Cobalt MOF-Based Porous Carbonaceous Spheres for Multimodal Soft Actuator Exhibiting Intricate Biomimetic Motions.

The advancement of active electrode materials is essential to meet the demand for multifaceted soft robotic interactions. In this study, a new type of porous carbonaceous sphere (PCS) for a multimodal soft actuator capable of both magnetoactive and electro-ionic responses is reported. The PCS, derived from the simultaneous oxidative and reductive breakdown of specially designed cobalt-based metal-organic frameworks (Co-MOFs) with varying metal-to-ligand ratios, exhibits a high specific surface area of 529 m2 g-1 and a saturated magnetization of 142.7 Am2 kg-1. The size of the PCS can be controlled through the Ostwald ripening mechanism, while the porous structure can be regulated by adjusting the metal-to-ligand mol ratio. Its exceptional compatibility with poly(3,4-ethylene-dioxythiophene)-poly(styrenesulfonate) enables the creation of uniform electrode, crucial for producing soft actuators that work in both magnetic and electrical fields. Operated at an ultralow voltage of 1 V, the PCS-based actuator generates a blocking force of 47.5 mN and exhibits significant bending deflection even at an oscillation frequency of 10 Hz. Employing this simultaneous multimodal actuation ensures the dynamic and complex motions of a balancing bird robot and a dynamic eagle robot. This advancement marks a significant step toward the realization of more dynamic and versatile soft robotic systems.

Janus CoMOF-SEBS Membrane for Bifunctional Dielectric Layer in Triboelectric Nanogenerators.

Considerable research has been conducted on the application of functional nano-fillers to enhance the power generation capabilities of triboelectric nanogenerators (TENGs). However, these additives often exhibit a decrease in output power at higher concentration. Here, a Janus cobalt metal-organic framework-SEBS (JCMS) membrane is reported as a dual-purpose dielectric layer capable of efficiently capturing and blocking charges for high-performance TENGs. The JCMS is produced asymmetrically through gravitational sedimentation, employing spherical CoMOFs within a diluted SEBS solution. Beyond its dual dielectric characteristics, the JCMS showcases exceptional mechanical durability, displaying notable stretchability of up to 475% and remarkable resilience when subjected to diverse mechanical pressures. Consequently, the JCMS-TENG produces a maximum peak-to-peak voltage of 936 V, a current of 42.8 µA, and a power density of 10.89 W m- 2 when exposed to an external force of 10 N at a 5 Hz frequency. This investigation highlights the potential of JCMS-TENGs with unique structures, known for their exceptional energy harvesting capabilities, mechanical strength, and flexibility. Additionally, the promising prospects of easily produced asymmetric structures is emphasized with bifunctionalities for developing efficient and flexible MOFs-based TENGs. These advancements are well-suited for self-powered wearables, rehabilitation devices, and energy harvesters.

Functionally antagonistic polyelectrolyte for electro-ionic soft actuator.

Electro-active ionic soft actuators have been intensively investigated as an artificial muscle for soft robotics due to their large bending deformations at low voltages, small electric power consumption, superior energy density, high safety and biomimetic self-sensing actuation. However, their slow responses, poor durability and low bandwidth, mainly resulting from improper distribution of ionic conducting phase in polyelectrolyte membranes, hinder practical applications to real fields. We report a procedure to synthesize efficient polyelectrolyte membranes that have continuous conducting network suitable for electro-ionic artificial muscles. This functionally antagonistic solvent procedure makes amphiphilic Nafion molecules to assemble into micelles with ionic surfaces enclosing non-conducting cores. Especially, the ionic surfaces of these micelles combine together during casting process and form a continuous ionic conducting phase needed for high ionic conductivity, which boosts the performance of electro-ionic soft actuators by 10-time faster response and 36-time higher bending displacement. Furthermore, the developed muscle shows exceptional durability over 40 days under continuous actuation and broad bandwidth below 10 Hz, and is successfully applied to demonstrate an inchworm-mimetic soft robot and a kinetic tensegrity system.

Polysulfonated covalent organic framework as active electrode host for mobile cation guests in electrochemical soft actuator.

Tailoring transfer dynamics of mobile cations across solid-state electrolyte-electrode interfaces is crucial for high-performance electrochemical soft actuators. In general, actuation performance is directly proportional to the affinity of cations and anions in the electrolyte for the opposite electrode surfaces under an applied field. Herein, to maximize electrochemical actuation, we report an electronically conjugated polysulfonated covalent organic framework (pS-COF) used as a common electrolyte-electrode host for 1-ethyl-3-methylimidazolium cation embedded into a Nafion membrane. The pS-COF-based electrochemical actuator exhibits remarkable bending deflection at near-zero voltage (~0.01 V) and previously unattainable blocking force, which is 34 times higher than its own weight. The ultrafast step response shows a very short rising time of 1.59 seconds without back-relaxation, and substantial ultralow-voltage actuation at higher frequencies up to 5.0 hertz demonstrates good application prospects of common electrolyte-electrode hosts. A soft fluidic switch is constructed using the proposed soft actuator as a potential engineering application.

Magnetically and Electrically Responsive Soft Actuator Derived from Ferromagnetic Bimetallic Organic Framework.

