bluuebunny/crossref_metadata_2025_split huggingface dataset:
Simultaneous Regulation of Organic and Inorganic Components in Interphase by Fiber Separator for High‐Stable Sodium Metal Batteries
Authors: Xue Zhixin , Zhang Tao , Li Xiao , Wang Fei , Xu Guiyin , Zhu Meifang 
Published: September 2024

AbstractUncontrollable side reactions at the metal interface have been identified as the root cause of the formation of a fragile solid electrolyte interphase, leading to irreversible sodium loss in sodium metal batteries. Here, we proposed an interface engineering strategy that employed a carboxyl functionalized cellulose separator to provide strong dipole moments and induce the cleavage of P−F bond to construct a solid electrolyte interphase (SEI) rich in NaF. In addition, we employed nuclear magnetic resonance technology confirmed that the separator with strong dipole moments prevented the reduction of organic solvents by attracting electrons, thereby inhibiting the formation of organic oligomers. SEI with high NaF content and few oligomers is smooth and robust, obviously decreasing the interface impedance of the Na anode. The symmetric Na||Na cells, equipped with the functionalized separator, efficiently operated for 1400 hours with a stable 72 mV overpotential at 0.25 mA cm−2, exhibiting low energy barrier and fast ion transport kinetics. The Na||Na3V2(PO4)3 cell also showed stable cycling performance, with the capacity remaining at 94.83 % of the initial capacity after 1000 cycles at 1C. The proposed separator could control the formation and composition of SEI, paving the way for the development of long‐life sodium metal batteries.
Guest‐Induced “Breathing‐Helical” Dynamic System of a Porphyrinic Metallo‐Organic Cage for Advanced Conformational Manipulation
Authors: Dong Qiangqiang , Liu Fengxue , Wang Jun , Han Ermeng , Zhao He , Chen Bangtang , Li Kaixiu , Yuan Jie , Jiang Zhilong , Chen Mingzhao , Li Yiming , Liu Die , Lin Yifan , Wang Pingshan 
Published: September 2024

AbstractHost‐guest dynamic systems in coordination‐driven metallo‐organic cages have gained significant attentions since their promising applications in chiral separation, drug delivery, and catalytical fields. To maximize guest‐binding affinity, hosts adopting multiple conformations are widely investigated on their structural flexibility for guest accommodation. In this study, a novel metallo‐organic cage S with breathing inner cavity and freely twisted side chains was proposed. Single‐crystal X‐ray diffraction analyses depicted a characteristic “breathing‐helical” dynamic system on the semiflexible framework, which led to an unprecedent co‐crystallisation of racemic and symmetric conformations via the encapsulation locking of C70 guests. By taking advantages of the high binding affinity, selective extraction of C70 was realized. This research provides new ideas for the modification on the helicities of metallo‐organic cages, which could pave a new way for advanced conformational manipulation of supramolecular host systems.
Theory‐Guided Design of Unconventional Phase Metal Heteronanostructures for Higher‐Rate Stable Li‐CO2 and Li‐Air Batteries
Authors: Zhou Jingwen , Xu Zhihang , Cui Kai , Yin Jian‐An , Chen Hsiao‐Chien , Wang Yunhao , Liu Fu , Wang Tianshuai , Hao Fengkun , Xiong Yuecheng , Wang Cheng , Ma Yangbo , Lu Pengyi , Yin Jinwen , Guo Liang , Meng Xiang , Ye Chenliang , Ming Chen Hao , Zhu Ye , Lu Jian , Fan Zhanxi 
Published: September 2024

