Transient Anisotropy Research Articles

Topology of anisotropic glasses from persistent homology analysis

Glasses are typically isotropic, but permanent or transient anisotropy can be induced by tensile strain. We use persistent homology (PH) analysis to explore the topological effects of such anisotropy in SiO2Na2O glass ensembles with variable alkali concentration as a function of frozen-in anisotropic strain. Statistical information was extracted on ring (H1) and cavity (H2) features, whereby anisotropic stretching was found to induce strong variations in the ring topology of the –O-Si-O- backbone, but only minor changes in the overall cavity statistics or in the Na distribution (the Na distribution was found to be governed by H2 persistence). Tensile fracture led to total recovery of network topology relative to the pristine (isotropic) glass. In revealing such reactions, PH and persistence similarity analysis may help to differentiate purely entropic orientation and irreversible structural alterations leading to glass anisotropy.

Fluence and Temperature Dependences of Laser-Induced Ultrafast Demagnetization and Recovery Dynamics in L10-FePt Thin Film.

The fundamental mechanisms of ultrafast demagnetization and magnetization recovery processes in ferromagnetic materials remain incompletely understood. The investigation of different dynamic features which depend on various physical quantities requires a more systematic approach. Here, the femtosecond laser-induced demagnetization and recovery dynamics in L10-Fe0.5Pt0.5 alloy film are studied by utilizing time-resolved magneto-optical Kerr measurements, focusing on their dependences of excitation fluence and ambient temperature over broad ranges. Ultrafast demagnetization dominated by Elliott-Yafet spin-flip scattering, and two-step magnetization recovery processes are found to be involved in all observations. The fast recovery time corresponding to spin-lattice relaxation is much shorter than that of many ferromagnets and increase with excitation fluence. These can be ascribed to the strong spin-orbit coupling (SOC) demonstrated in FePt and the reduction of transient magnetic anisotropy, respectively. Surprisingly, the demagnetization time exhibits no discernible correlation with ambient temperature. Two competitive factors are proposed to account for this phenomenon. On the other hand, the spin-lattice relaxation accelerates as temperature decreases due to enhanced SOC at lower ambient temperature. A semiquantitative analysis is given to get a visualized understanding. These results offer a comprehensive understanding of the dynamic characteristics of ultrafast demagnetization and recovery processes in iron-based materials with strong SOC, highlighting the potential for regulating the magnetization recovery process through temperature and laser fluence adjustments.

Dynamic Response of Surface-Bound Peptides to a pH Perturbation Under Controlled Electrostatic Conditions.

The dynamic conformations of a thin peptide film covalently-linked to the surface of a transparent electrode are characterized over the course of a perturbation to their local pH by a photoacid under a controlled electrostatic potential. The local environment at this functionalized electrified interface is probed by the ultrafast fluorescence intensity and transient anisotropy of chromophores sparsely attached to the peptide side chains. A partition of chromophores into two sub-populations is observed, one buried in the peptide layer and another that is solvent exposed, and their relative contributions to the observed fluorescence signal are affected by both pH and voltage stimuli. The photophysical properties of solvent-exposed chromophores reveal that while the average conformation of the peptide mat is dictated by the pH of the surrounding electrolyte, their fluctuations are largely determined by the local electrostatic conditions set by the electrode's surface potential.

Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer

In this work, the photoinduced charge separation (CS) via symmetry breaking in an orthogonal meso-β-linked boron dipyrromethene (BODIPY) dimer was investigated by polarized transient absorption spectroscopy. The time constant about 0.76 ps of the CS reaction determined in dimethyl sulfoxide is much faster than the solvation dynamics. The observed transient anisotropy of the BODIPY anion band implies that both hole and electron transfers occur with similar probabilities. The bidirectional charge transfer processes suggest that the locally excited state is weakly coupled to the polar solvent, and the solvation coupled excited-state structural relaxation within the BODIPY monomeric unit is rather limited. In combination with the electronic excitation analysis based on time-dependent density-functional theory calculations, we deduced that the CS in the orthogonal BODIPY dimer is enabled via the torsional motion associated with covalently connected BODIPY units, promoting the electronic coupling, and irrelevant to the dynamic solvent relaxation.

