bluuebunny/crossref_metadata_2025 huggingface dataset:
Enabling Efficient Anchoring‐Conversion Interface by Fabricating Double‐Layer Functionalized Separator for Suppressing Shuttle Effect
Authors: Feng Junan , Zhang Chaoyue , Liu Wendong , Yu Shunxian , Wang Lei , Wang Tianyi , Shi Chuan , Zhao Xiaoxian , Chen Shuangqiang , Chou Shulei , Song Jianjun
Published: July 2024

Lithium‐sulfur batteries (LiSBs) with high energy density still face challenges on sluggish conversion kinetics, severe shuttle effects of lithium polysulfides (LiPSs), and low blocking feature of ordinary separators to LiPSs. To tackle these, a novel double‐layer strategy to functionalize separators is proposed, which consists of Co with atomically dispersed CoN4 decorated on Ketjen black (Co/CoN4@KB) layer and an ultrathin 2D Ti3C2Tx MXene layer. The theoretical calculations and experimental results jointly demonstrate metallic Co sites provide efficient adsorption and catalytic capability for long‐chain LiPSs, while CoN4 active sites facilitate the absorption of short‐chain LiPSs and promote the conversion to Li2S. The stacking MXene layer serves as a microscopic barrier to further physically block and chemically anchor the leaked LiPSs from the pores and gaps of the Co/CoN4@KB layer, thus preserving LiPSs within efficient anchoring‐conversion reaction interfaces to balance the accumulation of “dead S” and Li2S. Consequently, with an ultralight loading of Co/CoN4@KB‐MXene, the LiSBs exhibit amazing electrochemical performance even under high sulfur loading and lean electrolyte, and the outperforming performance for lithium‐selenium batteries (LiSeBs) can also be achieved. This work exploits a universal and effective strategy of a double‐layer functionalized separator to regulate the equilibrium adsorption‐catalytic interface, enabling high‐energy and long‐cycle LiSBs/LiSeBs.
Tensile‐Strained Cu Penetration Electrode Boosts Asymmetric C−C Coupling for Ampere‐Level CO2‐to‐C2+ Reduction in Acid
Authors: Li Shoujie , Wu Gangfeng , Mao Jianing , Chen Aohui , Liu Xiaohu , Zeng Jianrong , Wei Yiheng , Wang Jiangjiang , Zhu Huanyi , Xia Jiayu , Wang Xiaotong , Li Guihua , Song Yanfang , Dong Xiao , Wei Wei , Chen Wei
Published: July 2024

The synthesis of multicarbon (C2+) products remains a substantial challenge in sustainable CO2 electroreduction owing to the need for sufficient current density and faradaic efficiency alongside carbon efficiency. Herein, we demonstrate ampere‐level high‐efficiency CO2 electroreduction to C2+ products in both neutral and strongly acidic (pH=1) electrolytes using a hierarchical Cu hollow‐fiber penetration electrode (HPE). High concentration of K+ could concurrently suppress hydrogen evolution reaction and facilitate C−C coupling, thereby promoting C2+ production in strong acid. By optimizing the K+ and H+ concentration and CO2 flow rate, a faradaic efficiency of 84.5 % and a partial current density as high as 3.1 A cm−2 for C2+ products, alongside a single‐pass carbon efficiency of 81.5 % and stable electrolysis for 240 h were demonstrated in a strong acidic solution of H2SO4 and KCl (pH=1). Experimental measurements and density functional theory simulations suggested that tensile‐strained Cu HPE enhances the asymmetric C−C coupling to steer the selectivity and activity of C2+ products.
Optimizing the Microenvironment in Solid Polymer Electrolytes by Anion Vacancy Coupled with Carbon Dots
Authors: Liu Huaxin , Ye Yu , Zhu Fangjun , Zhong Xue , Luo Dingzhong , Zhang Yi , Deng Wentao , Zou Guoqiang , Hou Hongshuai , Ji Xiaobo
Published: July 2024

The practical application of solid polymer electrolyte is hindered by the small transference number of Li+, low ionic conductivity and poor interfacial stability, which are seriously determined by the microenvironment in polymer electrolyte. The introduction of functional fillers is an effective solution to these problems. In this work, based on density functional theory (DFT) calculations, it is demonstrated that the anion vacancy of filler can anchor anions of lithium salt, thereby significantly increasing the transference number of Li+ in the electrolyte. Therefore, flower‐like SnS2‐based filler with abundant sulfur vacancies is prepared under the regulation of functionalized carbon dots (CDs). It is worth mentioning that the CDs dotted on the surface of SnS2 have rich organic functional groups, which can serve as the bridging agent to enhance the compatibility of filler and polymer, leading to superior mechanical performance and fast ion transport pathway. Additionally, the in situ formed Li2S/Li3N at the interface of Li metal and electrolyte facilitate the fast Li+ diffusion and uniform Li deposition, effectively mitigating the growth of lithium dendrites. As a result, the assembled lithium metal batteries exhibit excellent cycling stability, reflecting the superiority of the carbon dots derived vacancy‐rich inorganic filler modification strategy.
Modular, Scalable Total Synthesis of Lapparbin with a Noncanonical Biaryl Linkage
Authors: Zhang Jie , Yu Longhui , Ogawa Hiroshige , Nagata Yuuya , Nakamura Hugh
Published: July 2024