AbstractLithium‐carbon dioxide (Li‐CO2) and Li‐air batteries hold great potential in achieving carbon neutral given their ultrahigh theoretical energy density and eco‐friendly features. However, these Li‐gas batteries still suffer from low discharging‐charging rate and poor cycling life due to sluggish decomposition kinetics of discharge products especially Li2CO3. Here we report the theory‐guided design and preparation of unconventional phase metal heteronanostructures as cathode catalysts for high‐performance Li‐CO2/air batteries. The assembled Li‐CO2 cells with unconventional phase 4H/face‐centered cubic (fcc) ruthenium‐nickel heteronanostructures deliver a narrow discharge‐charge gap of 0.65 V, excellent rate capability and long‐term cycling stability over 200 cycles at 250 mA g−1. The constructed Li‐air batteries can steadily run for above 150 cycles in ambient air. Electrochemical mechanism studies reveal that 4H/fcc Ru−Ni with high‐electroactivity facets can boost redox reaction kinetics and tune discharge reactions towards Li2C2O4 path, alleviating electrolyte/catalyst failures induced by the aggressive singlet oxygen from solo decomposition of Li2CO3.
Are convection‐permitting climate projections reliable for urban planning over Africa? A case study of Johannesburg
Authors: Keat William J. , Short Chris J. , Kendon Elizabeth J. 
Published: September 2024

AbstractCities are particularly vulnerable to surface water flooding. It is also well‐known that they influence local rainfall themselves, which has important implications for climate change adaptation planning for cities. At km‐scale resolution, convection‐permitting climate models (CPCMs) better resolve cities and should better represent local urban temperature and rainfall modifications. However, using state‐of‐the‐art pan‐African CPCM simulations with the Met Office Unified Model (CP4), we show that for the city of Johannesburg, South Africa, this is not the case. A significant enhancement of rainfall occurs over the city compared with surrounding rural areas, which is not seen in available observations. We demonstrate this is associated with an overestimated urban heat island effect, which leads to additional triggering of rainfall. Urban signals in future rainfall change are small compared with changes in the wider surroundings, the latter of which we expect to be more reliable than in models with parameterized convection. This suggests that deficiencies in representation of urban processes are of secondary importance in terms of future percentage change in rainfall. We recommend urban planners apply relative changes in CP4 as an uplift to observations, where available, or treat absolute future rainfall as an upper estimate if used directly.
Nickel‐Manganese‐Based Layered Oxide for Sodium Ion Battery Cathode Materials
Authors: Gao Yuheng , Zhang Ping , Zhang Renyuan 
Published: September 2024

AbstractSodium‐ion batteries (SIBs) have demonstrated significant potential as alternatives to conventional lithium‐ion batteries (LIBs) for modern grid and mobile energy storage applications, due to the abundant natural resources and low cost of sodium. Layered transition metal oxides (LTMOs) have attracted much attention due to their high specific capacities, energy densities as well as the compatible preparation processes with those of LIBs cathode materials. Among these, Ni/Mn‐based LTMOs (NMLOs) are particularly noteworthy for their cost‐effectiveness and superior electrochemical performance, such as excellent capacity retention, voltage stability, high operating voltage and rate capability. In this review, we briefly introduce the synthesis methods of NMLOs, discuss the challenges, and summarize the solutions. The insights presented may contribute to the development of NMLOs based SIBs.
A mixed Ce/Eu metal–organic framework for ratiometric detection of Al3+ ion
Authors: Chen Dong , Wan Yating , Li Yanping , Qin Bowen , Zhang Bing , Wang Mengyao , Cai Yarui , Li Yanxia , Li Weidong , Wang Zhenling 
Published: September 2024

AbstractAs a heavy metal ion, excessive aluminum ions pose a serious threat to human health and the ecological environment. Developing a simple, efficient, and fast detection method to detect the content of aluminum ions is of great significance, especially for ensuring human health and ecological safety. Herein, the mixed rare earth metal–organic framework (Ce0.74Eu0.26TPTC and Ce0.62Eu0.38TPTC) were prepared based on simple ligand 1,1′:4′,1″‐Terphenyl‐2′,4,4″,5′‐tetracarboxylic acid (H4TPTC). The Ce0.74Eu0.26TPTC and Ce0.62Eu0.38TPTC have dual luminescence centers, which can be used as ratio fluorescent probes to detect Al3+ ions, making the detection results more accurate and reliable. Therefore, this work can promote the further development of rare earth‐based MOFs in the detection of heavy metal ions.
Novel Dipeptide Inhibitors of PfPNP: In‐Silico Identification of Promising New Antimalarials
Authors: Devi Kanika , Chandra Anshuman , Chaudhuri Susmita , Kumar Goel Vijay 
Published: September 2024

