bluuebunny/crossref_metadata_2025 huggingface dataset:
Deuterium Renders Fast Risc and Low Non‐Radiation Decays of TADF Emitters
Authors: Qin Yuanyuan , Xie Xin , Pang Zhi , Liu Guanhao , Dong Xiangyu , Shen Shaogang , Zhang Yaogang , Lee Chun‐Sing , Yi Yuanping , Wang Pengfei , Wang Ying
Published: August 2023

A simple strategy to simultaneously achieve fast reverse intersystem crossing (RISC) and low non‐radiative decay rates in thermally activated delayed fluorescence (TADF) emitters is still lacking. Here, the green TADF emitters containing aromatic ketones and prepared D‐Ph and D‐PhCz containing different amounts of deuterium are deuterated to study the mechanism of deuterium on the performance improvement of TADF devices. Due to the heavy atom effect of deuterium, the non‐radiative transition rate constant (knr) of D‐Ph and D‐PhCz decreases. Most importantly, deuterium reduces the reorganization energy (λ) of (T1‐S1), which greatly improves the reverse intersystem crossing rate constant (kRISC) and the exciton utilization efficiency. The results show that the external quantum efficiency of D‐Ph and D‐PhCz increases to 25.69% and 24.92%, respectively. This study provides a simple and efficient strategy for reducing non‐radiative energy loss and increasing kRISC to achieve high‐performance TADF emitters.
Visible Light Induced Difunctional Hetero‐Annulation of Unsaturated C−C Bonds
Authors: Samanta Apurba , Debnath Saradindu , Pratim Mondal Partha , Maity Soumitra
Published: August 2023

Heterocyclic scaffolds are beneficial structural architects in a wide range of pharmaceuticals, agrochemicals, biological and also functional materials. In this regard, several investigations have been performed to synthesize them. Among these, visible light‐induced difunctionalization cyclization strategy provides attractive solutions by adopting greener routes, breaking the monopoly of conventional thermal processes. A review on these methodologies is also desirable as unsaturated aliphatics, especially alkenes are one of the cheapest feedstocks available. They offer diverse options and modifications to generate different products, including heterocycles, which are highly sought after due to their applications in various sectors. To account for the advancements in this strategy, we summarized the visible light induced difunctionalization strategies that directly lead to the synthesis of heterocyclic scaffolds from unsaturated C−C bonds. We have categorized the relevant reaction schemes into four mechanistically distinct sections namely (i) Two component oxidative annulations (ii) Radical mediated annulations (iii) Polar radical crossover annulations and (iv) Three component oxidative annulations.
Self‐Solidifying Active Droplets Showing Memory‐Induced Chirality
Authors: Feng Kai , Ureña Marcos José Carlos , Mukhopadhyay Aritra K. , Niu Ran , Zhao Qiang , Qu Jinping , Liebchen Benno
Published: August 2023

Most synthetic microswimmers do not reach the autonomy of their biological counterparts in terms of energy supply and diversity of motions. Here, this work reports the first all‐aqueous droplet swimmer powered by self‐generated polyelectrolyte gradients, which shows memory‐induced chirality while self‐solidifying. An aqueous solution of surface tension–lowering polyelectrolytes self‐solidifies on the surface of acidic water, during which polyelectrolytes are gradually emitted into the surrounding water and induce linear self‐propulsion via spontaneous symmetry breaking. The low diffusion coefficient of the polyelectrolytes leads to long‐lived chemical trails which cause memory effects that drive a transition from linear to chiral motion without requiring any imposed symmetry breaking. The droplet swimmer is capable of highly efficient removal (up to 85%) of uranium from aqueous solutions within 90 min, benefiting from self‐propulsion and flow‐induced mixing. These results provide a route to fueling self‐propelled agents which can autonomously perform chiral motion and collect toxins.
Adipose METTL14‐Elicited N6‐Methyladenosine Promotes Obesity, Insulin Resistance, and NAFLD Through Suppressing β Adrenergic Signaling and Lipolysis
Authors: Kang Qianqian , Zhu Xiaorong , Ren Decheng , Ky Alexander , MacDougald Ormond A. , O'Rourke Robert W. , Rui Liangyou
Published: August 2023

White adipose tissue (WAT) lipolysis releases free fatty acids as a key energy substance to support metabolism in fasting, cold exposure, and exercise. Atgl, in concert with Cgi‐58, catalyzes the first lipolytic reaction. The sympathetic nervous system (SNS) stimulates lipolysis via neurotransmitter norepinephrine that activates adipocyte β adrenergic receptors (Adrb1‐3). In obesity, adipose Adrb signaling and lipolysis are impaired, contributing to pathogenic WAT expansion; however, the underling mechanism remains poorly understood. Recent studies highlight importance of N6‐methyladenosine (m6A)‐based RNA modification in health and disease. METTL14 heterodimerizes with METTL3 to form an RNA methyltransferase complex that installs m6A in transcripts. Here, this work shows that adipose Mettl3 and Mettl14 are influenced by fasting, refeeding, and insulin, and are upregulated in high fat diet (HFD) induced obesity. Adipose Adrb2, Adrb3, Atgl, and Cgi‐58 transcript m6A contents are elevated in obesity. Mettl14 ablation decreases these transcripts’ m6A contents and increases their translations and protein levels in adipocytes, thereby increasing Adrb signaling and lipolysis. Mice with adipocyte‐specific deletion of Mettl14 are resistant to HFD‐induced obesity, insulin resistance, glucose intolerance, and nonalcoholic fatty liver disease (NAFLD). These results unravel a METTL14/m6A/translation pathway governing Adrb signaling and lipolysis. METTL14/m6A‐based epitranscriptomic reprogramming impairs adipose Adrb signaling and lipolysis, promoting obesity, NAFLD, and metabolic disease.
Gigantic and Continuous Output Power in Ionic Thermo‐Electrochemical Cells by Using Electrodes with Redox Couples
Authors: Zhang Wencong , Qiu Liyu , Lian Yongjian , Dai Yongqiang , Yin Shi , Wu Chen , Wang Qianming , Zeng Wei , Tao Xiaoming
Published: August 2023

