Macroscopic Assembly Research Articles

Visible and selective gel assembly via covalent click chemistry

AbstractThis study marks the birth of visible and selective click covalent assembly. It is achieved by amplifying orthogonal alkyne−azide click chemistry through interfacial multisite interactions between azide/alkyne functionalized polymer hydrogels. Macroscopic assembly of hydrogels via host−guest chemistry or noncovalent interactions such as electrostatic interactions has been reported. Unlike macroscopic supramolecular assembly, here we report visible and selective “click” covalent assembly of hydrogels at the macroscale. LEGO‐like hydrogels modified with alkyne and azide groups, respectively, can click together via the formation of covalent bonds. Monomer concentration‐dependent assembly and selective covalent assembly have been studied. Notably, macroscopic gel assembly clearly elucidates click preferences and component selectivity not observed in the solution reactions of competing monomers.

Macroscopic Helical Assembly of One-Dimensional Coordination Polymers: Helicity Inversion Triggered by Solvent Isomerism.

Assembling macroscopic helices with controllable chirality and understanding their formation mechanism are highly desirable but challenging tasks for artificial systems, especially coordination polymers. Here, we utilize solvents as an effective tool to induce the formation of macroscopic helices of chiral coordination polymers (CPs) and manipulate their helical sense. We chose the Ni/R-,S-BrpempH2 system with a one-dimensional tubular structure, where R-,S-BrpempH2 stands for R-,S-(1-(4-bromophenyl)ethylaminomethylphosphonic acid). The morphology of the self-assemblies can be controlled by varying the cosolvent in water, resulting in the formation of twisted ribbons of R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-2T) in pure H2O; needle-like crystals of R-,S-Ni(Brpemp)(H2O)2·1/3CH3CN (R-,S-1C) in 20 vol % CH3CN/H2O; nanofibers of R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-3F) in 20-40 vol % methanol/H2O or ethanol/H2O; and superhelices of R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-4H or 5H) in 40 vol % propanol/H2O. Interestingly, the helicity of the superhelix can be controlled by using a propanol isomer in water. For the Ni/R-BrpempH2 system, a left-handed superhelix of R-4H(M) was obtained in 40 vol % NPA/H2O, while a right-handed superhelix of R-5H(P) was isolated in 40 vol % IPA/H2O. These results were rationalized by theoretical calculations. Adsorption studies revealed the chiral recognition behavior of these compounds. This work may contribute to the development of chiral CPs with a macroscopic helical morphology and interesting functionalities.

Multi-functional locomotion of collectively assembled shape-reconfigurable electronics

Beyond typical flexible electronics, stimuli-responsive shape-reconfigurable electronics are great candidates for the next-generation miniaturized electronics, carrying out complex missions by morphing their geometry and transferring their bodies to the desired positions. To achieve shape-reconfigurable electronics, it is essential to give shape-programmability as well as high electrical conductivity for polymeric materials. However, this is difficult to achieve due to a trade-off relationship between the shape-reconfigurability and the electrical conductivity of polymer composites that embed conductive fillers. Herein, we introduced highly conductive and physical intelligence-encoded polymeric composites based on MXene/liquid crystal elastomer (LCE) bilayer (MLB), for shape-reconfigurable electronics performing on-demand and reversible 3D morphing and locomotion. The MLB demonstrated remarkable photo-/electro-thermally driven bending and twisting performance under near-infrared (NIR) light with 0.4 W cm−2 and voltage application of 3.5 V without delamination due to both high photothermal conversion efficiency and electrical conductivity of ∼5,300 S cm−1. The MLB also proved structural durability after 1,000 cycles of bending originating from the stable interface induced by hydrogen bonding between MXene and LCE. Importantly, macroscopic collective assembly of the MLBs enabled dynamic locomotion inspired by nature. Collectively assembled MLBs demonstrated crawling, rotating, jumping, and sling-shooting by engineering the symmetricity of assembled structure and introducing snap-through instability.

Extreme Polarization Anisotropy in Resonant Third-Harmonic Generation from Aligned Carbon Nanotube Films.

