Renewable biomass-based aerogels: from structural design to functional regulation.

Global population growth and industrialization have exacerbated the nonrenewable energy crises and environmental issues, thereby stimulating an enormous demand for producing environmentally friendly materials. Typically, biomass-based aerogels (BAs), which are mainly composed of biomass materials, show great application prospects in various fields because of their exceptional properties such as biocompatibility, degradability, and renewability. To improve the performance of BAs to meet the usage requirements of different scenarios, a large number of innovative works in the past few decades have emphasized the importance of micro-structural design in regulating macroscopic functions. Inspired by the ubiquitous random or regularly arranged structures of materials in nature ranging from micro to meso and macro scales, constructing different microstructures often corresponds to completely different functions even with similar biomolecular compositions. This review focuses on the preparation process, design concepts, regulation methods, and the synergistic combination of chemical compositions and microstructures of BAs with different porous structures from the perspective of gel skeleton and pore structure. It not only comprehensively introduces the effect of various microstructures on the physical properties of BAs, but also analyzes their potential applications in the corresponding fields of thermal management, water treatment, atmospheric water harvesting, CO2 absorption, energy storage and conversion, electromagnetic interference (EMI) shielding, biological applications, etc. Finally, we provide our perspectives regarding the challenges and future opportunities of BAs. Overall, our goal is to provide researchers with a thorough understanding of the relationship between the microstructures and properties of BAs, supported by a comprehensive analysis of the available data.

Low-background interference detection of glyphosate, glufosinate, and AMPA in foods using UPLC-MS/MS without derivatization.

The abuse of herbicides has emerged as a great threat to food security. Herein, a low-background interference detection method based on UPLC-MS was developed for the simultaneous determination of glufosinate, glyphosate, and its metabolite aminomethylphosphonic acid (AMPA) in foods. Initially, this study proposed a simple and rapid pretreatment method, utilizing water extraction and PRiME HLB purification to isolate glyphosate, glufosinate, and AMPA from food samples. After the optimization of pretreatment conditions, the processed samples are then analyzed directly by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS) without pre-column derivatization. The method can effectively reduce interference from by-products of pre-column derivatization and background substrates of food sample, showing low matrix effects (ME) ranging from - 24.83 to 32.10%. Subsequently, the method has been validated by 13 kinds of food samples. The recoveries of the three herbicides in the food samples range from 84.2 to 115.6%. The limit of detection (LOD) is lower to 0.073 mg/kg, 0.017 mg/kg, and 0.037 mg/kg, respectively. Moreover, the method shows an excellent reproducibility with relative standard deviations (RSD) within 16.9%. Thus, the method can provide high trueness, reproducibility, sensitivity, and interference-free detection to ensure human health safety.

Dinuclear Cyclometalated Pincer Nickel(II) Complexes with Metal-Metal-to-Ligand Charge Transfer Excited States and Near-Infrared Emission.

Facile non-radiative decay of low-lying metal-centered (MC) d-d excited states has been well documented to pose a significant obstacle to the development of phosphorescent NiII complexes due to substantial structural distortions between the d-d excited state and the ground state. Herein, we prepared a series of dinuclear Ni2II,II complexes by using strong σ-donors, carbene-phenyl-carbene (CNHC^Cphenyl^CNHC) pincer ligands, and prepared their dinuclear Pt2II,II and Pd2II,II analogues. Dinuclear Ni2II,II complexes bridged by formamidinate/α-carbolinato ligand exhibit short Ni-Ni distances of 2.947-3.054 Å and singlet metal-metal-to-ligand charge transfer (1MMLCT) transitions at 500-550 nm. Their 1MMLCT absorption energies are red-shifted relative to the Pt2II,II and Pd2II,II analogues at ~450 nm and ≤420 nm respectively. One-electron oxidation of these Ni2II,II complexes produces valence-trapped dinuclear Ni2II,III species, which are characterized by EPR spectroscopy. Upon photoexcitation, these Ni2II,II complexes display phosphorescence (τ=2.6-8.6 µs) in the NIR (800-1400nm) spectral region in 2-MeTHF and in solid state at 77 K, which is insensitive to π-conjugation of the coordinated [CNHC^Cphenyl^CNHC] ligand. Combined with DFT calculations, the NIR emission is assigned to originate from the 3dd excited state. Studies have found that the dinuclear Ni2II,II complex can sensitize the formation of singlet oxygen and catalyze the oxidation of cyclo-dienes under light irradiation.

miR-6076 targets BCL6 in SH-SY5Y cells to regulate amyloid-ß-induced neuronal damage.

