bluuebunny/crossref_metadata_2025 huggingface dataset:
Electrolyte Additive Therapy Realizes Simultaneous Ni and Mn Redox for Spinel LiNi0.5Mn1.5O4 Cathode at 2.3–4.95 V
Authors: Hai Feng , Gao Xin , Chen Wenting , Xue Weicheng , Li Mingtao , Hua Weibo , Tang Wei
Published: September 2024

The development of cobalt‐free, high‐energy‐density cathode materials is an important prerequisite for the commercialization of the next generation of high‐energy‐density, cost‐effective lithium batteries. Co‐free spinel LiNi0.5Mn1.5O4 (LNMO) with simultaneous Ni and Mn multi‐cation redox reactions possesses a high theoretical specific capacity of 230 mAh g−1 and a theoretical energy density of 865 Wh kg−1. Unfortunately, LNMO cycled at 2.3–4.95 V suffered from severe interfacial dynamic evolution and electrolyte decomposition, leading to uncontrollable transition metal dissolution and a rapid decrease of reversible specific capacity. Here, It is demonstrated that the addition of an appropriate amount of lithium difluorophosphate (LiDFP) to a common carbonate‐based electrolyte can achieve stable cycling of LNMO in the voltage range of 2.3–4.95 V. The LNMO‐Li cell retained 82.8% of its initial capacity (175.2 mAh g−1) after 300 cycles. The improved cycle performance is attributed to the robust interface formed by the decomposition of LiDFP, which inhibits the dissolution of transition metals and the continued decomposition of the electrolyte. This work provides important insights for the development of the next generation of high‐energy‐density cobalt‐free lithium batteries.
Transparent MXene Microelectrode Arrays for Multimodal Mapping of Neural Dynamics
Authors: Shankar Sneha , Chen Yuzhang , Averbeck Spencer , Hendricks Quincy , Murphy Brendan , Ferleger Benjamin , Driscoll Nicolette , Shekhirev Mikhail , Takano Hajime , Richardson Andrew , Gogotsi Yury , Vitale Flavia
Published: September 2024

Transparent microelectrode arrays have proven useful in neural sensing, offering a clear interface for monitoring brain activity without compromising high spatial and temporal resolution. The current landscape of transparent electrode technology faces challenges in developing durable, highly transparent electrodes while maintaining low interface impedance and prioritizing scalable processing and fabrication methods. To address these limitations, we introduce artifact‐resistant transparent MXene microelectrode arrays optimized for high spatiotemporal resolution recording of neural activity. With 60% transmittance at 550 nm, these arrays enable simultaneous imaging and electrophysiology for multimodal neural mapping. Electrochemical characterization shows low impedance of 563 ± 99 kΩ at 1 kHz and a charge storage capacity of 58 mC cm⁻² without chemical doping. In vivo experiments in rodent models demonstrate the transparent arrays' functionality and performance. In a rodent model of chemically‐induced epileptiform activity, we tracked ictal wavefronts via calcium imaging while simultaneously recording seizure onset. In the rat barrel cortex, we recorded multi‐unit activity across cortical depths, showing the feasibility of recording high‐frequency electrophysiological activity. The transparency and optical absorption properties of Ti₃C₂Tx MXene microelectrodes enable high‐quality recordings and simultaneous light‐based stimulation and imaging without contamination from light‐induced artifacts.
Valence‐Transforming O2‐Depleting Nano‐Assembly Enable In Situ Tumor Depositional Embolization
Authors: Kong Weiheng , Meng Qingyao , Kong Rong‐Mei , Zhao Yan , Qu Fengli
Published: September 2024

Abnormal metabolism and blood supply/O2 imbalance in tumor cells affect drug transport delivery and increase the difficulty of tumor treatment. Controlling tumor growth by inhibiting tumor cell metabolism and regulating progressive embolization in the tumor region provides an innovative basis for constructing tumor therapeutic models. A highly biocompatible and efficient O2‐depleting agent has been investigated to enable in situ precipitation and embolization within the tumor microenvironment. In situ deformation embolizer, Fe‐GA@CaCO3 nano‐assembly (GA: gallic acid), can convert into the large granular size embolization components of Fe(III) precipitates and affluent Ca2+ within the tumor microenvironment. In situ progressive O2 depletion produces Fe(III) precipitates that embolize tumor regions, isolating O2 and nutrients by blocking supply. Meanwhile, affluent Ca2+ acts on the intracellular, causing mitochondrial dysfunction through calcium overload and contributing to irreversible tumor cell damage. Both internal and external routes work synergistically to produce precise functional inhibition of tumors from the inside out, simultaneously responding to both intracellular and the corresponding tumor regions, providing an innovative solution for anti‐tumor therapy.
Solution‐Processed Micro‐Nanostructured Electron Transport Layer via Bubble‐Assisted Assembly for Efficient Perovskite Photovoltaics
Authors: Yang Yongrui , Min Fanyi , Wang Yiyang , Guo Lutong , Long Haoran , Qu Zhiyuan , Zhang Kun , Wang Yang , Yang Juehan , Chen Yu , Meng Lei , Qiao Yali , Song Yanlin
Published: September 2024

