bluuebunny/crossref_metadata_2025 huggingface dataset:
Perspectives on Improving the Safety and Sustainability of High Voltage Lithium‐Ion Batteries Through the Electrolyte and Separator Region
Authors: Cavers Heather , Molaiyan Palanivel , Abdollahifar Mozaffar , Lassi Ulla , Kwade Arno
Published: May 2022

Lithium‐ion batteries (LIBs) are promising candidates within the context of the development of novel battery concepts with high energy densities. Batteries with high operating potentials or high voltage (HV) LIBs (>4.2 V vs Li+/Li) can provide high energy densities and are therefore attractive in high‐performance LIBs. However, a variety of challenges (including solid electrolyte interface (SEI), lithium plating, etc.) and related safety issues (such as gas formation or thermal runaway effects) must be solved for the practical, widespread application of HV‐LIBs. Most of these challenges arise in the region between the electrodes: the electrolyte region. This review provides an overview of recent development and progress on the electrolyte region, including liquid electrolytes, ionic liquids, gel polymer electrolytes, separators, and solid electrolytes for HV‐LIBs applications. A focus on improving the safety of these systems, with some perspectives on their relative cost and environmental impact, is given. Overall, the new information is encouraging for the development of HV‐LIBs, and this review serves as a guide for potential strategies to improve their safety, allowing the development of HV‐LIBs, including solid‐state batteries, to be accelerated to practical relevance.
Improving Heat Transfer Enables Durable Perovskite Solar Cells
Authors: Yang Ning , Pei Fengtao , Dou Jie , Zhao Yizhou , Huang Zijian , Ma Yue , Ma Sai , Wang Chenyue , Zhang Xiao , Wang Hao , Zhu Cheng , Bai Yang , Zhou Huanping , Song Tinglu , Chen Yihua , Chen Qi
Published: May 2022

Special attention should be devoted to the thermal stability of hybrid perovskite solar cells (PSCs), because they are often operated at elevated temperatures. However, effective strategies are lacking for manipulation of heat flow in PSCs to improve their thermal stability. Here, a holistic solution is reported for the rapid removal of dissipated heat within the absorber by introducing hexagonal boron nitride (h‐BN) inside and radiator fin outside of the device. This strategy significantly improves the thermal conductivity of perovskite and speeds up the heat transfer of device, which effectively reduces the cell temperature under illumination of simulated AM 1.5G standard spectrum by ≈6.5 °C. Regardless of device configurations, the corresponding PSCs exhibit prolonged lifetimes aged at different temperatures, continuously operated under white light‐emitting diode (LED) lamp or full‐spectrum illumination. Of particular note, the optimized h‐BN/Cu device with n–i–p structure keeps 88% and 93% of its initial PCE after 1776 h of 85 °C thermal aging and 2451 h of maximum power point (MPP) tracking, respectively, and the device with p–i–n structure maintains 96% and 92% of its original PCE after 1704 h of 85 °C thermal aging and 2164 h of MPP tracking.
An Overall Understanding of Sodium Storage Behaviors in Hard Carbons by an “Adsorption‐Intercalation/Filling” Hybrid Mechanism
Authors: Chen Xiaoyang , Tian Jiyu , Li Peng , Fang Youlong , Fang Yongjin , Liang Xinmiao , Feng Jiwen , Dong Jiao , Ai Xinping , Yang Hanxi , Cao Yuliang
Published: May 2022

Hard carbon has the potential to serve as a high‐capacity anode material for sodium‐ion batteries (SIBs), however, its Na+ storage mechanism, particularly on the low potential plateau, remains controversial. To overcome this issue, two types of hard carbons with different microstructures are employed and the relationship between the microstructures and Na+ storage behaviors is evaluated. By the combination of operando X‐ray diffraction, ex situ Raman spectroscopy, NMR, and theoretical calculation, it is found that the sodium storage capacities of the hard carbons in the low potential plateau region contain the concurrent contributions from both interlayer intercalation and micropores filling, and the ratio of the two contributors greatly depends on the microstructure of hard carbon materials. Moreover, an electrochemical pointer (potential inflection point at the end of the discharge curve) is found to distinguish the dominance of interlayer intercalation and the micropores filling processes of sodium ions in the low potential plateau region. Based on this new finding, a microstructure‐dependent mechanism (“adsorption‐intercalation/filling” hybrid mechanism) is proposed to achieve an overall understanding of the sodium storage behaviors in different hard carbon materials, which may provide deep insight into the rational design of hard carbon structures as high‐performance anode materials for advanced SIBs.
Reversible Activation of V4+/V5+ Redox Couples in NASICON Phosphate Cathodes
Authors: Xu Chunliu , Zhao Junmei , Wang Yi‐Ao , Hua Weibo , fu Qiang , Liang Xinmiao , Rong Xiaohui , Zhang Qiangqiang , Guo Xiaodong , Yang Chao , Liu Huizhou , Zhong Benhe , Hu Yong‐Sheng
Published: May 2022

