Photothermal-responsive lignin-based polyurethane with mechanically robust, fast self-healing, solid-state plasticity and shape-memory performance.

In light of the depletion of petrochemical resources and increase in environmental pollution, there has been a significant focus on utilizing natural biomass, specifically lignin, to develop sustainable and functional materials. This research presents the development of a lignin-based polyurethane (DLPU) with photothermal-responsiveness by incorporating lignin and oxime-carbamate bonds into polyurethane network. The abundant hydrogen bonds between lignin and the polyurethane matrix, along with its cross-linked structure, contribute to DLPU's excellent mechanical strength (30.2 MPa) and toughness (118.7 MJ·m-3). Moreover, the excellent photothermal conversion ability of DLPU (54.4 %) activates dynamic reversible behavior of oxime-carbamate bonds and hydrogen bonds, thereby endowing DLPU with exceptional self-healing performance. After 15 min of near-infrared irradiation, DLPU achieves self-healing efficiencies of 96.0 % for tensile strength and 96.3 % for elongation at break. Additionally, DLPU exhibits photocontrolled solid-state plasticity as well as an excellent phototriggered shape-memory effect (70 s), with shape fixity and recovery ratios reaching 98.8 % and 95.3 %, respectively. By exploiting the spatial controllability and photothermal-responsiveness of DLPU, we demonstrate multi-dimensional responsive materials with self-healing and shape-shifting properties. This work not only promotes the development of multi-functional polyurethanes but also provides a pathway for the high-value utilization of lignin.

Real-Time Evaluation of Adhesion Processes and Glucose Response of Cancer Cells onto Phenylboronic Acid-Functionalized Films Monitored by Quartz Crystal Microbalance with Dissipation.

Understanding the interactions between cancer cells and smart substrates is of great benefit to physiology and pathology. Herein, we successfully fabricated two phenylboronic acid (PBA)-functionalized films with different surface topographies using a PBA homopolymer (PBAH) and self-assembled nanoparticles (PBAS) via a layer-by-layer assembly technique. We used a quartz crystal microbalance with dissipation (QCM-D) to monitor the entire cell adhesion process and figured out the adhesion kinetics of HepG2 cells on the two PBA-functionalized films. As seen from the QCM-D data, the HepG2 cells displayed distinctly different adhesion behaviors on the two PBA-functionalized films (PBAS and PBAH films). The results showed that the PBAS film promoted cell adhesion and cell spreading owing to its specific physicochemical properties. Likewise, the slope changes in the D-f plots clearly revealed the evolution of the cell adhesion process, which could be classified into three stages during cell adhesion on the PBA-functionalized films. In addition, compared with the PBAH film, the PBAS film could also control cell detachment behavior in the presence of glucose based on the molecular recognition between the PBA group and the cell membrane. Such a glucose-responsive PBAS film is promising for biological applications, including cell-based diagnostics and tissue engineering. In addition, the QCM-D proved to be a useful tool for in situ and real-time monitoring and analysis of interactions between cells and surfaces of supporting substrates.

Unique Spindle-Like Bismuth-Based Composite toward Ultrafast Potassium Storage.

Bismuth (Bi)-based materials have attracted great attention as anodes in potassium ion batteries (PIBs) for their high theoretical capacity and suitable voltage range. Herein, the authors report a unique spindle-like structured Bi@N-doped carbon composite (SPB@NC) consisting of interconnected nano-Bi coated heteroatom-doped hard carbon layer via an interesting in situ carbon thermal reduction method. The special interconnected Bi nanoparticles gradually form porous structure with ample inner voids for accommodating volume variations while the N-doped carbon layer not only keeps the electrode stable, but also contributes to rapid electron/ion transfer. As a result, such a robust framework endows SPB@NC fast potassium storage with outstanding capacity of 276.5 mAh g-1  at 30 A g-1 (i.e., 1 min for discharge/charge) and durable cycling performance of 299.3 mAh g-1  at 5 A g-1  after 2000 cycles. Notably, a full cell assembled with potassium vanadate cathode is promising for practical applications. A series of ex situ techniques reveals the in-depth potassium storage mechanism and kinetics reactions. This work illuminates helpful insights into Bi-based anodes for PIBs.

