bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluating Platinum‐Based Ionic Polymer Metal Composites as Potentiometric Sensors for Dissolved Ozone in Ultrapure Water Systems
Authors: Grimmig Roman , Gillemot Philipp , Lindner Simon , Schmidt Philipp , Stucki Samuel , Günther Klaus , Baltruschat Helmut , Witzleben Steffen
Published: April 2023

Monitoring the content of dissolved ozone in purified water is often mandatory to ensure the appropriate levels of disinfection and sanitization. However, quantification bears challenges as colorimetric assays require laborious off‐line analysis, while commercially available instruments for electrochemical process analysis are expensive and often lack the possibility for miniaturization and discretionary installation. In this study, potentiometric ionic polymer metal composite (IPMC) sensors for the determination of dissolved ozone in ultrapure water (UPW) systems are presented. Commercially available polymer electrolyte membranes are treated via an impregnation‐reduction method to obtain nanostructured platinum layers. By applying 25 different synthesis conditions, layer thicknesses of 2.2 to 12.6 µm are obtained. Supporting radiographic analyses indicate that the platinum concentration of the impregnation solution has the highest influence on the obtained metal loading. The sensor response behavior is explained by a Langmuir pseudo‐isotherm model and allows the quantification of dissolved ozone to trace levels of less than 10 µg L−1. Additional statistical evaluations show that the expected Pt loading and radiographic blackening levels can be predicted with high accuracy and significance (R2adj.> 0.90,p< 10−10) solely from given synthesis conditions.
Chiral Active Surface Growth via Glutathione Control
Authors: Zheng Yonglong , Wang Qian , Sun Yiwen , Huang Jie , Ji Jin , Wang Zhu‐Jun , Wang Yawen , Chen Hongyu
Published: April 2023

It is shown that the chiral ligand glutathione can induce active surface growth in the deposition of Au on Au nanoplates, forming nano‐badges with complex surface patterns. The special feature of the growth mode is that the growth materials are diverted to a few active sites, causing deep valleys and high standing walls. The circular dichroism signal depends on the tilting degree of the walls, which likely arises from the different packing of the chiral ligands on the two pro‐chiral slopes. As a characteristic sign of the Active Surface Growth mode, low seed concentration is used to promote the rate of deposition, which expands the ridge–valley competition favoring growth at the active sites. The understanding and rational control of the chiral ridges will advance the synthetic control for chiral nanostructures.
Optical Glass Microsphere Enabled Rapid Single‐Molecular Fluoroimmunoassay
Authors: Wei Ziheng , Yang Xiaoli , Xu Lingrui , Si Shuhui , Wu Danhong , Zeng Hulie
Published: April 2023

Determination of low‐abundance proteins in body liquid is the significant strategy for the early diagnosis of diseases and the discovery of signal paths in pathobiology. Here, the limit of detection of 113 aM for model human IgA is successfully obtained by the fluoroimmunoassay developed on an optical soda lime glass microsphere in micrometers that is illumed by the microsphere amplified fluorescence (MAF), which can be identified to the most sensitive immunoassay so far. In this case, the fluorescence signal of fluoroimmunoassay can be physically amplified by MAF while the large reacting area will be supplied by the glass microsphere to complete the fluoroimmunoassay. Therefore, the assay time of the fluoroimmunoassay can be shortened to 12 min via the optical glass microsphere‐enabled ultrasensitive fluoroimmunoassay at the same time. The developed fluoroimmunoassay indicates a possibility to perform the ultrasensitive immunoassay on the optical glass microsphere in 10 min and more, which may greatly facilitate the development of the ultrasensitive immunoassay for the urgent measurements and promote the development of portable fluoroimmunoassay.
Semiconductor–Semimetal Transition‐Driven Photocurrent Spurt and Infrared Band Response in Lead Iodide at High Pressure
Authors: Cheng Peng , Ye Tingting , Yan Jinwei , Zhang Kai , Yao Deyuan , Pan Xiaomei , Wang Yunfeng , Xue Erqiao , Su Fuhai , Zhang Jie , Ding Junfeng
Published: April 2023

Topological semimetals have attracted flourishing interest as promising candidates for their unique advantages in achieving highly sensitive, low‐energy photodetection with ultrafast operation. Although various semimetals have been explored recently, new semimetals are still being pursued for high‐responsivity photodetectors with broadband response. Here, a pressure‐induced semiconductor–semimetal transition is observed in two‐dimensional wide‐band semiconducting lead iodide (PbI2). The photocurrent under visible light shows abrupt increases by two orders of magnitude at ≈25 GPa, where the crystalline structure transforms from the Pnma to I4/MMM phase. Meanwhile, the responding band expands from visible light to at least the telecom wavelength 1550 nm. The high‐pressure absorption spectra of PbI2 suggest that the electrical band is closed at the transition point, while the charge transport shows that the sample is still not metallic. Through first‐principles calculations, the photocurrent spurt and infrared band response are attributed to the appearance of a semimetal phase at high pressure, which well explains the nonmetallic transport. The prominent drop in lifetime to a few picoseconds in ultrafast spectroscopy under pressure further confirms the semiconductor–semimetal transition in PbI2. Pressure‐induced semimetallization opens a new strategy for designing a high‐performance photodetector with broadband response.
Population Control of Upconversion Energy Transfer for Stimulation Emission Depletion Nanoscopy
Authors: Liu Yongtao , Wen Shihui , Wang Fan , Zuo Chao , Chen Chaohao , Zhou Jiajia , Jin Dayong
Published: April 2023