The main obstacle of ionic thermo‐electrochemical cells (TECs) in continuous power supply lies in a low heat‐to‐electricity energy conversion efficiency because most TECs work in thermodiffusion mode in which the ions are confined in a liquid/electrolyte media. The introduction of the redox couple onto the electrode surface may overcome the obstacle by resolving the low mass transport rate of ions caused by the redox process occurring near but not on the electrode surface. Herein, the authors demonstrate enhancement of TECs by integrating the redox couple directly onto the electrode surface to maximize the mass transport efficiency. A discontinuous interfacial modification strategy is developed by using a carbon cloth/iron (II/III) phytate as the symmetric electrodes. The gelled electrolyte consisting of a polyacrylamide matrix and phytic acid is shown to promote selective ion diffusion. A synergistic combination consisting of the thermodiffusion effect and redox reactions on the electrode is established in a pre‐treated layout. Such TEC affords a high output voltage of 0.4 V, an excellent instantaneous output power density (20.26 mW m‐2 K‐2) and a record‐high 2 h output energy density (2451 J m‐2) under TH = 30 °C with TC = 15 °C, with an ultrahigh Carnot‐relative efficiency of 1.12%.
Green‐Processed Non‐Fullerene Organic Solar Cells Based on Y‐Series Acceptors
Authors: Liu Chunhui , Liu Jinfeng , Duan Xiaopeng , Sun Yanming
Published: August 2023

The development of environmentally friendly and sustainable processes for the production of high‐performance organic solar cells (OSCs) has become a critical research area. Currently, Y‐series electron acceptors are widely used in high‐performance OSCs, achieving power conversion efficiencies above 19%. However, these acceptors have large fused conjugated backbones that are well‐soluble in halogenated solvents, such as chloroform and chlorobenzene, but have poor solubility in non‐halogenated green solvents. To overcome this challenge, recent studies have focused on developing green‐processed OSCs that use non‐chlorinated and non‐aromatic solvents to dissolve bulk‐heterojunction photoactive layers based on Y‐series electron acceptors, enabling environmentally friendly fabrication. In this comprehensive review, an overview of recent progress in green‐processed OSCs based on Y‐series acceptors is provided, covering the determination of Hansen solubility parameters, the use of non‐chlorinated solvents, and the dispersion of conjugated nanoparticles in water/alcohol. It is hoped that the timely review will inspire researchers to develop new ideas and approaches in this important field, ultimately leading to the practical application of OSCs.
Soybean planting date and seeding rate effect on grain yield and profitability
Authors: Colet Fabiano , Lindsey Alexander J. , Lindsey Laura E.
Published: August 2023

Timely soybean [Glycine max (L.) Merr.] planting is ideal for maximizing grain yield. However, weather conditions often limit farmers’ ability to plant timely. The objectives of this study were to (a) measure the effect of soybean planting date and seeding rate on grain yield, (b) identify the agronomic optimum seeding rate (AOSR; the seeding rate where soybean yield is maximized), and (c) compare the net economic return of the base treatment (May 10 to 31 planting date and 370,000 seeds ha−1 seeding rate) to the other treatment combinations. The experiment was conducted in 2020 and 2021 in Ohio at the Western (WARS) and Northwest (NWARS) Agricultural Research Stations with a split‐plot randomized complete block design with four replications. The whole plot factor was four planting dates ranging from April 25 through July 1, and the sub‐plot factor was five seeding rates ranging from 123,500 to 618,000 seeds ha−1. When water was not limiting, soybean planted in April and May yielded 8% to 26% more than soybean planted late June. In general, planting in May resulted in a lower AOSR (247,000 to 303,000 seeds ha−1), compared to planting in June, where AOSR ranged from 430,000 to 618,000 seeds ha−1. Comparative net economic return was the lowest (from $237 ha−1 to $938 ha−1) when soybean was planted after mid‐June at 123,500 seeds ha−1. These findings can help farmers improve soybean grain yield by adjusting their seeding rate based on planting date to maximize profitability.
Poly(Ethylene Piperidinium)s for Anion Exchange Membranes
Authors: Chen Huanhuan , Bang Ki‐Taek , Tian Ye , Hu Chuan , Tao Ran , Yuan Yufei , Wang Rui , Shin Dong‐Myeong , Shao Minhua , Lee Young Moo , Kim Yoonseob
Published: August 2023

