Unveiling synergy of strain and ligand effects in metallic aerogel for electrocatalytic polyethylene terephthalate upcycling.

Recently, there has been a notable surge in interest regarding reclaiming valuable chemicals from waste plastics. However, the energy-intensive conventional thermal catalysis does not align with the concept of sustainable development. Herein, we report a sustainable electrocatalytic approach allowing the selective synthesis of glycolic acid (GA) from waste polyethylene terephthalate (PET) over a Pd67Ag33 alloy catalyst under ambient conditions. Notably, Pd67Ag33 delivers a high mass activity of 9.7 A mgPd-1 for ethylene glycol oxidation reaction (EGOR) and GA Faradaic efficiency of 92.7 %, representing the most active catalyst for selective GA synthesis. In situ experiments and computational simulations uncover that ligand effect induced by Ag incorporation enhances the GA selectivity by facilitating carbonyl intermediates desorption, while the lattice mismatch-triggered tensile strain optimizes the adsorption of *OH species to boost reaction kinetics. This work unveils the synergistic of strain and ligand effect in alloy catalyst and provides guidance for the design of future catalysts for PET upcycling. We further investigate the versatility of Pd67Ag33 catalyst on CO2 reduction reaction (CO2RR) and assemble EGOR//CO2RR integrated electrolyzer, presenting a pioneering demonstration for reforming waste carbon resource (i.e., PET and CO2) into high-value chemicals.

Hybrid Multimaterial 3D Printing Using Photocuring-While-Dispensing.

Three-dimensional (3D) printing methods, such as vat photopolymerization (VPP) and direct-ink-writing (DIW) processes, are known for their high-resolution and multimaterial capabilities, respectively. Here a novel hybrid 3D printing technique that combines the strengths of VPP and DIW processes to achieve multimaterial and high-resolution printing of functional structures and devices, is presented. The method involves dispensing liquid-like materials via syringes into a photocurable matrix material and subsequently using a Galvano mirror-controlled laser beam to selectively photocure the dispensed material trace or the matrix material surrounding the trace. The laser beam scanning and syringe dispensing are synchronized with a set delay to control liquid diffusion and in situ fixture. The versatility of the method is demonstrated by fabricating intricate 3D ant and wheel prototypes using various materials available for VPP and DIW technologies. The proposed photocuring-while-dispensing strategy offers advantages over conventional multimaterial 3D printing methods, such as integrating materials regardless of photocurability and viscosity, and fabricating heterogeneous structures with complex geometries and high resolution. With its principle demonstrated, this multimaterial 3D printing process will open up a wide range of potential applications with diverse functionalities and materials.

Interfacial Assembly of Nanocrystals on Nanofibers with Strong Interaction for Electrocatalytic Nitrate Reduction.

One-dimensional fiber architecture serves as an excellent catalyst support. The orderly arrangement of active materials on such a fiber substrate can enhance catalytic performance by exposing more active sites and facilitating mass diffusion; however, this remains a challenge. We developed an interfacial assembly strategy for the orderly distribution of metal nanocrystals on different fiber substrates to optimize their electrocatalytic performance. Using electrochemical nitrate reduction reaction (NO3 - RR) as a representative reaction, the iron-based nanofibers (Fe/NFs) assembly structure achieved an excellent nitrate removal capacity of 2317 mg N/g Fe and N2 selectivity up to 97.2 %. This strategy could promote the rational design and synthesis of fiber-based electrocatalysts.

Engineering the Distribution of Carbon in Silicon Oxide Nanospheres at the Atomic Level for Highly Stable Anodes.

The application of high-performance silicon-based anodes, which are among the most prominent anode materials, is hampered by their poor conductivity and large volume expansion. Coupling of silicon-based anodes with carbonaceous materials is a promising approach to address these issues. However, the distribution of carbon in reported hybrids is normally inhomogeneous and above the nanoscale, which leads to decay of coulombic efficiency during deep galvanostatic cycling. Herein, we report a porous silicon-based nanocomposite anode derived from phenylene-bridged mesoporous organosilicas (PBMOs) through a facile sol-gel method and subsequent pyrolysis. PBMOs show molecularly organic-inorganic hybrid character, and the resulting hybrid anode can inherit this unique structure, with carbon distributed homogeneously in the Si-O-Si framework at the atomic scale. This uniformly dispersed carbon network divides the silicon oxide matrix into numerous sub-nanodomains with outstanding structural integrity and cycling stability.

Real-Time Cell Temperature Fluctuation Monitoring System Using Precision Pt Sensors Coated with Low Thermal Capacity, Low Thermal Resistance, and Self-Assembled Multilayer Films.