Organic–inorganic halide perovskite solar cells (PSCs) have attracted significant attention in photovoltaic research, owing to their superior optoelectronic properties and cost‐effective manufacturing techniques. However, the unbalanced charge carrier diffusion length in perovskite materials leads to the recombination of photogenerated electrons and holes. The inefficient charge carrier collecting process severely affects the power conversion efficiency (PCE) of the PSCs. Herein, a solution‐processed SnO2 array electron transport layer with precisely tunable micro‐nanostructures is fabricated via a bubble‐template‐assisted approach, serving as both electron transport layers and scaffolds for the perovskite layer. Due to the optimized electron transporting pathway and enlarged perovskite grain size, the PSCs achieve a PCE of 25.35% (25.07% certificated PCE).
Bifunctionally Electrocatalytic Bromine Redox Reaction by Single‐Atom Catalysts for High‐Performance Zinc Batteries
Authors: Chen Shengmei , Peng Chao , Zhu Daming , Zhi Chunyi
Published: September 2024

Aqueous zinc‐bromine (Zn||Br2) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br3−) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN5) in a mesoporous carbon framework (FeSAC‐CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN5 species for enhanced confinement and electrocatalytic effect. The active FeN5 species can fix the bromine (Br0) species to suppress the formation of Br3− effectively and bifunctionally catalyze the bromide (Br−)/Br° conversion. These free up 1/3 Br− locked by Br3− complexing agent for enhanced bromine utilization efficiency and conversion reversibility. Accordingly, the Zn||Br2 battery with FeSAC‐CMK delivers an impressive specific capacity of 344 mAh g−1 at 0.2 A g−1 and superior rate capability with 164 mAh g−1 achieved even at 20 A g−1, much higher than that of inactive CMK (262 mAh g−1 at 0.2 A g−1; 6 mAh g−1 at only 8 A g−1). Furthermore, the battery demonstrates excellent cycling performance of 88% capacity retention after 2000 cycles.
Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides
Authors: Lee Juhyeok , Hassan Syed Zahid , Sim Hye Ryun , Lee Sangjun , Jeong Kyeong‐jun , Kwon Jieun , Son Chang Yun , Chung Dae Sung
Published: September 2024

Here a ligand exchange strategy for synthesizing sol–gel oxides is demonstrated to achieve multifunctionality including direct photolithography, high dielectric strength, and high charge carrier mobility, which is challenging to obtain in such oxides. For this purpose, a series of bidentate ligands with azide termini and ethylene‐glycol bridges is synthesized, and these ligands are universally applicable to the synthesis of a variety of dielectric and semiconductor oxides. Optimized photolithography conditions yield a high‐quality ZrO2 dielectric film with a high dielectric constant and strength of ≈18 and ≈7 MV cm−1, respectively. Additionally, this strategy is applied to semiconductor oxides such as In2O3 and ZnO, and the all‐oxide‐patterned solution‐processed thin‐film transistor (TFT) demonstrates a high charge carrier mobility of ≈40 cm2 V−1 s−1. An oxide TFT array is fully photopatterned on a 4‐inch Si wafer; uniform performances are observed across these devices. This study suggests the possibility of realizing multifunctional oxides for application in advanced electronics using simple ligand exchange chemistry.
Customization of 2D Atomic‐Molecular Heterojunction with Manipulatable Charge‐Transfer and Band Structure
Authors: Chen Weilin , Chen An , Liu Xue , Shu Fan , Zeng Jianmin , Zhang Jinying , Xu Hongbo , Peng Gaoliang , Yang Zhi , Li Jinjin , Liu Gang
Published: September 2024

Manipulating the properties of 2D materials through meticulously engineered artificial heterojunctions holds great promise for novel device applications. However, existing research on the crucial charge‐transfer interactions and energy profile regulation is predominantly focused on 2D van der Waals structures formed via weak van der Waals forces, limiting regulatory efficiency at high costs. Herein, a refined atomic‐molecular heterojunction strategy featuring strong covalent bonds between organic molecule and 2D violet phosphorus (VP) atomic crystal is developed, which enables enhanced charge‐transfer dynamics and customizable band structure regulation at the molecular level. Both experimentally and theoretically, it is demonstrated that grafting efficiency, charge redistribution, and energy gap regulation critically depend on organic electronegativity, providing a low‐cost yet high‐efficiency regulatory effect on a large scale. As a proof of concept, the novel VP‐molecular heterojunctions exhibit optimized performance in diverse application domains, presenting a general platform for future high‐performance device applications.
Innovative In Situ Passivation Strategy for High‐Efficiency Sb2(S,Se)3 Solar Cells
Authors: Zhao Yuqi , Xu Wentao , Wen Jing , Wang Xiaomin , Chen Xueling , Che Bo , Wang Haolin , Gong Junbo , Chen Tao , Xiao Xudong , Li Jianmin
Published: September 2024

An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb2(S,Se)3) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb2(S,Se)3 solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb2(S,Se)3 solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep‐level cation antisite SbSe defect within the Sb2(S,Se)3 films and significantly suppressing non‐radiative recombination in the devices. Space‐charge‐limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb2(S,Se)3 films, and fine‐tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep‐level defects in Sb2(S,Se)3 solar cells.
De‐Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes
Authors: Cao Jin , Wang Xu , Qian Shangshu , Zhang Dongdong , Luo Ding , Zhang Lulu , Qin Jiaqian , Zhang Xinyu , Yang Xuelin , Lu Jun
Published: September 2024