The lack of anion exchange membranes (AEMs) that possess both high hydroxide conductivity and stable mechanical and chemical properties poses a major challenge to the development of high‐performance fuel cells. Improving one side of the balance between conductivity and stability usually means sacrificing the other. Herein, we used facile, high‐yield chemical reactions to design and synthesize a piperidinium polymer with a polyethylene backbone for AEM fuel cell applications. To improve the performance, we introduced ionic crosslinking into high‐cationic‐ratio AEMs to suppress high water uptake and swelling while further improving the hydroxide conductivity. Remarkably, PEP80‐20PS achieved a hydroxide conductivity of 354.3 mS cm−1 at 80 °C while remaining mechanically stable. Compared with the base polymer PEP80, the water uptake of PEP80‐20PS decreased by 69 % from 813 % to 350 %, and the swelling decreased substantially by 85 % from 350.0 % to 50.2 % at 80 °C. PEP80‐20PS also showed excellent alkaline stability, 84.7 % remained after 35 days of treatment with an aqueous KOH solution. The chemical design in this study represents a significant advancement toward the development of simultaneously highly stable and conductive AEMs for fuel cell applications.
Triplet Generation Through Singlet Fission in Metal‐Organic Framework: An Alternative Route to Inefficient Singlet‐Triplet Intersystem Crossing
Authors: Surendran Rajasree Sreehari , Yu Jierui , Fry H. Christopher , Anderson Ryther , Xu Wenqian , Krishnan Riya , Duan Jiaxin , Goswami Subhadip , A. Gómez‐Gualdrón Diego , Deria Pravas
Published: August 2023

High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet‐triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy‐coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin‐orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution‐stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super‐exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency (kISC) but
form triplets in MOF in contrast to the frameworks that are built from linkers with sizable kISC but
. This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes.
Fragment Screening and Fast Micromolar Detection on a Benchtop NMR Spectrometer Boosted by Photoinduced Hyperpolarization
Authors: Stadler Gabriela R. , Segawa Takuya F. , Bütikofer Matthias , Decker Venita , Loss Sandra , Czarniecki Barbara , Torres Felix , Riek Roland
Published: August 2023

Fragment‐based drug design is a well‐established strategy for rational drug design, with nuclear magnetic resonance (NMR) on high‐field spectrometers as the method of reference for screening and hit validation. However, high‐field NMR spectrometers are not only expensive, but require specialized maintenance, dedicated space, and depend on liquid helium cooling which became critical over the recurring global helium shortages. We propose an alternative to high‐field NMR screening by applying the recently developed approach of fragment screening by photoinduced hyperpolarized NMR on a cryogen‐free 80 MHz benchtop NMR spectrometer yielding signal enhancements of up to three orders in magnitude. It is demonstrated that it is possible to discover new hits and kick‐off drug design using a benchtop NMR spectrometer at low micromolar concentrations of both protein and ligand. The approach presented performs at higher speed than state‐of‐the‐art high‐field NMR approaches while exhibiting a limit of detection in the nanomolar range. Photoinduced hyperpolarization is known to be inexpensive and simple to be implemented, which aligns greatly with the philosophy of benchtop NMR spectrometers. These findings open the way for the use of benchtop NMR in near‐physiological conditions for drug design and further life science applications.
Formation of aligned needle‐like crystals of 9,10‐dibromoanthracene in small droplets
Authors: Watanabe Masashi
Published: August 2023

One‐dimensional micromaterials are potentially applicable in various technologies, including sensor fabrications. Variations in the sensing performance of such materials can be ameliorated by their regular arrangement. For example, the materials can be aligned unidirectionally. However, controlling both their orientation and spacing remains challenging. In this study, small evenly spaced droplets were aligned on a surface and the solvent in the droplets was then evaporated in air to obtain evenly spaced, aligned needle‐like crystals of the solute. The droplets were confined to the concave portions of regular wrinkles formed due to buckling instability on a polydimethylsiloxane (PDMS) rubber surface. However, crystallization in small droplets with diameters of less than 100 μm was difficult to achieve because the probability of nucleus formation in each droplet was very low. To address this drawback, nuclei were added to the droplets externally, obtaining well‐aligned needle‐like crystals of 9,10‐dibromoanthracene (DBA), an organic semiconductor. The advantages of this method include its simplicity, cost efficiency, and applicability to fragile materials, because the application of mechanical force to the needle‐like crystals is not required.
SEMA4G targeted by miR‐363‐5p regulates the proliferation of granulosa cells in Yunshang black goats
Authors: Chen Yulin , Wang Peng , He Xiaoyun , Liu Yufang , Chu Mingxing
Published: August 2023

Proliferation of granular cells (GCs) plays an important role in ovary development, providing energy and a microenvironment for oocyte ovulation. In this study, we explored the spatiotemporal expression of SEMA4G and its effects on the growth and development of goat GCs using primary GCs cultured in vitro as a model. The results showed that the expression level of SEMA4G was significantly higher in the ovaries of high‐fertility goats than in those of low‐fertility goats (p < 0.05). The mRNA and protein expression levels of the cell proliferation markers of GCs were significantly increased after the overexpression of SEMA4G in goat primary GCs. The EdU and CCK8 results showed that cell viability was elevated in goat GCs and that proliferation was promoted by an increase in the number of proliferating cells. The proliferation of goat GCs was significantly inhibited by SEMA4G inhibition (p < 0.05). The results of online miRNA and target gene prediction software and dual luciferase activity analysis confirmed that SEMA4G could bind to mi‐363‐5p and was one of its target genes. The RT‒qPCR results showed that the expression level of miR‐363‐5p was significantly lower in the ovaries of high‐fertility goats than in those of low‐fertility goats in contrast to the expression level of SEMA4G (p < 0.05). After the overexpression of miR‐363‐5p in goat GCs, the expression of SEMA4G was significantly suppressed (p < 0.05). Collectively, the results of this study could lay the foundation for exploring the molecular mechanisms by which SEMA4G and miR‐363‐5p regulate the growth and development of goat GCs and provide targets for breeding high‐fertility goats.
Investigation of the impact of AXL, TLR3, and STAT2 in congenital Zika syndrome through genetic polymorphisms and protein–protein interaction network analyses
Authors: Gomes Julia A. , Sgarioni Eduarda , Boquett Juliano A. , Kowalski Thayne W. , Fraga Lucas R. , Terças‐Trettel Ana Cláudia P. , da Silva Juliana H. , Ribeiro Bethânia F. R. , Galera Marcial F. , de Oliveira Thalita M. , Carvalho de Andrade Maria Denise F. , Carvalho Isabella F. , Schüler‐Faccini Lavínia , Vianna Fernanda S. L.
Published: August 2023

