bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydroxypillar[5]arene‐Confined Silver Nanocatalyst for Selective Electrochemical Reduction of CO2 to Ethanol
Authors: Qin Junjie , Wang Tao , Zhai Mingming , Wu Chengyu , Liu Yahu A. , Yang Bo , Yang Hui , Wen Ke , Hu Weibo
Published: April 2023

CO is usually the dominant product on silver‐based catalysts in electrochemical CO2 reduction reaction (CO2RR) possibly due to weak *CO adsorption. In this report, a hydroxypillar[5]arene‐extended porous polymer‐confined silver catalyst (PAF‐PA5‐Ag‐0.8) for electrochemical CO2RR which can selectively produce ethanol with a maximum Faradaic efficiency of 55% at 11 mA cm−1 is described. The study reveals that the hydroxypillar[5]arene‐confined Ag clusters are the active sites for ethanol formation. Moreover, temperature‐programmed desorption measurements demonstrate an enhanced adsorption strength of CO* on PAF‐PA5‐Ag‐0.8 compared with that on commercial Ag nanoparticles, which is favored by the C‐C coupling to form ethanol. The density functional theory study indicates that the confined Ag clusters in PAF‐PA5‐Ag‐0.8 contribute to high C2 selectivity in CO2RR through facilitating *COOH formation, stabilizing *CO intermediates, and inhibiting hydrogen evolution. This work provides a new design strategy by modulating *CO adsorption strength on non‐copper electrocatalysts in converting CO2 into “green” C2 products.
Understanding Dopant–Host Interactions on Electronic Structures and Optical Properties in Ce‐Doped WS2 Monolayers
Authors: Ren Caixia , Peng Jiangbo , Chen Hu , Zhang Weili , Pan Xiaoguang , Bai Hangxin , Wang Yongzheng , Jing Fangli , Qiu Hailong , An Yukai , Hu Zhanggui , Liu Hongjun
Published: April 2023

Substitutional lanthanide doping of 2D transition metal dichalcogenides (TMDs) is expected to be a promising strategy to engineer optical, electronic, and optoelectronic properties of TMDs. Understanding the interactions between lanthanide dopants and 2D TMDs host is one of the key problems to be resolved for their profound research studies. Herein, the interactions between Ce dopants and monolayer WS2 in a physical vapor deposition grown Ce‐doped WS2 monolayer are studied by combining scanning tunneling microscopy with optical characterizations with high spatial and temporal resolution. It is found that the highly anisotropic crystal field can effectively split the energy levels of the Ce dopants’ f orbital. The electrons in the split energy levels can bind the holes in the valence band maximum of the Ce‐doped WS2, forming optical bright excitons. These excitons collide with the free A excitons when increasing the pump fluences, reducing the A exciton's lifetime. This study may be beneficial for the design and fabrication of optical, electronic, and optoelectronic devices based on lanthanide‐doped TMDs.
Freely Tailorable Yolk‐Shell Encapsulation: Versatile Applications in Ultralow‐k Dielectric, Drug Delivery Systems, and Catalysts
Authors: Zhang Zhe , He Peng , Ma Wenjun , Zuo Peiyuan , Liu Xiaoyun , Zhuang Qixin
Published: April 2023

Herein, a facile, controllable, and versatile method is reported to prepare monodisperse yolk‐shell and yolk‐multishell silica nanoparticles (NPs) with mesoporous shells by a novel selective etching strategy. The mechanism of selective etching based on fluoride‐silica chemistry is investigated in detail and thus provides a fundamentally novel principle for the fabrication of yolk‐shell NPs. Specifically, this unprecedented and versatile synthesis strategy can be used to encapsulate essentially any silica‐based, carbon‐based, metal, metal oxide, or other possible NPs. Noteworthy is that most of the yolk‐shell mesoporous silica (mSiO2) NPs are prepared for the first time. To demonstrate the major structural and compositional advantages of the designed yolk‐shell NPs, their applications in the fields of ultralow‐dielectric constant (k) materials, drug delivery systems, and catalysts were explored. In detail, the lowest k value of the prepared yolk‐shellordered mesoporous silica@mSiO2/fluorinated polybenzoxazole composite films is 2.02; The obtained yolk‐shell mSiO2/C@mSiO2/C NPs possess high hydrophilicity and pH‐responsive sensitivity; The conversion of the catalytic reaction of the designed magnetic yolk‐shell hollow Fe3O4@SiO2/Au@mSiO2 NPs at 20 min is 97% with a high conversion rate (92%) and recyclability even after 10 reuses. This innovative work lays a solid foundation for freely tailorable yolk‐shell encapsulation and will greatly stimulate more efforts devoted to relevant research and development.
Multifunctional Hyaluronic Acid Microneedle Patch Embedded by Cerium/Zinc‐Based Composites for Accelerating Diabetes Wound Healing
Authors: Yang Juan , Chu Zhaoyou , Jiang Yechun , Zheng Wang , Sun Jiangwei , Xu Lingling , Ma Yan , Wang Wanni , Shao Min , Qian Haisheng
Published: April 2023

Chronic nonhealing diabetic wounds are becoming increasingly severe, with high rates of mortality and disability, owing to the difficulty in wound healing caused by hyperglycemia, blocked angiogenesis, biofilm infection, and excessive oxidative stress. A multicomponent enzyme‐responsive natural polymer, a hyaluronic acid (HA) microneedle, embedded in a cerium/zinc‐based nanomaterial (ZCO) for the treatment of diabetic wounds is reported. ZCO‐HA can destroy the oxidation balance of bacteria, kill bacteria, and scavenge reactive oxygen species (ROS) to alleviate oxidative stress via the adjustable release of Zn2+ and Ce3+/4+. Additionally, ZCO‐HA exhibits good anti‐inflammatory activity through the nuclear factor kappa‐B (NF‐κB) pathway, which reduces the inflammatory state of macrophages and promotes cell proliferation, migration, and angiogenesis. In vitro experiments shows that ZCO‐HA accompanies mouse fibroblast migration, promoting human umbilical vein endothelial cell tube formation. In vivo studies in mice with streptozotocin‐induced (STZ)‐induced diabetes reveal that this microneedle accelerates wound healing without systemic toxicity. RNA transcriptome sequencing illustrates that the multicomponent HA microneedle accelerates wound healing in diabetes through cell migration and inhibits inflammatory reactions and oxidative damage in mice via the NF‐κB signaling pathway.
Azide‐Masked Resiquimod Activated by Hypoxia for Selective Tumor Therapy
Authors: Sun Jiali , Liu Zhilin , Yao Haochen , Zhang Honglei , Zheng Mengfei , Shen Na , Cheng Jianjun , Tang Zhaohui , Chen Xuesi
Published: April 2023