We report the development of a novel synthetic approach for the highly strained atrop‐Tyr C‐6‐to‐Trp N‐1′ linkage, which can be executed on a decagram scale using a modular strategy involving palladium‐catalyzed C−H arylation followed by Larock macrocyclization. The first total synthesis of lapparbin (1) was achieved by applying this synthetic strategy. Furthermore, the modular synthesis utilizing C−H arylation and Larock macrocyclization, discovered in the total synthesis of lapparbin (1), was demonstrated to be applicable to various arbitrary biaryl linkages, including non‐natural types.
Enantioselective (3+2) Annulation of Donor‐Acceptor Cyclopropanes with Aldehydes and Ketones Catalyzed by Brønsted Bases
Authors: Obregón Erlaitz B. , Rost Louise G. , Kocemba Ida R. , Kristensen Anne , McLeod David A. , Jørgensen Karl Anker
Published: July 2024

The substituted tetrahydrofuran core is a structural motif in many biologically active and natural compounds. However, the scarcity of enantioselective methods developed towards its synthesis makes this field challenging and attractive to explore. Herein, the first Brønsted‐base catalyzed enantioselective (3+2) annulation of donor‐acceptor cyclopropanes with aldehydes and ketones affording enantioenriched 2,3,5‐substituted tetrahydrofurans is reported. The reaction concept is based on activation of racemic β‐cyclopropyl ketones by a chiral bifunctional Brønsted base which catalyzes the (3+2) annulation for a range of aldehydes and ketones. For aldehydes, the annulation furnished tetrahydrofurans in excellent yield, good diastereoselectivity and with excellent enantioselectivity up to >99 % ee. Surprisingly, aromatic aldehydes afforded the cis‐2,5‐substituted tetrahydrofurans as the major diastereoisomer, while for aliphatic aldehydes the trans‐cycloadduct was favored. The reaction also proceeds well for ketones affording spiro tetrahydrofurans in excellent yields and enantioselectivities (up to 99 % ee). Hammett studies have been conducted to elucidate the influence of the electronic nature of benzaldehydes on the stereoselectivity. Based on the diastereochemical outcome for the aldehydes, two reaction paths for aromatic and aliphatic aldehydes are proposed. Finally, two diastereoselective synthetic transformations have been conducted to demonstrate the synthetic potential of the obtained products.
Organic‐Inorganic Hybrid Cuprous‐Based Metal Halides with Unique Two‐Dimensional Crystal Structure for White Light‐Emitting Diodes
Authors: Meng Xuan , Jiang Junke , Yang Xinyu , Zhao Hongyuan , Meng Qichao , Bai Yunfei , Wang Qiujie , Song Jitao , Katan Claudine , Even Jacky , Yu William W. , Liu Feng
Published: July 2024

Ternary cuprous (Cu+)‐based metal halides, represented by cesium copper iodide (e.g., CsCu2I3 and Cs3Cu2I5), are garnering increasing interest for light‐emitting applications owing to their intrinsically high photoluminescence quantum yield and direct band gap. Toward electrically driven light‐emitting diodes (LEDs), it is highly desirable for the light emitters to have a high structural dimensionality as it may favor efficient electrical injection. However, unlike lead‐based halide perovskites whose light‐emitting units can be facilely arranged in three‐dimensional (3D) ways, to date, nearly all ternary Cu+‐based metal halides crystallize into 0D or 1D networks of Cu−X (X=Cl, Br, I) polyhedra, whereas 3D and even 2D structures remain mostly uncharted. Here, by employing a fluorinated organic cation, we report a new kind of ternary Cu+‐based metal halides, (DFPD)CuX2 (DFPD+=4,4‐difluoropiperidinium), which exhibits unique 2D layered crystal structure. Theoretical calculations reveal a highly dispersive conduction band of (DFPD)CuBr2, which is beneficial for charge carrier injection. It is also of particular significance to find that the 2D (DFPD)CuBr2 crystals show appealing properties, including improved ambient stability and an efficient warm white‐light emission, making it a promising candidate for single‐component lighting and display applications.
Molecular Editing of Pyrroles to Benzenes/Naphthalenes by N2O Deletion.
Authors: Xiao Wen‐jie , Li Cheng‐xin , Lv Jing‐yi , Xu Shan , Shi Wen‐xia , Su Xiao‐can , Xue Jia‐ying , Huang Bao‐qin , Zou Yong , Yan Ming , Zhang Xue‐jing
Published: July 2024

Molecular editing promises to facilitate the rapid diversification of complex molecular architectures by rapidly and conveniently altering core frameworks. This approach has the potential to accelerate both drug discovery and total synthesis. In this study, we present a novel protocol for the molecular editing of pyrroles. Initially, N‐Boc pyrroles and alkynes are converted into N‐bridged compounds through a Diels–Alder reaction. These compounds then undergo deprotection of the Boc group, nitrosylation, and cheletropic N2O extrusion to yield benzene or naphthalene products. By using benzyne as a substrate, this method can be conceptually viewed as a fusion of skeletal editing of the pyrrole ring and site‐selective peripheral editing of the benzene ring. Furthermore, this proof‐of‐concept protocol has demonstrated its potential to transform the (hetero)arene motif from commercially available drugs, offering the possibility of generating new biologically active compounds.
Non‐Isocyanate Synthesis of Covalent Adaptable Networks Based on Dynamic Hindered Urea Bonds: Sequential Polymerization and Chemical Recycling
Authors: Lyu Jihong , Lee Seulchan , Bae Hyoung Eun , Jung Hyocheol , Park Young Il , Jin Young‐Jae , Jeong Ji‐Eun , Kim Jin Chul
Published: July 2024