Introduction

Zika virus (ZIKV) is a human teratogen that causes congenital Zika syndrome (CZS). AXL, TLR3, and STAT2 are proteins involved in the ZIKV's entry into cells (AXL) and host's immune response (TLR3 and STAT2). In this study, we evaluated the role of genetic polymorphisms in these three genes as risk factors to CZS, and highlighted which proteins that interact with them could be important for ZIKV infection and teratogenesis.

Materials and methods

We evaluate eighty‐eight children exposed to ZIKV during the pregnancy, 40 with CZS and 48 without congenital anomalies. The evaluated polymorphisms in AXL (rs1051008), TLR3 (rs3775291), and STAT2 (rs2066811) were genotyped using TaqMan® Genotyping Assays. A protein–protein interaction network was created in STRING database and analyzed in Cytoscape software.

Results

We did not find any statistical significant association among the polymorphisms and the occurrence of CZS. Through the analyses of the network composed by AXL, TLR3, STAT2 and their interactions targets, we found that EGFR and SRC could be important proteins for the ZIKV infection and its teratogenesis.

Conclusion

In summary, our results demonstrated that the evaluated polymorphisms do not seem to represent risk factors for CZS; however, EGFR and SRC appear to be important proteins that should be investigated in future studies.
Assessment and treatment of stereotypy in infants at risk of autism spectrum disorder
Authors: Scully Morgan , Couger Kathryn , MacDonald Rebecca
Published: August 2023

Individuals diagnosed with autism spectrum disorder (ASD) often engage in stereotypic behavior that is challenging to treat due to difficulties isolating the maintaining reinforcer. The purpose of this study was to identify and treat motor stereotypy in an infant at risk of ASD. Although several studies have investigated the prevalence and topographies of stereotypy in young children, none have identified the age at which it emerges and treated it before 1 year of age. Redirection of stereotypy to toy play and reinforcement for toy engagement was implemented in a multiple baseline design across topographies of stereotypy. Results indicate decreases in all topographies of stereotypy to near‐zero levels across the course of the study. These findings are discussed as they relate to the implications of identifying stereotypy in infancy and intervening as soon as it is identified.
Using enhanced development tools offered by analytical Quality by Design to support switching of a quality control method
Authors: Simeoni Philippe , Deissler Michael , Bienert Roland , Gritsch Manuela , Nerkamp Jörg , Kirsch Stephan , Roesli Christoph , Pohl Thomas , Anderka Oliver , Gellermann Gerald
Published: August 2023

Quality by Design (QbD) principles play an increasingly important role in the pharmaceutical industry. Here, we used an analytical QbD (AQbD) approach to develop a capillary electrophoresis sodium dodecyl sulfate under reducing conditions (rCE‐SDS), with the aim of replacing SDS‐polyacrylamide gel electrophoresis (SDS‐PAGE) as release and stability test method for a commercialized monoclonal antibody product. Method development started with defining analytical method performance requirements as part of an analytical target profile, followed by a systematic risk assessment of method input parameters and their relation to defined method outputs. Based on this, design of experiments studies were performed to identify a method operable design region (MODR). The MODR could be leveraged to improve method robustness. In a bridging study, it was demonstrated that the rCE‐SDS method is more sensitive than the legacy SDS‐PAGE method, and a conversion factor could be established to compensate for an off‐set due to the higher sensitivity, without losing the correlation to the historical data acquired with the former method. Overall, systematic application of analytical Quality by Design principles for designing and developing a new analytical method helped to elucidate the complex dependency of method outputs on its input parameters. The link of the method to product quality attributes and the definition of method performance requirements were found to be most relevant for derisking the analytical method switch, regarding impact on the control strategy.
Inside the world of stepsiblings: Linking global production networks to sustainable supply chain management
Authors: Yawar Sadaat Ali , Seuring Stefan
Published: August 2023

The theoretical foundation of (sustainable) supply chain management (SSCM) is an issue of frequent debate. Integrating it with the Global Production Networks (GPN), which is a kind of stepsibling, can help expanding the theoretical foundations of SSCM. The purpose of this paper is to explore how the GPN approach links to SSCM in analysing and explaining interorganizational sustainability. This paper is conceptual. Five central GPN constructs are identified: (1) the emerging supply chain structures and sustainability; (2) the importance and relevance of embeddedness and governance; (3) power dynamics; (4) the stakeholder approach; (5) the sustainability dimensions and the implementation strategies. They are explained in detail and then contrasted with how the related topics are dealt within SSCM. The paper provides insights into the ongoing discussions in GPN and integrates the political economy debate into SSCM research. Findings reveal that GPN offers an alternative and yet complementary explanation about network and cluster formation in supply chains, the effect of embeddedness (geopolitical, social, and cultural) power relationships and governance mechanisms and their role in implementing ecological and social sustainability across the supply chains. The comparison of these complementary disciplines allows for the exchange of ideas between the SSCM and GPN approaches, thereby providing an enriched understanding for managing supply chain sustainability. The selective comparison of the SSCM and GPN constructs is the first of its kind and should trigger further research at this intersection. Five propositions capture core directions for future research.
MitraClip used for severe mitral regurgitation after surgery for type A aortic dissection combined with Marfan syndrome
Authors: Wang Chaojie , Wang Ge , Lu Weihui , Fan Xiaoping
Published: August 2023

