Non‐Equilibrium Assembly of Light‐Activated Colloidal Mixtures

The collective phenomena exhibited by artificial active matter systems present novel routes to fabricating out‐of‐equilibrium microscale assemblies. Here, the crystallization of passive silica colloids into well‐controlled 2D assemblies is shown, which is directed by a small number of self‐propelled active colloids. The active colloids are titania–silica Janus particles that are propelled when illuminated by UV light. The strength of the attractive interaction and thus the extent of the assembled clusters can be regulated by the light intensity. A remarkably small number of the active colloids is sufficient to induce the assembly of the dynamic crystals. The approach produces rationally designed colloidal clusters and crystals with controllable sizes, shapes, and symmetries. This multicomponent active matter system offers the possibility of obtaining structures and assemblies that cannot be found in equilibrium systems.     

Photoactive and Intrinsically Fuel Sensing Metal–Organic Framework Motors for Tailoring Collective Behaviors of Active-Passive Colloids

Microorganisms display nonequilibrium predator–prey behaviors, such as chasing–escaping and schooling via chemotactic interactions. Even though artificial systems have revealed such biomimetic behaviors, switching between them by control over chemotactic interactions is rare. Here, a spindle-like iron-based metal–organic framework (MOF) colloidal motor which self-propels in glucose and H₂O₂, triggered by UV light is reported. These motors display intrinsic UV light-triggered fuel-dependent chemotactic interactions, which are used to tailor the collective dynamics of active-passive colloidal mixtures. In particular, the mixtures of active MOF motors with passive colloids exhibit distinctive “chasing–escaping” or “schooling” behaviors, depending on glucose or hydrogen peroxide being used as the fuel. The transition in the collective behaviors is attributed to an alteration in the sign of ionic diffusiophoretic interactions, resulting from a change in the ionic clouds produced. This study offers a new strategy on tuning the communication between active and passive colloids, which holds substantial potentials for fundamental research in active matter and practical applications in cargo delivery, chemical sensing, and particle segregation.     

From individual to collective chirality in metal nanoparticles

Recent reports have illustrated the promising potential of chiral metal nanostructures, which exploit the characteristic localized surface plasmon resonance of metal colloids, to produce intense optical activity. In this article we review the concepts, synthetic methods, and theoretical predictions underlying the chirality of metal colloids with a particular emphasis on the size range of 10–100 nanometers. The formation of individual colloidal nanoparticles with a chiral morphology and a plasmonic response remains elusive; however, collective chirality and the associated optical activity in nanoparticle assemblies is a promising alternative that has seen a few recent experimental demonstrations. We conclude with a perspective on chiral nanostructures built up from achiral anisotropic metal particles.     

Chemical Nanomotors at the Gram Scale Form a Dense Active Optorheological Medium

The rheological properties of a colloidal suspension are a function of the concentration of the colloids and their interactions. While suspensions of passive colloids are well studied and have been shown to form crystals, gels, and glasses, examples of energy‐consuming “active” colloidal suspensions are still largely unexplored. Active suspensions of biological matter, such as motile bacteria or dense mixtures of active actin–motor–protein mixtures have, respectively, reveals superfluid‐like and gel‐like states. Attractive inanimate systems for active matter are chemically self‐propelled particles. It has so far been challenging to use these swimming particles at high enough densities to affect the bulk material properties of the suspension. Here, it is shown that light‐triggered asymmetric titanium dioxide that self‐propel, can be obtained in large quantities, and self‐organize to make a gram‐scale active medium. The suspension shows an activity‐dependent tenfold reversible change in its bulk viscosity.     