Carbon nanotubes (CNTs) possess extremely anisotropic electronic, thermal, and optical properties owing to their 1D character. While their linear optical properties have been extensively studied, nonlinear optical processes, such as harmonic generation for frequency conversion, remain largely unexplored in CNTs, particularly in macroscopic CNT assemblies. In this work, macroscopic films of aligned and type-separated (semiconducting and metallic) CNTs are synthesized and polarization-dependent third-harmonic generation (THG) from the films with fundamental wavelengths ranging from 1.5 to 2.5µm is studied. Both films exhibited strongly wavelength-dependent, intense THG signals, enhanced through exciton resonances, and third-order nonlinear optical susceptibilities of 2.50×10-19 m2 V-2 (semiconducting CNTs) and 1.23×10-19 m2 V-2 (metallic CNTs), respectively are found, for 1.8µm excitation. Further, through systematic polarization-dependent THG measurements, the values of all elements of the susceptibility tensor are determined, verifying the macroscopically 1D nature of the films. Finally, polarized THG imaging is performed to demonstrate the nonlinear anisotropy in the large-size CNT film with good alignment. These findings promise applications of aligned CNT films in mid-infrared frequency conversion, nonlinear optical switching, polarized pulsed lasers, polarized long-wave detection, and high-performance anisotropic nonlinear photonic devices.

Falling-Leaves Stacking Aggregation of Two-Dimensional Macromolecular Graphene Oxide in Solution.

Understanding the dynamical behaviors of two-dimensional (2D) macromolecules is of fundamental importance for the precise modulation of their assembled structures and material performances. However, considerably less is known about how discrete macromolecular sheets aggregate into extended macroscopic assemblies in solutions. The absence of a quantitative description of the assembly process limits the precise structural control of assemblies. Here, we investigated the aggregation thermodynamic transition and kinetic behavior of 2D macromolecules in the model of single layer graphene oxide (GO). Combining Flory-Huggins theory with experimental observations, we unveiled the critical thermodynamic transition of GO to correlate with the solvent property. We proposed a theoretical falling-leaf model to quantitatively describe the kinetic aggregation process of 2D GO sheets. Experimental analysis validated the theoretical prediction that the thickness of GO aggregates has a power law relation with the poor solvent content. Our work provides a fundamental understanding of phase separation of 2D macromolecules and offers an insight into modulating the aggregated structures of their assembled materials.

Improvement on the Radiation Stability of Multi-scale Supramolecular Assembly in Ionic Liquid-Based Extraction.

The multi-scale supramolecular assembly (MSSA)-based extraction strategy with hydroxyl-functionalized ionic liquid (IL) is promising in the separation of metal ions from radioactive environments for which a comprehensive understanding toward the radiation stability of the MSSA system is necessary. Herein, we report on the analyses of the radiation stability of MSSA in extraction, especially the adopted ILs 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (IL-1) and 1-(2-hydroxyethyl)-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imide (IL-2), by UV-vis, 1H NMR, and ESI-HRMS. It was found that the macroscopic assembly (MA) sphere could not be formed after γ irradiation on the extraction system with IL-1. On the contrary, the trisubstituted IL-2 instead of the disubstituted IL-1 remarkably improved the radiation stability of the MSSA system to guarantee the formation of the MA sphere. The high extraction efficiency could be kept, and the mechanism of such an improvement was revealed.

Cyclic Macroscopic Assembly and Disassembly Driven by Ionic Strength Fuel: A Waste-Free Approach.

Nonequilibrium assembling systems developed so far have relied on chemical fuels to drive the programmable pH cycles, redox reactions, and metastable bond formations. However, these methods often result in the unwanted accumulation of chemical waste. Herein, we present a novel strategy for achieving cyclic and waste-free nonequilibrium assembly and disassembly of macroscopic hydrogels, utilizing an ionic strength-mediated approach. Our strategy involves using ammonium carbonate as a chemical fuel to temporally regulate the attractions between oppositely charged hydrogels via ionic strength-controlled charge screening and hydrogel elasticity changes. This chemical fuel effectively mediates the assembly/disassembly processes and prevents waste accumulation, as ammonium carbonate can completely decompose into volatile chemical waste. The cyclic and reversible assembly process can be achieved without significant damping due to the self-clearance mechanism, as long as the chemical fuel is repeatedly supplied. This concept holds promise for creating macroscopic and microscopic nonequilibrium systems and self-adaptive materials.

