Intermediate-range order governs dynamics in dense colloidal liquids.

The conventional wisdom is that liquids are completely disordered and lack nontrivial structure beyond nearest-neighbor distances. Recent observations have upended this view and demonstrated that the microstructure in liquids is surprisingly rich and plays a critical role in numerous physical, biological, and industrial processes. However, approaches to uncover this structure are either system-specific or yield results that are not physically intuitive. Here, through single-particle resolved three-dimensional confocal microscope imaging and the use of a recently introduced four-point correlation function, we show that bidisperse colloidal liquids have a highly nontrivial structure comprising alternating layers with icosahedral and dodecahedral order, which extends well beyond nearest-neighbor distances and grows with supercooling. By quantifying the dynamics of the system on the particle level, we establish that it is this intermediate-range order, and not the short-range order, which has a one-to-one correlation with dynamical heterogeneities, a property directly related to the relaxation dynamics of glassy liquids. Our experimental findings provide a direct and much sought-after link between the structure and dynamics of liquids and pave the way for probing the consequences of this intermediate-range order in other liquid state processes.

Observation of two-step melting on a sphere.

Melting in two-dimensional flat space is typically two-step and via the hexatic phase. How melting proceeds on a curved surface, however, is not known. Topology mandates that crystalline particle assemblies on these surfaces harbor a finite density of defects, which itself can be ordered, like the icosahedral ordering of 5-coordinated disclination defects on a sphere. Thus, melting even on a sphere, the simplest closed surface, involves the loss of both crystalline and defect order. Probing the interplay of these two forms of order, however, requires a system in which melting can be performed in situ, and this has not been achieved hitherto. Here, by tuning interparticle interactions in situ, we report an observation of an intermediate hexatic phase during the melting of colloidal crystals on a sphere. Remarkably, we observed a precipitous drop in icosahedral defect order in the hexatic phase where the shear modulus is expected to vanish. Furthermore, unlike in flat space, where disorder can fundamentally alter the nature of the melting process, on the sphere, we observed the signature characteristics of ideal melting. Our findings have profound implications for understanding, for instance, the self-assembly and maturation dynamics of viral capsids and also phase transitions on curved surfaces.

Harnessing Viscoelasticity to Suppress Irreversibility Buildup in a Colloidal Stirling Engine.

Typically, the rate at which a heat engine can produce useful work is constrained by the buildup of irreversibility with increasing operating speed. Here, using a recently developed reservoir engineering technique, we designed and quantified the performance of a colloidal Stirling engine operating in a viscoelastic bath. While the bath acts like a viscous fluid in the quasistatic limit, and the engine's performance agrees with equilibrium predictions, on reducing the cycle time to the bath's structural relaxation time, the increasingly elastic response of the bath aids suppress the buildup of irreversibility. We show that the elastic energy stored during the isothermal compression step of the Stirling cycle facilitates quick equilibration in the isothermal expansion step. This results in equilibriumlike efficiencies even for cycle times shorter than the equilibration time of the colloidal particle.

Motile Topological Defects Hinder Dynamical Arrest in Dense Liquids of Active Ellipsoids.

Recent numerical studies have identified the persistence time of active motion as a critical parameter governing glassy dynamics in dense active matter. Here we studied dynamics in liquids of granular active ellipsoids with tunable persistence and velocity. We show that increasing the persistence time at moderate supercooling is equivalent to increasing the strength of attraction in equilibrium liquids and results in reentrant dynamics not just in the translational degrees of freedom, as anticipated, but also in the orientational ones. However, at high densities, motile topological defects, unique to active liquids of elongated particles, hindered dynamical arrest. Most remarkably, for the highest activity, we observed intermittent dynamics due to the jamming-unjamming of these defects for the first time.

Synergistic action in colloidal heat engines coupled by non-conservative flows.

