Cyclooctatetraene-Embedded Carbon Nanorings.

With the prosperity of the development of carbon nanorings, certain topologically or functionally unique units-embedded carbon nanorings have sprung up in the past decade. Herein, we report the facile and efficient synthesis of three cyclooctatetraene-embedded carbon nanorings (COTCNRs) that contain three (COTCNR1 and COTCNR2) and four (COTCNR3) COT units in a one-pot Yamamoto coupling. These nanorings feature hoop-shaped segments of Gyroid (G-), Diamond (D-), and Primitive (P-) type carbon schwarzites. The conformations of the trimeric nanorings COTCNR1 and COTCNR2 are shape-persistent, whereas the tetrameric COTCNR3 possesses a flexible carbon skeleton which undergoes conformational changes upon forming host-guest complexes with fullerenes (C60 and C70), whose co-crystals may potentially serve as fullerene-based semiconducting supramolecular wires with electrical conductivities on the order of 10-7 S cm-1 (for C60⊂COTCNR3) and 10-8 S cm-1 (for C70⊂COTCNR3) under ambient conditions. This research not only describes highly efficient one-step syntheses of three cyclooctatetraene-embedded carbon nanorings which feature hoop-shaped segments of distinctive topological carbon schwarzites, but also demonstrates the potential application in electronics of the one-dimensional fullerene arrays secured by COTCNR3.

Cellulose-Based Conductive Materials for Energy and Sensing Applications.

Cellulose-based conductive materials (CCMs) have emerged as a promising class of materials with various applications in energy and sensing. This review provides a comprehensive overview of the synthesis methods and properties of CCMs and their applications in batteries, supercapacitors, chemical sensors, biosensors, and mechanical sensors. Derived from renewable resources, cellulose serves as a scaffold for integrating conductive additives such as carbon nanotubes (CNTs), graphene, metal particles, metal-organic frameworks (MOFs), carbides and nitrides of transition metals (MXene), and conductive polymers. This combination results in materials with excellent electrical conductivity while retaining the eco-friendliness and biocompatibility of cellulose. In the field of energy storage, CCMs show great potential for batteries and supercapacitors due to their high surface area, excellent mechanical strength, tunable chemistry, and high porosity. Their flexibility makes them ideal for wearable and flexible electronics, contributing to advances in portable energy storage and electronic integration into various substrates. In addition, CCMs play a key role in sensing applications. Their biocompatibility allows for the development of implantable biosensors and biodegradable environmental sensors to meet the growing demand for health and environmental monitoring. Looking to the future, this review emphasizes the need for scalable synthetic methods, improved mechanical and thermal properties, and exploration of novel cellulose sources and modifications. Continued innovation in CCMs promises to revolutionize sustainable energy storage and sensing technologies, providing environmentally friendly solutions to pressing global challenges.

Soluble and Processable Single-Crystalline Cationic Polymers.

Single-crystal-to-single-crystal (SCSC) polymerization offers an effective protocol for the environmentally friendly preparation of polymer single crystals (PSCs) with extremely high crystallinity and very large molecular weights. Single-crystal X-ray diffraction (SCXRD) serves as a powerful technique for the in-depth characterization of their structures at a molecular level. Hence, a fundamental understanding of the structure-property relationships of PSCs is within our reach. Most of the reported PSCs, however, suffer from poor solubility, a property which hampers their post-functionalization and solution processability when it comes to practical applications. Here, we report soluble and processable PSCs with rigid polycationic backbones by taking advantage of an ultraviolet-induced topochemical polymerization from an elaborately designed monomer that results in a multitude of photoinduced [2 + 2] cycloadditions. The high crystallinity and excellent solubility of the resulting polymeric crystals enable their characterization both in the solid state by X-ray crystallography and electron microscopy and in the solution phase by NMR spectroscopy. The topochemical polymerization follows first-order reaction kinetics to a first approximation. Post-functionalization of the PSCs by anion exchange renders them super-hydrophobic materials for water purification. Solution processability endows PSCs with excellent gel-like rheological properties. This research represents a major step towards the controlled synthesis and full characterization of soluble single-crystalline polymers, which may find application in the fabrication of PSCs with many different functions.

Chain-ring covalently interconnected cellulose nanofiber/MWCNT aerogel for supercapacitors and sensors.