Hysteretic dynamics of active particles in a periodic orienting field

Active motion of living organisms and artificial self-propelling particles has been an area of intense research at the interface of biology, chemistry and physics. Significant progress in understanding these phenomena has been related to the observation that dynamic self-organization in active systems has much in common with ordering in equilibrium condensed matter such as spontaneous magnetization in ferromagnets. The velocities of active particles may behave similar to magnetic dipoles and develop global alignment, although interactions between the individuals might be completely different. In this work, we show that the dynamics of active particles in external fields can also be described in a way that resembles equilibrium condensed matter. It follows simple general laws, which are independent of the microscopic details of the system. The dynamics is revealed through hysteresis of the mean velocity of active particles subjected to a periodic orienting field. The hysteresis is measured in computer simulations and experiments on unicellular organisms. We find that the ability of the particles to follow the field scales with the ratio of the field variation period to the particles'' orientational relaxation time, which, in turn, is related to the particle self-propulsion power and the energy dissipation rate. The collective behaviour of the particles due to aligning interactions manifests itself at low frequencies via increased persistence of the swarm motion when compared with motion of an individual. By contrast, at high field frequencies, the active group fails to develop the alignment and tends to behave like a set of independent individuals even in the presence of interactions. We also report on asymptotic laws for the hysteretic dynamics of active particles, which resemble those in magnetic systems. The generality of the assumptions in the underlying model suggests that the observed laws might apply to a variety of dynamic phenomena from the motion of synthetic active particles to crowd or opinion dynamics.     

Direct simulation of flowing colloidal dispersions by smoothed profile method

We developed a simulation scheme to predict the dynamic behavior of colloidal dispersion called “smoothed profile (SP) method”. SP method provides a coupling scheme between continuum fluid dynamics and rigid-body dynamics through smoothed profile of colloidal particles. Moreover, SP method can incorporate multi-component fluids, such systems as charged colloids in electrolyte solutions. Numerical results which assess hydrodynamic interactions of colloidal dispersions are presented to validate SP method. Application of SP method is not restricted to a Newtonian solvent, but any constitutive model can be handled. Henceforth, it can be suitable to treat colloidal dispersions in complex fluids where solvent-mediated interaction dominate dynamical behaviors of colloids.     

Au@pNIPAM SERRS Tags for Multiplex Immunophenotyping Cellular Receptors and Imaging Tumor Cells

Detection technologies employing optically encoded particles have gained much interest toward clinical diagnostics and drug discovery, but the portfolio of available systems is still limited. The fabrication and characterization of highly stable surface‐enhanced resonance Raman scattering (SERRS)‐encoded colloids for the identification and imaging of proteins expressed in cells are reported. These plasmonic nanostructures are made of gold octahedra coated with poly(N‐isopropylacrylamide) microgels and can be readily encoded with Raman active dyes while retaining high colloidal stability in biofluids. A layer‐by‐layer polyelectrolyte coating is used to seal the outer surface of the encoded particles and to provide a reactive surface for covalent conjugation with antibodies. The targeted multiplexing capabilities of the SERRS tags are demonstrated by the simultaneous detection and imaging of three tumor‐associated surface biomarkers: epidermal growth factor receptor (EGFR), epithelial cell adhesion molecule (EpCAM), and homing cell adhesion molecule (CD44) by SERRS spectroscopy. The plasmonic microgels are able to discriminate tumor A431 (EGFR+/EpCAM+/CD44+) and nontumor 3T3 2.2 (EGFR?/EpCAM?/CD44+) cells while cocultured in vitro.     

Theory ofT 2 heat capacities of monolayer helium films

Heat capacities of adsorbed monolayers of He³and He⁴indicate that the dominant thermal excitations at low temperatures are phonons rather than single-particle modes when the films are near maximum density. A recent theoretical study of noninteracting particles adsorbed on a crystalline substrate yielded a two-dimensional band structure, and explored the thermodynamic properties of the single-particle modes. The theory is now extended to include the influence of hard-core interactions between the particles moving in the lowest band. Resembling the high-density approximations for liquid and solid helium, the hard-core interactions are shown to give rise to a collective zero-point kinetic energy from which a two-dimensional pressure and a compressibility are derived. The corresponding velocity of sound and phonon heat capacity are calculated in the weak-binding and tight-binding approximations. Comparison with experiment indicates that the weak-binding approximation is more appropriate and that it yields effective mass ratiosm*/m1.7 for the two isotopes at the experimental film densities. A novel feature of the tight-binding calculation that may be applicable to other experimental systems is the prediction of phase condensation for adsorbed gases of relatively small molecular diameter.Research supported by the National Science Foundation.     

