Search

The rapid emergence of large language model (LLM) technology presents promising opportunities to facilitate the development of synthetic reactions. In this work, we leveraged the power of GPT-4 to build an LLM-based reaction development framework (LLM-RDF) to handle fundamental tasks involved throughout the chemical synthesis development. LLM-RDF comprises six specialized LLM-based agents, including Literature Scouter, Experiment Designer, Hardware Executor, Spectrum Analyzer, Separation Instructor, and Result Interpreter, which are pre-prompted to accomplish the designated tasks. A web application with LLM-RDF as the backend was built to allow chemist users to interact with automated experimental platforms and analyze results via natural language, thus, eliminating the need for coding skills and ensuring accessibility for all chemists. We demonstrated the capabilities of LLM-RDF in guiding the end-to-end synthesis development process for the copper/TEMPO catalyzed aerobic alcohol oxidation to aldehyde reaction, including literature search and information extraction, substrate scope and condition screening, reaction kinetics study, reaction condition optimization, reaction scale-up and product purification. Furthermore, LLM-RDF's broader applicability and versability was validated on various synthesis tasks of three distinct reactions (S N Ar reaction, photoredox C-C cross-coupling reaction, and heterogeneous photoelectrochemical reaction)., Competing Interests: Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

The use of chloride-based solid electrolytes derived from Lewis acid‒base reactions enables the construction of various new rechargeable batteries, such as chloride ion batteries (CIBs). However, a critical problem with these electrolytes is their poor stability under low-temperature, moist, or electrochemical conditions, which can lead to deterioration of the phase structure and a loss of ion conduction. Herein, the robust cubic structure of tin-based perovskite chloride-a chloride ion conductor-is achieved by alkali ion doping at the tin site via direct mechanical milling. The as-prepared cubic CsSn 0.925 Na 0.075 Cl 2.925 (CSNC) electrolyte exhibits outstanding structural stability over a broad temperature range of 213-473 K or under a high relative humidity of up to 90%, at which the typical chloride electrolytes previously reported deteriorate because of moisture. Importantly, mild annealing can modify the microstructure of the CSNC, resulting in a two fold increase in ionic conductivity and an increase in electrochemical stability, which is superior to those of other chloride electrolytes reported in previous studies. The effective chloride-ion transfer and wide electrochemical window of the CSNC are further demonstrated in different solid-state CIBs., (© 2024 Wiley‐VCH GmbH.)

Metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs)-based aerogels are garnering significant attention owing to their unique chemical and structural properties. These materials harmoniously combine the advantages of MOFs and COFs-such as high surface area, customizable porosity, and varied chemical functionality-with the lightweight and structured porosity characteristic of aerogels. This combination opens up new avenues for advanced applications in fields where material efficiency and enhanced functionality are critical. This review provides a comparative overview of the synthetic strategies utilized to produce pristine MOF/COF aerogels as well as MOF/COF-based hybrid aerogels, which are functionalized with molecular precursors and nanoscale materials. The versatility of these aerogels positions them as promising candidates for addressing complex challenges in environmental remediation, energy storage and conversion, sustainable water-energy technologies, and chemical separations. Furthermore, this study discusses the current challenges and future prospects related to the synthesis techniques and applications of MOF/COF aerogels., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small-molecule pharmaceuticals and serve as versatile intermediates in synthetic organic chemistry. Herein, we report an efficient Cu(I)/6-hydroxy picolinohydrazide-catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) in water. By establishing machine learning (ML) models, the design of ligands and optimization of reaction conditions were effectively accelerated. The N-(1,3-dimethyl-9H- carbazol-9-yl)-6-hydroxypicolinamide (L32, 6-HPA-DMCA) demonstrated high efficiency for (hetero)aryl bromides, promoting hydroxylation reactions with a minimal catalyst loading of 0.01 mol % (100 ppm) at 80 °C to reach 10000 TON; for substrates containing sensitive functional groups, the catalyst loading needs to be increased to 3.0 mol % under near-room temperature conditions. N-(2,7-Di-tert-butyl-9H-carbazol-9-yl)-6-hydroxypicolinamide (L42, 6-HPA-DTBCA) displayed superior reaction activity for chloride substrates, enabling hydroxylation reactions at 100 °C with 2-3 mol % catalyst loading. These represent the state of art for both lowest catalyst loading and temperature in the copper-catalyzed hydroxylation reactions. Furthermore, this method features a sustainable and environmentally friendly solvent system, accommodates a wide range of substrates, and shows potential for developing robust and scalable synthesis processes for key pharmaceutical intermediates., (© 2024 Wiley-VCH GmbH.)

Alite(C 3 S)-Ye'elimite(C 4 A 3 $) cement is a high cementitious material that incorporates a precise proportion of ye'elimite into the ordinary Portland cement. The synthesis and hydration behavior of Alite-Ye'elimite clinker with different lime saturation factors were investigated. The clinkers were synthesized using a secondary thermal treatment process, and their compositions were characterized. The hydrated pastes were analyzed for their hydration products, pore structure, mechanical strength, and microstructure. The clinkers and hydration products were characterized using XRD, TG-DSC, SEM, and MIP analysis. The results showed that the Alite-Ye'elimite cement clinker with a lime saturation factor (KH) of 0.93, prepared through secondary heat treatment, contained 64.88% C 3 S and 2.06% C 4 A 3 $. At this composition, the Alite-Ye'elimite cement clinker demonstrated the highest 28-day strength. The addition of SO 3 to the clinkers decreased the content of tricalcium aluminate (C 3 A) and the ratio of Alite/Belite (C 3 S/C 2 S), resulting in a preference for belite formation. The pore structure of the hydrated pastes was also investigated, revealing a distribution of pore sizes ranging from 0.01 to 10 μm, with two peaks on each differential distribution curve corresponding to micron and sub-micron pores. The pore volume decreased from 0.22 ± 0.03 to 0.15 ± 0.18 cm 3 g -1 , and the main peak of pore distribution shifted towards smaller sizes with increasing hydration time.

Metal halide-based broadband near-infrared (NIR) luminescent materials face problems such as complicated preparation, high cost, low photoluminescence quantum yield, and high excitation energy. Here, incorporating Sb 3+ and Br - into (C 20 H 20 P) 2 ZnCl 4 crystals allowed for the achievement of efficient broadband near-infrared emission under 400 nm excitation while maintaining satisfactory environmental and thermal stability. The compounds exhibit a broad range of emission bands from 550 to 1050 nm, with a photoluminescence quantum yield of 93.57%. This is a groundbreaking achievement for organic-inorganic hybrid metal halide NIR luminescent materials. The near-infrared emission is suggested to originate from [SbX 5 ] 2- , as supported by the femtosecond transient absorption spectra and density-functional theory calculations. This phosphor-based NIR LEDs successfully demonstrate potential applications in night vision, medical imaging, information encryption, and anticounterfeiting.