Resiquimod (R848) is an immunomodulator that causes a severe systemic inflammatory reaction due to low tumor selectivity, thus hindering its use in cancer therapy. Therefore, an azide‐masked prodrug (R848‐N3) of R848 is developed, which is selectively activated to R848 in hypoxic tumors. R848‐N3 significantly reduces pro‐inflammatory cytokines in treated mice to 1/12 compared to R848 at the same dose. In addition, combretastatin A4 nanoparticles (CA4‐NPs) are used to enhance the tumor selectivity of R848‐N3 by elevating the level of tumor hypoxia. R848‐N3+CA4‐NPs has higher tumor selectivity than the intratumoral injection of R848 at 1 h after administration. The concentration of the active R848 in the tumor is 21.45‐fold that in the heart. Benefiting from the high tumor selectivity of R848‐N3, R848‐N3+CA4‐NPs+anti‐PD1 exerted 94.1% tumor suppression and 40.0% tumor cure. Therefore, this work highlights the potential of azide‐masking strategy in the development of tumor‐selective prodrugs with reduced toxicity.
A Tumor‐Microenvironment‐Activatable Molecular Pro‐Theranostic Agent for Photodynamic and Immunotherapy of Cancer
Authors: Zhou Hui , Zhang Yuan , Zhang Ruru , Zhao Min , Chen Wan , Liu Yinghua , Jiang Yue , Li Qing , Miao Qingqing , Gao Mingyuan
Published: April 2023

Cancer‐associated fibroblasts (CAFs) are the major components of the tumor‐associated matrix and play an important role in tumor progression and immunosuppression. Therefore, precise theranostics of CAFs are beneficial for CAFs‐targeted therapies. However, imaging agents enabling precise theranostics of CAFs have been rarely exploited. To tackle this issue, a molecular pro‐theranostic probe (FMP) with activatable fluorescence, photoacoustic (PA) imaging, and photodynamic therapy (PDT) is developed in response to fibroblast activation protein α (FAPα) overexpressed in >90% types of CAFs and some tumor cells. Attributed to efficient activatable phototoxicity toward CAFs and tumor cells, together with activated immunogenic cell death (ICD), complete tumor regression of primary tumors and abscopal effect of distant tumors are observed in a 4T1‐tumor‐bearing mice model. By integration with PD‐L1 checkpoint blockade immunotherapy, enhanced systemic immune responses are evoked to obtain long‐lasting tumor suppression of both primary and distant tumors as well as arrest systemic cancer metastasis in living mice.
Synchronous Interventions of Glucose and Mitochondrial Metabolisms for Antitumor Bioenergetic Therapy
Authors: Li Meng , Luo Xiaoming , Lei Shan , Liu Yurong , Guo Huishan , Zhang Yu , Pan Yuantao , Chen Kaiwei , Lin Jing , Huang Peng
Published: April 2023

Hydrogen sulfide (H2S)‐based mitochondrial bioenergetic intervention is an attractive therapeutic modality. However, its therapeutic efficacy is limited owing to metabolic plasticity, which allows tumors to shift their metabolic phenotype between oxidative phosphorylation and glycolysis for energy compensation. To overcome this flexibility, a glycopolymer containing a caged H2S and hydrogen peroxide (H2O2) dual‐donor (1‐thio‐β‐D‐glucose [thioglucose]) is synthesized to wrap glucose oxidase (GOx) for complete depletion of tumorigenic energy sources. The loaded GOx catalyzes the glutathione‐activated thioglucose to generate cytotoxic H2S/H2O2, which further induces synergistic defects in mitochondrial function by suppressing cytochrome c oxidase expression and damaging the mitochondrial membrane potential. GOx also blocks glycolysis by depleting endogenous glucose. This synchronous intervention strategy exhibits good anticancer performance, broadening the horizon of antitumor bioenergetic therapy.
A Recyclable Standalone Microporous Layer with Interpenetrating Network for Sustainable Fuel Cells
Authors: Wen Qinglin , Li Yali , He Can , Shen Min , Ning Fandi , Dan Xiong , Liu Yiyang , Xu Pengpeng , Zou Siyi , Chai Zhi , Li Wei , He Lei , Tian Bin , Zhou Xiaochun
Published: April 2023

The commercialization of fuel cells inevitably brings recycling problems. Therefore, achieving high recyclability of fuel cells is particularly important for their sustainable development. In this work, a recyclable standalone microporous layer (standalone MPL) with interpenetrating network that can significantly enhance the recyclability and sustainability of fuel cells is prepared. The interpenetrating network enables the standalone MPL to have high strength (17.7 MPa), gas permeability (1.55 × 10−13 m2), and fuel‐cell performance (peak power density 1.35 W cm−2), providing the basic guarantee for its application in high‐performance and highly recyclable fuel cells. Additionally, the standalone MPL is highly adaptable to various gas‐diffusion backings (GDBs), providing high possibility to select highly recyclable GDBs. Outstandingly, anode standalone MPLs and GDBs can be easily detached from the spent membrane electrode assembly (MEA). This not only saves >90 vol% solvent in the recovery of the catalyst‐coated membrane (CCM), but also extends the service life of the GDBs and the anode standalone MPL at least 138 times (2 760 000 h assuming 20 000 h of CCM) comparing to CCM. Therefore, the standalone MPL significantly enhances the recyclability and sustainability of fuel cells and is promising to be an indispensable component in the next‐generation fuel cells.
Lest We Forget–The Importance of Heteroatom Interactions in Heterocyclic Conjugated Systems, from Synthetic Metals to Organic Semiconductors
Authors: Cameron Joseph , Kanibolotsky Alexander L. , Skabara Peter J.
Published: April 2023