Correction for particle-wall interactions in the separation of colloids by flow field-flow fractionation

In the characterization of materials by field-flow fractionation (FFF), the experienced analyst understands the importance of incorporating additives in the carrier liquid that minimize or eliminate interactions between the analyte and accumulation wall, particularly in aqueous systems. However, as FFF is applied to more difficult samples, such as those with high surface energies, it is increasingly difficult to find additives that completely eliminate particle-wall interactions. Furthermore, the analyst may wish to use specific conditions that preserve the high surface energy of particles, to study their interaction with other materials through their behavior in the FFF channel. With this in mind, Williams and co-workers developed a model that quantifies the effect of particle-wall interactions in FFF using an empirically determined interaction parameter. In this work, the model is evaluated for the application of flow FFF in carrier liquids of low ionic strength, where particle-wall interactions are magnified. The retention of particles ranging in size from 64 to 1000 nm is measured using a wide range of field strengths and retention levels. The model is found to be generally valid over the entire range, except for minor discrepancies at lower levels of retention. Although retention levels are dramatically affected by particle-wall interactions, the point of steric inversion (500 nm), where the size-based elution order reverses, is not affected. When particle-wall interactions are not accounted for, they lead to a bias in particle sizes calculated from standard retention theory of up to 70%. The model can also be used to refine the measurement of channel thickness, which is important for the accurate conversion of retention parameters to particle sizes. In this work, for example, errors in channel thickness led to systematic errors on the order of 10% in particle diameter.     

Fabrication of Patchy Silica Microspheres with Tailor-Made Patch Functionality using Photo-Iniferter Reversible-Addition-Fragmentation Chain-Transfer (PI-RAFT) Polymerization (Small 43/2023)

Their inherent directional information renders patchy particles interesting building blocks for advanced applications in materials science. In this study, a feasible method to fabricate patchy silicon dioxide microspheres is demonstrated, which they are able to equip with tailor-made polymeric materials as patches. Their fabrication method relies on a solid-state supported microcontact printing (µCP) routine optimized for the transfer of functional groups to capillary-active substrates, which is used to introduce amino functionalities as patches to a monolayer of particles. Acting as anchor groups for polymerization, photo-iniferter reversible addition-fragmentation chain-transfer (RAFT) is used to graft polymer from the patch areas. Accordingly, particles with poly(N-acryloyl morpholine), poly(N-isopropyl acrylamide), and poly(n-butyl acrylate) are prepared as representative acrylic acid-derived functional patch materials. To facilitate their handling in water, a passivation strategy of the particles for aqueous systems is introduced. The protocol introduced here, therefore, promises a vast degree of freedom in engineering the surface properties of highly functional patchy particles. This feature is unmatched by other techniques to fabricate anisotropic colloids. The method, thus, can be considered a platform technology, culminating in the fabrication of particles that possess locally precisely formed patches on particles at a low µm scale with a high material functionality.     

Collective modes and a theory of response ofd-wave superconductors

We present a theory of the response ofd-wave superconductors to weak applied fields, by taking account of the Coulomb interaction and all the collective degrees of freedom as well as crystal symmetry. We choose two representative phases: the d phase, which has point nodes in the energy gap, and theY _2–1 phase, which has line as well as point nodes. The former is a self-consistent solution for cubic as well as spherical symmetries and the latter is one for spherical, cubic, and hexagonal symmetries. We obtain obviously gauge-invariant expressions for the order-parameter fluctuations and the currents, having forms common not only to thed-wave states, but also to thep-wave states studied earlier. We also investigate the collective excitations; in the long-wavelength limit for spherically symmetric systems, there are, on the frequency-temperature plane, seven branches for eachd-wave phase considered, in addition to the common plasma mode and orbital Goldstone modes resulting from the spontaneous breakdown of the rotational invariance. In theY _2–1-phase two eigenmodes are found to become gapless at a finite temperature, below which they are purely imaginary. This implies instability of the phase. The effect of crystal anisotropy on the collective spectra is also studied.A preliminary report on the present work was published inJpn. J. Appl. Phys. Suppl. 26-3, 167 (1987).     

