Isotropic State Research Articles

Bridging Frontiers in Macromolecular and Supramolecular Sciences with Living Cationic Ring‐Opening Polymerization of Self‐Organizable Dendronized Cyclic‐Imino Ethers Generating Soft Frank–Kasper and Quasicrystal Arrays

AbstractLiving cationic ring‐opening polymerization accompanied by isomerization of cyclic imino ethers is performed at high temperatures that provide access to the synthesis of self‐organizable systems in their isotropic melt or solution state. This Perspective discusses fundamental mechanistic principles of this polymerization and bridges with the polymerization of dendronized cyclic iminoethers forming polymers that self‐organize soft Frank–Kasper and quasicrystal periodic and quasiperiodic arrays. These two fields represent frontiers in macromolecular and supramolecular science. A brief discussion of the impact of this polymerization on biomaterials and how it impacted contemporary mechanistic investigations is also made. Expected impacts via future synthetic developments and mechanistic investigations are discussed.

Long ranged stress correlations in the hard sphere liquid.

The smooth emergence of shear elasticity is a hallmark of the liquid to glass transition. In a liquid, viscous stresses arise from local structural rearrangements. In the solid, Eshelby has shown that stresses around an inclusion decay as a power law r-D, where D is the dimension of the system. We study glass-forming hard sphere fluids by simulation and observe the emergence of the unscreened power-law Eshelby pattern in the stress correlations of the isotropic liquid state. By a detailed tensorial analysis, we show that the fluctuating force field, viz., the divergence of the stress field, relaxes to zero with time in all states, while the shear stress correlations develop spatial power-law structures inside regions that grow with longitudinal and transverse sound propagation. We observe the predicted exponents r-D and r-D-2. In Brownian systems, shear stresses relax diffusively within these regions, with the diffusion coefficient determined by the shear modulus and the friction coefficient.

Being Smarter, Azobenzene-Containing Biomaterial Showing Triple Stimuli-Responsive Phase Change Property to Light, Humidity and Force at Room Temperature.

Multiple stimuli-responsiveness is an attractive property that is studied in physical chemistry and materials chemistry. While, multiple stimuli-responsive phase change in an isothermal way is rarely addressed for functional materials at room temperature. In this study, one azobenzene-containing surfactant AZO is designed for the fabrication of triple stimuli-responsive phase change biomaterial (Alg-AZO) through the electrostatic complexation with natural alginate. Thanks to the photoisomerization ability, molecular flexibility and hydrophilicity of AZO, together with the tailoring effect of alginate on AZO, Alg-AZO could perform reversible isothermal phase transition between liquid crystalline and isotropic liquid states under the stimuli of either light or humidity at room temperature. Furthermore, the humidity-induced isotropic state can also fast transit to ordered state under shear force, owing to the π-π interactions between planar trans-AZO in Alg-AZO material. With good biocompatibility, self-healing property and in vivo wound healing promoting capacity that is promoted by light, humidity and force, Alg-AZO would be suitable for working as a new smart biomaterial in biological and biomedical areas. This work provides a designing strategy for gaining multiple stimuli-responsive smart materials based on biomacromolecules, and also opening a new opportunity for gaining self-healing biomaterials capable of working in various conditions.

Photoresponsive protamine ionic complex towards a smart hemostatic biomaterial

Protamine (PA) is the only licensed antidote for reversing heparin anticoagulation by electrostatically binding with heparin. Efforts have been made on designing various heparin-scavengers, while, it remains a great challenge for gaining the external-stimuli responsive PA-release material. In this study, a generic strategy is developed for fabricating photoresponsive protein materials with the designed azobenzene-containing surfactant. For the first time, based on the isomerization of azobenzene, both cationic and anionic proteins could be phase change biomaterials which are capable of transiting to isotropic state under UV irradiation at room temperature. The formation of isotropic state could set the proteins free from the binding state, activating their intrinsic biological functions. Employing this mechanism, one smart PA material for inhibiting heparin is developed, which could effectively photo-modulate the heparin concentration by turning on-and-off the free state of PA from the binding state. With good biocompatibility, the PA material addresses photoresponsive hemostatic activity in biological studies, confirming its great potential clinical values. This work provides a new designing strategy for gaining photocontrollable hemostasis materials, also opening new opportunities for developing photoresponsive protein drugs and biomedical materials.