FAR knockout significantly inhibits Chilo suppressalis survival and transgene expression of double-stranded FAR in rice exhibits strong pest resistance.

Chilo suppressalis is one of the most prevalent and damaging rice pests, causing significant economic losses each year. Chemical control is currently the primary method of controlling C. suppressalis. However, the indiscriminate use of chemical insecticides increases pest resistance, pollutes the environment and poses a significant health threat to humans and livestock, highlighting the need to find safer, more pest-specific and more effective alternatives to pest control. Plant-mediated RNA interference (RNAi) is a promising agricultural pest control method that is highly pest-specific and has less of an impact on the environment. Using multi-sgRNAs/Cas9 technology to delete Fatty acyl-CoA reductase (FAR) of C. suppressalis in the G0 generation, we show that downregulating FAR transcription may significantly increase the mortality rate and darken the epidermis of C. suppressalis compared with the control. Subsequently, we developed dsFAR transgenic rice lines using Agrobacterium-mediated genetic transformation and then screened three strains expressing dsFAR at high levels using transcriptional level analysis. Using transgenic rice stems, a laboratory feeding bioassay indicated that at least one line (L#10) displayed a particularly high level of insect resistance, with an insect mortality rate of more than 80%. In the field trials, dsFAR transgenic rice displayed high levels of resistance to C. suppressalis damage. Collectively, these results suggest the potential of a new environment-friendly, species-specific strategy for rice pest management.

Dual-Carbon confinement strategy of antimony anode material enabling advanced potassium ion storage.

Antimony (Sb) has attracted considerable attention as an anode material for potassium ion batteries (PIBs) because of its high theoretical capacity. Nevertheless, owing to the large radius of K+, apparent volume expansion occurs during the reaction between Sb and K+, which will undermine the stability of the electrode. Accordingly, a dual-carbon confinement strategy is regarded as an effective method for handling this issue. Herein, Sb is firstly captured by mesoporous carbon sphere (MCS) to form a composite of Sb/MCS, and then reduced graphene oxide (rGO) is adopted as an outer layer to wrap the Sb/MCS to obtain the dual-carbon confinement material (Sb/MCS@rGO). Given the synergistic confinement effects of the MCS and rGO, the Sb/MCS@rGO electrode realizes an excellent rate capacity of 341.9 mAh g-1 at 1000 mA g-1 and prominent cycling stability with around 100% retention at 50 mA g-1 after 100 cycles. Besides, the discussion on galvanostatic charge-discharge test, cyclic voltammetry and ex-situ XRD illustrates the stepwise potassium storage mechanism of Sb. Benefiting from the dual-carbon confinement effects, the Sb/MCS@rGO electrode processes promising electrochemical reaction kinetics. Furthermore, the application of the Sb/MCS@rGO in full cells also demonstrates its superior rate capacity (212.3 mAh g-1 at 1000 mA g-1).

FeSb2 Nanoparticles Embedded in 3D Porous Carbon Framework: An Robust Anode Material for Potassium Storage with Long Activation Process.

Due to their characteristics of high capacity and appropriate potassiation/depotassiation potential, Sb-based materials have become a class of promising anode materials for potassium ion batteries (PIBs). However, the huge strain induced by potassiation/depotassiation limits their ability to periodically accept/release K+ . Herein, a composite with FeSb2 nanoparticles embedded in a 3D porous carbon framework (FeSb2 @3DPC) is successfully constructed as an extremely stable anode material for PIBs. Benefiting from the synergistic effect of the design of nano and porous structures, the introduction of the inactive metal Fe, the firm anchoring of the FeSb2 nanoparticles by the carbon material, and the incomplete reaction of the FeSb2 , the FeSb2 @3DPC can achieve an ultra-long cycle life of over 4000 cycles at a current density of 500 mA g-1 . Furthermore, ex situ X-ray diffraction and transmission electron microscopy reveal a gradual activation process of FeSb2 for potassium storage. Fortunately, after activation, the electrochemical polarization of the FeSb2 @3DPC anode gradually alleviates and the capacitance-controlled charge storage mode further dominates compared with the diffusion-controlled mode, all of which promote the FeSb2 @3DPC to maintain the stable potassium storage capability.

