Phase transition dynamics and mechanism for backbone-thermoresponsive hyperbranched polyethers

Heating-Induced Phase Transition of Bupropion Hydrobromide Polymorphs

When a ferromagnetic system is driven by an oscillating magnetic field, the system shows various intriguing magnetic properties. The two most common features are dynamic phase transition and dynamic hysteresis resulting from the competition between the period of the external field and the metastable lifetime of the system. In this article, we mainly review the similarities and dissimilarities between ferromagnetic systems in thermal equilibrium and those exposed to a driving time-dependent magnetic field. Extensive studies performed over two decades have shown that dynamic and thermodynamic phase transitions correspond to the same universality class and have similar phase diagrams, among other similarities. Remarkably, recent experimental studies have revealed that both fluctuations in dynamic order parameter and susceptibility can demonstrate anomalously sharp sidebands, which are known as metamagnetic anomalies, in the dynamically paramagnetic phase close to the critical point. This behavior is one of the most interesting behaviors observed in the magnetic systems driven by a time-dependent field which does not have an analog in the corresponding equilibrium counterparts. We discuss the general picture regarding the effects of the applied field components on the metamagnetic anomalies. As a main conclusion, we remark that a comprehensive literature overview reveals that the similarities between conventional thermodynamic phase transitions and corresponding dynamic counterpart are only limited to the vicinity of critical period regime with zero bias field, and they should be treated very carefully in the presence of surfaces. Finally, some of the main questions waiting to be answered and potential future research directions are underlined.

Phase transitions are a common phenomenon in condensed matter and act as a critical degree of freedom that can be employed to tailor the mechanical or electronic properties of materials. Understanding the fundamental mechanisms of the thermodynamics and kinetics of phase transitions is, thus, at the core of modern materials design. Conventionally, studies of phase transitions have, to a large extent, focused on pristine bulk phases. However, realistic materials exist in a complex form; their microstructures consist of different point and extended defects. The presence of defects impacts the thermodynamics and kinetics of phase transitions, but has been commonly ignored or treated separately. In recent years, with the significant advances in theoretical and experimental techniques, there has been an increasing research interest in modeling and characterizing how defects impact or even dictate phase transitions. The present review systematically discusses the recent progress in understanding the kinetics of defect-characterized phase transitions, derives the key mechanisms underlying these phase transitions, and envisions the remaining challenges and fruitful research directions. We hope that these discussions and insights will help to inspire future research and development in the field.

This paper evaluates the aggregation behavior of a potential drug and gene delivery system that combines branched polyethyleneimine (PEI), a positively-charged polyelectrolyte, and elastin-like polypeptide (ELP), a recombinant polymer that exhibits lower critical solution temperature (LCST). The LCST behavior of ELP has been extensively studied, but there are no quantitative ways to control the size of aggregates formed after the phase transition. The aggregate size cannot be maintained when the temperature is lowered below the LCST, unless the system exhibits hysteresis and forms irreversible aggregates. This study shows that conjugation of ELP with PEI preserves the aggregation behavior that occurs above the LCST and achieves precise aggregate radii when the solution conditions of pH (3, 7, 10), polymer concentration (0.1, 0.15, 0.3 mg/mL), and salt concentration (none, 0.2, 1 M) are carefully controlled. K-means cluster analyses showed that salt concentration was the most critical factor controlling the hydrodynamic radius and LCST. Conjugating ELP to PEI allowed crosslinking the aggregates and achieved stable particles that maintained their size below LCST, even after removal of the harsh (high salt or pH) conditions used to create them. Taken together, the ability to control aggregate sizes and use of crosslinking to maintain stability holds excellent potential for use in biological delivery systems.