Upconverting stimulated emission depletion microscopy (U‐STED) is emerging as an effective approach for super‐resolution imaging due to its significantly low depletion power and its ability to surpass the limitations of the square‐root law and achieve higher resolution. Though the compelling performance, a trade‐off between the spatial resolution and imaging quality in U‐STED has been recognized in restricting the usability due to the low excitation power drove high depletion efficiency. Moreover, it is a burden to search for the right power relying on trial and error as the underpinning mechanism is unknown. Here, a method is proposed that can easily predict the ideal excitation power for high depletion efficiency with the assistance of the non‐saturate excitation based on the dynamic cross‐relaxation (CR) energy transfer of upconversion nanoparticles. This allows the authors to employ the rate equation model to simulate the populations of each relevant energy state of lanthanides and predict the ideal excitation power for high depletion efficiency. The authors demonstrate that the resolution of STED with the assistance of nonsaturated confocal super‐resolution results can easily achieve the highest resolution of sub‐40 nm, 1/24th of the excitation wavelengths. The finding on the CR effect provides opportunities for population control in realizing low‐power high‐resolution nanoscopy.
Lymph Node Follicle‐Targeting STING Agonist Nanoshells Enable Single‐Shot M2e Vaccination for Broad and Durable Influenza Protection
Authors: Tsai Hsiao‐Han , Huang Ping‐Han , Lin Leon CW , Yao Bing‐Yu , Liao Wan‐Ting , Pai Chen‐Hsueh , Liu Yu‐Han , Chen Hui‐Wen , Hu Che‐Ming J.
Published: April 2023

The highly conserved matrix protein 2 ectodomain (M2e) of influenza viruses presents a compelling vaccine antigen candidate for stemming the pandemic threat of the mutation‐prone pathogen, yet the low immunogenicity of the diminutive M2e peptide renders vaccine development challenging. A highly potent M2e nanoshell vaccine that confers broad and durable influenza protectivity under a single vaccination is shown. Prepared via asymmetric ionic stabilization for nanoscopic curvature formation, polymeric nanoshells co‐encapsulating high densities of M2e peptides and stimulator of interferon genes (STING) agonists are prepared. Robust and long‐lasting protectivity against heterotypic influenza viruses is achieved with a single administration of the M2e nanoshells in mice. Mechanistically, molecular adjuvancy by the STING agonist and nanoshell‐mediated prolongation of M2e antigen exposure in the lymph node follicles synergistically contribute to the heightened anti‐M2e humoral responses. STING agonist‐triggered T cell helper functions and extended residence of M2e peptides in the follicular dendritic cell network provide a favorable microenvironment that induces Th1‐biased antibody production against the diminutive antigen. These findings highlight a versatile nanoparticulate design that leverages innate immune pathways for enhancing the immunogenicity of weak immunogens. The single‐shot nanovaccine further provides a translationally viable platform for pandemic preparedness.
Liquid NanoBiosensors Enable One‐Pot Electrochemical Detection of Bacteria in Complex Matrices
Authors: Imani Sara M. , Osman Enas , Bakhshandeh Fatemeh , Qian Shuwen , Sakib Sadman , MacDonald Michael , Gaskin Mark , Zhitomirsky Igor , Yamamura Deborah , Li Yingfu , Didar Tohid F. , Soleymani Leyla
Published: April 2023

There is a need for point‐of‐care bacterial sensing and identification technologies that are rapid and simple to operate. Technologies that do not rely on growth cultures, nucleic acid amplification, step‐wise reagent addition, and complex sample processing are the key for meeting this need. Herein, multiple materials technologies are integrated for overcoming the obstacles in creating rapid and one‐pot bacterial sensing platforms. Liquid‐infused nanoelectrodes are developed for reducing nonspecific binding on the transducer surface; bacterium‐specific RNA‐cleaving DNAzymes are used for bacterial identification; and redox DNA barcodes embedded into DNAzymes are used for binding‐induced electrochemical signal transduction. The resultant single‐step and one‐pot assay demonstrates a limit‐of‐detection of 102 CFU mL−1, with high specificity in identifying Escherichia coli amongst other Gram positive and negative bacteria including Klebsiella pneumoniae, Staphylococcus aureus, and Bacillus subtilis. Additionally, this assay is evaluated for analyzing 31 clinically obtained urine samples, demonstrating a clinical sensitivity of 100% and specify of 100%. When challenging this assay with nine clinical blood cultures, E. coli‐positive and E. coli‐negative samples can be distinguished with a probability of p < 0.001.
Ultrasensitive Near‐Infrared InAs Colloidal Quantum Dot‐ZnON Hybrid Phototransistor Based on a Gradated Band Structure
Authors: Kim Jong‐Ho , Jung Byung Ku , Kim Su‐Kyung , Yun Kwang‐Ro , Ahn Junhyuk , Oh Seongkeun , Jeon Min‐Gyu , Lee Tae‐Ju , Kim Seongchan , Oh Nuri , Oh Soong Ju , Seong Tae‐Yeon
Published: April 2023

Amorphous metal oxide semiconductor phototransistors (MOTPs) integrated with colloidal quantum dots (QDs) (QD‐MOTPs) are promising infrared photodetectors owing to their high photoconductive gain, low off‐current level, and high compatibility with pixel circuits. However, to date, the poor mobility of conventional MOTPs, such as indium gallium zinc oxide (IGZO), and the toxicity of lead (Pb)‐based QDs, such as lead sulfide and lead selenide, has limited the commercial applications of QD‐MOTPs. Herein, an ultrasensitive QD‐MOTP fabricated by integrating a high‐mobility zinc oxynitride (ZnON)–based MOTP and lead‐free indium arsenide (InAs) QDs is demonstrated. A new gradated bandgap structure is introduced in the InAs QD layer that absorbs infrared light, which prevents carriers from moving backward and effectively reduces electron–hole recombination. Chemical, optical, and structural analyses confirm the movement of the photoexcited carriers in the graded band structure. The novel QD‐MOTP exhibits an outstanding performance with a responsivity of 1.15 × 105 A W−1 and detectivity of 5.32 × 1016 Jones at a light power density of 2 µW cm−2 under illumination at 905 nm.
Metabolic Intervention Liposome Boosted Lung Cancer Radio‐Immunotherapy via Hypoxia Amelioration and PD‐L1 Restraint
Authors: Wang Saijun , Zhou Zaigang , Hu Rui , Dong Mingyue , Zhou Xiaobo , Ren Siyan , Zhang Yi , Chen Chengxun , Huang Ruoyuan , Zhu Man , Xie Wanying , Han Ling , Shen Jianliang , Xie Congying
Published: April 2023