Colloidal heat engines are model systems to analyze mechanisms of transduction of heat to work at the mesoscale. While engines developed hitherto were realized using conservative potentials and operated in isolation, biological micromotors - their real counterparts - seldom perform under such simplifications. Here, we examine thermodynamics beyond such idealizations by constructing a pair of engines from two colloidal microspheres in optical traps at close separation. We demonstrate that at such proximity, non-conservative scattering forces that were hitherto neglected affect the particle motion. Hydrodynamics generated while dissipating these are hindered by the microsphere in the adjacent trap and energy that was otherwise rejected into the medium gets reused. Thus, despite being in contact with the same reservoir, the particles are driven out of equilibrium and can exchange energy, allowing cooperative behavior. Leveraging this in a manner analogous to microswimmers and active Brownian particles that utilize such flows to enhance propulsion, we construct two colloidal engines in close proximity. To estimate thermodynamic quantities, we develop a minimal model that is appropriate in the asymptotic limit and is similar to active Brownian particles. While complete theoretical frameworks to understand such scenarios remain to be developed, results based on our model demonstrate the intuitive idea that a pair of Stirling engines at close proximity outperform those that are well separated. Although these results explore the simplest case of two Stirling engines, the concepts unraveled could aid in designing larger collections akin to biological systems.

Shear jamming and fragility in fractal suspensions under confinement.

Under applied stress, the viscosity of many dense particulate suspensions increases drastically, a response known as discontinuous shear-thickening (DST). In some cases, the applied stress can even transform the suspension into a solid-like shear jammed state. Although shear jamming (SJ) has been probed for dense suspensions with particles having well-defined shapes, such a phenomenon for fractal objects has not been explored. Here, using rheology and in situ optical imaging, we study the flow behaviour of ultra-dilute fractal suspensions of multi-walled carbon nanotubes (MWCNT) under confinement. We show a direct transition from flowing to SJ state without a precursory DST in fractal suspensions at an onset volume fraction, ϕ ∼ 0.5%, significantly lower than that of conventional dense suspensions (ϕ ∼ 55%). The ultra-low concentration enables us to demonstrate the fragility and associated contact dynamics of the SJ state, which remain experimentally unexplored in suspensions. Furthermore, using a generalized Wyart-Cates model, we propose a generic phase diagram for fractal suspensions that captures the possibility of SJ without prior DST over a wide range of shear stress and volume fractions.

Structural origin of excitations in a colloidal glass-former.

Despite decades of intense research, whether the transformation of supercooled liquids into glass is a kinetic phenomenon or a thermodynamic phase transition remains unknown. Here, we analyzed optical microscopy experiments on 2D binary colloidal glass-forming liquids and investigated the structural links of a prominent kinetic theory of glass transition. We examined a possible structural origin for localized excitations, which are building blocks of the dynamical facilitation theory-a purely kinetic approach for the glass transition. To accomplish this, we utilize machine learning methods to identify a structural order parameter termed "softness" that has been found to be correlated with reorganization events in supercooled liquids. Both excitations and softness qualitatively capture the dynamical slowdown on approaching the glass transition and motivated us to explore spatial and temporal correlations between them. Our results show that excitations predominantly occur in regions with high softness and the appearance of these high softness regions precedes excitations, thus suggesting a causal connection between them. Thus, unifying dynamical and thermodynamical theories into a single structure-based framework may provide a route to understand the glass transition.

Shear-Induced Ordering of Nanopores and Instabilities in Concentrated Surfactant Mesh Phases.

Mixed surfactant systems with strongly bound counterions show many interesting phases such as the random mesh phase consisting of a disordered array of defects (water-filled nanopores in the bilayers). The present study addresses the non-equilibrium phase transition of the random mesh phase under shear to an ordered mesh phase with a high degree of coherence between nanopores in three dimensions. In situ small-angle synchrotron X-ray study under different shear stress conditions shows sharp Bragg peaks in the X-ray diffraction, successfully indexed to the rhombohedral lattice with R3̅m space group symmetry. The ordered mesh phase shows isomorphic twinning and buckling at higher shear stress. Our experimental studies bring out rich non-equilibrium phase transitions in concentrated cationic surfactant systems with strongly bound counterions hitherto not well explored and provide motivation for a quantitative understanding.

Anomalous thermopower oscillations in graphene-nanowire vertical heterostructures.

