bluuebunny/crossref_metadata_2025 huggingface dataset:
Metal Single‐Site Molecular Complex–MXene Heteroelectrocatalysts Interspersed Graphene Nanonetwork for Efficient Dual‐Task of Water Splitting and Metal–Air Batteries
Authors: Nguyen Thanh Hai , Tran Phan Khanh Linh , Dinh Van An , Tran Duy Thanh , Kim Nam Hoon , Lee Joong Hee
Published: December 2022

Development of multifunctional electrocatalysts with high efficiency and stability is of great interest in recent energy conversion technologies. Herein, a novel heteroelectrocatalyst of molecular iron complex (FeMC)‐carbide MXene (Mo2TiC2Tx) uniformly embedded in a 3D graphene‐based hierarchical network (GrH) is rationally designed. The coexistence of FeMC and MXene with their unique interactions triggers optimum electronic properties, rich multiple active sites, and favorite free adsorption energy for excellent trifunctional catalytic activities. Meanwhile, the highly porous GrH effectively promotes a multichannel architecture for charge transfer and gas/ion diffusion to improve stability. Therefore, the FeMC–MXene/GrH results in superb performances towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in alkaline medium. The practical tests indicate that Zn/Al–air batteries derived from FeMC–MXene/GrH cathodic electrodes produce high power densities of 165.6 and 172.7 mW cm−2, respectively. Impressively, the liquid‐state Zn–air battery delivers excellent cycling stability of over 1100 h. In addition, the alkaline water electrolyzer induces a low cell voltage of 1.55 V at 10 mA cm−2 and 1.86 V at 0.4 A cm−2 in 30 wt.% KOH at 80 °C, surpassing recent reports. The achievements suggest an exciting multifunctional electrocatalyst for electrochemical energy applications.
Real‐Time Non‐Driving Behavior Recognition Using Deep Learning‐Assisted Triboelectric Sensors in Conditionally Automated Driving
Authors: Zhang Haodong , Tan Haiqiu , Wang Wuhong , Li Zhihao , Chen Facheng , Jiang Xiaobei , Lu Xiao , Hu Yanqiang , Li Lizhou , Zhang Jie , Si Yihao , Wang Xiaoli , Bengler Klaus
Published: December 2022

Real‐time recognition of non‐driving behaviors is of great importance in conditionally automated driving, as it determines the takeover time budget, which in turn has a huge impact on the performance of the takeover. Here, a novel real‐time non‐driving behavior recognition system (RNBRS) integrating self‐powered, low‐cost, easy‐to‐manufacture triboelectric sensors, and a deep learning model is proposed. The structure, working mechanism, and electrical characteristics of triboelectric sensors are investigated and analyzed. Through the ingenious structural design of single‐electrode triboelectric sensors and driving simulation experiments under conditional automated driving, non‐driving behaviors are captured in the form of electrical signals. A well‐trained long short‐term memory network model is adopted to recognize the five most typical non‐driving behaviors, including phone, console touchpad, driving, monitoring driving, and no operation, and test accuracy of 93.5% is achieved. Demonstration of a set of controlled experiments shows that RNBRS enables vehicles with conditional automation to dynamically adjust takeover time budget based on driver behavior, therefore significantly improving both safety and stability of takeover. This study opens new frontiers for the development of self‐powered electronics and inspires new thoughts on human‐machine interaction and the safety of autonomous vehicles.
Anode/Cathode Dual‐Purpose Aluminum Current Collectors for Aqueous Zinc‐Ion Batteries
Authors: Zhu Ruijie , Xiong Zetao , Yang Huijun , Wang Ning , Kitano Sho , Zhu Chunyu , Aoki Yoshitaka , Habazaki Hiroki
Published: December 2022

Rechargeable aqueous zinc (Zn)‐ion batteries (RAZIBs), which use non‐flammable aqueous electrolytes and low‐cost electrode materials, show great potential to boost the development of safe, cost‐effective, and highly efficient energy storage systems. The adoption of lightweight and inexpensive aluminum (Al) as current collectors seems to be a good vision, but Al exhibits an easily‐corroded nature and a high impedance in aqueous electrolytes, making it a challenge to realize the utilization of Al current collector in RAZIBs. In this study, through the direct current magnetron sputtering, niobium (Nb) coated Al (Al‐Nb) foils are prepared, which shows superior corrosion‐resistance in an aqueous solution, while maintaining a satisfying electronic conductivity. Moreover, the Al‐Nb foils can be adopted to both anode and cathode current collectors while exhibiting high coulombic efficiency and good cycling stability even when they are tested under a condition that can meet the real‐world application demands, e.g., the Zn||Al‐Nb half‐cell shows an average coulombic efficiency of 99.17% in 320 cycles under a current density of 25 mA cm−2 and a galvanizing capacity of 6.25 mAh cm−2. The superior performance of the modified Al current collectors may mark a significant step toward the development of high‐energy‐density aqueous batteries.
Diselenide‐Based Dual‐Responsive Prodrug as Pyroptosis Inducer Potentiates Cancer Immunotherapy
Authors: Wan Shu‐Cheng , Ye Meng‐Jie , Yang Qi‐Chao , Zhang Tian , Zhang Meng‐Jie , Ma Xian‐Bin , Xu Ji‐Ming , Wang Shuo , Wu Zhi‐Zhong , Yang Lei‐Lei , Shen Xue‐Meng , Xu Zhigang , Sun Zhi‐Jun
Published: December 2022