The field of synthetic metals is, and remains, highly influential for the development of organic semiconductor materials. Yet, with the passing of time and the rapid development of conjugated materials in recent years, the link between synthetic metals and organic semiconductors is at risk of being forgotten. This review reflects on one of the key concepts developed in synthetic metals – heteroatom interactions. The application of this strategy in recent organic semiconductor materials, small molecules and polymers, is highlighted, with analysis of X‐ray crystal structures and comparisons with model systems used to determine the influence of these non‐covalent short contacts. The case is made that the wide range of effective heteroatom interactions and the high performance that has been achieved in devices from organic solar cells to transistors is testament to the seeds sown by the synthetic metals research community.
Design of Piezoelectric Inertial Actuator with Wedge‐shaped Foot Structure for Cell Manipulation
Authors: Long Taofei , Wen Jianming , Lin Shengrong , Li Shengjie , Li Xinhui , Hu Yili
Published: April 2023

Aiming at the performance requirements of positioning accuracy and stability of piezoelectric inertial actuators in fields including micro‐operation and biomedical engineering, a piezoelectric inertial actuator with wedge‐shaped friction foot structure using bimorph films is proposed in this paper. The wedge‐shaped friction foot structure can adjust the friction force in different driving stages, which suppresses the backward motion and effectively improves the output performance of the actuator. And the bimorph films are processed by Micro Electromechanical Systems (MEMS) manufacturing process technology. It enables the actuator to move steadily with a small tip mass and facilitates the miniaturization of actuator. The simulation model is constructed based on the dynamic model of actuator and the prototype parameters are optimized from the results of simulation tests. Then a series of output performance experiments are carried out. Experimental results show that the proposed actuator has the advantages of high resolution, stability, and displacement linearity. And the highest resolution of 0.035 µm is achieved. Depending on above results, the cell drug injection simulation experiments are successfully conducted. The success of experiments shows that the prototype has good output performance and great application potential and value in the field of cell manipulation.
Stable Thermally Activated Delayed Fluorescence‐Sensitized Red Fluorescent Devices through Physical Suppression of Dexter Energy Transfer
Authors: Jeon Chae Yeon , Palanisamy Paramasivam , Lee Hyun Seung , Lee Hyuna , Kim Hae Ung , Chae Mi Young , Kwon Jang Hyuk
Published: April 2023

To date, thermally activated delayed fluorescence‐sensitized fluorescent organic light‐emitting diodes (TSF‐OLEDs) have undergone substantial research to achieve high efficiency and good operational stability in wide color gamut regions. Usually, to achieve a highly efficient TSF device, the Förster resonance energy transfer rate (kFRET) should be enhanced, whereas the Dexter energy transfer rate (kDET) should be suppressed. Even though highly efficient devices are achieved in all RGB color regions by satisfying the BT2020 requirements, achieving long device lifetimes is still challenging. Herein, a highly stable red‐TSF device is reported by adopting a new Dexter energy transfer suppressive layer (DSL) adjacent to the main emissive layer. Here, the DSL can improve the distance between the excitons generated from the host‐TADF layer and the final dopant (FD) of the TSF device, which allows for suppressing the kDET. Furthermore, the detailed device mechanistic pathways are analyzed by varying the DSL doping concentration with different thicknesses in different positions. Among the fabricated devices, the DSL‐TSF device manifested a longer operational lifetime (LT95) over 370 h at 5000 cd m‐2 and reduced efficiency roll‐off compared with TSF devices. Such long lifetime and high stability in DSL‐TSF OLEDs are owing to the decreased kDET than TSF devices.
Hollow Microneedle‐based Plasmonic Sensor for on Patch Detection of Molecules in Dermal Interstitial Fluid
Authors: Miranda Bruno , Battisti Mario , De Martino Selene , Nocerino Valeria , Dardano Principia , De Stefano Luca , Cangiano Giancarlo
Published: April 2023

Interstitial fluid (ISF) extraction and analysis are challenges that can be tackled by Hollow MicroNeedles (HMNs) technology, overcoming most of the difficulties associated with in situ detection. Herein, a plasmonic transducer, composed of gold nanoparticles embedded in poly(ethylene glycol) diacrylate (PEGDA) hydrogels, is integrated in the inner cavity of HMNs to detect biomarkers from the ISF‐based point‐of‐care. The wearable HMN‐based patch is used for minimally invasive pierce of the skin. The large swelling capability of the plasmonic transducer allows the uptake of ISF by capillarity. Biotin, as a small model molecule, is efficiently collected in the inner cavity of HMN and its high specificity with the streptavidin is exploited as a validation of the plasmonic nanocomposite functionality embedded within. The recognition of biotin is achieved in dual‐optical mode: the localized surface plasmon resonance (label‐free) and the metal‐enhanced fluorescence (label‐based). Overall, the proposed HMN‐based patch for target sensing in ISF can represent a novel point‐of‐use device for the detection of biomarkers as an alternative to conventional hospital or lab settings to help faster medical decision‐making.
A Centimeter‐Scale Type‐II Weyl Semimetal for Flexible and Fast Ultra‐Broadband Photodetection from Ultraviolet to Sub‐Millimeter Wave Regime
Authors: Yang Qi , Wang Ximiao , He Zhihao , Chen Yijun , Li Shuwei , Chen Huanjun , Wu Shuxiang
Published: April 2023