Mitral regurgitation is a rare but catastrophic condition in patients after surgery for type A aortic dissection. The second thoracotomy to complete the mitral valve operation could be fatal. Here, we report a case of severe mitral regurgitation treated with MitraClip in a 53‐year‐old woman after surgery for type A aortic dissection combined with Marfan syndrome. She was discharged uneventfully, and a significant reduction of regurgitation of mitral valve and tricuspid valve was observed at the 6‐month follow‐up. MitraClip could be an alternative device for such high‐risk patients.
Treatment response to Janus kinase inhibitor in a child affected by Aicardi‐Goutières syndrome
Authors: Galli Jessica , Cattalini Marco , Loi Erika , Ferraro Rosalba Monica , Giliani Silvia , Orcesi Simona , Pinelli Lorenzo , Badolato Raffaele , Fazzi Elisa
Published: August 2023

Key Clinical Message

Baricitinib, a Janus kinase inhibitor (JAK‐inhibitor), seems to contribute to an improvement of a child affected by Aicardi‐Goutières syndrome (AGS), reducing the interferon score and determining a recovery of cognitive, communicative, and relational dysfunctions, while the gross motor deficit persisted.

We report the treatment response to baricitinib, a JAK‐inhibitor, in a 4‐year‐old girl affected by Aicardi‐Goutières syndrome (AGS2, RNASEH2B mutation). Using quantitative measures, we detected a significant amelioration characterized by a complete recovery of cognitive, communicative, and relational skills after 8 and 16 months from the beginning of therapy.
Metal‐Metal Charge Transfer Properties of a Series of Trinuclear Fe2Ru and Corresponding Pentanuclear Fe2Ru2Ag Cyanido‐Bridged Complexes
Authors: Zeng Chen , Xu Qing‐Dou , Liu Xiao‐Lin , Yang Yu‐Ying , Hu Sheng‐Min , Wu Xin‐Tao , Sheng Tian‐Lu
Published: August 2023

A series of trimetallic cyanidometal‐bridged compounds [MenCp(dppe)FeII‐(μ‐NC)‐RuII(MeOpy)4‐(μ‐CN)‐FeII(dppe)CpMen] ‐ [PF6]2 (N[PF6]2, n=0, N =1; n=1, N=2; n=3, N=3; Cp=cyclopentadiene, dppe=1,2‐bis(diphenylphosphino)ethane, MeOpy=4‐methoxypyridine) and their one‐ and two‐electron oxidized compounds N3+ and N4+ were synthesized and characterized. Meanwhile, a series of corresponding linear cyanido‐bridged pentanuclear compounds [MenCp(dppe)FeIII‐(μ‐NC)‐RuII(MeOpy)4‐(μ‐NC)‐AgI‐(μ‐CN)‐RuII(MeOpy)4‐(μ‐CN)‐FeIII(dppe)CpMen][BF4]5 (M[BF4]5, n=0, M=4; n=1, M=5; n=3, M=6) were also obtained and well characterized. The investigations suggest that in the trinuclear system there exists remote interaction between the two Fe centers, but no significant interactions exist across the central silver unit between the metals on the two sides of the silver center in the pentanuclear system. In both the trinuclear N4+ and the pentanuclear M5+ complexes, there exists the neighboring RuII→FeIII MM′CT transitions, and the MM'CT energy in the corresponding trinuclear system is higher than those in the pentanuclear system in which no remote metal‐metal interaction occurs. Meanwhile, as the substituted methyl groups on the cyclopentadiene increases, the redox potential of the ruthenium in the trinuclear N4+ series increases, but that in the pentanuclear M5+ complexes decreases.
Supramolecular Chirogenesis in a Sterically Hindered Porphyrin: A Critical Theoretical Analysis
Authors: Osadchuk Irina , Luts Hanna‐Eliisa , Norvaiša Karolis , Borovkov Victor , Senge Mathias O.
Published: August 2023

Invited for the cover of this issue are the groups of Irina Osadchuk at Tallinn University of Technology and Mathias Senge at Trinity College Dublin. The image depicts how a porphyrin with two guest molecules (R)‐camphor sulfonic acid is irradiated with UV‐visible light to measure and simulate ECD and UV‐Vis spectra. Read the full text of the article at 10.1002/chem.202301408.
Carbon Nitride with Single‐Atom Nickel as Co‐Catalyst for Visible‐Light Promoted C—O Coupling†
Authors: Zhao En , Chen Lijie , Zhu Qi , Chen Zhaohui , Wei Yanping , Zhang Wenjun , Dong Lin , Fang Weiwei , Chen Zupeng
Published: August 2023

Comprehensive Summary

Solar‐driven cross‐coupling reactions by dual nickel/photocatalysis under mild conditions have received considerable attention. However, the existing photo/nickel dual catalytic cross‐coupling reactions require the addition of expensive photosensitizers and organic ligands, and the catalytic activity is inadequate. Herein, we report a nickel single‐atom heterogeneous catalyst supported on mesoporous carbon nitride for photocatalytic C—O coupling reaction between 4‐bromobenzonitrile and ethanol, affording 4‐ethoxybenzonitrile in excellent yield compared to a semi‐heterogeneous catalytic system. The catalytic system exhibits a broad substrate scope including ketones, aldehydes, esters, and amides. This work presents a simple and cost‐effective strategy for anchoring metal single atoms onto carbon nitride, providing a new platform for enabling high‐performance photocatalytic production of aryl ether compounds.
Fe‐Based Metal‐Organic Frameworks: From Various Synthesis, Diverse Structures to Multifunctional Applications
Authors: Wang Xiaokang , Xu Mingming , Fan Weidong , Sun Daofeng
Published: August 2023