Pyroptosis is demonstrated to trigger antitumor immunity and represents a promising new strategy to potentiate cancer immunotherapy. The number of potent pyroptosis inducers, however, is limited and without tumor‐targeting capability, which inevitably causes damage in normal tissues. Herein, a small molecular prodrug of paclitaxel‐oxaliplatin is rationally synthesized, which can be covalently self‐assembled with diselenide‐containing cross‐linking (Dse11), producing a diselenide nanoprodrug (DSe@POC) to induce pyroptosis for the first time. The diselenide bonds within DSe@POC can be split by high glutathione in the tumor microenvironment (TME) and reactive oxygen species induced by photodynamic therapy, thus possessing excellent TME on‐target effects. Additionally, DSe@POC is able to elicit intense pyroptosis to remodel the immunostimulated TME and trigger a robust immune response. Furthermore, combined αPD‐1 therapy effectively inhibits the growth of remote tumors through the abscopal effect, amplifies a long‐term immune memory response to reject rechallenged tumors, and prolongs survival. Collectively, DSe@POC, as the first TME dual‐responsive diselenide‐based pyroptosis inducer, will open up an attractive approach for cancer immunotherapy.
Unraveling the Plasma Protein Corona by Ultrasonic Cavitation Augments Active‐Transporting of Liposome in Solid Tumor
Authors: Wang Guowei , Jiang Yifan , Xu Junjun , Shen Jiaxin , Lin Tao , Chen Jifan , Fei Weidong , Qin Yating , Zhou Zhuxian , Shen Youqing , Huang Pintong
Published: December 2022

Ligand/receptor‐mediated targeted drug delivery has been widely recognized as a promising strategy for improving the clinical efficacy of nanomedicines but is attenuated by the binding of plasma protein on the surface of nanoparticles to form a protein corona. Here, it is shown that ultrasonic cavitation can be used to unravel surface plasma coronas on liposomal nanoparticles through ultrasound (US)‐induced liposomal reassembly. To demonstrate the feasibility and effectiveness of the method, transcytosis‐targeting‐peptide‐decorated reconfigurable liposomes (LPGLs) loaded with gemcitabine (GEM) and perfluoropentane (PFP) are developed for cancer‐targeted therapy. In the blood circulation, the targeting peptides are deactivated by the plasma corona and lose their targeting capability. Once they reach tumor blood vessels, US irradiation induces transformation of the LPGLs from nanodrops into microbubbles via liquid–gas phase transition and decorticate the surface corona by reassembly of the lipid membrane. The activated liposomes regain the capability to recognize the receptors on tumor neovascularization, initiate ligand/receptor‐mediated transcytosis, achieve efficient tumor accumulation and penetration, and lead to potent antitumor activity in multiple tumor models of patient‐derived tumor xenografts. This study presents an effective strategy to tackle the fluid biological barriers of the protein corona and develop transcytosis‐targeting liposomes for active tumor transport and efficient cancer therapy.
As Fiber Meets with AIE: Opening a Wonderland for Smart Flexible Materials
Authors: Li Haoxuan , Jin Bingqi , Wang Yuanwei , Deng Bingyao , Wang Dong , Tang Ben Zhong
Published: December 2022

Aggregation‐induced emission luminogens (AIEgens) have recently been developed at a tremendous pace in the area of organic luminescent materials by virtue of their superior properties. However, the practical applications of AIEgens still face the challenge of transforming AIEgens from molecules into materials. Till now, many AIEgens have been integrated into fiber, endowing the fiber with prominent fluorescence and/or photosensitizing capacities. AIEgens and fiber complement each other for making progress in flexible smart materials, in which the utilization of AIEgens creates new application possibilities for fiber, and the fiber provides an excellent carrier for AIEgens towards realizing the conversion from molecule to materials and an ideal platform to research the aggregate state of AIEgens in mesoscale and macroscale. This review begins with a brief summary of the recent advances related to some typical AIEgens with various functions and the technology for the fabrication of AIEgen‐functionalized fiber. The most representative applications are then highlighted by focusing on energy conversion, personal protective equipment, biomedical, sensor, and fluorescence‐related fields. Finally, the challenges, opportunities, and tendencies in future development are discussed in detail. This review hopes to inspire innovation in AIEgens and fiber from the view of mesoscale and macroscale.
Toxicogenomics Data for Chemical Safety Assessment and Development of New Approach Methodologies: An Adverse Outcome Pathway‐Based Approach
Authors: Saarimäki Laura Aliisa , Morikka Jack , Pavel Alisa , Korpilähde Seela , del Giudice Giusy , Federico Antonio , Fratello Michele , Serra Angela , Greco Dario
Published: December 2022

Mechanistic toxicology provides a powerful approach to inform on the safety of chemicals and the development of safe‐by‐design compounds. Although toxicogenomics supports mechanistic evaluation of chemical exposures, its implementation into the regulatory framework is hindered by uncertainties in the analysis and interpretation of such data. The use of mechanistic evidence through the adverse outcome pathway (AOP) concept is promoted for the development of new approach
methodologies (NAMs) that can reduce animal experimentation. However, to unleash the full potential of AOPs and build confidence into toxicogenomics, robust associations between AOPs and patterns of molecular alteration need to be established. Systematic curation of molecular events to AOPs will create the much‐needed link between toxicogenomics and systemic mechanisms depicted by the AOPs. This, in turn, will introduce novel ways of benefitting from the AOPs, including predictive models and targeted assays, while also reducing the need for multiple testing strategies. Hence, a multi‐step strategy to annotate AOPs is developed, and the resulting associations are applied to successfully highlight relevant adverse outcomes for chemical exposures with strong in vitro and in vivo convergence, supporting chemical grouping and other data‐driven approaches. Finally, a panel of AOP‐derived in vitro biomarkers for pulmonary fibrosis (PF) is identified and experimentally validated.
Optoelectronic Resistive Memory Based on Lead‐Free Cs2AgBiBr6 Double Perovskite for Artificial Self‐Storage Visual Sensors
Authors: Ye Haibo , Liu Zhiyong , Sun Bo , Zhang Xuning , Shi Tielin , Liao Guanglan
Published: December 2022