Given the increasingly severe environmental problems caused by water pollution, the degradation of organic dyes can be effectively achieved through the utilization of photocatalysis. In this work, metal alkoxides and a combination of alcohol/hydrophobic solvents are employed to prepare BaTiO 3 aerogels via a liquid-phase and template-free synthetic route. The preparation process of the aerogels solely entails facile agitation and supercritical drying, eliminating the need for additional heat treatment. The binary solvent of ethanol and toluene is identified as the optimal choice, resulting in a significantly enhanced surface area (up to 223 m 2 /g) and an abundant pore structure of BaTiO 3 aerogels compared to that of the BaTiO 3 nanoparticles. Thus, the removal efficiency of the BaTiO 3 aerogel sample for MO is nearly twice as high as that of the BaTiO 3 nanoparticles sample. Noble metal Ag nanoparticles' deposition onto the BaTiO 3 aerogel surface is further achieved via the photochemical deposition method, which enhances the capture of photogenerated electrons, thereby ensuring an elevated level of photocatalytic efficiency. As a result, Ag nanoparticles deposited on BaTiO 3 aerogel can degrade MO completely after 40 min of illumination, while the corresponding aerogel before modification can only remove 80% of MO after 60 min. The present work not only complements the preparatory investigation of intricate aerogels but also offers a fresh perspective for the development of diverse perovskite aerogels with broad applications.

A novel Cr-doped BaTiO 3 aerogel was successfully synthesized using a co-gelation technique that involves two metallic alkoxides and a supercritical drying method. This freshly prepared aerogel has a high specific surface area of over 100 m 2 /g and exhibits improved responsiveness to the simulated sunlight spectrum. Methyl orange (MO) was chosen as the simulated pollutant, and the results reveal that the Cr-doped BaTiO 3 aerogel, when modified with the noble metal silver (Ag), achieves a pollutant removal rate approximately 3.2 times higher than that of the commercially available P25, reaching up to 92% within 60 min. The excellent photocatalytic performance of the Ag-modified Cr-doped BaTiO 3 aerogel can be primarily attributed to its extensive specific surface area and three-dimensional porous architecture. Furthermore, the incorporation of Ag nanoparticles effectively suppresses the recombination of photo-generated electrons and holes. Stability and reusability tests have confirmed the reliability of the Ag-modified Cr-doped BaTiO 3 aerogel. Therefore, this material emerges as a highly promising candidate for the treatment of textile wastewater.

The high cost of noble Pd/Pt required for the oxygen reduction reaction (ORR) in the cathode restricts the wide applications of fuel cells. In this study, the synthesis of a novel Pd 3 CuFe 0.5 aerogel electrocatalyst is successfully demonstrated using self-assembly and lyophilization techniques, employing a mild reducing agent. The resulting aerogel electrocatalyst exhibits a distinctive 3D network structure, possessing a substantial BET-specific surface area of 75.19 m 2  g -1 . It is worth noting that the optimized Pd 3 CuFe 0.5 aerogel demonstrates exceptional ORR performance with a high half-wave potential of 0.92 V versus RHE, a significant limiting current density of 7.6 mA cm -2 , and the excellent electrocatalytic stability, superior to the reported noble metal electrocatalysts, with the ORR activity decays only 4.9% after 16 000 s. In addition, the Pd 3 CuFe 0.5 aerogel electrocatalyst shows superior cycling stability for ≈120 h at a charge/discharge current density of 10 mA cm -2 , indicating its promising application in fuel cells. Furthermore, the resulting composite aerogel possesses excellent hydrogen evolution reaction and ethanol oxidation reaction activity. The density functional theory calculations show that the partial oxidation of Pd 3 CuFe 0.5 aerogel leads to a negative shift of the d-band center, which energetically optimizes the binding strength of *O intermediates, therefore accelerating the ORR activity., (© 2023 Wiley‐VCH GmbH.)

Amine-functionalized silica aerogel globules (AFSAGs) were first synthesized via a simple ball drop casting method followed by amine grafting. The effect of grafting time on the structure and CO 2 adsorption performance of the AFSAGs was investigated. The CO 2 adsorption performance was comprehensively studied by breakthrough curves, adsorption capacity and rates, surface amine loading and density, amine efficiency, adsorption halftime, and cyclic stability. The results demonstrate that prolonging the grafting time does not lead to a significant increase in surface amine content owing to pore space blockage by superabundant amine groups. The CO 2 adsorption performance shows obvious dependence on surface amine density, determined by both the surface amine content and specific surface area, and working temperature. AFSAGs with a grafting time of 24 h (AFSAG24) with a moderate surface amine density have optimal CO 2 adsorption capacities, which are 1.78 and 2.14 mmol/g at 25 °C with dry and humid 400 ppm CO 2 , respectively. The amine efficiency of AFSAG24 with low CO 2 concentrations, 0.38-0.63 with dry 400 ppm-1% CO 2 , is the highest among the reported amine-functionalized adsorbents. After estimation with different diffusion models, the CO 2 adsorption process of AFSAG24 is governed by film diffusion and intraparticle diffusion. In the range of 1-4 mm, the ball size does not affect the CO 2 adsorption capacity of AFSAG24 obviously. AFSAG24 offers significant advantages for practical direct air capture compared with its state-of-the-art counterparts, such as high dynamic adsorption capacity and amine efficiency, excellent stability, and outstanding adaptation to the environment.

The physical properties of Ti6Al4V powder affect the spreadability of the powder and uniformity of the powder bed, which had a great impact on the performance of built parts made by powder bed fusion technology. Micro-computed tomography is a well-established technique used to analyze the non-destructivity of the objects' interior. Ti6Al4V powders were scanned with micro-CT to show the internal and external information of all the particles. The morphology, particle size distribution, hollow particle ratio, density, inclusion, and specific surface area of the powder samples were quantitatively characterized, and the relationship of flowability with these physical properties was analyzed in this work. The research results of this article showed that micro-CT is an effective way to characterize these items, and can be developed as a standard method of powder physical properties in the future.

In recent years, low-dimensional organic-inorganic hybrid metal halides (OIHMHs) have shown excellent photophysical properties due to their quantum structure, adjustable energy levels, and energy transfer between inorganic and organic components, which have attracted extensive attention from researchers. Herein, we synthesize a zero-dimensional (0D) OIHMH, Sb 3+ :(Gua) 3 InCl 6 , by introducing Sb 3+ into (Gua) 3 InCl 6 , which undergoes a significant enhancement of the emission peak at 580 nm with the photoluminescence quantum yield (PLQY) boosted from 17.86 to 95.72% when excited at 340 nm. This boost in photoluminescence of the doped sample was studied by combining ultrafast femtosecond transient absorption, temperature-dependent photoluminescence (PL) spectra, and density functional theory (DFT) calculation, revealing the process of self-trapped exciton (STE) recombination to emit light at both Sb and In sites in this 0D structure simultaneously. This material with the lowest dark STE level at the In site for emission in the undoped sample can amazingly yield very strong emission in the doped sample, which has never been observed before. Finally, we tested its application in a photoelectric device. This work not only helps to gain a deeper understanding of the formation of STEs in In-based halides but also plays a certain guiding role in the design of new luminescent materials.

Selective laser melting (SLM) has attracted increasing attention all over the world. As an important parameter, hatch spacing, which is the distance between scan lines, however, still needs a more systematic study. In this paper, the relationship between hatch spacing and mechanical properties, including microhardness, wear resistance, and porous density, was studied. The testing results revealed that when hatch spacing decreased, the overlapping rate increased which resulted in an increase in the convection in the molten pool. It led to the formation of pores in the molten pool. However, when hatch spacing was too large, the overlapping zone decreased, while the strength between each welding line was not strong enough. It caused a decrease in the quality of printed parts. Combined with the testing results gained in this work, it can be seen that a 0.06 mm hatch spacing was considered as a relatively optimal condition for part formation under 0.05 μm. Comparison of the morphology of the samples printed under different hatch spacing also confirmed the phenomenon observed here.