Amyloid-ß1-42 (Aß1-42 ) is strongly associated with Alzheimer's disease (AD). The aim of this study is to elucidate whether and how miR-6076 participates in the modulation of amyloid-ß (Aß)-induced neuronal damage. To construct the neuronal damage model, SH-SY5Y cells were treated with Aß1-42 . By qRT-PCR, we found that miR-6076 is significantly upregulated in Aß1-42 -treated SH-SY5Y cells. After miR-6076 inhibition, p-Tau and apoptosis levels were downregulated, and cell viability was increased. Through online bioinformatics analysis, we found that B-cell lymphoma 6 (BCL6) was a directly target of miR-6076 via dual-luciferase reporter assay. BCL6 overexpression mediated the decrease in elevated p-Tau levels and increased viability in SH-SY5Y cells following Aß1-42 treatment. Our results suggest that down-regulation of miR-6076 could attenuate Aß1-42 -induced neuronal damage by targeting BCL6, which provided a possible target to pursue for prevention and treatment of Aß-induced neuronal damage in AD.

Coupling Bifunctional Nanozyme-Mediated Catalytic Signal Amplification and Label-Free SERS with Immunoassays for Ultrasensitive Detection of Pathogens in Milk Samples.

Rapid and sensitive detection of foodborne bacteria is of great significance in guaranteeing food safety and preventing foodborne diseases. A bifunctional Au@Pt core-shell nanozyme with excellent catalytic properties and high surface-enhanced Raman scattering (SERS) activity was developed for the highly sensitive detection of Salmonella typhimurium based on a label-free SERS strategy. The ultrathin Pt shell (about 1 nm) can catalyze Raman-inactive molecules into Raman-active reporters, greatly amplifying the amount of signal molecules. Moreover, the Au core serves as an active SERS substrate to enhance the signal of reporter molecules, further significantly improving the detection sensitivity. Benefiting from the excellent properties, such a bifunctional Au@Pt nanozyme was integrated with a magnetic immunoassay to construct a label-free SERS platform for the highly sensitive detection of S. typhi with a low detection limit of 10 CFU mL-1. Also, the Au@Pt-based SERS platform exhibited excellent selectivity and was successfully utilized for the detection of S. typhi in milk samples by a portable Raman spectrometer. Our demonstration of the bifunctional nanozyme-based SERS strategy provides an efficient pathway to improve the sensitivity of label-free SERS detection of pathogens and holds great promise in food safety, environmental analysis, and other biosensing fields.

Preparation of a hydrophobic deep eutectic solvent and its application in the detection of quinolone residues in cattle urine.

Enrichment for the detection of quinolone residues is usually cumbersome and requires large amounts of toxic organic reagents. Therefore, this study synthesized a low-toxicity hydrophobic deep eutectic solvent (DES) with DL-menthol and p-cresol, which was then characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and thermal analysis. A simple and rapid vortex-assisted liquid-liquid microextraction method was developed based on this DES for the extraction of eight quinolones from cattle urine. The optimal extraction conditions were screened by examining the DES volume, extraction temperature, vortex time, and salt concentration. Under the optimal conditions, the linear ranges of the eight quinolones were 1 ~ 100 µg/L with good linearity (r2 was 0.998 ~ 0.999), and the limits of detection and quantification were 0.08 ~ 0.30 µg/L and 0.27 ~ 0.98 µg/L, respectively. The average extraction recoveries of spiked cattle urine samples were 70.13 ~ 98.50% with relative standard deviations below 13.97%. This method can provide a reference for the pre-treatment of quinolone residue detection.