Flexible photodetectors with ultra‐broadband sensitivities, fast response, and high responsivity are crucial for wearable applications. Recently, van der Waals (vdW) Weyl semimetals have gained much attention due to their unique electronic band structure, making them an ideal material platform for developing broadband photodetectors from ultraviolet (UV) to the terahertz (THz) regime. However, large‐area synthesis of vdW semimetals on a flexible substrate is still a challenge, limiting their application in flexible devices. In this study, centimeter‐scale type‐II vdW Weyl semimetal, Td‐MoTe2 films, are grown on a flexible mica substrate by molecular beam epitaxy. A self‐powered and flexible photodetector without an antenna demonstrated an outstanding ability to detect electromagnetic radiation from UV to sub‐millimeter (SMM) wave at room temperature, with a fast response time of ≈20 µs, a responsivity of 0.53 mA W−1 (at 2.52 THz), and a noise‐equivalent power (NEP) of 2.65 nW Hz−0.5 (at 2.52 THz). The flexible photodetectors are also used to image shielded items with high resolution at 2.52 THz. These results can pave the way for developing flexible and wearable optoelectronic devices using direct‐grown large‐area vdW semimetals.
BEST1 Positive Monocytes in Circulation: Visualize Intratumoral Crosstalk between Cancer Cells and Monocytes
Authors: Zhang Luyao , Wang Yiran , Yuan Wei , An Changming , Tan Qin , Ma Jie
Published: April 2023

Head and neck squamous cell carcinomas (HNSCCs) are characterized by an abundance of monocytes and macrophages recruited from the peripheral blood. However, it has not been determined whether these infiltrated cells can be released back into circulation with a tumor‐associated neobiosignature. This study reports that Bestrophin1 (BEST1), a component protein of Ca2+‐activated Cl− channels (CaCCs), is highly expressed on classical monocytes in the peripheral blood of HNSCC patients. This is due to monocyte education by tumor cells, in which tumoral VEGF‐A upregulates BEST1 expression on monocytes through the MEK‐ERK‐ELK1 pathway. This leads to improved secretion of IL‐6 and IL‐8, which promotes tumor cell proliferation. This work also finds that BEST1 facilitates the motility of monocytes, contributing to the migration of these cells back into circulation. These results suggest that the expression of BEST1 on peripheral monocytes may be a potential tool for monitoring tumor progression, and opens up the possibility of searching for cancer biomarkers on monocytes rather than on the tumor or its products.
Highly Mimetic Ex Vivo Lung‐Cancer Spheroid‐Based Physiological Model for Clinical Precision Therapeutics
Authors: Shie Ming‐You , Fang Hsin‐Yuan , Kan Kai‐Wen , Ho Chia‐Che , Tu Chih‐Yen , Lee Pei‐Chih , Hsueh Po‐Ren , Chen Chia‐Hung , Lee Alvin Kai‐Xing , Tien Ni , Chen Jian‐Xun , Shen Yu‐Cheng , Chang Jan‐Gowth , Shen Yu‐Fang , Lin Ting‐Ju , Wang Ben , Hung Mien‐Chie , Cho Der‐Yang , Chen Yi‐Wen
Published: April 2023

Lung cancer remains a major health problem despite the considerable research into prevention and treatment methods. Through a deeper understanding of tumors, patient‐specific ex vivo spheroid models with high specificity can be used to accurately investigate the cause, metastasis, and treatment strategies for lung cancer. Biofabricate lung tumors are presented, consisting of patient‐derived tumor spheroids, endothelial cells, and lung decellularized extracellular matrix, which maintain a radial oxygen gradient, as well as biophysicochemical behaviors of the native tumors for precision medicine. It is also demonstrated that the developed lung‐cancer spheroid model reproduces patient responses to chemotherapeutics and targeted therapy in a co‐clinical trial, with 85% accuracy, 86.7% sensitivity, and 80% specificity. RNA sequencing analysis validates that the gene expression in the spheroids replicates that in the patient's primary tumor. This model can be used as an ex vivo predictive model for personalized cancer therapy and to improve the quality of clinical care.
HOOK1 Inhibits the Progression of Renal Cell Carcinoma via TGF‐β and TNFSF13B/VEGF‐A Axis
Authors: Yin Lei , Li Wenjia , Chen Xuxiao , Wang Ronghao , Zhang Tao , Meng Jialin , Li Zhao , Xu Li , Yin Rui , Cheng Bo , Yang Huan
Published: April 2023

Accumulating evidence shows HOOK1 disordered in human malignancies. However, the clinicopathological and biological significance of HOOK1 in renal cell carcinoma (RCC) remains rarely studied. In this study, the authors demonstrate that HOOK1 is downregulated in RCC samples with predicted poorer clinical prognosis. Mechanistically, HOOK1 inhibits tumor growth and metastasis via canonical TGF‐β/ALK5/p‐Smad3 and non‐canonical TGF‐β/MEK/ERK/c‐Myc pathway. At the same time, HOOK1 inhibits RCC angiogenesis and sunitinib resistance by promoting degradation of TNFSF13B through the ubiquitin‐proteasome pathway. In addition, HOOK1 is transcriptionally regulated by nuclear factor E2F3 in VHL dependent manner. Notably, an agonist of HOOK1, meletin, is screened and it shows antitumor activity more effectively when combined with sunitinib or nivolumab than it is used alone. The findings reveal a pivotal role of HOOK1 in anti‐cancer treatment, and identify a novel therapeutic strategy for renal cell carcinoma.
Formation and Band Gap Tuning Mechanism of Multicolor Emissive Carbon Dots from m‐Hydroxybenzaldehyde
Authors: Li Yan , Liu Can , Sun Hao , Chen Menglin , Hou Defa , Zheng Yunwu , Xie Haijiao , Zhou Bei , Lin Xu
Published: April 2023