Na superionic conductor structured Na3V2(PO4)3 cathodes have attracted great interest due to their long cycling lifespan and high thermal stability rendered by the robust 3D framework. However, their practical application is still hindered by the high cost of raw materials and limited energy density. Herein, a doping strategy with low‐cost Fe2+ is developed to activate V4+/V5+ redox, in an attempt to increase the energy density of phosphate cathodes. It is also revealed that reversible activation of V4+/V5+ redox is related to the Na positions (Na1, 6b; Na2, 18e). Only the V‐based compounds with enough Na2 content can activate the V4+/V5+ reversibly. More importantly, without presodiation treatment and addition of any sodiation agent, Na3.4V1.6Fe0.4(PO4)3 is delicately designed as both cathode and the Na self‐compensation agent in full cells, allowing a promising energy density of ≈260 Wh kg−1. This work sheds light on enhancing the energy density, and designing Na self‐compensation for practical Na‐ions batteries.
Developing adaptive performance: A conceptual model to guide simulation‐based training design
Authors: Fernandez Rosemarie , Rosenman Elizabeth D. , Plaza‐Verduin Martiza , Grand James A.
Published: May 2022

Objectives

Effective emergency department care requires individuals and teams to adapt to changes in patient condition, team factors, environmental issues, and system‐level challenges. Adaptability is often listed as an important skill for emergency medicine physicians; however, conceptual models describing the processes involved in adaptive performance have not been translated for health care settings. Similarly, educators have not described training design strategies that support the development of adaptive performance.

Methods

We examined the team science and health care literatures for key concepts in adaptive performance, health care team performance, and diagnostic decision‐making. Using expert consensus, we integrated these concepts to develop the team adaptive performance model and to identify training design approaches that support the development of adaptability.

Results

We identify nine training principles supported by the team adaptive performance model and the adaptive learning system. Each training principle is accompanied by recommendations and mechanisms for implementation in emergency medicine simulation–based education.

Conclusion

Training experiences can be designed to target processes that support adaptive performance.
Effect of polyethylene pipe on wax deposition under different temperature and flow rate conditions
Authors: Zhang Yu , Huang Qiyu , Liu Yamei , Liu Yiran , Li Rongbin , Wang Yijie , Zhang Xun
Published: May 2022

Wax deposition is an important but troublesome boulder in petroleum industry that has always plagued pipeline engineering operators. In this study, wax deposition in the polyethylene pipes has different behaviors comparing wax deposition in stainless steel pipes such as smaller weight of wax deposits and lower wax content. After wax deposition experiments, some important parameters, including diffusivity and temperature gradient, were measured and calculated to explore the differences between two material pipes. Moreover, those factors can make a significant impact on radial mass flux. A series of results in polyethylene pipes suggests that higher diffusivity enhances diffusion flux of wax in the radial direction. But it was found that radial concentration gradient accounted for a larger proportion. These factors are the relationship of competition and cooperation and the combination of them results in different performances of wax deposition between polyethylene and stainless steel pipes.
A Stimuli‐Responsive Small‐Molecule Metal‐Carrying Prochelator: A Novel Prodrug Design Strategy for Metal Complexes
Authors: Huang Zeqian , Luo Yong , Zhang Tao , Ding Yaqing , Chen Meixu , Chen Jie , Liu Qiuxing , Huang Yanjuan , Zhao Chunshun
Published: May 2022

Selective activation of prodrugs is an important approach to reduce the side effects of disease treatment. We report a prodrug design concept for metal complexes, termed “metal‐carrying prochelator”, which can co‐carry a metal ion and chelator within a single small‐molecule compound and remain inert until it undergoes a specifically triggered intramolecular chelation to synthesize a bioactive metal complex in situ for targeted therapy. As a proof‐of‐concept, we designed a H2O2‐responsive small‐molecule prochelator, DPBD, based on the strong chelator diethyldithiocarbamate (DTC) and copper. DPBD can carry Cu2+ (DPBD‐Cu) and respond to elevated H2O2 levels in tumor cells by releasing DTC, which rapidly chelates Cu2+ from DPBD‐Cu affording a DTC–copper complex with high cytotoxicity, realizing potent antitumor efficacy with low systemic toxicity. Thus, with its unique intramolecularly triggered activation mechanism, this concept based on a small‐molecule metal‐carrying prochelator can help in the prodrug design of metal complexes.
Constructing Organic Electroluminescent Material with Very High Color Purity and Efficiency Based on Polycyclization of the Multiple Resonance Parent Core
Authors: Xu Yincai , Wang Qingyang , Wei Jinbei , Peng Xiaomei , Xue Jianan , Wang Zhiheng , Su Shi‐Jian , Wang Yue
Published: May 2022

Multiple resonance thermally activated delayed fluorescence (MR‐TADF) compounds have set off an upsurge of research because of their tremendous application prospects in the field of wide color gamut display. Herein, we propose a novel MR‐TADF molecular construction paradigm based on polycyclization of the multiple resonance parent core, and construct a representative multiple resonance polycyclic aromatic hydrocarbon (MR‐PAH) based on the para‐alignment of boron and nitrogen atoms into a six‐membered ring (p‐BNR). Through the retrosynthesis analysis, a concise synthesis strategy with wide applicability has been proposed, encompassing programmed sequential boron esterification, Suzuki coupling and Scholl oxidative coupling. The target model molecule BN‐TP shows green fluorescence with an emission peak at 523 nm and a narrow full‐width at half‐maximum (FWHM) of 34 nm. The organic light‐emitting diode (OLED) employing BN‐TP as an emitter exhibits ultrapure green emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.26, 0.70), and achieves a maximum external quantum efficiency (EQE) of 35.1 %.
Carbon dioxide embolism during posterior retroperitoneal adrenalectomy
Authors: Alexeev M. , Fedorov E. , Kuleshov O. , Rebrova D. , Efremov S.
Published: May 2022