Despite the widespread adoption of Zn anodes for aqueous energy storage, the presence of an inherent passivation layer and the polycrystalline interface of commercial Zn foil consistently lead to non‐uniform electrodeposition, undermining stability and practicality. Herein, the study introduces a chemically polished Zn metal anode (CP‐Zn) fabricated via a simple immersion method. This “chemically polishing” process can effectively remove the interfacial passivation layer (de‐passivation), providing ample active sites for plating/stripping and ensuring the uniformly distributed electric field and Zn2+ ion flux. Additionally, selective etching during chemical polishing exposes more (002) crystal planes, promoting homogeneous and smooth zinc deposition while suppressing related side reactions. Demonstrated by CP‐Zn anode, the symmetric cell exhibits stable cycling over 4600 h at 1 mA cm−2 and 240 h at 50% depth of discharge (DOD), with a CP‐Zn||VO2 full cell maintaining ≈75.3% capacity retention over 1000 cycles at 3 A g−1. This chemically polishing strategy presents a promising avenue for advancing the commercialization of aqueous zinc‐ion batteries.
Preparation and Properties of Antifreeze Rewarming Hydrogel Dressings
Authors: Yan Meng , Dong Xiaorong , Sun Jingjing , Liu Yijun , Yang Shengchao , Tian Xing , Zheng Shuang , Yin Lisha , Fu Yanan , Li Dongmei , Cui Lin , Li Gang , Qiu Zhongpeng , Liu Zhiyong
Published: September 2024

The Hydrogel wound dressing with good rewarming property, anti‐freezing property, and adhesion property has important practical significance in medical care for the first and second grade frostbite. The ears, hands, mouth, and nose of field workers on duty and training high cold region are prone to frostbite due to long‐term exposure to in severe cold. Therefore, rapid rewarming of wound surface is the key to the treatment of frostbite. In this paper, antifreeze and rewarming are achieved by photothermal conversion materials and quaternary ammonium salts. Herein, the PAM/CS/MXene30/Betaine5/AgNPs200(PCM30B5A200) hydrogel based on chitosan (CS) and acrylamide (AM) is designed and fabricated by thermally initiated free radical polymerization. The dressing has excellent rewarming properties, anti‐freezing properties, tensile properties, repeatable self‐adhesion and antibacterial properties. In this system, hydrogels are mainly cross‐linked by hydrogen bonds between CS and AM. Betaine is added to the material to make the hydrogel have good freeze‐resistance and flexibility at −24 °C, and can be combined with AgNPs and MXene, to achieve a triple antibacterial. The PCM30B5A200 hydrogel reached the rewarming temperature of 40.5 °C at 9 min. PCM30B5A200 multifunctional hydrogels have good application value in the first and second grade frostbite wounds.
Piezo‐Photocatalytically Induced Dual‐Channel Pathway of CdxZn1‐xS Solid‐Solution Nanorods for Hydrogen Peroxide Evolution
Authors: Lin Sen , Sun Shiyong , Zhang Xueyan , Tang Haoming , Liu Jun , Li Xiang
Published: September 2024

As a class of clean oxidants, the hydrogen peroxide (H2O2) has shown great application potential in a variety of fields due to its high energy density and convenient storage condition, while the synthesis of H2O2 by the utilization of green energy technology has currently become one of the attentions in energy field. In this paper, the CdxZn1‐xS (x = 0, 0.2, 0.4, 0.6, 0.8, 1) solid solutions with different zinc‐cadmium molar ratios are prepared by a simple solvothermal route, and the H2O2 evolution performances of materials under illumination and ultrasound conditions are explored. The results show that Cd0.4Zn0.6S has the highest H2O2 yield rate of 2866 µmol/g/h under the synergistic effect of ultrasound and illumination without any sacrificial agent, which is higher than those in ultrasonic or light condition alone, showing piezo‐photocatalytic coupling characteristic. The characterizations including piezoresponse force microscopy (PFM), finite element simulation, in situ electron spin resonance (ESR) reveal that the excellent H2O2 production property of the material should be mainly ascribed to its nanorod structure and e−‐h+ dual‐channel reactivity formed by the bending of its energy band under the piezoelectric effect. This work provides reference and enlightenment for the preparation of H2O2 through the green energy avenue.
Visible Light Photocatalyzed Norrish Type II Reaction of Acrylamides for the Synthesis of β‐Lactams
Authors: Li Hao‐Yuan , Zhang Shen‐Zhen , Niu Xiaoying , Meng Qing‐Yuan , Yang Xiu‐Long
Published: September 2024

Here, we present a strategy for the visible‐light‐catalyzed synthesis of β‐lactams based on the Norrish type II reaction. This protocol uses acetonitrile as solvent and commercially available photocatalyst to drive the reaction. Notably, various challenging substrate types reported in previous studies undergo conversion. DFT calculations further elucidate the reaction mechanism, while discussing the competitiveness between [2+2] cycloaddition and the Norrish II reaction.
A Random Forest Model for Predicting and Analyzing the Performance of CNT TFET with Highly Doped Pockets
Authors: Salah Ahmed , Yevick David
Published: September 2024

This paper presents a Random Forest (RF) machine learning model that relates the DC characteristics and high‐frequency response of a carbon nanotube (CNT) tunnel field‐effect transistor (TFET) with highly doped pockets to the transistor parameters. The analysis of multiple factors for a complex structure as the one studied here becomes expensive with the ordinary simulation techniques and hence machine learning (ML) offers a proficient method to model and enhance the understanding of the key factors that influence the CNT TFET with pockets in considerably reduced time. Numerical simulations are used to generate the data on which the model is trained. This dataset comprises ten input features and four output attributes. The tuned model is capable of predicting the output characteristics of the device with minimal mean squared error (MSE). The RF model is also compared to other ML algorithms to demonstrate its advantage.
Boosting Electrochemical Performance via Extra‐Role of La‐Doped CeO2‐δ Interlayer for “Oxygen Provider” at High‐Current SOFC Operation
Authors: Nguyen Xuan Dong , Lee Sang Won , Kim Su Ji , Park Jungdeok , Koo Bonseok , Lee Seok Hee , Lee Shiwoo , Lim Hyung Tae , Irvine John T.S. , Shin Tae Ho
Published: September 2024

