bluuebunny/crossref_metadata_2025 huggingface dataset:
N‐Rich Solid Electrolyte Interface Constructed In Situ Via a Binder Strategy for Highly Stable Silicon Anode
Authors: Wang Yuxiao , Yang Xiaofei , Yuan Ye , Wang Zhi , Zhang Hongzhang , Li Xianfeng
Published: May 2023

Silicon (Si) is regarded as a promising anode material for high‐energy‐density lithium‐ion batteries due to its high specific capacity (4200 mAh g−1) and low potential (0.3 V vs Li+/Li). However, the large volume change (over 300%) of Si during the lithiation/delithiation process leads to severe pulverization, electrode structure destruction, and finally capacity fading, which slows down its step to practical application. Herein, a poly(vinylamine) (PVAm) binder containing amino (NH2) and amide (NHCHO) is proposed to improve the stability of Si anodes from particle to electrode structure. The N‐containing functional groups show strong interaction with the Si particles and form a uniform and thin layer on the surface, which would decompose and form an N‐rich inorganic solid electrolyte interphase (SEI) layer during discharging. The high mechanical stability N‐rich SEI helps relieve the pulverization of Si particles through stress dissipation, maintains electrode structural stability, and reduces the loss of active materials. Thus, the Si anode with PVAm binder exhibits high capacity of ≈2000 mAh g−1 after 200 cycles, which is much higher than that of using Poly(vinylidene fluoride) (PVDF) binder (66 mAh g−1) and Poly(vinyl alcohol) PVA binder (820 mAh g−1). This facile and practical strategy provides a new perspective for the application of Si anodes in advanced batteries.
In Situ Reconstruction of Electrocatalysts for Lithium–Sulfur Batteries: Progress and Prospects
Authors: Zeng Pan , Su Bin , Wang Xiaolian , Li Xiaoqin , Yuan Cheng , Liu Genlin , Dai Kehua , Mao Jing , Chao Dongliang , Wang Qingyuan , Zhang Liang
Published: May 2023

The current research of Li–S batteries primarily focuses on increasing the catalytic activity of electrocatalysts to inhibit the polysulfide shuttling and enhance the redox kinetics. However, the stability of electrocatalysts is largely neglected, given the premise that they are stable over extended cycles. Notably, the reconstruction of electrocatalysts during the electrochemical reaction process has recently been proposed. Such in situ reconstruction process inevitably leads to varied electrocatalytic behaviors, such as catalytic sites, selectivity, activity, and amounts of catalytic sites. Therefore, a crucial prerequisite for the design of highly effective electrocatalysts for Li–S batteries is an in‐depth understanding of the variation of active sites and the influence factors for the in situ reconstruction behaviors, which has not achieved a fundamental understanding and summary. This review comprehensively summarizes the recent advances in understanding the reconstruction behaviors of different electrocatalysts for Li–S batteries during the electrochemical reaction process, mainly including metal nitrides, metal oxides, metal selenides, metal fluorides, metals/alloys, and metal sulfides. Moreover, the unexplored issues and major challenges of understanding the reconstruction chemistry are summarized and prospected. Based on this review, new perspectives are offered into the reconstruction and true active sites of electrocatalysts for Li–S batteries.
Amplification of Cerenkov Luminescence Using Semiconducting Polymers for Cancer Theranostics
Authors: Rosenkrans Zachary T. , Hsu Jessica C. , Aluicio‐Sarduy Eduardo , Barnhart Todd E. , Engle Jonathan W. , Cai Weibo
Published: May 2023

The therapeutic efficacy of photodynamic therapy is limited by the ability of light to penetrate tissues. Due to this limitation, Cerenkov luminescence (CL) from radionuclides has recently been proposed as an alternative light source in a strategy referred to as Cerenkov radiation‐induced therapy (CRIT). Semiconducting polymer nanoparticles (SPNs) have ideal optical properties, such as large absorption cross‐sections and broad absorbance, which can be utilized to harness the relatively weak CL produced by radionuclides. SPNs can be doped with photosensitizers and have ≈100% energy transfer efficiency by multiple energy transfer mechanisms. Herein, an optimized photosensitizer‐doped SPN is investigated as a nanosystem to harness and amplify CL for cancer theranostics. It is found that semiconducting polymers significantly amplify CL energy transfer efficiency. Bimodal positron emission tomography (PET) and optical imaging studies show high tumor uptake and retention of the optimized SPNs when administered intravenously or intratumorally. Lastly, it is found that photosensitizer‐doped SPNs have excellent potential as a cancer theranostics nanosystem in an in vivo tumor therapy study. This study shows that SPNs are ideally suited to harness and amplify CL for cancer theranostics, which may provide a significant advancement for CRIT that are unabated by tissue penetration limits.
Selective Surface Engineering of Perovskite Microwire Arrays
Authors: Li Dengji , Meng You , Zhang Yuxuan , Xie Pengshan , Zeng Zixin , Wang Wei , Lai Zhengxun , Wang Weijun , Tsang Sai‐Wing , Wang Fei , Liu Chuntai , Lan Changyong , Yip SenPo , Ho Johnny C.
Published: May 2023

The surface of low‐dimensional perovskites play a crucial role in determining their intrinsic property. Understanding their characteristics and the influence of certain surfaces is valuable in designing functional surface‐engineered structures. Meanwhile, surface passivation can also be applied to stabilize and optimize the state‐of‐the‐art perovskite‐based optoelectronics. Herein, cesium lead bromide (CsPbBr3) microwire parallel arrays are designed and fabricated with specific (100)‐terminated crystal planes, which exhibit excellent photodetection performance with long‐term environment stability >3000 h. Notably, it is uncovered experimentally and theoretically that environmental oxygen can not only passivate the Br‐vacancy‐related trap states on the (100) surface, but also create charge carrier nanochannels to enhance the (opto)electronic properties. The coupling effects between oxygen species and the specific terminated crystal planes of perovskites highlight the importance of surface engineering for designing and optimizing perovskite‐based devices.
Body Heat Powered Wirelessly Wearable System for Real‐time Physiological and Biochemical Monitoring
Authors: An Zijian , Fu QiQi , Lv Jingjiang , Zhou Tao , Wu Yue , Lu Yanli , Liu Guang , Shi Zhenghan , li Xin , Zhang Fenni , Liu Qingjun
Published: May 2023