Bifunctional Al-Doped Cobalt Ferrocyanide Nanocube Array for Energy-Saving Hydrogen Production via Urea Electrolysis.

The very slow anodic oxygen evolution reaction (OER) greatly limits the development of large-scale hydrogen production via water electrolysis. By replacing OER with an easier urea oxidation reaction (UOR), developing an HER/UOR coupling electrolysis system for hydrogen production could save a significant amount of energy and money. An Al-doped cobalt ferrocyanide (Al-Co2Fe(CN)6) nanocube array was in situ grown on nickel foam (Al-Co2Fe(CN)6/NF). Due to the unique nanocube array structure and regulated electronic structure of Al-Co2Fe(CN)6, the as-prepared Al-Co2Fe(CN)6/NF electrode exhibited outstanding catalytic activities and long-term stability to both UOR and HER. The Al-Co2Fe(CN)6/NF electrode needed potentials of 0.169 V and 1.118 V (vs. a reversible hydrogen electrode) to drive 10 mA cm-2 for HER and UOR, respectively, in alkaline conditions. Applying the Al-Co2Fe(CN)6/NF to a whole-urea electrolysis system, 10 mA cm-2 was achieved at a cell voltage of 1.357 V, which saved 11.2% electricity energy compared to that of traditional water splitting. Density functional theory calculations demonstrated that the boosted UOR activity comes from Co sites with Al-doped electronic environments. This promoted and balanced the adsorption/desorption of the main intermediates in the UOR process. This work indicates that Co-based materials as efficient catalysts have great prospects for application in urea electrolysis systems and are expected to achieve low-cost and energy-saving H2 production.

1+1>2: Fiber Synergy in Aggregation-Induced Emission.

Mesoscopic aggregate is important to transfer or even amplify the molecular information in macroscopic materials. As an important branch of aggregate science, aggregation-induced emissive luminogens (AIEgens) often show slight or even no emission in solutions but exhibit bright emission when they aggregate, which open a new avenue for the practical applications. Due to the flexible and rotor structure of AIEgens, the aggregate structure of AIEgens is highly sensitive to the surrounding microenvironment, resulting in adjustable optical properties. Fibers integrated of a multiplicity of functional components are ideal carriers to control the aggregation processes, further assembly of fibers produces large-scale fabrics with amplified functions and practical values. In this Concept article, we focus on the latest advances on the synergy between "AIE+Fiber" for the boosted performance that beyond AIE, and their applications are presented and abstracted out to stimulate new ideas for developing "AIE+Fiber" systems.

Nanoscale Laser Metallurgy and Patterning in Air Using MOFs.

We report metallurgy on the nanoscale to generate metal nanoparticles and their simultaneous patterning in a single step. This is achieved by the self-reduction of porous metal-organic framework crystals using nanosecond pulsed laser irradiation. Metal nanoparticles of Fe, Co, Ni, Cu, Zn, Cd, In, Bi, and Pb with uniform sizes (controllable between 3 to 200 nm) and gaps (as narrow as 2 nm) are produced by nine different metal-organic frameworks, where atomically dispersed non-noble metal ions are reduced and gathered across the pores. The instant light absorption and cooling at local positions by a laser allows for precise and efficient patterning of metal nanoparticles. This new method is suitable for device fabrication at a speed of 15 mm2 s-1 on glass, consuming only 1.5 W of power. A large variety of metal nanoparticle three-dimensional architectures are demonstrated, among which one architecture exhibits an enhanced plasmonic effect homogeneously across the entire pattern for the detection of molecules at an extremely low concentration (10-12 M). These architectures are extremely stable under air and humidity during production, use, and storage, without altering the oxidation state, for 6 months.

Combined Surface-Enhanced Raman Scattering Emissions for High-Throughput Optical Labels on Micrometer-Scale Objects.

