Macroscopic Assembly Research Articles

Macroscopic Assembly of Materials with Engineered Bacterial Spores via Coiled-Coil Interaction.

Herein, we report macroscopic materials formed by the assembly of engineered bacterial spores. Spores were engineered by using a T7-driven expression system to display a high density of pH-responsive self-associating proteins on their surface. The engineered surface protein on the spore surface enabled pH-dependent binding at the protein level and enabled the assembly of granular materials. Mechanical properties remained largely constant with changing pH, but erosion stability was pH-dependent in a manner consistent with the pH-dependent interaction between the engineered surface proteins. Our finding utilizes synthetic biology for the design of macroscopic materials and illuminates the impact of coiled-coil interaction across various length scales.

Recyclable MXene film as SERS sensor with high sensitivity and flexibility adjusted with ZnO quantum dots

Developing flexible substrates with high sensitivity, good reproducibility and recyclability is a major challenge in surface enhanced Raman scattering (SERS) research. Herein, we prepare a recyclable Ti3C2 MXene/ZnO quantum dots (Ti3C2/ZnO) heterostructure film as an efficient SERS sensor with remarkable flexibility using vacuum assisted filtration technique. Benefiting from the more charge transfer (CT) paths, higher CT efficiency provided by oxygen vacancies (OVs) in ZnO QDs and Schottky barrier between Ti3C2 and ZnO QDs, the limit of detection (LOD) for 4-mercaptopyridine (4-MPY) molecules was as low as 1×10−7 M. In addition, the prepared flexible SERS film provided uniform and stable signals for both temporal (storage at room temperature for 60 days) and spatial (RSD = 10.7 %) scales due to the optimal distribution of ZnO QDs in the macroscopic assembly of Ti3C2/ZnO hybrid with excellent reliability and durability. Moreover, the prepared novel flexible SERS sensor achieved self-cleaning by photocatalytically degrading methylene blue (MB) residues extracted from the surface of orange peels and showed exceptional reusability during the detection process. Thus, this high-efficiency and low-cost flexible recyclable SERS sensor may be useful for the in-situ molecular detection in food security and environmental protection.

Engineering Anisotropy into Organized Nanoscale Matter.

Programming the organization of discrete building blocks into periodic and quasi-periodic arrays is challenging. Methods for organizing materials are particularly important at the nanoscale, where the time required for organization processes is practically manageable in experiments, and the resulting structures are of interest for applications spanning catalysis, optics, and plasmonics. While the assembly of isotropic nanoscale objects has been extensively studied and described by empirical design rules, recent synthetic advances have allowed anisotropy to be programmed into macroscopic assemblies made from nanoscale building blocks, opening new opportunities to engineer periodic materials and even quasicrystals with unnatural properties. In this review, we define guidelines for leveraging anisotropy of individual building blocks to direct the organization of nanoscale matter. First, the nature and spatial distribution of local interactions are considered and three design rules that guide particle organization are derived. Subsequently, recent examples from the literature are examined in the context of these design rules. Within the discussion of each rule, we delineate the examples according to the dimensionality (0D-3D) of the building blocks. Finally, we use geometric considerations to propose a general inverse design-based construction strategy that will enable the engineering of colloidal crystals with unprecedented structural control.

Additive-assisted macroscopic self-assembly and control of the shape of assemblies based on host–guest interaction