The advancement in smart devices and soft robotics necessitates the use of multiresponsive soft actuators with high actuation stroke and stable reversibility for their use in real-world applications. Here, this work reports a magnetically and electrically dual responsive soft actuator based on neodymium and iron bimetallic organic frameworks (NdFeMOFs@700). The ferromagnetic NdFeMOFs@700 exhibits a porous carbon structure with excellent magnetization saturation (166.96 emu g-1 ) which allows its application to a dual functional material in both magnetoactive and electro-ionic actuations. The electro-ionic soft actuator, which is fabricated using NdFeMOFs@700 and PEDOT-PSS, demonstrates 4.5 times higher ionic charge storage capacity (68.21 mF cm-2 ) and has excellent cycle stability compared with the PEDOT-PSS based actuator. Under a low sinusoidal input voltage of 1 V, the dual-responsive actuator displays bending displacement of 15.46 mm and also generates deflection of 10 mm at 50 mT. Present results show that the ferromagnetic bimetallic organic frameworks can open a new way to make dual responsive soft actuators due to the hierarchically porous structures with its high redox activity, superior magnetic properties, and larger electrochemical capacitance. With the NdFeMOFs@700 based soft actuators, walking movement of a starfish robot is demonstrated by applying both the magnetic and electric fields.

Bisphenol-based cyanide sensing: Selectivity, reversibility, facile synthesis, bilateral "OFF-ON" fluorescence, C2ν structural and conformational analysis.

A structurally characterized novel dual-pocketed tetra-conjugated bisphenol-based chromophore (fluorescence = 652 nm) was synthesized in gram scale in ~90% yield from its tetraaldehyde. Highly selective, naked-eye detection of CN- (DMSO/H2O) was confirmed by interferent testing. A detection limit of 0.38 µM, within the permissible limit of CN- concentration in drinking water was achieved as mandated by WHO. The "reversibility" study shows potential applicability and reusability of Sen. Moreover, cost-effective and on-site interfaces, application tools such as fabricated cotton swabs, plastic Petri dishes, and filter papers further demonstrated the specific selectivity of Sen for the toxic CN-. In addition, an easily available and handy smartphone-assisted "Color Picker" app was utilized to help estimate the concentration of CN- ion present. A dual phenol deprotonation mechanism is active and supported by 1H NMR spectroscopic data and DFT calculation results.

Asynchronous Double Schiff Base Formation of Pyrazole Porous Polymers for Selective Pd Recovery.

Pyrazole-linked covalent organic polymer is synthesized using an asynchronous double Schiff base from readily available monomers. The one-pot reaction features no metals as a building block or reagent, hence facilitating the structural purity and industrial scalability of the design. Through a single-crystal study on a model compound, the double Schiff base formation is found to follow syn addition, a kinetically favored product, suggesting that reactivity of the amine and carbonyls dictate the order and geometry of the framework building. The highly porous pyrazole polymer COP-214 is chemically resistant in reactive conditions for over two weeks and thermally stable up to 425 °C in air. COP-214 shows well-pronounced gas capture and selectivities, and a high CO2/N2 selectivity of 102. The strongly coordinating pyrazole sites show rapid uptake and quantitative selectivity of Pd (II) over several coordinating metals (especially Pt (II)) at all pH points that are tested, a remarkably rare feature that is best explained by detailed analysis as the size-selective strong coordination of Pd onto pyrazoles. Density functional theory (DFT) calculations show energetically favorable Pd binding between the metal and N-sites of COP-214. The polymer is reusable multiple times without loss of activity, providing great incentives for an industrial prospect.

Inversion of Dispersion: Colloidal Stability of Calixarene-Modified Metal-Organic Framework Nanoparticles in Nonpolar Media.

Making metal-organic frameworks (MOFs) that are stabilized in nonpolar media is not as straightforward as making their inorganic nanoparticle counterparts, since surfactants penetrate through the porous structures or dissolve the secondary building units (SBUs) through ligand-exchange linker modulator mechanisms. Herein, we report that calixarenes stabilize UIO-66 nanoparticles effectively by remaining outside the grains through size exclusion, without pores becoming blocked, all the while providing amphiphilicity that permits the formation of stable colloidal dispersions with much narrower size distributions. Using the UIO-66 dispersed solutions, we show that smooth films from an otherwise immiscible polystyrene can be made feasibly.

Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid-State [2+2]-Photopolymerization.

An organic polymer containing cyclobutanes and amides as backbones and pyridyl groups as sidearms was synthesized by single-crystal-to-single-crystal (SCSC) [2+2]-photopolymerization in the coordination polymers (CPs) of diene. The diene molecule was photo-inactive in its crystals and formed a triply intertwined 1D-helical CP with Cd(NO3 )2 and Cu(NO3 )2 salts. The 1D-CP was transformed into a coordination polymer of organic polymers containing threefold interpenetrated 3D-networks of CdSO4 topology through a [2+2]-reaction in SCSC manner upon irradiation. The organic polymer was separated from its CPs and found to have an unusually high degree of polymerization for this type of reaction. Furthermore, the organic polymer was amenable for N-alkylation reactions such as methylation, propylation, and decylation. The formate salts of the organic polymer and the methylated polymer were shown to form plastic films with a combination of properties such as high transparency, tensile strengths, gas permeability, thermal stability, water-resistance, and resistance to other organic solvents. The methylated polymer was also able to capture chromate ions and anionic dyes from aqueous solutions.

Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: ß-sheet versus two-dimensional layers in solid-state photochemical [2†+†2] reactions.

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N-H⋯Npy versus N-H⋯O=C) and network geometries. In this series, a greater tendency towards the formation of N-H⋯O hydrogen bonds (ß-sheets and two-dimensional networks) over N-H⋯N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layer via N-H⋯O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

Coordination polymers of organic polymers synthesized via photopolymerization of single crystals: two-dimensional hydrogen bonding layers with amazing shock absorbing nature.

Crystalline coordination polymers of organic polymers (CPOPs) were synthesized via photopolymerization of Ag(I) coordination polymers of dienes which have a self-templating nature due to the formation of N-H···O hydrogen bonded layers. The shock absorbing nature of the H-bonded layer facilitated the SCSC [2+2] transformation upon irradiation to produce CPOPs.