Constructing Nitrogen-Doped Carbon Hierarchy Structure Derived from Metal-Organic Framework as High-Performance ORR Cathode Material for Zn-Air Battery.

The development of efficient and low-cost catalysts for cathodic oxygen reduction reaction (ORR) in Zn-air battery (ZAB) is a key factor in reducing costs and achieving industrialization. Here, a novel segregated CoNiPt alloy embedded in N-doped porous carbon with a nanoflowers (NFs)-like hierarchy structure is synthesized through pyrolyzing Hofmann-type metal-organic frameworks (MOFs). The unique hierarchical NFs structure exposes more active sites and facilitates the transportation of reaction intermediates, thus accelerating the reaction kinetics. Impressively, the resulting 15% CoNiPt@C NFs catalyst exhibits outstanding alkaline ORR activity with a half-wave potential of 0.93 V, and its mass activity is 7.5 times higher than that of commercial Pt/C catalyst, surpassing state-of-the-art noble metal-based catalysts. Furthermore, the assembled CoNiPt@C+RuO2 ZAB demonstrates a maximum power density of 172 mW cm-2 , which is superior to that of commercial Pt/C+RuO2 ZAB. Experimental results reveal that the intrinsic ORR mass activity is attributed to the synergistic interaction between oxygen defects and pyrrolic/graphitic N species, which optimizes the adsorption energy of the intermediate species in the ORR process and greatly enhances catalytic activity. This work provides a practical and feasible strategy for synthesizing cost-effective alkaline ORR catalysts by optimizing the electronic structure of MOF-derived catalysts.

Two-Dimensional Nanofluidic Membranes with Intercalated In-Plane Shortcuts for High-Performance Blue Energy Harvesting.

Two-dimensional nanofluidic membranes offer great opportunities for developing efficient and robust devices for ionic/water-nexus energy harvesting. However, low counterion concentration and long pathway through limited ionic flux restrict their output performance. Herein, it is demonstrated that rapid diffusion kinetics can be realized in two-dimensional nanofluidic membranes by introducing in-plane holes across nanosheets, which not only increase counterion concentration but also shorten pathway length through the membranes. Thus, the holey membranes exhibited an enhanced performance relative to the pristine ones in terms of osmotic energy conversion. In particular, a biomimetic multilayered membrane sequentially assembled from pristine and holey sections offers an optimized combination of selectivity and permeability, therefore generating a power density up to 6.78 W m-2 by mixing seawater and river water, superior to the majority of the state-of-the-art lamellar nanofluidic membranes. This work highlights the importance of channel morphologies and presents a general strategy for effectively improving ion transport through lamellar membranes for high-performance nanofluidic devices.

Sandwich Fibrous PEG Encapsulations for Thermal Energy Storage.

Phase change materials (PCMs) textiles have been developed for personal thermal management (PTM) while limited loading amount of PCMs in textiles reduced thermal buffering effect. In this work, we proposed a sandwich fibrous encapsulation to store polyethylene glycol (PEG) with PEG loading amount of 45 wt %, which consisted of polyester (PET) fabrics with hydrophobic coating as protection layers, polyurethane (PU) nanofibrous membranes as barrier layers and PEG-loaded viscose fabric as a PCM-loaded layer. The leakage was totally avoided by controlling weak interfacial adhesion between protection layer and melting PEG. The sandwich fibrous PEG encapsulations had an overall melting enthalpy value ranging from 50 J/g to 78 J/g and melting points ranging from 20 °C to 63 °C by using different PEGs. Besides, introduction of Fe microparticles in PCM-loaded layer enhanced thermal energy storage efficiency. We believe that the sandwich fibrous PEG encapsulation has a great potential in various fields.

Dityrosine-inspired photocrosslinking technique for 3D printing of silk fibroin-based composite hydrogel scaffolds.