Comprehensive Summary

Iron‐based metal‐organic frameworks (Fe‐MOFs) have attracted extensive interest from researchers due to their tunability, favorable properties, and chemical versatility. Compared with conventional porous materials, Fe‐MOFs exhibit better performance in a wide variety of applications. Herein, the structures of Fe‐MOFs are summarized to explore potential structures based on isoreticular chemistry, as well as the recent research progress in their synthesis and multifunctional applications. The rapid development of Fe‐MOFs has broadened the application range of Fe‐MOFs, and a brief description of Fe‐MOF applications in gas storage and separation, catalysis, bioimaging, and magnetism is outlined, with the aim to expand the prospects of Fe‐MOFs in more practical applications.
Electronic Structure of the Low‐Lying States of the Triatomic MoS2 Molecule: The Building Block of 2D MoS2
Authors: Mermigki Markella A. , Karapetsas Ioannis , Tzeli Demeter
Published: August 2023

Molybdenum disulfide (MoS2) is the building component of 1D‐monolayer, 2D‐layered nanosheets and nanotubes having many applications in industry, and it is detected in various molecular systems observed in nature. Here, the electronic structure and the chemical bonding of sixteen low‐lying states of the triatomic MoS2 molecule are investigated, while the connection of the chemical bonding of the isolated MoS2 molecule to the relevant 2D‐MoS2, is emphasized. The MoS2 molecule is studied via DFT and multireference methodologies, i. e., MRCISD(+Q)/aug‐cc‐pVQZ(−PP)Mo. The ground state,
3B1, is bent (Mo−S=2.133 Å and ϕ(SMoS)=115.9°) with a dissociation energy to atomic products of 194.7 kcal/mol at MRCISD+Q. In the ground and in the first excited state a double bond is formed between Mo and each S atom, i. e.,
. These two states differ in which d electrons of Mo are unpaired. The Mo−S bond distances of the calculated states range from 2.108 to 2.505 Å, the SMoS angles range from 104.1 to 180.0°, and the Mo−S bonds are single or double. Potential energy curves and surfaces have been plotted for the
3B1, 5A1 and 5B1 states. Finally, the low‐lying septet states of the triatomic molecule are involved in the material as a building block, explaining the variety of its morphologies.
Anion‐π Interactions: What's in the Name?
Authors: Rosokha Sergiy V.
Published: August 2023

The studies of the anion‐π interactions advanced during the last two decades from the discussion of the mere existence of this counter‐intuitive bonding to its utilization for anion recognition and transport, catalysis, and other applications. Yet, there are substantial differences in the interpretation of nature and the driving forces of anion‐π bonding. Most surprisingly, there are still different opinions about the meaning of this term (i. e., which associations can be considered anion‐π complexes). After a brief overview of the studies in this area (including early examples of such complexes), we suggested that anion‐π bonding occurs when there is evidence of a net attraction between a (close‐shell) anion and the face of an electrophilic π‐system. This definition encompasses fundamentally similar supramolecular complexes comprising diverse π‐systems and anions and its general acceptance would facilitate a discussion of the nature and distinct driving forces of this fascinating interaction.
Long Cycle‐Life Ca Batteries with Poly(anthraquinonylsulfide) Cathodes and Ca−Sn Alloy Anodes
Authors: Bier Daniel , Li Zhenyou , Klyatskaya Svetlana , Sbei Najoua , Roy Ananyo , Riedel Sibylle , Fichtner Maximilian , Ruben Mario , Zhao‐Karger Zhirong
Published: August 2023

Calcium (Ca) batteries are attractive post‐lithium battery technologies, due to their potential to provide high‐voltage and high‐energy systems in a sustainable manner. We investigated herein 1,5‐poly(anthraquinonylsulfide) (PAQS) for Ca‐ion storage with calcium tetrakis(hexafluoroisopropyloxy)borate Ca[B(hfip)4]2 [hfip=OCH(CF3)2] electrolytes. It is demonstrated that PAQS could be synthesized in a cost‐effective approach and be processed environmentally friendly into the electrodes. The PAQS cathodes could provide 94 mAh g−1 capacity at 2.2 V vs. Ca at 0.5C (1C=225 mAh g−1). However, cycling of the cells was severely hindered due to the fast degradation of the metal anode. Replacing the Ca metal anode with a calcium‐tin (Ca−Sn) alloy anode, the PAQS cathodes exhibited long cycling performance (45 mAh g−1 at 0.5C after 1000 cycles) and superior rate capability (52 mAh g−1 at 5C). This is mainly ascribed to the flexible structure of PAQS and good compatibility of the alloy anodes with the electrolyte solutions, which allow reversible quinone carbonyl redox chemistry in the Ca battery systems. The promising properties of PAQS indicate that further exploration of the organic cathode materials could be a feasible direction towards green Ca batteries.
Quantifying the Resistive Losses of the Catalytic Layers in Anion‐Exchange Membrane Fuel Cells
Authors: Douglin John C. , Vijaya Sankar Kalimuthu , Biancolli Ana Laura G. , Santiago Elisabete I. , Tsur Yoed , Dekel Dario R.
Published: August 2023

