Long-range Alignment Research Articles

Self-Assembled Piezoelectric Films from Aligned Lysozyme Protein Fibrils.

Piezoelectric organic polymers are promising alternatives to their inorganic counterparts due to their mechanical flexibility, making them suitable for flexible and wearable piezoelectric devices. Biological polymers such as proteins have been reported to possess piezoelectricity, while offering additional benefits, such as biocompatibility and biodegradability. However, questions remain regarding protein piezoelectricity, such as the impact of the protein secondary structure. This study examines the piezoelectric properties of lysozyme amyloid fibril films, plasticized by polyethylene glycol (PEG). The films demonstrated a measurable d33 coefficient of 1.4 ± 0.1 pCN-1, for the optimized PEG concentration, confirming piezoelectricity. The PEG was found to hydrogen-bond with the fibrils, likely impacting the piezoelectric response of the film. Polarization imaging revealed long-range alignment of the amyloid fibrils in a circumferential arrangement. These results demonstrate the potential of using amyloid fibrils, which can be formed from various proteins, to create bulk self-assembled piezoelectric materials.

Freeze-Casting Mold-Based Scalable Synthesis of Directional Graphene Aerogels with Long-Range Pore Alignment for Energy Applications.

In various applications, the pore structure of a porous medium must be controlled to facilitate heat and mass transfer, which considerably influence the system performance. Freeze-casting is a versatile technique for creating aligned pores; However, because of the complexity of the associated equipment and the energy inefficiency of liquid-nitrogen-based cooling in a room-temperature environment, limits scalability for industrial applications. This study is aimed at establishing a novel freeze-casting strategy with a simple mold design combining heat-conductive and insulating materials for long-range pore alignment via directional ice growth under deep-freezing conditions, rendering it feasible for large-scale production. Using this technique, axially aligned (Axial-GA) is developed, radially aligned (Radial-GA), and randomly distributed (Random-GA) pore structures within NaBr-impregnated graphene aerogel (GA-NaBr) configurations, demonstrating enhanced ammonia adsorption for thermal energy management. The pore structure exerted notable effects on the ammonia adsorption behavior, with Radial-GA exhibiting a higher adsorption rate due to reduced ammonia transit distance. The Radial-GA-NaBr structure demonstrated unique adsorption characteristics, retaining ≈85% of the adsorption capacity and achieving a ≈270% adsorption rate gain compared with pure NaBr powder. Overall, this research demonstrates the fabrication of aerogels with various configurations and orientations using facile and scalable methods, thereby expanding their industrial applications.

Collective behavior from surprise minimization

Collective motion is ubiquitous in nature; groups of animals, such as fish, birds, and ungulates appear to move as a whole, exhibiting a rich behavioral repertoire that ranges from directed movement to milling to disordered swarming. Typically, such macroscopic patterns arise from decentralized, local interactions among constituent components (e.g., individual fish in a school). Preeminent models of this process describe individuals as self-propelled particles, subject to self-generated motion and "social forces" such as short-range repulsion and long-range attraction or alignment. However, organisms are not particles; they are probabilistic decision-makers. Here, we introduce an approach to modeling collective behavior based on active inference. This cognitive framework casts behavior as the consequence of a single imperative: to minimize surprise. We demonstrate that many empirically observed collective phenomena, including cohesion, milling, and directed motion, emerge naturally when considering behavior as driven by active Bayesian inference-without explicitly building behavioral rules or goals into individual agents. Furthermore, we show that active inference can recover and generalize the classical notion of social forces as agents attempt to suppress prediction errors that conflict with their expectations. By exploring the parameter space of the belief-based model, we reveal nontrivial relationships between the individual beliefs and group properties like polarization and the tendency to visit different collective states. We also explore how individual beliefs about uncertainty determine collective decision-making accuracy. Finally, we show how agents can update their generative model over time, resulting in groups that are collectively more sensitive to external fluctuations and encode information more robustly.

Self-Assembly of Atomically Aligned Nanoparticle Superlattices from Pt-Fe3O4 Heterodimer Nanoparticles.