Theoretical and experimental study of elastocaloric responses in liquid crystalline elastomers

We carry out systematic experimental and theoretical study of elastocaloric (eC) response in nematic liquid crystal elastomers (LCEs), which possess the elastic properties of elastomers combined with the orientational order of liquid crystals. The chemical linking of mesogens to the polymer backbone enables thermomechanical response yielding a large spontaneous change in the LCE geometry on varying the temperature. In LCEs, a relatively large eC effect could be obtained upon adiabatic application or removal of a stress field in the isotropic state near phase transformation to the more ordered state. In these cases a change in the isothermal entropy or adiabatic temperature is compensated with the temperature change of liquid crystal elastomers. This effect could be exploited towards soft condensed state cooling technologies that gain increasing interest due to environmental issues, low-cost and low stimuli field. In the present study we measure directly the elastocaloric temperature change. Experimental measurements are interpreted using a modified Landau-de Gennes mesoscopic model taking into account both internal and external stress fields. Our systematic study identifies conditions yielding responsivity of a few K/MPa, which is two orders of magnitude larger than in the shape memory alloys, the most intensively studied materials for this effect.

Quantifying the performance of bidirectional quantum teleportation

Bidirectional teleportation is a fundamental protocol for exchanging quantum information between two parties by means of a shared resource state and local operations and classical communication (LOCC). In this paper, we develop two seemingly different ways of quantifying the simulation error of unideal bidirectional teleportation by means of the normalized diamond distance and the channel infidelity, and we prove that they are equivalent. By relaxing the set of operations allowed from LOCC to those that completely preserve the positivity of the partial transpose, we obtain semi-definite programming lower bounds on the simulation error of unideal bidirectional teleportation. We evaluate these bounds for several key examples: when there is no resource state at all and for isotropic and Werner states, in each case finding an analytical solution. The first aforementioned example establishes a benchmark for classical versus quantum bidirectional teleportation. Another example consists of a resource state resulting from the action of a generalized amplitude damping channel on two Bell states, for which we find an analytical expression for the simulation error that is in agreement with numerical estimates (up to numerical precision). We then evaluate the performance of some schemes for bidirectional teleportation due to (Kiktenko et al., Phys. Rev. A 93, 062305 (2016)) and find that they are suboptimal and do not go beyond the aforementioned classical limit for bidirectional teleportation. We offer a scheme alternative to theirs that is provably optimal. Finally, we generalize the whole development to the setting of bidirectional controlled teleportation, in which there is an additional assisting party who helps with the exchange of quantum information, and we establish semi-definite programming lower bounds on the simulation error for this task. More generally, we provide semi-definite programming lower bounds on the performance of bipartite and multipartite channel simulation using a shared resource state and LOCC.

Analytical solutions considering face advance and time-dependent behavior for back-analysis of convergence measurements in deep circular tunnels under isotropic initial stress state

A methodology is presented for the back-analysis of convergence measurements in deep tunnels to determine the constitutive parameters of the surrounding rock mass. Since increasing deformations and stresses with time are due to both the face advance and the time-dependent behavior of the ground, the two effects must be considered during the excavations. To that end, an analytical solution assuming an unlined circular tunnel excavated in a homogeneous isotropic ground under an initial isotropic stress field and assuming a fractional viscoelastic plastic behavior is developed. A second closed-form solution is also derived assuming an instantaneous excavation. Additionally, combining the developed analytical solution that takes into account the progressive face advance and an empirical approach, convergences are back-analyzed based on a least-squares optimization method to calibrate the constitutive parameters of the ground. The presented methodology aims to characterize the long-term behavior of tunnels and offers the advantage of being directly applicable during the excavation phase as soon as convergence measurements are available. Finally, the method is illustrated by two case studies related to the Fréjus road tunnel and the Saint-Martin-la-Porte access gallery (SMP2).

Exploring mesophase formation: Structural characterization approaches in a soft sphere model