AbstractMalaria, an infectious disease caused by Plasmodium falciparum, is becoming increasingly difficult to treat due to the emergence of drug‐resistant strains. Recent studies have proposed purine nucleoside phosphorylase from P. falciparum (PfPNP) as a potential target for malaria treatment. In the present study, we designed a virtual library of 400 dipeptides to discover novel anti‐malarial peptide inhibitors. A structure‐based molecular docking method was employed to virtually screen the designed library against the wild‐type structure of PfPNP (PDB: 5ZNC). The best four (Phe‐Arg, Arg‐His, Trp‐Arg and Tyr‐Arg) dipeptides, which were then investigated for their binding potential against PfPNP using Molecular Dynamics simulation studies. Parameters such as RMSD, RMSF, Rg, and SASA were analyzed to understand the structural changes, energetics, and overall behavior of PfPNP‐dipeptide complexes. The PfPNP demonstrated significant stability upon binding with each of the identified dipeptides with ΔG of over −168 kcal/mol. Additionally, DFT and ADME predictions indicated that the electronic structure, energetics, and pharmacokinetic properties of Phe‐Arg, Arg‐His, Trp‐Arg and Tyr‐Arg were favourable for drug development. Our comprehensive computational investigation has identified these four dipeptides as promising candidates. These designed and selected dipeptides may further be modified using peptidomimetic and medicinal chemistry tools to develop a novel class of promising antimalarials.
Whitaker syndrome: A case report of autoimmune polyendocrine syndrome type 1 with dilated cardiomyopathy
Authors: Gohar Ali , Ahmed Bilal , Azhar Shahroz , Iqbal Aqsa , Usman Ali , Ahmad Muhammad Husnain , Ali Masab , Jawaid Muhammad Daim 
Published: September 2024

Key Clinical MessageThis case report highlights dilated cardiomyopathy as a cardiovascular complication in autoimmune polyendocrine syndrome type 1 (APS‐1), emphasizing the need for early recognition and a multidisciplinary approach. Comprehensive care and regular follow‐up are crucial in managing these atypical presentations to optimize patient outcomes.AbstractAPS‐1, also known as Whitaker syndrome, is characterized by a triad of mucocutaneous candidiasis, adrenal insufficiency, and hypoparathyroidism. This rare autosomal recessive disorder results from mutations in the autoimmune regulator (AIRE) gene. Cardiovascular and pulmonary manifestations in APS‐1 are infrequently reported in the literature. We present a case of a 28‐year‐old male who presented with shortness of breath and pedal edema. Physical examination revealed alopecia, absence of eyebrows, hyperpigmentation on joints, oral candidiasis, and nail dystrophy. Echocardiography demonstrated dilated cardiomyopathy (DCM) and pericardial effusion. Chest x‐ray showed left‐sided pleural effusion. Laboratory investigations revealed hypocalcemia, hyperphosphatemia, low parathyroid hormone (PTH), low cortisol, and high adrenocorticotropic hormone (ACTH) levels. The combination of chronic mucocutaneous candidiasis (CMC), hypoparathyroidism, and adrenal insufficiency confirmed the diagnosis of APS‐1. To the best of our knowledge, this is the first Pakistani and second worldwide reported case of APS‐1 presenting with such a combination of manifestations. Early recognition and multidisciplinary management are crucial for improving outcomes in these patients.
Electron Paramagnetic Resonance Analysis of Hydroquinone Polymerization Catalyzed by Small Laccase
Authors: Liu Aokun , Kuang Jian , Wei Ruotong , Zhang Zhitao , Li Jiabin , Tian Changlin , Yu Lu 
Published: September 2024