At present, radiotherapy (RT) still acquires limited success in clinical due to the lessened DNA damage under hypoxia and acquired immune tolerance owing to the amplified programmed death ligand‐1 (PD‐L1) expression. Incredibly, intracellular PD‐L1 expression depression is proven to better sensitize RT by inhibiting DNA damage repair. However, the disability of the clinically used antibodies in disrupting the extracellular PD‐L1function still limits the effectiveness of radio‐immunotherapy. Therefore, better PD‐L1 regulation strategies are still urgently needed to better sensitize radio‐immunotherapy. Hence, for this purpose, TPP‐LND is synthesized by linking mitochondrial‐targeted triphenylphosphine cations (TPP+) to the antineoplastic agent lonidamine (LND), which significantly reduces the dose needed for LND to induce effective oxidative phosphorylation inhibition (2 vs 300 µM). Then, TPP‐LND is wrapped with liposomes to form TPP‐LND@Lip nanoparticles. By doing this, TPP‐LND@Lip nanoparticles can sensitize RT by reversing the hypoxic microenvironment of tumors to generate more DNA damage and reducing the expression of PD‐L1 via enhancing the adenosine 5′‐monophosphate‐activated protein kinase activation. As expected, these well‐designed economical TPP‐LND@Lip nanoparticles are more effective than conventional anti‐PD‐L1 antibodies to some extent.
The Formation Mechanism of (001) Facet Dominated α‐FAPbI3 Film by Pseudohalide Ions for High‐Performance Perovskite Solar Cells
Authors: Li Shengwen , Xia Junmin , Wen Zhaorui , Gu Hao , Guo Jia , Liang Chao , Pan Hui , Wang Xingzhu , Chen Shi
Published: April 2023

Formamidinium lead triiodide (α‐FAPbI3) has been widely used in high‐efficiency perovskite solar cells due to its small band gap and excellent charge‐transport properties. Recently, some additives show facet selectivity to generate a (001) facet‐dominant film during crystallization. However, the mechanism to realize such (001) facet selectivity is not fully understood. Here, the authors attempted to use three ammonia salts NH4X (X are pseudohalide anions) to achieve better (001) facet selectivity in perovskite crystallization and improved crystallinity. After addition, the (001) facet dominance is generally increased with the best effect from SCN− anions. The theoretical calculation revealed three mechanisms of such improvements. First, pseudohalide anions have larger binding energy than the iodine ion to bind the facets including (110), (210), and (111), slowing down the growth of these facets. The large binding energy also reduces nucleation density and improves crystallinity. Second, pseudohalide ions improve phase purity by increasing the formation energies of the δ‐phase and other hexagonal polytypes, retarding the α‐ to δ‐phase transition. Third, the strong binding of these anions can also effectively passivate the iodine vacancies and suppress nonradiative recombination. As a result, the devices show a power conversion efficiency of 24.11% with a Voc of 1.181 V.
Deep Learning Model to Denoise Luminescence Images of Silicon Solar Cells
Authors: Liu Grace , Dwivedi Priya , Trupke Thorsten , Hameiri Ziv
Published: April 2023

Luminescence imaging is widely used to identify spatial defects and extract key electrical parameters of photovoltaic devices. To reliably identify defects, high‐quality images are desirable; however, acquiring such images implies a higher cost or lower throughput as they require better imaging systems or longer exposure times. This study proposes a deep learning‐based method to effectively diminish the noise in luminescence images, thereby enhancing their quality for inspection and analysis. The proposed method eliminates the requirement for extra hardware expenses or longer exposure times, making it a cost‐effective solution for image enhancement. This approach significantly improves image quality by >30% and >39% in terms of the peak signal‐to‐noise ratio and the structural similarity index, respectively, outperforming state‐of‐the‐art classical denoising algorithms.
Bioinspired Super Thermal Insulating, Strong and Low Carbon Cement Aerogel for Building Envelope
Authors: Du Fengyin , Zhu Wenkai , Yang Ruizhe , Zhang Yun , Wang Jiawei , Li Weihuan , Zuo Wenqiang , Zhang Lizhi , Chen Liuyan , She Wei , Li Tian
Published: April 2023

The energy crisis has arisen as the most pressing concern and top priority for policymakers, with buildings accounting for over 40% of global energy consumption. Currently, single‐function envelopes cannot satisfy energy efficiency for next‐generation buildings. Designing buildings with high mechanical robustness, thermal insulation properties, and more functionalities has attracted worldwide attention. Further optimization based on bioinspired design and material efficiency improvement has been adopted as effective approaches to achieve satisfactory performance. Herein, inspired by the strong and porous cuttlefish bone, a cement aerogel through self‐assembly of calcium aluminum silicate hydrate nanoparticles (C‐A‐S‐H, a major component in cement) in a polymeric solution as a building envelop is developed. The as‐synthesized cement aerogel demonstrates ultrahigh mechanical performance in terms of stiffness (315.65 MPa) and toughness (14.68 MJ m−3). Specifically, the highly porous microstructure with multiscale pores inside the cement aerogel greatly inhibits heat transfer, therefore achieving ultralow thermal conductivity (0.025 W m−1 K−1). Additionally, the inorganic C‐A‐S‐H nanoparticles in cement aerogel form a barrier against fire for good fire retardancy (limit oxygen index, LOI ≈ 46.26%, UL94‐V0). The versatile cement aerogel featuring high mechanical robustness, remarkable thermal insulation, light weight, and fire retardancy is a promising candidate for practical building applications.
Flower‐Like Amorphous MoO3−x Stabilized Ru Single Atoms for Efficient Overall Water/Seawater Splitting
Authors: Feng Dong , Wang Pengyan , Qin Rui , Shi Wenjie , Gong Lei , Zhu Jiawei , Ma Qianli , Chen Lei , Yu Jun , Liu Suli , Mu Shichun
Published: April 2023