Multicomponent nanoparticle superlattices (SLs) promise the integration of nanoparticles (NPs) with remarkable electronic, magnetic, and optical properties into a single structure. Here, we demonstrate that heterodimers consisting of two conjoined NPs can self-assemble into novel multicomponent SLs with a high degree of alignment between the atomic lattices of individual NPs, which has been theorized to lead to a wide variety of remarkable properties. Specifically, by using simulations and experiments, we show that heterodimers composed of larger Fe3O4 domains decorated with a Pt domain at one vertex can self-assemble into an SL with long-range atomic alignment between the Fe3O4 domains of different NPs across the SL. The SLs show an unanticipated decreased coercivity relative to nonassembled NPs. In situ scattering of the self-assembly reveals a two-stage mechanism of self-assembly: translational ordering between NPs develops before atomic alignment. Our experiments and simulation indicate that atomic alignment requires selective epitaxial growth of the smaller domain during heterodimer synthesis and specific size ratios of the heterodimer domains as opposed to specific chemical composition. This composition independence makes the self-assembly principles elucidated here applicable to the future preparation of multicomponent materials with fine structural control.

TinO2n-1/MXene Hierarchical Bifunctional Catalyst Anchored on Graphene Aerogel toward Flexible and High-Energy Li-S Batteries.

The development of lithium-sulfur (Li-S) batteries with high-energy density, flexibility, and safety is very appealing for emerging implantable devices, biomonitoring, and roll-up displays. Nevertheless, the poor cycling stability and flexibility of the existing sulfur cathodes, flammable liquid electrolytes, and extremely reactive lithium anodes raise serious battery performance degradation and safety issues. Herein, a metallic 1T MoS2 and rich oxygen vacancies TinO2n-1/MXene hierarchical bifunctional catalyst (Mo-Ti/Mx) anchored on a reduced graphene oxide-cellulose nanofiber (GN) host (Mo-Ti/Mx-GN) was proposed to address the above challenges. By applying a directional freezing process, the hierarchical architecture of a flexible GN scaffold composed of waved multiarch morphology with long-range alignment is achieved. The synergetic effects of 1T MoS2 and TinO2n-1/MXene are beneficial to suppress the shuttling behavior of lithium polysulfides (LiPSs), expedite the redox kinetics of sulfur species, and promote the electrocatalytic reduction of LiPSs to Li2S. The electrode demonstrates improved electrochemical properties with high sulfur-mass loading (8.4 mgs cm-2) and lean electrolyte (7.6 μL mgs-1) operation. We also explored the feasibility of producing pouch cells with such flexible electrodes, gel polymer electrolytes, and a robust lithium anode, which exhibited reversible energy storage and output, wide temperature adaptability, and good safety against rigorous strikes, implying the potential for practical applications.

Microengineering 3D Collagen Hydrogels with Long-Range Fiber Alignment.

Aligned collagen I (COL1) fibers guide tumor cell motility, influence endothelial cell morphology, control stem cell differentiation, and are a hallmark of cardiac and musculoskeletal tissues. To study cell response to aligned microenvironments in vitro, several protocols have been developed to generate COL1 matrices with defined fiber alignment, including magnetic, mechanical, cell-based, and microfluidic methods. Of these, microfluidic approaches offer advanced capabilities such as accurate control over fluid flows and the cellular microenvironment. However, the microfluidic approaches to generate aligned COL1 matrices for advanced in vitro culture platforms have been limited to thin "mats" (<40 µm in thickness) of COL1 fibers that extend over distances less than 500 µm and are not conducive to 3D cell culture applications. Here, we present a protocol to fabricate 3D COL1 matrices (130-250 µm in thickness) with millimeter-scale regions of defined fiber alignment in a microfluidic device. This platform provides advanced cell culture capabilities to model structured tissue microenvironments by providing direct access to the micro-engineered matrix for cell culture.