AbstractLaccases are multi‐copper oxidases (MCOs) that oxidize a broad range of substrates while reducing molecular oxygen to water. Although much effort has been made to elucidate the catalytic mechanism of laccases, information about reactive catalytic intermediates during catalysis is not yet fully understood. Herein, hydroquinone (HQ) polymerization catalyzed by prokaryotic small laccase (SLAC) was investigated by electron paramagnetic resonance (EPR) spectroscopy to provide more information on the catalytic mechanism. Briefly, free radical intermediates during the catalysis were investigated by real‐time in situ EPR measurement to monitor the formation and transformation of free radicals. A paramagnetic species was identified which was attributed to a copolymer formed by hydroquinone, benzoquinone, and semiquinone radical. In addition, the low‐temperature EPR spectrum of the trinuclear copper center during catalysis not only revealed tentative rotational motion of the histidine imidazole rings coordinating the TNC upon electron uptake but also provided evidence of the formation of oxygen bridge at TNC during the reaction, represented by the observation of a new type 2 copper component featured larger g// values and smaller A// values. Together, EPR spectroscopic insights into the catalytic intermediates during enzymatic hydroquinone polymerization have extended the knowledge of the biophysical characteristics and catalytic mechanism of SLAC.
Engineering Amorphous/Crystalline Nanoflower Heterointerfaces for Enhanced Acidic Water Oxidation
Authors: Liu Chang , Zhang Bowen , Cao Rong , Cao Minna 
Published: September 2024

AbstractEfficient water electrolysis for green hydrogen production relies on the development of robust oxygen evolution reaction (OER) catalysts, particularly for acidic environments. This study introduces amorphous/crystalline Mn─Ru binary oxides nanoflowers (a/c‐Mn0.9Ru0.1O2) as a promising acidic OER catalyst, synthesized via a two‐step phase engineering approach. The optimized a/c‐Mn0.9Ru0.1O2‐200 composition exhibits exceptional OER activity, requiring a low overpotential of 168 mV to achieve a current density of 10 mA/cm2 and demonstrating remarkable stability over 28 h. This significantly outperforms commercial RuO2 catalysts, which require an overpotential of 320 mV at 10 mA/cm2 and exhibit a stability of only 0.5 h under identical conditions. X‐ray absorption spectroscopy (XAS) and X‐ray photoelectron spectroscopy (XPS) analysis results reveal the formation of Mn─O─Ru linkages and an optimized d‐band electronic structure, attributed to strong electronic coupling at the amorphous/crystalline interface. This unique architecture promotes optimal adsorption/desorption of OER intermediates, leading to enhanced catalytic performance. This study offers a novel strategy for the rational design and production of efficient acidic OER catalysts.
The Role of a Redox‐Active Ligand in Cu(II)‐Nitrenoid Formation and Its Aziridination Reactivity
Authors: Mahajan Mayank , Gangwar Ushma , Mondal Bhaskar 
Published: September 2024

AbstractMetal‐nitrenoid species are the key intermediate in nitrene transfer reactions. The bond formation between the open‐shell transition metal and the nitrene species dictates their overall reactivity. Herein, we present an in‐depth electronic structure investigation to uncover how the formation of a Cu(II)‐nitrenoid species is assisted by redox‐active iminosemiquinone (ISQ) ligand in the [CuII(LISQ)2] complex and impacts the nitrene transfer reactivity. The reaction energetics of the aziridination reaction between N‐tosyliminophenyliodinane and 4‐chlorostyrene is established by DFT calculations, where the formation of the Cu(II)‐nitrenoid intermediate (Int1) is found to be the rate‐determining step. Based on the natural orbital and spin populations obtained from the ab initio multiconfigurational CASSCF(13,13) calculation, the electronic nature of the elusive Cu(II)‐nitrenoid intermediate (Int1) could be formulated as “imidyl” [(LISQ)(LIBQ)CuII─•NTos] (Tos = Tosyl) species. A weak σ interaction between the Cu(II) center and the N‐atom of the nitrene moiety (Cu 20% + N 29%) involving a Cu─N distance of 1.92 Å defines the Cu‐nitrenoid bonding. The interplay between elongated Cu─N bond and high‐spin population on N‐atom (+0.96) corroborates its high nitrene transfer ability. Furthermore, the intrinsic bond orbital (IBO) analysis unravels a ligand‐to‐substrate electron transfer mechanism that facilitates the formation of the crucial Cu(II)‐nitrenoid species.
Photoinduced On and Off Polymeric Room Temperature Phosphorescence Based On Polycyclic Aromatic Hydrocarbon Isomers
Authors: Zhou Chenglin , Tian Quanchi , Ding Qiuyue , Qu Lunjun , Wang Kaiti , Tang Hailong , Yang Chaolong 
Published: September 2024