Utilizing rare earth doped ceria in solid oxide cells (SOCs) engineering is indeed a strategy aimed at enhancing the electrochemical devices' durability and activity. Particularly, Gd‐doped ceria (GDC) is actively used for barrier layer and catalytic additives in solid oxide fuel cells (SOFCs). In this study, experiments are conducted with La‐doped CeO2 (LDC), in which the Ce sites are predominantly occupied by La, to prevent the formation of the Ce‐Zr solid solution. This LDC is comparably used as a functional interlayer between the electrolyte and cathode if sintered at lower temperatures to avoid La2Zr2O7 impurity. In addition, the high substitution of La3+ into the ceria lattice improves the oxygen non‐stoichiometry of LDC, leading to accelerated electrochemical high performance by the additional role of LDC for oxygen supplier capacitance at high current operation. Thus, it is confirmed that the improved SOFC high performance is achieved at the maximum power density (MPD) of ≈2.15 W cm−2 at 800 °C when the optimized LDC buffer layer is hired at the anode‐supported typed‐Samsung's SOFC by lowering the sintering temperature to prevent LDC's impurity reaction.
Economic evaluation of corn relative maturity hybrids in corn–pennycress–soybean rotations
Authors: Mohammed Yesuf Assen , Gesch Russ W. , Wells Samantha , Heller Nicholas J. , Lindsey Alexander J. , Hard Alexander W. , Phippen Winthrop B.
Published: September 2024

This manuscript is a follow‐up of previously published results that presented findings on pennycress (Thlaspi arvense L.) establishment and agronomics in response to previous corn (Zea mays L.) relative maturity (CRM) hybrids grown for grain and silage in the corn–pennycress–soybean [Glycine max (L.)] rotations. In this manuscript, we compared the economics of grain corn–pennycress–soybean rotations (grain rotation) with silage corn–pennycress–soybean rotations (silage rotation). The treatments were CRM hybrids ranging from 76 to 95 days (full season) at northern sites (Morris and Rosemount, MN) and 95 to 113 days (full season) at southern sites (Lexington, IL, and Custar, OH). Full‐season corn harvested for silage was included as a control treatment representing optimum conditions for sowing pennycress. A partial budget procedure was used for economic analysis. The results showed that the annualized net benefits (ANBs) ranged from $315 to $945 ha−1. The silage rotation produced greater ANBs than the grain rotation at all sites due to increased pennycress seed yield. In the grain rotation, the 105 days in the south, 95 days corn at Morris, and 86 days corn at Rosemount resulted in minimal ANB losses compared with silage rotation. Among grain corn treatments, some of the early CRM hybrids resulted in greater ANBs (up to 40%) than the full season hybrid. Results demonstrate potential to integrate pennycress into a grain rotation using early CRM hybrids. In addition, valuing the diverse ecosystem benefits that pennycress offers as a cash cover crop during the offseason between corn and soybean rotation may help to attract growers.
PHF6 mutations in chronic myelomonocytic leukemia identify a unique subset of patients with distinct phenotype and superior prognosis
Authors: Tefferi Ayalew , Fathima Saubia , Alsugair Ali Khalid A. , Aperna Fnu , Natu Anuya , Abdelmagid Maymona G. , Csizmar Clifford M. , Gurney Mark , Lasho Terra L. , Finke Christy M. , Mangaonkar Abhishek A. , Al‐Kali Aref , Pardanani Animesh , Reichard Kaaren K. , He Rong , Gangat Naseema , Patnaik Mrinal M.
Published: September 2024

The current study was inspired by observations from exploratory analyses of an institutional cohort with chronic myelomonocytic leukemia (CMML; N = 398) that revealed no instances of blast transformation in the seven patients with plant homeodomain finger protein 6 (PHF6) mutation (PHF6MUT). A subsequent Mayo Clinic enterprise‐wide database search identified 28 more cases with PHF6MUT. Compared with their wild‐type PHF6 counterparts (PHF6WT; N = 391), PHF6MUT cases (N = 35) were more likely to co‐express TET2 (89% vs. 45%; p < .01), RUNX1 (29% vs. 14%; p = .03), CBL (14% vs. 2%; p < .01), and U2AF1 (17% vs. 6%; p = .04) and less likely SRSF2 (23% vs. 45%; p < .01) mutation. They were also more likely to display loss of Y chromosome (LoY; 21% vs. 2%; p < .01) and platelets <100 × 109/L (83% vs. 51%; p < .01). Multivariable analysis identified PHF6MUT (HR 0.28, 95% CI 0.15–0.50) and DNMT3AMUT (HR 5.8, 95% CI 3.3–10.5) as the strongest molecular predictors of overall survival. The same was true for blast transformation‐free survival with corresponding HR (95% CI) of 0.08 (0.01–0.6) and 9.5 (3.8–23.5). At median 20 months follow‐up, blast transformation was documented in none of the 33 patients with PHF6MUT/DNMT3AWT but in 6 (32%) of 19 with DNMT3AMUT and 74 (20%) of 374 with PHF6WT/DNMT3AWT (p < .01). The specific molecular signatures sustained their significant predictive performance in the context of the CMML‐specific molecular prognostic model (CPSS‐mol). PHF6MUT identifies a unique subset of patients with CMML characterized by thrombocytopenia, higher prevalence of LoY, and superior prognosis.
An Association Between Left‐Hand Digit Ratio (2D:4D) and Anthropometric Indexes in Chinese Children and Adolescents Aged 8–15 Years in Bengbu City
Authors: Zhang Ya , Cao Ruiyao , Li Wenxiu , Fu Han , Zhu Jiamin , Xu Xuemo , Wang Rui , Peng Ziyu , Fu Lianguo
Published: September 2024

Objectives

The digit ratio (2D:4D) is a possible marker of prenatal hormone exposure. The purpose of this study was to explore the relationships between digit ratio (2D:4D) and anthropometric indexes in Chinese children and adolescents.