Perovskite chloride, an anion conductor, is a promising candidate to be a solid electrolyte for high-energy and sustainable chloride ion batteries (CIB). However, it suffers from poor structural stability at low temperature and in ambient conditions, which leads to its transformation from an ionic conductor to an insulator. Herein, a bismuth and chlorine dual doping strategy is developed to stabilize the cubic structure of CsSnCl 3 in harsh environments. The as-prepared dual-doped CsSn 0.9 Bi 0.1 Cl 3.1 material with an optimized composition maintains its cubic structure at the extremely low temperature of 213 K for 10 days and at 40% relative humidity for 50 days, while the undoped cubic material deteriorates and transforms to a monoclinic phase under these conditions in less than 1 day. Consequently, the dual doping achieves efficient chloride ion conduction that is superior to single bismuth doping due to the introduction of interstitial chlorine facilitating chloride ion transport. Importantly, the practicality of the as-prepared solid electrolyte is demonstrated in different symmetric solid cells and by various CIBs using the organic electrode couple, a multivalent metal chloride cathode, or a new high-voltage metal oxychloride cathode., (© 2023 Wiley-VCH GmbH.)

There is a great demand for the fabrication of soft electronics using hydrogels due to their biomimetic structures and good flexibility. However, conventional hydrogels have poor mechanical properties, which restricts their applications as stretchable sensors. Herein, a facile one-step strategy is proposed to fabricate tough and conductive hydrogels by making use of the graftability of carboxymethyl chitosan without extra conductive matter and crosslinking agent. The obtained polyacrylamide/carboxymethyl chitosan composite hydrogels possess outstanding transmittance and excellent mechanical performances, with tensile breaking stress of 630 kPa, breaking strain of 4560 %, toughness of 8490 kJ/m 3 . These hydrogels have low modulus of 5-20 kPa, fast recoverability after unloading, high conductivity of ∼0.85 S/m without the addition of other conductive substances and good biocompatibility. The ionic conductivity of the gels originates from the counterions of carboxymethyl chitosan, affording the hydrogels as resistive-type sensors. The resultant hydrogel sensors demonstrate a broad strain window (0.12-1500 %), excellent linear response, high sensitivity with the gauge factor reaching 11.72, and great durability, capable of monitoring diverse human motions. This work provides a new strategy to develop stretchable conductive hydrogels with promising applications in the fields of artificial intelligence and flexible electronics., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Olivine dissolution plays an important role in environmental science and technology, from controlling global element circulation to carbon capture for climate change mitigation. Most studies have been focused on investigating its dissolution rates by monitoring chemical effluent changes under various conditions. However, only by observation of surface reactivity can we unravel the actual mechanism (s) of dissolution. Here, we studied the dissolution of an olivine (010) plane in a flow-through reaction cell with an acidic solution, a surface-controlled regime, and far-from-equilibrium conditions. Direct mineral surface topography measurements using vertical scanning interferometry and atomic force microscopy allowed for quantitative analyses of the spatial and temporal changes in the dissolution rate. The (010) plane dissolved discontinuously in time for different surface sites, resulting in a heterogeneously distributed rate map. Pits with different depths showed opposite dissolution rate distributions from the dislocation center to further out from the etch pit. Based on the step-wave model, we propose a mechanism of dissolution that is governed by the competition between Gibbs free energy of the dissolution process, ΔG, and the critical free energy of the opening of etch pits, i.e., Δ G crit . The migration of step waves, the distribution of surface defects, the strain field of etch pits, and other dynamic elements, resulting in the instantaneous change of Δ G crit on the surface, are important factors leading to the discontinuous dissolution of crystal materials. This discontinuous dissolution provides new insight into the guidance of crystalline mineral applications and the prediction of material properties regarding mineral dissolution variation.

Extracellular vesicles (EVs) originating from bacteria function critical roles in bacterial biologic physiology and host-pathogen interactions. Mycobacterium tuberculosis (M. tuberculosis) produces EVs both in vitro and in vivo, with membrane-bound nanoparticles facilitating the transmission of biological molecules including lipids, proteins, nucleic acids and glycolipids, while interacting remotely with the host. Although studies of EVs in mycobacterial infections is still in its infancy, it has already revealed an entirely new aspect of M. tuberculosis-host interactions that may have implications for tuberculosis (TB) pathogenesis. In this review, we discuss the significant functions of M. tuberculosis EVs in elucidating the mechanisms underlying vesicle biogenesis and modulating cellular immune responses, as well as the recent advances and challenges in the development of novel preventive and therapeutic or diagnostic strategies against TB., Competing Interests: Declaration of Competing Interest The authors in this manuscript declared that they have no conflicts of interest with any business or individual., (Copyright © 2023 The Authors. Published by Elsevier Masson SAS.. All rights reserved.)

Dual-carbon engineering combines the advantages of graphite and hard carbon, thereby optimizing the potassium storage performance of carbon materials. However, dual-carbon engineering faces challenges balancing specific capacity, capability, and stability. In this study, we present a coordination engineering of Zn-N 4 moieties on dual-carbon through additional P doping, which effectively modulates the symmetric charge distribution around the Zn center. Experimental results and theoretical calculations unveil that additional P doping induces an optimized electronic structure of the Zn-N 4 moieties, thus enhancing K + adsorption. A single-atom Zn metal coordinated with nitrogen and phosphorus reduces the K + diffusion barrier and improves fast K + migration kinetics. Consequently, Zn-NPC@rGO exhibits high reversible specific capacities, excellent rate capability, and impressive cycling stability, and remarkable power and energy densities for potassium-ion capacitors (PICs). This study provides insights into crucial factors for enhancing potassium storage performance., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Wang Jin reports financial support was provided by the National Natural Science Foundation of China., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Molybdenum selenium (MoSe 2 ) has tremendous potential in potassium-ion batteries (PIBs) due to its large interlayer distance, favorable bandgap, and high theoretical specific capacity. However, the poor conductivity and large K + insertion/extraction in MoSe 2 inevitably leads to sluggish reaction kinetics and poor structural stability. Herein, Coinduced engineering is employed to illuminate high-conductivity electron pathway and mobile ion diffusion of MoSe 2 nanosheets anchored on reduced graphene oxide substrate (Co-MoSe 2 /rGO). Benefiting from the activated electronic conductivity and ion diffusion kinetics, and an expanded interlayer spacing resulting from Co doping, combined with the interface coupling with highly conductive reduced graphene oxide (rGO) substrate through Mo-C bonding, the Co-MoSe 2 /rGO anode demonstrates remarkable reversible capacity, superior rate capability, and stable long-term cyclability for potassium storage, as well as superior energy density and high power density for potassium-ion capacitors. Systematic performance measurement, dynamic analysis, in-situ/ex-situ measurements, and density functional theory (DFT) calculations elucidate the performance-enhancing mechanism of Co-MoSe 2 /rGO in view of the electronic and ionic transport kinetics. This work offers deep atomic insights into the fundamental factors of electrodes for potassium-ion batteries/capacitors with superior electrochemical performance., (© 2023 Wiley-VCH GmbH.)