Mimicking the human visual memory system has attractive prospects in the field of artificial vision. However, the prominent challenge of realizing human visual memory is how to detect and store image information at the same time, which demands a multifunctional electronic device that can sense and memorize image information like the brain. In this work, simple two‐terminal optoelectronic resistive random access memory (ORRAM) devices are demonstrated based on lead‐free Cs2AgBiBr6 perovskite, exhibiting a unique optoelectronic resistive characteristic that can be reset by UV light illumination. A proof‐of‐concept artificial self‐storage visual system based on the ORRAM is constructed, which shows similar reinforcement learning and memory forgetting functions to the human visual memory system, and realizes the integrated functions of image sensing and memory for a long‐term retention time (>6000 s). Theoretical calculations indicate that UV light illumination will induce the annihilation of Br defects and cause the fracture of conductive filaments, resulting in the optical RESET phenomenon. Furthermore, by integrating with perovskite solar cells, an all‐optically controlled universal implication logic gate is constructed. This work provides an important step toward the mimicry of human visual memory and the multifunctional artificial visual integration of perception and storage.
Magnetic and Electric Field Dependent Charge Transfer in Perovskite/Graphene Field Effect Transistors
Authors: Cottam Nathan D. , Austin Jonathan S. , Zhang Chengxi , Patanè Amalia , Escoffier Walter , Goiran Michel , Pierre Mathieu , Coletti Camilla , Mišeikis Vaidotas , Turyanska Lyudmila , Makarovsky Oleg
Published: December 2022

Stable all‐inorganic CsPbX3 perovskite nanocrystals (PNCs) with high optical yield can be used in combination with graphene as photon sensors with high responsivity (up to 106 A W−1) in the VIS‐UV range. The performance of these perovskite/graphene field effect transistors (FET) is mediated by charge transfer processes at the perovskite – graphene interface. Here, the effects of high electric (up to 3000 kV cm−1) and magnetic (up to 60 T) fields applied perpendicular to the graphene plane on the charge transfer are reported. The authors demonstrate electric‐ and magnetic‐field dependent charge transfer and a slow (>100 s) charge dynamics. Magneto‐transport experiments in constant (≈0.005 T s−1) and pulsed (≈1000 T s−1) magnetic fields reveal pronounced hysteresis effects in the transfer characteristics of the FET. A magnetic time is used to explain and model differences in device behavior under fast (pulsed) and slowly (continuous) changing magnetic fields. The understanding of the dynamics of the charge transfer in perovskite/graphene heterostructures developed here is relevant for exploitation of these hybrid systems in electronics and optoelectronics, including ultrasensitive photon detectors and FETs for metrology.
Pipeline installation effects on soils and plants: A review and quantitative synthesis
Authors: Brehm Theresa , Culman Steve
Published: December 2022

Oil and natural gas pipelines are essential to the transport of energy materials, but construction of these pipelines commonly causes disturbance to ecosystems. Due to variability in pipeline installation practices and environments, drawing consensus about how pipeline installations typically impact ecosystems is challenging. Here, we performed a systematic literature review to compile studies that have evaluated impacts of pipeline installation on soil and plant properties. We found 34 studies reporting pipeline impacts on agricultural and natural ecosystems from eight countries. We quantified and synthesized the magnitude of responses and found that the majority of studies found pipeline installation resulted in soil degradation via increased compaction and soil mixing, paired with decreased aggregate stability and soil carbon (C) relative to adjacent, undisturbed areas. Averaged across all studies, aggregate stability decreased 44.8%, water infiltration was reduced 85.6%, and compaction via penetration resistance increased 40.9% over pipeline areas relative to nondisturbed adjacent areas. This soil degradation led to general declines in plant productivity, with 15 out of 25 studies documenting declines in crop yields (6.2–45.6%) and six out of nine studies reporting decreased biomass from natural ecosystems (1.7–56.8%). We conclude from our quantitative synthesis that pipeline installation typically results in degraded soil and vegetation resources, and this can persist for many years following installation.
Growth, yield, and yield stability of canola in the Northern Great Plains of the United States
Authors: Arinaitwe Unius , Clay Sharon A. , Nleya Thandiwe
Published: December 2022

Canola (Brassica napus L.) may diversify wheat‐based cropping systems in the Northern Great Plains. However, agronomic adaptability and stability of high‐yielding genotypes have not been widely evaluated over the diverse environmental conditions of South Dakota (SD). A 2‐year field experiment was conducted in two contrasting environments (Brookings—eastern SD and Pierre—Central SD) to evaluate genotypes (10 in 2019 and 12 in 2020) for days to 50% flower, lodging, pods plant−1, seed yield, 1000‐seed weight, and yield stability. Seed yield for all genotypes in Brookings averaged 1961 and 1740 kg ha−1, in 2019 and 2020, respectively, whereas at Pierre, yields averaged 1470 and 858 kg ha−1. Seed oil concentration was greater at Brookings (456 and 406 g kg−1 in 2019 and 2020, respectively) than at Pierre (356 g kg−1 in 2019). The additive main effects and multiplicative interaction model (AMMI) evaluated eight genotypes across locations and years for genotype × environment (GE) interactions and stability. Environment was the most dominant cause of variation among genotypes, explaining 67.7%, 41.4%, and 45.7%, of the variations in pods plant−1, 1000‐seed weight, and seed yield, respectively, whereas GE explained most of the remaining variation. A combination of AMMI‐1 biplots and AMMI stability values found variability in genotypic response to environments for seed yield suggesting cultivar recommendations should be environment specific.
Visualization of supramolecular assembly by aggregation‐induced emission
Authors: Guo Wu‐Jie , Peng Tuokai , Zhu Wenping , Ma Shixiang , Wang Guang , Li Ying , Liu Bin , Peng Hui‐Qing
Published: December 2022