Through harvesting energy from the environment or human body, self‐power wearable electronics have an opportunity to break through the limitations of battery supply and achieving long‐term continuous operation. Here, a wireless wearable monitoring system driven entirely by body heat is implemented. Based on the principle of maximizing heat utilization, while optimizing internal resistance and heat dissipation, the stretchable TEG improves the power density of previous similar devices from only a few microwatts per square centimeter to tens and makes it possible to continuously drive wireless wearable electronic systems. Furthermore, ceaseless self‐power energy gives wearable electronics unparalleled continuous working ability, which can realize the tracking and monitoring of biochemical and physiological indicators at different time scale. A practical system demonstrates the ability to real‐time monitor heart rate, sweat ingredient and body motion at a high sampling rate. This study marks an important advance of self‐powered wearable electronics for wirelessly real‐time healthy monitoring.
Development of a Novel DNA Aptamer Targeting Colorectal Cancer Cell‐Derived Small Extracellular Vesicles as a Potential Diagnostic and Therapeutic Agent
Authors: Cha Byung Seok , Jang Young Jun , Lee Eun Sung , Kim Do Yeon , Woo Ji Su , Son Jinseo , Kim Seokjoon , Shin Jiye , Han Jinjoo , Kim Seokhwan , Park Ki Soo
Published: May 2023

Colorectal cancer (CRC) as the second leading cause of global cancer deaths poses critical challenges in clinical settings. Cancer‐derived small extracellular vesicles (sEVs), which are secreted by cancer cells, have been shown to mediate tumor development, invasion, and even metastasis, and have thus received increasing attention for the development of cancer diagnostic or therapeutic platforms. In the present study, the sEV‐targeted systematic evolution of ligands by exponential enrichment (E‐SELEX) is developed to generate a high‐quality aptamer (CCE‐10F) that recognizes and binds to CRC‐derived sEVs. Via an in‐depth investigation, it is confirmed that this novel aptamer possesses high affinity (Kd = 3.41 nm) for CRC‐derived sEVs and exhibits a wide linear range (2.0 × 104–1.0 × 106 particles µL−1) with a limit of detection (LOD) of 1.0 × 103 particles µL−1. Furthermore, the aptamer discriminates CRC cell‐derived sEVs from those derived from normal colon cell, human serum, and other cancer cells, showing high specificity for CRC cell‐derived sEVs and significantly suppresses the critical processes of metastasis, including cellular migration, invasion, and angiogenesis, which are originally induced by sEVs themselves. These findings are highly encouraging for the potential use of the aptamer in sEV‐based diagnostic and therapeutic applications.
Multi‐Resonant Mie Resonator Arrays for Broadband Light Trapping in Ultrathin c‐Si Solar Cells
Authors: Lee Nayeun , Xue Muyu , Hong Jiho , van de Groep Jorik , Brongersma Mark Luitzen
Published: May 2023

Effective photon management is critical to realize high power conversion efficiencies for thin crystalline silicon (c‐Si) solar cells. Standard few‐100‐µm‐thick bulk cells achieve light trapping with macroscopic surface textures covered by thin, continuous antireflection coatings. Such sizeable textures are challenging to implement on ultrathin cells. Here, it is illustrated how nanoscale Mie‐resonator‐arrays with a bimodal size distribution support multiple resonances that can work in concert to achieve simultaneous antireflection and light‐trapping across the broad solar spectrum. The effectiveness of these light‐trapping antireflection coatings is experimentally demonstrated on a 2.8 µm‐thick c‐Si solar cell. The measured short‐circuit current and corresponding power conversion efficiency are notably improved, achieving efficiencies as high as 11.2%. Measurements of the saturation current density on completed cells indicate that thermal oxides can effectively limit surface recombination. The presented design principles are applicable to a wide range of solar cells.
Direct Probing of Lattice‐Strain‐Induced Oxygen Release in LiCoO2 and Li2MnO3 without Electrochemical Cycling
Authors: Kim Dongho , Hwang Jaejin , Byeon Pilgyu , Kim Wonsik , Kang Dong Gyu , Bae Hyung Bin , Lee Sang‐Gil , Han Seung Min , Lee Jaekwang , Chung Sung‐Yoon
Published: May 2023

Since the recognition of a significant oxygen‐redox contribution to enhancing the capacity of Li transition‐metal oxide cathodes, the oxygen release and subsequent structural variations together with capacity fading are critical issues to achieve better electrochemical performance. As most previous reports dealt with the structural degradation of cathodes after electrochemical cycling, it is fairly difficult to clarify how substantial the effect of lattice strain on the oxygen release will be while exclusively ruling out any electrochemical influences. By utilizing nanoindentation and mechanical surface polishing of single‐crystal LiCoO2 and Li2MnO3, the local variations of both the atomic structure and oxygen content are scrutinized. Atomic‐column‐resolved imaging reveals that local LiM (M = Co and Mn) disordering and further amorphization are induced by mechanical strain. Moreover, substantial oxygen deficiency in the regions with these structural changes is directly identified by spectroscopic analyses. Ab initio density functional theory calculations also demonstrate energetically favorable formation of oxygen vacancies under shear strain. Providing direct evidence of oxygen release as a consequence of lattice strain, the findings in this work suggest that efficient strain relaxation will be of great significance for longevity of the anion framework in layered oxide cathodes.
A Biodegradable, Waterproof, and Thermally Processable Cellulosic Bioplastic Enabled by Dynamic Covalent Modification
Authors: Zhou Guowen , Zhang Haishan , Su Zhiping , Zhang Xiaoqian , Zhou Haonan , Yu Le , Chen Chaoji , Wang Xiaohui
Published: May 2023

