composition range however, the InAs1-xSbx lattice constant varies from 6.24 to 6.39 Å, where a lack of conventional substrates has restricted progress on the growth and study of this material system. To bridge this lattice-constant gap while maintaining relatively low defect densities, we employed a metamorphic step-graded InAs1-xSbx buffer on GaSb, enabling the study of low-Eg InAs1-xSbx as a function of growth conditions. Using this method, we investigated the effect of substrate temperature (Tsub ) and group V to group III flux ratio (beam equivalent pressure, V/III) on Sb incorporation of the lowest-Eg cap layer [2]. We also used x-ray reciprocal space mapping (RSM) to examine the effect of growth conditions on strain and dislocation dynamics. Following these growth studies, we employed the metamorphic InAs1-xSbx in an InAs/InAsSb superlattice designed with a cutoff wavelength of 9 µm which leads to improved absorption compared with the lattice-matched counterpart.We first grew, via molecular beam epitaxy, several InAs1-xSbx step-graded structures in which the Sb/(As+Sb) flux ratio was varied from 0.05 to 0.50 in 0.05 increments (see figure), under various Tsub and V/III. Nomarski imaging revealed smoother surfaces under a V/III=10, the highest ratio we attempted. At this higher V/III, we observed the cross-hatch morphology expected for metamorphic materials and found that the cross-hatch spacing changes, implying a change in dislocation dynamics, with Tsub . We then used photoluminescence (PL) to measure the Sb-content in the cap layer as well as compare intensities between samples. We found the highest Sb-incorporation to occur when Tsub =415 C and V/III=10, while the most intense samples used Tsub =415-430 C and V/III=10 [2].Using RSM along [110] with (004) and (115) reflections, we identified the Sb composition in each layer. This allowed comparison of Sb-content as a function of Sb/(As+Sb) for various Tsub and V/III. The results suggest that V/III has little effect on Sb incorporation, in direct conflict with our previous PL results [2]. To understand the discrepancy between PL and RSM, we measured (004) RSM of the same three samples with the x-ray beam incident along [1-10], revealing extremely different strain relaxation compared to the [110] case (see figure). Asymmetric strain relaxation has been observed in other III-V graded buffer systems and has been explained by different dislocation formation energies and glide velocities along each direction resulting from the core structure of the dislocation being terminated with either a group-III or a group-V element [3]. Transmission electron microscopy is ongoing to further understand the dislocation dynamics in these samples.Taking this all together allowed us to investigate the effect of substrate lattice-constant on strain-balanced InAs/InAsSb superlattices designed for 9 µm cutoff wavelength [4]. Theoretically, by using a larger substrate lattice-constant the superlattice design results in larger electron-hole wavefunction overlap, ultimately increasing photon absorption. Our experimental results confirm this theory, even in the presence of increased threading dislocations inherent to the required lattice-mismatch.[1] I. Vurgaftman et al. JAP 89, 5815-5875 (2001).[2] Tomasulo et al. J. Vac. Sci. and Technol. B 36, 02D108 (2018).[3] France et al. J. Appl. Phys. 107, 103530 (2010); Gelczuk et al., J. Cryst. Growth 310, 3014 (2008).[4] Affouda, Tomasulo et al., Appl. Phys. Lett. 110, 181107 (2017). Figure 1

Colossal dielectric response and complex impedance analysis of LaFeO3 ceramics

The present investigations mainly focused on the colossal dielectric response and complex impedance analysis of LaFeO3 ceramics. The studied sample was prepared by a citrate gel method. Structural and microstructural properties are analyzed from the XRD pattern and SEM micrograph. The anomalies in the dielectric constant versus temperature plots are analyzed on the basis of polarization induced by the Maxwell-Wagner mechanisms and ferromagnetic interaction between the Fe[Formula: see text] ions driven by the oxygen vacancy mediated Fe[Formula: see text]–V[Formula: see text] –Fe[Formula: see text] exchange interaction A giant dielectric permittivity in the order of [Formula: see text]105 was observed in the sample even at the room temperature for 100 Hz. The colossal dielectric constant in LaFeO3 is mainly driven by the internal barrier layer capacitor (IBLC) formation. The formation of IBLC was explained on the basis of highly insulating grain boundary and less resistive/semiconducting grain, which was confirmed from both the resistance and capacitance of grain and grain boundary from the impedance analysis. The non-Debye-type relaxation process associated with the grain and grain boundary effect was investigated from the broad and asymmetric relaxation peak. The relaxation time for both the grain and grain boundary effect was also calculated. In addition to this, we have also analyzed the normalized bode plot of imaginary part of impedance and electrical modulus which suggests the relaxation process dominated by the short-range movement of charge carriers.