This study employs Molecular Dynamics simulations to enhance the structural characterization of sphere mixture systems, focusing on local order parameters to identify order-disorder transitions within lamellar and hexagonal mesophases. The structural characterization included the use of neural networks and the search for clusters with topological order. We have identified the order-disorder transition at a characteristic temperature TOD, effectively captured by the structural parameters analyzed. Below TOD, the system organizes into an ordered mesophase, while above this temperature, it transitions into an isotropic liquid state. Moreover, within the isotropic region, we observe that the liquid begins to form clusters. This clustering phenomenon becomes evident below a specific temperature, denoted as T⁎. At T⁎, there are noticeable changes in the volume versus temperature curves, indicating a process of micellization or clustering in the system. The structural parameters used in our study also register this behavioral change at T⁎, further supporting the occurrence of this phenomenon. Additionally, our analysis of the overlap in detecting ordered particles between the two structural parameters using the Sørensen-Dice similarity coefficient reveals a significant spatial correlation in the isotropic phase, with a correlation higher than what would be expected in a random case. This indicates that both neural networks and topological cluster classification detect statistically similar ordered regions in the isotropic phase, highlighting the clustering. Our findings reveal that the structural parameters effectively capture both the order-disorder transition at TOD and the clustering process at T⁎. These results provide valuable insights into the self-assembly mechanisms and phase behavior in this soft-sphere model, advancing our understanding of self-assembly processes in material science, particularly in exploring phase behavior in mesogenic nanoparticle systems.

Communication Complexity of Common Randomness Generation With Isotropic States

Communication Complexity of Common Randomness Generation With Isotropic States

Impact of ageing on structure of random sequential adsorption packings of discorectangles

The ageing processes in the systems of elongated particles (discorectangles) adsorbed on a plane was studied numerically. An off-lattice model with continuous positional and orientational degrees of freedom was tested. The initial jammed state was produced using the random sequential adsorption (RSA) model. The transition from the jammed to equilibrium states were performed via translational and rotational Brownian motions. An aspect ratio of the particles (length-to-width ratio) was varied within the range ε=1−12 . At ɛ < 10 the relaxation into the isotropic state was always observed. In the intermediate range, 10⩽ε⩽11 , the relaxation transition into the states with ordered domains was observed. Particularly, for ɛ = 10 this transition was related with significant finite size scaling effects. For particles with ɛ = 12 formation of the large scale quasi-nematic domains and unlimited domain growth was observed. The impact of the relaxation on the domain structure, porosity, percolation connectivity and tracer particle diffusion in such barrier systems was also discussed.

Impact of scan strategy on principal stresses in laser powder bed fusion

Additive manufacturing techniques, such as laser powder bed fusion (PBF-LB), are well known for their exceptional freedom in part design. However, these techniques are also characterized by the development of large thermal gradients during production and thus residual stress (RS) formation in produced parts. In this context, neutron diffraction enables the non-destructive characterization of the bulk RS distribution. By control of the thermal gradients in the powder-bed plane by scan strategy variation we study the impact of in-process scan strategy variations on the microstructure and the three-dimensional distribution of RS. Microstructural analysis by means of electron backscatter diffraction reveals sharp microstructure transitions at the interfaces ranging from 100-200 µm. The components of the RS tensor are determined by means of neutron diffraction and the principal stress directions and magnitudes are determined by eigenvalue decomposition. We find that the distribution of RS in the powder-bed plane corresponds to the underlying scan strategy. When the alternating scan vectors align with the x- and y sample coordinate axes, the principal stress directions co-align. In the present geometry, nearly transverse isotropic stress states develop when the scan vectors are either aligned 45° between x and y or continuously rotated by 67° between each layer.

Visible‐Light Responsive Ionic Columnar Self‐Assemblies Exhibiting Fast Photothermal Energy Conversion at Room‐Temperature

AbstractA visible‐light responsive ionic liquid crystalline (LC) system based on gallic ester and tetra‐ortho‐substituted azobenzene is designed and synthesized. All the prepared derivatives exhibit columnar hexagonal mesophases at room temperature either in their pristine form or on cooling from isotropic states. The strategic design of these molecules allows for rapid photoisomerization, which is further aided by the dynamic LC phase. These systems attains photostationary states (PSSs) within 5 min of charging and discharging. The maximum Z conversion on charging in the solid‐state at room‐temperature is ≈80% with a highest temperature rise of 9.1 °C on discharging. This new molecular design enables the efficient working of solar thermal fuels (STFs) even in low sunlight intensity conditions, potentially promoting widespread adoption for mitigating global energy demands.

Analytic computation of the entanglement of formation for bipartite isotropic states using their symmetry

It is well-known that computing the entanglement of formation of a general bipartite state is a difficult task. We use the local symmetry of bipartite isotropic states in arbitrary dimensions to compute their entanglement of formation analytically. Our computation is an explicit and detailed version of the computation performed by Terhal et al [B. M. Terhal and K. G. H. Vollbrecht, Phys. Rev. Lett. 85, 2625 (2000)]. However, it is not just a review but we also have our contribution and novelty. For instance, we provide a rigorous proof for the entanglement of formation of two qutrit isotropic states and notably we give a proof supporting the conjecture proposed by Terhal et al about the entanglement of formation of bipartite isotropic states for the last range of allowed parameter values.