The growing environmental concern over petrochemical‐based plastics continuously promotes the exploration of green and sustainable substitute materials. Compared with petrochemical products, cellulose has overwhelming superiority in terms of availability, cost, and biodegradability; however, cellulose's dense hydrogen‐bonding network and highly ordered crystalline structure make it hard to be thermoformed. A strategy to realize the partial disassociation of hydrogen bonds in cellulose and the reassembly of cellulose chains via constructing a dynamic covalent network, thereby endowing cellulose with thermal processability as indicated by the observation of a moderate glass transition temperature (Tg = 240 °C), is proposed. Moreover, the cellulosic bioplastic delivers a high tensile strength of 67 MPa, as well as excellent moisture and solvent resistance, good recyclability, and biodegradability in nature. With these advantageous features, the developed cellulosic bioplastic represents a promising alternative to traditional plastics.
BiFeO3 Nanoparticles: The “Holy‐Grail” of Piezo‐Photocatalysts?
Authors: Amdouni Wafa , Fricaudet Matthieu , Otoničar Mojca , Garcia Vincent , Fusil Stephane , Kreisel Jens , Maghraoui‐Meherzi Hager , Dkhil Brahim
Published: May 2023

Recently, piezoelectric‐based catalysis has been demonstrated to be an efficient means and promising alternative to sunlight‐driven photocatalysis, where mechanical vibrations trigger redox reactions. Here, 60 nm‐size BiFeO3 nanoparticles are shown to be very effective for piezo‐degrading Rhodamine B (RhB) model dye with record degradation rate reaching 13 810 L mol−1 min−1, and even 41 750 L mol−1 min−1 (i.e., 100% RhB degradation within 5 min) when piezocatalysis is synergistically combined with sunlight photocatalysis. These BiFeO3 piezocatalytic nanoparticles are also demonstrated to be versatile toward several dyes and pharmaceutical pollutants, with over 80% piezo‐decomposition within 120 min. The maintained high piezoelectric coefficient combined with low dielectric constant, high‐elastic modulus, and the nanosized shape make these BiFeO3 nanoparticles extremely efficient piezocatalysts. To avoid subsequent secondary pollution and enable their reusability, the BiFeO3 nanoparticles are further embedded in a polymer P(VDF‐TrFE) matrix. The as‐designed flexible, chemically stable, and recyclable nanocomposites still keep remarkable piezocatalytic and piezo‐photocatalytic performances (i.e., 92% and 100% RhB degradation, respectively, within 20 min). This work opens a new research avenue for BiFeO3 that is the model multiferroic and offers a new platform for water cleaning, as well as other applications such as water splitting, CO2 reduction, or surface purification.
Identification and Quantification of Charge Transfer in CaAl2O4:Eu2+,Nd3+ Persistent Phosphor
Authors: Kong Jintao , Meijerink Andries
Published: May 2023

Reversible charge transfer between lanthanide ions is identified as storage mechanism for the current workhorse persistent phosphors. Present evidence relies on sophisticated X‐ray absorption spectroscopy to detect the reversible charge transfer. Here, simple optical spectroscopy is used to study the charge transfer in one of the benchmark persistent phosphors CaAl2O4:Eu2+,Nd3+. Based on the observation that both the trapping and de‐trapping processes in CaAl2O4:Eu2+,Nd3+ are thermally activated, forward charge transfer from Eu2+ to Nd3+ and backward charge transfer from Nd2+ to Eu3+ are identified. The percentages of Eu2+ and Nd3+ involved in the charge transfer are >10%, which exceeds the previous estimates in other persistent phosphors. Furthermore, this strategy offers additional advantage of site selectivity, which enables the identification of the distinct contributions of different Nd3+ sites to the charge transfer. These findings underline the significance of reversible charge transfer in persistent phosphors and move towards a complete understanding of persistent luminescence mechanism.
Raman Spectroscopy of the Trapezoidal Bi2O2Se
Authors: Han Mengwei , Wu Shengqiang , Zhao Xiaoxu , He Qinming , Zhang Bangmin , Xiong Weiming , Luo Xin , Zheng Yue
Published: May 2023

The 2D Bi2O2Se has recently attracted significant interest with large Hall mobility at low temperature due to the depressed electron–phonon scattering. However, the phonon properties of Bi2O2Se are not well explored, and some Raman modes are under debate. Here, substrate engineering is used to grow an unexplored trapezoidal Bi2O2Se, which facilitates the Raman measurements in different orientation planes. Two additional Raman modes at 55 and 429 cm−1 are detected on the slope of the trapezoid besides the 159 and 362 cm−1 modes found on the top plane of the trapezoidal Bi2O2Se. Based on the polarized Raman spectroscopy, density functional theory calculations, and group theory analysis, the Raman modes of 55, 159, 362, and 429 cm−1 are assigned to the Eg, A1g, B1g, and Eg modes, respectively. There are two distinct types of angle‐resolved polarized Raman spectroscopy for the A1g mode on the top and edge planes of Bi2O2Se, which can be used to determine the crystal orientation unambiguously. Furthermore, strong thermal anisotropy is found in the top and edge planes of trapezoidal Bi2O2Se, as reflected from the first‐order temperature coefficient of A1g phonon mode. The novel growth strategy and interesting anisotropic phonon properties may open up potential applications of Bi2O2Se in nanoelectronics.
4D Optical Information Storage from LiGa5O8:Cr3+ Nanocrystal in Glass
Authors: Tang Haitao , Liu Zhichao , Zhang Hao , Zhu Xiaodie , Peng Qingpeng , Wang Wei , Ji Tao , Zhang Peng , Le Yakun , Yakovlev Aleksey Nikolaevich , Qiu Jianbei , Dong Guoping , Yu Xue , Xu Xuhui
Published: May 2023