Interacting many-body systems that are driven far away from equilibrium can exhibit phase transitions between dynamically emerging quantum phases, which manifest as singularities in the Loschmidt echo. Whether and under which conditions such dynamical transitions occur in higher-dimensional systems with spontaneously broken continuous symmetries is largely elusive thus far. Here, we study the dynamics of the Loschmidt echo in the three dimensional O(N) model following a quantum quench from a symmetry breaking initial state. The O(N) model exhibits a dynamical transition in the asymptotic steady state, separating two phases with a finite and vanishing order parameter, that is associated with the broken symmetry. We analytically calculate the rate function of the Loschmidt echo and find that it exhibits periodic kink singularities when this dynamical steady-state transition is crossed. The singularities arise exactly at the zero-crossings of the oscillating order parameter. As a consequence, the appearance of the kink singularities in the transient dynamics is directly linked to a dynamical transition in the order parameter. Furthermore, we argue, that our results for dynamical quantum phase transitions in the O(N) model are general and apply to generic systems with continuous symmetry breaking.

We have studied the dynamical evolution of the shock in a neutron star (NS). The conversion of nuclear to quark matter (QM) is assumed to take place at the shock discontinuity. The density and pressure discontinuity is studied both spatially and temporally as it starts near the center of the star and moves toward the surface. Polytropic equations of state (EoS), which mimic original nuclear and QM EoS, are used to study such dynamical phase transition (PT). Solving relativistic hydrodynamic equations for a spherically symmetric star, we study the PT, assuming a considerable density discontinuity near the center. We find that as the shock wave propagates outward, its intensity decreases with time; however, the shock velocity peaks up and reaches a value close to that of light. Such fast shock velocity indicates rapid PT in NS taking place on a timescale of some 10s of microseconds. Such a result is quite interesting, and it differs from previous calculations that the PT in NSs takes at least some 10s of milliseconds. Rapid PT can have significant observational significance, because such fast PT would imply rather strong gravitational wave (GW) signals that are rather short lived. Such short-lived GW signals would be accompanied with short-lived gamma-ray bursts and neutrino signals originating from the neutrino and gamma-ray generation from the PT of nuclear matter to QM.

Successful non-viral gene targeting requires vectors to meet two conflicting needs-strong binding to protect the genetic material during transit and weak binding at the target site to enable release. Responsive polymers could fulfil such requirements through the switching of states, e.g. the chain-extended coil to chain-collapsed globule phase transition that occurs at a lower critical solution temperature (LCST), in order to transport nucleic acid in one polymer state and release it in another. The ability of new synthetic polycations based on poly(ethyleneimine) (PEI) with grafted neutral responsive poly(N-isopropylacrylamide) (PNIPAm) chains to condense DNA into particles with architectures varying according to graft polymer LCST was assessed using a combination of fluorescence spectroscopy, dynamic light scattering (DLS), zeta sizing, gel retardation and atomic force microscopy studies. Transfection assays were conducted under experimental conditions wherein the polymer components were able to cycle across their LCST. Two PEI-PNIPAm conjugate polymers with different LCSTs displayed coil-globule transitions when complexed to plasmid DNA, leading to variations in molecular architecture as shown by changes in emission maxima of an environment-sensitive fluorophore attached to the PNIPAm chains. Gel retardation assays demonstrated differences in electrophoretic mobilities of polymer-DNA complexes with temperatures below and above polymer LCSTs. Atomic force micrographs showed changes in the structures of polymer-DNA complexes for a polymer undergoing a phase transition around body temperature but not for the polymer with LCST outside this range. Transfection experiments in C2C12 and COS-7 cells demonstrated that the highest expression of transgene occurred in an assay that involved a 'cold-shock' below polymer LCST during transfection. Designed changes in thermoresponsive polycation vector configuration via temperature-induced phase transitions enhanced transgene expression. The results indicate that changes in molecular architecture induced by a carefully chosen stimulus during intracellular trafficking can be used to enhance gene delivery.