Local extensional flows promote long-range fiber alignment in 3D collagen hydrogels

Randomly oriented type I collagen (COL1) fibers in the extracellular matrix are reorganized by biophysical forces into aligned domains extending several millimeters and with varying degrees of fiber alignment. These aligned fibers can transmit traction forces, guide tumor cell migration, facilitate angiogenesis, and influence tissue morphogenesis. To create aligned COL1 domains in microfluidic cell culture models, shear flows have been used to align thin COL1 matrices (<50 µm in height) in a microchannel. However, there has been limited investigation into the role of shear flows in aligning 3D hydrogels (>130 µm). Here, we show that pure shear flows do not induce fiber alignment in 3D atelo COL1 hydrogels, but the simple addition of local extensional flow promotes alignment that is maintained across several millimeters, with a degree of alignment directly related to the extensional strain rate. We further advance experimental capabilities by addressing the practical challenge of accessing a 3D hydrogel formed within a microchannel by introducing a magnetically coupled modular platform that can be released to expose the microengineered hydrogel. We demonstrate the platform’s capability to pattern cells and fabricate multi-layered COL1 matrices using layer-by-layer fabrication and specialized modules. Our approach provides an easy-to-use fabrication method to achieve advanced hydrogel microengineering capabilities that combine fiber alignment with biofabrication capabilities.

Detection of intralayer alignment in multicomponent lipids by dynamic speckle pattern analysis.

Multicomponent mixtures of bilayer lipids, thanks to the coexistence of liquid-crystalline phases in their structures, may be used in the development of functional membranes. In such membranes interlayer ordering distributes across membrane lamellae, resulting in long-range alignment of phase-separated domains. In this paper, we explore the dynamics of this phenomenon by laser speckle pattern analysis. We show that cholesterol content decreases the activity, and the rate of the domains size development is related to the change of physical roughness of the multicomponent lipid mixture. Our results are in agreement with the previous experimental reports. However, our experimental procedure is an easy-to-implement and effective methodology.

Deferred Polarization Saturation Boosting Superior Energy-Storage Efficiency and Density Simultaneously under Moderate Electric Field in Relaxor Ferroelectrics

High-temperature dielectric Bi0.5Na0.5TiO3 (BNT)-based relaxors near a morphotropic phase boundary are developed with excellent energy storage performance. Random distribution of polar nanoregions induced by composition modulation would disrupt the ferroelectric long-range dipolar alignment and weaken the coupling between the ferroelectric domains, yielding slender and deferred polarization–electric field hysteresis loops with relatively high saturation polarization. The reversible nano-domain orientation and growth in relaxors under a delayed electric field result in negligible remnant polarization and advantageous energy storage properties. Simultaneously, superior recoverable energy storage density and efficiency are gained, significantly surpassing the state-of-the-art dielectric energy storage materials under similar moderate electric fields. Vacancies, defect dipole behavior, and structural evolution that relied on an electric field and temperature are discussed to disclose the underlying mechanism associated with phase transition. Even thermal stability and large electrostrictive strain with low hysteresis are achieved in elevated temperatures. These features demonstrate the promising candidates for dielectric energy-storage application and provide a strategy in designing relaxors.

Atomic Edge-Guided Polyethylene Crystallization on Monolayer Two-Dimensional Materials

Here, we combine an advanced synthesis of two-dimensional (2D) materials (MoSe2) having well-defined atomic edge configurations with ab initio and atomistic molecular dynamics (MD) simulations to study how atomic edges interact with polyethylene (HDPE) chains in a dilute solution assembly process. Our results reveal that Mo-terminated zigzag (Mo-ZZ) edges act as preferred nucleation sites and strongly interact with HDPE chains. The HDPE chains align in parallel with the Mo-ZZ edges and form arrays of lamellae that are perpendicular to the edges. Interestingly, atomic edge configurations are observed to dramatically change such interactions. The crystallization discrepancy at different edges was demonstrated on the same piece of MoSe2 with different types of edges. The ab initio and MD simulations between n-alkane (n = 5 and 25), a segment of HDPE, and MoSe2 suggest that the atomic structures of MoSe2 can affect their interactions with n-alkane chains. Following the Mo-ZZ edge preferred nucleation principle, controlled long-range alignment of HDPE lamellae can be realized by creating multilayer MoSe2 with parallel atomic steps. This research opens a pathway toward an atomic level understanding of polymer–2D nanomaterial interactions. It also bridges the gap between atomic-level and long-range mesoscopic structures and introduces a novel strategy for long-range structural control.