Photoinduced self-crosslinking technology is a great facilitator of 3D bioprinting of silk fibroin (SF) by allowing rapid solidification of a deliberately formulated SF-based photocrosslinkable bioink. An SF-based, photocrosslinked hydrogel was fabricated with tyramine-modified sodium carboxymethyl cellulose (CMC-Na) as a co-crosslinkable constituent and Ru(bpy)3Cl2 (Ru(II)) and potassium persulfate (KPS) as blue light photoinitiators. Photorheological studies demonstrated that the photocrosslinking and viscoelasticity of the composite could be tuned by varying the relative content of the two constituents. Xanthan gum (XG) was employed in formulating the SF-based photocrosslinkable bioink, and the improved rheological properties and printability were evidenced by the resulting tunable shear-thinning behavior and shear thixotropy. 3D SF-based hydrogel scaffolds with uniform pores with a size of approximately 550 µm × 1000 µm were constructed via extrusion-based printing and a simple 30 s post-photocrosslinking combined process. Furthermore, the CMC-Na incorporated 3D hydrogel scaffolds exhibited sufficient structural strength, adequate filament fineness, and tunable transparency, which shows a promising prospect in the application of tissue engineering and regenerative medicine.

In-situ synthesis of Cu2O on cotton fibers with antibacterial properties and reusable photocatalytic degradation of dyes.

In this study, the cotton fabrics/cuprous oxide-nanocellulose (Cu2O-NC) flexible and recyclable composite material (COCO) with highly efficient photocatalytic degradation of dyes and antibacterial properties was fabricated. Using flexible cotton fabrics as substrates, Cu2O were in-situ synthesized to make Cu2O uniformly grew on cotton fibers and were wrapped with NC. The photocatalytic degradation ability of COCO-5 was verified by use methylene blue (MB), the degradation rate was as high as 98.32%. The mechanism of COCO-5 photocatalysis and the process of dye degradation were analyzed by using electron paramagnetic resonance (EPR) spectrum, transient photocurrent response (TPR) spectrum, Fourier transform infrared (FTIR) spectroscopy and ion chromatography (IC). This study analyzed the complete path from electron excitation to dye degradation to harmless small molecules. Qualitative and quantitative experiments demonstrate that COCO-5 has high antibacterial activity against S. aureus and E. coli, the highest antibacterial rate can reach 93.25%. Finally, the stability of COCO-5 was verified by recycling and mechanical performance tests. The textile-based Cu2O functionalized material has photocatalytic degradation and antibacterial properties, and the preparation process is simple and convenient for repeated use, so it has great potential in wastewater treatment containing dyes and bacteria.

Enhancing Oxygen Evolution Reaction through Modulating Electronic Structure of Trimetallic Electrocatalysts Derived from Metal-Organic Frameworks.

The construction of efficient, durable, and non-noble metal electrocatalysts for oxygen evolution reaction (OER) is of great value but challenging. Herein, a facile method is developed to synthesize a series of trimetallic (W/Co/Fe) metal-organic frameworks (MOFs)-derived carbon nanoflakes (CNF) with various Fe content, and an Fe-dependent volcano-type plot can be drawn out for WCoFex -CNF. The optimized WCoFe0.3 -CNF (when the feed ratio of Fe/Co is 0.3) demonstrates superior electrocatalytic performance with a low overpotential of only 254 mV@10 mA cm-2 and excellent durability of 100 h. Further researches show that appropriate amount of iron doping can regulate the electronic structure, resulting in a favorable synergistic environment. This method may stimulate the exploration of electrocatalysts by utilizing MOFs as precursors while realizing electronic modulation by multimetal doping.

Poly(acrylic acid)-regulated Synthesis of Rod-Like Calcium Carbonate Nanoparticles for Inducing the Osteogenic Differentiation of MC3T3-E1 Cells.

Calcium carbonate, especially with nanostructure, has been considered as a good candidate material for bone regeneration due to its excellent biodegradability and osteoconductivity. In this study, rod-like calcium carbonate nanoparticles (Rod-CC NPs) with desired water dispersibility were achieved with the regulation of poly (acrylic acid). Characterization results revealed that the Rod-CC NPs had an average length of 240 nm, a width of 90 nm with an average aspect ratio of 2.60 and a negative ζ-potential of -22.25 ± 0.35 mV. The degradation study illustrated the nanoparticles degraded 23% at pH 7.4 and 45% at pH 5.6 in phosphate-buffered saline (PBS) solution within three months. When cultured with MC3T3-E1 cells, the Rod-CC NPs exhibited a positive effect on the proliferation of osteoblast cells. Alkaline phosphatase (ALP) activity assays together with the osteocalcin (OCN) and bone sialoprotein (BSP) expression observations demonstrated the nanoparticles could induce the differentiation of MC3T3-E1 cells. Our study developed well-dispersed rod-like calcium carbonate nanoparticles which have great potential to be used in bone regeneration.