Laser‐Induced Transient Anisotropy and Large Amplitude Magnetization Dynamics in a Gd/FeCo Multilayer

AbstractUltrafast laser‐induced dynamics in a ferrimagnetic gadolinium iron cobalt (Gd/FeCo) multilayer with a magnetization compensation temperature of TM = 320 K is studied at room temperature as a function of laser‐fluence and strength of the applied magnetic field. The dynamics is found to be substantially different from that in archetypical GdFeCo alloys, and depending on the laser fluence one can distinguish two different regimes. At low laser fluence (⩽1.6 mJ cm‐2), ultrafast laser excitation of the medium triggers spin precession of an extraordinary large amplitude reaching over 30°. At high laser fluence (⩾2.2 mJ cm‐2), the pump heats the medium over the magnetization compensation point, spin precession reduces significantly in amplitude and the process of field‐assisted reversal of magnetization of Gd and FeCo is launched. It is argued that such a distinctly different laser‐induced magnetization dynamics in the multilayers compared to the alloys is due to the symmetry breaking at the numerous interfaces, giving rise to additional surface anisotropy. The temperature dependence of the latter is found to be the key ingredient in the mechanism of ultrafast laser‐induced magnetization dynamics in ferrimagnetic multilayers. Controlling the amount and properties of interfaces in multilayers can thus serve as a mean to achieve efficient ultrafast all‐optical control of magnetism.

Chiral control of spin-crossover dynamics in Fe(II) complexes.

Iron-based spin-crossover complexes hold tremendous promise as multifunctional switches in molecular devices. However, real-world technological applications require the excited high-spin state to be kinetically stable-a feature that has been achieved only at cryogenic temperatures. Here we demonstrate high-spin-state trapping by controlling the chiral configuration of the prototypical iron(II)tris(4,4'-dimethyl-2,2'-bipyridine) in solution, associated for stereocontrol with the enantiopure Δ- or Λ-enantiomer of tris(3,4,5,6-tetrachlorobenzene-1,2-diolato-κ2O1,O2)phosphorus(V) (P(O2C6Cl4)3- or TRISPHAT) anions. We characterize the high-spin-state relaxation using broadband ultrafast circular dichroism spectroscopy in the deep ultraviolet in combination with transient absorption and anisotropy measurements. We find that the high-spin-state decay is accompanied by ultrafast changes of its optical activity, reflecting the coupling to a symmetry-breaking torsional twisting mode, contrary to the commonly assumed picture. The diastereoselective ion pairing suppresses the vibrational population of the identified reaction coordinate, thereby achieving a fourfold increase of the high-spin-state lifetime. More generally, our results motivate the synthetic control of the torsional modes of iron(II) complexes as a complementary route to manipulate their spin-crossover dynamics.

Terahertz pump-probe of liquid water at 12.3 THz.

The dynamical complexity of the hydrogen-bonded water network can be investigated with intense Terahertz (THz) spectroscopy, which can drive the liquid into the nonlinear response regime and probe anharmonicity effects. Here we report single-color and polarization-dependent pump–probe experiments at 12.3 THz on liquid water, exciting the librational mode. By comparing results obtained on a static sample and a free-flowing water jet, we are able to disentangle the distinct contributions by thermal, acoustic, and nonlinear optical effects. We show that the transient transmission by the static water layer on a time scale of hundreds of microseconds can be described by thermal (slow) and acoustic (temperature-dependent) effects. In addition, during pump probe overlap we observe an anisotropic nonlinear optical response. This nonlinear signal is more prominent in the liquid jet than in the static cell, where temperature and density perturbations are more pronounced. Our measurements confirm that the THz excitation resonates with the rotationally-damped motion of water molecules, resulting in enhanced transient anisotropy. This model can be used to explain the non-linear response of water in the frequency range between about 1 and 20 THz.