Real-time monitoring of cell temperature fluctuation can help researchers better understand physiological phenomena and the effects of drug treatment on cells, which is a novel and important tool for cellular informatics. The platinum (Pt) temperature sensor is widely used in temperature measurement with the advantages of strong stability, great accuracy, and high sensitivity. However, the commercially available Pt sensors have large thermal resistance and heat capacity which are difficult to be applied for cell temperature measurement because only a very small amount of heat flux is generated by live cells. In this study, we designed a system using precision Pt thin-film temperature sensors with low heat capacity and thermal resistance. The Pt thin-film sensors are covered by a silicon nitride insulation layer grafted with a self-assembled multilayer silane film for promoting cell adhesion. The temperature coefficient of resistance of the Pt temperature sensor was about 2100 ppm/°C. The four-wire lead design next to the sensor detection area ensured maximum accuracy, resulting in a system noise below 0.01 °C over a long time. HEK-293T and HeLa cells were cultured on the sensor surface, respectively. The temperature fluctuation of 293T cells was monitored in a cell culture medium, showing a temperature increase of about 0.05-0.12 °C. The temperature fluctuation of HeLa cells treated with cisplatin was also measured and recorded, indicating a temperature decrease of 0.01 °C first and then a gradual temperature increase of 0.04 °C. The Pt sensor system we developed demonstrated high sensitivity and long stability for cell temperature fluctuation monitoring, which can be widely used in cell activity and cellular informatics studies.

Atomic Cu Sites Engineering Enables Efficient CO2 Electroreduction to Methane with High CH4/C2H4 Ratio.

Electrochemical reduction of CO2 into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO2 capture and utilization, resulting from their high catalytic activity and selectivity. The mobility and accessibility of active sites in Cu-based catalysts significantly hinder the development of efficient Cu-based catalysts for CO2 electrochemical reduction reaction (CO2RR). Herein, a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride (g-C3N4) as the active sites for CO2-to-CH4 conversion in CO2RR. By regulating the coordination and density of Cu sites in g-C3N4, an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH4 Faraday efficiency of 49.04% and produces the products with a high CH4/C2H4 ratio over 9. This work provides the first experimental study on g-C3N4-supported single Cu atom catalyst for efficient CH4 production from CO2RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO2RR by engineering Cu active sites in 2D materials with porous crystal structures.

Screening and Identification of Survival-Associated Splicing Factors in Lung Squamous Cell Carcinoma.

Lung squamous cell carcinoma (LUSC) is a disease with high morbidity and mortality. Many studies have shown that aberrant alternative splicing (AS) can lead to tumorigenesis, and splicing factors (SFs) serve as an important function during AS. In this research, we propose an analysis method based on synergy to screen key factors that regulate the initiation and progression of LUSC. We first screened alternative splicing events (ASEs) associated with survival in LUSC patients by bivariate Cox regression analysis. Then an association network consisting of OS-ASEs, SFs, and their targeting relationship was constructed to identify key SFs. Finally, 10 key SFs were selected in terms of degree centrality. The validation on TCGA and cross-platform GEO datasets showed that some SFs were significantly differentially expressed in cancer and paracancer tissues, and some of them were associated with prognosis, indicating that our method is valid and accurate. It is expected that our method would be applied to a wide range of research fields and provide new insights in the future.

Organic/Inorganic Hybrid Fibers: Controllable Architectures for Electrochemical Energy Applications.

Organic/inorganic hybrid fibers (OIHFs) are intriguing materials, possessing an intrinsic high specific surface area and flexibility coupled to unique anisotropic properties, diverse chemical compositions, and controllable hybrid architectures. During the last decade, advanced OIHFs with exceptional properties for electrochemical energy applications, including possessing interconnected networks, abundant active sites, and short ion diffusion length have emerged. Here, a comprehensive overview of the controllable architectures and electrochemical energy applications of OIHFs is presented. After a brief introduction, the controllable construction of OIHFs is described in detail through precise tailoring of the overall, interior, and interface structures. Additionally, several important electrochemical energy applications including rechargeable batteries (lithium-ion batteries, sodium-ion batteries, and lithium-sulfur batteries), supercapacitors (sandwich-shaped supercapacitors and fiber-shaped supercapacitors), and electrocatalysts (oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction) are presented. The current state of the field and challenges are discussed, and a vision of the future directions to exploit OIHFs for electrochemical energy devices is provided.

Flexible electrocatalysts: interfacial-assembly of iron nanoparticles for nitrate reduction.