Construction of three-dimensional nitrogen doped porous carbon flake electrodes for advanced potassium-ion hybrid capacitors.

It is of great significance to develop a new kind of green and environmentally friendly potassium ion energy storage device, with stable structures and large specific capacity. In this manuscript, a facile and robust way is reported to construct nitrogen doped porous carbon flake (NPCF) through NaCl template and pyrolysis method. 3D porous structures can be formed and interconnected NPCF are used as potassium ion batteries (PIBs) anode. High content of pyridinic N/pyrrolic N and enlarged interlayer distance of NPCF are obtained. Specifically, the anode delivers a high reversible capacity of 326.3 mAh g-1 at the current density of 50 mA g-1, and shows up outstanding cycle stability and represents long cycle life of 10,000 cycles at a current density of 5000 mA g-1. Moreover, the cyclic voltammetry kinetic analysis shows that the main capacitive process plays a leading role in the potassium storage mechanism. Consequently, equipped with activate carbon (AC) as cathode and NPCF as anode, the assembled potassium ion hybrid capacitors (PIHCs) achieve an energy density of 65.8 Wh kg-1 at 100 mA g-1, and maintains 30 Wh kg-1 even at a high current density of 5000 mA g-1.

In-Depth Mechanism Understanding for Potassium-Ion Batteries by Electroanalytical Methods and Advanced In Situ Characterization Techniques.

The advancement of potassium ion batteries (PIBs) stimulated by the dearth of lithium resources is accelerating. Major progresses on the electrochemical properties are based on the optimization of electrode materials, electrolytes, and other components. More significantly, the prerequisites for optimizing these key compositions are in-depth and comprehensive exploration of electrochemical reaction processes, including the evolution of morphology and structure, phase transition, interface behaviors, and K+ movement, etc. As a result, the obtained K+ storage mechanism via analyzing aforementioned reaction processes sheds light on furthering practical application of PIBs. Typical electrochemical analysis methods are capable of obtaining physical and chemical characteristics. The advent of in situ electrochemical measurements enables dynamic observation and monitoring, thereby gaining extensive insights into the intricate mechanism of capacity degradation and interface kinetics. By coupling with these powerful electrochemical characterization techniques, inspiring works in PIBs will burgeon into wide realms of energy storage fields. In this review, some typical electroanalytical tests and in situ hyphenated measurements are described with the main concentration on how these techniques play a role in investigating the potassium storage mechanism for PIBs and achieving encouraging results.

Carbon Hollow Tube-Confined Sb/Sb2S3 Nanorod Fragments as Highly Stable Anodes for Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) have attracted widespread attention in recent years due to their potential advantages such as low cost and high energy density. However, the large radius of K+ and the low potassium storage capacity of some electrode materials limit their development. Antimony (Sb)-based materials are considered to be promising anode materials for PIBs in view of their high K storage capacity and low potassiation potential. Nonetheless, the huge volume variation caused by potassiation/depotassiation often leads to their failure. Previous works have proved that carbon coating and nanostructure design are important means to alleviate the volume effect. Herein, the carbon-coating technology and nanostructure design were combined to prepare a Sb-based nanomaterial with Sb/Sb2S3 hybrid nanorod fragments confined in a carbon hollow tube (Sb/Sb2S3@CHT). Such a nanostructure is beneficial to alleviate the volume change of the Sb/Sb2S3 hybrids while facilitating the kinetics of the electrochemical reaction. As a consequence, the Sb/Sb2S3@CHT anode electrode exhibits high rate performance and outstanding cycle stability characterized by retaining a high specific capacity of 400.9 mA h g-1 after cycling for 200 cycles at 200 mA g-1.