Reported in 2004, carbon dots (CDs) have been widely used in various fields due to their excellent optical properties. However, the mechanism of their fluorescence modulation is still a controversial issue, which also seriously affects the further development of carbon dots. In this paper, m‐hydroxybenzaldehyde is used as a raw material to obtain multicolor luminescent CDs by pyrolysis under different reaction conditions, thereby revealing the forbidden band tuning and formation mechanism of CDs. Different acid–base conditions lead to different reaction paths of the precursors, forming molecular fluorophores with different conjugated structures, which aggregate to eventually form CDs and further enhance the photoluminescence of the system by inhibiting the movement of the fluorescent centers.
Large‐Scale Synthesis of Multifunctional Single‐Phase Co2C Nanomaterials
Authors: Yang Zhengyi , Zhao Tingting , Hao Shuyan , Wang Rutao , Zhu Chunyan , Tang Yunxiang , Guo Chan , Liu Jiurong , Wen Xiaodong , Wang Fenglong
Published: April 2023

Achieving scalable synthesis of nanoscale transition‐metal carbides (TMCs), regarded as substitutes for platinum‐group noble metals, remains an ongoing challenge. Herein, a 100‐g scale synthesis of single‐phased cobalt carbide (Co2C) through carburization of Co‐based Prussian Blue Analog (Co‐PBA) is reported in CO2/H2 atmosphere under mild conditions (230 °C, ambient pressure). Textural property investigations indicate a successful preparation of orthorhombic‐phased Co2C nanomaterials with Pt‐group–like electronic properties. As a demonstration, Co2C achieves landmark photo‐assisted thermal catalytic CO2 conversion rates with photo‐switched product selectivity, which far exceeds the representative Pt‐group‐metal–based catalysts. This impressive result is attributed to the excellent activation of reactants, colorific light absorption, and photo‐to‐thermal conversion capacities. In addition to CO2 hydrogenation, the versatile Co2C materials show huge prospects in antibacterial therapy, interfacial water evaporation, electrochemical hydrogen evolution reaction, and battery technologies. This study paves the way toward unlocking the potential of multi‐functional Co2C nanomaterials.
Small Size and Low‐Cost TENG‐Based Self‐Powered Vibration Measuring and Alerting System
Authors: Mehamud Idiris , Björling Marcus , Marklund Pär , Shi Yijun
Published: April 2023

Vibration measurement systems containing sensors, signal conditioning, and data acquisition devices, are important for monitoring motors, gearboxes, turbines, etc. Microelectromechanical and piezoelectric sensors are predominantly used for vibration measurements. However, they are not cost‐effective, flexible in design, and incapable of self‐powering. Recently, triboelectric nano‐generator (TENG)‐based vibration sensors have been considered as a possible alternative to resolve this problem, and tremendous progress has been achieved. Previous work on TENG‐based sensors is limited to optimizing the sensor design, while the signal conditioning and data acquisition of TENG signal still need investigation for actual applications. This work develops a TENG‐based vibration measurement device and self‐powered alerting system that is integrated with the signal condition and data acquisition systems. The experimental results show that the proposed measurement system successfully measures signals within the range of 0–1800 Hz frequency. Meanwhile, the TENG generates a high output, up to 80 V and 0.55 µA from small size TENG area (3.6 cm2). The signal is adequate to harvest energy for self‐powering to drive alerting components (harvest 320 mJ in 36 h, which drives alarming for duration of 1.5 s). The proposed device is cost‐effective (30 $), small (105 cm3), and consumes less power (0.18 W) in comparison to commercial devices.
Engineering Perovskite Precursor Inks for Scalable Production of High‐Efficiency Perovskite Photovoltaic Modules
Authors: Chung Jaehoon , Kim Seung‐Woo , Li You , Mariam Tamanna , Wang Xiaoming , Rajakaruna Manoj , Saeed Muhammad Mohsin , Abudulimu Abasi , Shin Seong Sik , Guye Kathryn N. , Huang Zixu , Westbrook Robert J. E. , Miller Emily , Subedi Biwas , Podraza Nikolas J. , Heben Michael J. , Ellingson Randy J. , Ginger David S. , Song Zhaoning , Yan Yanfa
Published: April 2023

Blade coating of perovskite solar cells (PSCs) and modules has progressed considerably toward the industrial production of perovskite photovoltaics. Developing stable perovskite precursors is critical for achieving uniform coating over large areas. Here, the engineering of a perovskite precursor solution consisting of 2‐methoxyethanol (2‐Me) and 1,3‐dimethyl‐imidazolidinone (DMI) with superior intermediate phase stability that enables scalable production of efficient perovskite solar modules is reported. With this perovskite precursor solution, uniform and pinhole‐less perovskite film is deposited over a large area of > 100 cm2 and higher‐efficiency PSCs and modules are obtained. The best‐performing unit cell and module with n‐i‐p configuration reach power conversion efficiencies of 23.4% and 20.1%, respectively. Additionally, a series of non‐destructive metrology methods, such as spectroscopic ellipsometry, hyperspectral photoluminescence, electroluminescence, and laser beam‐induced current mapping, are employed to assess and guide the development the blade‐coated perovskite modules. This results show that rational engineering of precursor inks for blade coating is promising for the scalable production of efficient perovskite solar modules.
Binder‐Induced Ultrathin SEI for Defect‐Passivated Hard Carbon Enables Highly Reversible Sodium‐Ion Storage
Authors: Li Wenbin , Guo Xiaoniu , Song Keming , Chen Jiacheng , Zhang Jiyu , Tang Guochuan , Liu Chuntai , Chen Weihua , Shen Changyu
Published: April 2023