Bio-inspired shape-memory structural color hydrogel film

Structural colors, derived from existing natural creatures, have aroused widespread attention in the materials regulation for different applications. Here, inspired by the color adjusting mechanism of hummingbird, we present a novel shape-memory structural color hydrogel film by introducing shape memory polymers (SMPs) into synthetic inverse opal scaffold structure. The excellent flexibility as well as the inverse opal structure of the hydrogel films imparts them with stable stretchability and brilliant structural colors. Benefiting from the transient structural anisotropy of copolymers, the hybrid films are possessed with shape-morphing behaviors capability. Based on the shape transformations and color responsiveness performance, we have demonstrated diverse structural color actuators with complex shapes for different tasks. Notably, as the photothermal responsive graphene quantum dots were integrated into the hydrogel, the hybrid films could also be endowed with the feature of light-controlled reversible deformation with synchronous structural color variation. These features demonstrate that the presented shape-memory structural color hydrogel film is valuable for soft robotics with multi-functions of sensing, communication and disguise.

Cardiac myosin-binding protein C interaction with actin is inhibited by compounds identified in a high-throughput fluorescence lifetime screen

Cardiac myosin-binding protein C (cMyBP-C) interacts with actin and myosin to modulate cardiac muscle contractility. These interactions are disfavored by cMyBP-C phosphorylation. Heart failure patients often display decreased cMyBP-C phosphorylation, and phosphorylation in model systems has been shown to be cardioprotective against heart failure. Therefore, cMyBP-C is a potential target for heart failure drugs that mimic phosphorylation or perturb its interactions with actin/myosin. Here we have used a novel fluorescence lifetime-based assay to identify small-molecule inhibitors of actin-cMyBP-C binding. Actin was labeled with a fluorescent dye (Alexa Fluor 568, AF568) near its cMyBP-C binding sites; when combined with the cMyBP-C N-terminal fragment, C0-C2, the fluorescence lifetime of AF568-actin decreases. Using this reduction in lifetime as a readout of actin binding, a high-throughput screen of a 1280-compound library identified three reproducible hit compounds (suramin, NF023, and aurintricarboxylic acid) that reduced C0-C2 binding to actin in the micromolar range. Binding of phosphorylated C0-C2 was also blocked by these compounds. That they specifically block binding was confirmed by an actin-C0-C2 time-resolved FRET (TR-FRET) binding assay. Isothermal titration calorimetry (ITC) and transient phosphorescence anisotropy (TPA) confirmed that these compounds bind to cMyBP-C, but not to actin. TPA results were also consistent with these compounds inhibiting C0-C2 binding to actin. We conclude that the actin-cMyBP-C fluorescence lifetime assay permits detection of pharmacologically active compounds that affect cMyBP-C-actin binding. We now have, for the first time, a validated high-throughput screen focused on cMyBP-C, a regulator of cardiac muscle contractility and known key factor in heart failure.

Synthesis and Photophysical Properties of Light-Harvesting Gold Nanoclusters Fully Functionalized with Antenna Chromophores.

The development of efficient light-harvesting systems is important to understand the key aspects of solar-energy conversion processes and to utilize them in various photonic applications. Here, atomically well-defined gold nanoclusters are reported as a new platform to fabricate artificial light-harvesting systems. An efficient amide coupling method is developed to synthesize water-soluble Au22 clusters fully protected with pyrene chromophores by taking advantage of their facile phase-transfer reaction. The synthesized Au22 clusters with densely packed 18 pyrene chromophores (Au22 -PyB18 ) exhibit triple-emission in blue, green, and red wavelength regions arising respectively from pyrene monomer, pyrene excimer, and Au22 emission, producing bright white light emission together. The photoluminescence of Au22 is enhanced by more than tenfold, demonstrating that pyrenes at the periphery efficiently channel the absorbed energy to the luminescent Au22 at the center. A combination of femtosecond transient absorption and anisotropy measurements of Au22 -PyB18 explicitly reveals three main decay components of 220 fs, 3.5ps, and 160ps that can be assigned to energy migration between pyrenes and energy transfer processes from pyrene monomer and excimer to the central Au22 , respectively.