AbstractAs family members of polycyclic aromatic hydrocarbons, compound anthracene (Ant) and phenanthrene (Phe) as isomers are widely used in organic optical materials and electronic materials. But their photochemical and physical properties are very different. In this work, the room temperature phosphorescence (RTP) properties of PVA−B‐Ant and PVA−B‐Phe are discussed carefully which are prepared by B−O click reaction through polyvinyl alcohol (PVA) with 9‐anthraceneboronic acid (B‐Ant) and 9‐phenanthrenylboronic acid (B‐Phe), respectively. PVA−B‐Phe 1 % film exhibits excellent fluorescence (FL) emission at 374 nm and RTP emission at 523 nm with green afterglow and around 1.9 s phosphorescence lifetime. However, PVA−B‐Ant 1 % film only shows strong blue FL emission at 414 nm, and the emission intensity decreases seriously with the extension of irradiation time. Experimental and theoretical calculations results suggest that the photodimer of Ant which is formed in PVA matrix under the UV light irradiation would be competitive with the process of RTP emission. This work demonstrates that the RTP properties of organic molecules might be probably affected by the photostability of the organic phosphor under UV irradiation.
Total Synthesis of Tosyl‐Samroiyotmycin A and Its Biological Profiling
Authors: Kolb Benedikt , Schmid Fabian , Weng Jessica , Altevogt Luca , Pereira Rebelo Ruben , Wank Bianca , Baro Angelika , Zens Anna , Shekhar Aditya , Bilitewski Ursula , Sax Sibylle , Wittlin Sergio , Taylor Dale , Müller Rudolf , Laschat Sabine 
Published: September 2024

AbstractA total synthesis of the enantiopure syn,syn‐tosyl‐samroiyotmycin A, a C2‐symmetric 20‐membered antimalarial macrodiolide with syn,syn‐configuration of the 8,24‐dihydroxy‐9,25‐dimethyl units and it's enantiopure anti,anti‐derivative is described. The synthesis was accomplished utilizing a linear approach in 7 steps and 3 % overall yield via a sequence of diastereoselective methylation of SuperQuat oxazolidinone auxiliary, cross metathesis and Yamaguchi macrolactonization of fully functionalized seco‐acids. By a similar approach we gained access to several samroiyotmycin analogues and precursors. Antimalarial activity was tested on multi‐resistant (K1) and sensitive (Nf54) P. falciparum strains providing insight into structure activity relationships. Both tosyl‐oxazol unit as well as the syn‐configuration of the two contiguous stereogenic centers turned out to be beneficial for antiplasmodial activity. For instance, syn,syn‐tosyl‐samroiyotmycin A showed 3.4 times higher activities than the “tosyl‐free” natural product.
Comparison of Standard and Prone‐Position Electrocardiograms in COVID‐19 Patients With Pulmonary Complications: Correlations and Implications
Authors: Makarawate Pattarapong , Chimtim Krissanachai , Mitsungnern Thapanawong , Phungoen Pariwat , Imoun Supap , Mootsikapun Piroon , Tangpaisarn Thanat , Kotruchin Praew 
Published: September 2024