Low Divergence Structured Beam In View Of Precise Long-Range Alignment

A new method of generation of a Structured Laser Beam (SLB) with non-diverging central core was proposed and is promising for creating long distance multipoint alignment systems. This beam is generated by a set-up consisting of two convex lenses in Kepler telescope arrangement. The first one is a high refractive index ball lens, second one is a standard lens. The beam, in cross-section consisting of light and dark concentric circles, propagates over a large distance. The central core of the SLB has a very small divergence which can be tuned. A divergence of 10 μrad was proven experimentally. In this experiment, the small initial beam core diameter of 10 μm, and its diameter of 1.5 mm at a distance of 150 m, show its ability for use as a multipoint fiducial reference line. This small beam divergence seemingly lies beyond the diffraction limit for laser beams.

Long-Range alignment of liquid crystalline small molecules on Metal-Organic framework micropores by physical anchoring

In this study, we are the first to observe the alignment behaviors of various assembling molecules with different feature sizes and shapes, including rod-, disc-, and column-shaped molecules, on zeolitic imidazolate framework-8 (ZIF-8) surfaces. Among the various rod-shaped 4-alkyl-4′-cyanobiphenyls (nCBs), those with short alkyl chains with less than nine hydrocarbons (e.g., 5CB, 6CB, 8CB, and 9CB) were vertically aligned on the ZIF-8 surface, while nCBs with long alkyl chains with more than 10 hydrocarbons (e.g., 10CB and 11CB) were randomly oriented on the surface. Unlike rod-shaped small molecules, the disc- and column-shaped molecules were randomly oriented on the ZIF-8 surface. A molecular dynamic simulation revealed that the vertical alignment of rod-shaped molecules on the ZIF-8 surface can be attributed to physical anchoring by the ZIF-8 micropores. Most portions of the alkyl chain of nCB with shorter alkyl chain lengths (n ≤ 9) can be inserted into the ZIF-8 aperture, while nCBs with longer alkyl chain lengths (n > 9) cannot be adequately anchored in the ZIF-8 aperture. According to these results, we believe that MOF materials with micropores can offer an effective tool for controlling the orientation of various functional small molecules.

Large-Scale Uniform-Patterned Arrays of Ultrathin All-2D Vertical Stacked Photodetector Devices.

The key to unlocking the full potential of two-dimensional (2D) materials in ultrathin opto-electronics is their layer-by-layer integration and the ability to produce them on the wafer scale using traditional industry-compatible technology. Here, we demonstrate a novel stacking method for assembling uniform-patterned periodic 2D arrays into vertical-layered heterostructures. The fabricated heterostructure can serve as photodetectors, with graphene electrodes and transition-metal dichalcogenides as the photo-absorber. All 2D materials used are grown into continuous films with only mono- or bilayer thickness. Each layer is prepatterned into a specific shape on a substrate and then transferred to the device substrate with aligned precision. In order to achieve long-range alignment across the wafer, interlocking marker pairs are used to help guide the lateral accuracy and reduce rotational error. We show hundreds of identical devices produced with 2D periodic spacing on a 1 cm × 1 cm SiO2/Si substrate, a fundamental prerequisite for future pixelated detectors. Statistics of the photovoltaic performance of the devices are reported, with values that are comparable to devices made by chemical vapor deposition-grown materials. Our work provides pathways for the large-scale fabrication of ultrathin all-2D opto-electronics that form the basis of the future in 2D-pixelated cameras and displays.

Wafer-Scale Unidirectional Alignment of Supramolecular Columns on Faceted Surfaces.