High-Throughput Fluorescence Lifetime-Based Screen Detects Compounds that Bind to Myosin-Binding Protein C and Modulate Interactions with Actin

Mutations in cardiac myosin-binding protein C (cMyBP-C) are a leading cause of hypertrophic cardiomyopathy (HCM) leading to heart failure. cMyBP-C is a potential target to treat HCM-related heart failure, and there are currently no drugs available to treat this disorder. cMyBP-C is naturally regulated by phosphorylation, resulting in reduced actin binding, and phosphorylation may be cardioprotective. Therefore, compounds that bind to cMyBP-C, reducing its interaction with F-actin and mimicking phosphorylation would be highly desirable to treat cMyBP-C-associated HCM. We developed a novel high-throughput screening (HTS) fluorescence lifetime-based assay to detect small-molecule modulators of actin-cMyBP-C binding. We attached a fluorescent dye, Alexa Fluor 568 (AF), to actin at Cys374 near its cMyBP-C binding site. When combined with human cMyBP-C N-terminal fragment (C0-C2), the fluorescence lifetime of AF-actin decreases. Phosphorylation of C0-C2 increases the lifetime of AF, indicating reduced binding. Our screen was for molecules that bind C0-C2 and mimic phosphorylation effects. Screening of a 1,280-compound small-molecule library identified 3 compounds (hits) showing significant effects in the micromolar range. These hits altered the lifetime of the AF-actin-cMyBP-C complex, but not AF-actin, in a dose-dependent manner. Binding of the compounds to cMyBP-C, but not actin, was also confirmed by isothermal titration calorimetry and transient phosphorescence anisotropy. Detailed analysis of the effects of these molecules on lifetime changes and F-actin binding, measured by a cosedimentation assay, suggest that in binding to C0-C2 the change in lifetime of AF-actin is caused by factors other than reducing binding, as seen by C0-C2 phosphorylation. We conclude that this HTS assay permits detection of compounds that bind C0-C2 when bound to actin, and sets the stage for screening larger compound libraries for modulators of the actin-cMyBP-C interaction.

Effect of single electrons on the excited state dynamics of rod-shaped Au25 nanoclusters.

The excited state dynamics of small-sized metal nanoclusters are dependent on their crystal structures, while the effect of the charge state remains largely unknown. Here, we report the influence of single electrons on the excited-state dynamics of non-superatom Au clusters by comparing the transient absorption isotropy and anisotropy dynamics of two rod-shaped Au25 nanoclusters protected by organic ligands. Two decay lifetimes (0.9 ps and 2.3 μs) can be identified in the excited state relaxation of Au252+ rods, which are assigned to the internal conversion from a higher to lower excited state and the relaxation to the ground state, respectively. With the addition of one electron, an additional 660 ps decay is observed in Au25+, which should originate from the presence of a single electron occupied molecular orbital. Transient anisotropy measurements reveal a 500 ps rotational diffusion process in both the nanoclusters, while the initial dipole moment orientation is found to be highly dependent on the charge state. These results are of importance to understanding the effect of the charge state on the optical properties of metal nanoclusters.

Deterministic control of an antiferromagnetic spin arrangement using ultrafast optical excitation

A central prospect of antiferromagnetic spintronics is to exploit magnetic properties that are unavailable with ferromagnets. However, this poses the challenge of accessing such properties for readout and control. To this end, light-induced manipulation of the transient ground state, e.g. by changing the magnetic anisotropy potential, opens promising pathways towards ultrafast deterministic control of antiferromagnetism. Here, we use this approach to trigger a coherent rotation of the entire long-range antiferromagnetic spin arrangement about a crystalline axis in GdRh2Si2 and demonstrate deterministic control of this rotation. Our observations can be explained by a laser-induced shift of the direction of the Gd spins’ local magnetic anisotropy, and allow for a quantitative description of the transient magnetic anisotropy potential.