The rapid development of tough conductive hydrogels has led to considerable progress in the fields of tissue engineering, soft robots, flexible electronics, etc. Compared to other kinds of traditional sensing materials, tough conductive hydrogels have advantages in flexibility, stretchability and biocompatibility due to their biological structures. Numerous hydrogel flexible sensors have been developed based on specific demands for practical applications. This review focuses on tough conductive hydrogels for flexible sensors. Representative tactics to construct tough hydrogels and strategies to fulfill conductivity, which are of significance to fabricating tough conductive hydrogels, are briefly reviewed. Then, diverse tough conductive hydrogels are presented and discussed. Additionally, recent advancements in flexible sensors assembled with different tough conductive hydrogels as well as various designed structures and their sensing performances are demonstrated in detail. Applications, including the wearable skins, bionic muscles and robotic systems of these hydrogel-based flexible sensors with resistive and capacitive modes are discussed. Some perspectives on tough conductive hydrogels for flexible sensors are also stated at the end. This review will provide a comprehensive understanding of tough conductive hydrogels and will offer clues to researchers who have interests in pursuing flexible sensors.

With the rapid development of industry and the acceleration of urbanization, oil pollution has caused serious damage to water, and its treatment has always been a research hotspot. Compared with traditional adsorption materials, aerogel has the advantages of light weight, large adsorption capacity and high selective adsorption, features that render it ideal as a high-performance sorbent for water treatment. The objective of this research was to develop novel hydrophobic polymer-reinforced silica aerogel microspheres (RSAMs) with water glass as the precursor, aminopropyltriethoxysilane as the modifier, and styrene as the crosslinker for oil removal from water. The effects of drying method and polymerization time on the structure and oil adsorption capacity were investigated. The drying method influenced the microstructure and pore structure in a noteworthy manner, and it also significantly depended on the polymerization time. More crosslinking time led to more volume shrinkage, thus resulting in a larger apparent density, lower pore volume, narrower pore size distribution and more compact network. Notably, the hydrophobicity increased with the increase in crosslinking time. After polymerization for 24 h, the RSAMs possessed the highest water contact angle of 126°. Owing to their excellent hydrophobicity, the RSAMs via supercritical CO 2 drying exhibited significant oil and organic liquid adsorption capabilities ranging from 6.3 to 18.6 g/g, higher than their state-of-the-art counterparts. Moreover, their robust mechanical properties ensured excellent reusability and recyclability, allowing for multiple adsorption-desorption cycles without significant degradation in performance. The novel sorbent preparation method is facile and inspiring, and the resulting RSAMs are exceptional in capacity, efficiency, stability and regenerability.

Recently, carbon nanomaterial-supported plasmonic nanocrystals used as high-performance surface-enhanced Raman scattering (SERS) substrates have attracted increasing attention due to their ultra-high sensitivity of detection. However, most of the work focuses on the design of 2-D planar substrates with traditional plasmonic structures, such as nanoparticles, nanorods, nanowires, and so forth. Here, we report a novel strategy for the preparation of high-yield Au nanohydrangeas on three-dimensional porous polydopamine (PDA)/polyvinyl alcohol (PVA)/carbon nanotube (CNT) foams. The structures and growth mechanisms of these specific Au nanocrystals are systematically investigated. PDA plays the role of both a reducing agent as well as an anchoring site for Au nanohydrangeas' growth. We also show that the ratio of surfactant KBr to the gold precursor (HAuCl 4 ) is key to obtain these structures in a manner of high production. Moreover, the substrate of the CNT foam-Au nanohydrangea hybrid can be employed as SERS sensors and can detect the analytes down to 10 -9 M., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

A systematic study was conducted to investigate the distinct mechanisms involved in the formation of the inner surfaces of cylindrical and parallelepipedic-shaped structures. The surface roughness, flatness, and sinking distance were used as key indices to measure the quality of overhanging surfaces, while the surface flatness and roughness were used to evaluate the quality of the side and bottom surfaces of the inner hole. The inner surface morphology was observed using a scanning electron microscope and a white light interferometer. The test results show that the quality of the overhanging surface had a significant impact on the quality of the parallelepipedic-shaped inner hole. In contrast, the cylindrical-shaped inner hole had a shorter but more uniformly distributed overhanging surface, resulting in a different behavior of the overhanging and side surface quality. An improved model of the overhanging surface was established by combining all of the above results and comparing them with the traditional Euler Bernoulli beam model. The factors affecting the quality of the overhanging surface were analyzed, and measures for improving the quality of the overhanging surface during the SLM manufacturing process were proposed.

Rechargeable magnesium batteries (RMB) have emerged as one of the most promising alternatives to lithium-ion batteries due to the prominent advantages of magnesium metal anodes. Nevertheless, their application is hindered by sluggish Mg-ion storage kinetics in cathodes, although various structural modifications of cathode materials have been performed. Herein, an electrolyte design using an anion-incorporated Mg-ion solvation structure is developed to promote the Mg-ion storage reactions of conversion-type cathode materials. The addition of the trifluoromethanesulfonate anion (OTf - ) in the ether-based Mg-ion electrolyte modulates the solvation structure of Mg 2+ from [Mg(DME) 3 ] 2+ to [Mg(DME) 2.5 OTf] + (DME = dimethoxy ethane), which facilitates Mg-ion desolvation and thus significantly expedites the charge transfer of the cathode material. As a result, the as-prepared CuSe cathode material on copper current collector exhibits a considerable increase in magnesium storage capacity from 61% (228 mAh g -1 ) to 95% (357 mAh g -1 ) of the theoretical capacity at 0.1 A g -1 and a more than twofold capacity increase at a high current density of 1.0 A g -1 . This work provides an efficient strategy via electrolyte modulation to achieve high-rate conversion-type cathode materials for RMBs. The incorporation of the trifluoromethanesulfonate anion in the Mg-ion solvation structure of the borate-based Mg-ion electrolyte enables the fast magnesium storage kinetics of the conversion-type cathode materials. The as-prepared copper selenide cathode achieved a more than twofold capacity increase at a high rate and the highest reversible capacities compared to those of the previously reported metal selenide cathodes., (© 2023 Wiley-VCH GmbH.)

Hydrogen generation through water electrolysis is an efficient technique for hydrogen production, but the expensive price and scarcity of noble metal electrocatalysts hinder its large-scale application. Herein, cobalt-anchored nitrogen-doped graphene aerogel electrocatalysts (Co-N-C) for oxygen evolution reaction (OER) are prepared by simple chemical reduction and vacuum freeze-drying. The Co (0.5 wt%)-N (1 wt%)-C aerogel electrocatalyst has an optimal overpotential (0.383 V at 10 mA/cm 2 ), which is significantly superior to that of a series of M-N-C aerogel electrocatalysts prepared by a similar route (M = Mn, Fe, Ni, Pt, Au, etc.) and other Co-N-C electrocatalysts that have been reported. In addition, the Co-N-C aerogel electrocatalyst has a small Tafel slope (95 mV/dec), a large electrochemical surface area (9.52 cm 2 ), and excellent stability. Notably, the overpotential of Co-N-C aerogel electrocatalyst at a current density of 20 mA/cm 2 is even superior to that of the commercial RuO 2 . In addition, density functional theory (DFT) confirms that the metal activity trend is Co-N-C > Fe-N-C > Ni-N-C, which is consistent with the OER activity results. The resulting Co-N-C aerogels can be considered one of the most promising electrocatalysts for energy storage and energy saving due to their simple preparation route, abundant raw materials, and superior electrocatalytic performance.