Methods

This study is a cross‐sectional study. A school‐based survey among 685 children and adolescents aged 8–15 years were conducted by stratified cluster sampling. The length of index finger (2D) and ring finger (4D) of the left hand, height, sitting height (ST), weight, chest circumference (CC), waist circumference (WC), hip circumference (HC), and abdominal skinfold thickness (AST) were measured. Pearson correlation and multivariate linear regression were used to analyze associations between 2D:4D and above indexes.

Results

In girls, 2D:4D was positively related to WC, AST, waist‐to‐height (WHtR), waist‐to‐hip ratio (WHR) after adjusting for ages (p < 0.05). The WC, AST, WHtR, and WHR among girls with 2D:4D ≥ 1 were significantly higher than those among girls with 2D:4D < 1, respectively (p < 0.05). However, there was no correlations between digit ratio (2D:4D) and above anthropometric indexes in boys (p > 0.05).

Conclusions

The 2D:4D was related to anthropometric indexes in girls, which suggests that the maternal prenatal hormone exposure might be related to the anthropometric indexes of their female offspring.
Heterogeneous Carbonylation of Alcohols on Charge‐Density‐Distinct Mo−Ni Dual Sites Localized at Edge Sulfur Vacancies
Authors: Yuan Qiao , Gu Yating , Chen Weimiao , Zhang Yue , Song Xiangen , Ding Yangming , Li Xingju , Zhu Lei , Jiang Zheng , Yan Li , Ma Jing , Ding Yunjie
Published: September 2024

Alcohols carbonylation is of great importance in industry but remains a challenge to abandon the usage of the halide additives and noble metals. Here we report the realization of direct alcohols heterogeneous carbonylation to carbonyl‐containing chemicals, especially in methanol carbonylation, with a remarkable space‐time‐yield (STY) of 4.74 molacetyl/kgcat./h and a durable stability as long as 100 h on Ni@MoS2 catalyst. Mechanistic analysis reveals that the Mo−Ni dual sites localized at edge sulfur vacancies of Ni@MoS2 exhibit distinct charge density, which strongly activate CH3OH to break its C−O bond and non‐dissociatively activate CO. Density functional theory calculations further suggest that the low charge density in Mo−Ni, the Ni site, could significantly lower the barrier for CO migration and nucleophilic attack of methoxy species, and finally leads to the rapid formation of acetyl products. Ni@MoS2 catalyst could also effectively realize the carbonylation of ethanol, n‐propanol and n‐butanol to their acyl products, which may demonstrate its universal application for alcohols carbonylation.
In Situ Generation of 1‐Acetylpyrene as a Visible‐Light Photocatalyst for the Thia‐Paternò‐Büchi Reaction
Authors: Cormier Gabriel , Allain Clémence , Boddaert Thomas
Published: September 2024

The thia‐Paternò‐Büchi reaction represents a straightforward approach to build thietane cores. Unfortunately, the significant instability of thiocarbonyls, particularly thioketones and thioaldehydes, has hitherto rendered this photochemical [2+2]‐cycloaddition underexploited. To address this limitation, we report herein a visible‐light photochemical domino reaction including: the in situ generation of thiocarbonyls though a Norrish type II fragmentation of pyrenacyl sulfides, and the aforementioned thia‐Paternò‐Büchi reaction with various non‐volatile electron‐rich alkenes. The highly efficient synthesis of a wide range of unprecedented thietanes from intrinsically highly unstable thiocarbonyls, such as thioaldehydes and aliphatic thioketones, was made possible by the multitasking capability of pyrenacyl sulfides as a source of thiocarbonyl substrates and as precursors of 1‐acetylpyrene, which acts as the photocatalyst for the thia‐Paternò‐Büchi reaction. The photosensitizer properties of the latter have been experimentally established and a triplet‐triplet Dexter energy transfer based mechanism is proposed.
Unlocking Self‐antioxidant Capability and Processability of Additive‐free MXene Ink towards High‐performance Customizable Supercapacitors
Authors: Zheng Yuanchuan , Wang Yalei , Liu Dongqi , Zhao Jiupeng , Li Yao
Published: September 2024

The solution processing of MXene ink is the feasible strategy to realize its state‐of‐the‐art applications. Nevertheless, achieving high stability and processability of additive‐free MXene ink is particularly challenging. Herein, we propose an oxyanion‐terminated Ti3C2Tx MXene ink that exhibits excellent self‐antioxidant capability and processability. The vertex‐connected polyhedrons of oxyanions capping on the Ti3C2 host serve as an in situ antioxidative shield, effectively preventing the attack of free H2O molecules while increasing the robustness of the Ti−C bond and reducing the susceptibility of surface Ti atoms to oxidation. Consequently, the shelf life of MXene ink can be extended up to 5 months at room temperature. Moreover, the high electron accumulation of oxyanions enhances the interlayer interactions among MXene sheets through electrostatic binding, which enables the formation of stable and uniform MXene inks with controlled rheological properties and processability. Inspired by Chinese calligraphy, we utilize the oxyanion‐terminated MXene ink to fabricate high‐performance and customizable paper supercapacitors, which exhibit exceptional flexibility and stability, allowing them to be tailored to desired capacity, stretchability, and shapes. This in situ surface chemistry strategy of oxyanions can activate the self‐antioxidant capability and solution processability of MXene, paving the way for its widespread applications in flexible and wearable electronics.
Mn−Ce Symbiosis: Nanozymes with Multiple Active Sites Facilitate Scavenging of Reactive Oxygen Species (ROS) Based on Electron Transfer and Confinement Anchoring
Authors: Zhang Juan , Wang Zhihua , Lin Xingen , Gao Xiaoping , Wang Qiuping , Huang Rui , Ruan Yaner , Xu Haonan , Tian Lin , Ling Chen , Shi Ran , Xu Suowen , Chen Kong , Wu Yuen
Published: September 2024