In these decades, considerable attention has focused on supramolecular polymers due to their unique structures and properties. More recently, macroscopic supramolecular polymers have attracted increasing interest from not only biologists but also materials scientists inspired by the sophisticated structures and functions of living organisms. Since the functions of supramolecular polymers are strongly dependent on their shape, control of the shape is an important issue in controlling the functions of supramolecular polymers. However, the control of shape in macroscopic supramolecular assemblies has not yet been sufficiently investigated. Previously, we studied the macroscopic self-assembly behavior of super absorbent polymer (SAP) microparticles modified with β-cyclodextrin (βCD) and adamantane (Ad) residues (βCD(x)-SAP and Ad(y)-SAP microparticles, where x and y are the mol% contents of βCD and Ad residues, respectively). More elongated assemblies were formed at higher y, indicating that the shape of assemblies can be controlled by varying the interaction strength. The noteworthy is that 1-adamantanamine hydrochloride (AdNH3Cl) assisted the formation of assemblies from βCD(x)-SAP and Ad(y)-SAP microparticles, indicating that AdNH3Cl acts as a chemical stimulus for macroscopic assemblies of βCD(x)-SAP and Ad(y)-SAP microparticles. In this study, we have thus studied the assembling behavior of βCD(x)-SAP microparticles with Ad(y)-SAP microparticles and unmodified SAP microparticles assisted by AdNH3Cl, as well as the shape of the resulting macroscopic assemblies. AdNH3Cl assisted the formation of assemblies from βCD(16.2)-SAP and Ad(15.1)-SAP microparticles, in which AdNH3Cl crosslinked the SAP microparticles through the formation of inclusion complexes of βCD residues with the Ad residue and the electrostatic interaction of ammonium and carboxylate residues. Assemblies of βCD(26.7)-SAP and unmodified SAP microparticles were formed at the concentrations of AdNH3Cl ([AdNH3Cl]0) higher than a certain level (ca. 0.05 mM). The aspect ratio (a/b) of assemblies showed a maximum at [AdNH3Cl]0 ~ 0.10 mM, indicating that the chemical stimulus, i.e., addition of AdNH3Cl, controls the shape of assemblies formed from βCD(26.7)-SAP and unmodified SAP microparticles. This study suggests that other stimuli, e.g., heat, pH, light, redox, and force, can be utilized to control the shape of macroscopic assemblies based on supramolecular interactions.

Dynamic surfactants drive anisotropic colloidal assembly.

Colloidal building blocks with re-configurable shapes and dynamic interactions can exhibit unusual self-assembly behaviors and pathways. In this work, we consider the phase behavior of colloids coated with surface-mobile polymer brushes that behave as "dynamic surfactants." Unlike traditional polymer-grafted colloids, we show that colloids coated with dynamic surfactants can acquire anisotropic macroscopic assemblies, even for spherical colloids with isotropic attractive interactions. We use Brownian Dynamics simulations and dynamic density functional theory to demonstrate that time-dependent reorganization of the dynamic surfactants leads to phase diagrams with anisotropic assemblies. We observed that the microscopic polymer distributions impose unique geometric constraints between colloids that control their packing into lamellar, string, and vesicle phases. Our work may help discover versatile building blocks and provide extensive design freedom for assembly out of thermodynamic equilibrium.

(Invited) High Temperature Exciton Properties in Aggregated Single-Walled Carbon Nanotubes

Individual single-walled carbon nanotubes (SWCNTs) at high temperatures have been reported to generate narrow-band thermal radiation in the near-infrared region due to thermally robust excitonic effects [1,2]. This phenomenon potentially offers a new opportunity for utilizing exciton properties in thermal engineering such as thermophotovoltaic energy harvesting requiring excellent wavelength selective near-infrared thermal emitter. However, for its realistic applications in macroscale, it is necessary to make the distinct exciton effect available under high temperature conditions in macroscopic assemblies of SWCNTs. As a first step toward this goal, we have recently determined broadband complex refractive index spectra of single-chirality SWCNT membranes in which SWCNTs are aligned two-dimensionally in a plane [3] and reported their birefringent properties [4]. In the presentation, we will discuss the change in the optical spectra of SWCNT assemblies with increasing temperature, as well as how the aggregation states affect the exciton properties. [1] T. Nishihara, A. Takakura, Y. Miyauchi, and K. Itami, Nat. Commun. 9, 3144 (2018). [2] S. Konabe, T. Nishihara, and Y. Miyauchi, Opt. Lett. 46, 3021 (2021). [3] T. Nishihara, A. Takakura, M. Shimasaki, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Nanophotonics 11, 1011 (2022). [4] H. Wu, T. Nishihara, A. Takakura, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Carbon, in press.