Supramolecular architectures are constructed by the self‐assembly of small building blocks via the use of metal‐ligand coordination, π–π stacking interactions, hydrogen bonding, host‐guest interactions, and other noncovalent driving forces, which confer unique dynamic reversibility and stimulus responsiveness to the supramolecular materials and also lead to the demand of expensive and complex equipment for the characterization of supramolecular assembly processes. Fortunately, the self‐assembly processes bring the monomeric chromophores together, offering possibilities to establish ties between the supramolecular assembly and aggregation‐induced emission (AIE) techniques. Compared to conventional luminescent molecules, AIE luminogens (AIEgens) exhibit significant fluorescence enhancement upon the restriction of molecular motions, thus displaying the advantages of signal amplification and low background noises. Given the above, the real‐time, sensitive, and in situ visualization of the formation of self‐assemblies and their stimuli responsiveness based on AIE becomes accessible. Here, we review recent works that encompass the visualization of supramolecular assembly‐related behaviors by means of AIE characteristics of chromophores. The organization of this review will be by different types of supramolecular architectures, including metallacycles/cages, micelles/vesicles, supramolecular polymers, and supramolecular gels. An overview of future opportunities and challenges for the real‐time monitoring of supramolecular assembly by AIE is also provided.
The impact of COVID‐19 on the number of births in Yucatan, Mexico
Authors: Azcorra Hugo , Salazar‐Rendón Juan Carlos , Rodríguez Luis , Vázquez‐Vázquez Adriana , Mendez‐Dominguez Nina
Published: December 2022

Objective

To analyze the impact of COVID‐19 on the number of births in Yucatan, Mexico during 2020 and 2021.

Material and Methods

A total of 470 651 live births occurred in Yucatan from January 1st, 2008, to December 31st, 2021, and were included in the analysis. The monthly number of births observed during January 2008–February 2020 was used to describe pre‐pandemic trends. Time‐series analysis was applied to examine whether the number of births observed from December 2020 (9 months after the beginning of the pandemic) to December 2021 differed from the expected values. Trends in the number of births according to maternal age, parity and education were examined to identify changes differentiated by sociodemographic characteristics.

Results

The number of births in 2021 decreased by 18% (5869 births) compared with 2019, which represents a reduction from 12.89 to 12.48 per thousand inhabitants. The observed number of births from December 2020 to July 2021 was significantly lower than the figure expected. April (expected = 2863 vs. observed = 1722), May (expected = 2948 vs. observed = 1990), and June (expected = 2997 vs. observed = 1978) 2021 showed the largest differences between expected and observed values. Then, from August to December 2021, the observed number of births fell within the expected range. Birth decline was slightly more pronounced among mothers between 20 and 29 years of age and in those without previous offspring.

Conclusion

We provide evidence of birth decline in Yucatan during the COVID‐19 pandemic. Birth rate reduction in Yucatan doubled the world average and young women without children were the most affected.
The ancient inhabitants of the Chonos Archipelago (~43°–47°S): Characterization of maritime hunter‐gatherers from Western Patagonia using mitochondrial DNA
Authors: Moraga Mauricio , de la Fuente Constanza , Galimany Jacqueline , Orellana‐Soto Michael , Reyes Omar
Published: December 2022

Background

Within the southern end of South America, Western Patagonia arises as an intricate region of channels, fjords, and islands. This region holds evidence of human occupation since ca. 14,500 cal years BP, with distinctive maritime adaptations developing around 7300 cal years BP. Historically, three major populations were characterized as part of these maritime traditions: Yámana, Kawésqar, and Chono. The arrival of European population had a profound impact in these communities, affecting their lifestyles, territory and population size and health. The northernmost populations, living within the Chonos Archipelago, were the most affected and the least known communities from Western Patagonia.

Objectives

This research aims to characterize the mitochondrial DNA diversity of ancient individuals from the Chonos Archipelago, evaluating their genetic affinities with other ancient and present‐day populations from Patagonia.

Materials and Methods

A total of 46 individuals from the region were sampled for ancient DNA analysis. Mitochondrial DNA haplogroups were characterized and compared with ancient and present‐day populations from Southern South America.

Results

All individuals from the Chonos Archipelago belong to C and D haplogroups, particularly to C1b, C1b13, D1, D1g, and D4h3a5. As a group, the individuals from Chonos Archipelago lay closer to ancient individuals from Kawésqar territory, immediately south of them. Using mitogenomes, we characterized two new D4h3a5 lineages almost exclusively associated with populations from Western Patagonia.

Discussion

Our results contribute to the understanding of the peopling and human interactions in Western Patagonia, suggesting these unique maritime traditions developed within local populations, genetically associated with earlier terrestrial populations.
A Telomerase‐Assisted Strategy for Regeneration of DNA Nanomachines in Living Cells
Authors: Zhang Qianying , Wang Yihan , Wang Wenjing , Min Qianhao , Zhang Jian‐Rong , Zhu Jun‐Jie
Published: December 2022