Regulating appropriate valence states of metal active centers, such as Ce3+/Ce4+ and Mn3+/Mn2+, as well as surface vacancy defects, is crucial for enhancing the catalytic activity of cerium‐based and manganese‐based nanozymes. Drawing inspiration from the efficient substance exchange in rhizobia‐colonized root cells of legumes, we developed a symbiosis nanozyme system with rhizobia‐like CeOx nanoclusters robustly anchored onto root‐like Mn3O4 nanosupports (CeOx/Mn3O4). The process of “substance exchange” between Ce and Mn atoms—reminiscent of electron transfer—not only fine‐tunes the metal active sites to achieve optimal Ce3+/Ce4+ and Mn3+/Mn2+ ratios but also enhances the vacancy ratio through interface defect engineering. Additionally, the confinement anchoring of CeOx on Mn3O4 ensures efficient electron transfer in catalytic reactions. The final CeOx/Mn3O4 nanozyme demonstrates potent catalase‐like (CAT‐like) and superoxide dismutase‐like (SOD‐like) activities, excelling in both chemical settings and cellular environments with high reactive oxygen species (ROS) levels. This research not only unveils a novel material adept at effectively eliminating ROS but also presents an innovative approach for amplifying the efficacy of nanozymes.
Can Deep Learning Search for Exceptional Chiroptical Properties? The Halogenated [6]Helicene Case
Authors: Uceda Rafael G. , Gijón Alfonso , Míguez‐Lago Sandra , Cruz Carlos M. , Blanco Víctor , Fernández‐Álvarez Fátima , Álvarez de Cienfuegos Luis , Molina‐Solana Miguel , Gómez‐Romero Juan , Miguel Delia , Mota Antonio J. , Cuerva Juan M.
Published: September 2024

The relationship between chemical structure and chiroptical properties is not always clearly understood. Nowadays, efforts to develop new systems with enhanced optical properties follow the trial‐error method. A large number of data would allow us to obtain more robust conclusions and guide research toward molecules with practical applications. In this sense, in this work we predict the chiroptical properties of millions of halogenated [6]helicenes in terms of the rotatory strength (R). We have used DFT calculations to randomly create derivatives including from 1 to 16 halogen atoms, that were then used as a data set to train different deep neural network models. These models allow us to i) predict the Rmax for any halogenated [6]helicene with a very low computational cost, and ii) to understand the physical reasons that favour some substitutions over others. Finally, we synthesized derivatives with higher predicted Rmax obtaining excellent correlation among the values obtained experimentally and the predicted ones.
Hydrogen Sulfide‐Triggered Artificial DNAzyme Switches for Precise Manipulation of Cellular Functions
Authors: Xie Xuan , Nan Hexin , Peng Jialong , Zeng Kaiqiang , Wang Hong‐Hui , Huang Yan , Nie Zhou
Published: September 2024

The development of synthetic molecular tools responsive to biological cues is crucial for advancing targeted cellular regulation. A significant challenge is the regulation of cellular processes in response to gaseous signaling molecules such as hydrogen sulfide (H2S). To address this, we present the design of Gas signaling molecule‐Responsive Artificial DNAzyme‐based Switches (GRAS) to manipulate cellular functions via H2S‐sensitive synthetic DNAzymes. By incorporating stimuli‐responsive moieties to the phosphorothioate backbone, DNAzymes are strategically designed with H2S‐responsive azide groups at cofactor binding locations within the catalytic core region. These modifications enable their activation through H2S‐reducing decaging, thereby initiating substrate cleavage activity. Our approach allows for the flexible customization of various DNAzymes to regulate distinct cellular processes in diverse scenarios. Intracellularly, the enzymatic activity of GRAS promotes H2S‐induced cleavage of specific mRNA sequences, enabling targeted gene silencing and inducing apoptosis in cancer cells. Moreover, integrating GRAS with dynamic DNA assembly allows for grafting these functional switches onto cell surface receptors, facilitating H2S‐triggered receptor dimerization. This extracellular activation transmits signals intracellularly to regulate cellular behaviors such as migration and proliferation. Collectively, synthetic switches are capable of rewiring cellular functions in response to gaseous cues, offering a promising avenue for advanced targeted cellular engineering.
A Smart Design of Non‐Noble Catalysts for Sustainable Propane Dehydrogenation
Authors: Smith Louise R. , Sun Zhao , Hutchings Graham J.
Published: September 2024