Hard carbon is one of the most promosing anodes for resource‐rich sodium‐ion batteries. However, an unsatisfactory solid–electrolyte‐interphase formed by irreversible electrolyte consumption caused by defects or oxygen‐containing functional groups of hard carbon impedes its further application. Herein, a novel composite binder that is composed of polar polymer chondroitin sulfate A (sodium salt) and polyethylene oxide by hydrogen bonding demonstrates defect passivation capability. This composite binder can reduce the exposure of defects by forming hydrogen bonds with oxygen functional groups on the hard carbon surface and inhibit the decomposition of electrolyte confirmed by in situ differential electrochemical mass spectrometry. In situ Raman and theoretical calculations reveal that multiple polar functional groups in chondroitin sulfate A (sodium salt) can accelerate the transport of Na+ by adsorbing and facilitate the decomposition of PF6− to form NaF. Additionally, polyethylene oxide in the composite binder can increase viscosity and accelerate the transport of Na+. As a result, an ultra‐thin (9 nm, cyro‐TEM) and NaF‐rich solid–electrolyte interphase is obtained, thereby the hard carbon anode achieves improved initial Coulombic efficiency (84%) and high‐capacity retention of 94% after 150 cycles in a NaPF6/ethylene carbonate/dimethyl carbonate electrolyte.
ROPS commentary—Addressing our fatal blind spot: Applying evidence‐based solutions to reduce the most frequent cause of death on U.S. farms
Authors: Sorensen Julie A. , Milkovich Pamela J. , Dorfman Lori , Mejia Pamela , Perez‐Sanz Sarah B.
Published: April 2023

Tractor overturns are the most prominent contributing factor to death on U.S. farms and have been for decades. While public health researchers hypothesized years ago that overturn fatalities would largely disappear as older tractors were replaced by newer ones, this has not happened. In the meantime, farmers continue to die in these easily preventable and tragic events. Not only are tractor rollover protective structures (ROPS) 99% effective in preventing death in the event of an overturn, a national program exists to connect farmers with ROPS. While this program has been popular with farmers, and the cost‐effectiveness of providing farmers with technical support and cost‐sharing rebates has been demonstrated, many states lack access to ROPS rebates, even those states with the highest number of overturn fatalities. Given the evidence, it is difficult to reconcile the lack of policy or public investment in a solution that decisively addresses the most pernicious contributor to death in the agricultural industry. In this commentary, we highlight the science behind this proven solution to tractor overturns and the essential role that the media and implementation science can play in encouraging policy‐makers to save lives.
Sensitivity of Resonant Axion Haloscopes to Quantum Electromagnetodynamics
Authors: Tobar Michael E. , Thomson Catriona A. , McAllister Benjamin T. , Goryachev Maxim , Sokolov Anton V. , Ringwald Andreas
Published: April 2023

Recently, interactions between putative axions and magnetic monopoles have been revisited by two of the authors.[1] It is shown that significant modifications to conventional axion electrodynamics arise due to these interactions, so that the axion–photon coupling parameter space is expanded from one parameter to three . Poynting theorem is implemented to determine how to exhibit sensitivity to and using resonant haloscopes, allowing new techniques to search for axions and a possible indirect way to determine if magnetically charged matter exists.
Ruthenium‐katalysierte entfernte Difunktionalisierung nicht‐aktivierter Alkene für die doppelte meta‐C(sp2)−H/C‐6(sp3)−H‐Funktionalisierung
Authors: Chen Shan , Yuan Binbin , Wang Yulei , Ackermann Lutz
Published: April 2023

Die zweifache distale C−H‐Funktionalisierung wurde durch Difunktionalisierung von nicht aktivierten Alkenen erreicht, um einen schnellen Zugang zu hochfunktionalisierten Molekülen zu ermöglichen. Wir berichten hier über die Mehrkomponten‐Ruthenium‐katalysierte 1,n‐Ferndifunktionalisierung (n=6,7) von nicht aktivierten Alkenen mit Fluoralkylhalogeniden und Heteroarenen in modularer Weise. Die distale meta‐C(sp2)−H/C‐6(sp3)−H‐Funktionalisierung zeichnete sich durch milde Bedingungen, einzigartige Selektivität und einen breiten Substratbereich mit einem Domino‐Prozess für die zweifache C(sp2)−H/C(sp3)−H‐Fernaktivierung der sequentiellen Bildung von drei verschiedenen kohlenstoff‐zentrierten Radikalen aus. Auf der Grundlage detaillierter experimenteller und rechnerischer Studien wurde ein plausibler Mechanismus vorgeschlagen.
A Simple, Selective, and General Catalyst for Ring Closing Depolymerization of Polyesters and Polycarbonates for Chemical Recycling
Authors: Gallin Connor F. , Lee Won‐Woo , Byers Jeffery A.
Published: April 2023

The ability to efficiently and selectively process mixed polymer waste is important to address the growing plastic waste problem. Herein, we report that the combination of ZnCl2 and an additive amount of poly(ethylene glycol) under vacuum can readily and selectively depolymerize polyesters and polycarbonates with high ceiling temperatures (Tc>200 °C) back to their constitute monomers. Mechanistic experiments implicate a random chain scission mechanism and a catalyst structure containing one equivalent of ZnCl2 per ethylene glycol repeat unit in the poly(ethylene glycol). In addition to being general for a wide variety of polyesters and polycarbonates, the catalyst system could selectively depolymerize a polyester in the presence of other commodity plastics, demonstrating how reactive distillation using the ZnCl2/PEG600 catalyst system can be used to separate mixed plastic waste.
Optically Controlled Construction of Three‐Dimensional Protein Arrays
Authors: Liu Qing , Zhou Yu , Shaukat Ahmed , Meng Zhuojun , Kyllönen Daniella , Seitz Iris , Langerreiter Daniel , Kuntze Kim , Priimagi Arri , Zheng Lifei , Kostiainen Mauri A.
Published: April 2023

Protein crystallization is an important tool for structural biology and nanostructure preparation. Here, we report on kinetic pathway‐dependent protein crystals that are controlled by light. Photo‐responsive crystallites are obtained by complexing the model proteins with cationic azobenzene dyes. The crystalline state is readily switched to a dispersed phase under ultraviolet light and restored by subsequent visible‐light illumination. The switching can be reversibly repeated for multiple cycles without noticeable structure deterioration. Importantly, the photo‐treatment not only significantly increases the crystallinity, but creates crystallites at conditions where no ordered lattices are observed upon directly mixing the components. Further control over the azobenzene isomerization kinetics produces protein single crystals of up to ≈50 μm. This approach offers an intriguing method to fabricate metamaterials and study optically controlled crystallization.
Arene‐Perfluoroarene Force Driven Sublimation‐Removable Chiral Coassemblies
Authors: Liu Bingyu , Gao Junjie , Hao Aiyou , Xing Pengyao
Published: April 2023