With the fast‐growing amount of data, the state‐of‐the‐art optical data storage has become a front‐runner in the competing data storage technologies. However, two‐dimensional (2D) spatial resolution in the conventional optical data storage media has almost reached the limit. Herein, LiGa5O8:Cr3+ nanoparticles (NCs) precipitated in situ from a transparent medium are prepared. The transparent LiGa5O8:Cr3+ glass ceramics show excellent deep‐trap carriers storage ability under blue light irradiation and can realize the bit‐by‐bit optical data in 3D space for write‐in and read‐out in a photon trapping/detrapping mode. Moreover, this optical storage mechanism is also extended to 4D by realizing temperature optical encryption. Notably, the written information can still be clearly displayed even after being recorded for 200 days. This work enables 4D high‐precision storage of information and provides new insights into the design and fabrication of next‐generation storage materials.
Polar Nitride Perovskite LaWN3‐δ with Orthorhombic Structure
Authors: Zhou Xuefeng , Xu Wenwen , Gui Zhigang , Gu Chao , Chen Jian , Xie Jianyu , Yao Xiaodong , Dai Junfeng , Zhu Jinlong , Wu Liusuo , Guo Er‐jia , Yu Xiaohui , Fang Leiming , Zhao Yusheng , Huang Li , Wang Shanmin
Published: May 2023

Nitride perovskite LaWN3 has been predicted to be a promising ferroelectric material with unique properties for diverse applications. However, due to the challenging sample preparation at ambient pressure, the crystal structure of this nitride remains unsolved, which results in many ambiguities in its properties. Here, the authors report a comprehensive study of LaWN3 based on high‐quality samples synthesized by a high‐pressure method, leading to a definitive resolution of its crystal structure involving nitrogen deficiency. Combined with theoretical calculations, these results show that LaWN3 adopts an orthorhombic Pna21 structure with a polar symmetry, possessing a unique atomic polarization along the c‐axis. The associated atomic polar distortions in LaWN3 are driven by covalent hybridization of W: 5d and N: 2p orbitals, opening a direct bandgap that explains its semiconducting behaviors. The structural stability and electronic properties of this nitride are also revealed to be closely associated with its nitrogen deficiency. The success in unraveling the structural and electronic ambiguities of LaWN3 would provide important insights into the structures and properties of the family of nitride perovskites.
A Bioinspired Manganese‐Organic Framework Ameliorates Ischemic Stroke through its Intrinsic Nanozyme Activity and Upregulating Endogenous Antioxidant Enzymes
Authors: Wang Jian , Wang Yang , Xiaohalati Xiakeerzhati , Su Qiangfei , Liu Jingwei , Cai Bo , Yang Wen , Wang Zheng , Wang Lin
Published: May 2023

Following stroke, oxidative stress induced by reactive oxygen species (ROS) aggravates neuronal damage and enlarges ischemic penumbra, which is devastating to stroke patients. Nanozyme‐based antioxidants are emerging to treat stroke through scavenging excessive ROS. However, most of nanozymes cannot efficiently scavenge ROS in neuronal cytosol and mitochondria, due to low‐uptake abilities of neurons and barriers of organelle membranes, significantly limiting nanozymes’ neuroprotective effects. To overcome this limitation, a manganese‐organic framework modified with polydopamine (pDA‐MNOF), capable of not only mimicking catalytic activities of natural SOD2's catalytic domain but also upregulating two endogenous antioxidant enzymes in neurons is fabricated. With such a dual anti‐ROS effect, this nanozyme robustly decreases cellular ROS and effectively protects them from ROS‐induced injury. STAT‐3 signaling is found to play a vital role in pDA‐MNOF activating the two antioxidant enzymes, HO1 and SOD2. In vivo pDA‐MNOF treatment significantly improves the survival of middle cerebral artery occlusion (MCAo) mice by reducing infarct volume and more importantly, promotes animal behavioral recovery. Further, pDA‐MNOF activates vascular endothelial growth factor expression, a downstream target of STAT3 signaling, thus enhancing angiogenesis. Taken together, the biochemical, cell‐biological, and animal‐level behavioral data demonstrate the potentiality of pDA‐MNOF as a dual ROS‐scavenging agent for stroke treatment.
Mechanically Robust and Room Temperature Self‐Healing Ionogel Based on Ionic Liquid Inhibited Reversible Reaction of Disulfide Bonds
Authors: Yang Lei , Sun Lijie , Huang Hongfei , Zhu Wenfan , Wang Yihan , Wu Zekai , Neisiany Rasoul Esmaeely , Gu Shijia , You Zhengwei
Published: May 2023