Benefitting from the maximum atom utilization efficiency, special size quantum effects and tailored active sites, single‐atom catalysts (SACs) have been promising candidates for bifunctional catalysts toward water splitting. Besides, due to the unique structure and properties, some amorphous materials have been found to possess better performance than their crystalline counterparts in electrocatalytic water splitting. Herein, by combining the advantages of ruthenium (Ru) single atoms and amorphous substrates, amorphous molybdenum‐based oxide stabilized single‐atomic‐site Ru (Ru SAs‐MoO3−x/NF) catalysts are conceived as a self‐supported electrode. By virtue of the large surface area, enhanced intrinsic activity and fast reaction kinetics, the as‐prepared Ru SAs‐MoO3−x/NF electrode effectively drives both oxygen evolution reaction (209 mV @ 10 mA cm−2) and hydrogen evolution reaction (36 mV @ 10 mA cm−2) in alkaline media. Impressively, the assembled electrolyzer merely requires an ultralow cell voltage of 1.487 V to deliver the current density of 10 mA cm−2. Furthermore, such an electrode also exhibits a great application potential in alkaline seawater electrolysis, achieving a current density of 100 mA cm−2 at a low cell voltage of 1.759 V. In addition, Ru SAs‐MoO3−x/NF only has very small current density decay in the long‐term constant current water splitting test.
Hepatic Phospholipid Remodeling Modulates Insulin Sensitivity and Systemic Metabolism
Authors: Tian Ye , Mehta Kritika , Jellinek Matthew J. , Sun Hao , Lu Wei , Shi Ruicheng , Ingram Kevin , Friedline Randall H. , Kim Jason K. , Kemper Jongsook Kim , Ford David A. , Zhang Kai , Wang Bo
Published: April 2023

The liver plays a central role in regulating glucose and lipid metabolism. Aberrant insulin action in the liver is a major driver of selective insulin resistance, in which insulin fails to suppress glucose production but continues to activate lipogenesis in the liver, resulting in hyperglycemia and hypertriglyceridemia. The underlying mechanisms of selective insulin resistance are not fully understood. Here It is shown that hepatic membrane phospholipid composition controlled by lysophosphatidylcholine acyltransferase 3 (LPCAT3) regulates insulin signaling and systemic glucose and lipid metabolism. Hyperinsulinemia induced by high‐fat diet (HFD) feeding augments hepatic Lpcat3 expression and membrane unsaturation. Loss of Lpcat3 in the liver improves insulin resistance and blunts lipogenesis in both HFD‐fed and genetic ob/ob mouse models. Mechanistically, Lpcat3 deficiency directly facilitates insulin receptor endocytosis, signal transduction, and hepatic glucose production suppression and indirectly enhances fibroblast growth factor 21 (FGF21) secretion, energy expenditure, and glucose uptake in adipose tissue. These findings identify hepatic LPCAT3 and membrane phospholipid composition as a novel regulator of insulin sensitivity and provide insights into the pathogenesis of selective insulin resistance.
Revealing the Role of Zinc Ions in Atherosclerosis Therapy via an Engineered Three‐Dimensional Pathological Model
Authors: Wang Ying , Huang Nan , Yang Zhilu
Published: April 2023

An incomplete understanding of the cellular functions and underlying mechanisms of zinc ions released from zinc‐based stents in atherosclerosis (AS) therapy is one of the major obstacles to their clinical translation. The existing evaluation methodology using cell monolayers has limitations on accurate results due to the lack of vascular architectures and pathological features. Herein, the authors propose a 3D biomimetic AS model based on a multi‐layer vascular structure comprising endothelial cells and smooth muscle cells with hyperlipidemic surroundings and inflammatory stimulations as AS‐prone biochemical conditions to explore the biological functions of zinc ions in AS therapy. Concentration‐dependent biphasic effects of zinc ions on cell growth are observed both in cell monolayers and 3D AS models. Nevertheless, the cells within 3D AS model exhibit more accurate biological assessments of the zinc ions, as evidenced by augmented pathological features and significantly higher half‐maximal inhibitory concentration values against zinc ions. Based on such a developed 3D biomimetic AS model, the inhibitory effects on the deoxyribonucleic acid (DNA) synthesis, significantly influenced biological processes like cell motility, proliferation, and adhesion, and several potential bio‐targets of zinc ions of cells are revealed.
Aspergillus Niger Derived Wrinkle‐Like Carbon as Superior Electrode for Advanced Vanadium Redox Flow Batteries
Authors: Deng Qi , Zhou Wei‐Bin , Wang Hong‐Rui , Fu Na , Wu Xiong‐Wei , Wu Yu‐Ping
Published: April 2023