The development of environmentally sustainable processes for polymer recycling is of paramount importance in the polymer industry. In particular, the implementation of chemical recycling for thermoset polymers via covalent adaptable networks (CANs), particularly those based on the dynamic hindered urea bond (HUB), has garnered intensive attention from both the academic and industrial sectors. This interest stems from its straightforward chemical structure and reaction mechanism, which are well‐suited for commercial polyurethane and polyurea applications. However, a substantial drawback of these CANs is the requisite use of toxic isocyanate curing agents for their synthesis. Herein, we propose a new HUB synthesis pathway involving thiazolidin‐2‐one and a hindered amine. This ring‐opening reaction facilitates the isocyanate‐free formation of a HUB and enables sequential reactions with acrylate and epoxide monomers via thiol–Michael and thiol–epoxy click chemistry. The CANs synthesized using this methodology exhibit superior reprocessability, chemical recyclability, and reutilizability, facilitated by specific catalytic and solvent conditions, through the reversible HUB, thiol–Michael addition, and transesterification processes.
Butadiene Sulfone Based Binary Deep Eutectic Electrolyte for High Performance Lithium Metal Batteries
Authors: Zhou Tiankun , Lei Chengjun , Li Jinye , Wang Huijian , Liu Tingting , He Xin , Liang Xiao
Published: July 2024

Deep eutectic electrolytes (DEEs) have attracted significant interest due to the unique physiochemical properties, yet challenges persist in achieving satisfactory Li anode compatibility through a binary DEE formula. In this study, we introduce a nonflammable binary DEE electrolyte comprising of lithium bis(trifluoro‐methane‐sulfonyl)imide (LiTFSI) and solid butadiene sulfone (BdS), which demonstrates enhanced Li metal compatibility while exhibiting high Li+ ion migration number (0.52), ionic conductivity (1.48 mS ⋅ cm−1), wide electrochemical window (~4.5 V vs. Li/Li+) at room temperature. Experimental and theoretical results indicate that the Li compatibility derives from the formation of a LiF‐rich SEI, attributed to the undesirable adsorption and deformation of BdS on Li surface that facilitates the preferential reactions between LiTFSI and Li metal. This stable SEI effectively suppresses dendrites growth and gas evolution reactions, ensuring a long lifespan and high coulombic efficiency in both the Li||Li symmetric cells, Li||LiCoO2 and Li||LiNi0.8Co0.1Mn0.1O2 full cells. Moreover, the BdS eutectic strategy exhibit universal applicability to other metal such as Na and Zn by pairing with the corresponding TFSI‐based salts.
First Main‐Group Element Lewis Acid Thionyl Chloride Adduct and its Chemistry
Authors: Tölke Katharina , Porath Sven , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold
Published: July 2024

Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]−, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and ‐indate, [M(C2F5)4]− (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M=Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally determined by the (modified) Gutmann‐Beckett method and their catalytic potential is showcased.
An Organic Molecular Mimetic Metal‐Free Heterogeneous Catalyst for Electrocatalytic Alkyne Semihydrogenation
Authors: Song Ziyang , Yang Rong , Liu Xinyu , Zhang Bin , Wu Yongmeng
Published: July 2024

The direct construction of metal‐free catalysts on conductive substrates for electrocatalytic organic hydrogenation reactions is significant but still unexplored. Here, learning from the homogeneous molecular catalysts, an organic molecular mimetic metal‐free heterogeneous catalyst is designed and constructed in situ on a graphite flake electrode via a mild electrochemical oxidation‐reduction relay strategy. The as‐prepared −COOH‐ and −OH‐functionalized metal‐free catalyst exhibits an electrocatalytic alkyne semihydrogenation performance with a 72 % Faradaic efficiency, 99 % selectivity and 96 % yield of the alkene product, which is comparable to that of noble metal catalysts. The removal of these oxygen‐containing groups leads to negligible activity. The experimental and calculation results reveal that the origin of the high activity can be assigned to the −COOH and −OH groups on graphite. A flow electrolytic cell delivers ten grams of hydrogenated products with 81 % Faradaic efficiency. This metal‐free catalyst is also suitable for gas‐phase acetylene semihydrogenation and other electrocatalytic hydrogenation reactions.
Subsurface Single‐Atom Catalyst Enabled by Mechanochemical Synthesis for Oxidation Chemistry
Authors: Guan Xuze , Han Rong , Asakura Hiroyuki , Wang Bolun , Chen Lu , Yan Jay Hon Cheung , Guan Shaoliang , Keenan Luke , Hayama Shusaku , van Spronsen Matthijs A. , Held Georg , Zhang Jie , Gu Hao , Ren Yifei , Zhang Lun , Yao Zhangyi , Zhu Yujiang , Regoutz Anna , Tanaka Tsunehiro , Guo Yuzheng , Wang Feng Ryan
Published: July 2024

Single‐atom catalysts have garnered significant attention due to their exceptional atom utilization and unique properties. However, the practical application of these catalysts is often impeded by challenges such as sintering‐induced instability and poisoning of isolated atoms due to strong gas adsorption. In this study, we employed the mechanochemical method to insert single Cu atoms into the subsurface of Fe2O3 support. By manipulating the location of single atoms at the surface or subsurface, catalysts with distinct adsorption properties and reaction mechanisms can be achieved. It was observed that the subsurface Cu single atoms in Fe2O3 remained isolated under both oxidation and reduction environments, whereas surface Cu single atoms on Fe2O3 experienced sintering under reduction conditions. The unique properties of these subsurface single‐atom catalysts call for innovations and new understandings in catalyst design.
Correction of the cracking mechanism ratio in catalytic cracking process to characterize the thermal cracking reaction and realize highly sensitive identification of catalysts
Authors: Li Di , Dai Xiaojun , Shi Baozhen
Published: July 2024