The existing gap in the ability to quantify the impacts of resistive losses on the performance of anion‐exchange membrane fuel cells (AEMFCs) during the lifetime of their operation is a serious concern for the technology. In this paper, we analyzed the ohmic region of an operating AEMFC fed with pure oxygen followed by CO2‐free air at various operating currents, using a combination of electrochemical impedance spectroscopy (EIS) and a novel technique called impedance spectroscopy genetic programming (ISGP). Presented here for the first time in this work, we isolated and quantified the individual effective resistance (Reff) values occurring in the AEMFC and their influence on performance as operating conditions change. We believe that this first work is vital to help distinguish the influence of the individual catalytic and mass‐transfer processes in this technology thereby providing valuable data to the AEMFC community, with potentially wider applicability to other electrochemical devices where individual physical processes occur simultaneously and need to be sequestered for deeper understanding.
A non‐isolated DC‐DC topology with high voltage rate based on magnetic coupling and voltage multiplier method
Authors: Yousefi Nasser , Mirabbasi Davar , Alfi Behrouz , Salimi Mahdi , Aghajani Gholamreza
Published: August 2023

In this study, a novel non‐isolated DC‐DC converter based on magnetic coupling and voltage multiplier technique has been proposed. The output voltage of the suggested converter can be enhanced by selecting the appropriate turn ratio of the coupled inductor. To further improve the voltage gain, a voltage multiplier circuit including the capacitors and diodes has been utilized in this converter. The main features of the proposed converter are a high voltage conversion ratio, high efficiency, and lower peak voltage throughout the semiconductor devices. Besides, there are soft switching conditions throughout the diodes of the presented topology, which leads to reducing the reverse recovery losses of the diodes and subsequently improving the overall efficiency of the system. Also, only one insulated‐gate field‐effect transistor (MOSFET) has been used in the structure of the converter. Thus, the switch with lower on‐state resistance can be selected for the suggested converter that decreases the conduction losses. To prove the performance of the suggested structure, the operational analysis, mathematical descriptions, efficiency analysis, and comparison survey with similar structures in the literature have been described. Finally, a laboratory prototype with 200 W output power with 95.14% load efficiency, 20 V input voltage, and 260 V output voltage at 50 kHz switching frequency has been provided.
Use of the SINBAD score as a predicting tool for major adverse foot events in patients with diabetic foot ulcer: A French multicentre study
Authors: Ha Van Georges , Schuldiner Sophie , Sultan Ariane , Bouillet Benjamin , Martini Jacques , Vouillarmet Julien , Menai Medhi , Foucher Aurélie , Bourron Olivier , Hartemann Agnes , Perrier Antoine
Published: August 2023

Objective

To assess the relationship between the site, ischaemia, neuropathy, bacterial infection, area, depth (SINBAD) score and major adverse foot events in patients with diabetes and foot ulcers.

Methods

For this retrospective ancillary study, patients (n = 537) followed for a diabetic foot ulcer (DFU) in six French hospitals were included between 1 February 2019 and 17 March 2019, and between 1 February 2020 and 17 March 2020. The SINBAD score was assessed at inclusion. The frequency of a composite outcome consisting of eight major adverse foot events (MAFE) was assessed after 5–6 months of follow‐up: hospitalisation for DFU, septic surgery, revascularisation, minor amputation, major amputation, death, secondary infection and ulcer recurrence. A logistical regression explored the link between the SINBAD score and MAFE and each of its component.

Results

A low SINBAD score (from 0 to 3) was observed in 61% of patients and a high (from 4 to 6) in 39%. MAFE occurred in, respectively, 24% and 28% of these patients. Multivariate analyses showed a significant relationship between the SINBAD score and MAFE, with the continuous SINBAD score: odds ratio (OR) 1.72 [95% CI (1.51–1.97)] or dichotomic SINBAD score (values: 0–3 and 4–6): OR 3.71 [95% CI (2.54–5.42)]. The SINBAD score (continuous or dichotomic) at inclusion was also significantly associated with six out of the eight components of the MAFE.

Conclusions

The SINBAD score is a useful tool for predicting major adverse foot events.
Antitangling and manufacturable Fog Harps for high‐efficiency water harvesting
Authors: Kaindu Jimmy K. , Murphy Kevin R. , Kowalski Nicholas G. , Jones Alexandra N. , Fleming Matthew Davis , Kennedy Brook S. , Boreyko Jonathan B.
Published: August 2023

Fog Harps harvest substantially more water than conventional mesh‐based harvesters. However, to date, all large‐scale Fog Harps have been impractically hand‐wound at low wire tensions and suffer from elastocapillary wire tangling. Here, we develop large‐scale and high‐tension Fog Harps that are manufacturable and antitangling. These Fog Harps retain the record‐setting fog harvesting efficiency (%) of their optimized scale‐model counterparts, while uniquely enabling practical real‐life implementation. Manufacturability was achieved by adapting the industrial process for making harp screens, a pre‐existing technology used for screening solid materials. The critical tension required to minimize wire tangling was rationalized by an improved elastocapillary tangling model.
Copper‐Catalyzed Synthesis of Alkynyl Thioamides: An Efficient Thioacylation of Alkynes
Authors: Du Jing , Zhao Shi‐Yi , Hu Zhi‐Chao , Yu Jun‐Xia , Dong Zhi‐Bing
Published: August 2023