High Capacity and Fast Kinetics of Potassium-Ion Batteries Boosted by Nitrogen-Doped Mesoporous Carbon Spheres.

In view of rich potassium resources and their working potential, potassium-ion batteries (PIBs) are deemed as next generation rechargeable batteries. Owing to carbon materials with the preponderance of durability and economic price, they are widely employed in PIBs anode materials. Currently, porosity design and heteroatom doping as efficacious improvement strategies have been applied to the structural design of carbon materials to improve their electrochemical performances. Herein, nitrogen-doped mesoporous carbon spheres (MCS) are synthesized by a facile hard template method. The MCS demonstrate larger interlayer spacing in a short range, high specific surface area, abundant mesoporous structures and active sites, enhancing K-ion migration and diffusion. Furthermore, we screen out the pyrolysis temperature of 900 °C and the pore diameter of 7 nm as optimized conditions for MCS to improve performances. In detail, the optimized MCS-7-900 electrode achieves high rate capacity (107.9 mAh g-1 at 5000 mA g-1) and stably brings about 3600 cycles at 1000 mA g-1. According to electrochemical kinetic analysis, the capacitive-controlled effects play dominant roles in total storage mechanism. Additionally, the full-cell equipped MCS-7-900 as anode is successfully constructed to evaluate the practicality of MCS.

Hydroxypropyl cellulose enhanced ionic conductive double-network hydrogels.

Ionic conductive hydrogels with both high-performance in conductivity and mechanical properties have received increasing attention due to their unique potential in artificial soft electronics. Here, a dual physically cross-linked double network (DN) hydrogel with high ionic conductivity and tensile strength was fabricated by a facile approach. Hydroxypropyl cellulose (HPC) biopolymer fibers were embedded in a poly (vinyl alcohol)­sodium alginate (PVA/SA) hydrogel, and then the prestretched PVA-HPC/SA composite hydrogel was immersed in a CaCl2 solution to prepare PVA-HPCT/SA-Ca DN hydrogels. The obtained composite hydrogel has an excellent tensile strength up to 1.4 MPa. Importantly, the synergistic effect of hydroxypropyl cellulose (HPC) and prestretching reduces the migration resistance of ions in the hydrogel, and the conductivity reaches 3.49 S/ m. In addition, these composite hydrogels are noncytotoxic, and they have a low friction coefficient and an excellent wear resistance. Therefore, PVA-HPCT/SA-Ca DN hydrogels have potential applications in nerve replacement materials and biosensors.

Flame Retardancy and Thermal Behavior of an Unsaturated Polyester Modified with Kaolinite-Urea Intercalation Complexes.

Organic modified kaolinite-urea intercalation complex (KUIC) was prepared using dimethyl sulfoxide (DMSO) as the precursor of kaolinite intercalation. Its structure was characterized by Fourier transform infrared (FTIR) and X-ray diffraction (XRD). Subsequently, as a synergistic agent, KUIC was combined with flame retardant ammonium polyphosphate (APP) to improve the flame retardant and smoke suppression performance of unsaturated polyester (UP) resin. A cone calorimeter (CONE) was used to study its flame retardancy and smoke suppression, and a scanning electron microscope (SEM) and thermogravimetry (TG) were used to study the micro morphology of the char and flame retardant mechanism. The results show that 12 phr of APP and 3 phr of KUIC were doped into UP to obtain a 28.0% limiting oxygen index (LOI) value. Compared with UP, the heat release rate and smoke production of UP/APP/KUIC composites were greatly decreased. Meanwhile, KUIC indeed enhanced the mechanical properties of UP.

Advanced Anode Materials of Potassium Ion Batteries: from Zero Dimension to Three Dimensions.