In this work, we have specially carried out the catalytic cracking experiments of heavy distillate oil in the high temperature range of 500~700°C. The composition of dry gas generated in the catalytic cracking process was analyzed, with emphasis on the variation of yield of C1 and C2 products. Two cracking mechanism ratios (CMRs) were redefined by replacing the (C1 + C2) products in the traditional definition of CMR with CH4, and the feasibility of using them to characterize the thermal cracking reaction in the catalytic cracking process in the high temperature range was investigated. The results showed that CH4 was more sensitive to temperature than (C1 + C2) and it was feasible and more accurate to use CH4 instead of (C1 + C2) corrected R3 to characterize the thermal cracking reaction in the catalytic cracking process in the high temperature range. In addition, it was found that the corrected R3 had the effect of distinguishing and identifying catalysts.
Advanced, high‐performance thermo‐insulating plaster
Authors: Athanasiadi A. , Andrikopoulou M. , Smyrnioti M. , Georgiou Y. , Zamparas M. , Dracopoulos V. , Ioannides T.
Published: July 2024

The main purpose of many current studies regarding energy efficiency is the improvement of the thermal resistance of buildings. To fulfill this goal, the development of advanced insulating materials, to be incorporated in the building envelopes, is imperative. Aerogels are ultralight porous materials typically produced via the sol‐gel process followed by supercritical drying of the wet gel. They exhibit very high porosities and a mesoporous‐macroporous structure which endows aerogels with extremely low thermal conductivity. This makes them ideal candidates for ambient thermal insulation applications. However, the cost for aerogel insulation is considerably higher than the one of standard insulation products. In the present work, highly porous aerogel‐like materials based on silica and commercial novolac resin were developed and added to common mortars. The prepared materials were dried under ambient pressure to minimize the manufacturing cost. The bulk density of silica quasi‐aerogels was 0.03 g/cm3–0.09 g/cm3 and that of the novolac resin samples 0.09 g/cm3–0.21 g/cm3. The aerogels were incorporated in mortars and cured for 28 days before measurement of thermal conductivity. The values of the thermal conductivity coefficient of the measured samples were 0.047 W/m K–0.058 W/m K for the silica reinforced mortars and 0.036 W/m K–0.044 W/m K for the novolac reinforced ones.
Isolation management to protect threatened native galaxiid fish species: Lessons from Aotearoa New Zealand
Authors: Jolly Martha E. , Warburton Helen J. , Bowie Sjaan , Challies Edward , Jellyman Phillip G. , McIntosh Angus R.
Published: July 2024

The use of barriers in freshwater systems to mitigate invasions, known as isolation management, has been increasingly implemented as a protection strategy for native fish. Barriers are crucial for securing vulnerable populations, but much remains to be learnt about the drivers of success and the implications of deliberate fragmentation.

In Aotearoa‐New Zealand, henceforth Aotearoa, native non‐migratory galaxiid (NMG) fishes are characterized by a disproportionate number of threatened species with introduced salmonids (trout) identified as a key driver of NMG declines.

We conducted a qualitative review of barriers protecting NMG in Aotearoa, illustrating varying outcomes and current knowledge gaps with case studies. Barrier types ranged from natural bedrock waterfalls, shallow velocity chutes and drying reaches to deliberately engineered structures (known commonly as exclusion barriers). Barriers were typically located in headwater streams or spring systems. NMG species secured by fragmentation often have high conservation value and barriers are essential for their protection.

Despite the critical role of these barriers, the isolated NMG populations above them are at risk of stochastic extirpation, invasion, or re‐invasion. Exclusion barriers may restrict access to habitat for native migratory fish species and can sometimes alter or remove ideal mesohabitat from protected populations.

Overall, when using exclusion barriers, managers must assess extinction risk for individual populations by isolation or invasion, balancing benefits and consequences. However, these assessments are frequently based on incomplete data and hindered by lack of general understanding of the underpinning processes. Despite well‐documented benefits to NMG population survival, key knowledge gaps such as long‐term viability of isolated populations, combinations of physical barrier parameters conferring exclusion under all flow regimes and extent of habitat loss to other native species still exist.
Design, synthesis, and biological evaluation of naphthalene imidazo[1,2‐b]pyridazine hybrid derivatives as VEGFR selective inhibitors
Authors: Wang Shuang , Gan LinLing , Han Lei , Deng Ping , Li Yihao , He Dongxiao , Chi Haoze , Zhu Liwei , Li Yuehui , Long Rui , Gan Zongjie
Published: July 2024