The phase transitions of poly(vinyl methyl ether) (PVME) in H2O and D2O have been investigated by Fourier transform infrared (FTIR) spectroscopy. IR spectra of PVME solution are measured as a function of temperature, and changes in the spectra induced by the phase transition are observed. The IR bands attributable to the vibration modes of backbone and methoxy side group exhibit critical changes at a lower critical solution temperature (LCST). Heating of the solution above the LCST leads shifts of C−H stretching bands toward lower wavenumber during a high-wavenumber shift of C−O stretching band (ν(C−O)). Among the C−H stretching bands, symmetric and antisymmetric C−H stretching bands due to the methyl group (νs(CH3) and νas(CH3)) shift to the largest extent (20 cm-1). The νs(CH3) band is composed of two components centered at 2839 and 2820 cm-1, which are assignable to hydrated and dehydrated methyl species, respectively. The molar fraction of the hydrated methyl species is close to 1 below 36 °C and is nearly 0 above 40 °C, insisting that most of the methyl groups are dehydrated above the LCST, whereas the peak position of the ν(C−O) band indicates only partial dehydration of the ether group above the LCST. Though PVME concentration dependence of the peak positions of the νs(CH3) and the ν(C−O) bands measured below the LCST shows that dehydration of the methyl group and the ether oxygen initiates at different water/monomer ratios (methyl, 5.5; ether, 2.8), the dehydration of these groups simultaneously proceeds in the course of the phase transition.

The molecular dynamics of linear poly(N-isopropylacrylamide) (pNIPAM) in aqueous media at temperatures below and above the lower critical solution temperature (LCST) are investigated using broadband dielectric relaxation spectroscopy in a frequency range from 10(-1) to 10(11) Hz. Below the LCST, two relaxation processes are observed in the megahertz and gigahertz region assigned to the reorientation of dipoles of the solvated polymer segments (p-process) and water molecules (w-process), respectively. Both relaxation processes are analyzed using the Havriliak-Negami (HN) function, taking special attention to the w-process. Above the LCST, the dielectric spectra of the pNIPAM solutions resemble that of pure water, showing only the high frequency relaxation process of the water molecules with a more or less Debye-type behavior. The non-Debye behavior of the w-process below the LCST is mainly induced by the interactions between water and pNIPAM chains via hydrogen bonding. The relaxation time and strength of the w-process is studied with dependence on the concentration, temperature, and the polymer chain length (molecular weight). The information obtained is useful for a deeper understanding of the dehydration behavior at the phase transition. The suggestion of dehydration of the pNIPAM chains at the LCST is confirmed by calculating a dehydration number.

1H NMR of thermoreversible polymers in solution and at interfaces: the influence of charged groups on the phase transition

Dynamic phase transition of natural gas hydrates confined within complex pore–throat structures is a key factor impacting the safe and efficient development of hydrate-bearing deposits. In this work, hydrate-bearing samples with varying saturation were first reconstructed with the proposed ice-seeding method using actual marine soil in hydrate-bearing sediments from the South China Sea. Dynamic evolution characteristics of hydrate formation in evolving porous media under different temperature and pressure conditions were analyzed in detail. Combined with high-resolution CT scanning, image processing, pore network extraction, and statistical analysis, the typical microscopic pore–throat structures of hydrate-bearing sediments were revealed, and the presence of nanopores was identified. Furthermore, highly controllable heterogeneous pore–throat structures were constructed for microfluidic chips by integrating stochastic modeling, equivalent modeling, and machine learning approaches. On this basis, a novel microfluidic testing method was developed for investigating the dynamic formation, dissociation, and phase transition characteristics of natural gas hydrates in complex pore structures by controlling the temperature. This study provides reliable data support and theoretical guidance for the productivity prediction of marine hydrate-bearing deposits.