Comprehensive profiling of lysine acetylation suggests the widespread function is regulated by protein acetylation in the silkworm, Bombyx mori.

Lysine acetylation in proteins is a dynamic and reversible PTM and plays an important role in diverse cellular processes. In this study, using lysine-acetylation (Kac) peptide enrichment coupled with nano HPLC/MS/MS, we initially identified the acetylome in the silkworms. Overall, a total of 342 acetylated proteins with 667 Kac sites were identified in silkworm. Sequence motifs analysis around Kac sites revealed an enrichment of Y, F, and H in the +1 position, and F was also enriched in the +2 and -2 positions, indicating the presences of preferred amino acids around Kac sites in the silkworm. Functional analysis showed the acetylated proteins were primarily involved in some specific biological processes. Furthermore, lots of nutrient-storage proteins, such as apolipophorin, vitellogenin, storage proteins, and 30 K proteins, were highly acetylated, indicating lysine acetylation may represent a common regulatory mechanism of nutrient utilization in the silkworm. Interestingly, Ser2 proteins, the coating proteins of larval silk, were found to contain many Kac sites, suggesting lysine acetylation may be involved in the regulation of larval silk synthesis. This study is the first to identify the acetylome in a lepidoptera insect, and expands greatly the catalog of lysine acetylation substrates and sites in insects.

Potential mode of protection of silkworm pupae from environmental stress by harboring the bacterial biofilm on the surfaces of silk cocoons.

The silkworm forms cocoon to protect its pupa that survives for months inside the cocoon without being affected by various environmental stresses. To understand the possible mode of pupal survival within the cocoon encasement, we investigate the cause that protects the cocoon. During the end of the spinning process, we have isolated different bacterial species from the cocoon surface. These are identified using molecular techniques and checked for their abilities to form biofilm in vitro. The bacteria are able to form biofilm either individually or in consortia. Of which, Bacillus and Erwinia species are prominent biofilm formers. Interestingly, these bacteria have the ability to form biofilm on the cocoon mimetic surface of the silk protein Sericin Hope that contains only sericin. The origin and the behavior of the bacteria lead us to hypothesize the possible role of biofilm layer on the cocoon surface, which provides protection from adverse environmental conditions.

One-step synthesis of natural silk sericin-based microcapsules with bionic structures.

Different techniques are being developed for fabricating microcapsules; it is still a challenge to fabricate them in an efficient and environment-friendly process. Here, a one-step green route to synthesize silk protein sericin-based microcapsules without any assistance of organic solvents is reported. By carefully changing the concentration of calcium ions accompanied with stirring, the morphology of the microcapsules can easily be regulated to form either discoidal, biconcave, cocoon-like, or tubular structures. The chelation of Ca(2+) and shearing force from agitation may induce the conformational transformation of sericin, which possibly results in the formation of microcapsules through the self-assembly of the protein subsequently. The as-prepared cocoon-like microcapsules exhibit pH-dependent stability. A potential application of microcapsules being fabricated from natural water-soluble silk protein sericin for controlled bioactive molecules loading and release system by a pH-triggered manner is quite feasible.

Structure, properties, and fabric applicability of sustainable paper yarn with high washing stability.

This research provides an in-depth assessment of two paper yarn variants, examining their structural, functional, and performance characteristics. These yarns demonstrated favorable properties, including suitable linear density, twist, typical cellulosic functional groups as confirmed by Infrared spectroscopy, minimal hairiness, moisture transfer, and creditable mechanical strength. These yarns have flat layered cross-sections and grooved longitudinal surfaces. In addition, a low hairiness index (1.3-1.33) further acknowledged their smooth surface. Their remarkable evenness (15.86% and 7.08%) supported their effective wicking properties. Despite average breaking strength (0.77 cN/dTex and 1.05 cN/dTex) and moderate elongation, these yarns exhibited exceptional water-washing resistance and retained over 89% breaking strength after 15 washes. This study ranks these paper yarns as highly suitable for durable clothing fabrics, providing promising sustainable alternatives in the textile industry.