Spherulite formation in green nonaqueous media: The impact of urea on gelation in glycerol

HypothesisLarge macroscopic assemblies formed by a surfactant, sodium dodecylsulfate (SDS), and glycerol, can be directed to assemble in a hierarchical manner by the addition of a strong hydrogen-bond donor/acceptor, such as urea. ContextSelf-assembly in complex media is important to a range of applications, for instance in biological media, which are multi-component, to industrial formulations, where additives are present for flavour, texture, and preservation. Here, the gelation and self-assembly of sodium dodecylsulfate (SDS) in glycerol is explored in the presence of an additive, urea. Urea was chosen due to its importance both fundamentally and industrially, but also because of its ability to form strong H-bonds and interact with both glycerol and SDS. ExperimentalTo cover the variety of length scales present in the gel-like phase, a combination of optical microscopy and small-angle X-ray scattering techniques were used to probe the micro- to nanoscale. FindingsOn the microscale, the formation of a spectacular spherulite phase, even at low urea contents - 0.1 wt%, upon cooling was observed, a stark difference to the microfibrillar phase observed in the absence of urea. Interestingly, the nanostructure of the two crystalline phases were similar and showed negligible differences. This suggests that urea is not involved in the SDS/glycerol microfibril formation but instead directs the assembly of spherulites by bundling the microfibrils. These ternary systems are also probed as a function of urea content, SDS concentration, and temperature. The observations in this work highlight the importance of small molecules in the self-assembly process, which is relevant both fundamentally but also industrially, where small molecules are often added to formulations.

A Universal Strategy for Constructing Hydrogel Assemblies Enabled by PAA Hydrogel Adhesive.

Hydrogel is a significant type of building block for constructing macroscopic assemblies, the construction of which usually entails the incorporation of supramolecular groups. However, supramolecular group recognition is specific and only suitable for assembling two particular modified hydrogels, but not a versatile strategy. Herein, a universal strategy without modification process is proposed using polyacrylic acid (PAA) hydrogel as the adhesive layer to assemble different kinds of hydrogels. Furthermore, hydrogel assemblies with various shapes and multi-stimuli responsiveness are constructed by assembling different stimuli-responsive hydrogels with PAA hydrogel. Therefore, hydrogel assemblies are able to complete bending motions upon applying corresponding stimuli. This strategy provides a universal approach for constructing hydrogel assemblies, and also shows the potential for developing soft robots with versatile functions.

A Precursor-Derived Ultramicroporous Carbon for Printing Iontronic Logic Gates and Super-Varactors.

A liquid precursor for 3D printing ultramicroporous carbons (pore width <0.7nm) to create a novel in-plane capacitive-analog of semiconductor-based diodes (CAPodes) is presented. This proof-of-concept integrates functional EDLCs into microstructured iontronic devices. The working principle is based on selective ion-sieving, controlling the size of the electrolyte ions, and the nanoporous sieving carbon's pore size. By blocking bulky electrolyte ions from entering the sub-nanometer pores, a unidirectional charging characteristic with controllable ion flux is achieved, leading to diodic U-I characteristics with a high rectification ratio. The liquid precursor approach enables successful printing of miniaturized in-plane CAPodes. A combination of inkjet and extrusion printing techniques with suitable inks is explored to fabricate electrode materials with engineered porosity. Deliberate fine-tuning of the ultramicroporous carbon's porosity and surface area is achieved using a customized carbon precursor and CO2 etching techniques. Electrochemical evaluation of the printed CAPodes demonstrates successful miniaturization compared with macroscopic film assembly. 3D manufacturing and miniaturization allow for the integration of CAPodes into logic gate circuits (OR, AND). For the first time, these switchable devices are used as variable capacitors in a high-pass filter application, adjusting the cut-off frequency of applied alternating voltage analogous to an I-MOS varactor.