The long-range alignment of supramolecular structures must be engineered as a first step toward advanced nanopatterning processes aimed at miniaturizing features to dimensions below 5 nm. This study introduces a facile method of directing the orientation of supramolecular columns over wafer-scale areas using faceted surfaces. Supramolecular columns with features on the sub-5 nm scale were highly aligned in a direction orthogonal to that of the facet patterning on unidirectional and nanoscopic faceted surface patterns. This unidirectional alignment of supramolecular columns is also observed by varying the thickness of the supramolecular film or by altering the dimensions of the facet pattern. The ordering behavior of the supramolecular columns can be attributed to the triangular depth profile of the bottom facet pattern. Furthermore, this directed self-assembly principle allows for the continuous alignment of supramolecular structures across ultralarge distances on flexible patterned substrates.

Silver Nanoparticles Decorated with PEGylated Porphyrins as Potential Theranostic and Sensing Agents.

Silver nanoparticles (AgNPs) stand out over other metal nanoparticles thanks to their peculiar bactericidal and spectroscopic properties. Tunability of the AgNPs chemical–physical properties could be provided through their organic covalent coating. On the other hand, PEGylated porphyrin derivatives are versatile heteromacrocycles investigated for uses in the biomedical field as cytotoxic and tracking agents, but also as sensors. In this work, an easy multi-step approach was employed to produce coated silver nanoparticles. Specifically, the AgNPs were functionalized with 5,10,15-[p-(ω-methoxy-polyethyleneoxy)phenyl]-20-(p-hydroxyphenyl)-porphyrin (P(PEG350)3), using chloropropanethiol as a coupling agent. The P(PEG350)3 was structurally characterized through MALDI-TOF mass spectrometry, NMR spectroscopy and thermal analyses. The functionalization of AgNPs was monitored step-by-step employing UV-Vis spectroscopy, dynamic light scattering and thermogravimetric techniques. HRTEM and STEM measurements were used to investigate the morphology and the composition of the resulting nanostructured system (AgNP@P(PEG350)3), observing a long-range alignment of the outer porphyrin layer. The AgNP@P(PEG350)3 combines the features of the P(PEG350)3 with those of AgNPs, producing a potential multifunctional theranostic tool. The nanosystem revealed itself suitable as a removable pH sensor in aqueous solutions and potentially feasible for biological environment applications.

A High Energy Density 2D Microsupercapacitor Based on an Interconnected Network of a Horizontally Aligned Carbon Nanotube Sheet

Highly aligned carbon nanotubes (HACNT sheets) have recently attracted great attention in developing high-performing ultrathin supercapacitors, which take advantage of the long-range alignment to improve electrochemical performance. While there are investigations into sandwich electrode CNT sheet devices, there are no known reports on interdigitated electrode (IDE) HACNT sheet microsupercapacitors (MSCs). This paper reports a facile method for rapidly fabricating high energy density ultrathin HACNT sheet-based MSCs with IDE planar configuration. Increasing the electrode thickness from 32 nm (5 layers) to 300 nm (50 layers) results in an approximately three times factor in performance. The 50 layer devices (MSC-50L) yield a top energy density of 10.52 mWhcm-3 and power density of 19.33 Wcm-3, making its performance comparable to those of microbatteries with potential for further improvement. Additionally, incorporation of MnO2 nanoparticles (NPs) within the MSCs-50L improves specific capacitance (242 Fcm-3), energy density (33.7 mWhcm-3), and power density (31 Wcm-3), outperforming current thin-film MSCs and matching the performance of 3D MSCs. MSCs also demonstrate a long cycle life (7000 charge-discharge cycles) with less than 5% capacitance fade. These findings suggest that HACNT sheets have substantial potential as active electrode materials for ultrathin high energy density microscale power sources.