Deep analysis of adsorption isotherm for rapid sorption of Acid Blue 93 and Reactive Red 195 on reactive graphene.

Graphene-based adsorbent was prepared by adopting a green synthetic route via the chemical exfoliation of graphite and low-temperature thermal activation. Prepared reactive graphene (RG) was characterized through various techniques, and its adsorption capabilities for textile dye removal were investigated for Acid Blue-93 (AB) and Reactive Red-195 (RR) under different operational conditions. The dye sorption equilibrium and mechanism were comprehensively studied using isotherm and kinetic models and compared statistically to explain the sorption behavior. Results show AB and RR adsorption by RG attains equilibrium in 60 min and 70 min, with a high sorption quantity of 397 mg g-1 and 262 mg g-1 (initial dye concentration of 100 mg L-1), respectively. The dye sorption anticipates that the high surface area (104.52 m2 gm-1) and constructed meso-macroporous features of RG facilitated the interaction between the dye molecules and graphitic skeleton. The R-P isotherm fitted the best of equilibrium data, having the least variance in residuals for both dyes (AB = 0.00031 and RR = 0.00047). The pseudo-second order model best fitted the kinetics of sorption on RG, with chemisorption being the predominant process delimiting step. The overall results promise the dye removal capability of RG to be an efficient adsorbent for azo-based dyes from textile effluents.

Superstructured Optoionic Heterojunctions for Promoting Ion Pumping Inspired by Photoreceptor Cells.

Photoreceptor cells of vertebrates feature ultrastructural membranes interspersed with abundant photosensitive ion pumps to boost signal generation and realize high gain in dim light. In light of this, superstructured optoionic heterojunctions (SSOHs) with cation-selective nanochannels are developed for manipulating photo-driven ion pumping. A template-directed bottom-up strategy is adopted to sequentially assemble graphene oxide (GO) and PEDOT:PSS into heterogeneous membranes with sculptured superstructures, which feature programmable variation in membrane topography and contain a donor-acceptor interface capable of maintaining electron-hole separation upon photoillumination. Such elaborate design endows SSOHs with a much higher magnitude of photo-driven ion flux against a concentration gradient in contrast to conventional optoionic membranes with planar configuration. This can be ascribed to the buildup of an enhanced transmembrane potential owing to the effective separation of photogenerated carriers at the heterojunction interface and the increase of energy input from photoillumination due to a synergistic effect of reflection reduction, broad-angle absorption, and wide-waveband absorption. This work unlocks the significance of membrane topographies in photo-driven transmembrane transportation and proposes such a universal prototype that could be extended to other optoionic membranes to develop high-performance artificial ion pumps for energy conversion and sensing.

Achieving ultrahigh uranium/vanadium selectivity of poly(amidoxime) via coupling MXene-enabled strong intermolecular interaction and separated photothermal interface.

Poly(amidoxime) (PAO) has been recognized as the most potential candidate for extracting uranium from seawater, owing to its merits of outstanding uranium affinity, low cost, and large-scale production. Despite remarkable achievements, existing PAO sorbents suffer from unsatisfactory uranium extraction efficiency and selectivity, as imposed by the inherently sluggish uranium adsorption kinetics and inevitable spatial configuration transition of amidoxime, which diminishes uranium affinity. Herein, we discover a facile and integrated design to elaborate a PAO/MXene nanocomposite that delivers ultrahigh and durable uranium/vanadium (U/V) selectivity. The key to our design lies in harnessing MXene-enabled strong intermolecular interactions to PAO to minimize the spatial configuration transition of amidoxime and stabilizing its superior uranium affinity, as well as creating a separated photothermal interface to maximize temperature-strengthened affinity for uranium over vanadium. Such a synergetic effect allows the nanocomposite to acquire over a 4-fold improvement in U/V selectivity compared to that of pure PAO as well as an unprecedented distribution coefficient of uranium compared to most state-of-the-art sorbents. We further demonstrate that our nanocomposite exhibits durable U/V selectivity with negligible attenuation and good antibacterial ability even in long-term operation. The design concept and extraordinary performance in this study bring PAO-based sorbents a step closer to practical uranium extraction from seawater.