The scarcity of high electrocatalysis composite electrode materials has long been suppressing the redox reaction of V(II)/V(III) and V(IV)/V(V) couples in high performance vanadium redox flow batteries (VRFBs). Herein, through ingeniously regulating the growth of Aspergillus Niger, a wrinkle‐like carbon (WLC) material that possesses edge‐rich carbon, abundant heteroatoms, and nature wrinkle‐like structure is obtained, which is subsequently successfully introduced and uniform dispersed on the surface of carbon fiber of graphite felt (GF). This composite electrode presents a lower overpotential and higher charge transfer ability, as the codoped multiheteroatoms increase the electrocatalysis activity and the wrinkled structure affords more abundant reaction area for vanadium ions in the electrolyte when compared with the pristine GF electrode, which is also supported by the density functional theory (DFT) calculations. Hence, the assembled battery using WLC electrodes achieves a high energy efficiency of 74.5% for 300 cycles at a high current density of 200 mA cm−2, as well as the highest current density of 450 mA cm−2. The WLC material not only uncovers huge potential in promoting the application of VRFBs, but also offers referential solution to synthesis microorganism‐based high‐performance electrode in other energy storage systems.
Mechanically Robust, Recyclable, and Self‐Healing Polyimine Networks
Authors: Yu Ping , Wang Haiyue , Li Ting , Wang Guimei , Jia Zichen , Dong Xinyu , Xu Yang , Ma Qilin , Zhang Dongen , Ding Hongliang , Yu Bin
Published: April 2023

To achieve energy saving and emission reduction goals, recyclable and healable thermoset materials are highly attractive. Polymer copolymerization has been proven to be a critical strategy for preparing high‐performance polymeric materials. However, it remains a huge challenge to develop high‐performance recyclable and healable thermoset materials. Here, polyimine dynamic networks based on two monomers with bulky pendant groups, which not only displayed mechanical properties higher than the strong and tough polymers, e.g., polycarbonate, but also excellent self‐repairing capability and recyclability as thermosets are developed. Owing to the stability of conjugation effect by aromatic benzene rings, the final polyimine networks are far more stable than the reported counterparts, exhibiting excellent hydrolysis resistance under both alkaline condition and most organic solvents. These polyimine materials with conjugation structure can be completely depolymerized into monomers recovery in an acidic aqueous solution at ambient temperature. Resulting from the bulky pendant units, this method allows the exchange reactions of conjugation polyimine vitrimer easily within minutes for self‐healing function. Moreover, the introduction of trifluoromethyl diphenoxybenzene backbones significantly increases tensile properties of polyimine materials. This work provides an effective strategy for fabricating high‐performance polymer materials with multiple functions.
Trap‐Assisted Memristive Switching in HfO2‐Based Devices Studied by In Situ Soft and Hard X‐Ray Photoelectron Spectroscopy
Authors: Zahari Finn , Marquardt Richard , Kalläne Matthias , Gronenberg Ole , Schlueter Christoph , Matveyev Yury , Haberfehlner Georg , Diekmann Florian , Nierhauve Alena , Buck Jens , Hanff Arndt , Kolhatkar Gitanjali , Kothleitner Gerald , Kienle Lorenz , Ziegler Martin , Carstensen Jürgen , Rossnagel Kai , Kohlstedt Hermann
Published: April 2023

Memristive devices are under intense development as non‐volatile memory elements for extending the computing capabilities of traditional silicon technology by enabling novel computing primitives. In this respect, interface‐based memristive devices are promising candidates to emulate synaptic functionalities in neuromorphic circuits aiming to replicate the information processing of nervous systems. A device composed of Nb/NbOx/Al2O3/HfO2/Au that shows promising features like analog switching, no electro‐forming, and high current‐voltage non‐linearity is reported. Synchrotron‐based X‐ray photoelectron spectroscopy and depth‐dependent hard X‐ray photoelectron spectroscopy are used to probe in situ different resistance states and thus the origin of memristive switching. Spectroscopic evidence for memristive switching based on the charge state of electron traps within HfO2 is found. Electron energy loss spectroscopy and transmission electron microscopy support the analysis. A device model is proposed that considers a two‐terminal metal–insulator–semiconductor structure in which traps within the insulator (HfO2/Al2O3) modulate the space charge region within the semiconductor (NbOx) and, thereby, the overall resistance. The experimental findings are in line with impedance spectroscopy data reported in the companion paper (Marquardt et al). Both works complement one another to derive a detailed device model, which helps to engineer device performance and integrate devices into silicon technology.
Impedance Spectroscopy on Hafnium Oxide‐Based Memristive Devices
Authors: Marquardt Richard , Zahari Finn , Carstensen Jürgen , Popkirov George , Gronenberg Ole , Kolhatkar Gitanjali , Kohlstedt Hermann , Ziegler Martin
Published: April 2023

Memristive devices for neuromorphic computing have been attracting ever growing attention over the last couple of years. In neuromorphic electronics, memristive devices with multi‐level resistance states are required to accurately reproduce synaptic weights. Here, a memristive device based on a multilayer oxide system (Nb/NbOx/Al2O3/HfO2/Au), which features a filamentary‐free, homogenous interfacial resistive switching mechanism, is investigated. To gain a deeper insight into the switching mechanism, impedance spectroscopy (ImpSpec), X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) are exploited. While this work focuses on the analysis of impedance and current‐voltage characteristics, XPS and TEM investigations can be found in a companion paper (Zahari et al.). In the course of this investigation, potentiodynamic impedance spectroscopy (PD‐ImpSpec) and time resolved impedance spectroscopy (TR‐ImpSpec) in combination with transient analysis are used. Evidence is presented of switching kinetics at voltages above 2.1 V directly related to changes in Schottky barrier resistance. These switching kinetics can in turn be interpreted by the charging and discharging of double positively charged oxygen vacancies  ≈ 0.9 eV. The results of the impedance analysis are translated into a more general model for memristive devices to map the physical processes during switching.
Ion Gel‐Gated Quasi‐Solid‐State Vertical Organic Electrochemical Transistor and Inverter
Authors: Jeong Sang Young , Moon Jung Woo , Lee Soonyong , Wu Ziang , Park Sung Hyeon , Cho Jeong Ho , Woo Han Young
Published: April 2023