Steel slag (SS) has been largely discharged but little utilized, causing an environmental problem in China. In this paper, SS-based composite cementitious materials with high strength were prepared by the high volume of SS (≥40%), granulated blast-furnace slag (GBFS), fly ash (FA), flue gas desulfurization gypsum (FGDG) and cement to promote the effective utilization of SS. The hydration and hardening properties were studied through setting time, compressive strength, length change, isothermal calorimetry (IC), X-ray diffraction (XRD), mercury intrusion porosimetry (MIP), and scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS) tests. The results show that SS-based composite cementitious material exhibited a lower hydration heat release, an appropriate setting time, and volume stability. The SS cementitious material with 40% SS could obtain high strength of over 65 MPa at 28 days and 80 MPa at 90 days. The strength value of > 60 MPa is present in the binder, with 50% SS at 56 days. GBFS promotes hydration reactions and the formation of AFt and C-(A)-S-H gel, thus enhancing compressive strength. FA has a beneficial effect on later strength. The small and fine pore structures contribute to the development of strength. The main hydration products of SS composite cementitious materials are C-(A)-S-H gel, and ettringite (AFt), with less Ca(OH) 2 . The C-(A)-S-H gel with a lower Ca/Si ratio and a higher Al/Ca ratio in cementitious material, promotes mechanical properties.

Dye wastewater has caused great harm to the environment, which is an urgent problem to be solved. As typical three-dimensional porous materials, aerogels have attracted great interest in dye wastewater treatment. In this work, spherical attapulgite/silica (ATP/SiO 2 ) gels were initially prepared by easily scalable sol-gel dripping methods and then dried to aerogels with three drying techniques, namely, supercritical CO 2 drying (SCD), freeze-drying (FD), and ambient pressure drying (APD). The effect of the drying techniques and heat-treated temperature on the physical characteristic, morphological properties, microstructure, and chemical structure of the spherical ATP/SiO 2 aerogels were investigated. The macroscopic morphology of the spherical ATP/SiO 2 aerogels was homogeneous and integrated without local cracking. The average pore diameter and specific surface area of the spherical ATP/SiO 2 aerogels prepared by the three drying techniques were in the range of 6.8-8.6 nm and 218.5-267.4 m 2 /g, respectively. The heat treatment temperature had a significant effect on the pore structure and the wetting properties of the aerogels. The 600 °C heat-treated aerogels were subjected to adsorption tests in methylene blue (MB) solution (60 mg/g, 100 mL), which exhibited a great adsorption capacity of 102.50 mg/g. Therefore, the resulting spherical ATP/SiO 2 aerogels possessed multipath preparation and exhibited an efficient adsorption performance, with the potential to be applied as an adsorbent for dye wastewater.

Switchable surfaces play an important role in the development of functional materials. However, the construction of dynamic surface textures remains challenging due to the complicated structural design and surface patterning. Herein, a pruney finger-inspired switchable surface (PFISS) is developed by constructing water-sensitive surface textures on a polydimethylsiloxane substrate by taking advantage of the hygroscopicity of the inorganic salt filler and the 3D printing technology. Like human fingertips, the PFISS shows high water sensitivity with obvious surface variation in wet and dry states, which is actuated by water absorption-desorption of the hydrotropic inorganic salt filler. Besides, when the fluorescent dye is optionally added into the matrix of the surface texture, water-responsive fluorescent emitting is observed, providing a feasible surface-tracing strategy. The PFISS shows effective regulation of the surface friction and performs a good antislip effect. The reported synthetic strategy for the PFISS offers a facile way for building a wide range of switchable surfaces.

It remains a big challenge to develop non-precious metal catalysts for oxygen evolution reaction (OER) in energy storage and conversion systems. Herein, a facile and cost-effective strategy is employed to in situ prepare the Ni/Fe oxyhydroxide anchored on nitrogen-doped carbon aerogel (NiFeO x (OH) y @NCA) for OER electrocatalysis. The as-prepared electrocatalyst displays a typical aerogel porous structure composed of interconnected nanoparticles with a large BET specific surface area of 231.16 m 2 ·g -1 . In addition, the resulting NiFeO x (OH) y @NCA exhibits excellent OER performance with a low overpotential of 304 mV at 10 mA·cm -2 , a small Tafel slope of 72 mV·dec -1 , and excellent stability after 2000 CV cycles, which is superior to the commercial RuO 2 catalyst. The much enhanced OER performance is mainly derived from the abundant active sites, the high electrical conductivity of the Ni/Fe oxyhydroxide, and the efficient electronic transfer of the NCA structure. Density functional theory (DFT) calculations reveal that the introduction of the NCA regulates the surface electronic structure of Ni/Fe oxyhydroxide and increases the binding energy of intermediates as indicated by the d-band center theory. This work provides a new method for the construction of advanced aerogel-based materials for energy conversion and storage.

The objective of this research was to develop new hydrophobic silica aerogel microspheres (HSAMs) with water glass and hexmethyldisilazane for oil adsorption. The effects of the hexmethyldisilazane concentration and drying method on the structure and organic liquid adsorption capacity were investigated. The hexmethyldisilazane concentration of the modification solution did not influence the microstructure and pore structure in a noteworthy manner, which depended more on the drying method. Vacuum drying led to more volume shrinkage of the silica gel microsphere (SGM) than supercritical CO 2 drying, thus resulting in a larger apparent density, lower pore volume, narrower pore size distribution, and more compact network. Owing to the large pore volume and pore size, the HSAMs synthesized via supercritical CO 2 drying had a larger organic liquid adsorption capacity. The adsorption capacities of the HSAMs with pore volumes of 4.04-6.44 cm 3 /g for colza oil, vacuum pump oil, and hexane are up to 18.3, 18.9, and 11.8 g/g, respectively, higher than for their state-of-the-art counterparts. The new sorbent preparation method is facile, cost-effective, safe, and ecofriendly, and the resulting HSAMs are exceptional in capacity, stability, and regenerability.

An efficient auto-continuous globing process was developed with a self-built apparatus to synthesize pure silica aerogel microspheres (PSAMs) using sodium silicate as a precursor and water as a solvent. A hydrophobic silica aerogel microsphere (HSAM) was obtained by methyl grafting. A reinforced silica aerogel microsphere (RSAM) was prepared by polymer cross-linking on the framework of the silica gel. The pH value of the reaction system and the temperature of the coagulating bath were critical to form perfect SAMs with a diameter of 3.0 ± 0.2 mm. The grafted methyl groups are thermally stable up to 400 °C. Polymer cross-linking increased the strength significantly, owing to the polymer coating on the framework of silica aerogel. The pore volumes of HSAM (6.44 cm 3 /g) and RSAM (3.17 cm 3 /g) were much higher than their state-of-the-art counterparts. Their specific surface areas were also at a high level. The HSAM and RSAM showed high organic sorption capacities, i.e., 17.9 g/g of pump oil, 11.8 g/g of hexane, and 22.2 mg/g of 10 mg/L methyl orange. The novel preparation method was facile, cost-effective, safe, and eco-friendly, and the resulting SAM sorbents were exceptional in capacity, dynamics, regenerability, and stability.