Propane dehydrogenation (PDH), an important process for propylene synthesis, relies on expensive noble metals or highly toxic oxides as catalysts. In a recent publication, Gong and co‐workers report a breakthrough discovery for PDH by introducing a sustainable catalyst composed of titanium oxide overlayers encapsulating nickel nanoparticles, termed Ni@TiOx. This innovative catalyst showcases exceptional performance in PDH, exhibiting high propylene selectivity and stability under industrially relevant conditions. The study elucidates the role of defective TiOx overlayers and the electronic promotional effect of subsurface Ni in enhancing catalytic activity, translating a traditional model catalyst system into a sustainable industrial catalyst for low‐carbon energy and the chemical industry.
Unlocking Oxetane Potential: Modular Synthetic Platform for the Concise Synthesis of Acyclic Oligo‐Isoprenoids and Terpenoids
Authors: Albitz Krisztián , Tóth Sára , Csókás Dániel , Soós Tibor
Published: September 2024

Terpenes occupy a unique place among the secondary metabolites due to their broad utility and extraordinary structural diversity. Their synthesis via polyene cyclization, either biomimetic or enzymatic, represents the cutting edge of modern synthetic chemistry. However, these endeavors have been inherently tied to the availability of natural and non‐natural acyclic polyene starting materials. Herein, we report an oxetane‐based platform for the modular construction of oxygenated polyolefins with precise geometric control. This “tail‐to head” iterative method leverages the site‐selective cross‐metathesis of terminal olefins to form an alkylidene oxetane moiety and the regioselective ring opening of alkenyl‐oxetanes for chain elongation. In addition, the unique and peculiar propensity of alkylidene oxetane fragment in various reactions was also revealed and exploited for site‐selective functionalization, cyclization, and as a protecting group in polyenes.
The Role of L‐Ligands in Silica‐Supported Ti Oxo/Imido Heterometathesis Catalysts
Authors: Bushkov Nikolai S. , Rumyantsev Andrey V. , Pichugov Andrey V. , Zhizhin Anton A. , Aleshin Dmitry Yu. , Gutsul Evgenii I. , Takazova Rina U. , Kitaeva Dinara Kh. , Dolgushin Fedor M. , Novikov Roman A. , Zhizhko Pavel A. , Zarubin Dmitry N.
Published: September 2024

We report here the preparation and characterization of new well‐defined silica‐supported Ti imido complexes that present an L‐ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=NtBu)(Me2Pyr)(py)2 (1s), where py is replaced with stronger electron‐donating 4‐(N,N‐dimethylamino)pyridine (2s) or bidentate 2,2′‐bipyridine (3s). The materials were characterized with elemental and mass balance analyses and IR and solid‐state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L‐ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development.
Design of a bio‐based flame‐retardant epoxy/amine cross‐linked coatings
Authors: Mansouri Siavash , Hazra Raj Shankar , Swarup Shanti , Quadir Mohiuddin
Published: September 2024

Epoxy cross‐linked coatings are widely used to protect and beautify many surfaces all around us. However, these coatings possess a dense carbonaceous structure, rendering them susceptible to ignition, spread, and propagation of flames. Therefore, flame‐retardant (FR) materials are added into these coatings as additives to improve flame resistance properties. Many of the commercially available FR additives are halogenated, metal oxide, and alkyl phosphate‐based compounds, often originating from nonrenewable resources. Some of these compounds produce undesirable toxic fumes and byproducts upon combustion. To overcome these challenges, we tested bio‐based phytic acid (PA) as an FR additive in epoxy resin, cross‐linked with bio‐based phenalkamine (NX)—a material derived from cashew oil nutshell. Our findings demonstrate that the incorporation of PA into an NX‐cross‐linked epoxy coating system significantly enhances the FR properties of the coatings while preserving their physico‐mechanical characteristics such as solvent resistance and hardness. Additionally, the inclusion of PA markedly enhances the FR performance of the coatings by reducing flame spread rate, minimizing dripping, and suppressing ignition temperature. Moreover, upon addition of 10% w/w PA increases the ignition time, decreases peak heat release rate (PHRR) by more than 25%, reduces total heat release (THR) by the similar amount, and suppresses total smoke production by >40% compared to the coatings containing FR‐ agents based on metal oxides and alkyl phosphates. Our work clearly demonstrates the feasibility of using PA as the FR additive for producing eco‐friendly and low‐flammable epoxy cross‐linked coatings.
The Impact of Parental Health Shocks on Child Schooling and Labour: Evidence From Thailand
Authors: Wongmonta Sasiwooth
Published: September 2024

This paper uses household panel data from the Thai Socio‐Economic Surveys of 2012 and 2017 to examine the effects of parental health shocks on child education and labour. Three measures of parental health are analysed: chronic illness, hospitalisation, and functional health status. The results show that the parentʼs illness decreases school enrolment and leads to fewer years of education completed. Boys are less likely to have attended school if any parent was chronically ill or had any health problems. Parentsʼ chronic illness increases the probability of entering the labour force for youths aged 15 and over; however, only maternal illness increases their time spent at work. Additionally, parental illness significantly increases household health expenditures, but there is a significant decline in education expenditures. The results suggest that targeted government support to low‐income families affected by major illnesses of parents could help them to maintain their children in school.
First Vesicular Self‐Assembly of an Apocarotenoid Bixin in Aqueous Liquids and Its Antibacterial Activity
Authors: Patra Soumen , Kar Sukhendu , Gopal Bag Braja
Published: September 2024