The vascular endothelial growth factor receptor (VEGFR) is a receptor tyrosine kinase that is regarded as an emerging target for abnormal angiogenesis diseases. In this study, novel naphthalene imidazo[1,2‐b]pyridazine hybrids as VEGFR selective inhibitors were designed and synthesized using a scaffold hopping strategy based on ponatinib, a multitarget kinase inhibitor. Among the evaluated compounds, derivative 9k (WS‐011) demonstrated the most potent inhibitory potency against VEGFR‐2 (IC50 = 8.4 nM) and displayed superior VEGFR selectivity over a panel of 70 kinases compared with ponatinib. Furthermore, 9k possessed good cytotoxic effects on various cancer cell lines, especially the colon cancer HT‐29 cells, with an acceptable oral bioavailability. Moreover, 9k significantly inhibited the migration and invasion of human umbilical vein endothelial cells (HUVEC) cells and induced apoptosis through the upregulation of apoptotic proteins in HT‐29 cells. 9k also effectively suppressed the activation of VEGFR‐2 signaling pathways, which in turn inhibited the growth of HT‐29 cells and the tube formation of HUVECs in vitro. All of the findings revealed that 9k could be considered a promising antiangiogenesis lead that merits further investigation.
Soft drug inhibitors for the epigenetic targets lysine‐specific demethylase 1 and histone deacetylases
Authors: Seitz Johannes , Auth Marina , Prinz Tony , Hau Mirjam , Tzortzoglou Pavlos , Schulz‐Fincke Johannes , Schmidtkunz Karin , Baniahmad Adina A. , Willmann Dominica , Metzger Eric , Hein Lutz , Preissl Sebastian , Schüle Roland , Jung Manfred
Published: July 2024

Epigenetic modulators such as lysine‐specific demethylase 1 (LSD1) and histone deacetylases (HDACs) are drug targets for cancer, neuropsychiatric disease, or inflammation, but inhibitors of these enzymes exhibit considerable side effects. For a potential local treatment with reduced systemic toxicity, we present here soft drug candidates as new LSD1 and HDAC inhibitors. A soft drug is a compound that is degraded in vivo to less active metabolites after having achieved its therapeutic function. This has been successfully applied for corticosteroids in the clinic, but soft drugs targeting epigenetic enzymes are scarce, with the HDAC inhibitor remetinostat being the only example. We have developed new methyl ester‐containing inhibitors targeting LSD1 or HDACs and compared the biological activities of these to their respective carboxylic acid cleavage products. In vitro activity assays, cellular experiments, and a stability assay identified potent HDAC and LSD1 soft drug candidates that are superior to their corresponding carboxylic acids in cellular models.
A new extended δ‐shock model with the consideration of shock magnitude
Authors: Lorvand Hamed , Eryilmaz Serkan
Published: July 2024

In this article, a new ‐shock model that takes into account the magnitude of shocks is introduced and studied from reliability perspective. According to the new model, the system breaks down if either a shock after non‐critical shock occurs in a time length less than or a shock after a critical shock occurs in a time length less than where . The distribution of the system's lifetime is studied for both discrete and continuous intershock time distributions. It is shown that a new model is useful to describe a certain cold standby repairable system.
Influences on androgen deprivation therapy prescribing before surgery in high‐risk prostate cancer
Authors: Dunsmore Jennifer , Duncan Eilidh , MacLennan Sara J. , N'Dow James , Cornford Philip , Esperto Francesco , Pavan Nicola , Ribal María J. , Roobol Monique J. , Skolarus Ted A. , MacLennan Steven
Published: July 2024

Objectives

To understand how best to further reduce the inappropriate use of pre‐surgical androgen deprivation therapy (ADT), we investigated the determinants (influences) of ADT prescribing in urologists in two European countries using an established behavioural science approach. Additionally, we sought to understand how resource limitations caused by COVID‐19 influenced this practice. Identification of key determinants, of undistributed and disrupted practice, will aid development of future strategies to reduce inappropriate ADT prescribing in current and future resource‐limited settings.

Participants and Methods

We conducted semi‐structured qualitative interviews with urologists practicing in Italy and the UK from February to July 2022. Interviews focussed on undisrupted (usual) practice and disrupted practice (changes made during COVID‐19 restrictions). Codes were generated inductively and were mapped to the 14 domains of the Theoretical Domains Framework. Relevant domains of influence were identified, and the similarities and differences between the UK and Italy were distinguished.

Results

We identified 10 domains that were influential to ADT prescribing in the UK and eight in Italy. The role of guidance and evidence, the cancer care setting, the patients and the urologist's beliefs and experiences were identified as areas that were influential to ADT prescribing before surgery. Twenty‐one similarities and 22 differences between the UK and Italy, for usual and COVID‐19 practice, were identified across these 10 domains.

Conclusion

Similarities and differences influencing ADT prescribing prior to surgery should be considered in behavioural strategy development and tailoring to reduce inappropriate ADT use. We gained an understanding of usual, undistributed care and resource‐limited or disrupted care due to COVID‐19 in two European countries. This gives an indication of how influences on ADT prescribing may change in future resource‐limited circumstances and where efforts can be focused now and in future.
Synthesis, Insecticide Evaluation & Molecular Docking Studies of Some New Functionalized Pyrazole Derivatives Against the Cotton Leafworm, Spodoptera littoralis
Authors: Mousa Sayed A. S. , El‐Qaliei Mohamed I. H. , Atalla Ahmed A. , Hussien Ahmed H. H. , Khodairy Ahmed , Abdou Aly , Drar Ali M. , Gad Mohamed A.
Published: July 2024