Hierarchical Self-Assembly of Multidimensional Functional Materials from Sequence-Defined Peptoids.

Hierarchical self-assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular-level understanding of the hierarchical assembly of sequence-defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron-based powder X-ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence-defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Hierarchical Self‐Assembly of Multidimensional Functional Materials from Sequence‐Defined Peptoids

AbstractHierarchical self‐assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular‐level understanding of the hierarchical assembly of sequence‐defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron‐based powder X‐ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence‐defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Biomechanical functions analysis of the Mallard webbed foot: A study of macroscopic and microscopic material assembly and tendon morphology

The mallard webbed foot represents an exemplary model of biomechanical efficiency in avian locomotion. This study delves into the intricate material assembly and tendon morphology of the mallard webbed foot, employing both macroscopic and microscopic analyses. Through histological slices and scanning electron microscopy (SEM), we scrutinized the coupling assembly of rigid and flexible materials such as skin, tendon, and bone, while elucidating the biomechanical functions of tendons across various segments of the tarsometatarsophalangeal joint (TMTPJ). The histological examination unveiled a complex structural hierarchy extending from the external integument to the skeletal framework. Notably, the bone architecture, characterized by compact bone and honeycombed trabeculae, showcases a harmonious blend of strength and lightweight design. Tendons, traversing the phalangeal periphery, surrounded by elastic fibers, collagen fibers, and fat tissue. Fat chambers beneath the phalanx, filled with adipocytes, provide effective buffering, enabling the phalanx to withstand gravity, provide support, and facilitate locomotion. Furthermore, SEM analysis provided insights into the intricate morphology and arrangement of collagen fiber bundles within tendons. Flexor tendons in proximal and middle TMTPJ segments adopt a wavy-type, facilitating energy storage and release during weight-bearing activities. In contrast, distal TMTPJ flexor tendons assume a linear-type, emphasizing force transmission across phalangeal interfaces. Similarly, extensor tendons demonstrate segment-specific arrangements tailored to their respective biomechanical roles, with wavy-type in proximal and distal segments for energy modulation and linear-type in middle segments for enhanced force transmission and tear resistance. Overall, our findings offer a comprehensive understanding of the mallard webbed foot's biomechanical prowess, underscoring the symbiotic relationship between material composition, tendon morphology, and locomotor functionality. This study not only enriches our knowledge of avian biomechanics but also provides valuable insights for biomimetic design and tissue engineering endeavors.

Reversible Constrained Dissociation and Reassembly of MXene Films.

Enabling materials to undergo reversible dynamic transformations akin to the behaviors of living organisms represents a critical challenge in the field of material assembly. The pursuit of such capabilities using conventional materials has largely been met with limited success. Herein, the discovery of reversible constrained dissociation and reconfiguration in MXene films, offering an effective solution to overcome this obstacle is reported. Specifically, MXene films permit rapid intercalation of water molecules between their distinctive layers, resulting in a significant expansion and exhibiting confined dissociation within constrained spaces. Meanwhile, the process of capillary compression driven by water evaporation reinstates the dissociated MXene film to its original compact state. Further, the adhesive properties emerging from the confined disassociation of MXene films can spontaneously induce fusion between separate films. Utilizing this attribute, complex structures of MXene films can be effortlessly foamed and interlayer porosity precisely controlled, using only water as the inducer. Additionally, a parallel phenomenon has been identified in graphene oxide films. This work not only provides fresh insights into the microscopic mechanisms of 2D materials such as MXene but also paves a transformative path for their macroscopic assembly applications in the future.

Hierarchical and reconfigurable interfibrous interface of bioinspired Bouligand structure enabled by moderate orderliness.