Parallel‐type organic electrochemical transistors (p‐OECTs) with aqueous electrolyte gate dielectrics have been widely studied for transducing biological signals into electrical signals. However, aqueous liquid electrolyte‐based p‐OECTs suffer from poor device stability, low transconductance (gm), and limited applications. In this study, a quasi‐solid‐state ion gel‐gated vertical‐type OECT (v‐OECT) and NOT logic gate are successfully demonstrated by combining both p‐type and n‐type v‐OECTs for the first time. Indacenodithiophene (IDT) polymers with alkyl (PIDTC16‐BT) and oligoethylene glycol (OEG) substituents (PIDTPEG‐BT) are studied as a channel material, and an ionic liquid in a crosslinked polymer matrix is adopted as a quasi‐solid electrolyte. Compared to aqueous devices, an enlarged electrochemical window and improved operational stability are observed. Notably, the v‐OECTs have a significantly larger channel area (50 × 50 µm2) and shorter channel length (≈30 nm), yielding a dramatically increased gm. As‐spun PIDTC16‐BT films exhibit a noticeably higher gm of 72.8 mS than that of previous p‐OECTs along with superior device stability, despite a low volumetric capacitance. In the case of v‐OECTs, face‐on intermolecular packing is required to increase the carrier transport in a vertical direction. Logic gates are successfully demonstrated using p‐ and n‐type v‐OECTs, suggesting the potential of OECT‐based next‐generation electronics.
Electronic, Optoelectronic, and Thermoelectric Single‐Molecule Devices with Different Molecular Unit‐Length
Authors: Li Chenyu , Cao Yi , Ru Jindou , Dong Jun , Sun Mengtao
Published: April 2023

Molecular devices have given impetus to the development of new electronic components. The transport process of organic molecules has a significant impact on device performance. Diketopyrrolopyrrole (DPPn, n = 1,2,3,4.) and derivative molecules have been widely explored due to their long‐range and efficient transport properties. In this paper, the electronic, optoelectronic, and thermoelectric properties of single diketopyrrolopyrrole molecular devices with different molecular units are investigated. By adjusting the bias voltage, the single molecular devices show a negative differential resistance effect, for which the reasons are given. Molecular orbital energy levels are regulated by gate voltages to enable conversion of conductivity. The transformation of molecular device functions in time‐varying alternating current transport is discussed in detail. Bias voltage regulation is performed for the molecular device optical response to produce better photocurrent, and finally the thermoelectric current of the device is also analyzed. This results reveal that single molecular electronic, optoelectronic, and thermoelectric properties are highly correlated with molecular unit‐length, which provides guidance for the development of molecular devices with different unit lengths.
Recent Progress in Multiterminal Memristors for Neuromorphic Applications
Authors: Leng Yan‐Bing , Zhang Yu‐Qi , Lv Ziyu , Wang Junjie , Xie Tao , Zhu Shirui , Qin Jingrun , Xu Runze , Zhou Ye , Han Su‐Ting
Published: April 2023

The essential step for developing neuromorphic systems is to construct more biorealistic elementary devices with rich spatiotemporal dynamics to exhibit highly separable responses in dynamic environmental circumstances. Unlike transistor‐based devices and circuits with zeroth‐order complexity, memristors intrinsically express some simple biomimetic functions. However, with only two‐terminal structure, precise control of operation principles to ensure large dynamic space, improved linearity and symmetry, multimodal operation as well as high‐order complexity is hard to achieve in a traditional memristor owing to its limited degree of freedom. Therefore, multiterminal memristors including both concrete terminals and virtual terminals (light, pressure, gas, ferroelectric polarity, etc.) have been proposed to obtain precise modulation of memristive characteristics. This review focuses on the recent progress in multiterminal memristors and their neuromorphic applications. The operation principle, application of multiterminal memristor on neuromorphic computing in different scenarios, existing challenges and future prospects are discussed.
Periodically Alternating Electric Field Layers Induces the Preferential Growth of Zn (002) Plane for Ultralow Overpotential Zinc‐Ion Batteries
Authors: Feng Jie , Li Xinyang , Cui Xiaofeng , Zhao Hongyang , Xi Kai , Ding Shujiang
Published: April 2023

The sluggish de‐solvation kinetics and uneven Zn2+ transport behavior at the Zn anode are undesirable for commercialization of zinc ion batteries. To address these issues, a periodically alternating electric field is introduced on the Zn anode by constructing a laponite nano‐clay layer with unique electric field separation properties. This layer exhibits negative and positive electric fields together in the same space but in different directions (negative electric field in the normal direction while the positive electric field is in the radial direction); thus, achieving both homogeneous Zn2+ transport and an effective de‐solvation effect. The laponite film (LAP@Zn) as a multifunctional artificial layer can induce Zn2+ nucleation for preferential orientation growth of Zn along the (002) planes, thereby suppressing dendrite growth on the Zn anode. Consequently, the LAP@Zn symmetric cells exhibit an ultralow overpotential (12 mV) and cycle smoothly over 1100 h at 0.5 mA cm−2. Even at an ultrahigh current density of 40 mA cm−2, the cell still operates stably for 500 h. More encouragingly, the effectiveness is also convincing in MnO2‐based full cells with excellent rate performance and cycle stability. The periodically alternating electric field strategy provides an effective path toward high‐performance and dendrite‐free Zn‐based storage systems.
In Situ Topological Interphases Boosting Stable Solid‐State Lithium Metal Batteries
Authors: Xu Hantao , Zhang Jianyong , Zhang Hong , Long Juncai , Xu Lin , Mai Liqiang
Published: April 2023