Peptoid-Based Programmable 2D Nanomaterial Sensor for Selective and Sensitive Detection of H2S in Live Cells

During the past few decades, a variety of two-dimensional (2D) nanomaterials have been developed through molecular self-assembly. Among them, those assembled from sequence-defined polymers have received particular attention because they enable a programmable display of functional groups, including fluorescent dyes, on their surfaces for applications. On the other hand, due to fluorescence self-quenching, synthesis of 2D nanomaterials exhibiting high fluorescence quantum yields is a significant challenge. Herein, we design and synthesize peptoid-based crystalline 2D nanomembranes (2DNMs) as a biocompatible and programmable sensor for selectively and sensitively detecting H2S in live cells. This 2DNM sensor is assembled from peptoids covalently attached with H2S-responsive molecular probes. Compared with its amorphous controls, this crystalline 2DNM sensor exhibits a significantly stronger fluorescence intensity and a higher sensitivity as a result of long-range structural ordering and alignment of H2S-responsive molecular probes. By sonication-cutting these 2DNM sensors into a colloidal form in an aqueous solution, we further demonstrated the use of colloidal 2DNMs for detecting exogenous and endogenous H2S inside cells and targeted cell organelles. Because peptoids are biocompatible and peptoid-based 2DNMs are programmable, we expect that this class of 2DNM sensors offer great potential for detecting H2S in live cells and for investigating H2S-related diseases.

Long-Range Lamellar Alignment in Diblock Bottlebrush Copolymers via Controlled Oscillatory Shear

A simple strategy is presented to achieve well-ordered nanostructures in microphase-separated diblock bottlebrush copolymers (dbBB) for potential opportunities in nanotechnology that require large ...

Gliding filament system giving both global orientational order and clusters in collective motion.

Emergence and collapse of coherent motions of self-propelled particles are affected more by particle motions and interactions than by their material or biological details. In the reconstructed systems of biofilaments and molecular motors, several types of collective motion including a global-order pattern emerge due to the alignment interaction. Meanwhile, earlier studies show that the alignment interaction of a binary collision of biofilaments is too weak to form the global order. The multiple collision is revealed to be important to achieve global order, but it is still unclear what kind of multifilament collision is actually involved. In this study, we demonstrate that not only alignment but also crossing of two filaments is essential to produce an effective multiple-particle interaction and the global order. We design the reconstructed system of biofilaments and molecular motors to vary a probability of the crossing of biofilaments on a collision and thus control the effect of volume exclusion. In this system, biofilaments glide along their polar strands on the turf of molecular motors and can align themselves nematically when they collide with each other. Our experiments show the counterintuitive result, in which the global order is achieved only when the crossing is allowed. When the crossing is prohibited, the cluster pattern emerges instead. We also investigate the numerical model in which we can change the strength of the volume exclusion effect and find that the global orientational order and clusters emerge with weak and strong volume exclusion effects, respectively. With those results and simple theory, we conclude that not only alignment but also finite crossing probability are necessary for the effective multiple-particles interaction forming the global order. Additionally, we describe the chiral symmetry breaking of a microtubule motion which causes a rotation of global alignment.

Hierarchically oriented organization in supramolecular peptide crystals.

Hierarchical self-assembly and crystallization with long-range ordered spatial arrangement is ubiquitous in nature and plays an essential role in the regulation of structures and biological functions. Inspired by the multiscale hierarchical structures in biology, tremendous efforts have been devoted to the understanding of hierarchical self-assembly and crystallization of biomolecules such as peptides and amino acids. Understanding the fundamental mechanisms underlying the construction and organization of multiscale architectures is crucial for the design and fabrication of complex functional systems with long-range alignment of molecules. This Review summarizes the typical examples for hierarchically oriented organization of peptide self-assembly and discusses the thermodynamic and kinetic mechanisms that are responsible for this specific hierarchical organization. Most importantly, we propose the concept of hierarchically oriented organization for self-assembling peptide crystals, distinct from the traditional growth mechanism of supramolecular polymerization and crystallization based on the Ostwald ripening rule. Finally, we assess critical challenges and highlight future directions towards the mechanistic understanding and versatile application of the hierarchically oriented organization mechanism.