Contribution to the experimental and theoretical study of the behavior of soil-structure interfaces

Designing civil engineering works often requires taking into consideration the contact and interface conditions between the soil and structure. These may refer to the discontinuity surfaces between the soil and a structure such as foundations, geotechnical works, and others. Current research aims to improve the calculation methods for structures through a better understanding of the behavior of materials and interfaces. The present work falls into this context. It involves two parts. The main purpose of the first part is to present the results of the monotonic and cyclic soil-structure interface tests which were carried out using a modified direct shear box apparatus. The tests were conducted using a local material, namely the sand from the town of Messâad in the Wilaya of Djelfa (Algeria), in accordance with a constant normal stress path. In addition, a parametric study, dealing with the effect of density, interface roughness, and type of adhesive used on the behavior of the interfaces, was carried out as well. As for the second part, it primarily aims to validate the Modjoin interface model, which was developed at the Lille Mechanical Laboratory, based on the tests that were carried out in the first part. It is important to know that this model includes the main concepts used in soil modeling, such as isotropic hardening, characteristic state, critical state, softening, and others. Moreover, several validation tests are also presented in this work in order to describe the behavior of the soil-structure interface under monotonic loading to assess the performance of the model.

A Two‐Stage Polymerization Strategy for Preparing Polymer‐Network Liquid Crystals with Oxygen‐Sensing Property

Polymer‐network liquid crystal (PNLC) possesses both advantages of low‐molecular‐weight liquid crystal (LMWLC) and liquid crystal (LC) polymer. Herein, a two‐stage polymerization strategy for the formation of unique PNLC with oxygen‐sensing properties is reported. The reaction mixture consists of 6% diacrylate RM257, 93.5% LMWLC 4‐cyano‐4′‐pentylbiphenyl (5CB), and 0.5% photoinitiator dimethoxy‐2‐phenylacetophenone (DMPA). In the first stage, the mixture is exposed to UV light for 2 min to form a primary polymer network, which is highly uniform with a planar orientation. However, some free radicals are trapped inside the LC due to the short UV exposure time. Subsequently, the trapped free radicals are released by heating the PNLC sample into an isotropic state. Under this condition, the free radicals can move freely and react with surrounding monomers to form a secondary polymer network, which is highly disordered and scatters light strongly. Because oxygen can deactivate free radicals trapped inside the PNLC, the phenomenon to detect oxygen and monitor the diffusion of oxygen through the PNLC is exploited. The PNLC‐based oxygen sensor is potentially useful for the detection of oxygen and monitoring the exposure time to oxygen.

Solvent-Dependent Dynamics of Cellulose Nanocrystals in Process-Relevant Flow Fields.

Flow-assisted alignment of anisotropic nanoparticles is a promising route for the bottom-up assembly of advanced materials with tunable properties. While aligning processes could be optimized by controlling factors such as solvent viscosity, flow deformation, and the structure of the particles themselves, it is necessary to understand the relationship between these factors and their effect on the final orientation. In this study, we investigated the flow of surface-charged cellulose nanocrystals (CNCs) with the shape of a rigid rod dispersed in water and propylene glycol (PG) in an isotropic tactoid state. In situ scanning small-angle X-ray scattering (SAXS) and rheo-optical flow-stop experiments were used to quantify the dynamics, orientation, and structure of the assigned system at the nanometer scale. The effects of both shear and extensional flow fields were revealed in a single experiment by using a flow-focusing channel geometry, which was used as a model flow for nanomaterial assembly. Due to the higher solvent viscosity, CNCs in PG showed much slower Brownian dynamics than CNCs in water and thus could be aligned at lower deformation rates. Moreover, CNCs in PG also formed a characteristic tactoid structure but with less ordering than CNCs in water owing to weaker electrostatic interactions. The results indicate that CNCs in water stay assembled in the mesoscale structure at moderate deformation rates but are broken up at higher flow rates, enhancing rotary diffusion and leading to lower overall alignment. Albeit being a study of cellulose nanoparticles, the fundamental interplay between imposed flow fields, Brownian motion, and electrostatic interactions likely apply to many other anisotropic colloidal systems.