Programmable Reversible Shape Transformation of Hydrogels Based on Transient Structural Anisotropy.

Stimuli-responsive shape-transforming hydrogels have shown great potential toward various engineering applications including soft robotics and microfluidics. Despite significant progress in designing hydrogels with ever more sophisticated shape-morphing behaviors, an ultimate goal yet to be fulfilled is programmable reversible shape transformation. It is reported here that transient structural anisotropy can be programmed into copolymer hydrogels of N-isopropylacrylamide and stearyl acrylate. Structural anisotropy arises from the deformed hydrophobic domains of the stearyl groups after thermomechanical programming, which serves as a template for the reversible globule-to-coil transition of the poly(N-isopropylacrylamide) chains. The structural anisotropy is transient and can be erased upon cooling. This allows repeated programming for reversible shape transformation, an unknown feature for the current hydrogels. The programmable reversible transformation is expected to greatly extend the technical scope for hydrogel-based devices.

Strong Anisotropy in Liquid Water upon Librational Excitation Using Terahertz Laser Fields.

Tracking the excitation of water molecules in the homogeneous liquid is challenging due to the ultrafast dissipation of rotational excitation energy through the hydrogen-bonded network. Here we demonstrate strong transient anisotropy of liquid water through librational excitation using single-color pump-probe experiments at 12.3 THz. We deduce a third-order response of χ3 exceeding previously reported values in the optical range by 3 orders of magnitude. Using a theory that replaces the nonlinear response with a material property amenable to molecular dynamics simulation, we show that the rotationally damped motion of water molecules in the librational band is resonantly driven at this frequency, which could explain the enhancement of the anisotropy in the liquid by the external terahertz field. By addition of salt (MgSO4), the hydration water is instead dominated by the local electric field of the ions, resulting in reduction of water molecules that can be dynamically perturbed by THz pulses.

Human cardiac myosin–binding protein C restricts actin structural dynamics in a cooperative and phosphorylation-sensitive manner

Cardiac myosin–binding protein C (cMyBP-C) is a thick filament-associated protein that influences actin-myosin interactions. cMyBP-C alters myofilament structure and contractile properties in a protein kinase A (PKA) phosphorylation-dependent manner. To determine the effects of cMyBP-C and its phosphorylation on the microsecond rotational dynamics of actin filaments, we attached a phosphorescent probe to F-actin at Cys-374 and performed transient phosphorescence anisotropy (TPA) experiments. Binding of cMyBP-C N-terminal domains (C0–C2) to labeled F-actin reduced rotational flexibility by 20–25°, indicated by increased final anisotropy of the TPA decay. The effects of C0–C2 on actin TPA were highly cooperative (n = ∼8), suggesting that the cMyBP-C N terminus impacts the rotational dynamics of actin spanning seven monomers (i.e. the length of tropomyosin). PKA-mediated phosphorylation of C0–C2 eliminated the cooperative effects on actin flexibility and modestly increased actin rotational rates. Effects of Ser to Asp phosphomimetic substitutions in the M-domain of C0–C2 on actin dynamics only partially recapitulated the phosphorylation effects. C0–C1 (lacking M-domain/C2) similarly exhibited reduced cooperativity, but not as reduced as by phosphorylated C0–C2. These results suggest an important regulatory role of the M-domain in cMyBP-C effects on actin structural dynamics. In contrast, phosphomimetic substitution of the glycogen synthase kinase (GSK3β) site in the Pro/Ala-rich linker of C0–C2 did not significantly affect the TPA results. We conclude that cMyBP-C binding and PKA-mediated phosphorylation can modulate actin dynamics. We propose that these N-terminal cMyBP-C–induced changes in actin dynamics help explain the functional effects of cMyBP-C phosphorylation on actin-myosin interactions.