DNA nanomachines have been engineered into diverse personalized devices for diagnostic imaging of biomarkers; however, the regeneration of DNA nanomachines in living cells remains challenging. Here, we report an ingenious DNA nanomachine that can implement telomerase (TE)‐activated regeneration in living cells. Upon apurinic/apyrimidinic endonuclease 1 (APE1)‐responsive initiation of the nanomachine, the walker of the nanomachine moves along tracks regenerated by TE, generating multiply amplified signals through which APE1 can be imaged in situ. Additionally, augmentation of the signal due to the regeneration of the nanomachines could reveal differential expression of TE in different cell lines. To the best of our knowledge, this is the first proof‐of‐concept demonstration of the use of biomarkers to assist in the regeneration of nanomachines in living cells. This study offers a new paradigm for the development of more applicable and efficient DNA nanomachines.
Ru3(CO)12‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates
Authors: Lin Lin , Zhang Xue‐jun , Xu Xinyu , Zhao Yue , Shi Zhuangzhi
Published: December 2022

Hemilabile ligands have been applied extensively in transition metal catalysis, but preparations of these molecules typically require multistep synthesis. Here, modular assembly of diverse phosphine‐amide ligands, including related axially chiral compounds, is first reported through ruthenium‐catalyzed C−H activation of phosphines with isocyanate directed by phosphorus(III) atoms. High reactivity and regioselectivity can be obtained by using a Ru3(CO)12catalyst with a mono‐N‐protected amino acid ligand. This transformation significantly expands the pool of phosphine‐amide ligands, some of which have shown excellent efficiency for asymmetric catalysis. More broadly, the discovery constitutes a proof of principle for facile construction of hemilabile ligands directly from the parent monodentate phosphines by C−H activation with ideal atom, step and redox economy. Several dinuclear ruthenium complexes were characterized by single‐crystal X‐ray diffraction analysis revealing the key mechanistic features of this transformation.
Low‐Valent MxAl3Cluster Salts with Tetrahedral [SiAl3]+and Trigonal‐Bipyramidal [M2Al3]2+Cores (M=Si/Ge)
Authors: Dabringhaus Philipp , Zedlitz Silja , Giarrana Luisa , Scheschkewitz David , Krossing Ingo
Published: December 2022

Schnöckel's [(AlCp*)4] and Jutzi's [SiCp*][B(C6F5)4] (Cp*=C5Me5) are landmarks in modern main‐group chemistry with diverse applications in synthesis and catalysis. Despite the isoelectronic relationship between the AlCp* and the [SiCp*]+fragments, their mutual reactivity is hitherto unknown. Here, we report on their reaction giving the complex salts [Cp*Si(AlCp*)3][WCA] ([WCA]−=[Al(ORF)4]−and [F{Al(ORF)3}2]−; RF=C(CF3)3). The tetrahedral [SiAl3]+core not only represents a rare example of a low‐valent silicon‐doped aluminium‐cluster, but also—due to its facile accessibility and high stability—provides a convenient preparative entry towards low‐valent Si−Al clusters in general. For example, an elusive binuclear [Si2(AlCp*)5]2+with extremely short Al−Si bonds and a high negative partial charge at the Si atoms was structurally characterised and its bonding situation analysed by DFT. Crystals of the isostructural [Ge2(AlCp*)5]2+dication were also obtained and represent the first mixed Al−Ge cluster.
Co‐Dissolved Isostructural Polyoxovanadates to Construct Single‐Atom‐Site Catalysts for Efficient CO2Photoreduction
Authors: Wang Yu‐Jie , Zhuang Gui‐Lin , Zhang Jiang‐Wei , Luo Fang , Cheng Xin , Sun Fu‐Li , Fu Shan‐Shan , Lu Tong‐Bu , Zhang Zhi‐Ming
Published: December 2022

We explored a co‐dissolved strategy to embed mono‐dispersed Pt center into V2O5support via dissolving [PtV9O28]7−into [V10O28]6−aqueous solution. The uniform dispersion of [PtV9O28]7−in [V10O28]6−solution allows [PtV9O28]7−to be surrounded by [V10O28]6−clusters via a freeze‐drying process. The V centers in both [PtV9O28]7−and [V10O28]6−were converted into V2O5via a calcination process to stabilize Pt center. These double separations can effectively prevent the Pt center agglomeration during the high‐temperature conversion process, and achieve 100 % utilization of Pt in [PtV9O28]7−. The resulting Pt‐V2O5single‐atom‐site catalysts exhibit a CH4yield of 247.6 μmol g−1 h−1, 25 times higher than that of Pt nanoparticle on the V2O5support, which was accompanied by the lactic acid photooxidation to form pyruvic acid. Systematical investigations on this unambiguous structure demonstrate an important role of Pt−O atomic pair synergy for highly efficient CO2photoreduction.
In situ Detection of Cobaloxime Intermediates During Photocatalysis Using Hollow‐Core Photonic Crystal Fiber Microreactors
Authors: Lawson Takashi , Gentleman Alexander S. , Pinnell Jonathan , Eisenschmidt Annika , Antón‐García Daniel , Frosz Michael H. , Reisner Erwin , Euser Tijmen G.
Published: December 2022

Hollow‐core photonic crystal fibers (HC‐PCFs) provide a novel approach for in situ UV/Vis spectroscopy with enhanced detection sensitivity. Here, we demonstrate that longer optical path lengths than afforded by conventional cuvette‐based UV/Vis spectroscopy can be used to detect and identify the CoI and CoII states in hydrogen‐evolving cobaloxime catalysts, with spectral identification aided by comparison with DFT‐simulated spectra. Our findings show that there are two types of signals observed for these molecular catalysts; a transient signal and a steady‐state signal, with the former being assigned to the CoI state and the latter being assigned to the CoII state. These observations lend support to a unimolecular pathway, rather than a bimolecular pathway, for hydrogen evolution. This study highlights the utility of fiber‐based microreactors for understanding these and a much wider range of homogeneous photocatalytic systems in the future.
Ligand Dilution Analysis Facilitates Aptamer Binding Characterization at the Single‐Molecule Level
Authors: Du Yulin , Lyu Yifan , Li Shiquan , Ding Ding , Chen Jianghuai , Yang Cai , Sun Yang , Qu Fengli , Xiao Zeyu , Jiang Jianhui , Tan Weihong
Published: December 2022