We report a case of massive carbon dioxide embolism associated with injury to the inferior vena cava, during posterior retroperitoneoscopic adrenalectomy. The presenting clinical features were tachycardia, rapid oxygen desaturation and severe respiratory acidosis, without evidence of bleeding. The patient was resuscitated by increasing the fraction of inspired oxygen, administering intravenous fluid and converting to an open procedure to suture the vein. This case demonstrates that gas embolism due to vessel injury during posterior retroperitoneal adrenalectomy may arise without evidence of bleeding, severe hypotension or an abrupt increase in end‐tidal carbon dioxide. Using a high carbon dioxide insufflation pressure in the retroperitoneal space enhances visualisation of the surgical field by decreasing small‐calibre vessel bleeding. However, it can contribute to, and delay recognition of, carbon dioxide embolism. Knowledge of the clinical features of carbon dioxide embolism, careful monitoring and vigilance for intra‐operative surgical challenges can assist with the detection of this rare but potentially fatal complication.
Excellent antioxidizing, thermally insulating and flame resistance silica‐polybenzoxazine aerogels for aircraft ablative materials
Authors: Xiao Yunyun , Liu Saihui , Hu Yangbiao , Zhang Sizhao , Li Zhenquan , Li Liangjun , Feng Jian
Published: May 2022

High‐performance thermal protective composites with lightweight, micro‐ ablation and high‐efficient thermal insulation are urgently required for thermal protection systems in advanced hypersonic speed vehicles. However, the practical applications of thermal protective composites have long been hampered by the main issues such as low mass residual rate and poor long‐term antioxidation of the matrix in high‐temperature aerobic environments. Here, we report a novel silica‐polybenz oxazine (SiO2‐PBO) aerogels with interpenetrated networks, possessing the ability to antioxidation, thermal insulation, and flame‐retardant properties. The resulting SiO2‐PBO aerogels exhibit low density (0.25 g/cm3), low thermal conductivity (0.035 W/(m·K)), and superior peak heat release rate value (15.3 W/g). Moreover, the mass residual rate is up to 70.46 wt% in the N2 atmosphere and remains 57.83 wt% despite existing in the air atmosphere and experiencing the highest temperature of 800°C. Briefly, SiO2‐PBO aerogels as‐prepared could be a potential matrix for a new gene ration of high‐performance thermal protective composites in the future.
Tuning the ionic conductivity of flexible polyvinyl alcohol/sodium bromide polymer electrolyte films by incorporating silver nanoparticles for energy storage device applications
Authors: Cyriac Vipin , Molakalu Padre Shilpa , Ismayil  , Sangam Chandrashekar Gurumurthy , Chavan Chetan , Fakeerappa Bhajantri Rajashekhar , Murari Mudiyaru Subrahmanya
Published: May 2022

In this present work, we have synthesized silver nanoparticles (AgNPs) using the chemical reduction method and systematically studied the effect of AgNPs of different loading into polyvinyl alcohol/sodium bromide (PVA/NaBr) polymer electrolytes. X‐ray diffraction and Fourier transform infrared spectroscopy confirmed the variation in the crystallinity and complexation with AgNPs loading, respectively. AgNPs are uniformly distributed in the polymer matrix as depicted in FESEM. According to transport property studies, it is observed that carrier concentration has a strong influence on ionic conductivity. Additionally, I‐t studies showed that most charge carriers are ions and not electrons. The sample PVA/NaBr with AgNPs, prepared from 6 mM AgNO3 solution (PNAg6) with ionic conductivity 1.22 × 10−4 S cm−1 (one order increase with respect to undoped sample) and highest electrochemical stability window (ESW) of 2.86 V, can be chosen as a suitable candidate for energy storage device applications.
Bacteria in cancer therapy: A new generation of weapons
Authors: Fan Jun Ying , Huang Yuan , Li Yi , Muluh Tobias Achu , Fu Shao Zhi , Wu Jing Bo
Published: May 2022

Tumors are presently a major threat to human life and health. Malignant tumors are conventionally treated through radiotherapy and chemotherapy. However, traditional therapies yield unsatisfactory results due to high toxicity to the normal cells, inability to treat deep tumor tissues, and the possibility of inducing drug resistance in the tumor cells. This has caused immunotherapy to emerge as an effective and alternate treatment strategy. To overcome the limitations of the conventional treatments as well as to avert the risk of various drug resistance and cytotoxicity, bacterial anti‐tumor immunotherapy has raised the interest of researchers. This therapeutic strategy employs bacteria to specifically target and colonize the tumor tissues with preferential accumulation and proliferation. Such bacterial accumulation initiates a series of anti‐tumor immune responses, effectively eliminating the tumor cells. This immunotherapy can use the bacteria alone or concomitantly with the other methods. For example, the bacteria can deliver the anti‐cancer effect mediators by regulating the expression of the bacterial genes or by synthesizing the bioengineered bacterial complexes. This review will discuss the mechanism of utilizing bacteria in treating tumors, especially in terms of immune mechanisms. This could help in better integrating the bacterial method with other treatment options, thereby, providing a more effective, reliable, and unique treatment therapy for tumors.
A Low‐Potential and Stable Bis‐Dimethylamino‐Substituted Anthraquinone for pH‐Neutral Aqueous Redox Flow Batteries
Authors: Xia Lixing , Zhang Yujing , Wang Fuzhi , Chu Fengming , Yang Yun , Li Hui , Tan Zhan'ao
Published: May 2022