ABSTRACTBackgroundPrevious research highlighted variability in electrocardiogram (ECG) readings across patient positions, particularly in the context of COVID‐19 patients with pulmonary complications requiring prone positioning as part of the treatment.ObjectiveThis study aimed to elucidate the effects of prone positioning on ECG parameters and explore its association with the severity of COVID‐19.MethodsA prospective cohort study involved 60 patients diagnosed with COVID‐19 and presenting pulmonary complications. ECGs were recorded in both supine and prone positions, and analyzed for various parameters including heart rate, QRS axis, and QTc interval. Clinical severity was assessed using APACHE II scores and SpO2/FiO2 ratios.ResultsProne positioning led to an increase in heart rate (mean difference: 2.100, 95% CI: 0.471–3.729, p = 0.012), with minor shifts in the QRS axis. Heart rate and QRS axis demonstrated strong positive correlations between positions, with Pearson's correlation coefficients of 0.927 and 0.894, respectively. The study also found a significant association between prolonged QTc intervals in the prone position and elevated APACHE II scores, with a relative risk of 10.75 (95% CI: 1.82–63.64, p = 0.008).ConclusionsThe prone positioning caused minor yet significant changes in heart rate and QRS axis. The correlation of prolonged QTc intervals in the prone position with higher APACHE II scores suggests the prognostic relevance of prone ECG in COVID‐19 patients. However, further research is needed to fully understand the clinical implications and mechanisms of these findings.
The American Cancer Society National Lung Cancer Roundtable strategic plan: Promoting guideline‐concordant lung cancer staging
Authors: Farjah Farhood , Barta Julie A. , Wood Douglas E. , Rivera M. Patricia , Osarogiagbon Raymond U. , Smith Robert A. , Mullett Timothy W. , Rosenthal Lauren S. , Henderson Louise M. , Detterbeck Frank C. , Silvestri Gerard A. 
Published: September 2024

AbstractAccurate staging improves lung cancer survival by increasing the chances of delivering stage‐appropriate therapy. However, there is underutilization of, and variability in, the use of guideline‐recommended diagnostic tests used to stage lung cancer. Consequently, the American Cancer Society National Lung Cancer Roundtable (ACS NLCRT) convened the Triage for Appropriate Treatment Task Group—a multidisciplinary expert and stakeholder panel—to identify knowledge and/or resource gaps contributing to guideline‐discordant staging and make recommendations to overcome these gaps. The task group determined the following: Gap 1: facilitators of and barriers to guideline‐concordant staging are incompletely understood; Recommendation 1: identify facilitators of and barriers to guideline‐concordant lung cancer staging; Gap 2: the level of evidence supporting staging algorithms is low‐to‐moderate; Recommendation 2: prioritize comparative‐effectiveness studies evaluating lung cancer staging; Gap 3: guideline recommendations vary across professional societies; Recommendation 3: harmonize guideline recommendations across professional societies; Gap 4: existing databases do not contain sufficient information to measure guideline‐concordant staging; Recommendation 4: augment existing databases with the information required to measure guideline‐concordant staging; Gap 5: health systems do not have a performance feedback mechanism for lung cancer staging; Recommendation 5: develop and implement a performance feedback mechanism for lung cancer staging; Gap 6: patients rarely self‐advocate for guideline‐concordant staging; Recommendation 6: increase opportunities for patient self‐advocacy for guideline‐concordant staging; and Gap 7: current health policies do not motivate guideline‐concordant lung cancer staging; Recommendation 7: organize a representative working group under the ACS NLCRT that promotes policies that motivate guideline‐concordant lung cancer staging.Plain language summaryStaging—determining the degree of cancer spread—is important because it helps clinicians choose the best cancer treatment. Receiving the best cancer treatment leads to the best possible patient outcomes. Practice guidelines are intended to help clinicians stage patients with lung cancer. However, lung cancer staging in the United States often varies from practice guideline recommendations. This report identifies seven opportunities to improve lung cancer staging.