Cell‐specific aptamers offer a powerful tool to study membrane receptors at the single‐molecule level. Most target receptors of aptamers are highly expressed on the cell surface, but difficult to analyze in situ because of dense distribution and fast velocity. Therefore, we herein propose a random sampling‐based analysis strategy termed ligand dilution analysis (LDA) for easily implemented aptamer‐based receptor study. Receptor density on the cell surface can be calculated based on a regression model. By using a synergistic ligand dilution design, colocalization and differentiation of aptamer and monoclonal antibody (mAb) binding on a single receptor can be realized. Once this is accomplished, precise binding site and detailed aptamer‐receptor binding mode can be further determined using molecular docking and molecular dynamics simulation. The ligand dilution strategy also sets the stage for an aptamer‐based dynamics analysis of two‐ and three‐dimensional motion and fluctuation of highly expressed receptors on the live cell membrane.
Nanostructured Heterogeneous Catalysts for Bioorthogonal Reactions
Authors: Sousa‐Castillo Ana , Mariño‐López Andrea , Puértolas Begoña , Correa‐Duarte Miguel A.
Published: December 2022

Bioorthogonal chemistry has inspired a new subarea of chemistry providing a powerful tool to perform novel biocompatible chemospecific reactions in living systems. Following the premise that they do not interfere with biological functions, bioorthogonal reactions are increasingly applied in biomedical research, particularly with respect to genetic encoding systems, fluorogenic reactions for bioimaging, and cancer therapy. This Minireview compiles recent advances in the use of heterogeneous catalysts for bioorthogonal reactions. The synthetic strategies of Pd‐, Au‐, and Cu‐based materials, their applicability in the activation of caged fluorophores and prodrugs, and the possibilities of using external stimuli to release therapeutic substances at a specific location in a diseased tissue are discussed. Finally, we highlight frontiers in the field, identifying challenges, and propose directions for future development in this emerging field.
Electronic Perturbation of Copper Single‐Atom CO2Reduction Catalysts in a Molecular Way
Authors: Zou Haiyuan , Zhao Gang , Dai Hao , Dong Hongliang , Luo Wen , Wang Lei , Lu Zhouguang , Luo Yi , Zhang Guozhen , Duan Lele
Published: December 2022

Fine‐tuning electronic structures of single‐atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron‐withdrawing/‐donating groups, we show herein the electronic perturbation of Cu single‐atom CO2reduction catalysts in a molecular way. The elaborately introduced functional groups (−F, −H and −OMe) can regulate the valance state of Cuδ+, which is found to be directly scaled with the selectivity of the electrochemical CO2‐to‐CH4conversion. An optimum CH4Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F‐substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cuδ+centers adjusted by the electron‐withdrawing group decrease the pKaof adsorbed H2O, promoting the hydrogenation of intermediates toward the CH4production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.
Boosting the Activity of Pd Single Atoms by Tuning Their Local Environment on Ceria for Methane Combustion
Authors: Yang Weiwei , Polo‐Garzon Felipe , Zhou Hua , Huang Zhennan , Chi Miaofang , Meyer Harry , Yu Xinbin , Li Yuanyuan , Wu Zili
Published: December 2022

Supported Pd single atom catalysts (SACs) have triggered great research interest in methane combustion yet with contradicting views on their activity and stability. Here, we show that the Pd SAs can take different electronic structure and atomic geometry on ceria support, resulting in different catalytic properties. By a simple thermal pretreatment to ceria prior to Pd deposition, a unique anchoring site is created. The Pd SA, taking this site, can be activated to Pdδ+ (0<δ<2) that has greatly enhanced activity for methane oxidation: T50 lowered by up to 130 °C and almost 10 times higher turnover frequency compared to the untreated catalyst. The enhanced activity of Pdδ+ site is related to its oxygen‐deficient local structure and elongated interacting distance with ceria, leading to enhanced capability in delivering reactive oxygen species and decomposing reaction intermediates. This work provides insights into designing highly efficient Pd SACs for oxidation reactions.
Polystyrene waste‐modified epoxy/nanoclay and hybrid composite coatings
Authors: Özmeral Nimet , Kocaman Suheyla , Soydal Ulku , Ahmetli Gulnare
Published: December 2022

In this study, phenolic novolac‐type epoxy (EPN) resin was modified with 4 wt% thermoplastic polystyrene (PS) waste and was used as the polymer matrix for the first time. Two types of composites were prepared: (i) nanocomposites with 1–3 wt% nanoclay (NC) and (ii) hybrid composites. Pristine (NC) and tetramethylammonium chloride modified nanoclays (MNC) were used at a 2 wt% ratio in hybrid composites with 25–35 wt% red mud waste (RMW). The corrosion protection properties of the coatings were determined by immersion test in 5 wt% NaOH, HCl, and NaCl solutions. The water sorption of hybrid composites varied between 1%–3.6% and 1%–5.3%, while it was between 0.82% and 1.02% in EPN‐PS/NC nanocomposites. The weight gain percentage values of hybrid composites in corrosive media for the base and salt solutions were determined much lower (0.59%–0.75% and 0.46%–0.59%, respectively) than water sorption. Surface morphologies of hybrid composites were examined by scanning electron microscopy before and after corrosion tests. MNC‐30 wt% RMW hybrid composite was found more suitable due to high corrosion resistance in basic and salty environments, storage modulus, loss modulus, and glass transition temperature (Tg) values (90.6°C) as compared with NC‐30 wt% RMW hybrid composite.
An enriched mixture model for functional clustering
Authors: Rigon Tommaso
Published: December 2022