Bending multi-walled carbon nanotubes (MWCNTs) into rings and structuring them into aerogels is difficult. In this study, cellulose nanofiber (CNF)-MWCNT composite fibers with chain-ring structures were prepared by covalently interconnecting carboxylated CNF and aminated MWCNT by dehydration condensation, solving the problems of the formation of MWCNT aerogels and their phase separation during the compounding process and providing CNF-based aerogels with electrical conductivity. The covalently interconnected aerogels (CAs) had hierarchical porous structures with mechanical resilience and chain-ring fibers, which drove the CNF and MWCNT to form a continuous homogeneous network resulting in a high compression resistance of 269.02 kPa. The CA-based flexible all-solid-state supercapacitor had a quality specific capacitance of 114.8 F g-1, a capacitance retention rate of 94.78% and a Coulomb efficiency of 100%. The CA-based flexible sensor can sense different pressures with a stable response for 1000 cycles. This first study of pulling and bending MWCNT through CNF is expected to inspire more applications of MWCNTs in the fields of flexible supercapacitors and sensors.

Flexible, anti-damage, and non-contact sensing electronic skin implanted with MWCNT to block public pathogens contact infection.

If a person comes into contact with pathogens on public facilities, there is a threat of contact (skin/wound) infections. More urgently, there are also reports about COVID-19 coronavirus contact infection, which once again reminds that contact infection is a very easily overlooked disease exposure route. Herein, we propose an innovative implantation strategy to fabricate a multi-walled carbon nanotube/polyvinyl alcohol (MWCNT/PVA, MCP) interpenetrating interface to achieve flexibility, anti-damage, and non-contact sensing electronic skin (E-skin). Interestingly, the MCP E-skin had a fascinating non-contact sensing function, which can respond to the finger approaching 0-20 mm through the spatial weak field. This non-contact sensing can be applied urgently to human-machine interactions in public facilities to block pathogen. The scratches of the fruit knife did not damage the MCP E-skin, and can resist chemical corrosion after hydrophobic treatment. In addition, the MCP E-skin was developed to real-time monitor the respiratory and cough for exercise detection and disease diagnosis. Notably, the MCP E-skin has great potential for emergency applications in times of infectious disease pandemics. Electronic Supplementary Material: Supplementary material (fabrication of MCP E-skin, laser confocal tomography, parameter optimization, mechanical property characterization, finite element simulation, sensing mechanism, signal processing) is available in the online version of this article at 10.1007/s12274-021-3831-z.

Confined Chemical Transitions for Direct Extraction of Conductive Cellulose Nanofibers with Graphitized Carbon Shell at Low Temperature and Pressure.

Cellulose is the most abundant renewable natural polymer on earth, but it does not conduct electricity, which limits its application expansion. The existing methods of making cellulose conductive are combined with another conductive material or high-temperature/high-pressure carbonization of the cellulose itself, while in the traditional method of sulfuric acid hydrolysis to extract nanocellulose, it is usually believed that a too high temperature will destroy cellulose and lead to experimental failure. Now, based on a new research perspective, by controlling the continuous reaction process and isolating oxygen, we directly extracted intrinsically conductive cellulose nanofiber (CNF) from biomass, where the confined range molecular chains of CNF were converted to highly graphitized carbon at only 90 °C and atmospheric pressure, while large-scale twisted graphene films can be synthesized bottom-up from CNFene suspensions, called CNFene (cellulose nanofiber-graphene). The conductivity of the best CNFene can be as high as 1.099 S/cm, and the generality of this synthetic route has been verified from multiple biomass cellulose sources. By comparing the conventional high-pressure hydrothermal and high-temperature pyrolysis methods, this study avoided the dangerous high-pressure environment and saved 86.16% in energy. These findings break through the conventional notion that nanocellulose cannot conduct electricity by itself and are expected to extend the application potential of pure nanocellulose to energy storage, catalysis, and sensing.

Smart nonwoven fabric with reversibly dual-stimuli responsive wettability for intelligent oil-water separation and pollutants removal.