Analysis of Transient Flow to an Extended Fully Penetrating Well at Constant-Head Pumping.

Vertical wells with radial extension at the well bottom can improve the rate of water production. No study has yet investigated the effects of the transient state and anisotropy in directional hydraulic conductivities on the wellbore flux rate for this type of well. This study derives a semianalytical transient drawdown solution for constant-head pumping at a fully penetrating well radially extended at the bottom of a confined, anisotropic aquifer by applying Laplace transform and separation of variables as well as conducting a Fourier analysis. The results of this new solution indicate that transient and steady-state wellbore flux rates can be increased by a factor of two for greater radial extension of the well. Compared with an isotropic aquifer (a ratio of vertical and horizontal hydraulic conductivities equal to one), an anisotropic aquifer with the ratio less than one may produce a higher transient wellbore flux rate and lower steady-state wellbore flux rate. Moreover, the time required to achieve the steady-state wellbore flux rate can be substantially affected by anisotropy of the aquifer.

High-throughput screen, using time-resolved FRET, yields actin-binding compounds that modulate actin–myosin structure and function

We have used a novel time-resolved FRET (TR-FRET) assay to detect small-molecule modulators of actin-myosin structure and function. Actin-myosin interactions play crucial roles in the generation of cellular force and movement. Numerous mutations and post-translational modifications of actin or myosin disrupt muscle function and cause life-threatening syndromes. Here, we used a FRET biosensor to identify modulators that bind to the actin-myosin interface and alter the structural dynamics of this complex. We attached a fluorescent donor to actin at Cys-374 and a nonfluorescent acceptor to a peptide containing the 12 N-terminal amino acids of the long isoform of skeletal muscle myosin's essential light chain. The binding site on actin of this acceptor-labeled peptide (ANT) overlaps with that of myosin, as indicated by (a) a similar distance observed in the actin-ANT complex as in the actin-myosin complex and (b) a significant decrease in actin-ANT FRET upon binding myosin. A high-throughput FRET screen of a small-molecule library (NCC, 727 compounds), using a unique fluorescence lifetime readout with unprecedented speed and precision, showed that FRET is significantly affected by 10 compounds in the micromolar range. Most of these "hits" alter actin-activated myosin ATPase and affect the microsecond dynamics of actin detected by transient phosphorescence anisotropy. We conclude that the actin-ANT TR-FRET assay enables detection of pharmacologically active compounds that affect actin structural dynamics and actomyosin function. This assay establishes feasibility for the discovery of allosteric modulators of the actin-myosin interaction, with the ultimate goal of developing therapies for muscle disorders.

Kinematic Model of Transient Shape-Induced Anisotropy in Dense Granular Flow.

Nonspherical particles are ubiquitous in nature and industry, yet previous theoretical models of granular media are mostly limited to systems of spherical particles. The problem is that in systems of nonspherical anisotropic particles, dynamic particle alignment critically affects their mechanical response. To study the tendency of such particles to align, we propose a simple kinematic model that relates the flow to the evolution of particle alignment with respect to each other. The validity of the proposed model is supported by comparison with particle-based simulations for various particle shapes ranging from elongated rice-like (prolate) to flattened lentil-like (oblate) particles. The model shows good agreement with the simulations for both steady-state and transient responses, and advances the development of comprehensive constitutive models for shape-anisotropic particles.

Behavior of a multilayered transversely isotropic half space due to horizontal transient loadings

Soils and the related structures are deeply influenced by horizontal transient loadings, such as the wind loads and the seismic forces on tall buildings, and the wave forces on offshore structures. So the stresses and displacements caused by horizontal transient loadings are worthy of study. This paper investigates the behavior of a multilayered transversely isotropic half space due to horizontal transient loadings over a circular area by using the analytical layer-element method. Numerical examples are given to make comparisons with ABAQUS and to expound the effect of transient loading characteristic, material anisotropy and loading depth on the behavior of media.