Electrospun silicon carbide nanowire film: A highly thermally conductivity and flexible material for advanced thermal management

As flexible electronic devices become increasingly compact and powerful, they generate more heat, necessitating efficient thermal management to ensure their reliable operation. Flexible substrates, which are essential components of these devices, often struggle to dissipate heat effectively due to their inherent low thermal conductivity. To overcome this challenge, the development of highly thermally conductive flexible substrates is crucial. By employing the electrospinning technique, large-area flexible films were successfully fabricated in this study. The film exhibited a notable in-plane thermal conductivity, reaching its maximum value at 38.4 Wm−1K−1. The film demonstrated its superior performance at a filler concentration of 50 wt%, displaying a thermal conductivity of 28.6 Wm−1K−1, a tensile strength of 27.8 MPa, and an elongation of 8.1%. Furthermore, the film exhibited exceptional flexibility, satisfying the requirements for next-generation flexible substrates. The present study unveils innovative findings concerning the fabrication of expansive and exceptionally thermally conductive flexible substrates, as well as the management of performance in filler-based macroscopic assemblies.

Thermal Conductivity of Carbon/Boron Nitride Heteronanotube and Boron Nitride Nanotube Buckypapers: Implications for Thermal Management Composites.

To date, there has been limited reporting on the fabrication and properties of macroscopic sheet assemblies (specifically buckypapers) composed of carbon/boron nitride core-shell heteronanotubes (MWCNT@BNNT) or boron nitride nanotubes (BNNTs). Herein we report the synthesis of MWCNT@BNNTs via a facile method involving Atmospheric Pressure Chemical Vapor Deposition (APCVD) and the safe h-BN precursor ammonia borane. These MWCNT@BNNTs were used as sacrificial templates for BNNT synthesis by thermal oxidation of the core carbon. Buckypaper fabrication was facilitated by facile sonication and filtration steps. To test the thermal conductivity properties of these new buckypapers, in the interest of thermal management applications, we have developed a novel technique of advanced scanning thermal microscopy (SThM) that we call piercing SThM (pSThM). Our measurements show a 14% increase in thermal conductivity of the MWCNT@BNNT buckypaper relative to a control multiwalled carbon nanotube (MWCNT) buckypaper. Meanwhile, our BNNT buckypaper exhibited approximately half the thermal conductivity of the MWCNT control, which we attribute to the turbostratic quality of our BNNTs. To the best of our knowledge, this work achieves the first thermal conductivity measurement of a MWCNT@BNNT buckypaper and of a BNNT buckypaper composed of BNNTs not synthesized by high energy techniques.

Mass photometric detection and quantification of nanoscale α-synuclein phase separation.

Protein liquid-liquid phase separation can lead to disease-related amyloid fibril formation. The mechanisms of conversion of monomeric protein into condensate droplets and of the latter into fibrils remain elusive. Here, using mass photometry, we demonstrate that the Parkinson's disease-related protein, α-synuclein, can form dynamic nanoscale clusters at physiologically relevant, sub-saturated concentrations. Nanoclusters nucleate in bulk solution and promote amyloid fibril formation of the dilute-phase monomers upon ageing. Their formation is instantaneous, even under conditions where macroscopic assemblies appear only after several days. The slow growth of the nanoclusters can be attributed to a kinetic barrier, probably due to an interfacial penalty from the charged C terminus of α-synuclein. Our findings reveal that α-synuclein phase separation occurs at much wider ranges of solution conditions than reported so far. Importantly, we establish mass photometry as a promising methodology to detect and quantify nanoscale precursors of phase separation. We also demonstrate its general applicability by probing the existence of nanoclusters of a non-amyloidogenic protein, Ddx4n1.