Quinone‐based aqueous redox flow batteries (RFBs) have drawn much attention due to their high safety, two‐electron involvement, rapid reaction kinetics, property tunability, and potentially low cost. RFBs operating in neutral solution feature a wide electrochemical window of around 2.5 V, which provides much more space for the design of redox‐active materials (RAMs) to realize a high voltage. However, it is still challenging to achieve low potential in the neutral condition for quinone‐based RAMs, owing to inherently pH‐dependent behaviors and deep LUMO (the lowest unoccupied molecular orbital) energy level. Herein, we report three low‐potential quinone‐based RAMs (1,4‐BDPAQCl2, 1,5‐BDPAQCl2, and 1,8‐BDPAQCl2) by bis‐dimethylamino substitution. The half‐wave potential of the quinones in 0.5 M KCl is approximately −0.55 to −0.57 V versus a normal hydrogen electrode. The low potential is ascribed to the introduced functional groups with two effects. First, the intramolecular hydrogen bonds formed between C=O and H−N can weaken the association between protons and dianion Q2−, resulting in a favorable distribution of products. Second, the functional groups can effectively increase the LUMO over 0.22 eV, compared with anthraquinone. Paired with Fe(glycine)2Cl2, the theoretical open‐circuit voltage of full RFBs is achieved at 1.27–1.29 V. We test full batteries using these quinones as negative RAMs at a lower concentration (0.1 M). The results show that 1,8‐BDPAQCl2 displays stability during 300 charge‐discharge cycles. In contrast, the other two quinones exhibit poor cycling stability due to side reactions. We further execute a higher concentration (0.4 M) for 1,8‐BDPAQCl2. The cycling stability of the quinone−iron RFBs is outstanding, with 0.048 % capacity decay per cycle and 0.88 % capacity decay per day. Our finding offers a feasible strategy to design low‐potential quinone molecules for the neutral RFBs.
Mapping Catalyst–Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions
Authors: Wodrich Matthew D. , Chang Miyeon , Gallarati Simone , Woźniak Łukasz , Cramer Nicolai , Corminboeuf Clemence
Published: May 2022

Group 9 metals, in particular RhIII complexes with cyclopentadienyl ligands, are competent C−H activation catalysts. Recently, a Cp*RhIII‐catalyzed reaction of alkenes with N‐enoxyphthalimides showed divergent outcome based on the solvent, with carboamination favored in methanol and cyclopropanation in 2,2,2‐trifluoroethanol (TFE). Here, we create selectivity and activity maps capable of unravelling the catalyst‐solvent interplay on the outcome of these competing reactions by analyzing 42 cyclopentadienyl metal catalysts, CpXMIII (M=Co, Rh, Ir). These maps not only can be used to rationalize previously reported experimental results, but also capably predict the behavior of untested catalyst/solvent combinations as well as aid in identifying experimental protocols that simultaneously optimize both catalytic activity and selectivity (solutions in the Pareto front). In this regard, we demonstrate how and why the experimentally employed Cp*RhIII catalyst represents an ideal choice to invoke a solvent‐induced change in reactivity. Additionally, the maps reveal the degree to which even perceived minor changes in the solvent (e. g., replacing methanol with ethanol) influence the ratio of carboamination and cyclopropanation products. Overall, the selectivity and activity maps presented here provide a generalizable tool to create global pictures of anticipated reaction outcome that can be used to develop new experimental protocols spanning metal, ligand, and solvent space.
Brain size and behavioral specialization in the jataí stingless bee (Tetragonisca angustula)
Authors: Valadares Lohan , Vieira Bruno Gusmão , Santos do Nascimento Fabio , Sandoz Jean‐Christophe
Published: May 2022

Social insects are instructive models for understanding the association between investment in brain size and behavioral variability because they show a relatively simple nervous system associated with a large set of complex behaviors. In the jataí stingless bee (Tetragonisca angustula), division of labor relies both on age and body size differences among workers. When young, both minors and soldiers engage in intranidal tasks and move to extranidal tasks as they age. Minors switch to foraging activities, while soldiers take over defensive roles. Nest defense performed by soldiers includes two different tasks: (1) hovering around the nest entrance for the detection and interception of heterospecific bees (a task relying mostly on vision) and (2) standing at the nest entrance tube for inspection of returning foragers and discrimination against conspecific non‐nestmates based on olfactory cues. Here, using different‐sized individuals (minors and soldiers) as well as same‐sized individuals (hovering and standing soldiers) performing distinct tasks, we investigated the effects of both morphological and behavioral variability on brain size. We found a negative allometric growth between brain size and body size across jataí workers, meaning that minors had relatively larger brains than soldiers. Between soldier types, we found that hovering soldiers had larger brain compartments related to visual processing (the optic lobes) and learning (the mushroom bodies). Brain size differences between jataí soldiers thus correspond to behavioral specialization in defense (i.e., vision for hovering soldiers) and illustrate a functional neuroplasticity underpinning division of labor.
A1D–0D–3Dcoupled model for simulating blood flow and transport processes in breast tissue
Authors: Fritz Marvin , Köppl Tobias , Oden John Tinsley , Wagner Andreas , Wohlmuth Barbara , Wu Chengyue
Published: May 2022