RIP-seq of BmAgo2-associated small RNAs reveal various types of small non-coding RNAs in the silkworm, Bombyx mori.

BACKGROUND: Small non-coding RNAs (ncRNAs) are important regulators of gene expression in eukaryotes. Previously, only microRNAs (miRNAs) and piRNAs have been identified in the silkworm, Bombyx mori. Furthermore, only ncRNAs (50-500nt) of intermediate size have been systematically identified in the silkworm. RESULTS: Here, we performed a systematic identification and analysis of small RNAs (18-50nt) associated with the Bombyx mori argonaute2 (BmAgo2) protein. Using RIP-seq, we identified various types of small ncRNAs associated with BmAGO2. These ncRNAs showed a multimodal length distribution, with three peaks at ~20nt, ~27nt and ~33nt, which included tRNA-, transposable element (TE)-, rRNA-, snoRNA- and snRNA-derived small RNAs as well as miRNAs and piRNAs. The tRNA-derived fragments (tRFs) were found at an extremely high abundance and accounted for 69.90% of the BmAgo2-associated small RNAs. Northern blotting confirmed that many tRFs were expressed or up-regulated only in the BmNPV-infected cells, implying that the tRFs play a prominent role by binding to BmAgo2 during BmNPV infection. Additional evidence suggested that there are potential cleavage sites on the D, anti-codon and TψC loops of the tRNAs. TE-derived small RNAs and piRNAs also accounted for a significant proportion of the BmAgo2-associated small RNAs, suggesting that BmAgo2 could be involved in the maintenance of genome stability by suppressing the activities of transposons guided by these small RNAs. Finally, Northern blotting was also used to confirm the Bombyx 5.8 s rRNA-derived small RNAs, demonstrating that various novel small RNAs exist in the silkworm. CONCLUSIONS: Using an RIP-seq method in combination with Northern blotting, we identified various types of small RNAs associated with the BmAgo2 protein, including tRNA-, TE-, rRNA-, snoRNA- and snRNA-derived small RNAs as well as miRNAs and piRNAs. Our findings provide new clues for future functional studies of the role of small RNAs in insect development and evolution.

Fascinating polyphenol lignin extracted from sawdust via a green and recyclable solvent route.

Due to the complexity, heterogeneity and recalcitrant structure of lignin, the extraction of multifunctional lignin directly from lignocellulose is still a challenge. Here, a green and recyclable route was proposed to separate high-quality lignin and tailor its functionalities. Through tuning the components of deep eutectic solvent (DES) and separation procedures, DES extracted lignin (DESL) exhibited high purity of 99.6 %, yield of 83.2 % and phenolic hydroxyl content of 8.33 wt%. The results of FTIR and 13C NMR demonstrated that DESL possessed more oxygen-containing reactive groups compared with commercial lignin (CL), enabling DESL with more superior functional activities. DESL exhibited higher antioxidant activity with the DPPH capture rate of 73.2 %. Meanwhile, DESL showed strong bactericidal effects against E. coli (100 %) and S. aureus (100 %) due to higher phenolic hydroxyl content, which could destroy bacterial cell membranes and inhibit bacterial metabolism by interacting with phospholipid layer and protein. Additionally, DESL displayed strong UV absorption and could be blended with polyurethane to enhance UV shielding property of polyurethane composite film with >50 of UPF value. In summary, DES treatment is a suitable strategy for high-quality lignin separation, which opens a broad spectrum of possibilities for lignin valorization.

Homogeneous wet-spinning construction of skin-core structured PANI/cellulose conductive fibers for gas sensing and e-textile applications.