Thermoelectric measurements have the potential to uncover the density of states (DOSs) of low-dimensional materials. Here, we present the anomalous thermoelectric behavior of monolayer graphene-nanowire (NW) heterostructures, showing large oscillations as a function of the doping concentration. Our devices consist of InAs NW and graphene vertical heterostructures, which are electrically isolated by thin (∼10 nm) hexagonal boron nitride (hBN) layers. In contrast to conventional thermoelectric measurements, where a heater is placed on one side of a sample, we use the InAs NW (diameter ∼50 nm) as a local heater placed in the middle of the graphene channel. We measure the thermoelectric voltage induced in graphene due to Joule heating in the NW as a function of temperature (1.5-50 K) and carrier concentration. The thermoelectric voltage in bilayer graphene (BLG)-NW heterostructures shows sign change around the Dirac point, as predicted by Mott's formula. In contrast, the thermoelectric voltage measured across monolayer graphene (MLG)-NW heterostructures shows anomalous large-amplitude oscillations around the Dirac point, not seen in the Mott response derived from the electrical conductivity measured on the same device. The anomalous oscillations are a signature of the modified DOSs in MLG by the electrostatic potential of the NW, which is much weaker in the NW-BLG devices. Thermal calculations of the heterostructure stack show that the temperature gradient is dominant in the graphene region underneath the NW, and thus sensitive to the modified DOSs resulting in anomalous oscillations in the thermoelectric voltage. Furthermore, with the application of a magnetic field, we detect modifications in the DOSs due to the formation of Landau levels in both MLG and BLG.

Symmetry induced phonon renormalization in few layers of 2H-MoTe2 transistors: Raman and first-principles studies.

Understanding of electron-phonon coupling (EPC) in two-dimensional (2D) materials manifesting as phonon renormalization is essential to their possible applications in nanoelectronics. Here we report in situ Raman measurements of electrochemically top-gated 2, 3 and 7 layered 2H-MoTe2 channel based field-effect transistors. While the [Formula: see text] and B2g phonon modes exhibit frequency softening and linewidth broadening with hole doping concentration (p) up to ∼2.3 × 1013/cm2, A1g shows relatively small frequency hardening and linewidth sharpening. The dependence of frequency renormalization of the [Formula: see text] mode on the number of layers in these 2D crystals confirms that hole doping occurs primarily in the top two layers, in agreement with recent predictions. We present first-principles density functional theory analysis of bilayer MoTe2 that qualitatively captures our observations, and explain that a relatively stronger coupling of holes with [Formula: see text] or B2g modes as compared with the A1g mode originates from the in-plane orbital character and symmetry of the states at valence band maximum. The contrast between the manifestation of EPC in monolayer MoS2 and those observed here in a few-layered MoTe2 demonstrates the role of the symmetry of phonons and electronic states in determining the EPC in these isostructural systems.

Anomalous Coulomb Drag between InAs Nanowire and Graphene Heterostructures.

Correlated charge inhomogeneity breaks the electron-hole symmetry in two-dimensional (2D) bilayer heterostructures which is responsible for nonzero drag appearing at the charge neutrality point. Here we report Coulomb drag in novel drag systems consisting of a two-dimensional graphene and a one-dimensional (1D) InAs nanowire (NW) heterostructure exhibiting distinct results from 2D-2D heterostructures. For monolayer graphene (MLG)-NW heterostructures, we observe an unconventional drag resistance peak near the Dirac point due to the correlated interlayer charge puddles. The drag signal decreases monotonically with temperature (∼T^{-2}) and with the carrier density of NW (∼n_{N}^{-4}), but increases rapidly with magnetic field (∼B^{2}). These anomalous responses, together with the mismatched thermal conductivities of graphene and NWs, establish the energy drag as the responsible mechanism of Coulomb drag in MLG-NW devices. In contrast, for bilayer graphene (BLG)-NW devices the drag resistance reverses sign across the Dirac point and the magnitude of the drag signal decreases with the carrier density of the NW (∼n_{N}^{-1.5}), consistent with the momentum drag but remains almost constant with magnetic field and temperature. This deviation from the expected T^{2} arises due to the shift of the drag maximum on graphene carrier density. We also show that the Onsager reciprocity relation is observed for the BLG-NW devices but not for the MLG-NW devices. These Coulomb drag measurements in dimensionally mismatched (2D-1D) systems, hitherto not reported, will pave the future realization of correlated condensate states in novel systems.

Phases and excitations of active rod-bead mixtures: simulations and experiments.

We present a large-scale numerical study, supplemented by experimental observations, on a quasi-two-dimensional active system of polar rods and spherical beads confined between two horizontal plates and energised by vertical vibration. For a low rod concentration Φr, our observations are consistent with a direct phase transition, as bead concentration Φb is increased, from the isotropic phase to a homogeneous flock. For Φr above a threshold value, an ordered band dense in both rods and beads occurs between the disordered phase and the homogeneous flock, in both experiments and simulations. Within the size ranges accessible, we observe only a single band, whose width increases with Φr. Deep in the ordered state, we observe broken-symmetry "sound" modes and giant number fluctuations. The direction-dependent sound speeds and the scaling of fluctuations are consistent with the predictions of field theories of flocking; sound damping rates show departures from such theories, but the range of wavenumbers explored is modest. At very high densities, we see phase separation into rod-rich and bead-rich regions, both of which move coherently.