Potassium ion batteries (PIBs) with the prominent advantages of sufficient reserves and economical cost are attractive candidates of new rechargeable batteries for large-grid electrochemical energy storage systems (EESs). However, there are still some obstacles like large size of K+ to commercial PIBs applications. Therefore, rational structural design based on appropriate materials is essential to obtain practical PIBs anode with K+ accommodated and fast diffused. Nanostructural design has been considered as one of the effective strategies to solve these issues owing to unique physicochemical properties. Accordingly, quite a few recent anode materials with different dimensions in PIBs have been reported, mainly involving in carbon materials, metal-based chalcogenides (MCs), metal-based oxides (MOs), and alloying materials. Among these anodes, nanostructural carbon materials with shorter ionic transfer path are beneficial for decreasing the resistances of transportation. Besides, MCs, MOs, and alloying materials with nanostructures can effectively alleviate their stress changes. Herein, these materials are classified into 0D, 1D, 2D, and 3D. Particularly, the relationship between different dimensional structures and the corresponding electrochemical performances has been outlined. Meanwhile, some strategies are proposed to deal with the current disadvantages. Hope that the readers are enlightened from this review to carry out further experiments better.

Mussel-Inspired General Interface Modification Method and Its Application in Polymer Reinforcement and as a Flame Retardant.

Inspired by the remarkable adhesion of mussels, the mimicking of natural adhesive molecules has been widely used for surface modification. In the present study, an economical and easily available biomimic material named as tannic acid-Fe3+ (TA-Fe3+) was first directly used as a surface modifier, carbonization agent, smoke inhibitor, and flame-retardant synergist. Compared with the flame-retardant magnesium hydroxide (Mg(OH)2), TA-Fe3+-modified Mg(OH)2 endowed polyamide 6 (PA 6) with improved mechanical performance and flame-retardant properties. The flame-retardant and smoke-suppressant properties were tested by the limiting oxygen index and cone calorimeter tests. The flame-retardation mechanism was investigated by thermogravimetric analysis, scanning electron microscopy, and X-ray photoelectron spectroscopy. The tensile strength could increase up to 90%, and the modified flame retardant was found to have higher UL-94 grade with the same dosage of flame-retardant additives. The peak heat release rate, total heat release, peak of smoke production rate, and total smoke production were significantly reduced. The synergistic effect between TA-Fe3+ and Mg(OH)2 was also discussed. This study provides new insights into the direct utilization of a biomimicking adhesive molecule, TA-Fe3+, to realize simultaneous composite reinforcement and flame-retardant property enhancement. Meanwhile, because of the extensive synergies of flame-retardant metal oxide with iron element and the universal growth characteristics of TA-Fe3+, it has potential applications in the preparation of various flame-retardant polymers.

One-step assembly of multi-layered structures with orthogonally oriented stripe-like patterns on the surface of a capillary tube.

We developed a robust method to construct large-scale multi-layered assemblies with orthogonally oriented stripes on a capillary tube using a confined evaporative self-assembly (CESA) method. A mixture of conductive polymer poly(3-hexylthiophene) (P3HT) and biocompatible polylactic acid (PLA) was chosen as the model polymer and the molecular chain orientation of P3HT in an individual stripe could be assessed by laser confocal polarization Raman spectroscopy. These structures could provide contact cues to guide the growth of smooth muscle cells for potential tissue engineering applications.

Development of shell cross-linked nanoparticles based on boronic acid-related reactions for self-regulated insulin delivery.

Shell cross-linked nanoparticles were fabricated by the complexation of poly(3-methacrylamido phenylboronic acid) (PMAPBA) and thiolated chitosan (chitosan-SH) via boronic acid-related reactions. The formation of PMAPBA/chitosan-SH nanoparticles was confirmed by transmission electron microscopy, dynamic light scattering, and UV spectroscopy. The nanoparticles had a narrow size distribution with a relatively high positive charge density, and the size and zeta potential of the nanoparticles correlated with the chitosan-SH concentration. Furthermore, owing to the cross-linking of the nanoparticle shell, insulin was encapsulated in the nanoparticles with a loading capacity of up to 18%. The release of insulin from the nanoparticles slowed down because of the presence of disulfide bonds and increased with increasing glucose level in the medium. The structure of the released insulin was not distorted. More importantly, the nanoparticles had good cytocompatibility, as demonstrated by in vitro experiments. The simplicity of this strategy along with a high loading capacity, glucose sensitivity, and cytocompatibility of the produced nanoparticles should significantly boost their application in self-regulated insulin delivery.