Aerogels have interconnected networks and preeminent pore structures. When used as the catalysts for oxygen reduction reaction (ORR), they can facilitate the mass transfer and expose more active sites. Here, we synthesized the Fe-doped titanium oxide-based aerogels (TA/Fes) by the sol-gel method combined with thermal treatment. The specific surface areas of the TA/Fes ranged from 475 to 774 m 2 ·g -1 , and the pore volumes varied from 0.96 to 1.72 cm 3 ·g -1 . The doping effect of the Fe ions and the oxygen vacancies in anatase enhance the electrical conductivity, leading to the low Rct (313.3-828.2 Ω). All samples showed excellent stability (2.0-4.5 mV) and 4e - pathway. The limiting current density of TA/Fe3 reached 5.34 mA·cm -2 , which was comparable to that of commercial Pt/C. The preparation method is inspiring and the as-prepared aerogel catalysts have potential in promoting the scale of fuel cells.

To investigate the effects of limestone powder and gypsum on the early hydration of ye'elimite, the hydration behavior of C 4 A 3 S¯-LP-CaSO 4 ·2H 2 O-H 2 O systems are researched. The hydration behavior of systems are researched by employing isothermal calorimetry, XRD technique and chemical shrinkage. The thermodynamic modelling method is employed to predict the equilibrium phase assemblages. The results show that the system with 5 wt.% LP has a comparable hydration heat evolution to limestone powder-free systems. Limestone powder can take part in the reaction to produce monocarboaluminate in the system with M-value (molar ratio of gypsum to ye'elimite) of 1, but monocarboaluminate is not found in the system with M-value of 2. The level off time of chemical shrinkage shortens with the increase of limestone powder dosage. Thermodynamic modelling results show that monocarboaluminate is no longer formed in all systems when M-value exceeds 1.27, which corresponds to the XRD results. This study can provide theoretical guidance for the rational utilization of limestone powder in calcium sulphoaluminate cement.

Extrusion-based ceramic printing is fast and convenient, but the green body strength is too low, and the application prospect is not high. An extrusion-based printing method of alumina ceramics toughened by short carbon fiber is reported in this paper. The bending strength and fracture toughness of 3D-printed alumina ceramics were improved by adding short carbon fiber. The toughening effects of four carbon fiber lengths (100 μm, 300 μm, 700 μm, and 1000 μm) and six carbon fiber contents (1, 2, 3, 4, 5, and 6 wt%) on ceramics were compared. The experimental results show that when the length of carbon fiber is 700 μm, and carbon fiber is 5 wt%, the toughening effect of fiber is the best, and the uniform distribution of fiber is an effective toughening method. Its bending strength reaches 33.426 ± 1.027 MPa, and its fracture toughness reaches 4.53 ± 0.46 MPa·m 1/2 . Compared with extrusion-based printed alumina ceramics without fiber, the bending strength and fracture toughness increase by 55.38% and 47.56%, respectively.

The therapeutic efficacy of tyrosine kinase inhibitors (TKIs) on solid tumors is limited by drug resistance and side effects. Currently, the combination therapy comprises of TKIs and angiogenesis inhibitors have been corroborated as an effective approach in cancer therapy. Ethoxy-erianin phosphate (EBTP) is an anti-angiogenic compound with low toxicity obtained by structural modification of the natural product erianin. Here, we aimed to evaluate whether EBTP can cooperate with TKIs to inhibit the proliferation and angiogenesis of tumor cells and reduce toxic effects. First, CCK-8 results showed that EBTP can effectively inhibit the proliferation of liver cancer cell line HepG2. We combined EBTP with four TKIs (Bosutinib, Apatinib, Afatinib and Erlotinib) to treat HepG2 cells and CompuSyn software analysis suggested that EBTP/Afatinib(Afa)shows the best synergistic inhibitory effect. Meanwhile, EBTP/Afa can significantly suppress the proliferation, invasion, migration and angiogenesis of HepG2 and HUVECs. ELISA results revealed that EBTP/Afa inhibits the secretion of VEGF in HepG2. EBTP/Afa down-regulates the expression of VEGF, p-VEGFR1, p-VEGFR2 and p-EGFR in both HepG2 and HUVECs. Further, the supernatant of HepG2 cells treated with EBTP/Afa blocks the intracellular downstream signal transduction shared by VEGF and EGFR in HUVECs. Finally, EBTP/Afa significantly inhibits tumor growth and angiogenesis in vivo. To conclude, EBTP/Afa targets VEGF and EGFR signaling pathways in liver cancer cells and tumor vasculature, thereby inhibiting the proliferation, motion and angiogenesis of liver cancer cells. Overall, this study provides a new combined strategy for the clinical treatment of hepatocellular carcinoma., (Copyright © 2022 Elsevier Inc. All rights reserved.)

RORγ is a dual-functional drug target, which involves not only induction of inflammation but also promotion of cancer immunity. The development of agonists of RORγ promoting Th17 cell differentiation could provide a novel mechanism of action (MOA) as an immune-activating anticancer agent. Herein, we describe new 2-(ortho-substituted benzyl)-indole derivatives as RORγ agonists by scaffold hopping based on clinical RORγ antagonist VTP-43742. Interestingly, subtle structural differences of the compounds led to the opposite biological MOA. After rational optimization for structure-activity relationship and pharmacokinetic profile, we identified a potent RORγ agonist compound 17 that was able to induce the production of IL-17 and IFNγ in tumor tissues and elicit antitumor efficacy in MC38 syngeneic mouse colorectal tumor model. This is the first comprehensive work to demonstrate the in vivo antitumor efficacy of an RORγ agonist.

Owing to its low cost, high theoretical capacity, and environmentally friendly characteristics, pyrite FeS 2 demonstrates promise as a cathode material for high-energy metal-anode-based rechargeable batteries. When it is used in a rechargeable magnesium battery (RMB), the electrode couple exhibits an extremely low theoretical volume change upon full discharge. However, its electrochemical Mg-ion storage is considerably hindered by slow reaction kinetics. In this study, a high-performance FeS 2 cathode for RMBs using a copper current collector is reported, which is involved in cathode reactions via a reversible redox process between copper and cuprous sulfide. This phase transformation with the formation of copper nanowires during discharge activates the redox reactions of FeS 2 via a two-step and four-electron Mg-ion transfer that dominates the cathode reactions. As a result, the as-prepared FeS 2 nanomaterial cathode delivers a significantly enhanced reversible capacity of 679 mAh g -1 at 50 mA g -1 . The corresponding energy density of 714 Wh kg -1 is superior to those of all previously reported metal chalcogenide cathodes in RMBs or hybrid batteries using a Mg metal anode. Notably, the as-assembled FeS 2 -Mg battery can operate over 1000 cycles with a good capacity retention at 400 mA g -1 ., (© 2021 Wiley-VCH GmbH.)