Asymmetric interface and growth mechanism in sputtered W/Si and WSi2/Si multilayers

This paper presents a comparative study on W/Si and WSi2/Si multilayers for analyzing the asymmetric interfacial effect in Si-based multilayers. The interfacial characteristic, crystallization and growth mechanism of W/Si and WSi2/Si multilayers were investigated using grazing incidence X-ray reflectivity, X-ray diffraction, X-ray diffuse scattering, total external reflection X-ray diffuse scattering and Transmission Electron Microscopy. Roughness characteristics including frequency response, conformity and replication were quantitatively determined from the simulation of diffuse scattering profiles and the calculation of resonant diffuse scattering sheets. The intrinsic power spectral density of W/Si and WSi2/Si multilayers was fitted to demonstrate the related growth mechanism of the interfacial roughness. The experimental results exhibit the diffusion-dominant interfaces of the W/Si multilayer are obvious asymmetric for the wider interfacial region of 0.37 nm in the W-on-Si interface than that of 0.28 nm in the Si-on-W interface. Interfaces of the WSi2/Si multilayer without the distinguishable interdiffusion present the roughness-dominant property with the asymmetric transverse relaxation. The asymmetric interfaces of W/Si and WSi2/Si multilayers were further interpreted by a modified ballistic argument with the interfacial relaxation and reaction analysis.

Anomalous relaxation from a non-equilibrium steady state: An isothermal analog of the Mpemba effect

The Mpemba effect denotes an anomalous relaxation phenomenon where a system initially at a hot temperature cools faster than a system that starts at a less elevated temperature. We introduce an isothermal analog of this effect for a system prepared in a non-equilibrium steady state that then relaxes towards equilibrium. Here, the driving strength, which determines the initial non-equilibrium steady state, takes the role of the temperature in the original version. As a paradigm, we consider a particle initially driven by a non-conservative force along a one-dimensional periodic potential. We show that for an asymmetric potential relaxation from a strongly driven initial state is faster than from a more weakly driven one at least for one of the two possible directions of driving. These results are first obtained through perturbation theory in the strength of the potential and then extended to potentials of arbitrary strength through topological arguments.

Investigation of AC Conductivity Scaling and Dielectric Relaxation Dynamics of Chitosan/Iron Complexes

Complexes of chitosan-iron (Cs/Fe) were prepared electrochemically in acidic aqueous media in one compartment cells. The AC electrical conductivity of the Cs/Fe complexes was investigated in a wide range of frequency at various temperatures. The general behavior of the AC conductivity was found to be characterized by three different regions and, therefore, it was analyzed based on the universal power law to interpret the dispersive behavior of the conductivity. The activation energy (Ea ) of the conductivity was estimated and was found to be frequency dependent. The AC conductivity scaling of the complexes was investigated using various parameters. It was found that the conductivity spectra of all samples could be successfully collapsed into a master curve confirming that the relaxation mechanism was temperature independent under conductivity formalism in a certain range of temperature. The dielectric relaxation dynamics of the Cs/Fe complexes were investigated using the electric modulus. The behavior of the imaginary part of the electric modulus, M//(ω), of all samples showed asymmetric relaxation peaks with a red shift toward higher frequencies upon increasing the temperature. The Cole-Cole and scaling behavior of the real and imaginary parts of the electric modulus were investigated.

Non-equilibrium structural dynamics of supercoiled DNA plasmids exhibits asymmetrical relaxation.

Many cellular processes occur out of equilibrium. This includes site-specific unwinding in supercoiled DNA, which may play an important role in gene regulation. Here, we use the Convex Lens-induced Confinement (CLiC) single-molecule microscopy platform to study these processes with high-throughput and without artificial constraints on molecular structures or interactions. We use two model DNA plasmid systems, pFLIP-FUSE and pUC19, to study the dynamics of supercoiling-induced secondary structural transitions after perturbations away from equilibrium. We find that structural transitions can be slow, leading to long-lived structural states whose kinetics depend on the duration and direction of perturbation. Our findings highlight the importance of out-of-equilibrium studies when characterizing the complex structural dynamics of DNA and understanding the mechanisms of gene regulation.