There is an increasingly rich literature about Bayesian nonparametric models for clustering functional observations. Most recent proposals rely on infinite‐dimensional characterizations that might lead to overly complex cluster solutions. In addition, while prior knowledge about the functional shapes is typically available, its practical exploitation might be a difficult modeling task. Motivated by an application in e‐commerce, we propose a novel enriched Dirichlet mixture model for functional data. Our proposal accommodates the incorporation of functional constraints while bounding the model complexity. We characterize the prior process through a urn scheme to clarify the underlying partition mechanism. These features lead to a very interpretable clustering method compared to available techniques. Moreover, we employ a variational Bayes approximation for tractable posterior inference to overcome computational bottlenecks.
Autism‐related language preferences of English‐speaking individuals across the globe: A mixed methods investigation
Authors: Keating Connor Tom , Hickman Lydia , Leung Joan , Monk Ruth , Montgomery Alicia , Heath Hannah , Sowden Sophie
Published: December 2022

Over the past two decades, there have been increasing discussions around which terms should be used to talk about autism. Whilst these discussions have largely revolved around the suitability of identity‐first language and person‐first language, more recently this debate has broadened to encompass other autism‐related terminology (e.g., ‘high‐functioning’). To date, academic studies have not investigated the language preferences of autistic individuals outside of the United Kingdom or Australia, nor have they compared levels of endorsement across countries. Hence, the current study adopted a mixed‐methods approach, employing both quantitative and qualitative techniques, to explore the linguistic preferences of 654 English‐speaking autistic adults across the globe. Despite variation in levels of endorsement between countries, we found that the most popular terms were similar—the terms ‘Autism’, ‘Autistic person’, ‘Is autistic’, ‘Neurological/Brain Difference’, ‘Differences’, ‘Challenges’, ‘Difficulties’, ‘Neurotypical people’, and ‘Neurotypicals’ were consistently favored across countries. Despite relative consensus across groups, both our quantitative and qualitative data demonstrate that there is no universally accepted way to talk about autism. Our thematic analysis revealed the reasons underlying participants’ preferences, generating six core themes, and illuminated an important guiding principle—to respect personal preferences. These findings have significant implications for informing practice, research and language policy worldwide.
A Climate Action Plan for the California Department of Water Resources
Authors: Arnold Wyatt , Spanos Katherine A. , Schwarz Andrew , Doan Chi , Deaver Katerina , Akens Mary U. , Maendly Romain , Selmon Michelle , Ekstrom Julia , Coombe Peter , Andrew John
Published: December 2022

Key Takeaways

Greenhouse gas mitigation and adaptation to climate change vulnerabilities should be incorporated into existing utility business and project management processes.

A comprehensive climate action plan can meet and exceed legal requirements, reduce risk, achieve business process efficiencies, apply best available science, and demonstrate social responsibility.

Focused internal workgroups, expert consultation, inspired management, feedback loops, breadth of application, and quantitative detail are critical to success.
Internet of Construction: Potenziale von LoRaWAN für die Qualitätssicherung im Ortbetonprozess
Authors: Wildemann Peter R. , Brell‐Cokcan Sigrid
Published: December 2022

Um bei der Verwendung von Ortbeton die hohen Qualitätssicherungsstandards zu erfüllen, ist bisweilen ein großer manueller Dokumentationsaufwand erforderlich. Insbesondere der Einbau bedarf großer Aufmerksamkeit, da die Verwendung des richtigen Betons im vorgesehenen Bauteil sichergestellt werden muss und Fehler einen zeitlichen und kostenmäßigen Mehraufwand bedeuten. In anderen Branchen ist zu beobachten, dass zur Unterstützung der Ausführungsprozesse sowie bei der Dokumentation bereits häufig Internet‐of‐Things (IoT)‐Systeme gewinnbringend eingesetzt werden. Trotz zahlreicher zur Verfügung stehender digitaler Lösungen ist der Einsatz von IoT‐Technologien für ebendiese Monitoringaufgaben auf der Baustelle jedoch nur selten zu beobachten. Dabei haben die Technologien das Potenzial, die Maßnahmen zur Qualitätssicherung zu vereinfachen und das Bauen attraktiver zu machen. Dieser Aufsatz behandelt den Prozessschritt des Betoneinbaus innerhalb der Wertschöpfungskette im Ortbetonbau, der bislang überwiegend manuell abläuft, ein hohes Fehlerrisiko birgt und sehr dokumentationsaufwendig ist. Es wird ein auf Long Range Wide Area Networt (LoRaWAN) basierendes IoT‐System konzipiert, das den Menschen bei der Dokumentation der Betonagen unterstützt. Anschließend wird das System auf einer Baustelle einem Praxistest unterzogen. Es erfolgt der Abgleich der Ergebnisse mit den prozessbezogenen Anforderungen, wobei sich zeigt, dass bereits mit dem präsentierten Setup einige wichtige Anforderungen zufriedenstellend erfüllt werden.
DEPDC1as a crucial factor in the progression of human osteosarcoma
Authors: Shen Lin , Li Han , Liu Ronghan , Zhou Chendan , Bretches Morgan , Gong Xuan , Lu Laitong , Zhang Ying , Zhao Kai , Ning Bin , Yang Shang‐You , Zhang Aijun
Published: December 2022

Objective

Novel therapeutic strategies are emerging with the increased understanding of the underlying mechanisms of human osteosarcoma. This current study tends to decipher the potentially critical role of DEP domain‐containing 1 (DEPDC1), a tumor‐related gene, during the progression of osteosarcoma.