High-throughput optical labeling technologies have become increasingly important with the growing demands for molecular detection, disease diagnosis, and drug discovery. In this thought, a series of CN-bridged coordination polymer encapsulated gold nanoparticles have been developed as a universal and interference-free optical label through a facile and auxiliary agent-free self-assembly route. Moreover, surface-enhanced Raman scattering (SERS) emissions of CN-bridge can be tuned flexibly by simple replacement of Fe2+/Fe3+ with other metal ions relying on the synthesis of three Prussian blue analogues encapsulated gold nanoparticles (Au@PBA NPs). Thus, three distinct Raman frequencies have been acquired, which merely replaced the metal irons. On the basis of the potential supermultiplex optical label, space-confined surface-enhanced Raman scattering (SERS) emissions have been realized. Relying on "Abbe theorem", the focused laser allows the pure and single triple bond-coded SERS emissions to be combined into a unique and independent output, so-called "combined SERS emission" (c-SERS), if the Au@PBA NPs were confined into one micrometer-scale object. This study demonstrated c-SERS may simultaneously provide 2n - 1 optical labels only using n single emissions in the Raman-silent region for micrometer-size objects.

Application of a 2-aryl indenylphosphine ligand in the Buchwald-Hartwig cross-coupling reactions of aryl and heteroaryl chlorides under the solvent-free and aqueous conditions.

An efficient solvent-free protocol for the Buchwald-Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.

An active catalytic system for Suzuki-Miyaura cross-coupling reactions using low levels of palladium loading.

An easily available Pd(OAc)2/(2-(anthracen-9-yl)-1H-inden-3-yl) dicyclohexylphosphine/toluene/iPrOH/water catalytic system was developed, which shows high catalytic activity in the Suzuki-Miyaura cross-coupling reactions of a diverse array of aryl and heteroaryl chlorides with Pd loadings down to 0.01 mol%.

Reliable SERS detection of nitrite based on pH and laser irradiance-dependent diazotization through a convenient sampling micro-chamber.

Nitrites (NO2(-) ions) in food and drink play an important role in human health but require complicated operations before detection. Herein, we present a rationally designed SERS-enabled micro-chamber that comprised a drawn glass capillary with a tiny orifice (∼50 µm) at the distal tip, wherein the gold nanoparticles (Au NPs) are compactly coated on the inner wall surface. In this chamber, nitrites specifically trigger a pH and laser irradiance-dependent diazotization starting from p-aminothiophenol (PATP) absorbed onto the surface of Au NPs to form p,p'-dimercaptoazobenzene (DMAB) molecules, in which the presence of NO2(-) ions above 30.7 µM (1.38 ppm) in the siphoned liquid sample can be identified relying on SERS peak (1141 cm(-1)) intensity of the emerging azo moiety. Except for pH conditions, laser irradiance is more important but easily neglected in previous studies, which is capable of preventing generation of errors when the detection sensitivity was pursued through increasing the laser power. In this case, several real samples (rather than simple water samples), including honey, pickled vegetable and fermented bean curd, had been successfully detected accurately through such a convenient sampling micro-chamber. The SERS-enabled device could potentially be facilely incorporated with portable Raman instruments for a special application of food inspection in rapid and field analysis of NO2(-) ions.

Hybrid Water-Harvesting Channels Delivering Wide-Range and Supersensitive Passive Fluorescence Humidity Sensors.

The development of optical humidity detection has been of considerable interest in highly integrated wearable electronics and packaged equipment. However, improving their capacities for color recognition at ultralow humidity and response-recovery rate remains a significant challenge. Herein, we propose a type of hybrid water-harvesting channel to construct brand-new passive fluorescence humidity sensors (PFHSs). Specifically, the hybrid water-harvesting channels involve porous metal-organic frameworks and a hydrophilic poly(acrylic acid) network that can capture water vapors from the ambient environment even at ultralow humidity, into which polar-responsive aggregation-induced emission molecules are doped to impart humidity-sensitive luminescence colors. As a result, the PFHSs exhibit clearly defined fluorescence signals within 0-98% RH coupling with desirable performances such as a fast response rate, precise quantitative feedback, and durable reversibility. Given the flexible processability of this system, we further upgrade the porous structure via electrostatic spinning to furnish a kind of Nano-PFHSs, demonstrating an impressive response time (<100 ms). Finally, we validate the promising applications of these sensors in electronic humidity monitoring and successfully fabricate a portable and rapid humidity indicator card.