Bixin 1 is the major constituent of the reddish carotenoids present in the seed‐coat of Bixa orellana. The use of the extract of the seed‐coat of Bixa orellana in food, cosmetics and garments is well known. The nano‐sized long 24 C chain molecule has nine conjugated double bonds having extended conjugation with the ‘‐COOH’ and ‘‐COOMe’ groups present at the two ends of the molecule. Herein, we report the first self‐assembly of bixin in several aqueous liquids. The molecule undergoes spontaneous self‐assembly in several liquids yielding vesicular self‐assembly. Characterizations of the self‐assemblies of bixin were carried out by various microscopic techniques, X‐ray diffraction and FTIR studies. The critical vesicular concentrations (CVCs) of the compound carried out in DMSO‐water in three different solvent ratios as 2: 1 (v/v), 1: 1 (v/v) and 1: 4 (v/v) were determined to be 100 μM, 90 μM and 60 μM respectively indicating lower CVC values at higher proportion of water. Utilization of the vesicular self‐assemblies of bixin have been demonstrated in the entrapment and release of fluorophores including the anticancer drugs doxorubicin and curcumin. Self‐assembled bixin and curcumin loaded self‐assembled bixin showed significant antibacterial activity with both Gram positive as well as Gram negative bacteria.
Transformative Hydrochloric Acid Treatment of Red Mud for Sustainable Cathode Material Production in Aqueous Zinc Ion Batteries
Authors: Faheem Muhammad , Hussain Arshad , Ahmed Johan Bashir , Saeed Alzahrani Atif , Abdul Aziz Md.
Published: September 2024

The aluminum industry generates a significant amount of red mud as solid waste. This waste is high in mineral content, particularly metal oxides, and difficult to treat, manage, and recycle, resulting in malignant environmental effects. A simple, scalable, and precisely controlled hydrochloric acid treatment transforms the red mud into a useful product by selectively removing electrochemically inactive phases. This process produces a highly porous material with a significantly increased surface area, which effectively serves as the cathode material in an aqueous zinc ion battery (AZIB). RM‐HCl, which was treated with acid, had better electrochemical performance than plain red mud (RM). It had an initial specific discharge capacity of 105 mAh g−1 at 0.2 to 1.8 voltage and a current density of 100 mA g−1, which stayed at 63 % after 250 cycles. It also showed long‐term cyclic stability at high currents of 500 mAg−1 and 1000 mAg−1 for 1000 cycles. The properties of a cathode material made from RM have the potential to be a cost‐effective and environmentally friendly option. This study proposes a practical, sustainable, and expandable technique for recycling RM that promotes eco‐friendly and sustainable growth in the aluminum industry.
An Adaptive Combined Method for Lithium‐Ion Battery State of Charge Estimation Using Long Short‐Term Memory Network and Unscented Kalman Filter Considering Battery Aging
Authors: Lyu Longchen , Jiang Bo , Zhu Jiangong , Wei Xuezhe , Dai Haifeng
Published: September 2024

The accurate estimation of battery state of charge (SOC) enables the reliable and safe operation of lithium‐ion batteries. Data‐driven SOC estimation is considered an emerging and effective solution. However, existing data‐driven SOC estimation methods typically involve direct estimation and lack effective feedback correction. Moreover, battery degradation poses additional challenges to accurate SOC estimation. Therefore, this study proposes an adaptive combined method for battery SOC estimation based on a long short‐term memory (LSTM) network and unscented Kalman filter (UKF) algorithm considering battery aging status. First, an LSTM model is constructed to characterize the battery's dynamic performance instead of traditional battery models. Then, the UKF algorithm is employed to perform SOC estimation through the feedback of terminal voltage prediction. To enhance estimation accuracy under different aging statuses, a proportional‐integral‐derivative controller is employed to correct the capacity fading during the SOC estimation process. Validation results indicate that the terminal voltage prediction model demonstrates exceptional robustness against interference from current and voltage noise. Compared to the traditional estimation method combining the deep learning model and Kalman filter algorithm, the proposed method demonstrates superior estimation accuracy under various complex operating conditions. Furthermore, the proposed method outperforms the traditional method in estimation performance during battery aging.
The causal association between epilepsy and amyotrophic lateral sclerosis: A two‐sample Mendelian randomization study
Authors: Cui Yayong , Chen Junyu , Li Hong , Zheng Dong , Shi Xiaolei
Published: September 2024

Objectives

Epilepsy and amyotrophic lateral sclerosis (ALS) are common neurological disorders. The association between the two disorders has been raised in observational studies. However, it is uncertain to what extent they have mutual causal effects. In this study, we aimed to investigate their causal association using a two‐sample Mendelian randomization (MR) method.

Methods

We performed a two‐sample bidirectional MR analysis to evaluate the causal association of epilepsy with the risk of ALS. Publicly published genome‐wide association study statistics for epilepsy and ALS were used in the study. The primary analysis included genetic variants with a p value of less than 1 × 10–5 as instrumental variables. We applied several alternative methods, including inverse variance weighting, weighted median, simple mode, weighted mode, MR‐Egger regression and MR pleiotropy residual sum and outlier, and statistical graphs to assess the associations of epilepsy and its subtype with the risk of ALS. Reverse MR analyses were also performed to examine the association of ALS with the risk of epilepsy.

Results

The primary MR analysis found no causal effect of epilepsy on risk of ALS (odds ration [OR]: 1.133, 95% confidence interval [CI]: 0.964–1.332, p = .130). Among subtypes of epilepsy, it also failed to observe any causal association between general epilepsy and ALS (OR: 1.036, 95% CI: 0.969–1.108, P = .300). However, focal epilepsy contributed to an increase in the risk of ALS (OR: 1.177, 95% CI: 1.027–1.348, p = .019). Moreover, the investigation of reverse causalities did not reveal significant results.

Conclusions

The current study supports a causal influence of focal epilepsy on ALS risk. Future studies are needed to explore its potential role in ALS.