A copper‐catalyzed efficient synthesis of alkynyl thioamides starting from tetraalkyl thiuram compounds (TMTM: tetramethyl thiuram monosulfide, TIBTM: tetraisobutyl thiuram monosulfide) and alkynes was reported. Thus, tetraalkyl thiurams reacted with alkynes smoothly, giving a variety of alkynyl thioamides promoted by CuI/Cs2CO3 system. This protocol features easy operation, inexpensive starting materials and good yields, illustrating its potential synthetic value for the synthesis of thioamides and their derivatives.
Bayesian spatio‐temporal survival analysis for all types of censoring with application to a wildlife disease study
Authors: Yao Kehui , Zhu Jun , O'Brien Daniel J. , Walsh Daniel
Published: August 2023

In this article, we consider modeling arbitrarily censored survival data with spatio‐temporal covariates. We demonstrate that under the piecewise constant hazard function, the likelihood for uncensored or right‐censored subjects is proportional to the likelihood of multiple conditionally independent Poisson random variables. To address left‐ or interval‐censored subjects, we propose to impute the exact event times and convert them into uncensored subjects, enabling the application of the integrated nested Laplace approximation to update model parameters using the imputed data. We introduce an iterative algorithm that alternates between imputing event times for left‐ and interval‐censored subjects and re‐estimating model parameters. The proposed method is assessed through a simulation study and applied to analyze a spatio‐temporal survival dataset in a wildlife disease study investigating bovine tuberculosis in white‐tailed deer in Michigan.
Predicting gully erosion susceptibility in South Africa by integrating literature directives with regional spatial data
Authors: Olivier George , Van De Wiel Marco J. , de Clercq Willem P.
Published: August 2023

Gully erosion has been identified as a severe land degradation process with environmental and socio‐economic consequences. Identifying areas susceptible to gully erosion will aid in developing strategies to inhibit future degradation. Various approaches have been implemented to predict and map gully erosion susceptibility but are mostly restricted to small geographical extents because of process limitations. Here, we introduce a novel method that predicts gully erosion susceptibility on a regional/national scale (1.22 million km2) by synthesising literature directives with a statistical approach. Findings from a literature review were used to extract physiographic properties associated with gully erosion that was conditioned to characterise susceptibility by using the Frequency Ratio model. The conditioned physiographic properties were aggregated by a weighted overlay procedure using an aggregation of controlling factors derived from the literature review as a weighting system. The gully susceptibility index (GSI) model was validated against a published gully inventory map (n = 163 019) and randomly generated 1‐km2 tessellation zones from which primary validation data were derived. Although uncertainties within the modelling procedure exist (e.g., gully site distribution, the spatial resolution of input data and determination of gully points), the validation shows that the GSI model is generally robust, identifying areas of contrasting susceptibilities. Furthermore, findings converge with other susceptibility metrics, which have been derived by different methodologies. Because empirical gully erosion research has been conducted worldwide, this model could be applied to regional‐scale gully susceptibility modelling assessments (as a solitary method or combined with primary data) in other parts of the world. Additionally, the GSI model can be adopted to model environmental change scenarios.
The multifactor pelvis: An alternative to the adaptationist approach of the obstetrical dilemma
Authors: Warrener Anna
Published: August 2023

The obstetrical dilemma describes the competing demands that a bipedally adapted pelvis and a large‐brained neonate place on human childbirth and is the predominant model within which hypotheses about the evolution of the pelvis are framed. I argue the obstetrical dilemma follows the adaptationist program outlined by Gould and Lewontin in 1979 and should be replaced with a new model, the multifactor pelvis. This change will allow thorough consideration of nonadaptive explanations for the evolution of the human pelvis and avoid negative social impacts from considering human childbirth inherently dangerous. First, the atomization of the pelvis into discrete traits is discussed, after which current evidence for both adaptive and nonadaptive hypotheses is evaluated, including childbirth, locomotion, shared genetics with other traits under selection, evolutionary history, genetic drift, and environmental and epigenetic influences on the pelvis.
Induction of more aggressive tumoral phenotypes in LNCaP and PC3 cells by serum exosomes from prostate cancer patients
Authors: Huertas‐Lárez Raquel , Muñoz‐Moreno Laura , Recio‐Aldavero Jorge , Román Irene Dolores , Arenas María Isabel , Blasco Ana , Sanchís‐Bonet Ángeles , Bajo Ana M.
Published: August 2023

Prostate cancer (PCa) is the second most frequent and sixth most fatal cancer in men worldwide. Despite its high prevalence, our understanding of its etiology and the molecular mechanisms involved in the progression of the disease is substantially limited. In recent years, the potential participation of exosomes in this process has been suggested. Therefore, we aim to study the effect of exosomes isolated from the serum of patients with PCa on various cellular processes associated with increased tumor aggressiveness in two PCa cell lines: LNCaP‐FGC and PC3. The exosomes were isolated by filtration wand ultracentrifugation. Their presence was confirmed by immunodetection of specific markers and their size distribution was analyzed by Dynamic Light Scattering (DLS). The results obtained demonstrated that serum exosomes from PCa patients increased migration of PC3 cells and neuroendocrine differentiation of LNCaP‐FGC cells regardless of the grade of the tumor. PCa serum exosomes also enhanced the secretion of enzymes related to invasiveness and resistance to chemotherapeutics, such as extracellular matrix metalloproteases 2 and 9, and gamma‐glutamyltransferase in both cell lines. Altogether, these findings support the pivotal participation of exosomes released by tumoral cells in the progression of PCa. Future studies on the molecular mechanisms involved in the observed changes could provide crucial information on this disease and help in the discovery of new therapeutic targets.