Although highly desired, it is difficult to develop mechanically robust and room temperature self‐healing ionic liquid‐based gels (ionogels), which are very promising for next‐generation stretchable electronic devices. Herein, it is discovered that the ionic liquid significantly reduces the reversible reaction rate of disulfide bonds without altering its thermodynamic equilibrium constant via small molecule model reaction and activation energy evolution of the dissociation of the dynamic network. This inhibitory effect would reduce the dissociated units in the dynamic polymeric network, beneficial for the strength of the ionogel. Furthermore, aromatic disulfide bonds with high reversibility are embedded in the polyurethane to endow the ionogel with superior room temperature self‐healing performance. Isocyanates with an asymmetric alicyclic structure are chosen to provide optimal exchange efficiencies for the embedded disulfide bonds relative to aromatic and linear aliphatic. Carbonyl‐rich poly(ethylene‐glycol‐adipate) diols are selected as soft segments to provide sufficient interaction sites for ionic liquids to endow the ionogel with high transparency, stretchability, and elasticity. Finally, a self‐healing ionogel with a tensile strength of 1.65 ± 0.08 MPa is successfully developed, which is significantly higher than all the reported transparent room temperature self‐healing ionogel and its application in a 3D printed stretchable numeric keyboard is exemplified.
2D Nanosheet Spray Coating for Scalable Processing of High‐Energy‐Density Dielectric Polymer Films
Authors: Shi Mengjiao , Li Xinhui , Jiang Yanda , Li Shuxuan , Li Baowen , Zhang Xin , Zhang Shujun , Nan Ce‐Wen
Published: May 2023

Dielectric film capacitors with high power density and rapid charge–discharge capability are widely used as key components in modern electronic and electrical systems, and polymers are primary dielectric for film capacitors due to their low cost, flexibility, and ease of processing. Here, a surface engineering approach is reported to improve the energy storage properties of polymer films by directly spray coating 2D nanosheets on the polymer film surface. The spraying of 2D calcium niobate nanosheets on the surface of biaxially oriented polypropylene (BOPP) films leads to remarkably increased breakdown strength and dielectric constant, resulting in a maximum 64% enhancement of energy density compared to the pristine BOPP films. Ultraviolet irradiation is further employed to improve the adhesion of nanosheets to the BOPP film surface, leading to an ultrahigh energy density of 11.6 J cm−3 with a high energy efficiency of 90%, which is the highest energy density ever achieved in polypropylene‐based films. This work provides a universal, cost‐effective, and scalable approach to improve the energy density of dielectric polymer films, which is of great significance for the application of high‐energy‐density polymer films in compact and efficient power systems.
Molten Salt‐Assisted Synthesis of Single‐Crystalline Nonstoichiometric Li1+xNi1–xO2 with Improved Structural Stability
Authors: Ding Guoyu , Yao Meng , Li Jinhan , Yang Tingting , Zhang Yudong , Liu Kuiming , Huang Xinhui , Wu Zhonghan , Chen Jiayu , Wu Ziyan , Du Jiayong , Rong Changru , Liu Qi , Zhang Wei , Cheng Fangyi
Published: May 2023

Cobalt‐free LiNiO2 is an attractive cathode material with high energy density and low cost but suffers from severe structural degradation and poor performance. Here, a molten salt‐assisted synthesis combined with a Li‐refeeding strategy is proposed to obtain nonstoichiometric Li1+xNi1‐xO2 with submicron particle size and superior rate performance. The slightly Li‐rich and single‐crystalline characters inhibit Li+/Ni2+ anti‐site defects and mitigates the undesirable phase evolution. Remarkably, single‐crystalline Li1.045Ni0.955O2 exhibits a high specific capacity (218.7 mAh g−1 at 0.1 C), considerable rate capability (187.0 mAh g−1 at 5 C), and an initial Coulombic efficiency (89.62% at 0.1 C) in the 1.27 Ah pouch full cell employing the graphite anode, significantly outperforming near stoichiometric LiNiO2. Furthermore, the particulate morphology of Li1.045Ni0.955O2 remains intact at charge voltages up to 4.8 V, whereas near stoichiometric LiNiO2 features intragranular cracks and irreversible lattice distortion. This study underscores the value of molten salt‐assisted synthesis and Li‐refeeding modification to upgrade Ni‐based layered oxide cathode materials for advanced Li‐ion batteries.
Rational Anion Selection of the Electrolyte Additive for Highly Reversible Lithium Plating/Stripping
Authors: Zhu Zhenglu , Ji Jie , Qi Xiaoqun , Ji Yongsheng , Liu Zhikang , Du Weichen , Pan Yujun , Yang Dan , Ma Jiwei , Qie Long , Huang Yunhui
Published: May 2023

Recruiting anions from electrolyte additives into the lithium ion solvation structure is a promising strategy for the construction of long‐lifespan Li‐metal batteries (LMBs). However, inadequate understanding of the anion‐involved Li+ solvation hinders the finding of new anion additives. Herein, using NO3− as an example, the effects of the newly‐introduced anion on the Li+ solvation structure are investigated. It is demonstrated that the added NO3− reduces the electrostatic potential of the Li+ solvation cluster, especially for solvated solvents, which improves electrolyte stability against the Li anode. However, such a conclusion is not universal for all anion additives. It is also confirmed that the anions with higher binding energy and smaller ion size are more apt to improve the Li stability and reversibility. Based on the above understanding, a new selection principle based on anion selection coefficient (the rate of the anion size to the binding energy toward Li+, unit: Å3 eV−1) is proposed, and with which a new hexafluorosilicate anion is found to be beneficial to LMBs.
Revisiting the impact of per‐unit duties on agricultural export prices
Authors: Fiankor Dela‐Dem , Santeramo Fabio G.
Published: May 2023