5‐(Cyanomethyl)‐3‐((5,5‐dimethyl‐3‐oxocyclohex‐1‐en‐1‐yl)amino)‐1H‐pyrazole‐4‐carbonitrile (3) is used as a key for the synthesis of arylidenes 5 a–fvia its reaction with some aldehydes 4 a–f. 5‐[(5,5‐Dimethyl‐3‐oxocyclohex‐1‐en‐1‐yl)amino]‐3‐(2‐imino‐2H‐chromen‐3‐yl)‐1H‐pyrazole‐4‐carbonitrile (7) was synthesized via the reaction of compound (3) with 2‐Hydroxybenzaldehyde in EtOH/piperidine. The target compounds were tested against cotton leafworm larvae in their second and fourth instar. The available data demonstrated that the LC50 values for commercial phenylpyrazole were 3.37 mg/L and 4.55 mg/L for the most affected synthesized compound, 5 b. The chemical structure of compound 5 bhas two cyano moieties, a pyrazole ring and a chlorophenyl, which may be increasing it efficiency. Evaluation of the latent effects of the examined synthesized compounds on various biological parameters, including adult longevity, pupal weight, proportion of normal, deformed pupae, adult emergency, fecundity, and egg hatchability, was done in an additional effort to slightly improve insecticidal compounds. Seven target synthesized compounds were subjected to a molecular docking analysis against glutamate‐activated chloride channels. Twelve artificial compounds with the PDB ID of 4COF were subjected to a molecular docking study against the gamma‐aminobutyric acid receptor (GABA).
Synthesis, Antimicrobial Evaluation, DFT, in Silico‐Docking, and ADMET Investigations of Novel Chromene‐Based 2,4‐Thiazolidinediones
Authors: Mohamed Ahmed Mohamed S. , Alfraiji Redhab AJ , Attaby Fawzy A. , Abdallah Zeinab A.
Published: July 2024

Three series of thiazolidinedione (TZD) derivatives (5a‐f, 7a‐f, and 9a‐f) were prepared efficiently. Afterward, the synthesized candidates’ antibacterial efficacy against both gram‐positive and gram‐negative bacteria was assessed. Compounds 7c, 7d, and 7f had values comparable to that of ampicillin, a reference antibiotic, whereas compounds 5c, 5d, and 7e exhibited the greatest values (23.0±1.0, 27.7±0.6, and 20.0±1.0, respectively) against gram‐positive bacteria (Staphylococcus aureus). The optimal structure of the produced molecules was determined by DFT computing. To assess the binding energy and elucidate the interaction between the potential candidates and different proteins, in silico docking is employed. ADMET analysis to assess the synthesized compounds’ toxicity, metabolism, excretion, distribution, and absorption.
Hypolipidemic Effects of Mesona chinensis Benth Polysaccharides with Different Structures and Molecular Weights
Authors: Du Jia‐lin , Xiao Lu‐Hua , Yang Jie‐hui , Luo Qing , Li Jing‐wen , Feng Ying‐shan , Zhan Ruo‐Ting , Yan Ping
Published: July 2024

Four novel Mesona chinensis Benth polysaccharides were isolated using aqueous alcohol precipitation. Their molecular weights were determined using high‐performance gel permeation chromatography: MA1 (2.3 kDa), MA2 (80.5 kDa), MA3 (180.9 kDa), and MA4 (635.2 kDa), and their compositions were analyzed using GC–MS. The polysaccharides were mainly D‐glucose, D‐galactose, L‐Rhamnose, D‐arabinose, D‐xylose, and D‐mannose. The structural characteristics were further analyzed using infrared spectrophotometry and were identified as a type of pyrrhic sugar. An insulin‐induced insulin resistance model of HepG2 cells and oleic acid‐induced fat accumulation model of insulin were established to evaluate the hypolipidemic effects. Three Bacteroides spp. [Bacteroides thetaiotaomicron (BT), B. ovatus (BO), and B. cellulosilyticus (BC)] that were negatively correlated with lipid‐lowering activity were used to evaluate the lipid‐lowering activity of polysaccharides. The Bacteroides metabolites of MA1 and MA2 exhibited hypolipidemic effects and antioxidant activities and could potentially be used as lipid‐lowering supplements.
Synthesis of Novel Benazepril‐Derived Trizole Compounds Assisted by Ultrasound: In Vitro and In Silico Analysis for Potential Anticancer Properties
Authors: Ettam Ashok , Rao L. Vaikunta , Balakishan Guniganti , Kancha Rama Krishna , Mullaguri Sai Chairitha , Kumar K. Shiva
Published: July 2024

Benazepril‐based novel trizole derivatives are being explored as potential anticancer agents, designed with an N‐substituted 1,2,3‐triazole moiety linked to Benazepril's N‐1 position via a methylene bridge. An ultrasound irradiated CuAAC method was used to prepare all these compounds and evaluated their anti‐proliferative activities against cancer and drug‐resistant cell lines. While some of these compounds demonstrated anti‐proliferative activity towards leukemic cancer cell line K562, two of them displayed complete inhibitory activity. Interestingly, the compounds 5n and 5o showed potent activity against imatinib‐resistant cell lines suggesting their promise to overcome cancer drug resistance. Furthermore, molecular docking analysis revealed that compounds 5n and 5o have higher predicted sensitivity towards ACE protein when compared to benazepril and lisinopril indicating their value as potential drug lead molecules. This research introduces a distinctive approach by employing ultrasound to facilitate CuAAC reactions in medicinal chemistry.
Integrated analysis of differentially m6A modified and expressed lncRNAs for biomarker identification in coronary artery disease
Authors: Jiang Rongli , Jia Qiaowei , Li Chengcheng , Gan Xiongkang , Zhou Yaqing , Pan Yang , Fu Yahong , Chen Xiumei , Liang Lanyu , Jia Enzhi
Published: July 2024