In this work, we present mixed dimensional models for simulating blood flow and transport processes in breast tissue and the vascular tree supplying it. These processes are considered, to start from the aortic inlet to the capillaries and tissue of the breast. Large variations in biophysical properties and flow conditions exist in this system necessitating the use of different flow models for different geometries and flow regimes. In total, we consider four different model types. First, a system of 1D nonlinear hyperbolic partial differential equations (PDEs) is considered to simulate blood flow in larger arteries with highly elastic vessel walls. Second, we assign 1D linearized hyperbolic PDEs to model the smaller arteries with stiffer vessel walls. The third model type consists of ODE systems (0D models). It is used to model the arterioles and peripheral circulation. Finally, homogenized 3D porous media models are considered to simulate flow and transport in capillaries and tissue within the breast volume. Sink terms are used to account for the influence of the venous and lymphatic systems. Combining the four model types, we obtain two different 1D–0D–3D coupled models for simulating blood flow and transport processes: The first model results in a fully coupled 1D–0D–3D model covering the complete path from the aorta to the breast combining a generic arterial network with a patient specific breast network and geometry. The second model is a reduced one based on the separation of the generic and patient specific parts. The information from a calibrated fully coupled model is used as inflow condition for the patient specific sub‐model allowing a significant computational cost reduction. Several numerical experiments are conducted to calibrate the generic model parameters and to demonstrate realistic flow simulations compared to existing data on blood flow in the human breast and vascular system. Moreover, we use two different breast vasculature and tissue data sets to illustrate the robustness of our reduced sub‐model approach.
DNA‐Directed Seeded Synthesis of Gold Nanoparticles without Changing DNA Sequence
Authors: Lu Chang , Zandieh Mohamad , Zheng Jinkai , Liu Juewen
Published: May 2022

DNA has been used for directing the growth of noble metal nanoparticles into different morphologies. Most previous studies focused on the effect of DNA sequence, while the effect of DNA adsorption was not thoroughly explored. In this work, we controlled the seeded growth of AuNPs by using the same DNA sequence but under different initial adsorption conditions: room temperature and heating. DNA adsorbed by heating induced more anisotropic nanoparticle growth, and the most effect was observed with 100 nM C30 DNA, where nanoflowers were obtained for the heated sample. By measuring DNA adsorption and desorption, heating did not increase DNA adsorption density but increased the adsorption affinity. The percentage of adsorbed DNA before the growth was only about 10%, regardless of heating, while after the growth, the associated DNA reached 75% or more, indicating that the free DNA also influenced the growth. This study offers fundamental insights into the effect of DNA adsorption on seeded AuNP growth, providing a method to tune the morphology of nanoparticles without changing DNA sequence.
A DFT Study on the Activity Origin of Fe−N−C Sites for Oxygen Reduction Reaction
Authors: Zhang Shishi , Qin Yanyang , Ding Shujiang , Su Yaqiong
Published: May 2022

Iron‐nitrogen‐carbon materials have been known as the most promising non‐noble metal catalyst for proton‐exchange membrane fuel cells (PEMFCs), but the genuine active sites for oxygen reduction reaction (ORR) are still arguable. Herein, by the thorough density functional theory investigations, we unravel that the planar Fe2N6 site exhibits excellent ORR catalytic activity over both FeN3 and FeN4 sites, and the potential‐determining step is determined to be the *OH hydrogenation step with an overpotential of 0.415 V. The ORR activity of Fe2N6 site originates from the low spin magnetic moment (1.11 μB), which leads to high antibonding states and low d‐band center of the Fe center, further leads to weak binding strength of *OH species. The density of FeN4 sites only has little influence on the ORR activity owing to the similar interaction between active site and intermediates in ORR. Our research sheds light on the activity origin of iron‐nitrogen‐carbon materials for ORR.
Metal Triflates as Catalysts in Organic Synthesis: Determination of Their Lewis Acidity by Mass Spectrometry
Authors: Massi Lionel , Gal Jean‐François , Duñach Elisabet
Published: May 2022

Metal triflates have shown a large variety of possibilities as catalysts in organic reactions. Some selected examples of their catalytic activity, in particular in C−O and C−C bond formation are presented. A better understanding of the mode of interaction between these Lewis acids and organic functional groups as ligands should allow for an easier choice of a tailored metal cation for a given reaction. Electrospray ionization mass spectrometry enables the characterization and the quantification of the donor/acceptor interactions involved in the catalytic processes. Both gas‐phase and solution‐phase interactions between various metal triflates and organic functionalities were studied. Based on an original probabilistic model, ligand displacement experiments lead us to establish quantitative affinity scales of ligands toward the metal centers. The main structural effects governing the ranking are identified and discussed.
Marine toxin (+)‐chaetocin‐induced apoptosis of lung large cell carcinoma cell lines through cell cycle arrest via CDKN1A expression and replicative stress
Authors: Qian Mengjia , Cao Xin
Published: May 2022