Excess wings and asymmetric relaxation spectra in a facilitated trap model.

In a recent computer study, we have shown that the combination of spatially heterogeneous dynamics and kinetic facilitation provides a microscopic explanation for the emergence of excess wings in deeply supercooled liquids. Motivated by these findings, we construct a minimal empirical model to describe this physics and introduce dynamic facilitation in the trap model, which was initially developed to capture the thermally activated dynamics of glassy systems. We fully characterize the relaxation dynamics of this facilitated trap model varying the functional form of energy distributions and the strength of dynamic facilitation, combining numerical results and analytic arguments. Dynamic facilitation generically accelerates the relaxation of the deepest traps, thus making relaxation spectra strongly asymmetric, with an apparent "excess" signal at high frequencies. For well-chosen values of the parameters, the obtained spectra mimic experimental results for organic liquids displaying an excess wing. Overall, our results identify the minimal physical ingredients needed to describe excess processes in the relaxation spectra of supercooled liquids.

Unmasking coupling between channel gating and ion permeation in the muscle nicotinic receptor.

Whether ion channel gating is independent of ion permeation has been an enduring, unresolved question. Here, applying single channel recording to the archetypal muscle nicotinic receptor, we unmask coupling between channel gating and ion permeation by structural perturbation of a conserved intramembrane salt bridge. A charge-neutralizing mutation suppresses channel gating, reduces unitary current amplitude, and increases fluctuations of the open channel current. Power spectra of the current fluctuations exhibit low- and high-frequency Lorentzian components, which increase in charge-neutralized mutant receptors. After aligning channel openings and closings at the time of transition, the average unitary current exhibits asymmetric relaxations just after channel opening and before channel closing. A theory in which structural motions contribute jointly to channel gating and ion conduction describes both the power spectrum and the current relaxations. Coupling manifests as a transient increase in the open channel current upon channel opening and a decrease upon channel closing.

The role of Ag on the stress-induced ordering of oxygen in the Ti-15Zr-15Mo alloy

In this study, the effect of substitutional Ag on the stress-induced ordering of oxygen in the Ti-15Zr-15Mo (wt%) alloy was investigated by dynamic mechanical analysis. The Ti-15Zr-15Mo-xAg (x = 0, 1, and 3) samples were produced by argon arc melting, submitted to a posterior homogenization heat treatment, hot rolling, and solution heat treatment. The dynamic mechanical analysis was performed in the tensile mode, at a maximum strain amplitude of 0.02%, between 425 and 725 K, at 1 K/min, and frequencies from 10 up to 30 Hz. The results showed a broadened and asymmetric anelastic relaxation peak around 450 and 725 K in all samples, with step decay in Young’s modulus typical of stress-induced ordering phenomena. The peaks shifted towards high temperature with the increase of the frequency, indicating a thermally activated process. The peak fitting stated the presence of oxygen-type processes, produced by the interaction of matrix (Ti-O) and substitutional (Zr-O) elements, and one clustering (Ti-O-O). The amount of Ag exhibited a significant effect on the Qp−1 and Tp relationship and in the diffusional parameters D0 and τ0 of the metallic matrix, which could be related to the changes in the bcc crystalline structure’s atomic bonding. Thus, the results show that the interaction of interstitial oxygen in the Ti-15Zr-15Mo alloy can be tunable by the addition of Ag, which could bring novel insights about industrial applications beyond the biomedical area.

Memory effects in glasses: Insights into the thermodynamics of out-of-equilibrium systems revealed by a simple model of the Kovacs effect.

Glasses are interesting materials because they allow us to explore the puzzling properties of out-of-equilibrium systems. One of them is the Kovacs effect in which a glass, brought to an out-of-equilibrium state in which all its thermodynamic variables are identical to those of an equilibrium state, nevertheless evolves, showing a hump in some global variable before the thermodynamic variables come back to their starting point. We show that a simple three-state system is sufficient to study this phenomenon using numerical integrations and exact analytical calculations. It also brings some light on the concept of fictive temperature, often used to extend standard thermodynamics to the out-of-equilibrium properties of glasses. We confirm that the concept of a unique fictive temperature is not valid, an show it can be extended to make a connection with the various relaxation processes in the system. The model also brings further insights on the thermodynamics of out-of-equilibrium systems. Moreover, we show that the three-state model is able to describe various effects observed in glasses such as the asymmetric relaxation to equilibrium discussed by Kovacs, or the reverse crossover measured on B_{2}O_{3}.