Strength of Mechanical Memories is Maximal at the Yield Point of a Soft Glass.

We show experimentally that both single and multiple mechanical memories can be encoded in an amorphous bubble raft, a prototypical soft glass, subject to an oscillatory strain. In line with recent numerical results, we find that multiple memories can be formed sans external noise. By systematically investigating memory formation for a range of training strain amplitudes spanning yield, we find clear signatures of memory even beyond yielding. Most strikingly, the extent to which the system recollects memory is largest for training amplitudes near the yield strain and is a direct consequence of the spatial extent over which the system reorganizes during the encoding process. Our study further suggests that the evolution of force networks on training plays a decisive role in memory formation in jammed packings.

Plasmon-induced efficient hot carrier generation in graphene on gold ultrathin film with periodic array of holes: Ultrafast pump-probe spectroscopy.

Using ultrafast pump-probe reflectivity with a 3.1 eV pump and coherent white light probe (1.1-2.6 eV), we show that graphene on gold nanostructures exhibits a strong coupling to the plasmonic resonances of the ordered lattice hole array, thus injecting a high density of hot carriers in graphene through plasmons. The system being studied is single-layer graphene on an ultrathin film of gold with periodic arrangements of holes showing anomalous transmission. A comparison is made with gold film with and without hole array. By selectively probing transient carrier dynamics in the spectral regions corresponding to plasmonic resonances, we show efficient plasmon induced hot carrier generation in graphene. We also show that due to high electromagnetic field intensities at the edge of the submicron holes, fast decay time (10-100 fs), and short decay length (1 nm) of plasmons, a highly confined density of hot carriers (very close to the edge of the holes) is generated by Landau damping of plasmons within the holey gold film. A contribution to transient decay dynamics due to the diffusion of the initial nonuniform distribution of hot carriers away from the hole edges is observed. Our results are important for future applications of novel hot carrier device concepts where hot carriers with tunable energy can be generated in different graphene regions connected seamlessly.

Site-specific colloidal crystal nucleation by template-enhanced particle transport.

The monomer surface mobility is the single most important parameter that decides the nucleation density and morphology of islands during thin-film growth. During template-assisted surface growth in particular, low surface mobilities can prevent monomers from reaching target sites and this results in a partial to complete loss of nucleation control. Whereas in atomic systems a broad range of surface mobilities can be readily accessed, for colloids, owing to their large size, this window is substantially narrow and therefore imposes severe restrictions in extending template-assisted growth techniques to steer their self-assembly. Here, we circumvented this fundamental limitation by designing templates with spatially varying feature sizes, in this case moiré patterns, which in the presence of short-range depletion attraction presented surface energy gradients for the diffusing colloids. The templates serve a dual purpose: first, directing the particles to target sites by enhancing their surface mean-free paths and second, dictating the size and symmetry of the growing crystallites. Using optical microscopy, we directly followed the nucleation and growth kinetics of colloidal islands on these surfaces at the single-particle level. We demonstrate nucleation control, with high fidelity, in a regime that has remained unaccessed in theoretical, numerical, and experimental studies on atoms and molecules as well. Our findings pave the way for fabricating nontrivial surface architectures composed of complex colloids and nanoparticles as well.

Dynamical facilitation governs glassy dynamics in suspensions of colloidal ellipsoids.

One of the greatest challenges in contemporary condensed matter physics is to ascertain whether the formation of glasses from liquids is fundamentally thermodynamic or dynamic in origin. Although the thermodynamic paradigm has dominated theoretical research for decades, the purely kinetic perspective of the dynamical facilitation (DF) theory has attained prominence in recent times. In particular, recent experiments and simulations have highlighted the importance of facilitation using simple model systems composed of spherical particles. However, an overwhelming majority of liquids possess anisotropy in particle shape and interactions, and it is therefore imperative to examine facilitation in complex glass formers. Here, we apply the DF theory to systems with orientational degrees of freedom as well as anisotropic attractive interactions. By analyzing data from experiments on colloidal ellipsoids, we show that facilitation plays a pivotal role in translational as well as orientational relaxation. Furthermore, we demonstrate that the introduction of attractive interactions leads to spatial decoupling of translational and rotational facilitation, which subsequently results in the decoupling of dynamical heterogeneities. Most strikingly, the DF theory can predict the existence of reentrant glass transitions based on the statistics of localized dynamical events, called excitations, whose duration is substantially smaller than the structural relaxation time. Our findings pave the way for systematically testing the DF approach in complex glass formers and also establish the significance of facilitation in governing structural relaxation in supercooled liquids.