Fibrous Aerogels with Tunable Superwettability for High-Performance Solar-Driven Interfacial Evaporation.

Solar-driven interfacial evaporation is an emerging technology for water desalination. Generally, double-layered structure with separate surface wettability properties is usually employed for evaporator construction. However, creating materials with tunable properties is a great challenge because the wettability of existing materials is usually monotonous. Herein, we report vinyltrimethoxysilane as a single molecular unit to hybrid with bacterial cellulose (BC) fibrous network, which can be built into robust aerogel with entirely distinct wettability through controlling assembly pathways. Siloxane groups or carbon atoms are exposed on the surface of BC nanofibers, resulting in either superhydrophilic or superhydrophobic aerogels. With this special property, single component-modified aerogels could be integrated into a double-layered evaporator for water desalination. Under 1 sun, our evaporator achieves high water evaporation rates of 1.91 and 4.20 kg m-2 h-1 under laboratory and outdoor solar conditions, respectively. Moreover, this aerogel evaporator shows unprecedented lightweight, structural robustness, long-term stability under extreme conditions, and excellent salt-resistance, highlighting the advantages in synthesis of aerogel materials from the single molecular unit.

Nacre-Mimetic Nanocomposite Aerogels with Exceptional Mechanical Performance for Thermal Superinsulation at Extreme Conditions.

Thermal protection under extreme conditions requires materials with excellent thermal insulation properties and exceptional mechanical properties to withstand a variety of complex external stresses. Mesoporous silica aerogels are the most widely used insulation materials due to their ultralow thermal conductivity. However, they still suffer from mechanical fragility and structural instability in practical applications. Herein, a nacre-mimetic nanocomposite aerogel, synthesized via in situ growth of inorganic minerals in a lamellar cellulose nanofibrous network, is reported. The multiscale structural adaptation of the inorganic-organic components endows nanocomposite aerogels with rapid configuration recovery during ambient pressure drying. The resulting aerogels show ultralow thermal conductivities (17.4 mW m-1  K-1 at 1.0 atm). These aerogels also integrate challenging mechanical properties, including high compressive stiffness to resist deformation under the pressure of an adult, superelasticity to prevent static and dynamic stress cracking even under the crushing of a vehicle (1.6 t), and high bending flexibility to adapt to any surface. Moreover, they exhibit excellent structural stability under fatigue stress/strain cycles over a wide temperature range (-196 to 200 °C). The combination of high thermal insulation performance and excellent mechanical properties offers a potential material system for robust thermal superinsulation under extreme conditions, especially for aerospace applications.

Surface ligand-assisted synthesis and biomedical applications of metal-organic framework nanocomposites.

Metal-organic framework (MOF) nanocomposites have recently gained intensive attention for biosensing and disease therapy applications owing to their outstanding physiochemical properties. However, the direct growth of MOF nanocomposites is usually hindered by the mismatched lattice in the interface between the MOF and other nanocomponents. Surface ligands, molecules with surfactant-like properties, are demonstrated to exhibit the robust capability to modify the interfacial properties of nanomaterials and can be utilized as a powerful strategy for the synthesis of MOF nanocomposites. Besides this, surface ligands also exhibit significant functions in the morphological control and functionalization of MOF nanocomposites, thus greatly enhancing their performance in biomedical applications. In this review, the surface ligand-assisted synthesis and biomedical applications of MOF nanocomposites are comprehensively reviewed. Firstly, the synthesis of MOF nanocomposites is discussed according to the diverse roles of surface ligands. Then, MOF nanocomposites with different properties are listed with their applications in biosensing and disease therapy. Finally, current challenges and further directions of MOF nanocomposites are presented to motivate the development of MOF nanocomposites with elaborate structures, enriched functions, and excellent application prospects.