Multiple constituent coassembly is an emerging strategy to manipulate supramolecular chirality and chiroptical properties such as circularly polarized luminescence (CPL). However, the second or third constituent could not be removed from pristine self‐assembly. Here we developed a constitute‐removable chiral coassembly using sublimation that could realize coassembly with tunable supramolecular chirality, luminescence and CPL properties. Octafluoronapthalene (OFN) with small sublimation enthalpy formed coassemblies with perylene‐conjugated peptoids via arene‐perfluoroarene (AP) interaction that induced the emergence of macroscopic chirality and hypsochromic luminescence from yellow to green. Coassembly with OFN accelerated one‐dimensional growth and induced the emergence of macroscopic chirality and CPL. Despite the stability at ambient conditions, vacuum‐treatment triggered fast sublimation of OFN, which behaved as a sacrificial template. Physical removal of OFN retained the helical nanoarchitectures as well as the basic features of Cotton effects and CPL activities. X‐ray diffraction suggested the back‐fill consolidation occurred on the molecular voids by OFN removal that slightly varied the templated molecular arrangements. Sublimation of perfluorinated building units is green and efficient and non‐destructive, which is potentially applicable in constructing template‐directed chiroptical materials and devices.
Ruthenium‐Catalyzed Remote Difunctionalization of Nonactivated Alkenes for Double meta‐C(sp2)−H/C‐6(sp3)−H Functionalization
Authors: Chen Shan , Yuan Binbin , Wang Yulei , Ackermann Lutz
Published: April 2023

Twofold distal C−H functionalization was accomplished by difunctionalization of nonactivated alkenes to provide rapid access to multifunctionalized molecules. The multicomponent ruthenium‐catalyzed remote 1,n‐difunctionalization (n=6,7) of nonactivated alkenes with fluoroalkyl halides and heteroarenes in a modular manner is reported. The meta‐C(sp2)−H/C‐6(sp3)−H distal functionalization featured mild conditions, unique selectivity, and broad substrate scope with a domino process for twofold remote C(sp2)−H/C(sp3)−H activation of the sequential formation of three different carbon‐centered radicals. A plausible mechanism was proposed based on detailed experimental and computational studies.
Functionalized Hydrocarbon Belts: Synthesis, Structure and Properties
Authors: Peng Yi , Tong Shuo , Zhang Yang , Wang Mei‐Xiang
Published: April 2023

Hydrocarbon belts have drawn great attention because of their unique structures and tantalizing properties. Although a few belts and heteroatom‐doped analogs have been synthesized, belt molecules containing non‐hexagonal rings remain rare. Herein we report the construction and application of unprecedented zigzag‐type hydrocarbon belts which contain functionalized eight‐membered rings. The synthesis features fourfold intramolecular acylation reactions of resorcin[4]arene‐derived intermediates, which affords C4‐symmetric tetrabenzobelt[4]arene[4]cyclooctatrienones. Stereoselective ketone reduction with LiAlH4 and nucleophilic addition with alkynyllithiums provide the corresponding tetrahydroxylated belts. The tetraol and its methyl ether are powerful and selective hosts to form 2 : 1 and 1 : 1 complexes with cesium ion, respectively, with binding constants up to (1.71±0.33)×1011 M−2 and (1.50±0.16)×106 M−1. In addition, enantiopure C4‐symmetric belts can emit CPL with |glum| being around 0.01.
Covalent Organic Frameworks for Energy Conversion in Photocatalysis
Authors: He Ting , Zhao Yanli
Published: April 2023

Intensifying energy crises and severe environmental issues have led to the discovery of renewable energy sources, sustainable energy conversion, and storage technologies. Photocatalysis is a green technology that converts eco‐friendly solar energy into high‐energy chemicals. Covalent organic frameworks (COFs) are porous materials constructed by covalent bonds that show promising potential for converting solar energy into chemicals owing to their pre‐designable structures, high crystallinity, and porosity. Herein, we highlight recent progress in the synthesis of COF‐based photocatalysts and their applications in water splitting, CO2reduction, and H2O2production. The challenges and future opportunities for the rational design of COFs for advanced photocatalysts are discussed. This Review is expected to promote further development of COFs toward photocatalysis.
Ru(II) and Ru(III) complexes containing N‐acylthiourea ligands: Supramolecular structures and synthons, reduction, and reaction pathway of aromatic nitro compounds
Authors: Uysal Muhammet Ebubekir , Solmaz Ummuhan , Arslan Hakan
Published: April 2023

Four ruthenium complexes {[RuCl(CO)(PPh3)2L1], [RuCl(CO)(PPh3)2L2], [RuCl2(PPh3)2L1] and [RuCl2(PPh3)2L2]} supported with N‐acylthiourea‐based ligands were synthesized. The compounds prepared were characterized by 1H NMR, 13C NMR, elemental analysis, UV–vis, and magnetic susceptibility methods. The characterization of the molecular structure of two ruthenium complexes {[RuCl(CO)(PPh3)2L1] and [RuCl2(PPh3)2L1]} was also performed using the single crystal X‐ray diffraction method. Single crystal X‐ray analyses indicates the existence of different non‐covalent interactions between different parts of the molecules, which led to the formation of three‐dimensional supramolecular architectures and synthons. The magnetic susceptibility and UV‐vis spectra of the prepared ruthenium complexes propose that they are of low‐spin states, where Ru(II) is d6 and Ru(III) is d5 low spin. These ruthenium compounds functioned as catalysts for the NaBH4‐mediated reduction of various nitro compounds. The catalytic results show that the [RuCl2(PPh3)2L] type complexes exhibit higher catalytic activity than the [RuCl(CO)(PPh3)2L] type complexes, and [RuCl2(PPh3)2L1] has high catalytic selectivity and efficiency in a short time (>99 yield with catalyst loading 0.01 mol in 0.5 h). Furthermore, the catalytic activity of [RuCl2(PPh3)2L1] was investigated using nitrobenzene as a model substrate to understand the reaction pathway, and this study proved that this nitro reduction proceeds via a direct pathway, with the formation of N‐hydroxylamine as the main intermediate followed by the occurrence of aniline.
Bio‐based flame‐retardant rigid polyurethane foam with high content of soybean oil polyols containing phosphorus
Authors: Wang Shuai , Yang Fukai , Sun Wei , Xu Xinyu , Deng Yuyuan
Published: April 2023