Incompatible interphases resulting from the irreconcilable contradiction between impedance and mechanical strength have become one of the major obstacles to the practical application of solid‐state lithium metal batteries (SSLMBs). With the employment of a decoupling strategy by rational topological design, herein a topological polymer‐reinforced interphase layer is in situ constructed using a synthesized solid polymer electrolyte. As a result, the constructed topological solid electrolyte interphase (SEI) layer harmonizes the enhanced mechanochemical stability and fast diffusion dynamics of Li+, which maintains the integrity and stability of the SEI layer during cycling. In addition, a highly stable and reversible Li nucleation/stripping behaviors exceeding 3000 h and the superior cycling performance of practical LiFePO4/Li metal battery beyond 500 cycles can be achieved by virtue of the formation of the topological interphase layer. This design strategy of constructing a topological interphase layer to decouple mechanical strength and the activation energy of Li+ transport provides a feasible paradigm for realizing practical SSLMBs.
Extraordinary Catalytic Performance of Nickel Half‐Metal Clusters for Light‐Driven Dry Reforming of Methane
Authors: Hu Qianqian , Li Yuanzhi , Wu Jichun , Hu Yaqi , Cao Huaming , Yang Yi
Published: April 2023

Global warming and the energy shortage due to the burning of fossil fuels are two major challenges. A strategy of light‐driven catalytic dry reforming of methane (DRM) using inexhaustible solar energy has provided an effective approach to tackle these challenges. Loaded metallic Ni nanoparticles have been identified as promising catalysts as alternatives to noble metals for DRM. However, they suffer from quick deactivation caused by severe coking due to thermodynamically inevitable side‐reactions. Herein, a unique nickel half‐metal catalyst of monolayer nickel clusters stabilized by alumina is reported, with 100% atomic utilization efficiency and extraordinary catalytic performance for light‐driven DRM, dramatically different from its counterpart of conventional metallic Ni nanoparticles. It has extremely high specific H2 and CO production rates of 8572.96 and 9614.26 mmol min−1 gNi−1, more than one order of magnitude higher than those of Ni nanoparticles. No detectable coke is formed due to the alteration of kinetic processes for DRM, resulting in the inhibition of coke deposition. It is discovered that light not only significantly enhances catalytic activity, but also enables quick thermocatalytic deactivation to be durable due to the oxidation of carbon species and the desorption of strongly adsorbed CO2 and CO being dramatically promoted by light.
Building Up an “Elemental Property—Adsorption Energy Descriptor—Decomposition Barrier” Three‐Tier Model for Screening Biatom Catalysts in Sodium–Sulfur Batteries
Authors: Fan Ke , Ying Yiran , Lin Zezhou , Tsang Yuen Hong , Huang Haitao
Published: April 2023

Developing highly efficient catalysts for the Na2S redox process and sodium polysulfide anchoring is becoming increasingly important for high‐performance sodium–sulfur (Na–S) batteries. The recently emerged graphene‐supported biatom catalysts (G‐BACs) exhibit great potential for providing high activity in both discharging and charging processes. However, the fast screening of promising G‐BACs for Na–S batteries is hindered by the formidable computational cost for calculating Na2S decomposition barriers (Eb). Herein, this work develops an “elemental property—adsorption energy descriptor—decomposition barrier” three‐tier model to accelerate this process and elucidates the origin of catalytic activity. It is found that Eb during the charging process is linearly correlated with the adsorption energy difference between the initial and final states of Na2S decomposition (Ediff) for both homonuclear and heteronuclear transition metal G‐BACs. This work further correlates Ediff with intrinsic properties of metal elements by machine learning approaches and unravels the most significant elemental feature to be the outer electron number. This work not only accelerates the design of highly efficient G‐BACs in Na–S batteries based on the structure–activity relationship, but also provides a feasible strategy for the fast screening of catalysts for other electrochemical reactions for potential experimental design.
A proposed new Japanese classification of synchronous peritoneal metastases from colorectal cancer: A multi‐institutional, prospective, observational study conducted by the Japanese Society for Cancer of the Colon and Rectum
Authors: Kobayashi Hirotoshi , Kotake Kenjiro , Kawasaki Masayasu , Kanemitsu Yukihide , Kinugasa Yusuke , Ueno Hideki , Maeda Kotaro , Suto Takeshi , Itabashi Michio , Funahashi Kimihiko , Ozawa Heita , Koyama Fumikazu , Noura Shingo , Ishida Hideyuki , Ohue Masayuki , Kiyomatsu Tomomichi , Ishihara Soichiro , Koda Keiji , Baba Hideo , Kawada Kenji , Hashiguchi Yojiro , Goi Takanori , Toiyama Yuji , Tomita Naohiro , Sunami Eiji , Akagi Yoshito , Watanabe Jun , Hakamada Kenichi , Nakayama Goro , Sugihara Kenichi , Ajioka Yoichi
Published: April 2023

Aim

To establish a new Japanese classification of synchronous peritoneal metastases from colorectal cancer.

Methods

This multi‐institutional, prospective, observational study enrolled patients who underwent surgery for colorectal cancer with synchronous peritoneal metastases. Overall survival rates were compared according to the various models using objective indicators. Each model was evaluated by Akaike's information criterion (AIC). The region of peritoneal metastases was evaluated by the peritoneal cancer index (PCI).