We report a novel template-assisted epitaxial assembly strategy to assemble carbon-coated iron nanoparticles on a functionalized carbon cloth (CC/Fe@C). This delicate assembled architecture provides a useful guideline for designing flexible iron-based electrocatalysts.

Interface Heteroatom-doping: Emerging Solutions to Silicon-based Anodes.

Silicon-based composites have been recognized as a promising anode material for high-energy lithium-ion batteries (LIBs). However, the intrinsically low conductivity and the huge volume expansion during lithiation/delithiation progresses impede its further practical applications. In the past decades, numerous efforts have been made for surface and interface modification of Si-based anodes. Among these, doping of active materials with heteroatoms is one promising method to endow silicon many unmatched electrochemical properties. In this review, we focus on the effects of heteroatom doping on the interfacial properties of Si-based anodes, and some typical strategies for the interface doping are highlighted. We aim to give some reference for interfacial doping of Si-based anodes in LIBs.

Interface-Amorphized Ti3C2@Si/SiOx@TiO2 Anodes with Sandwiched Structures and Stable Lithium Storage.

A new two-dimensional material (MXene) has been compounded lately with silicon as anodes for lithium-ion batteries to achieve excellent lithium storage performances on account of its unique properties, such as high electrical conductivities, low ion diffusion barrier, and large surface area. However, the exposed silicon particles may lead to fast capacity decaying upon direct contact with the electrolyte. To solve this issue, the porous silicon and SiOx are introduced into Ti3C2Tx to construct a conductive network, and then Ti3C2@Si/SiOx are covered with amorphous TiO2 to make a sandwiched Ti3C2@Si/SiOx@TiO2 composite. Owing to the cooperation of the Ti3C2 matrix, Si/SiOx interlayer, and amorphous TiO2 layer, the reversible capacity of the Ti3C2@Si/SiOx@TiO2 composite with a sandwiched structure can be maintained at 939 mA h g-1 after 100 cycles and enhanced capacity retention capabilities in the initial 10 cycles can be came ture. The combination of these four components also makes the Ti3C2@Si/SiOx@TiO2 composite material a promising application prospect in lithium-ion batteries.

CO2 assimilation, ribulose-1,5-bisphosphate carboxylase/oxygenase, carbohydrates and photosynthetic electron transport probed by the JIP-test, of tea leaves in response to phosphorus supply.

BACKGROUND: Although the effects of P deficiency on tea (Camellia sinensis (L.) O. Kuntze) growth, P uptake and utilization as well as leaf gas exchange and Chl a fluorescence have been investigated, very little is known about the effects of P deficiency on photosynthetic electron transport, photosynthetic enzymes and carbohydrates of tea leaves. In this study, own-rooted 10-month-old tea trees were supplied three times weekly for 17 weeks with 500 mL of nutrient solution at a P concentration of 0, 40, 80, 160, 400 or 1000 microM. This objective of this study was to determine how P deficiency affects CO2 assimilation, Rubisco, carbohydrates and photosynthetic electron transport in tea leaves to understand the mechanism by which P deficiency leads to a decrease in CO2 assimilation. RESULTS: Both root and shoot dry weight increased as P supply increased from 0 to 160 microM, then remained unchanged. P-deficient leaves from 0 to 80 muM P-treated trees showed decreased CO2 assimilation and stomatal conductance, but increased intercellular CO2 concentration. Both initial and total Rubisco activity, contents of Chl and total soluble protein in P-deficient leaves decreased to a lesser extent than CO2 assimilation. Contents of sucrose and starch were decreased in P-deficient leaves, whereas contents of glucose and fructose did not change significantly except for a significant increase in the lowest P leaves. OJIP transients from P-deficient leaves displayed a rise at the O-step and a depression at the P-step, accompanied by two new steps at about 150 mus (L-step) and at about 300 mus (K-step). RC/CSo, TRo/ABS (or Fv/Fm), ETo/ABS, REo/ABS, maximum amplitude of IP phase, PIabs and PItot, abs were decreased in P-deficient leaves, while VJ, VI and dissipated energy were increased. CONCLUSION: P deficiency decreased photosynthetic electron transport capacity by impairing the whole electron transport chain from the PSII donor side up to the PSI, thus decreasing ATP content which limits RuBP regeneration, and hence, the rate of CO2 assimilation. Energy dissipation is enhanced to protect P-deficient leaves from photo-oxidative damage in high light.

Encapsulation of core-satellite silicon in carbon for rational balance of the void space and capacity.