This work presents the first fabrication of smart nonwoven fabric (DSR-CZPP) with extraordinary reversible double-stimulus responsive wettability, where carboxyl groups of cellulose nanocrystals/zinc oxide (CNC/ZnO) nanohybrids deposited on fabric surface can bond with hydroxyl group of the PDMAEMA-b-PHEMA-b-PMAAAB triblock polymer brushes that was prepared by using methyl methacrylate (HEMA), dimethylaminoethyl methacrylate (DMAEMA) and methacrylamide-azobenzene monomer (MAAAB) via reversible addition-fragmentation chain transfer (RAFT). The peculiar reversible double-stimulus responsive wettability of the DSR-CZPP can be modulated by triggering hydrophilic/hydrophobic transitions and lipophilic/oleophobic transitions under dual-stimulations of pH and UV light irradiation. The special molecular structure of the triblock polymer brushes enabled DSR-CZPP to intelligent modulation of oil-water separation under the control of "UV & pH double switch", meanwhile CNC/ZnO simultaneously can induce the photocatalytic degradation of organic dyes. Moreover, DSR-CZPP can have high removal ratios of various pollutants, such as metal ion (Cu2+) and toxic organic solvent (silicone oil, acetone and chloroform). This smart and multifunctional fabric shows great potentials for treating complicated polluted water from most industrial fields.

Designing Highly Luminescent Cellulose Nanocrystals with Modulated Morphology for Multifunctional Bioimaging Materials.

Spherical cellulose nanocrystals (SCNs) and rod-shaped cellulose nanocrystals (RCNs) were extracted from different cellulose materials. The two shape forms of cellulose nanocrystals (CNs) were designed with a combination of isothiocyanate (FITC), and both the obtained FITC-SCNs and FITC-RCNs exhibited high fluorescence brightness. The surfaces of SCNs and RCNs were subjected to a secondary imino group by a Schiff reaction and then covalently bonded to the isothiocyanate group of FITC through a secondary imino group to obtain fluorescent cellulose nanocrystals (FITC-CNs). The absolute ζ-potential and dispersion stability of FITC-CNs (FITC-SCNs and FITC-RCNs) were improved, which also promoted the increase in the fluorescence quantum yield. FITC-RCNs had a fluorescence quantum yield of 30.7%, and FITC-SCNs had a morphological advantage (better dispersion, etc.), resulting in a higher fluorescence quantum yield of 35.9%. Cell cytotoxicity experiments demonstrated that the process of FITC-CNs entering mouse osteoblasts (MC3T3) did not destroy the cell membrane, showing good biocompatibility. On the other hand, FITC-CNs with good dispersibility can significantly enhance poly(vinyl alcohol) (PVA) and poly(lactic acid) (PLA); their mechanical properties were improved (the highest sample reached to 243%) and their fluorescent properties were imparted. This study provides a simple surface functionalization method to produce high-luminance fluorescent materials for bioimaging, multifunctional nanoenhancement/dispersion marking, and anticounterfeiting materials.

Supramolecular Self-Assembly of 3D Conductive Cellulose Nanofiber Aerogels for Flexible Supercapacitors and Ultrasensitive Sensors.

Nature employs supramolecular self-assembly to organize many molecularly complex structures. Based on this, we now report for the first time the supramolecular self-assembly of 3D lightweight nanocellulose aerogels using carboxylated ginger cellulose nanofibers and polyaniline (PANI) in a green aqueous medium. A possible supramolecular self-assembly of the 3D conductive supramolecular aerogel (SA) was provided, which also possessed mechanical flexibility, shape recovery capabilities, and a porous networked microstructure to support the conductive PANI chains. The lightweight conductive SA with hierarchically porous 3D structures (porosity of 96.90%) exhibited a high conductivity of 0.372 mS/cm and a larger area-normalized capacitance (Cs) of 59.26 mF/cm2, which is 20 times higher than other 3D chemically cross-linked nanocellulose aerogels, fast charge-discharge performance, and excellent capacitance retention. Combining the flexible SA solid electrolyte with low-cost nonwoven polypropylene and PVA/H2SO4 yielded a high normalized capacitance (Cm) of 291.01 F/g without the use of adhesive that was typically required for flexible energy storage devices. Furthermore, the supramolecular conductive aerogel could be used as a universal sensitive sensor for toxic gas, field sobriety tests, and health monitoring devices by utilizing the electrode material in lightweight supercapacitor and wearable flexible devices.