Lung large cell carcinoma is a common type of lung cancer with poor prognosis. Although targeted drugs have achieved enormous success in treating non‐small‐cell lung carcinoma (NSCLC), new chemotherapy is needed since the emerged drug resistance always hinders curative effects. The fungal toxin (+)‐chaetocin demonstrated strong antineoplastic activities against the tested lung large cell carcinoma cell lines H460 and H661 at submicromolar concentrations. Further research demonstrated that (+)‐chaetocin effectively induced H460 apoptosis at 10–30 nM concentrations, while cell death occurred at 60 nM concentrations due to DNA duplication errors. Cell cycle and transcriptional analyses proved that cell cycle arrest via CDKN1A expression and the comprehensive replicative stress of (+)‐chaetocin are key factors in the (+)‐chaetocin working mechanisms.
Topical niclosamide (ATx201) reduces Staphylococcus aureus colonization and increases Shannon diversity of the skin microbiome in atopic dermatitis patients in a randomized, double‐blind, placebo‐controlled Phase 2 trial
Authors: Weiss Anne , Delavenne Emilie , Matias Carina , Lagler Heimo , Simon Daniel , Li Ping , Hansen Jon U. , dos Santos Teresa Pires , Jana Bimal , Priemel Petra , Bangert Christine , Bauer Martin , Eberl Sabine , Nussbaumer‐Pröll Alina , Anne Österreicher Zoe , Matzneller Peter , Quint Tamara , Weber Maria , Nielsen Hanne Mørck , Rades Thomas , Johansen Helle Krogh , Westh Henrik , Kim Wooseong , Mylonakis Eleftherios , Friis Christian , Guardabassi Luca , Pace John , Lundberg Carina Vingsbo , M'Zali Fatima , Butty Pascal , Sørensen Nikolaj , Nielsen Henrik Bjørn , Toft‐Kehler Rasmus , Guttman‐Yassky Emma , Stingl Georg , Zeitlinger Markus , Sommer Morten
Published: May 2022

Background

In patients with atopic dermatitis (AD), Staphylococcus aureus frequently colonizes lesions and is hypothesized to be linked to disease severity and progression. Treatments that reduce S. aureus colonization without significantly affecting the skin commensal microbiota are needed.

Methods and findings

In this study, we tested ATx201 (niclosamide), a small molecule, on its efficacy to reduce S. aureus and propensity to evolve resistance in vitro. Various cutaneous formulations were then tested in a superficial skin infection model. Finally, a Phase 2 randomized, double‐blind and placebo‐controlled trial was performed to investigate the impact of ATx201 OINTMENT 2% on S. aureus colonization and skin microbiome composition in patients with mild‐to‐severe AD (EudraCT:2016‐003501‐33). ATx201 has a narrow minimal inhibitory concentration distribution (.125–.5 μg/ml) consistent with its mode of action – targeting the proton motive force effectively stopping cell growth. In murine models, ATx201 can effectively treat superficial skin infections of methicillin‐resistant S. aureus. In a Phase 2 trial in patients with mild‐to‐severe AD (N = 36), twice‐daily treatment with ATx201 OINTMENT 2% effectively reduces S. aureus colonization in quantitative colony forming unit (CFU) analysis (primary endpoint: 94.4% active vs. 38.9% vehicle success rate, p = .0016) and increases the Shannon diversity of the skin microbiome at day 7 significantly compared to vehicle.

Conclusion

These results suggest that ATx201 could become a new treatment modality as a decolonizing agent.
HSP90 N‐terminal inhibitors target oncoprotein MORC2 for autophagic degradation and suppress MORC2‐driven breast cancer progression
Authors: Yang Fan , Sun Rui , Hou Zeng , Zhang Fang‐Lin , Xiao Yi , Yang Yun‐Song , Yang Shao‐Ying , Xie Yi‐Fan , Liu Ying‐Ying , Luo Cheng , Liu Guang‐Yu , Shao Zhi‐Min , Li Da‐Qiang
Published: May 2022

Aims

MORC family CW‐type zinc finger 2 (MORC2), a GHKL‐type ATPase, is aberrantly upregulated in multiple types of human tumors with profound effects on cancer aggressiveness, therapeutic resistance, and clinical outcome, thus making it an attractive drug target for anticancer therapy. However, the antagonists of MORC2 have not yet been documented.

Methods and Results

We report that MORC2 is a relatively stable protein, and the N‐terminal homodimerization but not ATP binding and hydrolysis is crucial for its stability through immunoblotting analysis and Quantitative real‐time PCR. The N‐terminal but not C‐terminal inhibitors of heat shock protein 90 (HSP90) destabilize MORC2 in multiple cancer cell lines, and strikingly, this process is independent on HSP90. Mechanistical investigations revealed that HSP90 N‐terminal inhibitors disrupt MORC2 homodimer formation without affecting its ATPase activities, and promote its lysosomal degradation through the chaperone‐mediated autophagy pathway. Consequently, HSP90 inhibitor 17‐AAG effectively blocks the growth and metastatic potential of MORC2‐expressing breast cancer cells both in vitro and in vivo, and these noted effects are not due to HSP90 inhibition.

Conclusion

We uncover a previously unknown role for HSP90 N‐terminal inhibitors in promoting MORC2 degradation in a HSP90‐indepentent manner and support the potential application of these inhibitors for treating MORC2‐overexpressing tumors, even those with low or absent HSP90 expression. These results also provide new clue for further design of novel small‐molecule inhibitors of MORC2 for anticancer therapeutic application.
Experimental investigation of super‐wideband 8‐port Multiple‐Input‐Multiple‐Output antenna with high isolation for future wireless applications including Internet of Things
Authors: Addepalli Tathababu , Sharma Manish , Nella Anveshkumar , Ambalgi Ambresh P. , Kapula Prabhakara Rao
Published: May 2022