Streptococcus suis serotype 2 (S. suis 2) is an important zoonotic pathogen that presents a significant threat both to pigs and to workers in the pork industry. The initial steps of S. suis 2 pathogenesis are unclear. In this study, we found that the type II histidine triad protein HtpsC from the highly virulent Chinese isolate 05ZYH33 is structurally similar to internalin A (InlA) from Listeria monocytogenes, which plays an important role in mediating listerial invasion of epithelial cells. To determine if HtpsC and InlA function similarly, an isogenic htpsC mutant (ΔhtpsC) was generated in S. suis by homologous recombination. The htpsC deletion strain exhibited a diminished ability to adhere to and invade epithelial cells from different sources. Double immunofluorescence microscopy also revealed reduced survival of the ΔhtpsC mutant after co-cultivation with epithelium. Adhesion to epithelium and invasion by the wild type strain was inhibited by a monoclonal antibody against E-cadherin. In contrast, the htpsC-deficient mutant was unaffected by the same treatment, suggesting that E-cadherin is the host-cell receptor that interacts with HtpsC and facilitates bacterial internalization. Based on these results, we propose that HtpsC is involved in the process by which S. suis 2 penetrates host epithelial cells, and that this protein is an important virulence factor associated with cell adhesion and invasion., (© 2021. The Microbiological Society of Korea.)

A robust and sustainable C(sp2)-C(sp3) cross-electrophile coupling was developed via nickel/copper synergistic catalysis under micellar conditions. This protocol provided a general method to access alkylated arenes with good to excellent yields on a very large scale.

Autophagy is closely related to the growth and drug resistance of cancer cells, and autophagy related 4B (ATG4B) performs a crucial role in the process of autophagy. The long non-coding RNA (lncRNA) colorectal neoplasia differentially expressed (CRNDE) promotes the progression of hepatocellular carcinoma (HCC), but it is unclear whether the tumor-promoting effect of CRNDE is associated with the regulation of ATG4B and autophagy. Herein, we for the first time demonstrated that CRNDE triggered autophagy via upregulating ATG4B in HCC cells. Mechanistically, CRNDE enhanced the stability of ATG4B mRNA by sequestrating miR-543, leading to the elevation of ATG4B and autophagy in HCC cells. Moreover, sorafenib induced CRNDE and ATG4B as well as autophagy in HCC cells. Knockdown of CRNDE sensitized HCC cells to sorafenib in vitro and in vivo . Collectively, these results reveal that CRNDE drives ATG4B-mediated autophagy, which attenuates the sensitivity of sorafenib in HCC cells, suggesting that the pathway CRNDE/ATG4B/autophagy may be a novel target to develop sensitizing measures of sorafenib in HCC treatment., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Chen, Sun, Dai, Li, Yan, Zhang, Xiao, Shen, Huang, Xiang, Zhang, Tan, Yang, Nie, Huang, Lian and He.)

Atezolizumab is an anti-PD-L1 immune checkpoint inhibitor recommended for the treatment of locally advanced or metastatic urothelial carcinoma (mUC) after prior platinum-containing chemotherapy, regardless of PD-L1 status, among other treatment settings. We conducted a long-term follow-up to the exploratory analysis of overall survival (OS) and safety for the IMvigor211 intent-to-treat (ITT) population. Patients with mUC and disease progression during or following platinum-based chemotherapy were randomised 1:1 to receive atezolizumab 1200 mg or chemotherapy (vinflunine 320 mg/m 2 , paclitaxel 175 mg/m 2 , or docetaxel 75 mg/m 2 according to investigator choice) intravenously every 3 wk. Although the primary analysis did not demonstrate statistically significant longer OS for patients receiving atezolizumab versus chemotherapy, updated OS showed long-term durable remission. With a median of 33 mo of follow-up, the 24-mo OS rate was 23% with atezolizumab and 13% with chemotherapy. Safety findings were consistent with the primary analysis, with no new signals detected. Chemotherapy-treated patients experienced more grade 3/4 treatment-related adverse events (AEs; 43% vs 22%) and more AEs leading to treatment discontinuation (18% vs 9%). Atezolizumab-treated patients experienced more AEs of special interest (35% vs 20%), which tended to be grade 1-2. Our findings support the use of atezolizumab in platinum-treated patients with mUC regardless of PD-L1 status. PATIENT SUMMARY: We report follow-up results from a study of an immunotherapy treatment, atezolizumab, in patients with bladder cancer who had already received platinum-containing chemotherapy. This analysis compared the effectiveness of atezolizumab with chemotherapy over 2.5 years after starting treatment. The results show that patients who received atezolizumab lived longer and had manageable side effects compared with patients who received chemotherapy. This trial is registered at ClinicalTrials.gov as NCT02302807., (Copyright © 2021 European Association of Urology. Published by Elsevier B.V. All rights reserved.)

Minimally invasive approaches to detect residual disease after surgery are needed to identify patients with cancer who are at risk for metastatic relapse. Circulating tumour DNA (ctDNA) holds promise as a biomarker for molecular residual disease and relapse 1 . We evaluated outcomes in 581 patients who had undergone surgery and were evaluable for ctDNA from a randomized phase III trial of adjuvant atezolizumab versus observation in operable urothelial cancer. This trial did not reach its efficacy end point in the intention-to-treat population. Here we show that ctDNA testing at the start of therapy (cycle 1 day 1) identified 214 (37%) patients who were positive for ctDNA and who had poor prognosis (observation arm hazard ratio = 6.3 (95% confidence interval: 4.45-8.92); P < 0.0001). Notably, patients who were positive for ctDNA had improved disease-free survival and overall survival in the atezolizumab arm versus the observation arm (disease-free survival hazard ratio = 0.58 (95% confidence interval: 0.43-0.79); P = 0.0024, overall survival hazard ratio = 0.59 (95% confidence interval: 0.41-0.86)). No difference in disease-free survival or overall survival between treatment arms was noted for patients who were negative for ctDNA. The rate of ctDNA clearance at week 6 was higher in the atezolizumab arm (18%) than in the observation arm (4%) (P = 0.0204). Transcriptomic analysis of tumours from patients who were positive for ctDNA revealed higher expression levels of cell-cycle and keratin genes. For patients who were positive for ctDNA and who were treated with atezolizumab, non-relapse was associated with immune response signatures and basal-squamous gene features, whereas relapse was associated with angiogenesis and fibroblast TGFβ signatures. These data suggest that adjuvant atezolizumab may be associated with improved outcomes compared with observation in patients who are positive for ctDNA and who are at a high risk of relapse. These findings, if validated in other settings, would shift approaches to postoperative cancer care., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

A superflexible hydrophobic silica-based aerogel (FHSA) was prepared via a facile sol-gel process and ambient pressure drying method. The FHSA was treated at different temperatures varying from -196 to 450 °C to evaluate its thermal and mechanical performances. The evolutions of the physical property, hydrophobicity, microstructure, pore structure, and chemical structure of the FHSA with the various treatment temperatures were investigated comprehensively. The structure of the FHSA did not show an obvious change after treatment in the liquid nitrogen. The bulk density of the FHSA increased from 0.047 to 0.077 g cm -3 when the thermal treatment temperature increased from 25 to 450 °C. The specific surface area and pore volume of the FHSA increased with the treatment temperature owing to the decomposition of the organic moieties. The Fourier transform infrared spectra showed that the methyl groups in the FHSA had excellent thermostability up to 400 °C. The water contact angles of the FHSA after treatment at -196, 25, 200, 300, 350, 400, and 450 °C were 131, 151, 162, 150, 132, 119, and 34°, respectively. The thermal conductivity of the FHSA at a low temperature of -10 °C was 0.022 W m -1 K -1 . The reversible deformation rate of the FHSA was more than 80% within 100 compression cycles. After treatment in liquid nitrogen, the reversible deformation rate of the FHSA remained at 50%. The synthesis method of the FHSA is simple, the resulting FHSA showed good performance both in thermostability and flexibility, and it is promisingly applied for thermal insulation and sealing in ultralow-temperature environments.