The void space is widely used in anode materials for relieving the volume expansion during lithium insertion and extraction processes. Generally, the void is randomly generated or exceeded the expansion to ensure the structural stability, which thus sacrifices the capacity and energy density. In this research, a core-satellite architecture was constructed with an elaborate structural design to obtain a rational balance of the void space and capacity. Such well fabricated silicon@porous silicon@carbon (Si@pSi@C) core-satellite nanoparticles with a precise void space present a satisfactory capacity of 1002 mA h g-1 over 100 cycles at a current of 100 mA g-1. This delicate core-satellite architecture could promote the use of the structural design in high-energy density lithium-ion batteries.

Surface Anchoring Approach for Growth of CeO2 Nanocrystals on Prussian Blue Capsules Enable Superior Lithium Storage.

Prussian blue (PB) and its analogues (PBAs) have been acknowledged as promising materials for the catalysis, energy storage, and bioapplications because of different constructions and tunable composition. The approach for surface modification with metal oxides for boosting the performance, however, is rarely reported. Herein, a facile surface anchoring strategy has been proposed to realize CeO2 nanocrystals uniformly depositing on the surface of PB. Besides, the size, thickness, and depositing density of CeO2 nanocrystals can be regulated by adjusting the amount of the precursor and the proportion of ethanol and deionized water. Furthermore, after a step of confined pyrolysis treatment under an air atmosphere, CeO2 nanocrystals with an encapsulated iron oxide structure have been obtained. This shows a remarkable cycling and rate performance when evaluated as an anode of the lithium-ion battery. The surface anchoring approach of the CeO2 nanocrystals may not only promote the various applications of PB-based materials but also provide an opportunity for developing the architecture of other CeO2-based core-shell nanostructures.

FEM Modeling of In-Plane Stress Distribution in Thick Brittle Coatings/Films on Ductile Substrates Subjected to Tensile Stress to Determine Interfacial Strength.

The ceramic-metal interface is present in various material structures and devices that are vulnerable to failures, like cracking, which are typically due to their incompatible properties, e.g., thermal expansion mismatch. In failure of these multilayer systems, interfacial shear strength is a good measure of the robustness of interfaces, especially for planar films. There is a widely-used shear lag model and method by Agrawal and Raj to analyse and measure the interfacial shear strength of thin brittle film on ductile substrates. The use of this classical model for a type of polymer derived ceramic coatings (thickness ~18 µm) on steel substrate leads to high values of interfacial shear strength. Here, we present finite element simulations for such a coating system when it is subjected to in-plane tension. Results show that the in-plane stresses in the coating are non-uniform, i.e., varying across the thickness of the film. Therefore, they do not meet one of the basic assumptions of the classical model: uniform in-plane stress. Furthermore, effects of three significant parameters, film thickness, crack spacing, and Young's modulus, on the in-plane stress distribution have also been investigated. 'Thickness-averaged In-plane Stress' (TIS), a new failure criterion, is proposed for estimating the interfacial shear strength, which leads to a more realistic estimation of the tensile strength and interfacial shear strength of thick brittle films/coatings on ductile substrates.

Root release and metabolism of organic acids in tea plants in response to phosphorus supply.

Self-rooted, 10-month-old, uniform tea [Camellia sinensis (L.) O. Kuntze cv. Huangguanyin] plants were supplied for 17 weeks with 0, 40, 80, 160, 400, or 1000µM phosphorus (P) to investigate the effects of P supply on root citrate and malate release, the concentrations of malate and citrate and the activities of acid-metabolizing enzymes in leaves and roots. Root malate release and accumulation was induced by both 0 and 40µM P, while root citrate release and accumulation was induced only by 0µM P. Phosphorus-deficiency-induced malate and citrate release coincided with higher concentrations of root malate and citrate. The higher concentrations of malate and citrate were accompanied by increased activities of phosphoenolpyruvate carboxylase (PEPC), phosphoenolpyruvate phosphatase (PEPP), citrate synthase (CS) and NAD-malic enzyme (NAD-ME) and decreased activities of pyruvate kinase (PK), NADP-ME and NADP-isocitrate dehydrogenase (NADP-IDH) in roots. In contrast to roots, malate accumulated in the leaves only in response to 0µM P, and no change was observed in citrate levels. The P-deficiency-induced leaf malate accumulation coincided with increased activities of NADP-ME, NAD-ME and PK. Overall, the P-deficiency-induced changes in organic acid (OA) metabolism differed between roots and leaves. The high tolerance of tea plants to P-deficiency might be involved in two major processes: (a) increasing the availability of P by inducing root release of OA anions; and (b) improving the ability to use P efficiently by inducing bypass enzymes involved in tissue P economy.