Nonequilibrium statistical mechanics exhibit a variety of complex phenomena far from equilibrium. It inherits challenges of equilibrium, including accurately describing the joint distribution of a large number of configurations, and also poses new challenges as the distribution evolves over time. Characterizing dynamical phase transitions as an emergent behavior further requires tracking nonequilibrium systems under a control parameter. While a number of methods have been proposed, such as tensor networks for one-dimensional lattices, we lack a method for arbitrary time beyond the steady state and for higher dimensions. Here, we develop a general computational framework to study the time evolution of nonequilibrium systems in statistical mechanics by leveraging variational autoregressive networks, which offer an efficient computation on the dynamical partition function, a central quantity for discovering the phase transition. We apply the approach to prototype models of nonequilibrium statistical mechanics, including the kinetically constrained models of structural glasses up to three dimensions. The approach uncovers the active-inactive phase transition of spin flips, the dynamical phase diagram, as well as new scaling relations. The result highlights the potential of machine learning dynamical phase transitions in nonequilibrium systems.

Discrete time crystals are related to non-equilibrium dynamics of periodically driven quantum many-body systems where the discrete time translation symmetry of the Hamiltonian is spontaneously broken into another discrete symmetry. Recently, the concept of phase transitions has been extended to non-equilibrium dynamics of time-independent systems induced by a quantum quench, i.e. a sudden change of some parameter of the Hamiltonian. There, the return probability of a system to the ground state reveals singularities in time which are dubbed dynamical quantum phase transitions. We show that the quantum quench in a discrete time crystal leads to dynamical quantum phase transitions where the return probability of a periodically driven system to a Floquet eigenstate before the quench reveals singularities in time. It indicates that dynamical quantum phase transitions are not restricted to time-independent systems and can be also observed in systems that are periodically driven. We discuss how the phenomenon can be observed in ultra-cold atomic gases.

A novel monomer, N‐(2‐((3‐morpholine‐3‐isopropyl)thio)ethyl)methacrylamide (MTMA), is synthesized and polymerized by reversible addition‐fragmentation chain transfer (RAFT) polymerization to give a thermoresponsive polymer poly[N‐(2‐((3‐morpholino‐3‐oxopropyl)thio)ethyl)methacrylamide] (PMTMA). PMTMA exhibits reversible thermoresponsive phase transitions of the lower critical solution temperature (LCST) type in water and the upper critical solution temperature (UCST) type in ethanol and methanol. The degree of polymerization and concentration of PMTMA, and solvent type have a significant influence on the transition temperature. PMTMA shows complicated thermoresponse in water–alcohol mixtures. In water–ethanol mixtures, the phase diagram of PMTMA can be divided into three regions according to ethanol volume percentages, φ: 0 ≤ φ < 15% for an LCST region; 15% ≤ φ < 91.5% for a complete dissolution region; 91.5% ≤ φ ≤ 100% for a UCST region. At high water content, the LCST increases with increasing ethanol content; and at high ethanol content, the UCST decreases with increasing water content. In water–methanol mixtures, PMTMA shows more complex thermoresponse. In the range of 0–50 °C, the phase diagram can be divided into five regions, depending on the methanol volume percentages φ: 0 ≤ φ < 15% for LCST region; 15% ≤ φ < 25% for immiscible region; 25% ≤ φ < 85% for UCST region; 85% ≤ φ < 95% for fully dissolved region; 95% ≤ φ ≤ 100% for another UCST region.

This work reports for the first time the influence of degree of branching (DB) on the thermoresponsive phase transition behaviors of hyperbranched multiarm copolymers. Two series of PEHO-star-PEOs (series A) and PEHO-star-PDMAEMAs (series B) with the hydrophobic DB-variable PEHO core and different kinds of linear arms (PEO arms or PDMAEMA arms) were synthesized. It was found these two series demonstrate thermoresponsive phase transitions with the lower critical solution temperature (LCST). The studies on the LCST transition mechanism indicate that series A belongs to the thermoresponsive polymer system with LCST transition based on hydrophilic-hydrophobic balance, while series B belongs to the thermoresponsive polymer system with LCST transition based on coil-to-globule transition. Correspondingly, there is a big difference in the DB dependence of LCST transition between series A and series B. For series A, the LCST phase transition is highly dependent on the DB of the PEHO core in copolymers. For series B, the LCST phase transition is independent of the DB but dependent on solution pH. Such results may extend the knowledge on the structure-activity relationship of thermoresponsive highly branched polymers.