Fiber-based wearable electronic textiles have broad applications, but non-degradable substrates may contribute to electronic waste. The application of cellulose-based composite fibers as e-textiles is hindered by the lack of fast and effective preparation methods. Here, we fabricated polyaniline (PANI)/cellulose fibers (PC) with a unique skin-core structure through a wet-spinning homogeneous blended system. The conductive network formation was enabled at a mere 1 wt% PANI. Notably, PC15 (15 wt% PANI) shows higher electrical conductivity of 21.50 mS cm-1. Further, PC15 exhibits excellent ammonia sensing performance with a sensitivity of 2.49 %/ppm and a low limit of detection (LOD) of 0.6 ppm. Cellulose-based composite fibers in this work demonstrate good gas sensing and anti-static properties as potential devices for smart e-textiles.

Nanocellulose interface enhanced all-cellulose foam with controllable strength via a facile liquid phase exchange route.

The development of sustainable, biodegradable, non-toxic biomass foams with outstanding physical properties to replace traditional petroleum-based foams is urgent. In this work, we proposed a simple, efficient, and scalable approach to fabricate nanocellulose (NC) interface enhanced all-cellulose foam through ethanol liquid phase exchange and subsequent ambient drying. In this process, NCs served as reinforcer and binder were integrated with pulp fiber to improve cellulose interfibrillar bonding and interface adhesion between NCs and pulp microfibrils. The resultant all-cellulose foam displayed stable microcellular structure (porosity of 91.7-94.5 %), low apparent density (0.08-0.12 g/cm3), and high compression modulus (0.49-2.96 MPa) by regulating the content and size of NCs. Further, the strengthening mechanism of the structure and property of all-cellulose foam were investigated in detail. This proposed process enabled ambient drying, and is simple and feasible for low-cost, practicable, and scalable production of biodegradable, green bio-based foam without special apparatuses and other chemicals.

Strong and flexible lignocellulosic film fabricated via a feasible molecular remodeling strategy.

Biomass-derived sustainable film is a promising alternative to synthetic plastic, but hampered by strength, toughness and flexibility trade-off predicament. Here, a feasible and scalable strategy was proposed to fabricate strong and flexible lignocellulosic film through molecular reconstruction of cellulose and lignin. In this strategy, polyphenol lignin was absorbed and wrapped on the surface of cellulose fiber, forming strong interfacial adhesion and cohesion via intramolecular and intermolecular hydrogen bonding. Further, covalent ether bond was generated between the hydroxyl groups of lignocellulose to form chemical cross-linking network induced by epichlorohydrin (ECH). The synergistic effect of hydrogen bonding and stable chemical cross-linking enabled the resultant lignocellulosic film (ELCF) with outstanding mechanical strength of 132.48 MPa, the elongation at break of 9.77 %, and toughness of 9.77 MJ·m-3. Notably, the integration of polyphenol lignin synergistically improved the thermal stability, water resistance, UV-blocking performances of ELCF. Importantly, after immersion for 30 d, ELCF still possessed high wet strength of 70.38 MPa, and elongation at break of 7.70 %, suggesting excellent and durable mechanical performances. Moreover, ELCF could be biodegraded in the natural soil. Therefore, this study provides a new and versatile approach to reconstruct highly-performance lignocellulosic films coupling strength, toughness with flexibility for promising plastic replacement.

Enhancing the solubility and antimicrobial activity of cellulose through esterification modification using amino acid hydrochlorides.

Most amino acid molecules have good water solubility and are rich in functional groups, which makes them a promising derivatizing agent for cellulose. However, self-condensation of amino acids and low reaction efficiency always happen during esterification. Here, amino acid hydrochloride ([AA]Cl) is selected as raw material to synthesize cellulose amino acid ester (CAE). Based on TG-MS coupling technology, a significantly faster reaction rate of [AA]Cl compared to raw amino acid can be observed visually. CAE with the degree of substitution 0.412-0.516 is facilely synthesized under 130-170 °C for 10-50 min. Moreover, the effects of amounts of [AA]Cl agent, temperature, and time on the esterification are studied. The CAE can be well dissolved in 7 wt% NaOH aq., resulting in a 7.5 wt% dope. The rheological test of the dope demonstrated a shear-thinning behavior for Newtonian-like fluid, and a high gel temperature (41.7 °C). Further, the synthesized products show distinct antibacterial activity and the bacteriostatic reduction rate against E. coli can reach 99.5 %.