Introducing natural Bouligand structure into synthetics is expected to develop high-performance structural materials. Interfibrous interface is critical to load transfer, and mechanical functionality of bioinspired Bouligand structure yet receives little attention. Here, we propose one kind of hierarchical and reconfigurable interfibrous interface based on moderate orderliness to mechanically reinforce bioinspired Bouligand structure. The interface imparted by moderate alignment of adaptable networked nanofibers hierarchically includes nanofiber interlocking and hydrogen-bonding (HB) network bridging, being expected to facilitate load transfer and structural stability through dynamic adjustment in terms of nanofiber sliding and HB breaking-reforming. As one demonstration, the hierarchical and reconfigurable interfibrous interface is constructed based on moderate alignment of networked bacterial cellulose nanofibers. We show that the resultant bioinspired Bouligand structural material exhibits unusual strengthening and toughening mechanisms dominated by interface-microstructure multiscale coupling. The proposed interfibrous interface enabled by moderate orderliness would provide mechanical insight into the assembly of widely existing networked nanofiber building blocks toward high-performance macroscopic bioinspired structural assemblies.

Evaluating SWCNT assembly properties from the temperature dependence of electrical resistivity

We developed a theoretical model to describe the electrical resistivity in films and fibers made of single-walled carbon nanotubes (SWCNTs). The proposed model considers the formation of randomly oriented bundles of metallic and semiconducting nanotubes and takes into account the influence of temperature, while separating contributions of SWCNTs and their junctions to the total resistivity. To verify the model, we applied a powerful experimental tool – measurements of the temperature dependence of electrical resistivity of the investigated macroscopic SWCNT assemblies (pristine and doped SWCNT fibers). This allowed us to estimate various parameters of the material, such as the average length of SWCNT bundles, the acoustic phonon scattering length, and the bundle contact resistance, which are difficult to evaluate experimentally for entangled SWCNTs. The study highlights the importance of understanding the relationship between structural characteristics and electrical properties in SWCNT assemblies. The findings provide insights into optimizing the conductivity of these materials and offer a quick estimation method of the SWCNT network properties based on varying temperature measurements for future fiber and film-based applications.

Water-induced strong isotropic MXene-bridged graphene sheets for electrochemical energy storage.

Graphene and two-dimensional transition metal carbides and/or nitrides (MXenes) are important materials for making flexible energy storage devices because of their electrical and mechanical properties. It remains a challenge to assemble nanoplatelets of these materials at room temperature into in-plane isotropic, free-standing sheets. Using nanoconfined water-induced basal-plane alignment and covalent and π-π interplatelet bridging, we fabricated Ti3C2Tx MXene-bridged graphene sheets at room temperature with isotropic in-plane tensile strength of 1.87 gigapascals and moduli of 98.7 gigapascals. The in-plane room temperature electrical conductivity reached 1423 siemens per centimeter, and volumetric specific capacity reached 828 coulombs per cubic centimeter. This nanoconfined water-induced alignment likely provides an important approach for making other aligned macroscopic assemblies of two-dimensional nanoplatelets.

An energy-saving structural optimization strategy for high-performance multifunctional graphene films

Graphene has been widely studied for its excellent properties of outstanding conductivity, strength, and flexibility. However, interlayer defects formed during the macroscopic assembly of graphene nanosheets will severely degrade the performance of graphene films. Herein, a strategy combined with trace carboxyl graphene oxide (GO), mild reduction, and chemical crosslinking is employed to minimize the interlayer defects for enhancing both the conductivity and mechanical strength of graphene films. The trace carboxyl feature of GO allows nanosheets to assemble orderly into highly oriented GO films. Subsequently, the mild chemical reduction preserves the highly oriented and packed microstructure. Coupling with further crosslinking by introducing conjugated molecules with pyrene terminal groups (1-pyrene butyric acid-1,6-hexane diamine, PHD) to provide extra π-π bonds, both the mechanical strength and conductivity of graphene films are improved to 548.4 MPa and 1.7 × 105 S m−1, respectively. In addition, the graphene film with only ∼2 μm in thickness possesses an excellent electromagnetic interference shielding effectiveness (EMI SE) of ∼40 dB and a specific shielding effectiveness of up to 74 278 dB cm2 g−1 in a wide frequency range of 8.2–40.0 GHz. Thus, this study provides an energy-saving fabrication route for mechanically strong, effective thermal management and EMI shielding films.