Photothermal and Humidity Stimulus-Responsive Self-Sensing Soft Actuators for Smart Packaging

Soft actuators with both actuation and self-sensing characteristics can better adapt to the environment and more effectively realize intelligent human–machine interactions, which is highly desired for the upcoming era of soft robotics. Herein, a multi-stimulus response actuator (MSRA) is constructed based on the asymmetric expansion principle, and the sensing function is simply and quickly integrated into the soft actuator by screen printing technology. Taking advantage of the good photothermal conversion performance of the dopamine-modified graphene oxide (DGO) layer and the difference in the expansion coefficient between the DGO layer and the poly(vinylidene fluoride)/polydimethylsiloxane layer, the soft actuators exhibit different actuation behaviors under photothermal and humidity stimuli, respectively. Meanwhile, the introduction of a printed carbon black/highly elastic transparent adhesive cement sensing layer gives MSRA a self-sensing function which can provide feedback on its actuation process in real time. In addition, various complex deformations can be achieved by the macroscopic assembly of several actuators. Finally, we show that this soft actuator can be used as a smart packaging material to realize smart packaging. We believe that actuators with sensing feedback are significant in soft robots and smart packaging.

Phonon-Assisted Intertube Electronic Transport in an Armchair Carbon Nanotube Film.

The electrical conductivity of a macroscopic assembly of nanomaterials is determined through a complex interplay of electronic transport within and between constituent nano-objects. Phonons play dual roles in this situation: their increased populations tend to reduce the conductivity via electron scattering, while they can boost the conductivity by assisting electrons to propagate through the potential-energy landscape. We identified a phonon-assisted coherent electron transport process between neighboring nanotubes in temperature-dependent conductivity measurements on a macroscopic film of armchair single-wall carbon nanotubes. Through atomistic modeling of electronic states and calculations of both electronic and phonon-assisted junction conductances, we conclude that phonon-assisted conductance is the dominant mechanism for observed high-temperature transport in armchair carbon nanotubes. The unambiguous manifestation of coherent intertube dynamics proves a single-chirality armchair nanotube film to be a unique macroscopic solid-state ensemble of nano-objects promising for the development of room-temperature coherent electronic devices.

Robust Electrostatically Interactive Hydrogel Coatings for Macroscopic Supramolecular Assembly via Rapid Wet Adhesion

A macroscopic supramolecular assembly (MSA) refers to non-covalent interactions between building blocks over a micrometer scale, which provides insights into bio-/wet adhesion, self-healing, and so on and new fabrication strategies to heterogeneous structures and bio-scaffolds. The key to realize the MSA of rigid materials is pre-modifying a compliant coating known as a "flexible spacing coating" beneath the interactive moieties. However, available coatings are limited to polyelectrolyte multilayers with shortcomings of tedious fabrication, weak adhesion to substrates, susceptibility to external reagents, and so on. Here, we develop a facile method to induce a new "flexible spacing coating" of a poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel with electrostatic interactions to achieve MSA of diverse rigid materials (quartz, metal, rubber, and plastics). Selective self-assembly of positive-negative charged surfaces is observed by the naked eye under 3 min of shaking in water, providing strategies to rapid wet adhesion. The interfacial binding force between positive-negative interacted surfaces is 1018.1 ± 299.2 N/m2, which is over two magnitudes larger than that of control groups, that is, positive-positive (24.4 ± 10.0 N/m2) and negative-negative (67.5 ± 16.7 N/m2) interacted surfaces. In situ force measurements and control experiments of identically charged building blocks have strongly supported the improved binding strength and chemical selectivity between interactive building blocks. The coating is advantageous with a simple fabrication, strong adhesion to materials, robust solvent tolerance to assembly solutions, and feasibility of photo-patterning. We envision that the above strategy would broaden the material choices of flexible spacing coatings for efficient MSA and new methods for rapid interfacial adhesion.