Among first experimentally discovered two-dimensional (2D) ferromagnetic materials, chromium triiodide (CrI 3 ) monolayers have attracted particular attention due to their potential applications in electronics and spintronics. However, the Curie temperature T c of the CrI 3 monolayer is below room temperature, which greatly limits practical development of the devices. Herein, using density functional theory calculation, we explore how the electronic and magnetic properties of CrI 3 monolayers change upon adsorption of 3d transition-metal (TM) atoms (from Sc to Zn). Our results indicate that the electronic properties of the TM-CrI 3 system can be tuned from semiconductor to metal/half-metal/spin gapless semiconductor depending on the choice of the adsorbed TM atoms. Moreover, the adsorption can improve the ferromagnetic stability of CrI 3 monolayers by increasing both magnetic moments and T c . Notably, T c of CrI 3 with Sc and V adatoms can be increased by nearly a factor of 3. We suggest postsynthesis doping of 2D CrI 3 by deposition of TM atoms as a new route toward potential applications of TM-CrI 3 systems in nanoelectronic and spintronic devices.

An acidified SnO 2 /rGO aerogel (ASGA) is an attractive contributor in ethanol gas sensing under ultralow concentration because of the sufficient active sites and adsorption pores in SnO 2 and the rGA, respectively. Furthermore, a p-n heterojunction is successfully constructed by the high electron mobility between ASP and rGA to establish a brand-new bandgap of 2.72 eV, where more electrons are released and the surface energy is decreased, to improve the gas sensitivity. The ASGA owns a specific surface area of 256.1 m 2 /g, far higher than SnO 2 powder (68.7 m 2 /g), indicating an excellent adsorption performance, so it can acquire more ethanol gas for a redox reaction. For gas-sensing ability, the ASGA exhibits an excellent response of R a / R g = 137.4 to 20 ppm of ethanol at the optimum temperature of 210 °C and can reach a response of 1.2 even at the limit detection concentration of 0.25 ppm. After the concentration gradient change test, a nonlinear increase between concentration and sensitivity ( S - C curve) is observed, and it indirectly proves the chemical adsorption between ethanol and ASGA, which exhibits charge transfer and improves electron mobility. In addition, a detailed energy band diagram and sensor response diagram jointly depict the gas-sensitive mechanism. Finally, a conversed calculation explains the feasibility of the nonlinear S - C curve from the atomic level, which further verifies the chemical adsorption during the sensing process.

Amorphous polymer-derived silicon oxycarbide (SiOC) is an attractive candidate for Li-ion battery anodes, as an alternative to graphite, which is limited to a theoretical capacity of 372 mAh/g. However, SiOC tends to exhibit poor transport properties and cycling performance as a result of sparsely distributed carbon clusters and inefficient active sites. To overcome these limitations, we designed and fabricated a layered graphene/SiOC heterostructure by solvent-assisted infiltration of a polymeric precursor into a modified three-dimensional (3D) graphene aerogel skeleton. The use of a high-melting-point solvent facilitated the precursor's freeze drying, which following pyrolysis yielded SiOC as a layer supported on the surface of nitrogen-doped reduced graphene oxide aerogels. The fabrication method employed here modifies the composition and microstructure of the SiOC phase. Among the studied materials, the highest levels of performance were obtained for a sample of moderate SiOC content, in which the graphene network constituted 19.8 wt % of the system. In these materials, a stable reversible charge capacity of 751 mAh/g was achieved at low charge rates. At high charge rates of 1480 mA/g, the capacity retention was ∼95% (352 mAh/g) after 1000 consecutive cycles. At all rates, Coulombic efficiencies >99% were maintained following the first cycle. Performance across all indicators was majorly improved in the graphene aerogel/SiOC nanocomposites, compared with unsupported SiOC. The performance was attributed to mechanisms across multiple length scales. The presence of oxygen-rich SiO 4- x C x tetrahedral units and a continuous free-carbon network within the SiOC provides sites for reversible lithiation, while high ionic and electronic transport is provided by the layered graphene/SiOC heterostructure.

The utilization of coral waste is an economical way of using concrete in coastal and offshore constructions. Coral waste with more than 96% CaCO 3 can be ground to fines and combined with supplementary cementitious materials (SCMs) such as fly ash, silica fume, granulated blast furnace slag in replacing Portland cement to promote the properties of cement concrete. The effects of coral sand powder (CSP) compared to limestone powder (LSP) blended with SCMs on hydration and microstructure of mortar were investigated. The result shows CSP has higher activity than LSP when participating in the chemical reaction. The chemical effect among CSP, SCMs, and ordinary Portland cement (OPC) results in the appearance of the third hydration peak, facilitating the production of carboaluminate. CSP-SCMs mortar has smaller interconnected pores on account of the porous character of CSP as well as the filler and chemical effect. The dilution effect of CSP leads to the reduction of compressive strength of OPC-CSP and OPC-CSP-SCMs mortars. The synergic effects of CSP with slag and silica fume facilitate the development of compressive strength and lead to a compacted isolation and transfer zone (ITZ) in mortar.

Layered 1T-type TiS 2 powders were pretreated by an ethanol-based shear pulverization process, which showed outstanding effectiveness in reducing the average grain size and narrowing the size distribution while maintaining high crystallinity and plate-shaped morphology. The resulting bulk ceramics densified by spark plasma sintering possessed a highly (00 l )-oriented texture and pronounced anisotropy. They showed a noticeably increased σ and an unaffected S in the in-plane direction due to the increased carrier mobility μ and the constant carrier concentration n , which resulted in a significant enhancement of the in-plane power factor, optimally to an unprecedented high level of 1.6-1.8 mW m -1 K -2 in a range of 323-673 K. Meanwhile, the lattice thermal conductivity was reduced by approximately 20% due to the intensified grain boundary phonon scattering that overwhelmed the effect due to texturing. These effects not only demonstrated the powder shear pulverization pretreatment as a facial and reliable route toward a high-textured TiS 2 but also enabled a remarkable increase of ZT record for TiS 2 -based thermoelectrics (TEs) to approximately 0.7 at 673 K, indicating clearly the significant effect of texture engineering on TE performance.

Aqueous rechargeable batteries show great application prospects in large-scale energy storage because of their reliable safety and low cost. However, a key challenge in developing this battery system lies in its low energy density. Herein, a high-energy manganese-metal hydride (Mn-MH) hybrid battery is reported in which a Mn-based cathode operated by the Mn 2+ /MnO 2 deposition-dissolution reactions, a hydrogen-storage alloy anode that absorbs and desorbs hydrogen in an alkaline solution, and a proton-exchange membrane separator are employed. Given the benefit derived from the high solubility and high specific capacity of the Lewis acidic MnCl 2 in the cathode and the low electrode potential of the MH anode, this aqueous Mn-MH hybrid battery exhibits impressive electrochemical properties with admirable discharge voltage plateaus up to 2.2 V, a competitive energy density of about 240 Wh kg -1 (based on the total mass of the 5.5 m MnCl 2 solution and the hydrogen storage alloy electrode system), good cycling stability over 130 cycles, and a desirable rate capability. This work demonstrates a new strategy for achieving high-performance and low-cost aqueous rechargeable batteries., (© 2020 Wiley-VCH GmbH.)