Risk assessment, fitness cost, cross-resistance, and mechanism of tetraniliprole resistance in the rice stem borer, Chilo suppressalis.

The rice stem borer (RSB), Chilo suppressalis, a notorious rice pest in China, has evolved a high resistance level to commonly used insecticides. Tetraniliprole, a new anthranilic diamide insecticide, effectively controls multiple pests, including RSB. However, the potential resistance risk of RSB to tetraniliprole is still unknown. In this study, the tetraniliprole-selection (Tet-R) strain was obtained through 10 continuous generations of selection with tetraniliprole 30% lethal concentration (LC30 ). The realized heritability (h2 ) of the Tet-R strain was 0.387, indicating that resistance of RSB to tetraniliprole developed rapidly under the continuous selection of tetraniliprole. The Tet-R strain had a high fitness cost (relative fitness = 0.53). We established the susceptibility baseline of RSB to tetraniliprole (lethal concentration at LC50  = 0.727 mg/L) and investigated the resistance level of 6 field populations to tetraniliprole. All tested strains that had resistance to chlorantraniliprole exhibited moderate- to high-level resistance to tetraniliprole (resistance ratio = 27.7-806.8). Detection of ryanodine receptor (RyR) mutations showed that the Y4667C, Y4667D, I4758M, and Y4891F mutations were present in tested RSB field populations. RyR mutations were responsible for the cross-resistance between tetraniliprole and chlorantraniliprole. Further, the clustered regularly interspaced palindromic repeats (CRISPR) / CRISPR-associated protein 9-mediated genome-modified flies were used to study the contribution of RyR mutations to tetraniliprole resistance. The order of contribution of a single RyR mutation to tetraniliprole resistance was Y4667D > G4915E > Y4667C ≈ I4758M > Y4891F. In addition, the I4758M and Y4667C double mutations conferred higher tetraniliprole resistance than single Y4667C mutations. These results can guide resistance management practices for diamides in RSB and other arthropods.

Fibrous aggregates: Amplifying aggregation-induced emission to boost health protection.

Environmental monitoring and personal protection are critical for preventing and for protecting human health during all infectious disease outbreaks (including COVID-19). Fluorescent probes combining sensing, imaging and therapy functions, could not only afford direct visualizing existence of biotargets and monitoring their dynamic information, but also provide therapeutic functions for killing various bacteria or viruses. Luminogens with aggregation-induced emission (AIE) could be well suited for above requirements because of their typical photophysical properties and therapeutic functions. Integration of these molecules with fibers or textiles is of great interest for developing flexible devices and wearable systems. In this review, we mainly focus on how fibers and AIEgens to be combined for health protection based on the latest advances in biosensing and bioprotection. We first discuss the construction of fibrous sensors for visualization of biomolecules. Next recent advances in therapeutic fabrics for individual protection are introduced. Finally, the current challenges and future opportunities for "AIE + Fiber" in sensing and therapeutic applications are presented.

Fibrous Aerogels for Solar Vapor Generation.

Solar-driven vapor generation is emerging as an eco-friendly and cost-effective water treatment technology for harvesting solar energy. Aerogels are solid materials with desirable high-performance properties, including low density, low thermal conductivity, and high porosity with a large internal surface, which exhibit outstanding performance in the area of solar vapor generation. Using fibers as building blocks in aerogels could achieve unexpected performance in solar vapor generation due to their entangled fibrous network and high surface area. In this review, based on the fusion of the one-dimensional fibers and three-dimensional porous aerogels, we discuss recent development in fibrous aerogels for solar vapor generation based on building blocks synthesis, photothermal materials selection, pore structures construction and device design. Thermal management and water management of fibrous aerogels are also evaluated to improve evaporation performance. Focusing on materials science and engineering, we overview the key challenges and future research opportunities of fibrous aerogels in both fundamental research and practical application of solar vapor generation technology.