Methods

Bioinformatics analysis of 25,035 genes from the National Center for Biotechnology Information (NCBI) databases was performed to screen differentially expressed genes between osteosarcoma and normal control groups, complemented by the examination of 85 clinical osteosarcoma specimens. Furthermore, the manipulation ofDEPDC1expression levels by using silencing RNA (siRNA) or lentiviral vector intervention on human osteosarcoma cells was performed to reveal its role and interactions in in vitro and in vivo settings.

Results

Gene expression profile analysis and immunohistochemical (IHC) examination suggested thatDEPDC1is highly expressed in human osteosarcoma cells and tumor tissue. The silencing ofDEPDC1arrested osteosarcoma cell proliferation, promoted apoptosis, and ceased tumor metastasis. Studies involving clinical human osteosarcoma cases exhibited a strong correlation ofDEPDC1over‐expressed osteosarcoma specimens with a reduced patient survival rate.

Conclusions

Collectively, this study demonstrated thatDEPDC1is a critical driver in the promotion of osteosarcoma progression and results in poor patient prognosis. Genetically targeting or pharmacologically inhibitingDEPDC1may serve as a promising strategy for treating human osteosarcoma.
Neoadjuvant chemotherapy and radiotherapy outcomes in borderline‐resectable and locally‐advanced pancreatic cancer patients
Authors: Botta Gregory P. , Huynh Tridu R. , Spierling‐Bagsic Samantha R. , Agelidis Alexander , Schaffer Randolph , Lin Ray , Sigal Darren
Published: December 2022

Background

There is no agreed upon standard of care for borderline‐resectable pancreatic cancer (BRPC) or locally‐advanced pancreatic cancer (LAPC) patients regarding the benefit of chemotherapy or radiation alone or in combination.

Patients and Methods

We completed a retrospective cohort analysis of BRPC and LAPC patients at a cancer center with expertise in multi‐disciplinary pancreatic ductal adenocarcinoma (PDAC) treatment over a 5‐year period from 03/01/2014 to 03/01/2019 (cut‐off date). The total evaluable newly diagnosed, treatment naïve, BRPC, and LAPC patients with adequate organ function and ability to obtain treatment after multidisciplinary review was 52 patients. After analysis, patients were evaluated for rates of resection, extent of resection (R0 or R1), median progression‐free survival (mPFS), and median overall survival (mOS).

Results

Patients were treated with chemotherapy alone (gemcitabine and nab‐paclitaxel = 77% (20/26); FOLFIRINOX = 19% (5/26); single agent gemcitabine 3.8% (1/26)), or chemotherapy followed by chemoradiation (gemcitabine +5 Gy × 5 weeks), or chemoradiation alone prior to re‐staging and potential resection. Of the 29% (15/52) of patients who went on to surgical resection, 73% (11/15) achieved R0 resection. An R0 resection was achieved in 35% (9/26) of patients treated with chemotherapy alone, 7.6% (1/13) in a patient treated with chemotherapy followed by radiation, and 7.6% (1/13) with concurrent chemoradiotherapy alone. Chemotherapy alone achieved a mPFS of 16.4 months (p  < 0.0025) and mOS of 26.2 months (p  < 0.0001), chemotherapy followed by chemoradiation was 13.0 months and 14.9 months respectively, while concurrent chemoradiotherapy was 6.9 months and 7.3 months.

Conclusions and Relevance

BRPC and LAPC patients capable of surgery after only receiving neoadjuvant treatment with chemotherapy had higher rates of R0 resection with prolonged median PFS and OS compared with any patient needing combination chemotherapy with radiotherapy.
Application of Date Palm Surface Fiber as an Efficient Biosorbent for Wastewater Treatment
Authors: Al Arni Saleh , Elwaheidi Mahmoud , Converti Attilio , Benaissa Mhamed , Salih Alsamani A. M. , Ghareba Saad , Abbas Nadir
Published: December 2022

The significance of using date palm surface fiber as a biosorbent to remove pollutants from wastewater is evaluated. This material, which has advantages over other natural adsorbing materials, for being inexpensive, renewable, eco‐friendly, and available in large scale worldwide, has been widely used for the removal of several types of pollutants such as acid and basic dyes, heavy metals, pesticides, oils, and organic compounds. In addition to its use as an effective biosorbent to remove pollutants from wastewater, date palm surface fiber exhibits wide future perspectives in several other applications.
Single arterial access closure of post‐infarction ventricular septal defect: A case series
Authors: Doost Ata , Chilmeran Ahmed , Gomes Arionilson , Dworakowski Rafal , Eskandari Mehdi , MacCarthy Philip , Cockburn James , Byrne Jonathan , Hildick‐Smith David
Published: December 2022

Background

Post‐infarction ventricular septal defect (PIVSD) carries a very poor prognosis. Surgical repair offers reasonable outcomes in patients who survive the initial healing period. Percutaneous device implantation remains a potentially effective earlier alternative.

Methods and Results

From March 2018 to May 2022, 11 trans‐arterial PIVSD closures were attempted in 9 patients from two centers (aged 67.2 ± 11.1 years; 77.8% male). Two patients had a second procedure. Myocardial infarction was anterior in four patients (44.5%) and inferior in five cases (55.5%). Devices were successfully implanted in all patients. There were no major immediate procedural complications. Immediate shunt grade postprocedure was significant (11.1%), minimal (77.8%), or none (11.1%). Median length of stay after the procedure was 14.8 days. Five patients (55%) survived to discharge and were followed up for a median of 605 days, during which time no additional patients died.

Conclusion

Single arterial access for percutaneous closure of PIVSD is a good option for these extremely high‐risk patients, in the era of effective large‐bore arterial access closure. Mortality remains high, but patients who survive to discharge do well in the longer term.