Large-scale fabrication of flexible macroscopic SERS substrates with high sensitivity and long-term stability by wet-spinning technique: Uniform encapsulation of plasmon in graphene oxide fibers

Graphene oxide has attracted wide interest for theoretical research and application exploration in surface enhancement Raman scattering (SERS). However, how to break the geometric limitations of the nanoscale and extend its properties to the macroscopic level remains an urgent problem. Here, we prepared flexible graphene oxide/Au nanoparticles (GO/AuNP) fibers with high sensitivity and reproducibility for SERS sensing using wet spinning method. Benefitting from the plasmonic coupling of GO/AuNP fibers in vertical direction and uniform adsorption of the target molecules, the limit of detection for fiber was as low as 5 × 10-11 M for rhodamine 6G (R6G) and crystal violet (CV) molecules. In addition, due to the optimal distribution of AuNP in the macroscopic assembly of GO/AuNP hybrid, the fiber substrates provided uniform and stable signals for both temporal (6 months) and spatial (RSD = 8.18 %) scales, exhibited excellent reliability and durability. Moreover, an ultra-low concentrations of the pesticide thiram residues could be rapidly traced by direct sampling from the apple peel with a sensitivity of 5 × 10-9 M, which is much lower than the residue limit set by the US environmental protection agency. We envision that this work could provide new insights into the large-scale and economical fabrication of high-performance flexible SERS sensors for real world applications.

Precise and selective macroscopic assembly of a dual lock-and-key structured hydrogel.

Macroscopic assembly offers immense potential for constructing complex systems due to the high design flexibility of the building blocks. In such assembly systems, hydrogels are promising candidates for building blocks due to their versatile chemical compositions and ease of property tuning. However, two major challenges must be addressed to facilitate application in a broader context: the precision of assembly and the quantity of orthogonally matching pairs must both be increased. Although previous studies have attempted to address these challenges, none have successfully dealt with both simultaneously. Here, we propose topology-based design criteria for the selective assembly of hydrogel building blocks. By introducing the dual lock-and-key structures, we demonstrate highly precise assembly exclusively between the matching pairs. We establish principles for selecting multiple orthogonally matching pairs and achieve selective assembly involving simple one-to-one matching and complex assemblies with multiple orthogonal matching points. Moreover, by harnessing hydrogel tunability and the abundance of matching pairs, we synthesize complementary single-stranded structures for programmable assembly and successfully assemble them in the correct order. Finally, we demonstrate a hydrogel-based self-assembled logic gate system, including a YES gate, an OR gate, and an AND gate. The output is generated only when the corresponding inputs are provided according to each logic.

Droplet-based assembly of magnetic superballs

The self-assembly of materials driven by the inherent directionality of the constituent particles is of both practical and fundamental interest because it enables the fabrication of complex and hierarchical structures with tailored functionalities. By employing evaporation assisted self-assembly, we form opal-like structures with micro-sized magnetic superball particles. We study the structure formation of different superball shapes during evaporation of a dispersion droplet with in-situ small angle x-ray scattering with microradian resolution in the absence and presence of an external magnetic field. In the absence of a magnetic field, strong shape-dependent structures form as the water evaporates from the system. Applying a magnetic field to the droplet has a unique effect on the system; strong magnetic fields inhibit the growth of well-ordered assemblies due to the formation of out-of-equilibrium dipolar structures while lower magnetic fields allow particles to rearrange and orient without inhibition. In this work, we show how the superball assembly inside a droplet can be controlled by the magnetic field strength and the superball shape. The tunability of these parameters not only enables the controllable formation of macroscopic colloidal assemblies but also opens up possibilities for the development of functional materials with tailored properties on a macro-scale.