Theoretical analysis for dynamic contact angle hysteresis on chemically patterned surfaces

A dynamic wetting problem is studied for a moving thin fiber inserted in fluid and with a chemically inhomogeneous surface. A reduced model is derived for contact angle hysteresis by using the Onsager principle as an approximation tool. The model is simple and captures the essential dynamics of the contact angle. From this model, we derive an upper bound of the advancing contact angle and a lower bound of the receding angle, which are verified by numerical simulations. The results are consistent with the quasi-static results. The model can also be used to understand the asymmetric dependence of the advancing and receding contact angles on the fiber velocity, which was observed recently in the physical experiments reported in the work of Guan et al. [“Asymmetric and speed-dependent capillary force hysteresis and relaxation of a suddenly stopped moving contact line,” Phys. Rev. Lett. 116, 066102 (2016)].

Asymmetric magnetic relaxation behavior of domains and domain walls observed through the FeRh first-order metamagnetic phase transition

The phase coexistence present through a first-order phase transition means there will be finite regions between the two phases where the structure of the system will vary from one phase to the other, known as a phase boundary wall. This region is said to play an important but unknown role in the dynamics of the first-order phase transitions. Here, by using both x-ray photon correlation spectroscopy and magnetometry techniques to measure the temporal isothermal development at various points through the thermally activated first-order metamagnetic phase transition present in the near-equiatomic FeRh alloy, we are able to isolate the dynamic behavior of the domain walls in this system. These investigations reveal that relaxation behavior of the domain walls changes when phase coexistence is introduced into the system and that the domain wall dynamics is different to the macroscale behavior. We attribute this to the effect of the exchange coupling between regions of either magnetic phase changing the dynamic properties of domain walls relative to bulk regions of either phase. We also believe this behavior comes from the influence of the phase boundary wall on other magnetic objects in the system.

Asymmetric spin relaxation induced by residual electron spin in semiconductor quantum-dot-superlattice hybrid nanosystem

Asymmetric spin relaxation induced by the residual electron spin in semiconductor quantum dots (QDs) adjacent to a superlattice (SL) was studied using spin- and time-resolved photoluminescence under the selective photoexcitation of the SL miniband states. Spin-polarized electrons were photoexcited in the SL barrier and then injected into the QDs through spin-conserving tunneling. The spin-polarized electron transport and the faster transport of the electrons as compared to the holes generate the residual majority electron spins in the QDs. A reversal of the optical spin polarity was observed at the ground state of the QDs, depending on the excitation powers. A rate equation analysis considering the individual spin-flip times between spin-split QD states indicates that the polarity reversal originates from the asymmetric spin-flip process at the excited state of the QDs. The asymmetric spin relaxation is associated with the selective relaxation of the spin-flipped electron and hole to the unoccupied ground state, which is induced by the existence of the residual majority electron spin at this state. In addition, we observed a clear recovery of the optical spin polarity by eliminating the existence of the residual electron spin through heavy p-doping. These findings are important to attain a fundamental understanding of the spin relaxation mechanism within the QDs and provide an insight into the manipulation of the optical spin polarity by controlling the residual electron spins in the QDs.

Dielectric relaxation study of aqueous diethylamine using a time domain reflectometry

The dielectric relaxation studies of Diethylamine (DEA) + water mixtures over 11 different concentrations, at different temperature and in the frequency range 0.01 ≤ ν/GHz ≤ 50 has been determined using Time Domain Reflectometry (TDR). The dielectric relaxation parameters such as static dielectric constant (εs), dielectric constant at high frequency (ε∞), relaxation time (τ in ps), asymmetric relaxation distribution parameter (β) and conductivity (κ) in the mixture has been obtained. The conductivity in water rich region confirms the formation of ammonium ion and hydroxide ion in Diethylamine-water mixtures. The heterogeneous molecular interactions and association in different species of Diethylamine-water molecules has been discussed using the Kirkwood correlation factor, Excess properties, Bruggeman factor and thermodynamic parameters and it has been confirmed that dipoles are arranged in parallel direction in a aqueous solutions.