Preparation of lysozyme imprinted magnetic nanoparticles via surface graft copolymerization.

Molecular imprinting as a facile and promising separation technique has received considerable attention because of their high selectivity for target molecules. In this study, we imprinted lysozyme (Lys) on the surface of core-shell magnetic nanoparticles via surface imprinting. The magnetic supports were functionalized with maleic acid and then coated with imprinted polymer layers. The structure and morphology of the resulting magnetic imprinted nanoparticles were characterized by transmission electron microscopy, scanning electron microscope, dynamic light scatting, vibrating sample magnetometer, and thermogravimetric analysis. Binding experiments were carried out to evaluate the properties of magnetic molecularly imprinted polymers (magnetic MIPs) and magnetic non-molecularly imprinted polymers (magnetic NIPs). The protein adsorption results showed that the magnetic MIPs had significant specific recognition toward the template protein and could be easily separated from solution by an external magnetic field. Moreover, the MIPs exhibited fast kinetics for the rebinding of the target protein due to the thin-imprinted layer and showed good reusability by four adsorption-desorption cycles. Therefore, the surface imprinting approach combined with magnetic nanoparticles provided an easy and fast method for the specific recognition of Lys.

Development of phenylboronic acid-functionalized nanoparticles for emodin delivery.

Stable and monodisperse phenylboronic acid-functionalized nanoparticles (PBA-NPs) were fabricated using 3-((acrylamido)methyl)phenylboronic acid homopolymer (PBAH) via solvent displacement technique. The effect of operating parameters, including stirring time, initial polymer concentration and the proportion of methanol on the self-assembly process were systematically investigated. The diameters of the PBA-NPs were increased as increasing the initial PBAH concentration and the proportion of methanol. Likewise, there was a linear dependence between the size of self-assembled nanoparticles and the polymer concentration. Moreover, the dissipative particle dynamics (DPD) simulation technique was used to investigate the mechanism of self-assembly behavior of PBAH, which indicated that the interior of PBA-NPs was hydrophobic and compact, and the boronic acid groups were displayed on both the outermost and interior of PBA-NPs. The resulting PBA-NPs could successfully encapsulate emodin through PBA-diol interaction and the encapsulation efficiency (EE%) and drug loading content (DLC%) of drug-loaded PBA-NPs were 78% and 2.1%, respectively. Owing to the acid-labile feature of the boronate linkage, a reduction in environmental pH from pH 7.4 to 5.0 could trigger the disassociation of the boronate ester bonds, which could accelerate the drug release from PBA-Emodin-NPs. Besides, PBA-Emodin-NPs showed a much higher cytotoxicity to HepG2 cells (cancer cells) than that to MC-3T3-E1 cells (normal cells). These results imply that PBA-NPs would be a promising scaffold for the delivery of polyphenolic drugs.

Epstein-Barr virus gene polymorphism in different parts of the same nasopharyngeal carcinoma patient.

In most previous studies, comparisons of Epstein-Barr virus (EBV) gene polymorphisms and genotypes were made between strains from tumors and normal throat washings (TWs) from different individuals. However, it remains controversial whether different EBV subtypes are present in different parts of the same NPC patient. In order to address this question, in this study, we compared the genotypes in sets of paired throat washings (TW) and paraffin-embedded tissues of 20 patients with nasopharyngeal carcinoma (NPC), and we found the same genotype in throat washings (TWs) and tumor cells from the same individual in most cases. The subtypes of EBER and EBNA1 genes were furthermore sequenced, and identical EBV strains were identified in tumor tissues and TWs. In conclusion, different sites of the same individual are infected by the same EBV strains, except for a few differences in occasional cases, suggesting that the EBV subtype detected in throat washings is a reasonable guide to the subtype present in the carcinoma tissue.