Phase transitions, soft modes, and critical fluctuations

This paper gives an introductory review of the field of phase transitions. The first part contains a general discussion of the dynamical mechanism of phase transitions. The interactions between the particles are shown to yield a feedback effect in the collective response of the system to small external perturbations. This feedback provides the mechanism which can give rise to instabilities for certain critical values of the external parameters. It is pointed out how the static aspects of the instability (characterized by a singularity in the static response function) are intimately related to dynamic aspects, namely the occurrence of soft collective modes and of critical fluctuations. In the second part, the general picture is illustrated by a number of specific examples. Experimental results on soft mode behavior and critical fluctuations are shown for ferromagnetic, antiferromagnetic, ferroelectric, and structural phase transitions. It is further demonstrated that the existence of critical fluctuations near a phase transition gives rise to anomalous behavior of various physical properties of the system. Finally, some problems are indicated which arise in connection with instabilities occurring in nonequilibrium systems.     

Phase separation and charge density waves: Possible sources of non-Fermi liquid behavior and pairing in high-temperature superconductors

In the absence of a sufficiently singular interaction between the particles, the Fermi-liquid state is stable above one dimension. To reconcile this finding with the observed anomalies in the cuprates one is therefore led to the search for mechanisms giving singular interactions. A recent proposal indicates the cuprates as being close to a charge instability, which would drive the system toward phase separation (in the absence of long-range Coulomb forces between the carriers) or toward the formation of incommensurate charge-density waves in the more physical case of charged carriers. Close to these instabilities strong singular and attractive scattering arises between the quasiparticles at the Fermi surface. This scattering would easily account for both the anomalous behavior of the normal metallic phase and for the strong pairing mechanism leading to high-temperature superconductivity. The strong momentum dependence of the singular attraction would also give rise to the (likely) observed unusuald-wave symmetry of the superconducting order parameter in these systems.     

Lubrication mechanisms of hollow-core inorganic fullerene-like nanoparticles: coupling experimental and computational works

Inorganic fullerene-like (IF) nanoparticles made of metal dichalcogenides have previously been recognized to be good friction modifiers and anti-wear additives under boundary lubrication conditions. The tribological performance of these particles appears to be a result of their size, structure and morphology, along with the test conditions. However, the very small scale of the IF nanoparticles makes distinguishing the properties which affect the lubrication mechanism exceedingly difficult. In this work, a high resolution transmission electron microscope equipped with a nanoindentation holder is used to manipulate individual hollow IF-WS(2) nanoparticles and to investigate their responses to compression. Additional atomistic molecular dynamics (MD) simulations of similarly structured, individual hollow IF-MoS(2) nanoparticles are performed for compression studies between molybdenum surfaces on their major and minor axis diameters. MD simulations of these structures allows for characterization of the influence of structural orientation on the mechanical behavior and nano-sheet exfoliation of hollow-core IF nanoparticles. The experimental and theoretical results for these similar nanoparticles are qualitatively compared.     

Observation of empty liquids and equilibrium gels in a colloidal clay

The relevance of anisotropic interactions in colloidal systems has recently emerged in the context of the rational design of new soft materials. Patchy colloids of different shapes, patterns and functionalities are considered the new building blocks of a bottom-up approach toward the realization of self-assembled bulk materials with predefined properties. The ability to tune the interaction anisotropy will make it possible to recreate molecular structures at the nano- and micro-scales (a case with tremendous technological applications), as well as to generate new unconventional phases, both ordered and disordered. Recent theoretical studies suggest that the phase diagram of patchy colloids can be significantly altered by limiting the particle coordination number (that is, valence). New concepts such as empty liquids—liquid states with vanishing density—and equilibrium gels—arrested networks of bonded particles, which do not require an underlying phase separation to form—have been formulated. Yet no experimental evidence of these predictions has been provided. Here we report the first observation of empty liquids and equilibrium gels in a complex colloidal clay, and support the experimental findings with numerical simulations.     