Results

Between October 2012 and December 2016, 150 patients were enrolled. The AIC of the present Japanese classification was 1020.7. P1 metastasis was defined as confined to two regions. The minimum AIC was obtained with the cutoff number of 10 or less for P2 metastasis and 11 or more for P3 metastasis. As for size, the best discrimination ability between P2 and P3 metastasis was obtained with a cutoff value of 3 cm. The AIC of the proposed classification was 1014.7. The classification was as follows: P0, no peritoneal metastases; P1, metastases localized to adjacent peritoneum (within two regions of PCI); P2, metastases to distant peritoneum, number ≤10 and size ≤3 cm; P3, metastases to distant peritoneum, number ≥11 or size >3 cm; P3a, metastases to distant peritoneum, number ≥11 and size ≤3 cm, or number ≤10 and size >3 cm; P3b, metastases to distant peritoneum, number ≥11 and size >3 cm.

Conclusion

This objective classification could improve the ability to discriminate prognosis in patients with synchronous peritoneal metastases from colorectal cancer.
Cachexia index as a prognostic predictor after resection of pancreatic ductal adenocarcinoma
Authors: Shimagaki Tomonari , Sugimachi Keishi , Mano Yohei , Onishi Emi , Iguchi Tomohiro , Nakashima Yuichiro , Sugiyama Masahiko , Yamamoto Manabu , Morita Masaru , Toh Yasushi
Published: April 2023

Aim

This study was performed to investigate the relationship between the preoperative cachexia index (CXI) and long‐term outcomes in patients who have undergone radical resection of pancreatic ductal adenocarcinoma (PDAC).

Methods

In total, 144 patients who underwent pancreatic resection for treatment of PDAC were retrospectively analyzed. The relationship between the CXI and the patients' long‐term outcomes after PDAC resection was investigated. The CXI was calculated based on the preoperative skeletal muscle index, serum albumin level, and neutrophil‐to‐lymphocyte ratio. After propensity‐score matching, we compared clinicopathological features and outcomes.

Results

The multivariate analysis showed that lymph node metastasis (hazard ratio [HR], 1.93; 95% confidence interval [CI], 1.16–3.23; P = 0.0118), R1 resection (HR, 57.20; 95% CI, 9.39–348.30; P < 0.0001), and a low CXI (HR, 2.10; 95% CI, 1.27–3.46; P = 0.0038) were independent and significant predictors of disease‐free survival (DFS) after PDAC resection. Moreover, a low CXI (HR, 3.14; 95% CI, 1.71–5.75; P = 0.0002) was an independent and significant predictor of overall survival (OS) after PDAC resection. After propensity‐score matching, the low CXI group had a significantly worse prognosis than the high CXI group for both DFS and OS.

Conclusion

The CXI can be a useful prognostic factor for DFS and OS after pancreatic resection for treatment of PDAC.
Localized Ligands Assist Ultrafast Multivalent‐Cation Intercalation Pseudocapacitance
Authors: Xie Luting , Xu Kui , Sun Wenlu , Fan Yingzhu , Zhang Junyu , Zhang Yixiao , Zhang Hui , Chen Jun , Shen Yanbin , Fu Fang , Kong Huabin , Wu Guan , Wu Jihuai , Chen Liwei , Chen Hongwei
Published: April 2023

Rechargeable batteries based on multivalent cation (Mvn+, n>1) carriers are considered potentially low‐cost alternatives to lithium‐ion batteries. However, the high charge‐density Mvn+ carriers generally lead to sluggish kinetics and poor structural stability in cathode materials. Herein, we report an Mvn+ storage via intercalation pseudocapacitance mechanism in a 2D bivalve‐like organic framework featured with localized ligands. By switching from conventional intercalation to localized ligand‐assisted‐intercalation pseudocapacitance, the organic cathode exhibits unprecedented fast kinetics with little structural change upon intercalation. It thus enables an excellent power density of 57 kW kg−1 over 20000 cycles for Ca2+ storage and a power density of 14 kW kg−1 with a long cycling life over 45000 cycles for Zn2+ storage. This work may provide a largely unexploited route toward constructing a local dynamic coordination microstructure for ultrafast Mvn+ storage.
Formal Insertion of Alkenes Into C(sp3)−F Bonds Mediated by Fluorine‐Hydrogen Bonding
Authors: Garg Arushi , Gerwien Nils J. , Fasting Carlo , Charlton Alex , Hopkinson Matthew N.
Published: April 2023

C−F Insertion reactions represent an attractive approach to prepare valuable fluorinated compounds. The high strength of C−F bonds and the low reactivity of the fluoride released upon C−F bond cleavage, however, mean that examples of such processes are extremely scarce in the literature. Here we report a reaction system that overcomes these challenges using hydrogen bond donors that both activate C−F bonds and allow for downstream reactions with fluoride. In the presence of hexafluoroisopropanol, benzyl and propargyl fluorides undergo efficient formal C−F bond insertion across α‐fluorinated styrenes. This process, which does not require any additional fluorinating reagent, occurs under mild conditions and delivers products featuring the gem‐difluoro motif, which is attracting increasing interest in medicinal chemistry. Moreover, readily available organic bromides can be engaged directly in a one‐pot process that avoids the isolation of organic fluorides.
Electrocatalytic oxygen reduction reaction promoted by titanium‐based tetrapyrazinoporphyrazines
Authors: Sordello Fabrizio , Prantsidou‐Georgiadou Pelagia‐Nefeli , Azzi Emanuele , Tschauder Yannick , Formenti Dario , Pellegrino Francesco , Renzi Polyssena
Published: April 2023

In this study, we unveiled titanium‐based tetrapyrazinoporphyrazines as a valuable alternative to noble metals in the oxygen reduction reaction (ORR). By simply modifying the synthetic conditions, we were able to tune the ORR selectivity while showing that the introduction of substituents on the macrocycle periphery is detrimental to the ability of the complex to reduce molecular oxygen. A complete electrochemical characterization in different conditions is reported together with rotating ring‐disk electrode measurements, which assessed the possibility of selectively switching from 2‐ to a 4‐electron reduction product changing the titanium precursor amounts during the complex synthesis.