Topological defects as nucleation points of the nematic-isotropic phase transition in liquid crystal shells.

The transition from a nematic to an isotropic state in a self-closing spherical liquid crystal shell with tangential alignment is a stimulating phenomenon to investigate, as the topology dictates that the shell exhibits local isotropic points at all temperatures in the nematic phase range, in the form of topological defects. The defects may thus be expected to act as nucleation points for the phase transition upon heating beyond the bulk nematic stability range. Here we study this peculiar transition, theoretically and experimentally, for shells with two different configurations of four +1/2 defects, finding that the defects act as the primary nucleation points if they are co-localized in each other's vicinity. If the defects are instead spread out across the shell, they again act as nucleation points, albeit not necessarily the primary ones. Beyond adding to our understanding of how the orientational order-disorder transition can take place in the shell geometry, our results have practical relevance for, e.g., the use of curved liquid crystals in sensing applications or for liquid crystal elastomer actuators in shell shape, undergoing a shape change as a result of the nematic-isotropic transition.

Structural Regulation of Microcellular Thermotropic Liquid Crystalline Polymer with Low‐Dielectric Properties During Supercritical Fluid Foaming Process

With the development of radio technology, 5G electronic equipment has higher requirements for materials. This has become an imperative matter to realize the controllable preparation of Thermotropic liquid crystal polyester (TLCP) foams with homogeneous microcellular. Accordingly, the foaming behavior of TLCP in isotropic state is investigated. TLCP foams are prepared by a one‐step rapid depressurization foaming method at different temperature pressures, with cell diameter in the range of 67.5–283.9 μm and the material density in the range of 0.37–0.25 g/cm3. In order to broaden the distribution of cell diameter and the density of TLCP foams, the mixture foaming agent of N2 and CO2 is used in foaming process. When mixture foaming agents are used, the cell diameter is widened to the range of 40.5–283.9 μm, and the material density is widened to the range of 0.70–0.25 g/cm3, which realizes the controllable preparation of cell diameter and material density of TLCP. The dielectric constant and dielectric loss of TLCP foams can be as low as 1.35‰ and 0.85‰ at 10 GHz, respectively. The structural regulation of low‐dielectric TLCP microcellular materials is achieved for the first time by way of varying the temperature, pressure, and co‐blowing agent ratio.

Simulating the Lyotropic Phase Behavior of a Partially Self-Complementary DNA Tetramer.

DNA oligomers in solution have been found to develop liquid crystal phases via a hierarchical process that involves Watson-Crick base pairing, supramolecular assembly into columns of duplexes, and long-range ordering. The multiscale nature of this phenomenon makes it difficult to quantitatively describe and assess the importance of the various contributions, particularly for very short strands. We performed molecular dynamics simulations based on the coarse-grained oxDNA model, aiming to depict all of the assembly processes involved and the phase behavior of solutions of the DNA GCCG tetramers. We find good quantitative matching to experimental data at both levels of molecular association (thermal melting) and collective ordering (phase diagram). We characterize the isotropic state and the low-density nematic and high-density columnar liquid crystal phases in terms of molecular order, size of aggregates, and structure, together with their effects on diffusivity processes. We observe a cooperative aggregation mechanism in which the formation of dimers is less thermodynamically favored than the formation of longer aggregates.

An effective stress-based DSC model for predicting hydromechanical shear behavior of unsaturated collapsible soils subjected to initial shear stress

Evaluation of hydromechanical shear behavior of unsaturated soils is still a challenging issue. The time and cost needed for conducting precise experimental investigation on shear behavior of unsaturated soils have encouraged several investigators to develop analytical, empirical, or semi-empirical models for predicting the shear behavior of unsaturated soils. However, most of the previously proposed models are for specimens subjected to the isotropic state of stress, without considering the effect of initial shear stress. In this study, a hydromechanical constitutive model is proposed for unsaturated collapsible soils during shearing, with consideration of the effect of the initial shear stress. The model implements an effective stress-based disturbed state concept (DSC) to predict the stress-strain behavior of the soil. Accordingly, material/state variables were defined for both the start of the shearing stage and the critical state of the soil. A series of laboratory tests was performed using a fully automated unsaturated triaxial device to verify the proposed model. The experimental program included 23 suction-controlled unsaturated triaxial shear tests on reconstituted specimens of Gorgan clayey loess wetted to different levels of suctions under both isotropic and anisotropic stress states. The results show excellent agreement between the prediction by the proposed model and the experimental results.