We replicate the findings of Emlinger and Guimbardr (ERAE, 2021) on the heterogeneous effects of per‐unit tariffs on trade patterns for developed and developing countries. Analyzing import and export data from 2001 to 2013, they confirm the Alchian‐Allen conjecture that per‐unit trade costs induce higher export unit values. However, the effects are more pronounced for developed country exporters. Understanding the effects of per‐unit trade costs vis‐a‐vis ad valorem tariffs is important to level the playing field of trade negotiations that involve pricing and non‐pricing policies. We extend the original study with data for 191 exporting (190 importing) countries, and 670 HS6 digit products, covering the period 2001–2019 period. The general findings of the original study hold, with remarkable differences. First, using a data set that is constructed in a replicable way and introducing highly relevant bilateral fixed effects reduce effect sizes and the level of statistical significance. Second, the Alchian‐Allen effect is not clearly separated by the economic development dimension of the exporter, but rather dependent on the price levels of the traded goods. These results have important policy implications as they call for deeper investigation of countries' industrial structures of exports to better shape the international debate on trade negotiations.
Cu‐Based Catalytic Materials for Electrochemical Carbon Dioxide Reduction: Recent Advances and Perspectives
Authors: Ma Liang , Yang Zhuxian , Wang Yuan , Xia Yongde
Published: May 2023

Electrocatalytic CO2 reduction reaction (CRR) is a promising way to convert carbon dioxide (CO2) into value‐added hydrocarbons to alleviate the ever‐increasing environmental problem and accelerate the realization of carbon cycling. Cost‐effective and stable electrocatalytic materials with low overpotential, superior selectivity, excellent activity and great stability are critically important to achieve such a target. Cu‐based electrocatalysts are promising candidates for electrochemical CRR due to their versatile abilities of converting CO2 into various products. This review analyzes and summarizes the current progress in utilization of Cu‐based catalytic materials for electrochemical CRR. Monometallic, bimetallic, trimetallic, and multimetallic Cu‐based electrocatalysts with variable elemental compositions and tunable morphologies, including Cu nanowires, Cu nanocubes (NCs), Cu porous structures, Cu‐based alloys, Cu‐oxide/hydrogen oxide, Cu single atoms, and 2D substrate‐supported Cu electrocatalysts for CRR, are surveyed. Substantial advances in overcoming the existing bottlenecks of eletrocatalysts and effectively improving CRR performance of Cu‐based electrocatalysts for future applications are systematically discussed. Challenges and perspectives of Cu‐based electrocatalytic materials for CRR are also offered, which may shed light on further development of Cu‐based electrocatalysts with superior performance. It is anticipated that this review will provide a valuable insight into the rational design and synthesis of highly efficient Cu‐based electrocatalysts for large‐scale CRR utilization.
Establishment of thresholds for alternate wetting and drying irrigation management in rice
Authors: Atwill Richard L. , Spencer G. Dave , Bond Jason A. , Walker Timothy W. , Phillips J. Mike , Mills Brian E. , Krutz L. Jason
Published: May 2023

The long‐term viability of rice production in the midsouthern United States could be affected by irrigation management strategy. This study was conducted to determine if rice sustainability can be improved through manipulation of the irrigation threshold. The effects of an alternate wetting and drying (AWD) irrigation threshold and cultivar on water applied, rice grain yield, seed quality, irrigation water use efficiency, and net returns were investigated at Stoneville, MS, on a Sharkey clay (very fine, smectitic, thermic Chromic Epiaquert) during the 2015 through 2017 growing seasons. Water applied increased exponentially from 316 mm for the AWD threshold of −40 cm to 1061 mm for the conventional flood. For both hybrid and inbred lines, rice grain yield decreased linearly at a rate of 14 kg ha−1 for each centimeter decrease in irrigation threshold. Alternate wetting and drying irrigation threshold had no effect on seed quality parameters including chalk, milling total, and milling whole. Net returns were higher for AWD compared to a conventional flood for all cultivars. The economically optimal irrigation threshold was dependent on cultivar and rice price. Converting from a conventional flood to AWD will likely improve the sustainability of rice production in the midsouthern United States.
Photoredox synthesis of Vicinal Dichloride using FeCl3 as chlorine source
Authors: Wang Xinren , Shi Changyi , Yang Mengyu , Ma Yule , Chen Yadong , Lu Tao , Tang Weifang , Feng Jie
Published: May 2023

This work presents a photo‐redox vicinal dichlorination of acrylamides using a naturally abundant chlorine source (FeCl3). The LMCT of FeCl3 is responsible for the chlorine radical inducement, while the tetra‐n‐butylammonium decatungstate (TBADT) catalytic system enhanced the process. This method exhibits extraordinarily mild conditions, not requiring external ligands and low E factors, which enables scalable synthesis.
I2‐Mediated Oxidation of Amines in Water toward Imines and Amides
Authors: Wang Manman , Yu Wenquan , Chang Junbiao
Published: May 2023

A sustainable oxidation reaction of amines in water is established for the synthesis of imines and amides employing environmentally benign molecular iodine as the sole oxidant. The features of the present reaction also include no use of transition metals, operational simplicity and gram‐scale synthesis. It provides a facile access to imine and amide derivatives including bioactive molecules from readily accessible amine precursors.
Shared Genetic Risk Factors for Multiple Sclerosis/Psoriasis Suggest Involvement of Interleukin‐17 and Janus Kinase–Signal Transducers and Activators of Transcription Signaling
Authors: Patrick Matthew T. , Nair Rajan P. , He Kevin , Stuart Philip E. , Billi Allison C. , Zhou Xiang , Gudjonsson Johann E. , Oksenberg Jorge R. , Elder James T. , Tsoi Lam C.
Published: May 2023

Objective

Psoriasis and multiple sclerosis (MS) are complex immune diseases that are mediated by T cells and share multiple comorbidities. Previous studies have suggested psoriatic patients are at higher risk of MS; however, causal relationships between the two conditions remain unclear. Through epidemiology and genetics, we provide a comprehensive understanding of the relationship, and share molecular factors between psoriasis and MS.

Methods

We used logistic regression, trans‐disease meta‐analysis and Mendelian randomization. Medical claims data were included from 30 million patients, including 141,544 with MS and 742,919 with psoriasis. We used genome‐wide association study summary statistics from 11,024 psoriatic, 14,802 MS cases, and 43,039 controls for trans‐disease meta‐analysis, with additional summary statistics from 5 million individuals for Mendelian randomization.