Direct mask-free fabrication of patterned hierarchical graphene electrode for on-chip micro-supercapacitors

• Functionalized membrane with customized pattern is prepared by fast laser carving. • Selective permeable membrane complemented with vacuum filtration is used to develop intact interdigital thin film. • Macroscopic assembly based on size effect rationally guide the structural design and precise fabrication of flexible electrode with expected high performances. • Flexible high-performance on-chip micro-supercapacitors with planar arbitrary shape are fabricated. Graphene-based electrodes with rational structural design have shown extraordinary prospect for enhanced electrical double-layer capacitance of micro-supercapacitors (MSCs). Herein, a facile fabrication method for flexible planar MSCs based on hierarchical graphene was demonstrated by using a laser-treated membrane for electrode patterning, complemented with hierarchical electrode configuration taking full advantages of size-determined functional graphene. The in-plane interdigital shape of MSCs was defined through vacuum filtration with the assistance of the functionalized polypropylene (PP) membrane. The hierarchical graphene films were built by macroscopic assembly based on size effect of different lateral sized graphene sheets (rGO-LSL). The sample of MSCs based on rGO-LSL (MSCs-LSL) exhibited excellent volumetric capacitance of 6.7 F cm −3 and high energy density of 0.37 mWh cm −3 . The MSCs-LSL presented superb flexibility and cycling stability with no capacitance deteroriated after 2000 cycles. This newly developed fabrication strategy is of good scalability and designability to manufacture flexible electrode for MSCs with customized shapes, while the construction of hierarchical graphene can enlighten the structural design of analogous two-dimensional materials for potential advanced electronics. A facile mask-free filtration approach is developed for the fabrication of patterned onchip micro-supercapacitors based on hierarchical graphene. The use of the functionalized membrane complemented with macroscopic assembly based on size effect provides the control over the planar configuration of micro-supercapacitors, and rationally guide the structural design of flexible electrode with expected high performances.

Development of an artificial neural network model for generating macroscopic cross-sections for RAST-AI

Homogenized macroscopic cross-sections (XS) are necessary for running core-wise nodal diffusion calculations. XS sets are usually generated using time-consuming lattice physics codes. In this study, a pre-trained artificial neural network was developed and used for XS generation. The model was trained to produce macroscopic XS, pin powers, and assembly discontinuity factors for 16 × 16 and 17 × 17 fuel assembly types with independent variable enrichments of each fuel pin loaded with fresh UO2 fuel without burnable poisons. The training dataset optimization method was described and used for defining the required number of variations in input parameters, such as pin arrangements and thermal hydraulics parameters. The optimized dataset's generation took only 248 core-hours, which is below 3 days on a modern 4-core CPU. For the worst-case out-of-range testing data, the maximum observed difference with the reference was found below 3% for pin powers, and below 4.5% for XS values.

A Microwave-Assisted, Solvent-Free Approach for the Versatile Functionalization of Carbon Nanotubes

While the functionalization of carbon nanotubes (CNTs) has attracted extensive interest for a wide range of applications, a facial and versatile strategy remains in demand. Here, we report a microwave-assisted, solvent-free approach to directly functionalize CNTs both in raw form and in arbitrary macroscopic assemblies. Rapid microwave irradiation was applied to generate active sites on the CNTs while not inducing excessive damage to the graphitic network, and a gas-phase deposition afforded controllable grafting for thorough or regioselective functionalization. Using methyl methacrylate (MMA) as a model functional group and a CNT sponge as a model assembly, homogeneous grafting was exhibited by the increased robust hydrophobicity (contact angle increase from 30 to 140°) and improved structural stability (compressive modulus increased by 135%). Therefore, when our MMA-functionalized CNTs served as a solar absorber for saline distillation, high operating stability with a superior water evaporation rate of ∼2.6 kg m-2 h-1 was observed. Finally, to highlight the efficacy and versatility of this functionalization approach, we fabricated asymmetrically hydrophobic CNT sponges by regioselective functionalization to serve as a moisture-driven generator, which demonstrated a stable open-circuit voltage of 0.6 mV. This versatile, solvent-free approach can complement conventional solution-based techniques in the design and fabrication of multifunctional nanocarbon-based materials.

Scalable, Highly Pure, and Diameter-Sorted Boron Nitride Nanotube by Aqueous Polymer Two-Phase Extraction.