N6‐methyladenosine (m6A) is the most prevalent internal RNA modification in mammals. However, limited research has been conducted on the role of m6A in coronary artery disease (CAD). We conducted methylated RNA immunoprecipitation sequencing and RNA sequencing to obtain a genome‐wide profile of m6A‐modified long noncoding RNAs (lncRNAs) in human coronary artery smooth muscle cells either exposed to oxidized low‐density lipoprotein treatment or not, and the characteristics of the expression profiles were explored using Gene Ontology and Kyoto Encyclopedia of Genes and Genomes analyses. The predictive effects of seven selected lncRNAs on CAD were evaluated in peripheral blood mononuclear cells (PBMCs). The differentially m6A‐modified and expressed lncRNAs related genes were predominantly enriched in small GTPase‐mediated signal transduction, ErbB signaling, and Rap1 signaling. Additionally, the expression levels of uc003pes.1, ENST00000422847, and NR_110155 were significantly associated with CAD, with uc003pes.1 identified as an independent risk factor and NR_110155 as an independent protective factor for CAD. NR_110155 and uc003pes.1 in PBMCs have the potential to serve as biomarkers for predicting CAD.
A rare case of pericardial sarcoidosis presenting as chest pain
Authors: El Sharu Husam , Jain Prarthana , Singer Bart , Snyder E. Amanda
Published: July 2024

Key Clinical Message

Pericardial sarcoidosis is an uncommon cause of chest pain to consider, and it requires a heightened level of suspicion and thorough history gathering. If there is suspicion of inflammatory disease, pursuing advanced imaging and biopsies is crucial, as early immunosuppressive treatment can enhance outcomes.

Pericardial involvement in sarcoidosis is a rare condition with limited research. This case study discusses a 52‐year‐old African American woman who presented with subacute chest pain and was diagnosed with pericardial sarcoidosis. Diagnostic evaluation revealed extensive lymphadenopathy and pericardial effusion, and a pericardial biopsy confirmed non‐caseating granulomatous inflammation. Treatment with steroids and methotrexate resulted in clinical improvement. Eight months follow‐up showed near resolution of pericardial disease. This case emphasizes the importance of considering cardiac sarcoidosis in sarcoidosis patients, utilizing advanced imaging for accurate diagnosis, and tailoring treatment to the level of cardiac involvement.
Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material
Authors: Ding Kun , Zhuang Bo , Deng Bo‐Wen , Li Zhi‐Long , Lu Hai‐Feng , Zhang Zhi‐Xu , Fu Da‐Wei
Published: July 2024

The lone pair electrons in the electronic structure of molecules have been a prominent research focus in chemistry for more than a century. Stable s2 lone pair electrons significantly influence material properties, including thermoelectric properties, nonlinear optical properties, ferroelectricity, and electro(photo)catalysis. While major advances have been achieved in understanding the influence of lone pair electrons on material characteristics, research on this effect in organic‐inorganic hybrid materials is in its initial stage. In this work, we successfully obtained a novel organic‐inorganic hybrid multifunctional material incorporating Ge with 4s2 lone pair electrons, (MeHDabco)2[GeBr3]4‐H2O (MeHDabco=N‐methyl‐1,4‐diazabicyclo[2.2.2]octane) (1). Driven by the stereochemically active lone pair electrons on the Ge2+, 1 crystallizes in the noncentrosymmetric space group P21 at room temperature and exhibits good second harmonic generation (SHG) responses. Interestingly, 1 also shows electrocatalytic activity for the hydrogen evolution reaction (HER) due to the existence of lone pair electrons on Ge2+ cations. The electrochemical experiment combined with the density functional theory (DFT) calculations revealed that the lone pair electrons act as both an active site for proton adsorption and facilitate the ionization of water. This work not only emphasizes the important role of lone pair electrons in material properties and functions but also provides new insight for designing novel Ge‐based multifunctional hybrid materials.
Kinetics of cashew apple drying through mechanistic models and analysis of the effects of drying conditions on the retention of bioactive compounds
Authors: Shirsat Vikramaditya R. , Vaidya Prakash D. , Dalvi Vishwanath H. , Singhal Rekha S. , Kelkar Anil K. , Joshi Jyeshtharaj B.
Published: July 2024

Global cashew nut production is nearly 4 million tons per year, valued at 7 billion US dollars. Remarkably, almost the entire cashew apple crop, amounting to 20 million tons annually, goes to waste. However, the cashew apple contains valuable nutraceutical compounds, including tannins, polyphenols, and carotenoids, estimated to be worth 150 million US dollars annually. Due to the highly perishable nature of cashew apples, degradation is a significant issue. In response, the current work has established drying as an effective preservation technique for these bioactive components. The effect of drying temperature on bioactive compounds has been thoroughly investigated. The non‐random two liquid (NRTL) activity coefficient model effectively captures the thermodynamics of the drying process. To facilitate the selection and design of drying equipment, two mechanistic mass transfer models were developed. The first model employs the Maxwell‐Stefan framework to account for internal diffusion, with external mass transfer resistance appearing as a boundary condition. While this model works well for products like grapes, it proved inadequate for explaining the drying behaviour of cashew apples. Consequently, a second model was developed, postulating rapid moisture transport by capillary action within the cashew apple. This model effectively captures the effects of a wide range of operating conditions, using only external mass transfer resistance as the tuneable kinetic parameter. This mechanistic model is more suitable for dryer design compared to conventional phenomenological models like the logarithmic model and the two‐term exponential model.
Self‐Assembled Bioinspired Short Metallopeptide Nanostructures for Plausible Biomedical Applications
Authors: Sharma Shruti , Kautu Aanand , Kumar Nikunj , Swain Narayan , Kumar Vikas , Singh Ramesh , Kesharwani Khushboo , Singh Narendra , Gupta Puneet , Ballabh Joshi Khashti
Published: July 2024