Results

Psoriatic patients have a significantly higher risk of MS (4,637 patients with both diseases; odds ratio [OR] 1.07, p = 1.2 × 10−5) after controlling for potential confounders. Using inverse variance and equally weighted trans‐disease meta‐analysis, we revealed >20 shared and opposing (direction of effect) genetic loci outside the major histocompatibility complex that showed significant genetic colocalization (in COLOC and COLOC‐SuSiE v5.1.0). Co‐expression analysis of genes from these loci further identified distinct clusters that were enriched among pathways for interleukin‐17/tumor necrosis factor‐α (OR >39, p < 1.6 × 10−3) and Janus kinase–signal transducers and activators of transcription (OR 35, p = 1.1 × 10−5), including genes, such as TNFAIP3, TYK2, and TNFRSF1A. Mendelian randomization found psoriasis as an exposure has a significant causal effect on MS (OR 1.04, p = 5.8 × 10−3), independent of type 1 diabetes (OR 1.05, p = 4.3 × 10−7), type 2 diabetes (OR 1.08, p = 2.3 × 10−3), inflammatory bowel disease (OR 1.11, p = 1.6 × 10−11), and vitamin D level (OR 0.75, p = 9.4 × 10−3).

Interpretation

By investigating the shared genetics of psoriasis and MS, along with their modifiable risk factors, our findings will advance innovations in treatment for patients suffering from comorbidities. ANN NEUROL 2023;94:384–397
Fabrication of Antifouling/Antimicrobial Polysulfonium‐Coated Surface Against Biofilms and Water Bacterial Contamination
Authors: Ma Xutao , Lin Min , Sun Jing , Chen Xuesi
Published: May 2023

Bacterial attachment and colonization on the surface have caused a severe threat to human healthcare. The development of surface coatings with high antibacterial activity and low toxicity is highly desired. Herein, a series of sulfonium‐containing polypeptoids with various structural motifs on the side chains is synthesized, which are efficiently grafted on the silicone surface via plasma and ultraviolet light treatment. The resulting coating demonstrates excellent antibacterial properties against both Gram‐positive and Gram‐negative bacteria, as well as a sustained antibacterial effect at ambient temperature for up to one week. Moreover, the coating exhibits excellent in vitro antibiofilm and protein resistance properties, as well as excellent hemo/biocompatibility. Further, by fabricating a decontamination system with the coated substrates, the obtained coating materials show high efficiency in bacterial decontamination of water, which has great potential for use in water disinfection systems. All these results suggest that prepared coating with dual antibacterial and antifouling properties has great potential in combating bacterial contamination.
In Situ Formed, Peritoneum‐Adhesive Immunogels Synergizing Low‐Dose Fractionated Radiotherapy Against Colorectal Peritoneal Carcinomatosis
Authors: Liu Xun , Wang Mengru , Yan Jing , Wu Fan , Zhao Ziyin , Yang Qiang , Zhou Renxiang , Zheng Yiran , Zhu Rongying , Chen Yongbing , Yin Lichen
Published: May 2023

Immune checkpoint blockade (ICB) therapy holds great potentials for the treatment of colorectal peritoneal carcinomatosis (CRPC). However, its efficacy is often suboptimal due to the low immunogenic tumor phenotype, immunosuppressive tumor microenvironment (TME), and low antibody bioavailability at the peritoneal site. Herein, an in situ formed, anti‐cluster of differentiation 47 (aCD47) and anti–programmed cell death 1 ligand 1 (aPDL1) co‐loaded hydrogel (aCD47/aPDL1@PB–TA gel) with excellent peritoneum‐adhesive property and reactive oxygen species (ROS)‐responsive degradation is developed, bridging low‐dose fractionated radiotherapy (LDFRT) and ICB therapy for CRPC. The aCD47/aPDL1@PB‐TA gel is formed instantly upon mixing of the intraperitoneally injected, antibody‐containing solutions of phenylboronic acids‐containing polymer (PB) and tannic acid (TA), which can adhere to the peritoneum over 4 d. LDFRT promotes an immunogenic tumor phenotype by upregulating CD47 and PDL1, and reverses the immunosuppressive TME by fostering M1‐type macrophage polarization, dendritic cell maturation, and T cell infiltration. Moreover, LDFRT generates ROS to degrade the hydrogel and release the antibodies, consequently activating innate and adaptive immune responses. LDFRT and ICB therapy then cooperate to eliminate peritoneally metastasized CT26 colon tumor nodules in mice. Herein, a promising strategy is provided for LDFRT‐reinforced immunotherapy of CRPC, especially for patients with low immunogenic tumor.
Ultra‐microporous MAF stu‐1 modified by ammonia for efficient CO2 capture
Authors: Wei Xiaojuan , Li Mianjing , Jiang Tao , Lou Shi Nee , Wang Shengping
Published: May 2023

A series of ultra‐microporous rod‐shaped three‐dimensional metal organic frameworks MAF stu‐1 modified with different amounts of ammonia water were synthesized by solvothermal method using chelated nitrogen‐containing ligands, which was applied to CO2 capture and exhibited excellent adsorption performance and CO2/N2 (15:85, v/v) separation efficiency. MAF stu‐1‐C regulated by .13 mol NH3 had small pore size of 4.9 Å and uncoordinated imidazole nitrogen sites in the channel, which were beneficial to improving CO2 adsorption capacity and selectivity. The maximal CO2 adsorption capacity of MAF stu‐1‐C was 110 cm3/g, exhibiting excellent CO2 capture ability and cycle stability. The ideal adsorption solution theory (IAST) model was used to calculate the adsorption and separation ratio of CO2 to N2. The CO2 to N2 selectivity of the modified adsorbent was more than 100. Furthermore, the adsorption heat of MAF stu‐1‐C for CO2 was calculated to be about 35 kJ/mol by virial equation fitting method, indicating that the modified adsorbent also had remarkable regeneration performance.
Design, Synthesis and Biological Evaluation of Novel Catalpol Derivatives as Potential Pancreatic Cancer Inhibitors
Authors: Kong Yuanfang , Liu Shuanglin , Wang Shaopei , Xu Jindan , Hu Yulong , Jiang Shiqing , Dong Chunhong
Published: May 2023