Rigid polyurethane foam (RPUF) is prepared from petroleum‐based polyols and isocyanate, which consumes a large amount of petroleum. To alleviate the consumption of petroleum, it is necessary to synthesize green and sustainable polyols. However, the greatest disadvantage of RPUF is its flammability. To reduce the risk of fire caused by RPUF, phosphorylated soybean oil polyol (Polyol‐P) and phenyl phospho‐soybean oil polyol (Polyol‐PPOA) were synthesized by ring‐opening reactions of epoxy soybean oil with phosphoric acid and phenylphosphonic acid, respectively. A flame‐retardant RPUF was prepared via polymeric 4,4‐diphenylmethane diisocyanate (p‐MDI), which reacted after mixing Polyol‐P and Polyol‐PPOA with polyether polyol‐330N in different proportions. Scanning electron microscopy (SEM) showed that the cell sizes of the RPUF‐P and RPUF‐PPOA increased first and then decreased and the cell number decreased first and then increased with the increase in the contents of Polyol‐P and Polyol‐PPOA. Mechanical property tests showed that the compressive strength of the RPUF‐P4 reached 0.1 MPa, and the compressive strength of the RPUF‐PPOA4 reached 0.07 MPa. The limiting oxygen index values of the RPUF‐P4 and RPUF‐PPOA4 were 20.9% and 24.3%, respectively. The UL 94 of the RPUFs indicated that the rating of the RPUF‐PPOA3 was improved to V‐1. The results showed that the flame‐retardancy mechanism of the Polyol‐P and Polyol‐PPOA in the RPUF was based on the charred surface as a physical barrier, which slowed down the decomposition of RPUF and prevented heat and mass transfer between the gas and the condensed phase.
Feasibility of a self‐sustaining microbial fuel cell incorporating natural processes of bacteria and microalgae towards a circular bioeconomy
Authors: Yahampath Arachchige Don Chamath D. Y. , Babel Sandhya
Published: April 2023

A microbial fuel cell (MFC) consisting of a bacterial anode chamber and a microalgal cathode chamber was operated under various conditions to assess its technical feasibility. Maximum achievable power density reached up to 7.13 mW m–2. The traditional MFC process of conversion of carbon sources to bioelectricity in the anodic chamber was compared with a system circulating anodic effluent to the cathode chamber. The bacteria and microalgae simultaneously carried out the carbon recycling and recovery of energy and resources synergizing the performance of MFC. Results indicated a comparable chemical oxygen demand removal efficiencies at 50% of the retention time compared to the traditional system. The dissolved oxygen concentration varied between 11.95 and 7.44 mg L–1 with Chlorella vulgaris under alternative light and dark cycles. Despite the variations in electricity output, the system showed its technical feasibility to harness energy for photosynthesis under natural sunlight conditions.
Magnetic Domain Change Induced by In‐Plane Electric Polarization Switching in Bi(Fe, Co)O3 Thin Film
Authors: Shigematsu Kei , Katsumata Marin , Itoh Takuma , Ozawa Keita , Shimizu Haruki , Shimizu Keisuke , Azuma Masaki
Published: April 2023

Perovskite BiFe0.9Co0.1O3 with electric‐field‐induced magnetization reversal is a promising material for low‐power non‐volatile memory devices because spontaneous magnetization perpendicular to the electric polarization can be reversed by out‐of‐plane polarization reversal. In this study, magnetic and ferroelectric domain changes in BiFe0.9Co0.1O3 after applying an in‐plane electric field with counter electrodes fabricated by lithography is investigated. Electric poling can be performed up to 100 times via 71° polarization switching without disrupting the ferroelectric domains. It is determined that the correlation between the ferroelectric and magnetic domains is preserved, while in‐plane 71° polarization switching without reconstructing the ferroelectric domains does not change its out‐of‐plane magnetization. Lastly, possible differences in the antiferromagnetic spin vector and magnetization direction for in‐plane and out‐of‐plane 71° switching is discussed.
Novel Insights of Enhanced Magnetization and Magnetoelectric Coupling in the Nanocomposite of BiFeO3 with Lanthanum Strontium Manganite
Authors: Parvathy N. S. , Govindaraj R.
Published: April 2023

Novel insights on the magnetic, ferroelectric and magnetoelectric coupling of the nano composites of BiFeO3 (BFO) and La0.7Sr0.3Mn0.95Fe0.05O3 (LSMFO) with the latter exhibiting colossal magnetoresistance (CMR) behavior are provided in this study for the first time. Appreciable magnetoelectric coupling is observed in the composite and is seen to be significantly varying at temperatures below the blocking temperature of LSMFO. The local structure and magnetic properties of both the BFO and LSMFO particles in the composite are investigated in a detailed manner using Mössbauer spectroscopy studies specially devised to address the problem concerned. Enhanced values of the effective magnetic fields are observed at the Fe sites associated with BFO particles which are in contact with LSMFO particles. Interestingly, an appreciable increase in the magnetic hyperfine fields at Fe sites corresponding to LSMFO is also observed in the nanocomposites. New insights are derived based on the results of Mössbauer studies toward comprehending the magnetic and magnetoelectric coupling effects as deduced in these composites.