Metal chelation, characterized by its precise interactions with diverse functional groups, assumes a pivotal role in providing structural stability and generating reactive centers within metalloproteins and metallopeptides. This, in turn, orchestrates the architecture and functionality of various biological processes in living organisms. In our biomimetic approach inspired by the intricacies of natural metallopeptides, we have purposefully designed pyridine‐bis‐tyrosine, a concise Metallopeptide Conjugate (sMPC). Demonstrating the capacity to form complexes with various bioactive metal ions, sMPC emerges as a promising tool for advancing our understanding of metal‐binding proteins and catalyzing the development of cutting‐edge biotechnological materials and technologies. Our investigations underscore the hierarchical self‐assembly of these abridged conjugates into toroidal to vesicle nanostructures, influenced by concentration, and their susceptibility to spatial manipulation through metal ion coordination with functional groups. These biocompatible metal peptide complexes and their resultant nanomaterials present specific potential as exceptional therapeutic agents to address problems associated with metal ion deficiencies, offering a facile and low‐cost alternative to traditional metallodrugs.
Diagnostic utility of transfer learning by using convolutional neural network for cytological diagnosis of malignant effusions
Authors: Panda Manisha , Dehuri Priyadarshini , Mohapatra Debahuti , Pandey Ankesh Kumar
Published: July 2024

Introduction

Cytological analysis of effusion specimens provides critical information regarding the diagnosis and staging of malignancies, thus guiding their treatment and subsequent monitoring. Keeping in view the challenges encountered in the morphological interpretation, we explored convolutional neural networks (CNNs) as an important tool for the cytological diagnosis of malignant effusions.

Materials and Methods

A retrospective review of patients at our institute, over 3.5 years yielded a dataset of 342 effusion samples and 518 images with known diagnoses. Cytological examination and cell block preparation were performed to establish correlation with the gold standard, histopathology. We developed a deep learning model using PyTorch, fine‐tuned it on a labelled dataset, and evaluated its diagnostic performance using test samples.

Results

The model exhibited encouraging results in the distinction of benign and malignant effusions with area under curve (AUC) of 0.8674, F‐measure or F1 score which denotes the harmonic mean of precision and recall, to be 0.8678 thus, demonstrating optimal accuracy of our CNN model.

Conclusion

The study highlights the promising potential of transfer learning in enhancing the clinical pathology laboratory efficiency when dealing with malignant effusions.
In emotion and reading motivation, children with a diagnosis of dyslexia are not just the end of a continuum
Authors: Donolato Enrica , Toffalini Enrico , Cornoldi Cesare , Mammarella Irene C.
Published: July 2024

Children with dyslexia (CwD) often report poor psychological well‐being. We examined (i) whether anxiety, self‐concept and reading motivation in CwD differed from those of typically developing children (TDC; case–control design, Study 1a) and (ii) whether these differences mirrored the linear relationships that these variables present with reading ability in the TDC group (dimensional approach, Study 1b). In Study 1a, 34 CwD were compared with 191 TDC in grades 4–8 on anxiety, self‐concept, reading motivation and reading strategy using self‐reports (controlling for sex, intelligence and math ability scores). In Study 1b, the differences that emerged in Study 1a were compared with the results obtained from a simulation procedure that generated dyslexia observations under the assumptions of a dimensional hypothesis. The CwD group presented small‐to‐moderate difficulties, which partially mirrored the predictions in the TDC group. However, violations of predictions based on the population without dyslexia were found for reading self‐concept, social anxiety and reading competitiveness. In sum, children's diagnoses affect their self‐perception as readers and social anxiety in a way that cannot be inferred from linear relationships. CwD need support to preserve an adequate image of themselves as readers and cope with social anxiety.
Comparison of soil eDNA to camera traps for assessing mammal and bird community composition and site use
Authors: Tetzlaff Sasha J. , Katz Aron D. , Wolff Patrick J. , Kleitch Matthew E.
Published: July 2024

Species detections often vary depending on the survey methods employed. Some species may go undetected when using only one approach in community‐level inventory and monitoring programs, which has management and conservation implications. We conducted a comparative study of terrestrial mammal and bird detections in the spring and summer of 2021 by placing camera traps at 30 locations across a large military installation in northern Michigan, USA and testing replicate soil samples from these sites for environmental DNA (eDNA) using an established vertebrate metabarcoding assay. We detected a total of 48 taxa from both survey methods: 26 mammalian taxa (excluding humans, 24 to species and two to genus) and 22 avian taxa (21 to species and one to genus). We detected a relatively even distribution of mammalian taxa on cameras (17) and via eDNA analysis (15), with seven taxa detected from both methods. Most medium‐to‐large carnivores were detected only on cameras, whereas semi‐fossorial small mammals were detected only via eDNA analysis. We detected higher bird diversity with camera traps (18 taxa) compared to eDNA analysis (eight taxa; four taxa were detected with both methods), but cameras alone were most effective at detecting smaller birds that frequently occupy arboreal environments. We also used Bayesian spatial occupancy models for two widely distributed game species (white‐tailed deer, Odocoileus virginianus, and ruffed grouse, Bonasa umbellus) that were moderately detected with both survey methods and found species‐specific site use (occupancy) estimates were similar between cameras and eDNA analysis. Concordant with similar studies, our findings suggest that a combination of camera trap and eDNA surveys could be most useful for assessing the composition of terrestrial mammal communities. Camera traps may be most efficient for assessing bird diversity but can be complemented with eDNA analysis, particularly for species that spend considerable time on the ground.