Boron nitride nanotube (BNNT) has attracted recent attention owing to its exceptional material properties; yet, practical implementation in real-life applications has been elusive, mainly due to the purity issues associated with its large-scale synthesis. Although different purification methods have been discussed so far, there lacks a scalable solution method in the community. In this work, a simple, high-throughput, and scalable purification of BNNT is reported via modification of an established sorting technique, aqueous polymer two-phase extraction. A complete partition mapping of the boron nitridespecies is established, which enables the segregation of the highly pure BNNT with a major impurity removal efficiency of > 98%. A successful scaling up of the process is illustrated and provides solid evidence of its diameter sorting behavior. Last, towards its macroscopic assemblies, a liquid crystal of the purified BNNT is demonstrated. The effort toward large-scale solution purification of BNNT is believed to contribute significantly to the macroscopic realization of its exceptional properties in the near future.

Concentration-modulated global organizational chirality at the liquid/solid interface.

Understanding the origin of homochirality in macroscopic assemblies and manipulating organizational chirality still remain a challenge. Herein, homochirality is achieved by combination of the majority-rules principle and concentration-dependent molecular assembly at the liquid/solid interface. A lower molecular concentration in solution facilitates more efficient amplification of chirality, which is formulated by a cooperative equilibrium model based on the Langmuir adsorption isotherm. Our results contribute to gain a new insight into chiral amplification in supramolecular assemblies. Particularly, a homochiral monolayer can be obtained just through modulating the molecular concentration in mixed enantiomer systems.

A synergistic interfacial and topological strategy for reinforcing aramid nanofiber films.

While nanomaterials possess impressive mechanical properties at the microscale level, their macroscopic assemblies usually exhibit inferior properties due to ineffective stress transfer among individual nanomaterials. This issue is addressed in this work by achieving strong interfacial interactions between aramid nanofibers and graphene oxide nanosheets through a neutralization reaction in a dipolar solvent and regulating the topological properties using polymer micelles to form a compact structure, leading to the formation of a super-strong and super-tough nanofiber film. The film was prepared through a sol-gel-film transition process and possesses a nacre-like microstructure that deflects microcracks and prevents them from propagating straight through the film. Remarkably, it demonstrates a tensile strength of 599.0 MPa and a toughness of 37.7 MJ m-3, which are 491.0% and 1094.5% that of a pristine aramid nanofiber film, respectively. In addition, it exhibits excellent tolerance to extreme temperatures (-196 to 300 °C) and fatigue resistance to folding 10 000 times. Overall, this study presents a synergistic interfacial and topological enhancement strategy for constructing nanomaterial-based composites with inherited properties from the nanoscale building blocks to the macroscale structural material.

3D printing of cellulose/leaf-like zeolitic imidazolate frameworks (CelloZIF-L) for adsorption of carbon dioxide (CO2) and heavy metal ions.

Metal-organic frameworks (MOFs) have advanced several technologies. However, it is difficult to market MOFs without processing them into a commercialized structure, causing an unnecessary delay in the material's use. Herein, three-dimensional (3D) printing of cellulose/leaf-like zeolitic imidazolate frameworks (ZIF-L), denoted as CelloZIF-L, is reported via direct ink writing (DIW, robocasting). Formulating CelloZIF-L into 3D objects can dramatically affect the material's properties and, consequently, its adsorption efficiency. The 3D printing process of CelloZIF-L is simple and can be applied via direct printing into a solution of calcium chloride. The synthesis procedure enables the formation of CelloZIF-L with a ZIF content of 84%. 3D printing enables the integration of macroscopic assembly with microscopic properties, i.e., the formation of the hierarchical structure of CelloZIF-L with different shapes, such as cubes and filaments, with 84% loading of ZIF-L. The materials adsorb carbon dioxide (CO2) and heavy metals. 3D CelloZIF-L exhibited a CO2 adsorption capacity of 0.64-1.15 mmol g-1 at 1 bar (0 °C). The materials showed Cu2+ adsorption capacities of 389.8 ± 14-554.8 ± 15 mg g-1. They displayed selectivities of 86.8%, 6.7%, 2.4%, 0.93%, 0.61%, and 0.19% toward Fe3+, Al3+, Co2+, Cu2+, Na+, and Ca2+, respectively. The simple 3D printing procedure and the high adsorption efficiencies reveal the promising potential of our materials for industrial applications.