The paper reports an experimental investigation of an 8 × 8 MIMO antenna fabricated on a commercially available FR4 substrate. A fractal printed monopole radiator is introduced as a good prospect for super‐wideband (2.85–20.0 GHz) multiple‐input‐multiple‐output (SWB‐MIMO) configuration. The MIMO antenna is printed on both the planes (Plane A and Plane B) where four antennas are printed on Plane A and remaining on Plane B which are fed asymmetric to achieve wider impedance bandwidth. An inverted‐L type strip is embedded in a rectangular elliptical slotted ground to match the impedance. Also, a circular ring is embedded on both planes with a novel stub connected to each antenna ground providing isolation of more than 30 dB. The diversity performance of the antenna is also investigated with measured envelope correlation coefficient (ECC) < 0.025, directive gain (DG) > 9.995 dB, total active reflection coefficient (TARC) < −40 dB, and channel capacity loss (CCL) < 0.30b/s/Hz in the entire operating band.
An energy aware cluster‐based routing and adaptive semi‐synchronized MAC for energy harvesting WSN
Authors: Movva Pavani , Kamarajugadda Kishore Kumar , Polipalli Trinatha Rao
Published: May 2022

Medium access control (MAC) layer scheduling is an intelligent solution to protract the lifetime of energy harvesting wireless sensor network (WSN) which is challenging issue in recent times. Self‐adaptive MAC protocol was working upon reinforcement learning. However, this decentralized adaptive scheduling introduces collisions and degrades the overall network performance. To fix this problem, this paper proposes novel semi‐synchronized MAC approach for energy harvesting WSN. The major objective of this work is to improve energy efficiency of the network by minimizing energy consumption which is the major issue in WSN. Proposed WSN network is modeled with dual mobile sinks with circular moving path and static sensor nodes to monitor the environment. Our novel MAC approach is initiated with unequal cluster formation by correlation based unequal clustering scheme in which multi‐objective elephant herding optimization (CUC‐MEHO) algorithm is incorporated for cluster head (CH) selection. In clustered network, all sensor nodes follow semi‐synchronized adaptive active period MAC scheduling (S2A2MAC) protocol. In this work, S2A2MAC operates upon hidden Markov model (HMM) which controls the active time period of a node in an adaptive manner. Energy efficient hop‐by‐hop intra‐cluster routing is empowered by Bayes rule enabled perfect matching (BR‐PM) algorithm. Before route selection, all candidate nodes are regarded into perfect match, partially match, and no match nodes. Furthermore, emergency data is identified by CH based on flag value and transmitted without any time delay. For emergency data transmission, extremity aware routing (EAR) algorithm is presented and EAR algorithm is functioning on hopcount and distance criteria. Finally, proposed network is evaluated by extensive simulations in NS‐3.26. Simulation upshots show better performance in percentage of dead nodes, network lifetime, energy consumption, PDR, and delay.
Ortho‐F,F‐DPEphos: Synthesis and Coordination Chemistry in Rhodium and Gold Complexes, and Comparison with DPEphos
Authors: Race James J. , Webb Matthew J. , Morgan Boyd Timothy , Weller Andrew S.
Published: May 2022

The synthesis of a new ortho‐fluorine substituted diphosphine ligand based upon the DPEphos ligand is reported: o‐F,F‐DPEphos (DPEphos=bis(2‐diphenylphosphinophenyl)ether). The corresponding bimetallic gold complex Au2Cl2(o‐F,F‐DPEphos) and Schrock‐Osborn type Rh(I) complex [Rh(o‐F,F‐DPEphos)(NBD)][BArF4] have been synthesized (ArF=3,5‐(CF3)2‐C6H3). The solid‐state and solution phase NMR data are examined in comparison with the o‐H,H‐DPEphos equivalents, and demonstrate the influence of ortho‐fluorine substitution through the control of aurophilic and Rh⋅⋅⋅X interactions (X=H or F). Characterization of the organometallic products upon hydrogenation of the Schrock‐Osborn complexes in 1,2‐F2C6H4 revealed a Rh dimeric complex [Rh(H)(fac‐κ3‐P,O,P‐μ‐CH‐DPEphos)]2[BArF4]2 with a bridging C−H agostic interaction for the parent DPEphos. The substituted variant formed a Rh(III) monomer [Rh(mer‐κ3‐P,O,P‐o‐F,F‐DPEphos)H2][BArF4], highlighting the structural consequences of ortho‐fluorine substitution.
New Insight into Effects of Higher Upper Cutoff Voltage on the Cycling Performance of Graphite‐SiOx/Li‐rich Layered Oxide Pouch‐Type Batteries
Authors: Liu Xingge , Gao Min , Zhao Jingling , Sun Xueyi , Li Zhao , Wang Jiantao , Huang Xiaowei , Zhuang Weidong
Published: May 2022

High‐energy‐density lithium‐ion batteries based on the graphite–SiOx anode and Li‐rich layered oxide (LLO) cathode are expected to solve the “range anxiety” of electric vehicles, but face undesired capacity degradation. Usually, the rise in upper cutoff voltage (UCV) can increase the capacity but reduce the cycle life. Herein, the effect of different UCVs (4.4, 4.5, 4.6 V) on graphite–SiOx/LLO pouch‐type battery capacity degradation is investigated. Unexpectedly, the batteries at 4.5 and 4.6 V UCVs exhibit the minimum and maximum capacity after 300 cycles, separately. The comprehensive analysis shows that after 300 cycles, a greater loss of anode active material for the battery at 4.5 V UCV occurs, and a larger reversible lithium loss at 4.4 V UCV appears. Nevertheless, for the battery at 4.6 V UCV, a more stable solid electrolyte interphase film generated on the anode slows down the capacity degradation.
A width‐based approach to estimating historical changes in coarse sediment fluxes at river reach and network scales
Authors: Brenna Andrea , Bizzi Simone , Surian Nicola
Published: May 2022