A series of C10‐position imidazole‐modified catalpol derivatives are specifically designed and synthesized for serving as potential pancreatic cancer inhibitors, which are characterized by 1H NMR, 13C NMR and high‐resolution mass spectrometry (HRMS). They were evaluated by the 3‐[4, 5‐dimethylthiazol‐2‐yl]‐2, 5‐diphenyltetrazolium bromide (MTT) test on two human pancreatic cancer cells PANC‐1, BxPC‐3 and normal pancreatic cell HPDE6‐C7, which showed the significant inhibitory effected on the growth of human pancreatic cancer cells of PANC‐1 and BxPC‐3, especially 91.6% efficacy on BxPC‐3, and 73.1% on PANC‐1. Simulation studies like molecular docking supported strong binding of vascular endothelial growth factor receptor 2 (VEGFR‐2) protein tyrosine kinase (PDB ID: 4AGD), a target of pancreatic cancer. A novel imidazol‐modified catalpol compound 3i with strong inhibitory effect on pancreatic cancer cells, which could potentially develop into anti‐pancreatic cancer drug candidates in the future.
Phosphate Adsorption on Cerium/Terephthalic Acid Metal–Organic Frameworks (Ce‐MOF) Driven by Effective Electrostatic Attraction and Ligand Exchange in a Wide pH Range
Authors: Zhou Zhenyu , Li Dexuan , Huang Weiming , Wang Rongyue , Zhong Jiapeng , Zhang Yangyang , Meng Jiazhou , Li Chuanhao
Published: May 2023

Eutrophication has posed a threat to aquatic ecosystems, so it's urgent to remove excessive phosphate from water. In this study, we developed an adsorbent material, cerium/terephthalic‐acid metal‐organic‐frameworks (Ce‐MOF), to remove phosphate from different water systems. The optimal Ce‐MOF presented a maximum phosphate adsorption capacity of 377.2 mg/g, approximately 3.7 times higher than that of the commercial phosphate adsorbent (Phoslock: 101.6 mg/g). Experimental and computational analysis suggested that pH dominated the adsorption process. The main forces driving the adsorption process changed from the synergistic effect of electrostatic attraction and ligand exchange at lower pH to only ligand exchange at the increased pH values. Hence, the Ce‐MOF is applicable for phosphate adsorption in a wide pH range. Impressively, the adsorbent remained an excellent phosphate adsorption performance in the real water containing various interfering ions and organic matters, indicating the potential of Ce‐MOF for the practical use to solve the water eutrophication issue.
Evaluation of the reboot coaching workshops among urology trainees: A mixed method approach
Authors: Al‐Ghunaim Tmam , Johnson Judith , Biyani Chandra Shekhar , Coleman Rebecca , Simms‐Ellis Ruth , O'Connor Daryl B.
Published: May 2023

Background

Urology trainees experience high burnout, and there is an urgent need for acceptable and effective interventions. The current study evaluated Reboot coaching workshops (Reboot‐C), a tailored intervention based on cognitive–behavioural principles, with urology trainees.

Objective

Our primary objective was to evaluate the acceptability of Reboot‐C among urology trainees. In addition, this study aimed to investigate whether there were changes in confidence, resilience, depression and burnout levels.

Materials and method

A single‐arm design was used, including pre‐ and post‐online questionnaires and semi‐structured interviews.

Result

Twenty‐one urology trainees replied to the survey, attended both Reboot‐C workshops and responded to the post‐intervention questionnaire. Thirteen of 21 (61%) urology trainees participated in the interview. Participating in Reboot‐C was associated with significant improvements in resilience and confidence and a significant reduction in burnout. However, there was no significant reduction in depression. Qualitative data indicated that Reboot was acceptable and helped participants develop useful skills.

Conclusion

These findings pave the way for more conclusive studies on the efficacy of Reboot‐C for surgeons.
Implementing a differential reinforcement of low rates schedule to alter vocal stereotypy and task engagement in two adolescents with autism spectrum disorder
Authors: Mantzoros Theoni , Lee David L. , Ajemigbitse Ashley R. , Stover Laura J.
Published: May 2023

Vocal stereotypy (VS) is often observed in individuals with autism spectrum disorder (ASD) which at high rates can interfere with socialization or functioning in structured settings. There are multiple effective interventions available; yet, many procedures target the complete omission of the behavior or are only assessed at short intervals, making it unclear how they will generalize in applied settings. One intervention yet to be assessed as an individual intervention for automatically reinforced VS is differential reinforcement of low rates of behavior (DRL). In the present study, a functional analysis determined that the VS of two female adolescents with ASD was maintained by automatic reinforcement. A DRL procedure was implemented which incorporated: (a) a specified interval for reinforcement; (b) the behavioral expectations; (c) the permissible instances of VS within the interval; (d) learner feedback; and (e) the reset/non‐reset aspect of the schedule. As the targeted behavior decreased across sessions, the DRL interval was systematically increased in order to thin out the schedule of reinforcement. The intervention reduced VS and increased untargeted task engagement for both participants. Applied and theoretical implications of the study as well as social validity, limitations, and future research are discussed.