Moving Frontiers in Transition Metal Catalysis: Synthesis,Characterization and Modeling

Nanosized transition metal particles are important materials in catalysis with a key role not only in academic research but also in many processes with industrial and societal relevance. Although small improvements in catalytic properties can lead to significant economic and environmental impacts, it is only now that knowledge‐based design of such materials is emerging, partly because the understanding of catalytic mechanisms on nanoparticle surfaces is increasingly improving. A knowledge‐based design requires bottom‐up synthesis of well‐defined model catalysts, an understanding of the catalytic nanomaterials “at work” (operando), and both a detailed understanding and a prediction by theoretical methods. This article reports on progress in colloidal synthesis of transition metal nanoparticles for preparation of model catalysts to close the materials gap between the discoveries of fundamental surface science and industrial application. The transition metal particles, however, often undergo extensive transformations when applied to the catalytic process and much progress has recently been achieved operando characterization techniques under relevant reaction conditions. They allow better understanding of size/structure–activity correlations in these systems. Moreover, the growth of computing power and the improvement of theoretical methods uncover mechanisms on nanoparticles and have recently predicted highly active particles for CO/CO₂ hydrogenation or direct H₂O₂ synthesis.     

The collective excitations of the order parameter in HTSC and heavy fermion superconductors (HFSC) underD-pairing

Within the path integral model ofd-pairing for HTSC and HFSC developed recently by P. N. Brusov and N. P. Brusova¹, the whole collective mode spectrum has been calculated for the first time for five states of HTSC that arise in their symmetry classification as well as for three states of HFSC. For HTSC the calculations have been made for the state which is a candidate for the superconducting state of HTSC in light of numerous recent experiments as well as for , d_xy, d_xz, d_yz states. For HFSC we considered three states, among themdγ and Y₂₋₁ states treated by Hirashima and Namaizawa² who used the theory of response. The number of the collective modes in each phase of both superconducting systems is equal to 10, among which five are high frequency modes while five others are Goldstone or Goldstone-like ones. The spectrum can be used to identify the superconducting states through ultrasound and microwave absorption experiments as well as to interpret these experiments.     

Precipitate alterations in the heat-affected zone of a Grade 100 microalloyed steel

Microalloy precipitate alterations (particularly dissolution) in the heat-affected zone (HAZ) of a Grade 100 steel, microalloyed by titanium, niobium, and vanadium and produced in the form of a plate with a thickness of 8 mm, was examined both theoretically and experimentally. For theoretical analysis of precipitate dissolution, pairs of effective peak temperature and holding time were extracted from the thermal cycles of welding, and were superimposed on the Ashby and Easterling non-equilibrium solubility curves for different fractions of precipitate dissolution. Intersections between the effective T–t curves and the non-equilibrium solubility curves gave critical pairs of effective peak temperature and holding time for dissolution of different fractions of a precipitate, which resulted in the establishment of precipitate dissolution profiles in the HAZ. Experimental analysis of precipitate alterations was carried out using carbon extraction replicas in a transmission electron microscope. The theoretical analyses were in agreement with experimental results, showing that it is the dissolution of small Nb-rich particles that paves the way to grain growth in the coarse-grained HAZ. Reprecipitation was generally suppressed in the low heat-input weld sample. There was some reprecipitation in the higher heat-input weld samples. Coarsening of TiN did not occur in the HAZ, due to the large size of these particles in the steel examined.     

Falling process of a rectangular granular step

This study experimentally investigates the falling process of a dry granular step in a transparent plexiglass chute by particle image analysis. Three types of uniform spherical beads and one type of quartz sand were piled up with various bed slopes and widths to elucidate their flow characteristics. The surface angles during the early slipping phase are close to the failure angles that are associated with the active earth pressure, based on the Mohr-Coulomb friction law. For a given size of particles (d) and slope (θ), the retreating upper granular surface follows a theoretical curve, and dimensionless mobile length decreases as the dimensionless time parameter t* increases. Velocity profiles measured at the side wall exhibit an exponential-like tail close to the static region at the bottom of the chute. As determined by the conservation of mass and momentum, the relationship between the characteristic velocity and the characteristic depth is linear in the transient flow.