Knowledge about historical changes in sediment fluxes in most coarse‐bedded rivers worldwide is extremely limited. In consideration of this deficiency, we developed a width‐based approach to estimating multi‐decade changes in coarse sediment fluxes occurring at reaches of the Po River and 21 of its tributaries in northern Italy. The estimation was based on temporal variations in the reach‐averaged width of the river's active channel, and such width was expressed through a dimensionless index of coarse bed material load (Iq). The index was determined in two periods: 1954–1998 and 1998–2020. Statistically significant relationships were found between temporal variations in Iq occurring in reaches of the Po River and at key locations of each specific reach (i.e., upstream reaches and tributaries). Such evidence of coherent changes in sediment transfer through space and time led us to conclude that Iq variations can be regarded as a reliable proxy for historical changes in sediment transport in a river reach. The application of the approach to the investigation of the Po River catchment provided new insights into the historical changes characterizing coarse sediment fluxes along the river and its major tributaries. From 1954 to 1998, an average decrease in coarse sediment fluxes of about −20% and −30% occurred along the river and the terminal sectors of its tributaries, respectively. The estimations showed that coarse sediment fluxes exhibited a slightly lower decrease in the last two decades, with sediment flux recovery occurring only in some tributaries. The results suggest that a profound change in sediment dynamics and fluxes has occurred, and is likely still ongoing, in the Po River system, despite the decrease in human disturbances (e.g., in‐channel sediment mining) in more recent times.
Morpho‐sedimentary evolution of a microtidal meandering channel driven by 130 years of natural and anthropogenic modifications of the Venice Lagoon (Italy)
Authors: Finotello Alvise , Capperucci Ruggero M. , Bartholomä Alexander , D'Alpaos Andrea , Ghinassi Massimiliano
Published: May 2022

Tidal channels form the pathways for tidal currents to propagate and distribute clastic sediments and nutrients, thus providing a primary control on tidal‐landscape ecomorphodynamics. Most tidal channels in both estuarine and lagoonal environments have a tendency to meander, yet very few studies exist that investigate the full spectrum of processes controlling tidal meander morpho‐sedimentary evolution. The Venice Lagoon (Italy) offers a unique opportunity to shed light on this topic, because a long record of morphological and sedimentary data is available, which allows one to relate tidal channel evolution to the hydrodynamic and morphological changes undergone by the lagoon. In particular, during the last 130 years, feedback between rising relative sea levels and anthropogenic interventions has caused severe modifications of the Lagoon hydro‐ and morphodynamics. Here we investigate how these modifications fed back into the morpho‐sedimentary evolution of a meandering tidal channel located in the northern lagoon. Combining extensive datasets of aerial photographs, topographic and bathymetric surveys, geophysical investigations, sedimentary core analysis, and numerical modelling, we show that enhanced local tidal ranges and water discharges determined adjustments of channel cross‐sectional geometries proportional to increasing tidal prisms, while changes in local tidal asymmetries caused modifications of the local sediment transport regime, resulting in the development of bar–pool patterns according to the dominant tidal phase. Such bar–pool patterns eventually determined channel migration through a bar‐push mechanism controlled by a fluvial‐like, quasi‐linear relationship between local channel curvature and lateral migration rates. Critical differences in sediment transport regime are, however, highlighted between fluvial and tidal meanders the latter being potentially characterized by high concentrations of suspended sediment during periods of slack waters when wind‐driven sediment transport processes are not negligible. This could hamper the formation of high‐relief bedforms, with profound implications for the sedimentology of tidal point‐bar deposits.
NAFLD improves risk prediction of type 2 diabetes: with effect modification by sex and menopausal status
Authors: Kim Yejin , Chang Yoosoo , Ryu Seungho , Wild Sarah H. , Byrne Christopher D.
Published: May 2022

Background and Aims

The effects of sex and menopausal status on the association between NAFLD and incident type 2 diabetes (T2D) remain unclear. We investigated the effect modification by sex and menopause in the association between NAFLD and T2D; also, the added predictive ability of NAFLD for the risk of T2D was assessed.

Approach and Results

This cohort study comprised 245,054 adults without diabetes (109,810 premenopausal women; 4958 postmenopausal women; 130,286 men). Cox proportional hazard models were used to estimate hazard ratios (HRs; 95% confidence intervals [CIs]) for incident T2D according to NAFLD status. The incremental predictive role of NAFLD for incident T2D was assessed using the area under the receiver operating characteristic curve, net reclassification improvement, and integrated discrimination improvement. A total of 8381 participants developed T2D (crude incidence rate/103 person‐years: 2.9 premenopausal women; 12.2 postmenopausal women; 9.3 men) during median follow‐up of 5.3 years. NAFLD was positively associated with incident T2D in all groups. After adjustment for potential confounders, the multivariable‐adjusted HRs (95% CIs) for incident T2D comparing NAFLD to no NAFLD were 4.63 (4.17–5.14), 2.65 (2.02–3.48), and 2.16 (2.04–2.29) in premenopausal women, postmenopausal women, and men, respectively. The risks of T2D increased with NAFLD severity as assessed by serum fibrosis markers, and the highest relative excess risks were observed in premenopausal women. The addition of NAFLD to conventional risk factors improved risk prediction for incident T2D in both sexes, with a greater improvement in women than men.

Conclusions

NAFLD, including more severe NAFLD, is a stronger risk factor for incident T2D in premenopausal women than in postmenopausal women or men; protection against T2D is lost in premenopausal women with NAFLD.