Occult metabolic bone disease in chronic pancreatitis.

BACKGROUND: Chronic pancreatitis (CP) leads to malabsorption and metabolic bone disease (MBD). Alcoholic CP (ACP) and tropical CP (TCP) are the two common types of CP. OBJECTIVE: We investigated the presence of occult MBD in patients with CP and compared the same between ACP and TCP. MATERIALS AND METHODS: In this cross-sectional, observational study, we included serial patients of CP in different stages and are grouped as ACP (Group 1; n = 67) and TCP (Group 2; n = 35). We determined serum calcium, phosphorus, alkaline phosphatase, 25-hydroxyvitamin D (25OHD), and intact parathyroid hormone (PTH) levels. Bone mineral density (BMD) was measured by dual-energy X-ray absorptiometry in the neck of the left femur. MBD was defined by the presence of either low bone mass (Z-score Results: The study participants (85 males; 17 females) had a mean age of 40.8 ± 12.6 years, CP duration of 3.7 ± 4.7 years, and Body Mass Index of 22.5 ± 3.2 kg/m2. A total of 37 (36%) patients had MBD (osteomalacia in 31 and low bone mass in 6). The frequency of MBD was same in the TCP (16/35) and ACP (21/65) groups (P = 0.1940). Elevated PTH (>70 pg/mL) was seen in 14 patients with 25OHD deficiency and low calcium (<8.5 mg/dL) in 29 patients. BMD did not show a significant correlation with the duration of CP. CONCLUSION: Occult MBD is seen in a third of patients with CP and is similar irrespective of the etiology. The disease is silent and mandates active screening in all susceptible individuals.

Enhanced strain and temperature sensing by reduced graphene oxide coated etched fiber Bragg gratings.

This Letter reports on an etched fiber Bragg grating (eFBG) sensor coated with reduced graphene oxide (RGO) having enhanced sensitivity for physical parameters such as strain and temperature. The synergetic effect of the changes in grating pitch and refractive index of RGO with change in temperature or strain enhances the shift in Bragg wavelength (λB). The RGO-coated eFBG sensors exhibit a strain sensitivity of 5.5 pm/µÏµ (∼5 times that of bare fiber Bragg gratings) and temperature sensitivity of 33 pm/°C (∼3 times that of bare fiber Bragg gratings). The resolutions of ∼1 µÏµ and ∼0.3°C have been obtained for strain and temperature respectively, using RGO-coated eFBG sensors.

Localized Excitations and the Morphology of Cooperatively Rearranging Regions in a Colloidal Glass-Forming Liquid.

We develop a scheme based on a real space microscopic analysis of particle dynamics to ascertain the relevance of dynamical facilitation as a mechanism of structural relaxation in glass-forming liquids. By analyzing the spatial organization of localized excitations within clusters of mobile particles in a colloidal glass former and examining their partitioning into shell-like and corelike regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a collective activated hopping-dominated one close to the glass transition. This crossover occurs in the vicinity of the area fraction at which the peak of the mobility transfer function exhibits a maximum and the morphology of cooperatively rearranging regions changes from stringlike to a compact form. Collectively, our findings suggest that dynamical facilitation is dominated by collective hopping close to the glass transition, thereby constituting a crucial step towards identifying the correct theoretical scenario for glass formation.

Reversible shear-induced crystallization above equilibrium freezing temperature in a lyotropic surfactant system.

We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature (T(K)°) in weakly swollen isotropic (Li) and lamellar (La) mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase Lc melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below T(K)°, which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the Li phase to an La phase induced by shear flow, before the nucleation of the Lc phase. Shear diagram of the Li phase constructed in the parameter space of shear rate (γ) vs. temperature exhibits Li → Lc and Li → La transitions above the equilibrium crystallization temperature T(K)°, in addition to the irreversible shear-driven nucleation of Lc in the Li phase below T(K)°. In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems.